CN110055617A - A kind of Biodegradable polyester staple fiber and preparation method thereof - Google Patents
A kind of Biodegradable polyester staple fiber and preparation method thereof Download PDFInfo
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- CN110055617A CN110055617A CN201910390587.4A CN201910390587A CN110055617A CN 110055617 A CN110055617 A CN 110055617A CN 201910390587 A CN201910390587 A CN 201910390587A CN 110055617 A CN110055617 A CN 110055617A
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- polyester staple
- biodegradable polyester
- staple fiber
- temperature
- pbs
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a kind of Biodegradable polyester staple fiber and preparation method thereof, the polyester staple fibers are by including that the raw material of following parts by weight is made: PBS is sliced 200-260 parts；30-40 parts of poly-epsilon-caprolactone；10-15 parts of chitin fiber element；0.5-1.8 parts of molecule chain extender；10-12 parts of phosphite ester antioxidant；5-8 parts of norvaline；10-20 parts of dispersing agent.The present invention has the advantages that prepare with degradability and elasticity and the good polyester staple fibers of cross-linking properties.
Description
Technical field
The present invention relates to the technical field of chemical fibre, more particularly, to a kind of Biodegradable polyester staple fiber and its
Preparation method.
Background technique
It is raw material that chemical fibre, which is with natural polymer or artificial synthesized high-molecular compound, by preparation
The processes such as spinning solution, the spinning and post-processing fiber obtained with textile performance.
Natural or synthesis polymer substance or inorganic matter are usually first made spinning and melted by the preparation of chemical fibre
Body or solution are extruded as liquid thread by spinning head then by filtering, metering, and then solidification forms fiber.PBS is one
The biodegradable polyester of kind, is one of hot spot of research of the field of polymers, but since PBS molecular weight of polyesters is small and divides
Cloth is wide, so that the fiber produced in fabrication processes with PBS merely is in terms of elasticity and cross-linking properties all not as good as tradition
Fiber.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of Biodegradable polyester staple fiber
And preparation method thereof, reacted by the way that PBS slice and auxiliary material and chain extender are carried out melt blending, prepare elasticity and
The short fibre of the good PBS of cross-linking properties.
Above-mentioned purpose of the invention has the technical scheme that
A kind of Biodegradable polyester staple fiber, the polyester staple fibers are by including that the raw material of following parts by weight is made:
By using above-mentioned technical proposal, PBS slice, poly-epsilon-caprolactone and chitin fiber element pass through copolymerization mixing system
At short fibre, it is the raw material of obtained short fibre that PBS slice, which is that poly butylene succinate is sliced, and poly-epsilon-caprolactone and first
Auxiliary raw material of the chitin cellulose as the short fibre of production, poly-epsilon-caprolactone and PBS slice are all can be degradable by microorganism
Material, it is environment friendly and pollution-free.And chitin fiber element can increase the elasticity of short fibre, and the amino in chitin fiber element
It is easy to form hydrogen bond between fibrous strands during copolymerization, so that " bridge formation " is carried out between adjacent fiber molecule chain,
Crosslinking degree is improved, so that the molecular weight of fiber is improved, but the content of chitin fiber element is not high, so the degree of crosslinking
Will not be too high, the synthesis of short fibre can be effectively ensured.The addition of molecule chain extender first carries out with raw material pre- for before the polymerization
Poly- reaction, molecule chain extender can make strand extend with the functional group reactions on polymer chain, and molecular weight increases.Molecule expands
Powder molecule enters the main chain of polymer, and by secondary substitution reaction, to increase the degree of polymerization of polymer, improves and divide
Son amount, improves viscosity, to make copolymer molded.Norvaline can be reacted with chitin fiber element, generate norvaline end group
Prepolymer, the prepolymer of norvaline end group with molecule chain extender reaction, extend again so that strand is spread.And norvaline
It can directly be reacted with low molecule quality oligomer, form " bridge formation " between two polymer chains, dramatically increase molecular mass, mention
The viscosity of high system reduces content of carboxyl end group.Phosphite ester antioxidant can prevent the product after polymerization to be oxidized, and improve
The quality of polymerizate.Dispersing agent plays the role of dispersion to reactant, so that reactant diffusion is uniformly, stable reaction.
The present invention is further arranged to: the PBS slice molecular weight is 20000-80000.
By using above-mentioned technical proposal, when the molecular weight of PBS slice is lower than 20000, poly butylene succinate gathers
It is right too low, even if under the action of molecule chain extender, it is also difficult to form stable copolymer, cannot get required short fine production
Object.And when the molecular weight of PBS slice is higher than 80000, the degree of polymerization of poly butylene succinate is excessively high, in molecule chain extender
Under the action of, the product degree of polymerization increase after copolymerization is faster higher, is unable to get short fine product.
The present invention is further arranged to: the chain extender includes following components in percentage by weight:
By using above-mentioned technical proposal, macromolecular produces fracture polymer under the action of heat, and breaking part generates activity
Group, the terminal reactive base that molecule chain extender is coupled again by the active epoxy group of itself, branching degradation breaking part generates
Group, reaction generate the high polymer of high molecular weight.Contain in styrene, methyl methacrylate and Malaysia acid glycidyl ester
Carbon-carbon double bond, addition reaction occurs for the hydroxyl that can be formed after polymer macromolecule fracture, to expand polymer molecule
Chain increases the molecular weight of polymer.2- imidazolidinone has imino group active hydrogen, can react with norvaline terminal prepolymer,
Molecular weight is caused to extend.
The present invention is further arranged to: also sweet added with the double-β-hydroxyethyl ethers of resorcinol and shrink in the chain extender
Oily allyl ether, the weight percent of component in the chain extender are as follows:
By using above-mentioned technical proposal, resorcinol bis-beta-hydroxyethyl ether and glycidol allyl ether are for crust
The hard segment that the soft chain segment and two norvalines that matter cellulose can be such that polyalcohols macromolecular constitutes are constituted generates microcell to separation, makes
Urethane hard segment crystallinity it is more preferable, and crystallinity and align so that being more readily formed between polymer molecule
Hydrogen chain, it means that polymer molecule can obtain preferable orderly crystallization, the resistance rotation effect of crystallization and polymer segment
Migration finally shows polymer with excellent toughness.
A kind of preparation method of Biodegradable polyester staple fiber, it is characterised in that:
(1) control temperature is dried PBS slice lower than 80 DEG C；
(2) by molecule chain extender and phosphite ester antioxidant, dispersing agent and PBS slice, poly-epsilon-caprolactone and crust
Matter cellulose mixes in proportion, and then under the protection of auxiliary warm dry nitrogen gas, into being plasticized in twin-screw, controls
Pressure is 20-35MPa；
(3) spinning handles to obtain polyester staple fibers after carrying out the fiber after plasticizing.
By using above-mentioned technical proposal, PBS slice is first dried to reduce moisture and bring reaction into, so that polymerization
The reactive polymeric degree of reaction declines.Temperature is dried when being higher than 80 DEG C can make PBS that more serious softening occur, and be sliced
It is easy to happen bonding and influences subsequent copolyreaction.It is protected in copolyreaction using nitrogen, nitrogen is a kind of inertia
Gas, pole torpescence can play the role of being protected from oxidation to reaction.Pressure when control plasticizing is higher than atmospheric pressure,
So that under high pressure, the forward reaction journey of the copolymerization chain extending reaction of PBS slice, poly-epsilon-caprolactone and chitin fiber element
Degree is more complete, and the quality of obtained polyester staple fibers is higher.
The present invention is further arranged to: in the step (2) when mixed raw material, addition has amino acid type surfactant,
The ratio between weight and raw material gross weight of the amino acid type surfactant are 1:3, and the amino acid type surfactant is N-
Acyl amino acid sodium-salt.
Through the above technical solution: amino acid surfactant can play the collaboration to reactant together with dispersing agent
Synergistic effect reduces the surface energy on polymer macromolecule surface, increases peptizaiton, improve the extent of reaction.And amino acid table
Amino is had in the activating agent of face, can be more easier to form hydrogen bond between polymer macromolecule, to crosslink altogether
It is poly-, improve reaction efficiency.
The present invention is further arranged to: the control of conical double-screw feed zone temperature is in 180-200 DEG C, compression section temperature
200-220 DEG C, homogenizing metering section temperature is 220-240 DEG C；The good Melt Pump of devolatilization is kneaded toward spinning manifold, temperature control exists
220-250,20-25 DEG C of circular blow air temperature.
The present invention is further arranged to: it is as follows that treatment process is spun after in step (3):
Spinning speed 700-1300m/min；Stretch 60-85 DEG C of sink temperature；Preliminary draft multiplying power 1.05-1.10；One drawing-off
Multiplying power 1.5-2.3；Two draft ratio 1.02-1.1；Cutting off after curling, tension heat setting, the loose thermal finalization of baking oven can be made into
Fiber number 0.8-15D, the Biodegradable polyester staple fiber of length 3-86mm plurality of specifications.
By using above-mentioned technical proposal, if control spinning speed is lower than 700m/min when rear spinning processing, spinning is held
Easily bend fold, influences the stretching quality of spinning.And when the speed of spinning is higher than 1300m/min, then spinning is easy quilt
What is stretched is meticulous, is easy to happen fracture, and toughness reduces.When the temperature for stretching sink is lower than 60 DEG C, temperature is too low, and spinning is held
It is easily hardened, drawing effect is deteriorated.When the temperature for stretching sink is higher than 85 DEG C, spinning is excessively soft, stretches too long meeting so that spinning
The degraded toughness of silk.
Compared with prior art, the beneficial effects of the present invention are:
1, by the way that PBS slice is prepared biodegradable polyester staple fiber through melt polycondensation dehydration, be conducive to improve
White pollution；
2, it is crosslinked by adding a small amount of chitin fiber element raw material and PBS in the feed, increases polyester staple fibers
The toughness and elasticity of dimension.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail.
Embodiment 1:
A kind of Biodegradable polyester staple fiber disclosed by the invention and preparation method thereof, preparation method includes following step
It is rapid:
S1: control temperature is dried PBS slice lower than 80 DEG C；
S2: by molecule chain extender and phosphite ester antioxidant, dispersing agent and PBS slice, poly-epsilon-caprolactone and crust
Matter cellulose mixes in proportion, and the amino acid surface activity that the ratio between weight and raw material gross weight are 1:3 is then added simultaneously
Agent N- acyl amino acid sodium-salt, into being plasticized in twin-screw, controls pressure then under the protection of auxiliary warm dry nitrogen gas
For 20MPa, for the control of conical double-screw feed zone temperature at 180 DEG C, compression section temperature is 200 DEG C, and homogenizing metering section temperature is
220℃；The good Melt Pump of devolatilization is kneaded toward spinning manifold, temperature is controlled at 220 DEG C, 20 DEG C of circular blow air temperature.
Wherein the parts by weight of each component are as follows:
Molecule chain extender includes following weight percentage components:
S3: spinning is handled after the polymer after plasticizing is carried out, and rear spinning process is as follows:
Spinning speed 700m/min；Stretch sink temperature 60 C；Preliminary draft multiplying power 1.05；One draft ratio 1.5；Two lead
Stretch multiplying power 1.02；Cutting can be made into fiber number 1D, more kinds of length 36mm rule after curling, tension heat setting, the loose thermal finalization of baking oven
The Biodegradable polyester staple fiber of lattice.
Embodiment 2-4 is the difference from embodiment 1 is that the raw material for preparing short fibre is calculated by weight as following table:
The difference of embodiment 5-13 and embodiment 1 under each component is by weight percentage in molecule chain extender
Table:
The difference of embodiment 14-17 and embodiment 1 is being calculated as following table in spinning speed and stretching sink temperature:
| Embodiment | Spinning speed (m/min) | It stretches sink temperature (DEG C) |
| Embodiment 14 | 850 | 66 |
| Embodiment 15 | 1000 | 72 |
| Embodiment 16 | 1150 | 78 |
| Embodiment 17 | 1300 | 85 |
Comparative example
Comparative example 1 is terylene chemical fibre；
Comparative example 2 is the difference from embodiment 1 is that be not added with chitin fiber element；
Comparative example 3 the difference from embodiment 1 is that do not added in molecule chain extender resorcinol bis-beta-hydroxyethyl ether and
Glycidol allyl.
Detection method
Biodegradability test
ISO14855-99/GB/T19277-2003 detection method: it is put into after sample material is mixed with compost inoculum
In Composting container, in certain oxygen, temperature (58 ± 2 DEG C) carries out sufficient compost under conditions of humidity (50-55%)
Change, CO after measurement material degradation 45 days2Final burst size (6 months can be extended to), with actual CO2Burst size and its theory
The ratio of maximum discharging amount indicates the biological degradation rate of material.Detection object of reference is cellulose of the partial size less than 20 μm, only
When having after object of reference 45 days degradation rate be greater than 70%, the experiment is effective.
Fibre strength test
Fiber samples are tested with YG001A electronics strength tester.
| Biological degradation rate | Breaking strength (cN/dtex) | |
| Embodiment 1 | 46% | 0.8 |
| Embodiment 2 | 43% | 0.7 |
| Embodiment 9 | 42% | 0.6 |
| Embodiment 10 | 43% | 0.6 |
| Comparative example 1 | 99% | 0.5 |
| Comparative example 2 | 38% | 0.4 |
| Comparative example 3 | 39% | 0.6 |
Conclusion: embodiment 1 and embodiment 2 and embodiment 9 and embodiment 10 can be seen that all than comparison according to upper table
The biological degradation rate of example 1 is high, illustrates that the polyester staple fibers prepared with PBS can achieve the effect of degradation environment protection.Pass through breaking strength
Between comparison, it can be deduced that chitin fiber element and resorcinol bis-beta-hydroxyethyl ether and glycidol in chain extender
The addition of allyl has a certain upgrade effect for the intensity of fiber.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned reality
Example is applied, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for this technology
For the those of ordinary skill in field, several improvements and modifications without departing from the principles of the present invention, these are improved and profit
Decorations also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of Biodegradable polyester staple fiber, it is characterised in that the polyester staple fibers are by the raw material including following parts by weight
It is made:
2. a kind of Biodegradable polyester staple fiber according to claim 1, it is characterised in that the PBS is sliced molecule
Amount is 20000-80000.
3. a kind of Biodegradable polyester staple fiber according to claim 1, it is characterised in that: the chain extender include with
The component of lower weight percent:
4. a kind of Biodegradable polyester staple fiber according to claim 1, it is characterised in that: also add in the chain extender
Added with resorcinol bis-beta-hydroxyethyl ether and glycidol allyl ether, the weight percent of component in the chain extender are as follows:
5. a kind of preparation method of any Biodegradable polyester staple fiber of claim 1-4, it is characterised in that:
(1) control temperature is dried PBS slice lower than 80 DEG C；
(2) molecule chain extender and phosphite ester antioxidant, dispersing agent and PBS slice, poly-epsilon-caprolactone and chitin is fine
Dimension element mixes in proportion, and then under the protection of auxiliary warm dry nitrogen gas, into being plasticized in twin-screw, controlling pressure is
20-35MPa；；
(3) spinning handles to obtain polyester staple fibers after carrying out the fiber after plasticizing.
6. a kind of Biodegradable polyester staple fiber preparation method according to claim 5, it is characterised in that: the step
(2) in when mixed raw material, addition has amino acid type surfactant, and the weight and raw material of the amino acid type surfactant are total
Weight ratio is 1:3, and the amino acid type surfactant is N- acyl amino acid sodium-salt.
7. a kind of Biodegradable polyester staple fiber preparation method according to claim 5, it is characterised in that: conical double ribbon
For the control of bar feed zone temperature at 180-200 DEG C, compression section temperature is 200-220 DEG C, and homogenizing metering section temperature is 220-240 DEG C；
The good Melt Pump of devolatilization is kneaded toward spinning manifold, temperature is controlled in 220-250,20-25 DEG C of circular blow air temperature.
8. a kind of Biodegradable polyester staple fiber preparation method according to claim 5, it is characterised in that: step (3)
In after spin treatment process it is as follows:
Spinning speed 700-1300m/min；Stretch 60-85 DEG C of sink temperature；Preliminary draft multiplying power 1.05-1.10；One draft ratio
1.5-2.3；Two draft ratio 1.02-1.1；Cutting can be made into fiber number after curling, tension heat setting, the loose thermal finalization of baking oven
0.8-15D, the Biodegradable polyester staple fiber of length 3-86mm plurality of specifications.
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| CN201910390587.4A CN110055617B (en) | 2019-05-10 | 2019-05-10 | Biodegradable polyester staple fiber and preparation method thereof |
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| CN201910390587.4A CN110055617B (en) | 2019-05-10 | 2019-05-10 | Biodegradable polyester staple fiber and preparation method thereof |
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| CN110055617B CN110055617B (en) | 2023-01-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113026127A (en) * | 2021-02-08 | 2021-06-25 | 东华大学 | Degradable silk and preparation method thereof |
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2019
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| CN102070880A (en) * | 2010-12-24 | 2011-05-25 | 金发科技股份有限公司 | Biodegradable resin composition and product thereof |
| CN105368022A (en) * | 2015-11-05 | 2016-03-02 | 东华大学 | Method for preparing polycaprolactone self-reinforced material |
| CN108033738A (en) * | 2018-01-03 | 2018-05-15 | 山东润展汽车服务有限公司 | A kind of aqueous high molecular anti-skid surface material and its construction method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113026127A (en) * | 2021-02-08 | 2021-06-25 | 东华大学 | Degradable silk and preparation method thereof |
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