WO2024104374A1

WO2024104374A1 - Degradable filament, preparation method therefor, and use thereof

Info

Publication number: WO2024104374A1
Application number: PCT/CN2023/131752
Authority: WO
Inventors: 武玉和; 许向东; 邓铁军; 兰宇轩; 韩白; 章义鑫
Original assignee: 北京微构工场生物技术有限公司
Priority date: 2022-11-18
Filing date: 2023-11-15
Publication date: 2024-05-23

Abstract

The present invention relates to the technical field of biodegradable materials, and specifically relates to a degradable filament, a special material for the filament, and a preparation method therefor and a use thereof. The filament comprises a main base material of PHA, or a pure PHA base material and auxiliary agents such as a nucleating agent and/or a reinforcing agent. According to the present invention, by further cooperating with an initial spinning process comprising cooling and stretching, the preparation of a pure PHA-based filament is achieved; the phenomena such as low melt strength, poor thermal stability, low crystallization speed, weak mechanical properties, and serious adhesion during PHA spinning are improved; the comprehensive properties, in particular the mechanical properties, of the pure PHA-based filament are improved; and the requirements of the application fields of conventional fabric products and industrial textile products are met.

Description

A kind of degradable filament and its preparation method and application

Technical Field

The invention relates to the technical field of biodegradable materials, and in particular to a degradable filament and a special material thereof.

Background technique

With the popularization of environmental protection concepts such as carbon peak and carbon neutrality, people's demand for degradable materials is also growing. The research on degradable materials has gradually expanded from various plastic application fields such as injection molding, film materials, and sheet materials to rubber, leather, or textiles. Among them, the preparation of new fibers with degradable materials has become a research hotspot. This direction has expanded new types of chemical fibers and made the two major application directions of textiles and non-wovens more possible.

As an emerging material that is purely bio-sourced and 100% degradable, polyhydroxyalkanoate (PHA) is greener and more biofriendly in production, purification and application compared to degradable materials such as polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate/terephthalate (PBAT), and polypropylene carbonate (PPC). It does not require petroleum-based industrial products as a synthetic source. In addition, it has lower environmental requirements for degradation and can be naturally degraded without composting. Therefore, it is more in line with the concepts of carbon peak and carbon neutrality, and is a truly environmentally friendly material throughout its life cycle.

However, the application of PHA in textiles and nonwovens is still in the exploratory stage, and is generally blended with materials such as PLA, PBAT, and PPC to improve spinnability. Even so, PHA only accounts for a small proportion of it, especially in ready-made clothes or other products, where its content is often less than 10%, far from giving full play to its advantages of rapid degradation, bioaffinity, antibacterial, and easy dyeing. The incompatibility between blended materials can easily cause the instability of the overall material, so there is an urgent need to explore the reasonable formula of pure PHA-based filaments and their processing and preparation methods.

Patent document CN114262952A provides a composite material, which is composed of a skin component A and a core component B, wherein PHA is the main component in component A and nylon is the main component in component B, thereby combining the advantages of PHA being dyeable and fully biodegradable with the advantages of nylon being high toughness and high strength to produce a composite filament with a skin-core structure. However, the presence of nylon makes it not a fully degradable material, and the processing temperature of nylon as a core layer is relatively high, so it is difficult for the PHA of the skin layer to completely cover it, and the performance stability of the filament is poor.

Patent document CN111501117A prepares PLA/PHA fibers through an online device for preparing PLA/PHA fibers in combination with a specific ratio, thereby improving the quality and mechanical properties of the fibers and effectively reducing costs. However, the proportion of PHA is very low, and the fibers are not mainly PHA-based, and perform poorly in terms of dyeing and heat resistance.

Patent document CN109183191B melt-extrudes the blended slices of P3HB4HB and PLA to obtain nascent fibers, and the nascent fibers are placed and hot-drawn to obtain flexible blended fibers, but the PHA content is less than 40%, which still cannot be used as the main body. In addition, the raw materials need to go through the processes of melt granulation, melt-to-make slices, melt-extrude nascent fibers, hot-drawing, etc., which are repeatedly heated and cooled, and it is easy to cause degradation or thermal decomposition, resulting in a decrease in material performance, making the quality of the final obtained fiber not stable enough; during the production process, the drafting multiple is very small, and the spinning machine speed is slow, which affects the production efficiency.

Patent document CN102392318A combines PHA (PHBV) with PLA to obtain bio-based degradable fibers, which have good spinnability at lower spinning temperatures and higher spinning speeds, and have higher mechanical strength and a softer, more stable feel. Its preparation method can effectively improve production efficiency and reduce costs. However, PLA accounts for a considerable proportion of the fibers, and the processing performance of the materials is improved only by physical blending of the two materials, without other modification methods. Therefore, the overall heat resistance is still poor.

Patent document CN114318588A uses PHA (P4HB) and PLA to blend and modify them with reactive and physical compatibilizers, which greatly improves the compatibility of the two materials and helps to improve the toughness and strength of the fiber. PHA is the main component, but the second drawing temperature during processing is not high, which will strengthen the post-crystallization phenomenon, easily causing the mechanical properties to decrease, i.e., brittleness, and is not conducive to improving efficiency.

Patent document CN105603569A unexpectedly improves the crystallization rate by blending carbon nanotubes with PHBHHx, thereby improving the spinning efficiency and reducing the cost. However, its processing method adopts a method of stretching orientation after crystallization and then tensile heat setting. Since the melt extrusion speed is too slow, a larger stretching multiple is required. However, the stretching temperature is not much higher than the crystallization temperature. Crystallization will continue during the stretching orientation stage. That is, a large stretching multiple combined with a low stretching temperature is likely to cause breakage during the stretching process. Therefore, the process is not stable.

Based on the above patent documents, there are currently few reports on pure PHA-based filaments or fibers. The preparation process of PHA-containing fibers mostly encounters problems such as slow crystallization speed, fiber adhesion, low strength, poor toughness, and narrow processing window. Therefore, the art needs to develop a filament and a preparation method thereof that can improve the low melt strength, poor thermal stability, slow crystallization speed, weak mechanical properties, and severe adhesion that exist during PHA spinning.

Summary of the invention

The purpose of the present invention is to overcome the shortcomings of the prior art in making filament materials using PHA, improve the processing performance of PHA by using appropriate additives and pure PHA materials as substrates, and use special processing technology to further improve the comprehensive properties of pure PHA filaments, especially the mechanical properties and antibacterial properties, improve the low melt strength, poor thermal stability, slow crystallization rate, weak mechanical properties, severe adhesion and other phenomena existing in PHA spinning, and expand the application of PHA in the textile and non-woven fields.

In a first aspect, a filament is provided, wherein the filament (or its raw material) comprises a substrate and an auxiliary agent.

The substrate comprises any value of PHA in the mass percentage range of 50%-100%, preferably any value of PHA in the mass percentage range of 80%-100%, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9% or 100% PHA.

Preferably, the filament (or its raw material) comprises a base material and an auxiliary agent, and the base material is PHA.

Further preferably, the filament (or its raw material) comprises PHA and an auxiliary agent.

In a specific embodiment of the present invention, the filament (or its raw material) is made of PHA and an auxiliary agent. Preferably, the filament is made of PHA as the main raw material and is physically or chemically modified by adding various auxiliary agents.

Preferably, the mass ratio of the substrate to the auxiliary agent is any value in the range of (50-150):(0.1-28), for example, (50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150):(0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28). For example, 50:0.1, 100:0.1, 150:0.1, 100:5.75, 100:7.5, 100:7.75, 100:8.25, 100:8.5, 100:10.35, 50:14.05, 100:14.05, 100:14.5, 100:16.5, 100:16.75, 150:14.05, 100:20.5, 50:28, 100:28, or 150:28.

The auxiliary agent may be any auxiliary agent known in the prior art, which can physically or chemically modify PHA.

The auxiliary agents include but are not limited to one or a combination of two or more of nucleating agents, reinforcing agents, nanomaterials, tetrachlorophthalic anhydride, thermal stabilizers, chain extenders, antioxidants, anti-hydrolysis agents, anti-blocking agents, crosslinking agents, coupling agents and plasticizers.

Preferably, the auxiliary agent comprises a nano material. Further preferably, the nano material comprises, but is not limited to, one or a combination of two or more of nano magnesium oxide, nano calcium carbonate, gas phase nano silicon dioxide, nano cellulose, nano zinc oxide, nano titanium boride or nano titanium carbide.

Preferably, the mass ratio of PHA to nanomaterial is any value in 100:(0.0001-4), preferably any value in 100:(0.0001-3.25) or 100:(1-4), for example, 100:(0.0001, 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.25, 1.5, 1.6, 1.7, 1.75, 1.8, 1.9, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5 or 4).

Preferably, the auxiliary agent includes a nucleating agent and/or a reinforcing agent.

Further preferably, the nucleating agent includes but is not limited to one or a combination of two or more of nano magnesium oxide, nano calcium carbonate, MILLAD 3905, MILLAD 3988, NA-21, and ACLYN 285A.

More preferably, the enhancer includes, but is not limited to, one or a combination of two or more of fumed nano-silica, talcum powder, nano-cellulose, DH-2 enhancer, DH-3 enhancer, DH-4 enhancer, and tetrachlorophthalic anhydride. More preferably, the enhancer at least includes tetrachlorophthalic anhydride.

Preferably, the mass ratio of the nucleating agent to the reinforcing agent is any value among (0.0001-5):(0.1-25), and more preferably any value among (0.0001-3):(0.1-18) or (0.2-3):(1-20) or (0.2-3):(1-18). For example, (0.0001, 0.0002, 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.7, 0.75, 0.8, 0.9, 1, 2, 3, 4, or 5): (0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25).

In a specific embodiment of the present invention, the mass ratio of the nucleating agent to the reinforcing agent is 0.75:5.

In a specific embodiment of the present invention, the auxiliary agent includes nanomaterials and tetrachlorophthalic anhydride. Preferably, the nanomaterials include nanomagnesium oxide, nanocalcium carbonate, gas-phase nanosilica or nanocellulose.

In a specific embodiment of the present invention, the mass ratio of PHA to tetrachlorophthalic anhydride is 100: any value in (0.05-5), preferably 100: any value in (1.5-2), for example, 100: (0.05, 0.1, 0.5, 1, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4 or 5).

Preferably, the auxiliary agent also includes one or a combination of two or more of a heat stabilizer, a chain extender, an antioxidant, an anti-hydrolysis agent, an anti-blocking agent, a cross-linking agent, a coupling agent and a plasticizer.

Preferably, the auxiliary agent also includes a heat stabilizer. Further preferably, the heat stabilizer includes but is not limited to one or a combination of two or more of magnesium 2-ethylhexanoate, zinc 2-ethylhexanoate, zinc stearate, calcium stearate, calcium laurate, and magnesium laurate.

Preferably, the auxiliary agent also includes a chain extender. Further preferably, the chain extender includes but is not limited to one or a combination of two or more of BASF ADR4300F, BASF ADR 4400, Vertellus E60P, 2,2'-(1,3-phenylene)-bisoxazoline, trimethylolpropane, and EK-145 polyester chain extender.

Preferably, the auxiliary agent also includes an antioxidant. Further preferably, the antioxidant includes but is not limited to one or a combination of two or more of antioxidant CA, LOWINOX 44B25, antioxidant RIANOX 1098, antioxidant RIANOX 1790, antioxidant RIANOX 168, and antioxidant RIANOX 626.

Preferably, the auxiliary agent also includes an anti-hydrolysis agent. Further preferably, the anti-hydrolysis agent includes but is not limited to one or a combination of two or more of polycarbodiimide UN-03, double bond anti-hydrolysis agent CHINOX P-500, DuPont 132F NC010, anti-hydrolysis stabilizer 3600, and KANEKA M732.

Preferably, the auxiliary agent also includes an anti-adhesive agent. Further preferably, the anti-adhesive agent includes but is not limited to one or a combination of two or more of oleic acid amide, stearic acid amide, BYK3700 organic silicone leveling agent, silica opening agent AB-MB-09, and antistatic agent MOA3-PK.

Preferably, the auxiliary agent also includes a crosslinking agent, such as an environmentally friendly crosslinking agent. Further preferably, the environmentally friendly crosslinking agent includes but is not limited to hydroxypropyl methacrylate, methyltriethoxysilane, HTDI, DAP, isobutyloxymethylacrylate, multifunctional aziridine crosslinking agent SaC-100, aluminum citrate, and multifunctional polycarbodiimide UN-557, or a combination of two or more thereof.

Preferably, the auxiliary agent also includes a coupling agent, such as an environmentally friendly coupling agent. Further preferably, the environmentally friendly coupling agent includes but is not limited to one or a combination of two or more of silane coupling agent Z-6020, silane coupling agent KH-550, silane coupling agent KBM-602, TTS, and KR-38S.

Preferably, the auxiliary agent also includes a plasticizer, such as an environmentally friendly plasticizer. Further preferably, the environmentally friendly plasticizer includes but is not limited to one or a combination of two or more of TBC, ATBC, and BNTXIB.

Preferably, in the filament (or its raw material), the mass content of the PHA is any value in the range of 64.10%-99.933% (preferably 72%-99%), for example, 64.10%, 65%, 70%, 72%, 75%, 80%, 85%, 87%, 90%, 95%, 98%, 99% or 99.933%.

Preferably, in the filament (or its raw material), the mass content of the auxiliary agent is any value in the range of 0.067%-35.90% (preferably 1%-28% or 0.67%-35.90%), for example, 0.067%, 0.67%, 1%, 5%, 10%, 11%, 12%, 13%, 15%, 20%, 25%, 28%, 30%, 35% or 35.90%.

Preferably, the mass ratio of the PHA to the adjuvant is any value in (50-150):(0.1-28), for example, 50:0.1, 100:0.1, 150:0.1, 100:5.75, 100:7.5, 100:7.75, 100:8.25, 100:8.5, 100:10.35, 50:14.05, 100:14.05, 100:14.5, 100:16.5, 100:16.75, 150:14.05, 100:20.5, 50:28, 100:28 or 150:28.

In a specific embodiment of the present invention, the filament (or its raw material) contains 100 parts of PHA and 14.5 parts of auxiliary agent.

Preferably, the PHA can be any PHA known in the prior art, can be of any molecular weight, for example, 300,000-6,000,000 (specifically, 300,000, 500,000, 100,000, 200, 300, 400, 500, or 6,000,000), and can be prepared in any manner, such as bacterial fermentation or chemical synthesis.

Further preferably, the PHA includes but is not limited to 3-hydroxypropionic acid (3HP), 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 4-hydroxybutyric acid and 5-hydroxyvaleric acid or any one or more of their derivatives, various homopolymers, random copolymers and block copolymers, more preferably, the PHA includes but is not limited to poly-3-hydroxybutyrate (PHB), Poly-3-hydroxyvalerate (PHV), poly-3-hydroxypropionate (P3HP), copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid (PHBV), poly-3-hydroxyoctanoate (PHO), poly-3-hydroxynonanoate (PHN), copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid (P3HB4HB), copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid (PHBHHx), copolymer of 3-hydroxybutyric acid, 4-hydroxybutyric acid and 3-hydroxyvaleric acid (P3HB4HB3HV) or copolymer of 3-hydroxybutyric acid, 4-hydroxybutyric acid and 5-hydroxyvaleric acid (P3HB4HB5HV) or a combination of two or more thereof.

Preferably, the PHA includes but is not limited to one or a combination of two or more of PHB, P3HB4HB, PHBHHx, PHBV, P3HB4HB3HV and P3HB4HB5HV.

Preferably, the molar content of 3HV in PHBV is any value in the range of 1-80%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70% or 80%.

Preferably, the molar content of 4HB in P3HB4HB is any value between 1-80%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70% or 80%.

Preferably, the molar content of HHx in PHBHHx is any value in the range of 1-80%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70% or 80%.

Preferably, the molar content of 4HB or 3HV in P3HB4HB3HV is any value in the range of 1-80%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70% or 80%.

Preferably, the molar content of 4HB or 5HV in P3HB4HB5HV is any value in the range of 1-80%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70% or 80%.

According to the requirements of the specific implementation, the PHA can be one kind, or a combination of two or more kinds.

In one embodiment of the present invention, the PHA comprises PHB and P3HB4HB blended in a mass ratio of 1:10-10:1, for example (1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100):10.

In one embodiment of the present invention, the PHA comprises PHB and PHBV blended in a mass ratio of 1:10-10:1, for example (1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100):10.

In one embodiment of the present invention, the PHA comprises PHB and PHBHHx blended in a mass ratio of 1:10-10:1, for example (1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100):10.

In one embodiment of the present invention, the PHA comprises PHB blended with P3HB4HB and PHBV in a mass ratio of (1-10):(1-6):(1-4), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3, 4, 5 or 6):(1, 2, 3 or 4).

In one embodiment of the present invention, the PHA comprises PHB blended with P3HB4HB and PHBHHx in a mass ratio of (1-10):(1-5):(1-5), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3, 4 or 5):(1, 2, 3, 4 or 5).

In one embodiment of the present invention, the PHA comprises PHB blended with PHBV and PHBHHx in a mass ratio of (1-10):(1-4):(1-6), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3 or 4):(1, 2, 3, 4, 5 or 6).

In one embodiment of the present invention, the PHA comprises PHB and PHBV, PHBHHx, P3HB4HB blended in a mass ratio of (1-15):(1-4):(1-5):(1-6), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15):(1, 2, 3 or 4):(1, 2, 3, 4 or 5):(1, 2, 3, 4, 5 or 6).

PHB and P3HB4HB3HV are blended in a mass ratio of 1:10-10:1, for example (1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100):10;

PHB and P3HB4HB5HV are blended in a mass ratio of 1:10-10:1, for example (1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100):10;

PHB is blended with P3HB4HB3HV and P3HB4HB5HV in a mass ratio of (1-10):(1-4):(1-5), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3 or 4):(1, 2, 3, 4 or 5);

PHB is blended with PHBV and P3HB4HB3HV in a mass ratio of (1-10):(1-5):(1-6), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3, 4 or 5):(1, 2, 3, 4, 5 or 6);

PHB is blended with PHBV and P3HB4HB5HV in a mass ratio of (1-10):(1-5):(1-6), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3, 4 or 5):(1, 2, 3, 4, 5 or 6);

PHB is blended with PHBHHx and P3HB4HB3HV in a mass ratio of (1-10):(1-4.5):(1-5.5), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5):(1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or 5.5);

PHB is blended with PHBHHx and P3HB4HB5HV in a mass ratio of (1-10):(1-4.5):(1-5.5), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5):(1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or 5.5);

PHB is blended with P3HB4HB and P3HB4HB3HV in a mass ratio of (1-10):(1-5):(1-4.5), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3, 4 or 5):(1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5);

PHB is blended with P3HB4HB and P3HB4HB5HV in a mass ratio of (1-10):(1-5):(1-4.5), for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10):(1, 2, 3, 4 or 5):(1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5);

In parts by mass, in one embodiment of the present invention, PHA is 75 parts of PHB and 25 parts of P3HB4HB. In another embodiment of the present invention, PHA is 55 parts of PHB and 45 parts of PHBV. In another embodiment of the present invention, PHA is 65 parts of PHB, 20 parts of PHBHHx and 15 parts of P3HB4HB. In another embodiment of the present invention, PHA is 65 parts of PHB, 15 parts of PHBV and 20 parts of P3HB4HB. In another embodiment of the present invention, PHA is 65 parts of PHB, 22 parts of PHBHHx and 13 parts of PHBV. In another embodiment of the present invention, PHA is 55 parts of PHB, 18 parts of PHBHHx, 10 parts of PHBV and 17 parts of P3HB4HB. In another embodiment of the present invention, PHA is 80 parts of PHB and 20 parts of P3HB4HB3HV. In another embodiment of the present invention, PHA is 82 parts of PHB and 18 parts of P3HB4HB5HV. In another embodiment of the present invention, the PHA is 81 parts PHB, 10 parts P3HB4HB3HV and 9 parts P3HB4HB5HV. In another embodiment of the present invention, the PHA is 70 parts PHB, 12 parts PHBV and 18 parts P3HB4HB3HV. In another embodiment of the present invention, the PHA is 70 parts PHB, In another embodiment of the present invention, the PHA is 72 parts PHB, 14 parts PHBHHx and 14 parts P3HB4HB3HV. In another embodiment of the present invention, the PHA is 72 parts PHB, 16 parts PHBHHx and 12 parts P3HB4HB5HV. In another embodiment of the present invention, the PHA is 75 parts PHB, 12 parts P3HB4HB and 13 parts P3HB4HB3HV. In another embodiment of the present invention, the PHA is 75 parts PHB, 15 parts P3HB4HB and 10 parts P3HB4HB5HV.

In a specific embodiment of the present invention, the filament (or its raw material) comprises, by mass:

PHA: any value between 50 and 150 parts, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150 parts;

Auxiliary agent: any value in the range of 0.1-28 parts, for example 0.1, 1, 1.5, 2, 3, 4, 5, 6, 7, 7.5, 8, 9, 10, 11, 12, 13, 14, 14.5, 15, 16, 17, 18, 19, 20, 25 or 28 parts.

Preferably, the auxiliary agent includes:

Heat stabilizer: any value between 0 and 2.5 parts, for example, 0, 0.1, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1.0, 1.1, 1.2, 1.25, 1.3, 1.5, 2, 2.4 or 2.5 parts;

Nucleating agent: any value in the range of 0.0001-1.5 parts, for example, 0.0001, 0.001, 0.01, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1.0 or 1.5 parts;

Chain extender: any value between 0 and 2.5 parts, for example, 0, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 2 or 2.5 parts;

Antioxidant: any value between 0 and 1.5 parts, for example, 0, 0.1, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1.0 or 1.5 parts;

Anti-hydrolysis agent: any value between 0 and 1.5 parts, for example, 0, 0.1, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1.0 or 1.5 parts;

Enhancer: any value in the range of 0.1-10.0 parts, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 7.0, 9.0 or 10.0 parts;

Anti-adhesive agent: any value between 0 and 2.0 parts, for example, 0, 0.1, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1.0, 1.5 or 2.0 parts;

Cross-linking agent: any value between 0 and 2.5 parts, for example, 0, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 2.0 or 2.5 parts;

Coupling agent: any value in the range of 0-3.0 parts, for example, 0, 0.1, 0.3, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 2.0, 2.5 or 3.0 parts;

Plasticizer: any value between 0 and 2.0 parts, for example, 0, 0.1, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1.0, 1.5 or 2.0 parts.

Preferably, the molecular weight of the PHA is any value between 300,000 and 6,000,000.

Preferably, the filaments are in the form of, but not limited to, POY, FDY, and DTY.

The filament (or its raw material) of the present invention is mainly composed of PHA (for example, the mass percentage in the whole product is greater than 60%), which can be the only degradable component or can contain other common degradable materials, such as PLA, PBAT, PPC, PBS, nylon, etc., but these common degradable materials are not used as the main components (for example, the mass percentage in the whole product is less than 20%).

In a second aspect, a method for preparing the above-mentioned special material for filaments is provided, characterized in that the preparation method comprises:

Step 1, vacuum drying the raw materials;

Step 2: Weigh each raw material, physically mix them with a high-speed mixer, melt-extrude them with a twin-screw extruder, and cool and granulate them with air cooling to obtain pellets for filaments.

Preferably, the drying temperature in step 1 is any value between 60-105°C, for example, 60, 65, 70, 75, 80, 85, 90, 95, 100 or 105°C.

Preferably, the drying time in step 1 is any value between 2 and 12 hours, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours.

Preferably, in step 1, the moisture content is controlled below 180 ppm.

Preferably, the physical mixing in step 2 is any value of 10-60 min, for example 10, 15, 20, 30, 40, 50 or 60 min.

Preferably, in step 2, the barrel temperature is set to any value between 140-220°C, for example, 140, 150, 160, 170, 180, 190, 200, 210 or 220°C.

Preferably, the air supply temperature in step 2 is any value between 5 and 75°C, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or 75°C.

The raw materials include a substrate. The substrate includes PHA.

Preferably, the raw materials also include auxiliary agents.

The substrate and PHA are the same as those defined in the first aspect above.

The auxiliary agent is the same as defined in the first aspect above.

In a third aspect, a method for preparing the above-mentioned filaments is provided, the method comprising melting and granulating the raw materials, and then spinning to obtain the filaments.

Preferably, the preparation method comprises melting and granulating the raw materials and then performing a primary spinning process.

The raw materials include a base material and an auxiliary agent. Preferably, the base material includes PHA.

The substrate and PHA are the same as those defined in the first aspect above.

The auxiliary agent is the same as defined in the first aspect above.

The raw material melt granulation is to mix the raw materials in a barrel, melt extrude them by a twin-screw extruder, and cool and granulate them by air cooling to obtain filament-specific pellets. Preferably, the barrel temperature is set to any value in the range of 140-220°C, preferably any value in the range of 150-210°C, such as 140, 150, 160, 170, 180, 190, 200, 210 or 220°C. Preferably, the air supply temperature is any value in the range of 5-75°C, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or 75°C.

Preferably, the filament pellets are dried before the initial spinning process. Preferably, the drying is performed to control the moisture content to below 180 ppm.

Preferably, the drying is vacuum drying, and the temperature is set to any value between 60-105°C, for example, 60, 65, 70, 75, 80, 85, 90, 95, 100 or 105°C.

The drying time can be appropriately adjusted according to the drying temperature, and is preferably any value between 1 and 12 hours, and more preferably any value between 1 and 4 hours, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 or 12 hours.

The initial spinning process includes cooling and simultaneous stretching.

Preferably, the cooling and stretching simultaneously includes water cooling and stretching simultaneously or air cooling and stretching simultaneously.

Preferably, the water cooling temperature in the water-cooled simultaneous stretching is any value in the range of 0-30°C, and further preferably any value in the range of 4-25°C, 4-10°C or 4-15°C, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30°C.

Preferably, the stretching ratio in the water-cooled simultaneous stretching is any value in the range of 2-12, and more preferably 4-12 or 6-10 or 4-10, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 or 12.

Preferably, an antistatic agent is added to the water during the water cooling and stretching. Preferably, any value of 0.05-0.3% of the antistatic agent is added, such as 0.05, 0.1, 0.15, 0.2, 0.25 or 0.3%. The antistatic agent includes but is not limited to one of Tween 20, Tween 40, Tween 60 or a combination of two or more thereof.

In a specific embodiment of the present invention, 0.15% Tween 40 is added to the water during the water cooling and simultaneous stretching.

In a specific embodiment of the present invention, the water cooling is carried out in a horizontal water tank, and its length can be any required length, such as 0.5, 1, 2, 3, 4, 5m and above.

The temperature of the initial spinning process is any value in the range of 150-210°C, preferably any value in the range of 160-200°C or 165-195°C, for example, 150, 160, 165, 170, 175, 180, 185, 190, 195, 200, 210°C.

The pressure of the initial spinning process is any value in the range of 5-15 MPa, preferably any value in the range of 6-13 MPa, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 MPa.

The extrusion speed of the initial spinning process is any value in the range of 40-200 m/min, preferably any value in the range of 60-100 m/min or 40-120 m/min, for example, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 m/min.

The number of die holes set in the initial spinning process is single hole, 12, 24, 36, 48, 60, 72, 84 or 96 or more.

The initial spinning process also includes drying, oiling, and then a forming process.

The drying is an annular air tunnel drying, preferably, the air supply temperature is any value in the range of 35-105° C., preferably any value in the range of 40-100° C., 50-100° C., or 85-102° C., such as 35, 40, 45, 50, 60, 70, 80, 85, 90, 95, 100, 102, or 105° C. Preferably, the annular air tunnel is vertically arranged, and the length is any required length, preferably any value in the range of 1.5-5 m, such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10 m and above.

Among them, drying and oiling at the same time.

Preferably, the oiling is performed by an oil roller, and preferably, the speed of the oil roller is any value in the range of 400-1600 m/min, preferably any value in the range of 600-1400 m/min, 1000-1500 m/min, 1200-1400 m/min, or 480-1440 m/min. Values, for example 400, 450, 480, 500, 600, 700, 800, 900, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1440, 1450, 1500, 1550 or 1600 m/min.

The forming process comprises feeding the oiled filaments into two or more godet rollers, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10 godet rollers, preferably 3 godet rollers, and then collecting the filaments, wherein the latter godet roller is stretched with respect to the former godet roller.

Preferably, the forming process comprises feeding the oiled filaments into a first guide roller, a second guide roller, and a third guide roller in sequence and then collecting them.

Preferably, stretching occurs between the first guide roller and the second guide roller, and the stretching ratio is controlled to be any value in the range of 1.5-4, such as 1.5, 2, 2.5, 3, 3.5 or 4.

The temperature of the first godet is set to any value in the range of 25-90°C, preferably any value in the range of 45-70°C, for example 25, 35, 45, 50, 55, 60, 65, 70, 80 or 90°C.

The first godet is set at a speed of any value in the range of 500-2000 m/min, preferably any value in the range of 1200-1800 m/min, 1300-1500 m/min, or 750-1750 m/min, for example 500, 600, 700, 750, 800, 900, 1000, 1100, 1200, 1300, 1350, 1400, 1450, 1500, 1600, 1700, 1750, 1800, 1900 or 2000 m/min.

The second godet is set at a temperature of any value in the range of 70-115°C, preferably any value in the range of 75-110°C, for example 70, 75, 80, 85, 90, 95, 100, 105, 110 or 115°C.

The second godet roller is set at any value in the range of 1500-5500 m/min, preferably any value in the range of 2400-4800 m/min, 3000-4200 m/min, or 2800-4200 m/min, for example, 1500, 1800, 2000, 2200, 2400, 2500, 2800, 3000, 3200, 3300, 3500, 3800, 4000, 4200, 4500, 4800, 5000, 5200 or 5500 m/min;

The third godet roller is set at a speed of any value in the range of 1750-6000 m/min, preferably any value in the range of 2500-5000 m/min, 3300-4600 m/min, or 3000-4500 m/min, for example, 1750, 2000, 2200, 2500, 3000, 3300, 3500, 4000, 4500, 4600, 5000, 5500 or 6000 m/min.

The oiling is performed using an oil roller, and the speed of the oil roller is any value in the range of 400-1600 m/min, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500 or 1600 m/min.

A ring-blown air flow is arranged between the oil roller used for oiling and the first guide wire roller, and the temperature is any value in the range of 15-45°C, preferably any value in the range of 18-45°C, for example, 15, 18, 20, 25, 30, 35, 40 or 45°C.

Circular blowing is arranged between the second guide roller and the third guide roller, and the temperature is any value in the range of 15-45°C, preferably any value in the range of 18-45°C, for example, 15, 18, 20, 25, 30, 35, 40 or 45°C.

The collecting comprises winding on a bobbin, and the winding speed is preferably set to any value in the range of 1750-6000 m/min, further preferably any value in the range of 2500-5000 m/min, 3300-4600 m/min or 3000-4500 m/min, for example, 1750, 2000, 2500, 2750, 3000, 3300, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 5000, 5500 or 6000 m/min.

In a specific embodiment of the present invention, the preparation method comprises:

A) drying the raw materials, mixing them, melting and extruding them, and cooling and granulating them by air cooling to obtain pellets for filaments;

B) subjecting the filament-specific pellets to a preliminary spinning process to obtain a spun fiber, wherein the preliminary spinning process includes water cooling and simultaneous stretching, wherein the water cooling temperature is 0-30° C., the stretching ratio is 2-12, and an antistatic agent is added to the water, the preliminary spinning process temperature is 150-210° C., the pressure is 5-15 MPa, and the extrusion speed is 40-200 m/min;

C) drying the nascent fiber in an annular blowing tunnel and oiling it with an oil roller, wherein the air supply temperature is 35-105° C. and the speed at the oil roller is 400-1600 m/min;

D) subjecting the oiled filaments to a forming process, wherein the forming process comprises sequentially feeding the oiled filaments to a first godet roller, a second godet roller, and a third godet roller, and then collecting the filaments to obtain filaments;

Among them, the first godet roller is set at a temperature of 25-90°C and a speed of 500-2000m/min, the second godet roller is set at a temperature of 70-115°C and a speed of 1500-5500m/min, and the third godet roller has a speed of 1750-6000m/min;

Circular blowing is arranged between the oil roller and the first guide wire roller, and the temperature is 15-45°C; and circular blowing is arranged between the second guide wire roller and the third guide wire roller, and the temperature is 15-45°C.

If the first guide roller and the second guide roller are removed, and the annular blowing between the oil roller and the first guide roller, the second guide roller and the third guide roller is removed, the winding speed is controlled to 800-3200m/min, and a POY filament product can be obtained; the POY filament can also be further subjected to false twisting to obtain a DTY filament product.

In a specific embodiment of the present invention, the filaments in the form of POY can be further subjected to false twisting to obtain filament products in the form of DTY.

In a specific embodiment of the present invention, the filaments are in the form of FDY, and preferably, a ring blowing is arranged between the oil roller and the first godet roller;

Preferably, the temperature of the annular air blowing between the oil roller and the first godet roller is controlled at any value in the range of 15-45°C, preferably any value in the range of 18-45°C, for example, 15, 18, 20, 25, 30, 35, 40 or 45°C;

Preferably, an annular blowing is arranged between the second godet roller and the third godet roller, and the temperature is controlled at any value in the range of 15-45°C, preferably any value in the range of 18-45°C, for example, 15, 18, 20, 25, 30, 35, 40 or 45°C;

Preferably, the winding speed is any value in the range of 1750-6000 m/min, more preferably 2500-5000 m/min or 3300-4600 m/min or 3000-4500 m/min, for example 1750, 2000, 2500, 3000, 3300, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 5000, 5500 or 6000 m/min.

In a specific embodiment of the present invention, the filament is in the form of POY. Preferably, the winding speed is any value in the range of 800-3200 m/min, further preferably any value in the range of 2000-3000 m/min, for example, 800, 900, 1000, 1500, 1750, 2000, 2500, 3000 or 3200 m/min.

In a specific embodiment of the present invention, the filaments are in the form of DTY. Preferably, the preparation method further comprises false twist texturing.

In a fourth aspect, provided are filaments or special materials for filaments obtained by the above-mentioned preparation method.

A fifth aspect provides a product, wherein the product comprises the above-mentioned filament or the filament obtained by the above-mentioned preparation method or Special material for filaments, or the product is prepared from the above-mentioned filaments or special material for filaments.

In a sixth aspect, there is provided a use of the above-mentioned filaments or the filaments obtained by the above-mentioned preparation method or special materials for filaments in the preparation of products requiring materials to have biodegradable properties.

Preferably, the products include but are not limited to traditional fabric products or industrial textile products.

Preferably, the traditional fabric products include but are not limited to yarn, thread, sewing thread, embroidery thread, knitted fabrics, woven fabrics, non-woven fabrics, clothing, clothing accessories, home textiles, decorative fabric products, gloves, hats, socks, bags, blankets, fabric toys, lighting, handicrafts, hand-crocheted fabrics, kesi, belts, ropes, ribbons, Velcro, fabric packaging, etc.

Preferably, the industrial textile products include but are not limited to wigs, hair pieces, false eyelashes, false beards, hair for doll making, car interiors, aerospace interiors, life-saving equipment, geotextiles, building fabrics, agricultural fabrics, sail-type textile products, artificial leather fabrics, medical sutures, ligatures, fixing lines, health fabrics, gauze, bandages, medical tapes, cotton swabs, cotton balls, wound dressings, protective masks, Band-Aids, surgical supplies (including surgical gowns, caps, covering cloths), gloves, medical protective clothing, military textile products, etc.

"A and B at the same time" described in the present invention means that the process of A and the process of B overlap in time in whole or in part. For example, "cooling and stretching at the same time". For example, "water cooling and stretching at the same time" means that water cooling and stretching are carried out simultaneously, wherein "simultaneously" means that the process of water cooling and the process of stretching overlap in whole or in part, and does not only include starting at the same time, and/or ending at the same time, and/or, the process of water cooling and the process of stretching completely overlap in time. Of course, the total time of water cooling is not necessarily consistent with the total time of stretching, and the water cooling time can be longer than the stretching time, or the stretching time can be longer than the water cooling time, or the time can be consistent. However, at least ensure that more than 50% (for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, 99.1%, 99.5%, 99.9%, 100%) of the shorter time of the water cooling time and the stretching time completely overlaps with the longer time.

The physical modification described in the present invention is to enhance or improve the corresponding properties of PHA by physically blending heat stabilizers, nucleating agents, antioxidants, anti-hydrolysis agents, reinforcing agents, anti-blocking agents, environmentally friendly coupling agents, environmentally friendly plasticizers, etc., during which physical changes occur.

The chemical modification described in the present invention is such as increasing the molecular weight by chain extenders and changing the polymer from a linear structure to a network structure (branched chains are connected to form a cross-linked structure of a three-dimensional network macromolecule) by environmentally friendly cross-linking agents, during which chemical changes occur.

Through the above technical solution, the present invention has the following advantages:

1. The filament of the present invention uses only PHA as the main degradable material, and is not blended with other materials such as PLA, PBS, PBAT, etc., which further improves the quality of the degradable filament and the stability of the process, and ensures that it degrades faster and has more environmentally friendly ingredients.

2. The main components of the filaments of the present invention are degradable, and since PHA accounts for the largest proportion and PHA is a 100% degradable material, the overall requirements for the degradation environment are relatively low, and the degradation speed is greatly improved. It can be completely decomposed in the natural environment without composting, which is green and sustainable.

3. The filaments of the present invention have skin-friendly properties and excellent biocompatibility. Therefore, whether used in close-fitting textiles or medical products such as personal protection, the use experience is soft and comfortable, without any adverse experiences such as itching, allergies, static electricity, dullness, etc. Compared with traditional chemical fiber fabrics, the safety, comfort of use and wearing performance are significantly improved.

4. The filaments of the present invention, wherein the addition of nanomaterials, can not only act as nucleating agents, accelerate the crystallization rate of PHA, but also improve the antibacterial properties of the finished filaments, which is related to the fact that the nano-scale particles can interact with the bacterial surface, thereby causing damage to the bacterial surface. In particular, nanoparticles produce ROS (such as hydrogen peroxide, hydroxyl radicals, oxygen anions and hydroperoxides, etc.) in bacterial cells, which can induce a series of biological reactions, such as bacterial membrane damage, thereby causing bacteriolysis or promoting the aggregation of nanoparticles in bacteria. In the experiment, it was confirmed by adjusting the formula that although PHA itself has antibacterial properties, the presence of nano magnesium oxide, nano cellulose, gas-phase nano silicon dioxide, etc. in the special granular formula of PHA filaments will enhance the antibacterial effect. In addition, the addition of nanomaterials also plays a certain flame retardant effect. It is shared with tetrachlorophthalic anhydride, and surprisingly obtains good flame retardant properties under the premise of low addition, and exceeds the effect of a single addition amount, proving that a synergistic effect is produced.

5. In the preparation method of the filament of the present invention, due to the effect of the nucleating agent, chain extender, environmentally friendly cross-linking agent and environmentally friendly coupling agent of appropriate types and proportions in the formula, the melt strength and crystallization speed of PHA are significantly improved, so the entire filament preparation process does not require long-term crystallization, and the one-step method can achieve the production of filament products. The process line is efficient and continuous, and the spinning speed is basically the same as that of polyester and nylon, thereby reducing processing costs and improving production efficiency.

6. The preparation method of the filament of the present invention creatively adopts the FDY processing technology of first cooling and rapid stretching, then air-heat drying, rapid crystallization, and further stretching orientation, heat setting, rapid cooling and winding. Compared with the traditional FDY processing technology, the processing stability is better, and the final stretching orientation degree and crystallinity are higher. In particular, after experiments, it was found that only the process of initial cooling and simultaneous stretching can lay a better foundation for subsequent further orientation and crystallization, that is, after this process, the toughness of the filament will be better, greatly reducing the probability of subsequent breakage; in addition, the stretching multiple is enlarged and the spinning speed is increased, thereby significantly accelerating the production efficiency of pure PHA filaments.

7. The preparation method of the filament of the present invention creatively adds an antistatic agent during the water cooling process and combines it with a rapid air-heat drying process. This process combination, on the one hand, cooperates with the subsequent oil agent to improve the electrostatic effect on the surface of the filament, making it easier to hold and bundle. On the other hand, it cooperates with the anti-adhesion agent to improve the wetting properties of the filament surface, making it relatively more hydrophilic and moist, and greatly reduces the adhesion phenomenon, which is beneficial to subsequent processing and application.

8. The method for preparing filaments of the present invention firstly uses water cooling and rapid stretching to make the PHA extruded strips quickly extend and thin. The occurrence of breakage can be reduced in water than in air. On the one hand, this is because the buoyancy partially offsets the gravity, and on the other hand, the presence of water helps to maintain the rubber state of the PHA material, making it easier to deform, thereby facilitating its stretching and thinning. Next, air-heat drying is performed rapidly to remove moisture from the surface of the PHA primary fiber. The antistatic agent and the anti-adhesive agent in the fiber work together to make the fiber surface immediately dry and non-adhesive. The subsequent oiling roller further enhances its antistatic effect, which is beneficial to its subsequent bonding, bundling, stretching and winding. Next, air cooling and rapid crystallization are performed in the fastest crystallization temperature range above the glass transition temperature and below the melting point to rapidly increase the crystallinity of the fiber and then improve its mechanical strength. Then, high-speed stretching and orientation are carried out at a mild temperature of the first godet roller to make the molecular orientation more complete, and obtain fibers with high orientation and medium crystallinity; after intense heat setting on the second godet roller, the fiber crystallization is further developed and improved, the molecular arrangement is more regular, the orientation effect is strengthened, and the energy accumulated in the fiber is completely released to achieve stress relaxation. Finally, the crystallization is strengthened by rapid cooling, while avoiding surface adhesion, and it is smoothly wound on the bobbin. The entire filament preparation process is continuous, fast, and energy-efficient.

The term “include” or “comprising” described in the present invention is an open description, which includes the specified components or steps described and other specified components or steps that will not be substantially affected.

The English abbreviations and the Chinese full names of the present invention are shown in Table 1.

Table 1: English abbreviations and Chinese full names

Detailed ways

The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only some embodiments of the present invention, not all. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Unless otherwise specified, the materials used in the embodiments of the present invention are all commercially available.

Unless otherwise specified, the parts, percentages or ratios described in the embodiments of the present invention are all based on mass.

Test items and test methods in the embodiment:

①Specifications: Linear density (dtex) is tested in accordance with GB/T 14343-2008 “Test method for linear density of chemical fiber filaments”; the number of strands (f) refers to the number of die holes.

② The breaking strength (cN/dtex), breaking strength CV (%), breaking elongation (%) and breaking elongation CV (%) are tested in accordance with GB/T 14344-2008 “Test method for tensile properties of chemical fiber filaments”.

The breaking strength retention rate is the breaking strength retention rate after 3 months of storage: a high retention rate indicates that the post-crystallization phenomenon is improved.

③Limiting oxygen index (%): Tested according to the method in FZ/T 50017-2011 "Test method for flame retardancy of polyester fibers - Oxygen index method".

④Inhibition rate (%): The inhibition rate against Staphylococcus aureus and Escherichia coli was obtained by testing according to the method in GB/T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method".

⑤ Skin-friendliness: A subjective evaluation method was used, and two types of people were selected as subjects for masks made of filaments.

One category consists of 10 experts or experienced subjects, with a weight of 1. They are familiar with the meaning of the subjective evaluation scale and its description, and know the human feeling corresponding to each level in the terminology, and can quickly and accurately evaluate and quantify the performance of the filament;

The other group consists of 10 consumers who have received simple training, with a weight of 0.5. Before the experiment, these subjects need to be given knowledge about filament performance and explanations of evaluation scale terms so that they can make correct evaluations of filament performance and ensure the rigor of the results.

Experimental conditions: temperature 20℃±2℃, relative humidity 65%±2%, wind speed ≤0.1m/s.

The subjective evaluation scale and descriptive vocabulary of skin-friendliness are shown in Table 2:

When the grade is ≤3, it is judged that the skin affinity is poor;

When 3＜level≤4, the skin affinity is judged to be average;

When 4＜grade≤4.5, it is judged that the skin affinity is good;

When 4.5＜grade≤5, it is judged that the skin affinity is excellent.

Table 2: Subjective evaluation scale for skin-friendliness

Example 1: Preparation of PHB+P3HB4HB filaments (including various additives)

Step 1: vacuum dry each raw material at 70-95°C for 6-10h to control the moisture content below 180ppm;

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of Fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Step 3, after vacuum drying the PHA filament pellets at 70-105°C for 2.5h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100m/min, cooling is performed through a horizontal 1m long water tank, and stretching is performed at the same time, the stretching ratio is 6-10, the water temperature is 4°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fibers;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 85-102° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 1200-1400 m/min at the oil roller;

Step 5: The PHA filaments obtained by oiling in step 4 are sequentially fed into the first godet roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second godet roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third godet roller. Ring blowing is set between the oil roller and the first godet roller, and the temperature is controlled at 18-45°C; stretching is generated between the first godet roller and the second godet roller, and the stretching ratio is controlled to be 2-4; ring blowing is set between the second godet roller and the third godet roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through the winding device, and the winding speed is 3300-4600m/min to obtain the PHA filament finished product in the form of FDY. The various properties are shown in Table 3.

Example 2: Preparation of PHB+PHBV filaments (containing two basic additives: nucleating agent and reinforcing agent)

Step 1: vacuum dry each raw material at 70-95°C for 6-10 hours to control the moisture content below 180ppm;

Step 2: weigh 55 parts of PHB, 45 parts of PHBV, 0.25 parts of nano-magnesium oxide, 0.2 parts of MILLAD 3988, 0.3 parts of NA-21, 1 part of talcum powder, 1 part of nano-cellulose, 1 part of DH-3 enhancer, and 2 parts of tetrachlorophthalic anhydride by mass, and physically mix them for 10-30 minutes by a high-speed mixer, and then melt-extrude them by a twin-screw extruder and cool them by air cooling to obtain pellets. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain pellets for PHA filaments;

Step 4: The PHA nascent fibers obtained by cooling in step 3 are dried in a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 85-102°C, and are immediately oiled by an oil roller, and multiple fibers are bundled into filaments, and the speed at the oil roller is 1200-1400m/min;

Example 3: Preparation of PHB+PHBHHx+P3HB4HB filaments (containing heat stabilizer, nucleating agent, chain extender, reinforcing agent)

Step 2: weigh 65 parts of PHB, 20 parts of PHBHHx, 15 parts of P3HB4HB, 0.75 parts of zinc 2-ethylhexanoate, 0.5 parts of calcium stearate, 0.2 parts of nano calcium carbonate, 0.3 parts of MILLAD 3905, 0.25 parts of NA-21, 0.4 parts of BASF ADR 4400, 0.5 parts of Vertellus E60P, 0.35 parts of trimethylolpropane, 1.5 parts of nanocellulose, 2 parts of DH-4 enhancer, and 1.5 parts of tetrachlorophthalic anhydride, and mix them physically for 10-30 minutes through a high-speed mixer, and then melt extrude them through a twin-screw extruder and cool them by air cooling to obtain pellets. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament pellets.

Example 4: Preparation of PHB+PHBV+P3HB4HB filaments (containing nucleating agent, antioxidant, anti-hydrolysis agent, reinforcing agent)

Step 2: weigh 65 parts of PHB, 15 parts of PHBV, 20 parts of P3HB4HB, 0.25 parts of nano calcium carbonate, 0.25 parts of MILLAD 3988, 0.25 parts of ACLYN 285A, 0.25 parts of LOWINOX 44B25, 0.2 parts of antioxidant RIANOX 1790, 0.3 parts of antioxidant RIANOX 168, 0.45 parts of double bond anti-hydrolysis agent CHINOX P-500, 0.3 parts of KANEKA M732, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 enhancer, and 2 parts of tetrachlorophthalic anhydride, and mix them physically for 10-30 minutes through a high-speed mixer, and then melt extrude them through a twin-screw extruder and cool them by air cooling to granulate them. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament-specific pellets;

Example 5: Preparation of PHB+PHBHHx+PHBV filaments (containing nucleating agent, reinforcing agent, anti-blocking agent, environmentally friendly plasticizer)

Step 2, by mass, weigh 65 parts of PHB, 22 parts of PHBHHx, 13 parts of PHBV, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of TBC, 0.6 parts of ATBC, and physically mix them by a high-speed mixer for 10-30 minutes, then melt-extrude through a twin-screw extruder and cool and granulate by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special pellets;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through the winding device. The winding speed is 3300-4600 m/min to obtain the PHA filament product in the form of FDY. The various properties are shown in Table 3.

Example 6: Preparation of PHB+PHBHHx+PHBV+P3HB4HB filaments (containing nucleating agent, reinforcing agent, environmentally friendly crosslinking agent, and environmentally friendly coupling agent)

Step 2: weigh 55 parts of PHB, 18 parts of PHBHHx, 10 parts of PHBV, 17 parts of P3HB4HB, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, and 0.9 parts of silane coupling agent KH-550 by mass, and mix them physically for 10-30 minutes by a high-speed mixer, and then melt-extrude them by a twin-screw extruder and cool them by air cooling to obtain pellets. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament-specific pellets;

Step 5: The PHA filaments obtained by oiling in step 4 are sequentially fed into the first godet roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second godet roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third godet roller. A ring blowing is set between the oil roller and the first godet roller, and the temperature is controlled at 18-45°C; stretching is generated between the first godet roller and the second godet roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second godet roller and the third godet roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through the winding device, and the winding speed is 3300-4600m/min to obtain the PHA filament finished product in the form of FDY. The various properties are shown in Table 4.

Example 7: Preparation of PHB+P3HB4HB3HV filaments (including various additives)

Step 2: Weigh 80 parts of PHB, 20 parts of P3HB4HB3HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, and 0.25 parts of antioxidant RIANOX. 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, and then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Example 8: Preparation of PHB+P3HB4HB5HV filaments (including various additives)

Step 2: Weigh 82 parts of PHB, 18 parts of P3HB4HB5HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of calcium laurate, 0.25 parts of nano-magnesium oxide, 0.2 parts of MILLAD 3988, 0.3 parts of NA-21, 0.5 parts of BASF ADR 4300F, 0.35 parts of 2,2'-(1,3-phenylene)-dioxazoline, 0.4 parts of trimethylolpropane, 0.25 parts of antioxidant CA, 0.2 parts of antioxidant RIANOX 1790, 0.3 parts of antioxidant RIANOX 168, 0.35 parts of double bond anti-hydrolysis agent CHINOX P-500, 0.4 parts of DuPont 132F NC010, 1 part of talcum powder, 1 part of Nanocellulose, 1 part of DH-3 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.4 parts of silica opening agent AB-MB-09, 0.2 parts of antistatic agent MOA3-PK, 0.3 parts of hydroxypropyl methacrylate, 0.5 parts of HTDI, 0.45 parts of multifunctional aziridine crosslinking agent SaC-100, 0.7 parts of silane coupling agent KH-550, 0.8 parts of silane coupling agent KBM-602, 0.5 parts of TBC, and 0.5 parts of BNTXIB are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets, the barrel temperature is set to 150-210° C., and the air supply temperature is 15-75° C. to obtain PHA filament special pellets;

Step 5: The PHA filaments obtained by oiling in step 4 are sequentially fed to the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller. A ring blower is set between the oil roller and the first guide roller to heat the PHA filaments. The temperature is controlled at 18-45℃; stretching is generated between the first godet roller and the second godet roller, and the stretching ratio is controlled to be 2-4; an annular blower is set between the second godet roller and the third godet roller, and the temperature is controlled at 18-45℃, and then the PHA filament is wound on the bobbin through a winding device at a winding speed of 3300-4600m/min to obtain a PHA filament product in the form of FDY. The various properties are shown in Table 4.

Example 9: Preparation of PHB+P3HB4HB3HV+P3HB4HB5HV filaments (including various auxiliaries)

Step 2: Weigh 81 parts of PHB, 10 parts of P3HB4HB3HV, 9 parts of P3HB4HB5HV, 0.75 parts of zinc 2-ethylhexanoate, 0.5 parts of calcium stearate, 0.2 parts of nano calcium carbonate, 0.3 parts of MILLAD 3905, 0.25 parts of NA-21, 0.4 parts of BASF ADR 4400, 0.5 parts of Vertellus E60P, 0.35 parts of trimethylolpropane, 0.25 parts of LOWINOX 44B25, 0.2 parts of antioxidant RIANOX 1098, 0.3 parts of antioxidant RIANOX 626, 0.35 parts of polycarbodiimide UN-03, and 0.4 parts of DuPont 132F NC0. 10. 1.5 parts of nanocellulose, 2 parts of DH-4 reinforcing agent, 1.5 parts of tetrachlorophthalic anhydride, 0.35 parts of stearic acid amide, 0.35 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of HTDI, 0.35 parts of DAP, 0.5 parts of multifunctional polycarbodiimide UN-557, 0.65 parts of silane coupling agent KH-550, 0.85 parts of TTS, 0.4 parts of ATBC and 0.6 parts of BNTXIB are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament-specific pellets;

Step 3, after vacuum drying the PHA filament pellets at 70-105°C for 2.5h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100m/min, and cooling is performed through a horizontal 1m long water tank, and stretching is performed at the same time, the stretching ratio is 6-10, the water temperature is 4°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fiber;

Example 10: Preparation of PHB+PHBV+P3HB4HB3HV filaments (including various auxiliaries)

Step 2: Weigh 70 parts of PHB, 12 parts of PHBV, 18 parts of P3HB4HB3HV, 0.6 parts of zinc 2-ethylhexanoate, 0.65 parts of magnesium laurate, 0.25 parts of nano-calcium carbonate, 0.25 parts of MILLAD 3988, 0.25 parts of ACLYN 285A, 0.55 parts of BASF ADR 4400, 0.3 parts of 2,2'-(1,3-phenylene)-dioxazoline, 0.4 parts of EK-145 polyester chain extender, 0.25 parts of LOWINOX 44B25, 0.2 parts of antioxidant RIANOX 1790, 0.3 parts of antioxidant RIANOX 168, 0.45 parts of double bond anti-hydrolysis agent CHINOX P-500, 0.3 parts of KANEKA M732, 1.5 parts of fumed nano-silica, 1.5 DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of stearic acid amide, 0.25 parts of silica opening agent AB-MB-09, 0.35 parts of antistatic agent MOA3-PK, 0.4 parts of methyl triethoxysilane, 0.4 parts of HTDI, 0.45 parts of isobutoxy methyl acrylate, 0.75 parts of silane coupling agent Z-6020, 0.75 parts of KR-38S, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Example 11: Preparation of PHB+PHBV+P3HB4HB5HV filaments (including various additives)

Step 2: Weigh 70 parts of PHB, 14 parts of PHBV, 16 parts of P3HB4HB5HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, and 0.25 parts of anti-hydrolysis stabilizer 360. 0, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Step 4: The PHA nascent fibers obtained by cooling in step 3 are dried in a vertical 3.5 m long annular air tunnel, wherein: The air supply temperature is 85-102℃, and the air is immediately oiled by the oil roller. Multiple strands are bundled into silk strips. The speed at the oil roller is 1200-1400m/min.

Step 5: The PHA filaments obtained by oiling in step 4 are sequentially fed into the first godet roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second godet roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third godet roller. A ring blowing is set between the oil roller and the first godet roller, and the temperature is controlled at 18-45°C; stretching is generated between the first godet roller and the second godet roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second godet roller and the third godet roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through the winding device, and the winding speed is 3300-4600m/min to obtain the PHA filament finished product in the form of FDY. The various properties are shown in Table 5.

Example 12: Preparation of PHB+PHBHHx+P3HB4HB3HV filaments (including various additives)

Step 2: Weigh 72 parts of PHB, 14 parts of PHBHHx, 14 parts of P3HB4HB3HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, and 0.25 parts of anti-hydrolysis stabilizer 36. 00, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to granulate, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Example 13: Preparation of PHB+PHBHHx+P3HB4HB5HV filaments (including various additives)

Step 2: Weigh 72 parts of PHB, 16 parts of PHBHHx, 12 parts of P3HB4HB5HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, and 0.25 parts of anti-hydrolysis stabilizer 36. 00, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Example 14: Preparation of PHB+P3HB4HB+P3HB4HB3HV filaments (including various auxiliaries)

Step 2: Weigh 75 parts of PHB, 12 parts of P3HB4HB, 13 parts of P3HB4HB5HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, and 0.25 parts of antioxidant RIANOX. 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, and then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Example 15: Preparation of PHB+P3HB4HB+P3HB4HB5HV filaments (including various auxiliaries)

Step 2: Weigh 75 parts of PHB, 15 parts of P3HB4HB, 10 parts of P3HB4HB5HV, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, and 0.25 parts of anti-hydrolysis stabilizer 36. 00, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Step 5: The PHA filaments obtained by oiling in step 4 are sequentially fed to the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller. A ring blower is set between the oil roller and the first guide roller to heat the PHA filaments. The temperature is controlled at 18-45℃; stretching is generated between the first godet roller and the second godet roller, and the stretching ratio is controlled to be 2-4; an annular blower is set between the second godet roller and the third godet roller, and the temperature is controlled at 18-45℃, and then the PHA filament is wound on the bobbin through a winding device at a winding speed of 3300-4600m/min to obtain a PHA filament product in the form of FDY. The various properties are shown in Table 5.

Example 16: Preparation of PHB+P3HB4HB filaments without tetrachlorophthalic anhydride (compared with Example 1, without tetrachlorophthalic anhydride)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament-specific pellets;

Embodiment 17

The process is the same as that of Example 1, except that the amount of additives added is: 1 part of magnesium 2-ethylhexanoate, 1.5 parts of zinc stearate, 0.0001 parts of nano magnesium oxide, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nanosilica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling Agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC.

Embodiment 18

The process is the same as that in Example 1, except that the amount of additives added is: 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.5 parts of nano magnesium oxide, 0.5 parts of MILLAD 3905, 0.5 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant Oxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 0.1 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC.

Embodiment 19

The process is the same as that in Example 1, except that the amount of additives added is: 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 1 part of BASF ADR 4300F, 0.5 parts of Vertellus E60P, 1 part of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626 , 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.8 parts of oleic acid amide, 0.6 parts of BYK3700 silicone leveling agent, 0.6 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC.

Embodiment 20

The process is the same as that in Example 1, except that the amount of additives added is: 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.5 parts of antioxidant CA, 0.5 parts of antioxidant RIANOX1098, 0.5 parts of antioxidant RIANOX 6 26, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.8 parts of methyltriethoxysilane, 1 part of HTDI, 0.7 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC.

Embodiment 21

The process is the same as that in Example 1, except that the amount of additives added is: 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 1 part of polycarbodiimide UN-03, 0.5 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 1.2 parts of silane coupling agent Z-6020, 1.8 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC.

Embodiment 22

The process is the same as that in Example 1, except that the amount of additives added is: 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 3 parts of fumed nano-silica, 3 parts of DH-2 enhancer, 4 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.8 parts of TBC, and 1.2 parts of ATBC.

Example 23: Preparation of PHB+P3HB4HB filaments

The raw materials and proportions are the same as those in Example 1, except that:

Step 1: vacuum dry each raw material at 60-80°C for 10-12h to control the moisture content below 180ppm;

Step 2: Physically mix the raw materials by a high-speed mixer for 30-60 minutes, then melt extrude through a twin-screw extruder and cool and granulate by air cooling, the barrel temperature is set to 150-220°C, the air supply temperature is 5-65°C, and special pellets for PHA filaments are obtained;

Step 3, the PHA filament pellets obtained in step 2 are vacuum dried at 60° C. for 4 hours, and then spun through a twin-screw melt spinning machine, the spinning temperature is set to 165-210° C., the pressure in the melt metering pump is controlled to 5-13 MPa, the number of die holes is 24, the extrusion speed is controlled to 100-200 m/min, and the PHA filament is cooled through a horizontal 0.5 m long water tank and stretched at the same time, the stretching ratio is 2-8, the water temperature is 0° C., and 0.3% Tween 60 is added to the water to obtain PHA primary fibers;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a 10 m long vertical annular air tunnel, wherein the air supply temperature is 35-85° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 400-800 m/min at the oil roller;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-90°C, and the spinning speed is controlled at 600-1200m/min), the second guide roller (the shaping heating temperature is controlled at 75-115°C, and the stretching speed is controlled at 2400-4500m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2.5-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 2700-5000m/min to obtain FDY-formed PHA filament finished products.

Example 24: Preparation of PHB+P3HB4HB filaments

Step 1: vacuum dry each raw material at 85-105°C for 6-8h to control the moisture content below 180ppm;

Step 2: Physically mix the raw materials through a high-speed mixer for 10-30 minutes, then melt-extrude through a twin-screw extruder and cool and granulate by air cooling, with the barrel temperature set at 140-210°C and the air supply temperature at 35-75°C to obtain PHA filament-specific pellets;

Step 3: After the PHA filament pellets are vacuum dried at 105°C for 1 hour, they are melt-spinned by a twin-screw spinning machine. Spinning, the spinning temperature is set to 150-205°C, the pressure in the melt metering pump is controlled to 6-15MPa, the number of holes in the die is 72, the extrusion speed is controlled to 40-120m/min, and the fiber is cooled through a horizontal water tank of 1m in length, and stretched at the same time, with a stretch ratio of 6-12, a water temperature of 15°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fibers;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a 2.5 m long vertical annular air tunnel, wherein the air supply temperature is 90-105° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 480-1440 m/min at the oil roller;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 25-70°C, and the spinning speed is controlled at 500-1500m/min), the second guide roller (the shaping heating temperature is controlled at 70-110°C, and the stretching speed is controlled at 1500-2250m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 1.5-3; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 1750-2750m/min to obtain FDY-formed PHA filament products.

Example 25: Preparation of PHB+P3HB4HB filaments

Step 2, physically mixing the raw materials through a high-speed mixer for 10-30 minutes, then melt-extruding through a twin-screw extruder and cooling and granulating by air cooling, with the barrel temperature set at 150-210°C and the air supply temperature at 15-75°C, to obtain PHA filament-specific pellets;

Step 3, after vacuum drying the PHA filament pellets at 70-105°C for 2.5h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 12, the extrusion speed is controlled to 120-200m/min, cooling is performed through a horizontal 1m long water tank, and stretching is performed at the same time, the stretching ratio is 6-12, the water temperature is 4°C, and 0.25% Tween 60 is added to the water to obtain PHA primary fiber;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 85-102° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 1200-1600 m/min at the oil roller;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-90°C, and the spinning speed is controlled at 1500-2000m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3200-5500m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching occurs between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-3; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 3500-6000m/min to obtain FDY-formed PHA filament finished products.

Example 26: Preparation of PHB+P3HB4HB filaments

Step 1: vacuum dry each raw material at 85°C for 8 hours to control the moisture content below 180 ppm;

Step 2: Physically mix the raw materials in a high-speed mixer for 30 minutes, and then melt extrude them through a twin-screw extruder. The pelletizing process is carried out by air cooling, the barrel temperature is set at 150-210°C, and the air supply temperature is set at 15-75°C, to obtain pellets specially used for PHA filaments;

Step 3, after vacuum drying the PHA filament pellets at 100° C. for 1.5 h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 160-200° C., the pressure in the melt metering pump is controlled to 6-13 MPa, the number of die holes is 96, the extrusion speed is controlled to 60-120 m/min, and the PHA filament is cooled through a horizontal 5 m long water tank and stretched at the same time, the stretching ratio is 4-10, the water temperature is 30° C., and 0.05% Tween 20 is added to the water to obtain PHA primary fibers;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a vertical 4m long annular air tunnel, wherein the air supply temperature is 85-100°C, and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 480-1200m/min at the oil roller;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 600-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 1600-4000m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 1800-4500m/min to obtain FDY-formed PHA filament finished products.

The performance indicators of the FDY filament products obtained in the above Examples 17-26 can meet the requirements of subsequent applications.

Comparative Example 1: Preparation of PHB+PBS filaments (Compared with Example 1, P3HB4HB was replaced by PBS)

Step 2: Weigh 75 parts of PHB, 25 parts of PBS, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of gas phase Nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special pellets;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching occurs between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the filaments are wound on the bobbin through a winding device, and the winding speed is 3300-4600m/min to obtain a filament product in the form of FDY.

The filament product obtained in Control Example 1 has yellowing phenomenon, which may be caused by the higher processing temperature than PBS, resulting in oxidative degradation and post-crystallization. Therefore, the breaking strength, breaking strength retention rate, breaking strength CV, breaking elongation CV, antibacterial rate and skin affinity of the filament product obtained in Control Example 1 are all worse than those in Example 1 (as shown in Table 3 and Table 6).

Comparative Example 2: Preparation of PHB+P3HB4HB filaments without nanoparticles (compared with Example 1, without nano-magnesium oxide and fumed nano-silicon dioxide)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 3300-4600m/min to obtain a PHA filament finished product in the form of FDY.

The filament product obtained in Comparative Example 2 has poor thermal stability and slow crystallization speed due to the lack of nanoparticles. The process is unstable, the roller sticking phenomenon occurs, and the spinning temperature must be selected in the low temperature range during processing, otherwise thermal degradation will occur if it exceeds 180°C. Therefore, the breaking strength, breaking strength retention rate, breaking strength CV, breaking elongation CV, limiting oxygen index and antibacterial rate of the filament product obtained in Control Example 2 are all worse than those in Example 1 (as can be seen from Table 3 and Table 6).

Comparative Example 3: Preparation of PHB+P3HB4HB filaments without nanomaterials and tetrachlorophthalic anhydride (compared with Example 1, without nano magnesium oxide, fumed nano silicon dioxide, and tetrachlorophthalic anhydride)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, and 0.25 parts of anti-hydrolysis stabilizer 3600. , 1.5 parts of DH-2 reinforcing agent, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to granulate, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

The filament product obtained in Control Example 3, due to the lack of nanoparticles and tetrachlorophthalic anhydride, leads to poor thermal stability, slow crystallization speed, unstable processing technology, roller sticking phenomenon, and the spinning temperature must be selected in the low temperature range during processing, otherwise thermal degradation will occur if it exceeds 180°C. Therefore, the breaking strength, breaking strength retention rate, breaking strength CV, breaking elongation CV, limiting oxygen index and antibacterial rate of the filament product obtained in Control Example 3 are all worse than those in Example 1 (as shown in Table 3 and Table 6).

Combining the analysis of control examples 2 and 3 with examples 1 and 16, it can be seen that the nanoparticles (nano-magnesium oxide, fumed nano-silicon dioxide) and tetrachlorophthalic anhydride have a synergistic effect on mechanical and flame retardant properties.

Comparative Example 4: Preparation of PHB+P3HB4HB filaments without nucleating agent (compared with Example 1, without nucleating agent)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nanosilica, 1.5 parts of DH-2 enhancer, 2 0.4 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

The filament product obtained in Control Example 4, due to the lack of nucleating agent, leads to poor thermal stability, slow crystallization speed, unstable processing technology, roller sticking phenomenon, and the spinning temperature must be selected in the low temperature section during processing, otherwise thermal degradation will occur if it exceeds 180°C. Therefore, the breaking strength, breaking strength retention rate, breaking strength CV, breaking elongation CV, limiting oxygen index and antibacterial rate of the filament product obtained in Control Example 4 are all worse than those in Example 1 (as shown in Table 3 and Table 7).

Comparative Example 5: Preparation of PHB+P3HB4HB filaments without nano-magnesium oxide (compared with Example 1, without nano-magnesium oxide)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nanosilica, 1.5 parts of DH-2 enhancer, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, and 0.3 parts of BYK3700. Organic silicon leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, and then melt-extruded by a twin-screw extruder and granulated by air cooling. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain special pellets for PHA filaments;

The filament product obtained in Control Example 5, due to the lack of nano-magnesium oxide, leads to poor thermal stability, slow crystallization speed, unstable processing technology, roller sticking phenomenon, and the spinning temperature must be selected in the low temperature section during processing, otherwise thermal degradation will occur if it exceeds 185°C. Therefore, the breaking strength, breaking strength retention rate, breaking strength CV, breaking elongation CV, limiting oxygen index and antibacterial rate of the filament product obtained in Control Example 5 are all worse than those in Example 1 (as shown in Table 3 and Table 7).

Comparative Example 6: Preparation of PHB+P3HB4HB filaments without fumed nano-silica (compared with Example 1, without fumed nano-silica)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.25 parts of MILLAD 3905, 0.5 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, and 0.25 parts of anti-hydrolysis stabilizer 360. 0, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special pellets;

Step 3: After the PHA filament pellets are vacuum dried at 70-105°C for 2.5 hours, they are spun through a twin-screw melt spinning machine. The spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, and the number of die holes is 48. holes, controlling the extrusion speed to be 60-100 m/min, cooling through a horizontal 1 m long water tank, and stretching at the same time, with a stretching ratio of 6-10, a water temperature of 4°C, and 0.15% Tween 40 added to the water to obtain PHA primary fibers;

Comparing the control examples 2, 5 and 6 with the embodiment 1, it can be seen that the nano-magnesium oxide and other nanoparticles have a synergistic effect on the antibacterial rate.

The breaking strength, breaking strength retention, breaking strength CV, breaking elongation CV and antibacterial rate of the filament product obtained in Control Example 6 are all worse than those in Example 1 (as can be seen from Tables 3 and 7).

Comparative Example 7: Preparation of PHB+P3HB4HB filaments without reinforcing agent (compared with Example 1, without reinforcing agent)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 0.4 parts of anti-hydrolysis stabilizer 3600, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Step 5: The PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500 m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, The stretching speed is controlled at 3000-4200m/min), the third guide roller is provided, a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching occurs between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filament is wound on the bobbin through a winding device, and the winding speed is 3300-4600m/min to obtain a PHA filament finished product in the form of FDY.

The filament product obtained in Control Example 7 does not contain a reinforcing agent and also contains gas-phase nano-silica and tetrachlorophthalic anhydride, so its strength is greatly reduced. Compared with Example 1, its breaking strength, breaking strength retention rate, breaking strength CV, breaking elongation CV, flame retardancy, and antibacterial rate are all worse (as can be seen from Table 3 and Table 7).

Comparative Example 8: Preparation of PHB+P3HB4HB pure air-cooled filament (compared with Example 1, air cooling was used instead of water cooling)

Step 3, after vacuum drying the PHA filament pellets at 70-105° C. for 2.5 h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195° C., the pressure in the melt metering pump is controlled to 6-13 MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100 m/min, and the PHA spun fiber is cooled by a horizontal 1 m long air cooling device and stretched at the same time, with a stretching ratio of 6-10 and an air cooling temperature of 4° C. to obtain PHA nascent fibers;

However, fiber breakage is very likely to occur during the filament preparation process, the process is unstable, and the finished product is obviously brittle. The various properties are shown in Table 8.

Comparative Example 9: Preparation of PHB+P3HB4HB filaments at excessively high speed (compared with Example 1, the drawing speed and winding Too fast)

Step 5. The PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 6500-8000m/min), and the third guide roller. A ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 5-6; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 6600-8200m/min to obtain the PHA filament finished product in the form of FDY. The various properties are shown in Table 8.

Comparative Example 10: Preparation of PHB+P3HB4HB filaments at too low speed (compared with Example 1, the drawing speed and winding speed are too slow)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, and 0.25 parts of antioxidant RIANOX. 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets. The barrel temperature is set at 150-210°C and the air supply temperature is 15-75°C to obtain pellets for PHA filaments.

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 1560-2250m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 1.2-1.5; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 1650-2400m/min to obtain a PHA filament finished product in the form of FDY. The various properties are shown in Table 8.

Comparative Example 11: Preparation of PHB+P3HB4HB filaments first air-cooled and then stretched and then water-cooled (compared with Example 1, the cooling molding process is different)

Step 2: Weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano-magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of anti-hydrolysis stabilizer 3600, 1.5 parts of Fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, then melt-extruded by a twin-screw extruder and cooled by air cooling to obtain pellets, the barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament-specific pellets;

Step 3, after vacuum drying the PHA filament pellets at 70-105° C. for 2.5 hours, the pellets are spun through a twin-screw melt spinning machine, the spinning temperature is set to 165-195° C., the pressure in the melt metering pump is controlled to 6-13 MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100 m/min, and the pellets are dried through a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 85-102° C., and the PHA spun fiber is stretched at the same time, and the stretching ratio is 6-10, to obtain the PHA spun fiber;

Step 4: Cool the PHA nascent fibers obtained in step 3 through a 1m long horizontal water tank at a water temperature of 4°C, add 0.15% Tween 40 to the water, and immediately oil the fibers through an oil roller. Bundle the fibers into filaments at a speed of 1200-1400m/min;

However, the filament preparation process is prone to roller sticking, the process is unstable, the fiber is easy to break, and the finished product has post-crystallization phenomenon. The various properties are shown in Table 8.

Comparative Example 12: Preparation of PHB+P3HB4HB filaments that were first water-cooled but not simultaneously stretched (different cooling and molding process compared to Example 1)

Step 3, after vacuum drying the PHA filament pellets at 70-105°C for 2.5h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100m/min, and cooling is performed through a horizontal 1m long water tank with a water temperature of 4°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fibers;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a 3.5 m long vertical annular air tunnel, wherein the air supply temperature is 85-102° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 200-300 m/min at the oil roller;

However, fiber breakage is prone to occur during the filament preparation process, the process is unstable, and post-crystallization occurs in the finished product. The various properties are shown in Table 9.

Comparative Example 13: Preparation of PHB+P3HB4HB filaments first water-cooled, then air-cooled, and then warm-water stretched (compared with Example 1, the cooling molding process is different)

Step 4, drying the PHA nascent fibers obtained by cooling in step 3 through a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 18-45° C., and then continuing to cool through a horizontal 1 m long water tank, wherein the water temperature is 18-45° C., 0.15% Tween 40 is added to the water, and the fibers are stretched at the same time, and oiled through an oil roller, and multiple fibers are bundled into filaments, and the speed at the oil roller is 1200-1400 m/min;

However, the filament preparation process is prone to roller sticking, the process is unstable, and the fiber is prone to breakage. The various properties are shown in Table 9.

Comparative Example 14: Preparation of PHB+P3HB4HB filaments with accelerated spinning speed (spinning speed is too fast compared with Example 1)

Step 2: weigh 75 parts of PHB, 25 parts of P3HB4HB, 0.5 parts of magnesium 2-ethylhexanoate, 0.75 parts of zinc stearate, 0.25 parts of nano magnesium oxide, 0.15 parts of MILLAD 3905, 0.35 parts of ACLYN 285A, 0.5 parts of BASF ADR 4300F, 0.25 parts of Vertellus E60P, 0.5 parts of EK-145 polyester chain extender, 0.25 parts of antioxidant CA, 0.25 parts of antioxidant RIANOX 1098, 0.25 parts of antioxidant RIANOX 626, 0.5 parts of polycarbodiimide UN-03, 0.25 parts of Anti-hydrolysis stabilizer 3600, 1.5 parts of fumed nano-silica, 1.5 parts of DH-2 reinforcing agent, 2 parts of tetrachlorophthalic anhydride, 0.4 parts of oleic acid amide, 0.3 parts of BYK3700 silicone leveling agent, 0.3 parts of antistatic agent MOA3-PK, 0.4 parts of methyltriethoxysilane, 0.5 parts of HTDI, 0.35 parts of aluminum citrate, 0.6 parts of silane coupling agent Z-6020, 0.9 parts of silane coupling agent KH-550, 0.4 parts of TBC, and 0.6 parts of ATBC are physically mixed by a high-speed mixer for 10-30 minutes, and then melt-extruded by a twin-screw extruder and cooled and granulated by air cooling. The barrel temperature is set to 150-210°C, and the air supply temperature is 15-75°C to obtain PHA filament special granules;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 2600-3000m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 1.1-1.5; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 3300-4600m/min to obtain a PHA filament finished product in the form of FDY.

However, fiber breakage is prone to occur during the filament preparation process. The various properties are shown in Table 9.

Comparative Example 15: Preparation of PHB+P3HB4HB filaments with slowed spinning speed (spinning speed is too slow compared with Example 1)

Step 3: After the PHA filament pellets are vacuum dried at 70-105°C for 2.5h, they are spun through a twin-screw melt spinning machine. The spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100m/min, and the pellets are cooled through a 1m long horizontal water tank and stretched at the same time. The ratio is 3.5-7, the water temperature is 4°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fiber;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 85-102° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 350-450 m/min at the oil roller;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 360-480m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 4-7; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 3300-4600m/min to obtain FDY-formed PHA filament finished products.

However, fiber breakage is prone to occur during the filament preparation process, and post-crystallization occurs in the finished product. The various properties are shown in Table 9.

Comparative Example 16: Preparation of PHB+P3HB4HB filaments with too high water cooling temperature (compared with Example 1, the water cooling temperature is too high)

Step 3, after vacuum drying the PHA filament pellets at 70-105°C for 2.5h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100m/min, cooling is performed through a horizontal 1m long water tank, and stretching is performed at the same time, the stretching ratio is 6-10, the water temperature is 40°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fiber;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1300-1500m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through the winding device. The winding speed is 3300-4600 m/min to obtain the PHA filament finished product in the form of FDY.

However, the filaments are prone to roller sticking and fiber breakage during preparation, and the finished products have post-crystallization and cannot meet the requirements of subsequent applications. The various properties are shown in Table 9.

Comparative Example 17: Preparation of PHB+P3HB4HB filaments with excessive water-cooling stretching ratio (compared with Example 1, the water-cooling stretching ratio is too large)

Step 3, after vacuum drying the PHA filament pellets at 70-105°C for 2.5h, spinning is performed through a twin-screw melt spinning machine, the spinning temperature is set to 165-195°C, the pressure in the melt metering pump is controlled to 6-13MPa, the number of die holes is 48, the extrusion speed is controlled to 60-100m/min, and cooling is performed through a horizontal 1m long water tank, and stretching is performed at the same time, the stretching ratio is 14-18, the water temperature is 4°C, and 0.15% Tween 40 is added to the water to obtain PHA primary fiber;

Step 4: drying the PHA spun fibers obtained by cooling in step 3 through a vertical 3.5 m long annular air tunnel, wherein the air supply temperature is 85-102° C., and immediately oiling the fibers through an oil roller, and bundling the fibers into filaments at a speed of 1400-1800 m/min at the oil roller;

Step 5, the PHA filaments obtained by oiling in step 4 are sequentially fed into the first guide roller (the stretching heating temperature is controlled at 45-70°C, and the spinning speed is controlled at 1600-2100m/min), the second guide roller (the shaping heating temperature is controlled at 75-110°C, and the stretching speed is controlled at 3000-4200m/min), and the third guide roller, and a ring blowing is set between the oil roller and the first guide roller, and the temperature is controlled at 18-45°C; stretching is generated between the first guide roller and the second guide roller, and the stretching ratio is controlled to be 2-4; a ring blowing is set between the second guide roller and the third guide roller, and the temperature is controlled at 18-45°C, and then the PHA filaments are wound on the bobbin through a winding device, and the winding speed is 3300-4600m/min to obtain FDY-formed PHA filament finished products.

Due to the excessively large water-cooling stretching ratio, in order to maintain the fiber tension, the speed of the subsequent oil roller and the first guide roller are also forced to increase, resulting in the incoordination of the overall stretching and crystallization process, extremely unstable filament quality, unstable process, and easy fiber breakage. The various properties are shown in Table 9.

The test results of the above embodiments are summarized in Tables 3 to 5, and the test results of the control examples are summarized in Tables 6 to 9. Compared with the filaments produced in the embodiments, the comprehensive performance of the filaments of the control examples is affected, and the filaments of the present application have better technical effects.

Table 3: Test results of Examples 1-5

Table 4: Test results of Examples 6-10

Table 5: Test results of Examples 11-16

Table 6: Test results of comparative examples 1-3

Table 7: Test results of comparative examples 4-7

Table 8: Test results of control examples 8-11

Table 9: Test results of control examples 12-17

It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

A filament, characterized in that the filament comprises a base material and an auxiliary agent, and the base material comprises 50%-100% PHA in terms of mass percentage.
The filament according to claim 1, characterized in that the filament comprises a base material and an auxiliary agent, and the base material is PHA;

Preferably, the filaments are made from PHA and an auxiliary agent.
The filament according to claim 1 or 2 is characterized in that the mass ratio of the base material to the auxiliary agent is (50-150): (0.1-28).
The filament according to any one of claims 1 to 3, characterized in that the auxiliary agent comprises a nano material;

Preferably, the nanomaterial includes one or a combination of two or more of nano magnesium oxide, nano calcium carbonate, gas phase nano silicon dioxide, nano cellulose, nano zinc oxide, nano titanium boride or nano titanium carbide;

Preferably, the mass ratio of PHA to nanomaterial is 100:(0.0001-3.25).
The filament according to any one of claims 1 to 4, characterized in that the auxiliary agent comprises a nucleating agent and a reinforcing agent,

Preferably, the nucleating agent includes one or a combination of two or more of nano magnesium oxide, nano calcium carbonate, MILLAD 3905, MILLAD 3988, NA-21, ACLYN 285A;

Preferably, the enhancer comprises one or a combination of two or more of fumed nano-silica, talcum powder, nano-cellulose, DH-2 enhancer, DH-3 enhancer, DH-4 enhancer, and tetrachlorophthalic anhydride;

Further preferably, the mass ratio of the nucleating agent to the reinforcing agent is (0.0001-3): (0.1-18).
The filament according to any one of claims 1 to 5, characterized in that the auxiliary agent further comprises one or a combination of two or more of a heat stabilizer, a chain extender, an antioxidant, an anti-hydrolysis agent, an anti-blocking agent, a cross-linking agent, a coupling agent and a plasticizer;

Preferably, the heat stabilizer includes one or a combination of two or more of magnesium 2-ethylhexanoate, zinc 2-ethylhexanoate, zinc stearate, calcium stearate, calcium laurate, and magnesium laurate;

Preferably, the chain extender includes one or a combination of two or more of BASF ADR 4300F, BASF ADR 4400, Vertellus E60P, 2,2'-(1,3-phenylene)-bisoxazoline, trimethylolpropane, and EK-145 polyester chain extender;

Preferably, the antioxidant comprises one or a combination of two or more of antioxidant CA, LOWINOX 44B25, antioxidant RIANOX 1098, antioxidant RIANOX 1790, antioxidant RIANOX 168, and antioxidant RIANOX 626;

Preferably, the anti-hydrolysis agent includes one or a combination of two or more of polycarbodiimide UN-03, double bond anti-hydrolysis agent CHINOX P-500, DuPont132F NC010, anti-hydrolysis stabilizer 3600, and KANEKA M732;

Preferably, the anti-adhesive agent includes one or a combination of two or more of oleic acid amide, stearic acid amide, BYK3700 silicone leveling agent, silica opening agent AB-MB-09, and antistatic agent MOA3-PK;

Preferably, the crosslinking agent includes an environmentally friendly crosslinking agent, and further preferably includes one or a combination of two or more of hydroxypropyl methacrylate, methyltriethoxysilane, HTDI, DAP, isobutyloxymethylacrylate, multifunctional aziridine crosslinking agent SaC-100, aluminum citrate, and multifunctional polycarbodiimide UN-557;

Preferably, the coupling agent includes an environmentally friendly coupling agent, and further preferably includes one or a combination of two or more of silane coupling agent Z-6020, silane coupling agent KH-550, silane coupling agent KBM-602, TTS, and KR-38S;

Preferably, the plasticizer includes an environmentally friendly plasticizer, and further preferably includes one of TBC, ATBC, BNTXIB. or a combination of two or more.
The filament according to any one of claims 1 to 6, characterized in that the PHA comprises any one or more of 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 4-hydroxybutyric acid and 5-hydroxyvaleric acid, a homopolymer, a random copolymer and a block copolymer.
The filament according to any one of claims 1 to 7, characterized in that the PHA comprises one or more of PHB, P3HB4HB, PHBV, PHV, P3HP, PHBHHx, PHO, PHN, P3HB4HB3HV or P3HB4HB5HV.
The filament according to any one of claims 1 to 8, characterized in that the PHA comprises one of the following groups:

PHB and P3HB4HB are blended in a mass ratio of 1:10-10:1;

PHB and PHBV are blended in a mass ratio of 1:10-10:1;

PHB and PHBHHx are blended in a mass ratio of 1:10-10:1;

PHB and P3HB4HB3HV are blended in a mass ratio of 1:10-10:1;

PHB and P3HB4HB5HV are blended in a mass ratio of 1:10-10:1;

PHB is blended with P3HB4HB and PHBV in a mass ratio of (1-10):(1-6):(1-4);

PHB is blended with P3HB4HB and PHBHHx in a mass ratio of (1-10):(1-5):(1-5);

PHB is blended with PHBV and PHBHHx in a mass ratio of (1-10):(1-4):(1-6);

PHB is blended with PHBV, PHBHHx, and P3HB4HB in a mass ratio of (1-15):(1-4):(1-5):(1-6);

PHB is blended with P3HB4HB3HV and P3HB4HB5HV in a mass ratio of (1-10):(1-4):(1-5);

PHB is blended with PHBV and P3HB4HB3HV in a mass ratio of (1-10):(1-5):(1-6);

PHB is blended with PHBV and P3HB4HB5HV in a mass ratio of (1-10):(1-5):(1-6);

PHB is blended with PHBHHx and P3HB4HB3HV in a mass ratio of (1-10):(1-4.5):(1-5.5);

PHB is blended with PHBHHx and P3HB4HB5HV in a mass ratio of (1-10):(1-4.5):(1-5.5);

PHB is blended with P3HB4HB and P3HB4HB3HV in a mass ratio of (1-10):(1-5):(1-4.5); or,

PHB is blended with P3HB4HB and P3HB4HB5HV in a mass ratio of (1-10):(1-5):(1-4.5).
The filament according to any one of claims 1 to 9, characterized in that the filament comprises, by mass:

PHA: 50-150 parts;

Additives: 0.1-28 parts;

Preferably, the auxiliary agent includes:

Heat stabilizer: 0-2.5 parts;

Nucleating agent: 0.0001-1.5 parts;

Chain extender: 0-2.5 parts;

Antioxidant: 0-1.5 parts;

Anti-hydrolysis agent: 0-1.5 parts;

Enhancer: 0.1-10.0 parts;

Anti-adhesive agent: 0-2.0 parts;

Cross-linking agent: 0-2.5 parts;

Coupling agent: 0-3.0 parts;

Plasticizer: 0-2.0 parts.
The filament according to any one of claims 1-10, characterized in that the molecular weight of the PHA is 300,000-6,000,000.
The filament according to any one of claims 1-11 is characterized in that the filament is in the form of POY, FDY or DTY.
A method for preparing filaments as described in any one of claims 1-12, characterized in that the preparation method comprises melting and granulating raw materials, and then spinning to obtain filaments, and the raw materials include a base material and an auxiliary agent.
The preparation method according to claim 13 is characterized in that the preparation method includes melt-granulating the raw materials and then performing an initial spinning process, and the initial spinning process includes cooling and stretching at the same time.
The preparation method according to claim 14 is characterized in that the cooling and stretching comprises water cooling and stretching or air cooling and stretching.
The preparation method according to claim 15 is characterized in that the water cooling temperature in the water-cooling and simultaneous stretching is 0-30°C.
The preparation method according to any one of claims 14 to 16, characterized in that the stretching ratio is 2 to 12.
The preparation method according to any one of claims 15-17 is characterized in that an antistatic agent is added to the water during the water cooling and stretching.
The preparation method according to any one of claims 14-18 is characterized in that the temperature of the initial spinning process is 150-210°C.
The preparation method according to any one of claims 14-19 is characterized in that the pressure of the initial spinning process is 5-15 MPa.
The preparation method according to any one of claims 14-20 is characterized in that the extrusion speed of the initial spinning process is 40-200 m/min.
The preparation method according to any one of claims 14-21 is characterized in that the initial spinning process also includes drying, oiling, and then a molding process.
The preparation method according to claim 22 is characterized in that the molding process comprises feeding the oiled filaments into a first guide roller, a second guide roller, and a third guide roller in sequence and then collecting them;

Preferably, the first godet roller is set at a temperature of 25-90°C;

Preferably, the first godet roller is set at a speed of 500-2000 m/min;

Preferably, the second godet roller is set at a temperature of 70-115°C;

Preferably, the second godet roller is set at a speed of 1500-5500 m/min;

Preferably, the third guide roller is set at a speed of 1750-6000 m/min.
The preparation method according to claim 22 or 23 is characterized in that the oiling is performed using an oil roller. The speed is 400-1600m/min.
The preparation method according to any one of claims 22-24 is characterized in that a ring blowing air is arranged between the oil roller used for oiling and the first guide wire roller, and the temperature is 15-45°C.
The preparation method according to any one of claims 23-25 is characterized in that a ring blowing air is arranged between the second guide roller and the third guide roller, and the temperature is 15-45°C.
The preparation method according to any one of claims 13 to 26, characterized in that the preparation method comprises:

A) drying the raw materials, mixing them, melting and extruding them, and cooling and granulating them by air cooling to obtain pellets for filaments;

B) subjecting the filament-specific pellets to a preliminary spinning process to obtain a spun fiber, wherein the preliminary spinning process includes water cooling and simultaneous stretching, wherein the water cooling temperature is 0-30° C., the stretching ratio is 2-12, and an antistatic agent is added to the water, the preliminary spinning process temperature is 150-210° C., the pressure is 5-15 MPa, and the extrusion speed is 40-200 m/min;

C) drying the nascent fiber in an annular blowing tunnel and oiling it with an oil roller, wherein the air supply temperature is 35-105° C. and the speed at the oil roller is 400-1600 m/min;

D) subjecting the oiled filaments to a forming process, wherein the forming process comprises sequentially feeding the oiled filaments to a first guide roller, a second guide roller, and a third guide roller and then collecting them to obtain filaments;

Among them, the first godet roller is set at a temperature of 25-90°C and a speed of 500-2000m/min, the second godet roller is set at a temperature of 70-115°C and a speed of 1500-5500m/min, and the third godet roller has a speed of 1750-6000m/min;

Circular blowing is arranged between the oil roller and the first guide wire roller, and the temperature is 15-45°C; and circular blowing is arranged between the second guide wire roller and the third guide wire roller, and the temperature is 15-45°C.
A use of the filament described in any one of claims 1 to 12 or the filament obtained by the preparation method described in any one of claims 13 to 27 in the preparation of products requiring materials to have biodegradable properties.
The use according to claim 28 is characterized in that the product comprises a traditional fabric product or an industrial textile product.