CN115613155B

CN115613155B - Filament or staple fiber and preparation method thereof

Info

Publication number: CN115613155B
Application number: CN202211459135.5A
Authority: CN
Inventors: 许向东; 邓铁军; 武玉和; 章义鑫; 韩白; 兰宇轩
Original assignee: Beijing Micro Structure Factory Biotechnology Co ltd
Current assignee: Beijing Micro Structure Factory Biotechnology Co ltd
Priority date: 2022-11-18
Filing date: 2022-11-18
Publication date: 2023-05-16
Anticipated expiration: 2042-11-18
Also published as: CN115613155A

Abstract

The invention relates to the technical field of fiber preparation, in particular to a filament or a staple fiber and a preparation method thereof. The filaments or the short fibers only take P3HB4HB as a main degradable material, are not blended with other degradable materials or even are not blended with other types of PHAs, so that additives such as compatilizers, lubricants and the like are not needed to be added, the purity of the components of the fiber materials is ensured, the quality and the process stability of filament or short fiber products are further improved, the degradation speed is higher, the components are more environment-friendly and single, the filaments or the short fiber products can be completely decomposed in natural environment, and the filaments or the short fiber products are green and sustainable. Because of the skin-friendly property, compared with the traditional chemical fiber fabric, the safety, the use comfort and the service performance are obviously improved.

Description

Filament or staple fiber and preparation method thereof

Technical Field

The invention relates to the technical field of fiber preparation, in particular to a filament or a staple fiber and a preparation method thereof.

Background

At present, the development prospect of the bio-based fiber or the degradable fiber is very wide, the fiber mainly made of PLA, PBAT, PBST, PCL and other materials and the product thereof are mature, and some of the fiber and the product reach the industrialization degree. However, the use of PHAs in woven, non-woven, etc. applications is still under investigation, typically by blending with other materials to enhance spinnability. Therefore, the PHA-based fiber and the PHA-based product are fresh, the content of the PHA-based fiber is often lower than 30%, the advantages of rapid degradation, bioaffinity, bacteriostasis, easiness in dyeing and the like of the PHA-based fiber are not exerted, and the PHA-based fiber is particularly obvious in the application field of medium-high-end textiles. With the gradual popularization of new energy automobiles, environment-friendly materials matched with the environment-friendly concept of the new energy automobiles also rapidly develop, wherein the degradable automobile interior textile material is an important direction.

The university of the same and the upper steam group disclose natural fiber and polylactic acid fiber blend fiber boards and methods for their preparation (CN 103302864B), wherein it is mentioned that PHA can be used as a top layer to blend PLA, but the PHA content is not more than 10% calculated on the basis of the gram weight ratio, and the PHA morphology is film rather than fiber, and high content application of PHA in automotive interior textile materials is not achieved.

Le Jinhua Australian Co., ltd. Discloses a resin composition for automotive interior material and a molded article (CN 104508050B) of automotive interior material, which are formed into a sheet or surface-treated layer by using a biomass thermoplastic resin, a plasticizer, an inorganic filler and other auxiliaries. In example 7, PHA was used, but the amount was only 5.7%, and the PHA was not formed into fibers, and the mechanical reinforcing property of the textile material could not be exerted.

The European Miya International group discloses multifilament polyester fibers (CN 106661767B), wherein the polyester used comprises PHA, and the obtained fiber textile product can be applied to automobile decoration and the like, but a large amount of the fiber textile product adopts micron-sized calcium carbonate as a filler, influences the color of a finished product and easily blocks spinning holes during spinning; and the spinning process is not suitable for PHA (PHA fiber with high orientation and certain strength can not be obtained only in the step of quenching), and has no significance in industrialized implementation.

The Anhui Jing Anrun biotechnology limited responsible company discloses a degradable sheath-core polymer, a high melt index degradable polymer, a degradable composite fiber net fabric, a preparation method and application thereof (CN 112663171A), wherein the PHA (polyhydroxyalkanoate) in the core layer of each embodiment accounts for 20 percent, but the obtained fabric is only in a non-woven form, and PLA is still used as a main raw material, so that the current situation that the PHA is used as an auxiliary material for the textile field is not broken through.

However, there are few reports of pure PHA-based filaments or fibers at present, particularly in the field of medium-high end textiles such as automotive interiors. Therefore, there is a need for preparing automotive interior materials from pure PHA-based filaments or staple fibers, and their specialty materials.

Disclosure of Invention

According to the invention, the P3HB4HB is used as a main material, and an auxiliary agent and a spinning process are preferred, so that the spinnability of the P3HB4HB is improved, and the multifunctional wear-resistant, ultraviolet-resistant, flame-retardant, antibacterial, hydrophobic and the like multifunctional filament can be provided, the performance requirements in the automotive interior field are met, and the environment-friendly multifunctional filament which is fully biodegradable and can be applied to the automotive interior field and the special material thereof are obtained.

In a first aspect of the invention, a filament or staple is provided.

Preferably, the filaments or staple fibers (or raw materials thereof) comprise P3HB4HB and/or an auxiliary agent.

Preferably, the filaments or staple fibers are modified by adding various auxiliary agents to the filaments or staple fibers using P3HB4HB as a main raw material.

In one embodiment of the invention, the filaments or staple fibers (or raw materials thereof) are made from P3HB4HB and an auxiliary agent.

Preferably, the molar content of 4HB monomer in the P3HB4HB ranges from 1 to 80 mole percent, preferably any of 3 to 40 mole percent, such as 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 mole percent.

The filaments or staple fibers may be selected from the same molar content of 4HB starting materials, or from different molar contents of 4HB monomers of P3HB4HB starting materials, as desired in particular embodiments.

Preferably, the different 4HB monomer molar content of the P3HB4HB starting material comprises a 4HB monomer molar content of any one of 1% -30%, preferably 3% -20%, e.g. 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% of P3HB4HB.

In one embodiment of the invention, the raw materials of P3HB4HB with different 4HB monomer mole contents are P3HB4HB with 5% of 4HB monomer mole content and P3HB4HB with 10% of 4HB monomer mole content, and the mass ratio of the two P3HB4HB is 1:1.

In one embodiment of the invention, the P3HB4HB raw materials with different 4HB monomer mole contents are P3HB4HB with 3% of 4HB monomer mole content and P3HB4HB with 15% of 4HB monomer mole content, and the mass ratio of the two P3HB4HB is 1:1.

in one embodiment of the invention, the raw materials of P3HB4HB with different 4HB monomer mole contents are P3HB4HB with 3% of 4HB monomer mole content and P3HB4HB with 20% of 4HB monomer mole content, and the mass ratio of the two P3HB4HB is 1:1.

preferably, the molecular weight of the P3HB4HB is in the range of 30 to 600 ten thousand, preferably in the range of any one of 50 to 400 ten thousand, for example 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600 ten thousand.

In one embodiment of the present invention, the 4HB monomers in the P3HB4HB are of the same molar content, the 4HB monomers are of 8% molar content, and the P3HB4HB has a molecular weight of 60 ten thousand.

In one embodiment of the present invention, the 4HB monomers in the P3HB4HB are of the same molar content, the 4HB monomers are of 10% molar content, and the P3HB4HB has a molecular weight of 60 ten thousand.

In one embodiment of the present invention, the 4HB monomers in the P3HB4HB are of the same molar content, the 4HB monomers are of 15% molar content, and the P3HB4HB has a molecular weight of 60 ten thousand.

In one specific embodiment of the invention, the 4HB monomers in the P3HB4HB have different molar contents, and the molar contents of the 4HB are respectively 5% and 10%, and the mass ratio is 1:1, the molecular weight of the P3HB4HB of the 4HB monomers with different molar contents is 100 ten thousand.

In one specific embodiment of the invention, the 4HB monomers in the P3HB4HB have different molar contents, and the molar contents of the 4HB are respectively 3% and 15%, and the mass ratio is 1:1, the molecular weight of the P3HB4HB of the different molar contents of the 4HB monomers is 80 ten thousand.

In one specific embodiment of the invention, the 4HB monomers in the P3HB4HB have different molar contents, and the molar contents of the 4HB are respectively 3% and 20%, and the mass ratio is 1:1, the molecular weight of the P3HB4HB of the different molar contents of the 4HB monomers is 60 ten thousand.

Preferably, the adjuvants include, but are not limited to, nucleation enhancers, resistance aids, and/or environmental plasticizers.

The nucleation reinforcing agent, the resistance auxiliary agent and the environment-friendly plasticizer are coordinated in proportion, so that the effects of strength, wear resistance, ultraviolet resistance and the like of the pure P34HB fiber are greatly improved.

Preferably, the nucleation enhancer comprises any one of 0.01% -3%, preferably 0.02% -2%, such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% of the mass of P3HB4HB in the filament or staple fiber (or its raw material).

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4 and 0.01 to 3 parts, preferably any one of 0.02 to 2 parts, for example 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3 parts of a nucleation enhancer.

Preferably, the nucleation enhancer includes, but is not limited to, one or a combination of two or more of nano zinc oxide, nano titanium boride, nano titanium carbide and/or nano microcrystalline cellulose. The nucleation reinforcing agent is prepared from nano-scale particles, has a large length-diameter ratio, can form a microscopic reinforced concrete structure with the P34HB substrate, greatly improves the final fiber forming strength and wear resistance, and can accelerate the crystallization speed of P3HB4HB and provide the antibacterial performance of P3HB4HB filament or staple fiber products (particularly nano zinc oxide).

In one specific embodiment of the invention, the nucleation enhancer is nano zinc oxide and nano titanium boride, and the mass ratio of the nano zinc oxide to the nano titanium boride is 2:1, wherein the addition mass of the nano zinc oxide is 0.02 part.

In one specific embodiment of the invention, the nucleation enhancer is nano zinc oxide and nano titanium carbide, and the mass ratio of the nano zinc oxide to the nano titanium carbide is 2:1, wherein the addition mass of the nano zinc oxide is 0.02 part.

In one specific embodiment of the invention, the nucleation enhancer is nano zinc oxide, nano titanium carbide and nano microcrystalline cellulose, and the mass ratio of the nano zinc oxide to the nano titanium carbide to the nano microcrystalline cellulose is 2:1:1, wherein the addition mass of the nano zinc oxide is 0.02 part.

In one specific embodiment of the invention, the nucleation enhancer is nano zinc oxide and nano titanium boride, and the mass ratio of the nano zinc oxide to the nano titanium boride is 7:3, the addition mass of the nano zinc oxide is 0.007 parts.

In one specific embodiment of the invention, the nucleation enhancer is nano zinc oxide and nano titanium boride, and the mass ratio of the nano zinc oxide to the nano titanium boride is 2:1, wherein the addition mass of the nano zinc oxide is 2 parts.

Preferably, in the filaments or staple fibers (or raw materials thereof), the resistance auxiliary agent accounts for 0.05% -4.5% of the mass of P3HB4HB, preferably any value of 0.2% -3.5%, for example, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.66%, 0.67%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%.

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4HB and 0.05 to 4.5 parts, preferably any one of 0.2 to 3.5 parts, for example 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.66, 0.6%, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 parts of the resistance auxiliary agent.

Preferably, the resistance aid includes, but is not limited to, one or more of calcium ricinoleate, sodium isooctanoate, antioxidant CYANOX 1790, antioxidant CYANOX 2777, antioxidant CYANOX XS4, antioxidant WESTON 619, trisnonylphenyl phosphite (TNPP), tributyl phosphate, 2-hydroxy-4-dodecyloxybenzophenone (ultraviolet absorber UV-1200), 2- (2 '-hydroxy-5' -tert-octyl) phenylbenzotriazol (ultraviolet absorber UV-329), bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate (light stabilizer 292).

Wherein, calcium ricinoleate/sodium isooctanoate and tributyl phosphate/TNPP are synergistic, namely phosphorus-containing substances and organic acid salts, which can obviously improve the thermal stability of the system. However, the addition of nano zinc oxide also unexpectedly enhances the heat stability and antioxidant effect, and various nano particles and phosphate esters have improved flame retardant properties of the system.

In addition, the addition of the nanoparticle (nucleation enhancer) and the phosphate heat stabilizer (such as tributyl phosphate) can continuously strengthen the hydrophobic performance of the P34HB, and the synergistic effect of the two is greatly superior to that of the single type. This is probably due to the low surface energy of phosphate based heat stabilizers (e.g., tributyl phosphate) coupled with the micro-nano structure of the nanoparticles, achieving near superhydrophobic effects.

Based on the fact that the P34HB has good ultraviolet resistance, the ultraviolet absorber (such as 2-hydroxy-4-dodecyloxybenzophenone, 2- (2 '-hydroxy-5' -tert-octyl) phenyl benzotriazole and/or bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate) further improves the ultraviolet irradiation resistance effect, and the ultraviolet absorber interacts with phosphate heat stabilizer (such as tributyl phosphate), a certain antistatic effect is obtained unexpectedly, the disadvantages of the P34HB fiber material are offset, convenience and stability of the P34HB filament or staple fiber finished product in the subsequent processing and use process are guaranteed, and the antistatic and hydrophobic effects cooperate, so that the fiber and the obtained textile product have waterproof and antifouling functions.

Preferably, the resistance aid comprises an organic acid salt, an antioxidant, a phosphate ester heat stabilizer and/or an ultraviolet absorber.

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4 and 0.005 to 0.5 part of organic acid salt, preferably any one of 0.01 to 0.2 part, for example, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.13 and 0.2 part.

Preferably, the organic acid salts include, but are not limited to, calcium ricinoleate and/or sodium isooctanoate.

In one specific embodiment of the invention, the organic acid salt is calcium ricinoleate, and the added mass of the calcium ricinoleate is 0.02 part.

In one specific embodiment of the invention, the organic acid salt is calcium ricinoleate and sodium isooctanoate, and the added mass of the calcium ricinoleate and the sodium isooctanoate is 0.01 part.

In one specific embodiment of the present invention, the organic acid salt is sodium isooctanoate, and the added mass of the sodium isooctanoate is 0.02 part.

In one specific embodiment of the present invention, the organic acid salt is calcium ricinoleate, and the added mass of the calcium ricinoleate is 0.005 part.

In one specific embodiment of the invention, the organic acid salt is calcium ricinoleate, and the added mass of the calcium ricinoleate is 0.13 part.

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4 and 0.005 to 1.5 parts of antioxidant, preferably any one of 0.01 to 0.2 parts, for example, 0.005, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, 0.1, 0.14, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.03 and 1.5 parts.

Preferably, the antioxidants include, but are not limited to, antioxidant CYANOX 1790, antioxidant CYANOX 2777, antioxidant CYANOX XS4, antioxidant WESTON 619, and the like.

In one specific embodiment of the invention, the antioxidants are an antioxidant CYANOX 1790 and an antioxidant CYANOX XS4, and the antioxidant CYANOX 1790 is added in an amount of 0.05 part by weight; the adding mass of the antioxidant CYANOX XS4 is 0.1 part.

In one specific embodiment of the invention, the antioxidant is an antioxidant CYANOX 2777 and an antioxidant WESTON 619, wherein the antioxidant CYANOX 2777 is added in an amount of 0.06 part; the antioxidant WESTON 619 is added in an amount of 0.08 part by weight.

In one specific embodiment of the invention, the antioxidants are an antioxidant CYANOX 1790 and an antioxidant CYANOX XS4, and the antioxidant CYANOX 1790 is added in an amount of 0.005 part by weight; the adding mass of the antioxidant CYANOX XS4 is 0.01 part.

In one specific embodiment of the invention, the antioxidants are an antioxidant CYANOX 1790 and an antioxidant CYANOX XS4, and the antioxidant CYANOX 1790 is added in an amount of 0.33 part by weight; the adding mass of the antioxidant CYANOX XS4 is 0.7 part.

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4, 0.005-2 parts of phosphate heat stabilizer, preferably any one of 0.01-1.5 parts, for example, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.4, 1.5, 2 parts.

Preferably, the phosphate ester heat stabilizer includes, but is not limited to, TNPP and tributyl phosphate.

In one specific embodiment of the invention, the phosphate heat stabilizer is TNPP, and the addition amount of the TNPP is 0.2 part.

In one specific embodiment of the invention, the phosphate ester heat stabilizer is tributyl phosphate, and the adding amount of the tributyl phosphate is 0.2 part.

In one specific embodiment of the invention, the phosphate heat stabilizer is TNPP, and the addition amount of the TNPP is 0.01 part.

In one specific embodiment of the invention, the phosphate heat stabilizer is TNPP, and the addition amount of the TNPP is 1.4 parts.

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4 and 0.005-2.5 parts of ultraviolet absorber, preferably any one of 0.01-2 parts, such as 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 1.94, 2, 2.5 parts.

Preferably, the ultraviolet light absorber includes one or more than two of 2-hydroxy-4-dodecyloxybenzophenone (ultraviolet light absorber UV-1200), 2- (2 '-hydroxy-5' -tert-octyl) phenylbenzotriazol (ultraviolet light absorber UV-329), bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate (light stabilizer 292).

In one embodiment of the invention, the ultraviolet absorber is ultraviolet absorber UV-1200 and light stabilizer 292, and the ultraviolet absorber UV-1200 is added in an amount of 0.15 parts by weight; the addition mass of the light stabilizer 292 is 0.15 part.

In one embodiment of the invention, the ultraviolet absorber is an ultraviolet absorber UV-329 and a light stabilizer 292, wherein the ultraviolet absorber UV-329 is added in an amount of 0.2 part by weight; the addition mass of the light stabilizer 292 is 0.1 part.

In one embodiment of the invention, the ultraviolet absorber is ultraviolet absorber UV-1200 and light stabilizer 292, and the ultraviolet absorber UV-1200 is added in an amount of 0.01 part by weight; the addition mass of the light stabilizer 292 is 0.01 part.

In one embodiment of the invention, the ultraviolet absorber is ultraviolet absorber UV-1200 and light stabilizer 292, and the ultraviolet absorber UV-1200 is added in an amount of 0.97 parts by weight; the addition mass of the light stabilizer 292 was 0.97 parts.

In a specific embodiment of the invention, the resistance auxiliary agent is calcium ricinoleate, an antioxidant CYANOX 1790, an antioxidant CYANOX XS4, TNPP, an ultraviolet absorbent UV-1200 and a light stabilizer 292, wherein the mass ratio of the calcium ricinoleate to the antioxidant CYANOX 1790 to the antioxidant CYANOX XS4 to the antioxidant TNPP to the ultraviolet absorbent UV-1200 to the light stabilizer 292 is 2:5:10:20:15:15.

in one specific embodiment of the invention, the resistance auxiliary agent is calcium ricinoleate, sodium iso-octoate, an antioxidant CYANOX 2777, an antioxidant WESTON 619, tributyl phosphate, an ultraviolet absorbent UV-329 and a light stabilizer 292, and the mass ratio of the calcium ricinoleate to the sodium iso-octoate to the antioxidant CYANOX 2777 to the antioxidant WESTON 619 to the antioxidant tributyl phosphate to the ultraviolet absorbent UV-329 to the light stabilizer 292 is 1:1:6:8:20:20:10.

in one specific embodiment of the invention, the resistance auxiliary agent is sodium isooctanoate, an antioxidant CYANOX 1790, an antioxidant CYANOX XS4, TNPP, an ultraviolet absorbent UV-1200 and a light stabilizer 292, and the mass ratio of the sodium isooctanoate, the antioxidant CYANOX 1790, the antioxidant CYANOX XS4, TNPP, the ultraviolet absorbent UV-1200 and the light stabilizer 292 is 2:5:10:20:15:15.

Preferably, the environmentally friendly plasticizer comprises any one of 0.5% -4%, preferably 0.8% -3%, for example 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.75%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4% of the mass of P3HB4 in the filament or staple fiber (or its raw material).

Preferably, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4, and 0.5 to 4 parts, preferably any one of 0.8 to 3 parts, such as 0.5, 0.6, 0.7, 0.8, 0.9, 1%, 1.5, 1.75, 1.8, 2, 2.5, 3, 3.5, 4 parts of an environmentally friendly plasticizer.

Preferably, the environment-friendly plasticizer includes, but is not limited to, one or a combination of two or more of epoxidized soybean oil, isosorbide, acetyl tributyl citrate (ATBC).

The environment-friendly plasticizer (especially isosorbide) has the plasticizing effect, so that the toughness of the P3HB4HB material is better, the post-crystallization phenomenon of the P3HB4HB can be improved, and the fiber product of the environment-friendly plasticizer still keeps good softness and toughness after being stored for a long time, and does not cause embrittlement.

In one specific embodiment of the invention, the environment-friendly plasticizer is isosorbide and ATBC, and the mass ratio of the isosorbide to the ATBC is 5:1, wherein the addition mass of the isosorbide is 1.5 parts.

In one specific embodiment of the invention, the environment-friendly plasticizer is isosorbide and epoxidized soybean oil, and the mass ratio of the isosorbide to the epoxidized soybean oil is 6:1, wherein the addition mass of the isosorbide is 1.5 parts.

In one specific embodiment of the invention, the environment-friendly plasticizer is isosorbide and ATBC, and the mass ratio of the isosorbide to the ATBC is 4:1, wherein the addition mass of the isosorbide is 0.4 part.

In one specific embodiment of the invention, the environment-friendly plasticizer is isosorbide and ATBC, and the mass ratio of the isosorbide to the ATBC is 4:1, wherein the addition mass of the isosorbide is 3.2 parts.

Preferably, the mass content of the P3HB4 in the filaments or staple fibers (or raw materials thereof) is 60 to 140 parts, preferably any one of 80 to 120 parts, for example, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, or 120, 125, 130, 135 or 140 parts.

Preferably, the mass content of the auxiliary agent in the filaments or staple fibers (or raw materials thereof) is any one of 0.1 to 11.5 parts, preferably 1 to 3 parts, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.56, 0.6, 0.69, 0.7, 0.71, 0.8, 0.9, 1, 1.5, 2, 2.44, 2.5, 2.51, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11 or 11.5 parts.

Preferably, the mass ratio of the P3HB4HB to the auxiliary agent is (20-60): 1, preferably (30-50): 1, for example 20: 1. 25: 1. 30: 1. 35: 1. 39.84: 1. 40: 1. 40.98: 1. 45: 1. 50: 1. 55: 1. 60:1.

in one embodiment of the present invention, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4HB (4 HB mole content 8%, molecular weight 60 ten thousand) and 2.44 parts of an auxiliary agent.

In one embodiment of the invention, the filaments or the short fibers (or raw materials thereof) comprise 100 parts of two types of P3HB4HB (the molar content of 4HB is 5 percent, the mass ratio is 1:1, the molecular weight is 100 ten thousand) with the molar concentration of 4HB respectively, and 2.5 parts of auxiliary agent.

In one embodiment of the invention, the filaments or the short fibers (or raw materials thereof) comprise 100 parts of two types of P3HB4HB (the molar content of 4HB is 3 percent, the mass ratio is 1:1, the molecular weight is 80 ten thousand respectively) with the molar concentration of 4HB and 2.51 parts of auxiliary agent.

In one embodiment of the invention, the filaments or the short fibers (or raw materials thereof) comprise 100 parts of two types of P3HB4HB (the molar content of 4HB is 3 percent, the mass ratio is 1:1, the molecular weight is 60 ten thousand respectively) with the molar concentration of 4HB and 2.44 parts of auxiliary agent.

In one embodiment of the present invention, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4HB (having a 4HB molar content of 10% and a molecular weight of 60 ten thousand) and 2.44 parts of an auxiliary agent.

In one embodiment of the present invention, the filaments or staple fibers (or raw materials thereof) comprise 100 parts of P3HB4HB (having a 4HB molar content of 15% and a molecular weight of 60 ten thousand) and 2.44 parts of an auxiliary agent.

Preferably, the filament forms include, but are not limited to POY, FDY, DTY, ATY.

Preferably, the length of the staple fibers is 10-200mm, preferably any value from 30-150mm, such as 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200mm.

Preferably, the filaments or staple fibers may be prepared by any of the methods known in the art.

In a second aspect of the invention, a method of making filaments or staple fibers is provided.

The definition of the P3HB4HB and the auxiliary agent is as described in the first aspect.

Preferably, the preparation method comprises the following steps:

1) P3HB4HB and/or an auxiliary agent are mixed and then are subjected to melt extrusion granulation by a double-screw extruder, so that special granules of P3HB4HB filaments or short fibers are obtained;

2) Spinning the special granules of the P3HB4HB filaments or short fibers obtained in the step 1) by a double-screw melt spinning machine, and simultaneously stretching the special granules by water cooling to obtain P3HB4HB primary fibers;

3) The P3HB4HB primary fiber obtained in 2) was dried by circular air drying and then oiled to obtain a P3HB4HB yarn.

Preferably, the step 1) is preceded by a step of drying and controlling water of the P3HB4HB and/or auxiliary.

Further preferably, the drying includes vacuum or forced air drying.

Further preferably, the temperature of the drying is not higher than 105 ℃.

Further preferably, the drying time is any one of 8 to 12 hours, for example 8, 9, 10, 11, 12 hours.

Preferably, the step of controlling water includes controlling the water content to be 50ppm or less.

Preferably, the mixing of 1) comprises using a high speed disperser, said high speed disperser mixing for a mixing time of from 30 to 60 minutes, preferably for any one of the values from 40 to 50 minutes, such as 30, 35, 40, 45, 50, 55, 60 minutes;

Preferably, the high speed disperser speed is 8000-16000rpm, preferably any one of 10000-15000rpm, e.g. 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000rpm;

the barrel temperature of the twin screw extruder is in the range of 150-220 ℃, preferably any value in the range of 150-210 ℃, such as 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220 ℃.

The screw speed is in the range of 30-240rpm, preferably any one of 60-180rpm, for example 30, 40, 50, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240rpm.

The granulation is water-cooled and/or air-cooled, preferably the granulation is air-cooled granulation, the air-cooled temperature being in the range of 5-50 ℃, preferably any value in the range of 10-40 ℃, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 ℃.

Preferably, the step 2) is preceded by a step of drying and controlling water of the special pellets of the P3HB4HB filaments or staple fibers.

Further preferably, the drying includes vacuum or forced air drying.

Further preferably, the temperature of the drying is not higher than 105 ℃.

Preferably, the twin screw melt spinning machine described in 2) has a spinning temperature of 150-205 ℃, preferably any one of 155-205 ℃, such as 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205 ℃.

The pressure in the melt metering pump is 5-15MPa, preferably any one of 7-12MPa, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15MPa.

The water cooling temperature in the water cooling simultaneous stretching is 0-25 ℃, preferably any one of 0-20 ℃, such as 0, 5, 10, 15, 20, 25 ℃. The draw ratio is in the range of 2.5 to 12, preferably any one of values 3 to 10, for example 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, 12.

Preferably, an antistatic agent is also added into the water-cooled water tank; the antistatic agent comprises one or more of Tween 20, tween 40 and Tween 60.

3) The blow-down air supply temperature is 35-80 ℃, preferably any one of 40-70 ℃, such as 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 ℃.

The oiling includes the use of an oil roller at a speed of 500-1500m/min, preferably any one of 800-1200m/min, such as 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500m/min.

Preferably, the preparation method further comprises 4): and (3) feeding the P3HB4HB yarn obtained in step (3) into a first godet, a second godet and a third godet in sequence, and collecting the yarn.

It is further preferred that the temperature of the first godet in 4) is in the range of 25-85 ℃, preferably any one of the values of 40-70 ℃, e.g. 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 ℃.

The first godet has a speed of 600-1800m/min, preferably any one of 800-1500m/min, for example 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800m/min.

The temperature of the second godet is in the range of 70-110 ℃, preferably any one of 75-105 ℃, such as 70, 75, 80, 85, 90, 95, 100, 105, 110, 115 ℃.

The second godet has a speed of 1700-5100m/min, preferably any one of 2000-4500m/min, for example 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100m/min.

Preferably, the collecting comprises winding onto a bobbin by a winding device at a winding speed of 1800-5400m/min, preferably any one of 2000-4500m/min, such as 800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400m/min.

Preferably, a loop air blast is arranged between the oiling roller and the first godet roller, and the temperature is 15-45 ℃, preferably 20-40 ℃, such as 15, 20, 25, 30, 35, 40, 45 ℃.

Preferably, a stretch is created between the first godet and the second godet, the stretch ratio being 1.5-4, preferably 2-3.5, such as 1.5, 2, 2.5, 3, 3.5, 4.

Preferably, a loop air is provided between the second godet and the third godet at a temperature of 18-45 ℃, preferably 20-40 ℃, such as 18, 19, 20, 25, 30, 35, 40, 45 ℃.

According to the requirements of specific embodiments, the preparation method can also not comprise the step of feeding the first godet and the second godet.

Preferably, the preparation method further comprises 4): feeding the P3HB4HB silk yarn obtained in the step 3) after oiling into a third godet roller and collecting;

The collection comprises winding onto a bobbin by a winding device at a winding speed of 1000-3000m/min, preferably 1500-2500m/min, such as 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000.

In one embodiment of the present invention, the preparation method comprises:

1) Drying P3HB4HB and/or adjuvants under vacuum or air blast at 105deg.C for 8-12 hr to control water content below 50ppm, adding into high speed dispersing machine, mixing at 8000-16000rpm (preferably any value of 10000-15000rpm such as 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000 rpm) for 30-60min (preferably any value of 40-50min such as 30, 35, 40, 45, 50, 55, 60 min), cooling granulating by twin screw extruder and air cooling, and mixing at barrel temperature of 150-220deg.C (preferably any value of 150-210deg.C), such as 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220 ℃), screw speed of 30-240rpm (preferably any value from 60-180rpm, such as 30, 40, 50, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 rpm), air cooling temperature of 5-50 ℃ (preferably any value from 10-40 ℃, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 ℃) to obtain P3HB4HB filaments or staple fiber-specific pellets;

2) After the special pellets of the P3HB4HB filaments or staple fibers obtained in 1) are subjected to vacuum or air drying at not higher than 105 ℃, the moisture is controlled to be 50 ppm or less, and then the spinning is carried out by a twin-screw melt spinning machine under the conditions of 150-205 ℃ (preferably any one of values of 155-205 ℃, such as 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205 ℃), the pressure in the melt is 5-15Mpa (preferably any one of values of 7-12Mpa, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 Mpa), the spun filament bundles are cooled by a horizontal water tank while stretching, the stretching ratio is 2.5-12 (preferably any one of values of 3-10, such as 2.5, 3, 3.5, 4, 4.5, 5 ℃ (5, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12 ℃ and water cooling temperature is 0-25 ℃ and the raw fiber is obtained at 0.25 ℃ C.) (preferably any one of values of 0.5, 11, 12 ℃ C.) and the P-20, such as HB is obtained; preferably, an antistatic agent is further added into the water-cooled water tank, wherein the antistatic agent comprises one or more than two of Tween 20, tween 40 and Tween 60;

3) Drying the P3HB4HB primary fiber obtained in 2) by circular blowing at 35-80deg.C (preferably at any value of 40-70deg.C, such as 35, 40, 45, 50, 55, 60, 65, 70, 75, 80deg.C), and oiling by an oil roller at a speed of 500-1500m/min (preferably at any value of 800-1200m/min, such as 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500 m/min) to obtain P3HB4HB silk;

4) The P3HB4HB yarn obtained in 3) after oiling is fed into a first godet, a second godet and a third godet in sequence and collected, wherein the collection comprises winding on a bobbin by a winding device at a winding speed of 1800-5400m/min (preferably any value of 2000-4500m/min, such as 800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400 m/min).

Preferably, the filaments obtained by the preparation method are filaments in FDY form.

In one embodiment of the present invention, the preparation method comprises:

2) After the special pellets of the P3HB4HB filaments or staple fibers obtained in 1) are subjected to vacuum or air drying at not higher than 105 ℃, the moisture is controlled to be 50ppm or less, and then the spinning is carried out by a twin-screw melt spinning machine under the conditions of 150-205 ℃ (preferably any one of values of 155-205 ℃, such as 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205 ℃), the pressure in the melt is 5-15Mpa (preferably any one of values of 7-12Mpa, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 Mpa), the spun filament bundles are cooled by a horizontal water tank while stretching, the stretching ratio is 2.5-12 (preferably any one of values of 3-10, such as 2.5, 3, 3.5, 4, 4.5, 5 ℃ (5, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12 ℃ and water cooling temperature is 0-25 ℃ and the raw fiber is obtained at 0.25 ℃ C.) (preferably any one of values of 0.5, 11, 12 ℃ C.) and the P-20, such as HB is obtained; preferably, an antistatic agent is further added into the water-cooled water tank, wherein the antistatic agent comprises one or more than two of Tween 20, tween 40 and Tween 60;

4) The P3HB4HB yarn obtained in 3) after oiling is fed into a third godet and collected, said collection comprising winding on a bobbin by a winding device at a winding speed of 1000-3000m/min (preferably 1500-2500m/min, such as 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000).

Preferably, the filaments produced by the preparation method are POY-type filaments.

According to the requirement of the specific embodiment, the preparation method further comprises the step of false twisting the POY-form filament to obtain a DTY-form filament;

spraying the POY-type filament through compressed air to obtain an ATY-type filament;

alternatively, the staple fibers are obtained by further bundling, stretching, shaping, crimping, oiling, and cutting POY-form filaments.

In a third aspect of the present invention, there is provided a filament or staple obtained by the production method of the second aspect described above.

In a fourth aspect of the invention, there is provided a filament or staple as defined above, and the use of a filament or staple obtainable by a method as defined above.

Preferably, the applications include, but are not limited to, household textiles, decorative cloth articles, interior trim for various ground vehicles, aerospace interior trim, and/or military textiles.

The term "water-cooling simultaneous stretching" as used herein means that water-cooling and stretching are performed simultaneously, wherein "simultaneously" means that the water-cooling process and the stretching process are overlapped in part time, and does not only include starting at the same time and/or ending at the same time, and/or that the water-cooling process and the stretching process are completely overlapped in time. Of course, the total time of water cooling and the total time of stretching do not necessarily coincide, and the water cooling time may be longer than the stretching time or the stretching time may be longer than the water cooling time.

The terms "comprising" or "includes" are used in this specification to be open-ended, having the specified components or steps described, and other specified components or steps not materially affected.

The term "and/or" in this disclosure encompasses all combinations of items to which the term is attached, and should be taken as the individual combinations have been individually listed herein. For example, "a and/or B" includes "a", "a and B", and "B". Also for example, "A, B and/or C" include "a", "B", "C", "a and B", "a and C", "B and C" and "a and B and C".

Through the technical scheme, the invention has the following advantages:

1. the P3HB4HB filament or staple fiber and the special material thereof only take P3HB4HB as the main degradable material, but do not blend with other degradable materials such as PLA, PBS, PBAT and the like, even blend with other types of PHA, so that no auxiliary agents such as compatilizer, lubricant and the like are needed to be added, the purity of the fiber material components is ensured, the quality and the process stability of the P3HB4HB filament or staple fiber product are further improved, the degradation speed is higher, and the components are more environment-friendly and single.

2. The P3HB4HB filament or staple fiber and the special material thereof have lower overall requirements on degradation environment and greatly improve the degradation speed. The household compost can be completely decomposed in natural environment, and is green and sustainable. Because of the skin-friendly characteristic and excellent biocompatibility, the P3HB4HB filament or staple fiber product has soft and comfortable use experience, is softer than PLA and other materials, does not have bad experiences such as itching, allergy, static electricity, clunk and the like, and obviously improves the safety, the use comfort and the service performance compared with the traditional chemical fiber fabrics.

3. The addition of the nucleating reinforcing agent nano zinc oxide not only quickens the crystallization speed of the P34HB, but also improves the antibacterial property of the P34HB filament or staple fiber product. This is due in part to the fact that nano zinc oxide can continuously release zinc ions in an aqueous environment, which can enter the cell membrane and destroy the cell membrane, and when reacting with certain groups of proteins in the cell, the space structures of bacteria and proteins in the cell are destroyed, so that proteases in the cell are inactivated and the bacteria are killed. After destruction, zinc ions are released from the bacteria and the sterilization process is repeated. On the other hand, nano zinc oxide can interact with the cell wall of the bacterial surface to destroy the cell wall, so that the content is released to kill the bacteria. The third aspect is that under the irradiation of ultraviolet rays, nano zinc oxide can generate hole electron pairs, electrons and holes respectively migrate to the surface of zinc oxide particles from conduction bands and valence bands, water or hydroxyl adsorbed on the surface is converted into hydroxyl radicals, and the adsorbed oxygen is converted into active oxygen, so that the hydroxyl radicals and the active oxygen have extremely strong chemical activity and can react with most organic matters to kill most bacteria and viruses. Because the particle size of the nano zinc oxide is too small, the time for electrons and holes to reach the crystal surface from the conduction band and the valence band is greatly reduced, and the probability of the recombination of the holes and the electrons is also reduced, so that the zinc oxide with the particle size of nano level has better antibacterial performance.

In the test, although P34HB itself has antibacterial property, the existence of nano particles such as nano zinc oxide, nano titanium boride, nano titanium carbide, nano microcrystalline cellulose and the like in the special granule formula can obviously strengthen the antibacterial effect, and proves that the synergistic effect exists.

In addition, on the basis of the nano-scale particle size and the higher length-diameter ratio of the nucleation enhancer, good nucleation and enhancement effects can be achieved on the premise of low addition, and particularly, the possibility of agglomeration is greatly reduced due to the low addition, so that the stability of a spinning process is facilitated, the phenomenon of fiber breakage caused by blocking of spinneret holes and the like by agglomerated particles is avoided, the cost of raw materials and additives is saved, and the industrialization stability is improved.

4. According to the P3HB4HB filament or staple fiber and the special material thereof, the isosorbide is added, so that the plasticizing effect is achieved, the toughness of the P34HB material is more excellent, the post-crystallization phenomenon of the P34HB is surprisingly improved, and the fiber product still maintains good softness and toughness after being stored for a long time, and does not generate embrittlement. This may be a synergistic effect with the nanoparticles, increasing the crystallization rate and reducing the occurrence of post-crystallization, i.e., the inorganic nanoparticles and organic components together promote the nucleation effect of P34 HB.

5. The P3HB4HB filament or staple fiber and the special material thereof have excellent softness, moisture absorption and perspiration, low boiling water shrinkage and high rebound rate, and thus completely meet the requirements of post-processing for preparing the staple fiber or weaving, dyeing and finishing without being blended with other materials because the P34HB is relative to PLA.

The nucleation reinforcing agent, the resistance auxiliary agent and the environment-friendly plasticizer are coordinated in proportion, so that the effects of strength, wear resistance, ultraviolet resistance and the like of the pure P34HB fiber are greatly improved. The nucleation reinforcing agent is prepared from nano-sized particles, has a large length-diameter ratio, can form a microscopic reinforced concrete structure with a P34HB substrate, greatly improves final fiber strength and wear resistance, and breaks through the technical bottleneck that the general strength of PHA-containing fibers is lower than 3cN/dtex by taking pure P34HB as a main substrate.

The calcium ricinoleate/sodium isooctanoate and tributyl phosphate/TNPP heat stabilizer, namely the phosphorus-containing substance and the organic acid salt, have synergistic effect, and can obviously improve the heat stability of the system. However, the addition of nano zinc oxide also unexpectedly enhances the heat stability and antioxidant effect, and various nano particles and phosphate esters have improved flame retardant properties of the system.

In addition, the addition of the nano particles and the phosphate heat stabilizer can continuously strengthen the hydrophobic performance of the P34HB, and the synergistic effect of the nano particles and the phosphate heat stabilizer is greatly superior to that of a single type. This is probably due to the low surface energy of phosphate heat stabilizers coupled with the micro-nano structure of the nanoparticles, achieving near superhydrophobic effects.

Based on the fact that the P34HB has good ultraviolet resistance, the ultraviolet irradiation resistance effect of the ultraviolet absorber (ultraviolet absorber UV-1200, ultraviolet absorber UV-329 and light stabilizer 292) is further improved, the ultraviolet absorber interacts with the phosphate heat stabilizer, a certain antistatic effect is obtained accidentally, the disadvantages of the P34HB fiber material are compensated, convenience and stability of the P34HB filament or staple fiber finished product in the subsequent processing and use process are guaranteed, the antistatic and hydrophobic effects are matched, and the fiber and the obtained textile product have waterproof and antifouling functions.

6. According to the preparation method of the P3HB4HB filament or staple fiber and the special pellet thereof, the adopted P34HB molecular weight is 30-600 ten thousand, and the higher molecular weight can improve the processing stability and finally improve the strength of the P34HB fiber product. In addition, the extremely low screw rotating speed is adopted in the granulating process, so that the shearing force in the processing process is reduced, the molecular weight of the P34HB can still be kept at 15-300 ten thousand after granulating, the subsequent spinning is facilitated, and the quality of the P34HB filament or staple finished product is further ensured.

7. According to the preparation method of the P3HB4HB filament or staple fiber, firstly, the water cooling is adopted for rapid stretching, so that the extruded P34HB strip is rapidly prolonged and thinned, and the occurrence of fracture can be reduced in water compared with the water in the air, on one hand, because the buoyancy is partially offset to the gravity, on the other hand, the existence of water is helpful to maintain the rubbery state of the P34HB material, the P34HB filament or staple fiber is easier to deform, and the stretching and thinning are facilitated. And then, the PHA primary fiber is rapidly dried by wind heat, so that the moisture on the surface of the PHA primary fiber is removed, wherein the antistatic agent and the anti-blocking agent in the fiber act together, so that the surface of the fiber is immediately dry and non-blocking, and the antistatic effect of the subsequent oiling roller is enhanced, thereby being beneficial to subsequent cohesion, bundling, stretching and winding. Then, air-cooled rapid crystallization is carried out in the fastest crystallization temperature range above the glass transition temperature and below the melting point, so that the crystallinity of the fiber is rapidly improved, and the mechanical strength of the fiber is further improved. Then, carrying out high-speed stretching orientation at the mild temperature of the first godet to ensure that the molecular orientation is more complete, and obtaining the fiber with high orientation degree and medium crystallinity; and the second godet is subjected to tension heat setting, so that the fiber crystallization is further developed and perfected, the molecular arrangement is more regular, the orientation effect is enhanced, the energy accumulated in the fiber is completely released, and the stress relaxation is realized. Finally, the crystallization is enhanced by rapid cooling, and meanwhile, the surface adhesion is avoided, and the winding on a bobbin is smooth.

The whole filament preparation process is continuous, quick in operation, efficient and energy-saving, convenient to combine with a post-processing procedure, simple in steps and capable of realizing industrialization of P34HB filaments or staple fiber products.

The fiber product obtained by the preparation method of the P3HB4HB filament or staple fiber has stable quality, high strength and high toughness, breaks through the performance bottleneck of the conventional P34 HB-containing fiber, and meets the requirements of the automobile interior trim level, thereby expanding the application of PHA in the field of medium-high-end textiles.

The abbreviations and full scale controls of the present invention are shown in Table 1.

Table 1: abbreviation and full scale control

。

Detailed Description

Some of the sources of materials used in the examples:

nano zinc oxide: beijing De Kodak gold technologies Co., ltd;

nano titanium boride: boHuasi nanotechnology (Ningbo Co., ltd.);

nano titanium carbide: boHuasi nanotechnology (Ningbo Co., ltd.);

nanocrystalline cellulose: beijing North Cork New Material technologies Co., ltd;

calcium ricinoleate: hubei Chu Chengwei chemical Co., ltd;

sodium isooctanoate: sanjing chemical (Shandong) Inc.;

TNPP: shenzhen Shensheng Plastic auxiliary agent Co., ltd;

tributyl phosphate: jinan Hao melt chemical Co., ltd;

ultraviolet absorber UV-329: tianjin Li Anlong New Material stock Co.Ltd;

Ultraviolet absorber UV-1200: tianjin Li Anlong New Material stock Co.Ltd;

light stabilizer 292: tianjin Li Anlong New Material stock Co.Ltd;

isosorbide: pharmaceutical grade, shandong Wantai chemical Co., ltd;

p3HB4HB was derived from Beijing micro construction plant biotechnology Co.

The materials used in the examples of the present invention are commercially available unless otherwise specified.

Test items and test methods in the embodiments:

1. specification of: the linear density (dtex) was tested according to GB/T14343-2008 "chemical fiber filament yarn Density test method"; the number (f) is the number of die holes.

2. The breaking strength (cN/dtex), breaking strength CV (%), breaking elongation CV (%) were measured according to GB/T14344-2008 method for testing tensile Property of chemical fiber filaments;

retention of breaking strength after 3 months of storage: a high retention indicates improved post crystallization.

Number of wear-resistant times: determination of abrasion resistance of textile Martindale fabrics according to GB/T21196.2-2007 part 2: test pieces were tested in the method of "test piece breakage", and 9kPa, 600-mesh sandpaper was used.

3. Limiting oxygen index (%): the test is carried out according to the method in FZ/T50017-2011 oxygen index method of flame retardant property test method of polyester fiber.

4. Antibacterial rate (%): evaluation of antimicrobial Properties of textiles according to GB/T20944.3-2008, section 3: the method in the oscillation method is tested to obtain the antibacterial rate to staphylococcus aureus and escherichia coli.

5. Skin-friendly properties: and selecting two types of people as subjects for the mask prepared from the filaments by adopting a subjective evaluation method.

One class consisted of 10 experts or experienced subjects, with a weight of 1. The method is familiar with subjective evaluation scales and the meanings of descriptions thereof, and the human body feeling corresponding to each level in the terms is defined, so that the performance of the filaments can be rapidly and accurately assessed and quantified;

the other class consisted of 10 consumers with simple training, weighing 0.5. These subjects need to have knowledge about the properties of the filaments and interpretation in terms of scale terms of evaluation before they can make a correct assessment of the properties of the filaments, ensuring the stringency of the results.

Experimental conditions: the temperature is 20+/-2 ℃, the relative humidity is 65+/-2%, and the wind speed is less than or equal to 0.1m/s.

Skin-friendly subjective evaluation scale and description vocabulary are shown in Table 2.

Table 2: subjective evaluation scale for skin-friendly performance

6. Surface resistivity (Ω): evaluation of textile static Properties according to GB/T12703.4-2010 section 4: and testing the surface resistivity of the textile by a method in resistivity.

7. Water contact angle (°): the water contact angle of the textile is obtained by testing with a German KRUSS DSA100E droplet shape analyzer.

8. Uv protection factor (UPF value): testing is carried out according to the method in GB/T18830-2009 evaluation of ultraviolet resistance of textiles, and ultraviolet protection coefficients of the textiles are obtained.

9. Degradation rate: referring to the test method of "biodegradability" in EN13432, textiles were finally converted to the ratio of the mass of water, carbon dioxide and minerals to the total mass of the degradable components therein after 6 months under aerobic composting conditions.

10. Shrinkage in boiling water: the test was carried out with reference to GB/T6505-2017 method for test method for thermal shrinkage of chemical fiber filaments (after treatment).

11. Constant elongation rebound rate: that is, the difference between the length after the constant elongation and the length after the recovery of the filament sample is the percentage of the difference between the length after the constant elongation and the initial length of the sample.

The constant elongation rebound test is typically performed on a monofilament power machine. The specific test method is as follows:

the 60cm original filament sample is taken, the upper end is fixed in an upper chuck of a strength machine, the lower end is hung with pretension of 0.05cN/dtex, a lower chuck is clamped, and a mark M is made at a jaw of the chuck. Then the lowest first gear speed of the powerful machine is used for descending, when the lower clamp holder descends to enable the original elongated wire to be 3% or 5%, the descending is immediately stopped, the lower clamp holder is kept for 1-3 min, then the lower clamp holder is lifted to the original position, the lower clamp holder is loosened, after the sample wire naturally retracts for 30s, the original pretension is added to the lower end of the sample wire, the clamp holder is clamped down, the jaw of the lower clamp holder is marked with M ', the lower clamp holder is opened, the distance between M and M', namely the residual value length of the sample wire, is measured, and then calculation is carried out:

Constant elongation rebound rate = (L ₁ -L ₂ )/(L ₁ -L ₀ )*100%

Wherein:L ₀ original clamping length of sample (distance between upper clamp and lower clamp M mark);

L ₁ -the length of the sample after elongation at a defined elongation;

L ₂ recovery length of the stretched sampleL ₀ + MM' distance).

Example 1

1) P3HB4HB (4 HB mole content 8%, molecular weight 60 ten thousand) and other solid auxiliaries are dried in vacuum or air blast for 10 hours under the condition of not higher than 105 ℃ to control the water content below 50 ppm;

2) Weighing 100 parts of P3HB4HB, 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorber UV-1200, 0.15 part of light stabilizer 292, 1.5 part of isosorbide and 0.3 part of ATBC, and performing physical mixing for 45min through a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

3) Drying the special P3HB4HB filament or short fiber granules by vacuum or air blast at the temperature of not higher than 105 ℃ and controlling the water content below 50 ppm; spinning by a double-screw melt spinning machine, wherein the spinning temperature is set to 155-205 ℃, the pressure in a melt metering pump is controlled to 7-12MPa, the ejected filament bundles are cooled by a water tank with the length of 2m, and are stretched at the same time, the stretching ratio is 3-10, and the water temperature is 0-20 ℃, so that P3HB4HB nascent fibers are obtained;

4) Drying the P3HB4HB primary fiber obtained by the cooling of the 3) through a circular blowing channel with the length of 3m vertically, wherein the blowing temperature is 40-70 ℃, and immediately oiling the fiber through an oil roller, and forming a plurality of bunches into silk yarns, wherein the speed of the oil roller is 500-1500m/min;

5) Feeding the P3HB4HB silk yarns obtained in the step 4) into a first silk guide roller (the stretching heating temperature is controlled at 40-70 ℃, the spinning speed is controlled at 600-1800 m/min), a second silk guide roller (the shaping heating temperature is controlled at 75-105 ℃, the stretching speed is controlled at 1700-5100 m/min) and a third silk guide roller in sequence, arranging annular air blowing between the oil roller and the first silk guide roller, and controlling the temperature at 15-45 ℃; drawing is generated between the first godet and the second godet, and the drawing ratio is controlled to be 2-3.5; and arranging annular blowing air between the second godet and the third godet, controlling the temperature at 18-45 ℃, and then winding on a bobbin through a winding device, wherein the winding speed is 1800-5400m/min, so as to obtain the PHA filament finished product in the FDY form.

The FDY filament finished product obtained in the embodiment 1 can be woven into fabrics with various specifications and is applied to the field of automotive interiors.

Example 2

1) Two kinds of P3HB4HB (4 HB molar contents are 5% and 10% respectively, and the mass ratio is 1:1, the molecular weight is 100 ten thousand) and other solid auxiliaries are dried for 10 hours under vacuum or air blast at the temperature of not higher than 105 ℃ so that the water content is controlled below 50 ppm;

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium carbide, 0.01 part by mass of calcium ricinoleate, 0.01 part by mass of sodium isooctanoate, 0.06 part by mass of antioxidant CYANOX 2777, 0.08 part by mass of antioxidant WESTON 619, 0.2 part by mass of tributyl phosphate, 0.2 part by mass of ultraviolet absorber UV-329, 0.1 part by mass of light stabilizer 292, 0.25 part by mass of epoxidized soybean oil and 1.5 part by mass of isosorbide, and physically mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 100rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

3) Drying the special P3HB4HB filament or short fiber granules by vacuum or air blast at the temperature of not higher than 105 ℃ and controlling the water content below 50 ppm; spinning by a double-screw melt spinning machine, wherein the spinning temperature is set to 155-205 ℃, the pressure in a melt metering pump is controlled to 9-15MPa, and the ejected tows are cooled by a water tank with the length of 2m, and are stretched at the same time, the stretching ratio is 3-10, and the water temperature is 0-20 ℃, so that P3HB4HB nascent fibers are obtained;

The FDY filament finished product obtained in the embodiment 2 can be woven into fabrics with various specifications and is applied to the field of military textiles.

Example 3

1) Two kinds of P3HB4HB (4 HB molar contents are 3% and 15% respectively, and the mass ratio is 1:1, the molecular weight is 80 ten thousand) and other solid auxiliaries are dried for 10 hours under vacuum or air blast at the temperature of not higher than 105 ℃ so that the water content is controlled below 50 ppm;

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium carbide, 0.01 part by mass of nano microcrystalline cellulose, 0.02 part by mass of sodium isooctanoate, 0.05 part by mass of antioxidant CYANOX 1790, 0.1 part by mass of antioxidant CYANOX XS4, 0.2 part by mass of TNPP, 0.15 part by mass of ultraviolet absorber UV-1200, 0.15 part by mass of light stabilizer 292, 1.5 parts by mass of isosorbide and 0.3 part by mass of ATBC, and physically mixing for 45 minutes by a high-speed dispersing machine at the rotating speed range of 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is 80rpm, and the air cooling temperature is 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament finished product obtained in the embodiment 3 can be woven into fabrics with various specifications and is applied to the field of aerospace interiors.

Example 4

1) Two kinds of P3HB4HB (4 HB molar contents are 3% and 20% respectively, and the mass ratio is 1:1, the molecular weight is 60 ten thousand) and other solid auxiliaries are dried for 10 hours under vacuum or air blast at the temperature of not higher than 105 ℃ so that the water content is controlled below 50 ppm;

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium boride, 0.02 part by mass of calcium ricinoleate, 0.05 part by mass of antioxidant CYANOX 1790, 0.1 part by mass of antioxidant CYANOX XS4, 0.2 part by mass of TNPP, 0.15 part by mass of ultraviolet absorber UV-1200, 0.15 part by mass of light stabilizer 292, 1.5 part by mass of isosorbide and 0.3 part by mass of ATBC, and physically mixing by a high-speed dispersing machine for 45min at a rotating speed range of 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

5) And 4) feeding the P3HB4HB silk yarn obtained in the step 4) into a third godet, winding the silk yarn on a bobbin through a winding device at a winding speed of 1000-3000m/min to obtain a POY type filament semi-finished product, and false twisting and deforming the POY type filament to obtain a DTY type PHA filament finished product.

The finished DTY filament product obtained in the embodiment 4 can be woven into fabrics with various specifications and is applied to the field of aviation interior decoration.

Example 5

1) Drying P3HB4HB (4 HB mol content is 10%, molecular weight is 60 ten thousand) and other solid auxiliaries in vacuum or air blast at a temperature of not higher than 105 ℃ for 10 hours to control the water content below 50 ppm;

5) And 4) feeding the P3HB4HB silk yarn obtained in the step 4) into a third godet, then winding the silk yarn on a bobbin through a winding device at a winding speed of 1000-3000m/min to obtain a semi-finished product of the POY type filament, and carrying out compressed air jet treatment on the POY type filament to obtain a PHA filament finished product in an ATY type.

The ATY filament finished product obtained in the embodiment 5 can be woven into fabrics with various specifications and is applied to the field of decorative fabric products.

Example 6

1) Drying P3HB4HB (4 HB mol content is 15%, molecular weight is 60 ten thousand) and other solid auxiliaries in vacuum or air blast for 10h at a temperature not higher than 105 ℃ to control water content below 50 ppm;

2) Weighing 100 parts of P3HB4HB, 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorber UV-1200, 0.15 part of light stabilizer 292, 1.5 part of isosorbide and 0.3 part of ATBC, and performing physical mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

5) And (3) feeding the P3HB4HB silk yarn obtained in the step (4) into a third godet, winding the silk yarn on a bobbin through a winding device at a winding speed of 1000-3000m/min to obtain a POY type filament semi-finished product, and further bundling, stretching, shaping, curling, oiling and cutting the POY type filament to obtain a PHA (polyhydroxyalkanoate) short fiber finished product.

The PHA staple fiber finished product obtained in the embodiment 6 can be spun into yarns, and the yarns can be woven into fabrics with various specifications, so that the PHA staple fiber finished product can be applied to the field of household textiles.

Example 7

The process is the same as in example 1, except that the addition amount of the auxiliary agent is as follows: 0.007 part of nano zinc oxide, 0.003 part of nano titanium boride, 0.005 part of calcium ricinoleate, 0.005 part of antioxidant CYANOX 1790, 0.01 part of antioxidant CYANOX XS4, 0.01 part of TNPP, 0.01 part of ultraviolet absorbent UV-1200, 0.01 part of light stabilizer 292, 1.5 parts of isosorbide and 0.3 part of ATBC.

The FDY filament finished product obtained in the embodiment 7 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 8

The process is the same as in example 1, except that the addition amount of the auxiliary agent is as follows: 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorbent UV-1200, 0.15 part of light stabilizer 292, 0.4 part of isosorbide and 0.1 part of ATBC.

The FDY filament finished product obtained in the embodiment 8 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 9

The process is the same as in example 1, except that the addition amount of the auxiliary agent is as follows: 2 parts of nano zinc oxide, 1 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorber UV-1200, 0.15 part of light stabilizer 292, 3.2 parts of isosorbide and 0.8 part of ATBC.

The FDY filament finished product obtained in the embodiment 9 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 10

The process is the same as in example 1, except that the addition amount of the auxiliary agent is as follows: 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.13 part of calcium ricinoleate, 0.33 part of antioxidant CYANOX 1790, 0.7 part of antioxidant CYANOX XS4, 1.4 parts of TNPP, 0.97 part of ultraviolet absorbent UV-1200, 0.97 part of light stabilizer 292, 3.2 parts of isosorbide and 0.8 part of ATBC.

The FDY filament finished product obtained in the embodiment 10 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 11

The same auxiliaries and process as in example 1, except for P3HB4HB: the molar contents of 4HB are respectively 1 percent and 80 percent, and the mass ratio is 10:1, the molecular weight is 60 ten thousand.

The FDY filament finished product obtained in the embodiment 11 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 12

The same auxiliaries and process as in example 1, except for P3HB4HB: the molar content of 4HB is 8%, the molecular weight is 30 ten thousand, 60 ten thousand and 600 ten thousand respectively, and the mass ratio is 2:6:0.1.

the FDY filament finished product obtained in the embodiment 12 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 13

The same P3HB4HB and adjuvants used in example 1, other processes, except:

drying P3HB4HB and other solid auxiliaries at 105 ℃ for 8 hours under vacuum or air blast, so that the water content is controlled below 50 ppm;

the various raw materials are physically mixed for 30min by a high-speed dispersing machine, and the rotating speed is 16000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, wherein the temperature of a charging barrel is set to 185-220 ℃, and the rotating speed of a screw is set to 30rpm.

The FDY filament finished product obtained in the embodiment 13 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Example 14

The same P3HB4HB and adjuvants used in example 1, other processes, except:

drying P3HB4HB and other solid auxiliaries in vacuum or air blast at 95 ℃ for 12 hours to control the water content below 50 ppm;

the various raw materials are physically mixed for 60min by a high-speed dispersing machine, and the rotating speed is 8000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-185 ℃, and the rotating speed of a screw is set to be 180rpm.

The FDY filament finished product obtained in the embodiment 14 can be woven into fabrics with various specifications, meets the application requirements of the automotive interior field, and is applied to the automotive interior field.

Comparative example 1: the nucleation enhancer is added in an excessive amount as compared with example 1

1) P3HB4HB (4 HB mole content 8%, molecular weight 60 ten thousand) and other solid auxiliaries are dried in vacuum or air blast for 10 hours at the temperature of not higher than 105 ℃ to control the water content below 50 ppm;

2) Weighing 100 parts of P3HB4HB, 2 parts of nano zinc oxide, 2 parts of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorbent UV-1200, 0.15 part of light stabilizer 292, 1.5 parts of isosorbide and 0.3 part of ATBC, and physically mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

3) Drying the special P3HB4HB filament or short fiber granules by vacuum or air blast at the temperature of not higher than 105 ℃ and controlling the water content below 50 ppm; spinning by a double-screw melt spinning machine, wherein the spinning temperature is set to 155-205 ℃, the pressure in a melt metering pump is controlled to 7-12MPa, the ejected filament bundles are cooled by a water tank with the length of 2m, and are stretched at the same time, the stretching ratio is 3-5, and the water temperature is 0-20 ℃, so that P3HB4HB nascent fibers are obtained;

4) Drying the P3HB4HB primary fiber obtained by the cooling of the 3) through a circular blowing channel with the length of 3m vertically, wherein the blowing temperature is 40-70 ℃, and immediately oiling the fiber through an oil roller, and forming a plurality of bunches into silk yarns, wherein the speed of the oil roller is 500-800m/min;

5) Feeding the P3HB4HB silk yarns obtained in the step 4) into a first silk guide roller (the stretching heating temperature is controlled to be 40-70 ℃, the spinning speed is controlled to be 600-1000 m/min), a second silk guide roller (the shaping heating temperature is controlled to be 75-105 ℃, the stretching speed is controlled to be 1500-2000 m/min) and a third silk guide roller in sequence, arranging annular air blowing between the oil roller and the first silk guide roller, and controlling the temperature to be 15-45 ℃; drawing is generated between the first godet and the second godet, and the drawing ratio is controlled to be 2-3.5; and arranging a circular air blower between the second godet and the third godet, controlling the temperature to be 18-45 ℃, and then winding on a bobbin through a winding device, wherein the winding speed is 1600-2200m/min, so as to obtain the PHA filament finished product in the FDY form.

Since the nucleation reinforcing agent in comparative example 1 is too much, agglomeration particles are easy to block spinneret holes, the quality of the obtained FDY filament finished product is unstable, the yield is not high in the production process, the phenomenon of fiber breakage is easy to occur, and the spinning speed is forced to be reduced and regulated.

The finished FDY filaments obtained were each inferior to the filaments prepared in example 1 (see tables 3, 4).

Comparative example 2: compared with example 2, no nanoparticles (nucleation enhancer)

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.01 part by mass of calcium ricinoleate, 0.01 part by mass of sodium isooctanoate, 0.06 part by mass of antioxidant CYANOX 2777, 0.08 part by mass of antioxidant WESTON 619, 0.2 part by mass of tributyl phosphate, 0.2 part by mass of ultraviolet absorbent UV-329, 0.1 part by mass of light stabilizer 292, 0.25 part by mass of epoxidized soybean oil and 1.5 parts by mass of isosorbide, and physically mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 100rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament product obtained in comparative example 2 has a roll sticking phenomenon in the spinning process due to the lack of nano particles, namely a nucleation enhancer, and the crystallization speed is low, so that the unwinding is difficult, and the mechanical property is also greatly reduced.

The obtained FDY filament finished product has various indexes which are inferior to those of the filament prepared in the example 1, in particular indexes such as breaking strength, retention of breaking strength after 3 months of storage, wear resistance times, bacteriostasis rate, limiting oxygen index (flame retardant property), water contact angle (hydrophobic property) and the like (see tables 3 and 4).

Comparative example 3: compared with example 3, no ultraviolet absorber is contained

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium carbide, 0.01 part by mass of nano microcrystalline cellulose, 0.02 part by mass of sodium isooctanoate, 0.05 part by mass of antioxidant CYANOX 1790, 0.1 part by mass of antioxidant CYANOX XS4, 0.2 part by mass of TNPP, 1.5 parts by mass of isosorbide and 0.3 part by mass of ATBC, and carrying out physical mixing for 45 minutes by a high-speed dispersing machine at the rotating speed range of 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is 80rpm, and the air cooling temperature is 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament product obtained in comparative example 3 was inferior in UPF value (anti-UV property) and surface resistivity (antistatic property) to example 3 due to the lack of the ultraviolet absorber (see tables 3, 4).

Comparative example 4: compared with the example 4, the environment-friendly plasticizer is excessively added

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium boride, 0.02 part by mass of calcium ricinoleate, 0.05 part by mass of antioxidant CYANOX 1790, 0.1 part by mass of antioxidant CYANOX XS4, 0.2 part by mass of TNPP, 0.15 part by mass of ultraviolet absorber UV-1200, 0.15 part by mass of light stabilizer 292, 5 parts by mass of isosorbide and 1.5 parts by mass of ATBC, and physically mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The DTY filament product obtained in comparative example 4 was inferior in indexes such as breaking strength, breaking strength CV, elongation at break and elongation at break CV, abrasion resistance number, and elongation at constant rebound rate to example 4 due to the addition of excessive amount of the environment-friendly plasticizer (see tables 3 and 4).

Comparative example 5: compared with example 5, no nano zinc oxide is contained

2) Weighing 100 parts of the P3HB4HB, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorbent UV-1200, 0.15 part of light stabilizer 292, 1.5 parts of isosorbide and 0.3 part of ATBC according to parts by weight, and carrying out physical mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-185 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

3) Drying the special P3HB4HB filament or short fiber granules by vacuum or air blast at the temperature of not higher than 105 ℃ and controlling the water content below 50 ppm; spinning by a double-screw melt spinning machine, wherein the spinning temperature is set to 145-185 ℃, the pressure in a melt metering pump is controlled to 7-12MPa, the ejected tows are cooled by a water tank with the length of 2m, and are stretched at the same time, the stretching ratio is 3-10, and the water temperature is 0-20 ℃, so that P3HB4HB nascent fibers are obtained;

The ATY filament finished product obtained in comparative example 5 is poor in thermal stability and slow in nucleation speed due to the lack of nano zinc oxide, namely, the spinning temperature must be selected to be low-temperature section during processing, otherwise, thermal degradation occurs at the temperature exceeding 185 ℃, and the phenomenon of sticking to rollers exists in the spinning process; finally, the various indexes of the fiber are inferior to those of the filament prepared in the example 5, especially the indexes of bacteriostasis rate, flame retardance and hydrophobicity (see tables 3 and 4).

Comparative example 6: in comparison with example 6, no isosorbide is present

2) Weighing 100 parts of P3HB4HB, 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorber UV-1200, 0.15 part of light stabilizer 292 and 0.3 part of ATBC according to parts by weight, and carrying out physical mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The PHA staple fiber product obtained in comparative example 6 was less likely to have a roll sticking phenomenon during spinning due to the lack of isosorbide and a slower crystallization rate, and was more difficult to unwind.

The PHA staple fiber obtained after 3 months of storage had lower retention of breaking strength, breaking strength CV, elongation at break CV, and rebound at constant elongation than those obtained in example 6 (see tables 3 and 4).

Comparative example 7: compared with example 1, no TNPP was contained

2) Weighing 100 parts of the P3HB4HB, 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.15 part of ultraviolet absorbent UV-1200, 0.15 part of light stabilizer 292, 1.5 parts of isosorbide and 0.3 part of ATBC according to parts by weight, and carrying out physical mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-180 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

3) Drying the special P3HB4HB filament or short fiber granules by vacuum or air blast at the temperature of not higher than 105 ℃ and controlling the water content below 50 ppm; spinning by a double-screw melt spinning machine, wherein the spinning temperature is set to 145-180 ℃, the pressure in a melt metering pump is controlled to 7-12MPa, the ejected filament bundles are cooled by a water tank with the length of 2m, and are stretched at the same time, the stretching ratio is 3-10, and the water temperature is 0-20 ℃, so that P3HB4HB nascent fibers are obtained;

The FDY filament product of comparative example 7 was poor in heat stability due to lack of TNPP, and the spinning temperature had to be selected in a low temperature range during processing, otherwise thermal degradation occurred at more than 180 ℃.

The obtained FDY filament finished product has indexes such as flame retardant property, hydrophobic property, antistatic property and the like which are inferior to those of the FDY filament prepared in the example 7 (see tables 3 and 5).

Comparative example 8: compared with example 2, the heat stabilizer does not contain organic acid salt

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium carbide, 0.06 part by mass of antioxidant CYANOX 2777, 0.08 part by mass of antioxidant WESTON 619, 0.2 part by mass of tributyl phosphate, 0.2 part by mass of ultraviolet absorbent UV-329, 0.1 part by mass of light stabilizer 292, 0.25 part by mass of epoxidized soybean oil and 1.5 parts by mass of isosorbide, and carrying out physical mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-180 ℃, the rotating speed of a screw is set to be 100rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

3) Drying the special P3HB4HB filament or short fiber granules by vacuum or air blast at the temperature of not higher than 105 ℃ and controlling the water content below 50 ppm; spinning by a double-screw melt spinning machine, wherein the spinning temperature is set to 145-180 ℃, the pressure in a melt metering pump is controlled to 9-15MPa, the ejected filament bundles are cooled by a water tank with the length of 2m, and are stretched at the same time, the stretching ratio is 3-10, and the water temperature is 0-20 ℃, so that P3HB4HB nascent fibers are obtained;

The FDY filament product obtained in comparative example 8 had poor thermal stability due to the absence of organic acid salt, and the spinning temperature had to be selected in the low temperature range during processing, otherwise thermal degradation occurred at temperatures exceeding 180 ℃.

Comparative example 9: compared with example 3, no nanoparticle or TNPP was contained

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of sodium isooctanoate, 0.05 part by mass of an antioxidant CYANOX 1790, 0.1 part by mass of an antioxidant CYANOX XS4, 0.15 part by mass of an ultraviolet absorber UV-1200, 0.15 part by mass of a light stabilizer 292, 1.5 parts by mass of isosorbide and 0.3 part by mass of ATBC, and physically mixing for 45 minutes by a high-speed dispersing machine at a rotating speed range of 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is 80rpm, and the air cooling temperature is 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament product of comparative example 9 had poor thermal stability and a slow nucleation rate due to the lack of nanoparticles and TNPP, so that the spinning temperature had to be selected in the low temperature section during processing, otherwise thermal degradation occurred at temperatures exceeding 180 ℃.

The obtained FDY filament finished product has various indexes inferior to those of the example 3, in particular indexes such as breaking strength, retention of breaking strength after 3 months of storage, wear resistance times, flame retardant property, antibacterial rate, antistatic property, hydrophobic property, and fixed elongation rebound rate (see tables 3 and 5).

In comparison with comparative examples 2, 7 and 9, the synergistic effect of the nanoparticle and the phosphate heat stabilizer on flame retardant property and hydrophobic property can be seen.

Comparative example 10: the molecular weight of P3HB4HB is too low as compared with example 4

1) Two kinds of P3HB4HB (4 HB molar contents are 3% and 20% respectively, and the mass ratio is 1:1, the molecular weight is 18 ten thousand) and other solid auxiliaries are dried for 10 hours under vacuum or air blast at the temperature of not higher than 105 ℃ so that the water content is controlled below 50 ppm;

The DTY filament product obtained in comparative example 10 had a very low molecular weight of P3HB4HB, and thus had poor breaking strength, and was difficult to weave into an ideal fabric, and the retention of breaking strength and the rebound of elongation after 3 months of storage were both inferior to those of example 4 (see tables 3 and 5).

Comparative example 11: compared with example 5, the screw rotation speed is too high

2) Weighing 100 parts of P3HB4HB, 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorber UV-1200, 0.15 part of light stabilizer 292, 1.5 part of isosorbide and 0.3 part of ATBC, and performing physical mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 280rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The ATY filament finished product obtained in comparative example 11 can be woven into fabrics with various specifications and is applied to the field of decorative fabric products.

However, the molecular weight of P3HB4HB in the finished filament was too low due to too high a screw speed, and the breaking strength, retention of breaking strength after 3 months of storage, abrasion resistance and the like were all inferior to those of example 5 (see tables 3 and 5).

Comparative example 12: compared with example 6, PLA was mixed in the raw material

1) P3HB4HB (4 HB mole content is 15%, molecular weight is 60 ten thousand), PLA (molecular weight is 12 ten thousand) and other solid auxiliary agents are dried for 10 hours under vacuum or air blast under the condition of not higher than 105 ℃ so as to control the water content to be below 50 ppm;

2) Weighing 60 parts of P3HB4HB, 40 parts of PLA, 0.02 part of nano zinc oxide, 0.01 part of nano titanium boride, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorbent UV-1200, 0.15 part of light stabilizer 292, 1.5 part of isosorbide and 0.3 part of ATBC, and physically mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is 80rpm, and the air cooling temperature is 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The PHA staple fiber product obtained in comparative example 12 was spun into yarn, which was woven into various types of fabrics, but because of the PLA mixed in the raw material, the indexes such as retention of breaking strength, skin-friendly property, degradation rate, shrinkage in boiling water, and rebound in constant elongation were all inferior to those of example 6 (see tables 3 and 5).

Comparative example 13: in comparison with example 1, no isosorbide or nanoparticles are present

2) Weighing 100 parts of the P3HB4HB, 0.02 part of calcium ricinoleate, 0.05 part of antioxidant CYANOX 1790, 0.1 part of antioxidant CYANOX XS4, 0.2 part of TNPP, 0.15 part of ultraviolet absorbent UV-1200, 0.15 part of light stabilizer 292 and 0.3 part of ATBC by mass, and physically mixing for 45 minutes by a high-speed dispersing machine, wherein the rotating speed range is 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 60rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament obtained in comparative example 13 was difficult to unwind due to the presence of a roll sticking phenomenon in the spinning process caused by the lack of nanoparticles and isosorbide, due to the slow crystallization speed, and the mechanical properties were greatly reduced.

The obtained FDY filament finished product has various indexes which are inferior to those of the filament prepared in the example 1, in particular indexes such as breaking strength, breaking strength retention rate after 3 months of storage, breaking strength CV, breaking elongation CV, bacteriostasis and flame retardance, hydrophobicity, constant elongation rebound rate and the like (see tables 3 and 6).

In comparison with comparative examples 2, 6 and 13, it was found that the synergistic effect of isosorbide and the nanoparticles was exhibited in overcoming the post-crystallization phenomenon (in improving the retention of breaking strength after 3 months of storage).

Comparative example 14: no tributyl phosphate and UV absorber

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.01 part by mass of nano titanium carbide, 0.01 part by mass of calcium ricinoleate, 0.01 part by mass of sodium isooctanoate, 0.06 part by mass of antioxidant CYANOX 2777, 0.08 part by mass of antioxidant WESTON 619, 0.25 part by mass of epoxidized soybean oil and 1.5 part by mass of isosorbide, and physically mixing for 45 minutes by a high-speed dispersing machine at the rotating speed of 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is set to be 100rpm, and the air cooling temperature is set to be 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament product obtained in comparative example 14 was poor in heat stability due to lack of ultraviolet absorber and TNPP, and the spinning temperature had to be selected in a low temperature range during processing, otherwise thermal degradation occurred at a temperature exceeding 180 ℃.

The resulting FDY filament product had a UPF value (UV resistance), surface resistivity (antistatic properties), flame retardant properties, and hydrophobic properties that were inferior to those of example 2 (see tables 3 and 6).

In comparison with comparative examples 3, 7 and 14, the synergistic effect of the phosphate-based heat stabilizer and the ultraviolet absorber on the antistatic property was seen.

Comparative example 15: does not contain nano titanium carbide and nano microcrystalline cellulose

2) Weighing 100 parts by mass of the P3HB4HB composition, 0.02 part by mass of nano zinc oxide, 0.02 part by mass of sodium isooctanoate, 0.05 part by mass of an antioxidant CYANOX 1790, 0.1 part by mass of an antioxidant CYANOX XS4, 0.2 part by mass of TNPP, 0.15 part by mass of an ultraviolet absorber UV-1200, 0.15 part by mass of a light stabilizer 292, 1.5 parts by mass of isosorbide and 0.3 part by mass of ATBC, and physically mixing for 45 minutes by a high-speed dispersing machine at a rotating speed range of 12000rpm; and then the mixture is melted and extruded by a double-screw extruder and cooled and granulated by adopting an air cooling mode, the temperature of a charging barrel is set to be 150-210 ℃, the rotating speed of a screw is 80rpm, and the air cooling temperature is 5-50 ℃, so that the special P3HB4HB filament or staple fiber granules are obtained.

The FDY filament finished product obtained in comparative example 15 is poor in thermal stability and slow in nucleation speed due to the lack of nano titanium carbide and nano microcrystalline cellulose, namely, the spinning temperature during processing is required to be selected to be low temperature, otherwise, thermal degradation occurs at the temperature exceeding 185 ℃, and the phenomenon of sticking to rollers exists in the spinning process; finally, the various indexes of the fiber are inferior to those of the filament prepared in the example 5, especially the indexes of bacteriostasis rate, flame retardance and hydrophobicity (see tables 3 and 6).

In comparison with comparative examples 2, 5 and 15, a synergistic effect of various nanoparticles on antibacterial properties was seen.

Table 3: test results of the fibers or fabrics obtained in examples 1-6

Table 4: test results of comparative examples 1 to 6

Table 5: test results of comparative examples 7 to 12

Table 6: test results of comparative examples 13 to 15

It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.

Claims

1. A filament or staple fiber, wherein the filament or staple fiber is prepared from P3HB4HB and an auxiliary agent, and the molar content of 4HB monomer in the P3HB4HB ranges from 1 mol% to 80mol%;

the auxiliary agent comprises nano particles and TNPP;

the nano particles comprise nano zinc oxide, nano titanium carbide and nano microcrystalline cellulose, or the nano particles comprise nano zinc oxide and nano titanium carbide.

2. The filament or staple fiber of claim 1, wherein the mass ratio of P3HB4HB to the auxiliary agent is (20-60): 1.

3. the filament or staple fiber of claim 2, wherein the mass ratio of P3HB4HB to the auxiliary agent is (30-50): 1.

4. the filament or staple fiber according to claim 1, wherein the filament or staple fiber or raw material thereof comprises 100 parts of P3HB4HB and 0.01-3 parts of nano particles in parts by weight.

5. The filament or staple fiber according to claim 4, wherein the filament or staple fiber or raw material thereof comprises 100 parts of P3HB4HB and 0.02-2 parts of nano particles in parts by weight.

6. The filament or staple fiber of claim 1, wherein the 4HB monomers in the P3HB4HB are in the same molar content or in different molar contents;

The molecular weight of the P3HB4HB is 30-600 ten thousand.

7. The filament or staple of claim 1 wherein said filament comprises POY, FDY, DTY, ATY;

the length of the short fiber is 10-200mm.

8. The filament or staple fiber of claim 1 wherein said adjuvant further comprises one or both of a resistance adjuvant or an environmentally friendly plasticizer, wherein,

the resistance auxiliary agent comprises one or more than two of calcium ricinoleate, sodium isooctanoate, an antioxidant CYANOX 1790, an antioxidant CYANOX 2777, an antioxidant CYANOX XS4, an antioxidant WESTON 619, tributyl phosphate, 2-hydroxy-4-dodecyloxybenzophenone, 2- (2 '-hydroxy-5' -tert-octyl) phenyl benzotriazole and bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate;

the environment-friendly plasticizer comprises one or a combination of more than two of epoxidized soybean oil, isosorbide and acetyl tributyl citrate.

9. A process for the preparation of filaments or staple fibers according to any one of claims 1 to 8, said process comprising:

1) Drying the P3HB4HB and the auxiliary agent until the water content is below 50ppm, mixing, and then carrying out melt extrusion granulation by a double screw extruder to obtain special granules of P3HB4HB filaments or short fibers;

2) Drying the special granules of the P3HB4HB filaments or short fibers obtained in the step 1) until the water content is below 50ppm, spinning by a double-screw melt spinning machine, and simultaneously stretching by water cooling to obtain P3HB4HB primary fibers;

3) The P3HB4HB primary fiber obtained in the step 2) is oiled after being dried by circular blowing, and the P3HB4HB silk strip is obtained;

the auxiliary agent comprises nano particles and TNPP;

10. The method according to claim 9, wherein the mixing time of the mixing in 1) is 30 to 60 minutes at 8000 to 16000rpm;

the temperature of a charging barrel of the double-screw extruder is 150-220 ℃, and the rotating speed of a screw is 30-240rpm;

the granulation is air-cooled granulation, and the air-cooled temperature is 5-50 ℃;

2) The spinning temperature of the double-screw melt spinning machine is 150-205 ℃, and the pressure in a melt metering pump is 5-15MPa;

the water cooling temperature is 0-25 ℃ in the water cooling and stretching process, the stretching ratio is 2.5-12, and antistatic agent is added into the water;

3) The temperature of the circular blowing air supply is 35-80 ℃, and the oil feeding is carried out by using an oil roller, wherein the speed of the oil roller is 500-1500m/min.

11. The method according to claim 9 or 10, wherein the method further comprises 4): feeding the P3HB4HB silk yarns obtained in the step 3) into a first godet, a second godet and a third godet in sequence, and collecting the silk yarns;

4) The temperature of the first godet is 25-85 ℃; the speed of the first godet is 600-1800m/min, the temperature of the second godet is 70-110 ℃, and the speed of the second godet is 1700-5100m/min;

the collection comprises winding on a bobbin by a winding device, wherein the winding speed is 1800-5400m/min;

the oil roller used for oiling is provided with annular air blowing between the first godet roller and the second godet roller, the temperature is 15-45 ℃, stretching is generated between the first godet roller and the second godet roller, the stretching ratio is 1.5-4, and the annular air blowing is arranged between the second godet roller and the third godet roller, and the temperature is 18-45 ℃.

12. The method according to claim 9 or 10, wherein the method further comprises 4): feeding the P3HB4HB silk yarn obtained in the step 3) after oiling into a third godet roller and collecting;

the collection comprises winding on a bobbin by a winding device, wherein the winding speed is 1000-3000m/min.

13. The method according to claim 12, further comprising the steps of false twist texturing, compressed air jet treatment, and/or bundling, stretching, shaping, crimping, oiling, cutting.

14. Use of a filament or staple according to any one of claims 1 to 8, obtained by a process according to any one of claims 9 to 13, characterized in that said use comprises household textiles, decorative cloth, various ground vehicle interiors, aerospace interiors and/or military textiles.