CN114213817A - Preparation method of PBAT/PLA/CaCO3 full-biodegradable composite material - Google Patents
Preparation method of PBAT/PLA/CaCO3 full-biodegradable composite material Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 96
- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 70
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000010216 calcium carbonate Nutrition 0.000 title description 24
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004626 polylactic acid Substances 0.000 claims description 41
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 25
- 239000007822 coupling agent Substances 0.000 claims description 23
- 238000001746 injection moulding Methods 0.000 claims description 20
- 239000004970 Chain extender Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 23
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 238000000520 microinjection Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a PBAT/PLA/CaCO3The preparation method of the full-biodegradable composite material takes PBAT, PLA and calcium carbonate as main raw materials, does not destroy the inherent biodegradable property of the raw materials, and has the advantage of complete biodegradation. The introduction of a small amount of PLA endows the composite material with high strength, and the addition of calcium carbonate greatly reduces the production cost of the composite material while improving the strength of the composite material, is beneficial to industrial production and achieves the purposes of environmental protection and energy conservation; the composite material has simple processing technology and does not need to add a compatilizer and a plasticizer.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to PBAT/PLA/CaCO3A preparation method of a full-biodegradable composite material.
Background
The traditional plastic wastes can not be self-degraded, causing serious white pollution and causing great harm to the ecological environment, and the development of plastics which can be degraded in the nature is trendy. The PBAT serving as a thermoplastic biodegradable material contains a flexible aliphatic chain and a rigid aromatic chain on a molecular chain, so that the material has good ductility, elongation at break, impact property and heat resistance, can be used as an effective substitute of a traditional membrane material, is in accordance with government environmental protection treatment ideas, and has wide development prospects.
Although the PBAT has excellent performance, the application range of the PBAT is limited by the defects of high price, low tensile strength, low modulus and the like. Calcium carbonate comes from nature, and has low price, rich yield and various varieties. The calcium carbonate is used as a plastic additive, so that the production cost can be effectively reduced, and the good mechanical property of a plastic matrix is kept. Polylactic acid (PLA) is a biodegradable thermoplastic polymer, has the characteristics of high strength, good biocompatibility and the like, but has poor toughness and thermal stability and is expensive. Edelene et al (Journal of Composite Materials,2019,54(10):002199831988028.) investigated the ADR chain extender pair PBAT/CaCO3Effect of the Properties of the composite, CaCO3At a content of 30%, the tensile strength of the composite material was only 12.4 MPa. Daniel et al (Journal of Applied Polymer Science,2018,135(35):46660.) use different levels of CaCO3Particle-reinforced PBAT/PLA composite film, 62 of whichPBAT28PLA10CaCO3The prepared film has the most excellent mechanical property, the tensile strength is 15MPa, and the elongation at break is only 80%. Zhangting et al (Journal of Applied Polymer Science,2021,138 (38)) improved the properties of PBAT/PLA films by silane modification with a 30 wt% CaCO content3The formulation coated with 2 wt% of an aliphatic silane coupling agent (CA1) provided the best combination of properties. The tensile strength of the P7C3/CA1-2 film in the transverse direction and the longitudinal direction is about 20 MPa. Surplus material, etc. in the patent publication No. CN 111647183A, a preparation method of inorganic micropowder/PBAT full-degradable composite film is proposed, in which the content of PBAT/CaCO is 25%3The composite film shows 32MPa of strength in a mechanical property test, but the breaking elongation is only 110%.
Thus, PBAT, PLA and CaCO3And blending can theoretically obtain the composite material with the advantages of several materials and excellent performance. However, the interface compatibility of the three materials is poor, and the inorganic powder is easy to agglomerate and has poor dispersibility, so that the mechanical property of the composite material is reduced, and the use requirement cannot be fully met.
Disclosure of Invention
The invention aims to provide PBAT/PLA/CaCO3A preparation method of a full-biodegradable composite material. The invention adopts PBAT as a main matrix, and PLA and CaCO which are environment-friendly3As an additive, the cost of the PBAT can be effectively reduced, a small amount of PLA can be well dispersed in the PBAT matrix, and the strength and the modulus of the composite material can be effectively improved under the synergistic effect of the PLA and calcium carbonate. The material of the invention has the characteristics of biodegradability, good component compatibility, lower manufacturing cost, excellent comprehensive performance and the like, and is expected to be widely applied to the aspects of disposable plastic products, food packaging materials and the like.
PBAT/PLA/CaCO of the invention3The full-biodegradable composite material comprises the following raw materials in parts by weight:
60-80 parts of poly (butylene adipate-terephthalate), 20-40 parts of calcium carbonate, 5 parts of polylactic acid, 0.1-2 parts of coupling agent and 0.1-2 parts of chain extender.
More preferably: 65-75 parts of polybutylene terephthalate-adipate, 25-35 parts of calcium carbonate, 5 parts of polylactic acid, 0.5-1 part of coupling agent and 0.5-1 part of chain extender.
The poly (butylene adipate-terephthalate) has a number average molecular weight of 20000-35000, preferably 25000-35000.
The number average molecular weight of the polylactic acid is 5000-50000, and preferably 25000-35000.
The average particle size of the calcium carbonate is 1000-3000nm, preferably 1000-2000 nm.
The coupling agent is selected from one or more of titanate coupling agent, aluminate coupling agent and silane coupling agent, and preferably is one or more of titanate coupling agent and aluminate coupling agent.
The chain extender is one or more of multifunctional epoxy oligomer ADR-4468, GMA, EGMA and SAG, preferably one or more of ADR-4468 and SAG.
According to the invention, by adding the calcium carbonate micro powder, selecting the auxiliary agent and adjusting the content of each component, the prepared full-biodegradable composite material has good mechanical property, is beneficial to environmental protection and has wide application value.
PBAT/PLA/CaCO of the invention3The preparation method of the full-biodegradable composite material comprises the following steps:
step 1: adding calcium carbonate and a coupling agent into a high-speed mixer, stirring and mixing uniformly, and activating the calcium carbonate;
step 2: mixing polybutylene terephthalate-adipate resin and a chain extender, adding the mixture into an internal mixer, and carrying out internal mixing to obtain plasticized PBAT;
and step 3: mixing the plasticized PBAT, the activated calcium carbonate and the polylactic acid, adding the mixture into an internal mixer, and internally mixing to obtain PBAT/PLA/CaCO3And (3) carrying out injection molding on the full-biodegradable composite material by using an injection molding machine to obtain a sample.
In the step 1, the temperature of the high-speed mixer is controlled to be 50-120 ℃ during stirring and mixing.
In the step 2, the temperature is controlled to be 130-180 ℃ during banburying.
In the step 3, the banburying temperature is controlled to be 130-180 ℃.
The rotating speed of the screw is 40-60 r/min during banburying, and the processing time is 10-20 min.
The invention has the beneficial effects that:
1. the material is compounded by taking PBAT and calcium carbonate as main raw materials, does not destroy the inherent biodegradable property of the raw materials, and has the advantage of complete biodegradation;
2. in the invention, when the content of calcium carbonate reaches 35%, the composite material still keeps excellent mechanical properties by the synergistic effect of a small amount of PLA, thereby being beneficial to market popularization;
3. the PBAT is firstly plasticized and then blended with the calcium carbonate, and a cross-linked network structure formed by the PBAT plasticization can better wrap the inorganic filler, so that the product has better appearance and mechanical property;
4. the process is simple, only simple blending is needed, and no additional compatilizer or plasticizer is needed.
Drawings
FIG. 1 shows PBAT/PLA/CaCO prepared in examples 1-43Mechanical property test chart of the full-biodegradable composite material.
FIG. 2 shows PBAT/PLA/CaCO with different chain extender contents3Mechanical property test chart of the full-biodegradable composite material.
FIG. 3 is PBAT/PLA/CaCO prepared in example 33A micro-topography of the fully biodegradable composite.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (3) drying 20 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.20 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, 75 parts of PBAT and 5 parts of PLA are dried in a vacuum drying oven for 12 hours at the temperature of 80 ℃, 0.75 part of ADR chain extender is added into the dried PBAT, the mixture is uniformly mixed and then added into an internal mixer, the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 5 min; then blending and injection molding the chain-extended PBAT, PLA and CaCO3 with different mass ratios by adopting an internal mixer and a micro injection molding machine to prepare dumbbell-shaped splines, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; the temperature of the micro injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: young's modulus is 130 MPa; the tensile strength was 17.45MPa, and the elongation at break was 252%.
Example 2:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (2) drying 25 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.25 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 70 parts of PBAT and 5 parts of PLA in a vacuum drying oven at 80 ℃ for 12 hours, adding 0.7 part of ADR chain extender into the dried PBAT, uniformly mixing, and then adding into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 5 min; then blending and injection molding the chain-extended PBAT, PLA and CaCO3 with different mass ratios by adopting an internal mixer and a micro injection molding machine to prepare dumbbell-shaped splines, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; the temperature of the micro injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: the Young modulus is 140 MPa; the tensile strength was 18.31MPa, and the elongation at break was 209%.
Example 3:
PBAT/PLA/CaCO3The full-biodegradable composite material and the preparation method thereof comprise the following steps:
(1) preparing a modified inorganic filler: and (3) drying 30 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.3 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain the activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 65 parts of PBAT and 5 parts of PLA in a vacuum drying oven at 80 ℃ for 12 hours, adding 0.65 part of ADR chain extender into the dried PBAT, uniformly mixing, and then adding into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 5 min; then adopting an internal mixer and a micro injection molding machine to carry out chain extension on PBAT, PLA and CaCO with different mass ratios3Blending and injection molding to prepare dumbbell-shaped sample bars, wherein the rotating speed of an internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; the temperature of the micro injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: young's modulus is 171 MPa; the tensile strength is 19.27MPa, the elongation at break is 156%, and the performance is relatively excellent.
Example 4:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (3) drying 35 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.35 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 60 parts of PBAT and 5 parts of PLA in a vacuum drying oven at 80 ℃ for 12 hours, adding 0.6 part of ADR chain extender into the dried PBAT, uniformly mixing, and then adding into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 5 min; then adopting an internal mixer and a micro injection molding machine to carry out chain extension on PBAT, PLA and CaCO with different mass ratios3Blending and injection molding to prepare dumbbell-shaped sample bars, wherein the rotating speed of an internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; the temperature of the micro injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: young's modulus is 132 MPa; the tensile strength is 17.3MPa, and the elongation at break is 131%; FIG. 2 shows PBAT/PLA/CaCO3The micro-topography of the composite material shows good dispersibility, and the performance also meets the application requirements.
Example 5:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (2) drying 25 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.25 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 70 parts of PBAT and 5 parts of PLA in a vacuum drying oven at 80 ℃ for 12 hours, uniformly mixing the dried PBAT, PLA and activated calcium carbonate, and adding the mixture into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; then, a miniature injection molding machine is adopted to prepare the dumbbell-shaped sample bar by injection molding, the temperature of the miniature injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: the Young modulus is 127 MPa; the tensile strength was 14.92MPa, and the elongation at break was 313%.
Example 6:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (2) drying 25 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.25 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 70 parts of PBAT and 5 parts of PLA in a vacuum drying oven at the temperature of 80 ℃ for 12 hours, adding 0.35 part of ADR chain extender into the dried PBAT, PLA and activated calcium carbonate, uniformly mixing, and adding into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; then, a miniature injection molding machine is adopted to prepare the dumbbell-shaped sample bar by injection molding, the temperature of the miniature injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: young's modulus is 128 MPa; the tensile strength was 16.23MPa, and the elongation at break was 251%.
Example 7:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (2) drying 25 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.25 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 70 parts of PBAT and 5 parts of PLA in a vacuum drying oven at the temperature of 80 ℃ for 12 hours, adding 0.7 part of ADR chain extender into the dried PBAT, PLA and activated calcium carbonate, uniformly mixing, and adding into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; then, a miniature injection molding machine is adopted to prepare the dumbbell-shaped sample bar by injection molding, the temperature of the miniature injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: young modulus is 129 MPa; the tensile strength was 17.31MPa, and the elongation at break was 229%.
Example 8:
PBAT/PLA/CaCO3The full-biodegradable composite material comprises the following steps:
(1) preparing a modified inorganic filler: and (2) drying 25 parts of calcium carbonate in a vacuum drying oven at 80 ℃ for 12h, adding 0.25 part of titanate coupling agent after drying, and reacting in a high-speed mixer at 100 ℃ for 20min to obtain activated calcium carbonate.
(2) Preparing a PBAT-based fully degradable material: firstly, drying 70 parts of PBAT and 5 parts of PLA in a vacuum drying oven at the temperature of 80 ℃ for 12 hours, adding 1.05 parts of ADR chain extender into the dried PBAT, PLA and activated calcium carbonate, uniformly mixing, and adding into an internal mixer, wherein the rotating speed of the internal mixer is 50r/min, the temperature is 170 ℃, and the time is 10 min; then, a miniature injection molding machine is adopted to prepare the dumbbell-shaped sample bar by injection molding, the temperature of the miniature injection molding machine is 190 ℃, the injection pressure is 35MPa, and the injection time is 10 s.
The stretching results show that: young modulus is 139 MPa; the tensile strength was 20.25MPa and the elongation at break was 178%.
Claims (10)
1. PBAT/PLA/CaCO3The preparation method of the full-biodegradable composite material is characterized by comprising the following steps:
step 1: adding calcium carbonate and a coupling agent into a high-speed mixer, stirring and mixing uniformly, and activating the calcium carbonate;
step 2: mixing polybutylene terephthalate-adipate resin and a chain extender, adding the mixture into an internal mixer, and carrying out internal mixing to obtain plasticized PBAT;
and step 3: mixing the plasticized PBAT, the activated calcium carbonate and the polylactic acid, adding the mixture into an internal mixer, and internally mixing to obtain PBAT/PLA/CaCO3Carrying out injection molding on the full-biodegradable composite material by using an injection molding machine to obtain a sample;
the raw materials comprise the following components in parts by weight:
60-80 parts of poly (butylene adipate-terephthalate), 20-40 parts of calcium carbonate, 5 parts of polylactic acid, 0.1-2 parts of coupling agent and 0.1-2 parts of chain extender.
2. The preparation method of claim 1, wherein the raw materials comprise the following components in parts by mass:
65-75 parts of polybutylene terephthalate-adipate, 25-35 parts of calcium carbonate, 5 parts of polylactic acid, 0.5-1 part of coupling agent and 0.5-1 part of chain extender.
3. The method of claim 1, wherein:
the number average molecular weight of the polybutylene adipate-terephthalate is 20000-50000.
4. The method of claim 1, wherein:
the number average molecular weight of the polylactic acid is 5000-.
5. The method of claim 1, wherein:
the average particle size of the calcium carbonate is 1000-3000 nm.
6. The method of claim 1, wherein:
the coupling agent is selected from one or more of titanate coupling agent, aluminate coupling agent and silane coupling agent.
7. The method of claim 1, wherein:
the chain extender is one or more of multifunctional epoxy oligomer ADR-4468, GMA, EGMA and SAG.
8. The method of claim 1, wherein:
in the step 1, the temperature of the high-speed mixer is controlled to be 50-120 ℃ during stirring and mixing.
9. The method of claim 1, wherein:
in the step 2, the temperature is controlled to be 130-180 ℃ during banburying.
10. The method of claim 1, wherein:
in the step 3, the banburying temperature is controlled to be 130-180 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524959A (en) * | 2022-04-14 | 2022-05-24 | 安徽大学 | Ceramic nano-cellulose reinforced full-biodegradable material composite membrane and preparation method thereof |
| CN114621564A (en) * | 2022-03-29 | 2022-06-14 | 湖南金悦降解塑料制品有限公司 | Manufacturing process and application of environment-friendly degradable plastic |
| CN115124827A (en) * | 2022-07-11 | 2022-09-30 | 三峡大学 | Preparation method of degradable polymer/calcium carbonate master batch |
| CN116162335A (en) * | 2023-02-14 | 2023-05-26 | 中科南京绿色制造产业创新研究院 | Composite material and preparation method thereof |
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| CN113652063A (en) * | 2021-08-02 | 2021-11-16 | 安徽瑞鸿新材料科技有限公司 | Calcium carbonate filled PBAT/PLA degradable film and preparation method thereof |
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| CN113652063A (en) * | 2021-08-02 | 2021-11-16 | 安徽瑞鸿新材料科技有限公司 | Calcium carbonate filled PBAT/PLA degradable film and preparation method thereof |
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| 石慧: "多元环氧扩链剂对PLA/PBAT共混物及PLA/PBAT/淀粉复合材料微观形貌及性能的影响" * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621564A (en) * | 2022-03-29 | 2022-06-14 | 湖南金悦降解塑料制品有限公司 | Manufacturing process and application of environment-friendly degradable plastic |
| CN114524959A (en) * | 2022-04-14 | 2022-05-24 | 安徽大学 | Ceramic nano-cellulose reinforced full-biodegradable material composite membrane and preparation method thereof |
| CN114524959B (en) * | 2022-04-14 | 2024-01-30 | 安徽大学 | Ceramic nanocellulose reinforced full-biodegradable material composite membrane and preparation method thereof |
| CN115124827A (en) * | 2022-07-11 | 2022-09-30 | 三峡大学 | Preparation method of degradable polymer/calcium carbonate master batch |
| CN115124827B (en) * | 2022-07-11 | 2023-08-29 | 三峡大学 | Preparation method of degradable polymer/calcium carbonate master batch |
| CN116162335A (en) * | 2023-02-14 | 2023-05-26 | 中科南京绿色制造产业创新研究院 | Composite material and preparation method thereof |
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| CN114213817B (en) | 2023-12-19 |
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