CN115679474A - Hydrolysis-resistant polylactic acid fiber composite material and preparation method thereof - Google Patents
Hydrolysis-resistant polylactic acid fiber composite material and preparation method thereof Download PDFInfo
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- CN115679474A CN115679474A CN202211491875.7A CN202211491875A CN115679474A CN 115679474 A CN115679474 A CN 115679474A CN 202211491875 A CN202211491875 A CN 202211491875A CN 115679474 A CN115679474 A CN 115679474A
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- polylactic acid
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 94
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 93
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 64
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000000835 fiber Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000002667 nucleating agent Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 22
- 229960001545 hydrotalcite Drugs 0.000 claims description 21
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 21
- 238000004804 winding Methods 0.000 claims description 19
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 17
- 238000002074 melt spinning Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 230000000655 anti-hydrolysis Effects 0.000 claims description 11
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- -1 polybutylene succinate Polymers 0.000 claims description 7
- 229920002961 polybutylene succinate Polymers 0.000 claims description 7
- 239000004631 polybutylene succinate Substances 0.000 claims description 7
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 5
- 239000004593 Epoxy Chemical group 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001432 poly(L-lactide) Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a hydrolysis-resistant polylactic acid fiber composite material which comprises the following raw materials in parts by weight: 90-100 parts of polylactic acid, 5-10 parts of toughening agent, 0.5-2 parts of compatilizer, 0.1-0.5 part of composite hydrolysis resistant agent and 1-3 parts of modified nucleating agent. According to the polylactic acid fiber composite material, a high molecular weight polylactic acid raw material is added, and a polymer hydrolysis resistant agent and a modified nucleating agent are added at the same time, so that the crystallization property of polylactic acid is modified, and the prepared polylactic acid fiber has high hydrolysis resistance, and also has good mechanical property and heat resistance.
Description
Technical Field
The invention belongs to the technical field of polylactic acid fiber composite materials, and particularly relates to a hydrolysis-resistant polylactic acid fiber composite material and a preparation method thereof.
Background
Polylactic acid (PLA) is a novel polyester material taking lactic acid as a raw material, is colorless and nontoxic, has thermal performance similar to polystyrene, has good biocompatibility, can be decomposed and absorbed biologically and finally degraded into carbon dioxide, and has wide application prospect. PLA is made from crops such as sugarcane, corn and sweet potato, starch raw material is saccharified and converted into glucose, then certain strains are fermented into lactic acid, the lactic acid is prepared by a chemical synthesis method, and the lactic acid can be decomposed into H under the influence of environment and hydrolysis 2 O and CO 2 Is closely influenced in environmental protectionAttention is paid. PLA is widely used in the fields of medical treatment, food packaging, and the like because of its relatively good biocompatibility and biodegradability.
Although the non-biological hydrolysis of the ester bonds in the PLA segment favours assimilation and mineralization of the microorganisms. When PLA is hydrolyzed and degraded, ester bonds are broken, molecular chains are shortened, and the mechanical property is reduced. When the PLA material is used as an environment-friendly plastic bag or a product for non-biological application, the PLA material is easy to hydrolyze in the storage and use processes, and particularly the service life of the PLA product is seriously influenced under high-temperature and high-humidity environments in summer, so that the PLA material has very important significance in toughening and hydrolysis-resistant modification of the PLA material. In the prior art, the method for solving the problem of high degradation speed of polylactic resin mainly adopts crystallization and end capping.
The crystallization makes the polylactic acid molecules arranged orderly, improves the hydrolysis resistance of the polylactic acid, but can not thoroughly change the hydrolysis resistance problem of the polylactic acid. In the polylactic acid material, the crystalline part has a slow hydrolysis rate, while the amorphous part has a fast hydrolysis rate, so that the higher the crystallinity, the stronger the hydrolysis resistance of polylactic acid. However, poly-L-lactic acid and poly-D-lactic acid homopolymers belong to semicrystalline polymers. In fact, it is difficult to obtain a homopolymer of polylactic acid, such as poly-L-lactic acid, which is a random copolymer having a certain amount of D-configuration, and when the D-configuration content is higher, the crystallization rate is slower, and when the D-configuration content exceeds 20%, the poly-L-lactic acid is in an amorphous state and cannot be crystallized. In the case of polylactic acid resin, the degree of crystallinity is too high, and the problem of difficulty in screw feeding during product processing is caused, and in the case of polylactic acid products, materials with low degree of crystallinity are often required to achieve some properties of the products.
Chinese patent application number 201210096514.2 discloses a preparation method of hydrolysis-resistant modified polylactic acid fiber, which comprises the following steps: 70-98.9 parts of polylactic acid, 1-30 parts of low molecular weight polyester and 0.1-5.0 parts of multifunctional polycarbodiimide are mixed according to the parts by weight, the mixture is uniformly mixed and then is subjected to melt blending granulation to obtain master batches, the obtained master batches are subjected to vacuum drying and then are subjected to melt spinning and winding to obtain winding yarns, and finally, the winding yarns are drafted to obtain the modified polylactic acid fibers. Although the method can improve the hydrolysis resistance of the polylactic acid fiber, the polyfunctional compound reacts with the carboxyl at the tail end of the polylactic acid molecular chain, so that gel points appear in a reaction system easily due to uneven dispersion of the hydrolysis resistance agent, and the quality of a modified polylactic acid product is affected. In addition, the crystallization performance of the polylactic acid fiber is not modified, so that the mechanical property and the heat resistance of the polylactic acid fiber are not improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hydrolysis-resistant polylactic acid fiber composite material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the hydrolysis-resistant polylactic acid fiber composite material comprises the following raw materials in parts by weight:
90-100 parts of polylactic acid, 5-10 parts of toughening agent, 0.5-2 parts of compatilizer, 0.1-0.5 part of composite hydrolysis resistant agent and 1-3 parts of modified nucleating agent.
Preferably, the weight average molecular weight of the polylactic acid is 40 to 100 ten thousand.
Preferably, the toughening agent is one or more of polybutylene succinate and ethylene-vinyl acetate copolymer; the compatilizer is one or more of maleic anhydride, diphenylmethane diisocyanate or epoxy chain extender.
Preferably, the preparation method of the composite hydrolysis resistant agent comprises the following steps:
(1) Adding dicyclohexylcarbodiimide and succinic anhydride into toluene, then adding 4-dimethylaminopyridine, carrying out stirring reaction, and evaporating to remove toluene after the reaction is finished to obtain a product A;
(2) And (2) uniformly mixing the product A in the step (1) and hyperbranched polyester, then adding aminopropyl trimethoxy silane and p-toluenesulfonic acid, heating for reaction, and obtaining the composite hydrolysis resistant agent after the reaction is completed.
Preferably, the mass ratio of the dicyclohexylcarbodiimide, the succinic anhydride and the 4-dimethylaminopyridine in the step (1) is 20:10:0.05 to 0.1; the stirring reaction temperature is 80-100 ℃, and the reaction time is 3-5h.
Preferably, the mass ratio of the product A, the hyperbranched polyester, the aminopropyltrimethoxysilane and the p-toluenesulfonic acid in the step (2) is 30:80-120:15-20:2-4; the heating reaction temperature is 70-90 ℃, and the reaction time is 4-8h.
Preferably, the preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing hydrotalcite and carbon nano tubes, adding a hydrogen peroxide solution for impregnation, and filtering and drying after the impregnation is finished to obtain mixed powder;
and S2, adding the mixed powder obtained in the step S1 into ethanol, then adding hexadecyl trimethyl ammonium bromide, reacting for 3 hours at the temperature of 60 ℃, adding gamma-glycidyl ether oxypropyl trimethoxy silane and carboxymethyl cellulose after the reaction is finished, carrying out constant temperature reaction, and cooling, filtering, drying and ball-milling after the reaction is finished to obtain the modified nucleating agent.
Preferably, the mass ratio of the hydrotalcite to the carbon nanotubes in step S1 is 10:2-4, wherein the mass concentration of the hydrogen peroxide solution is 15-20%, and the dipping time is 5-10h; in the step S2, the mass ratio of the mixed powder, the hexadecyl trimethyl ammonium bromide, the gamma-glycidyl ether oxygen propyl trimethoxy silane and the carboxymethyl cellulose is 100:10-20:4-8:2-5, wherein the constant temperature reaction is carried out at 60-75 ℃ for 3-5h.
The invention also provides a preparation method of the hydrolysis-resistant polylactic acid fiber composite material, which comprises the following steps:
weighing raw materials according to a formula, drying the polylactic resin, adding the dried polylactic resin, a toughening agent, a compatilizer, a composite hydrolysis resistant agent and a modified nucleating agent into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, granulating and drying to obtain master batches; and carrying out melt spinning, winding and drafting on the master batch through a spinning machine to obtain the polylactic acid fiber composite material.
Preferably, the temperature of each zone of the double-screw extruder is 170-210 ℃, and the screw rotating speed is 150-300rpm; the melt spinning temperature is 190-250 ℃, and the winding speed is 1000-1500m/min; the drafting process comprises the steps of drafting the mixture by a first hot roller at 70-110 ℃, drafting the mixture by a second hot roller at 90-130 ℃ and drafting multiplying power of 2-4 times. .
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the anti-hydrolysis polylactic acid fiber composite material provided by the invention, dicyclohexylcarbodiimide reacts with succinic anhydride, a product A is obtained under the catalysis of 4-dimethylamino pyridine, then the product A and hyperbranched polyester are subjected to esterification reaction, due to the fact that the hyperbranched polyester contains a plurality of hydroxyl groups, the hyperbranched polyester can react with carboxyl in the product A, aminopropyltrimethoxysilane is added at the same time and is introduced into the hyperbranched polyester, a composite anti-hydrolysis agent is obtained, finally the anti-hydrolysis agent containing the hyperbranched polyester is introduced into polylactic acid, the residual hydroxyl in the hyperbranched polyester can seal the terminal carboxyl in polylactic acid resin, the initial terminal carboxyl concentration is reduced, the terminal carboxyl which is generated continuously in the hydrolysis process is consumed, the terminal carboxyl concentration is kept at a lower level, the hydrolysis reaction rate is controlled, the service life of the material in a moist-heat working environment is prolonged, meanwhile, the anti-hydrolysis agent can also play a role in chain extension to a certain extent, and the hydrolysis inhibition effect is better; and the polylactic acid molecule introduces a hydrophobic siloxane-containing chain segment, the silicon-containing molecular chain segment is easy to migrate to the surface, the surface energy and the surface tension of a system can be greatly reduced, the hydrophobicity of the polylactic acid is improved, and thus the hydrolytic stability of the material is improved. In addition, the added dicyclohexylcarbodiimide is introduced into the hyperbranched polyester in a grafting mode and can be uniformly distributed in the hyperbranched polyester, so that the problem that the quality of a modified polylactic acid product is influenced due to the fact that gel points appear in a reaction system caused by uneven dispersion of an anti-hydrolysis agent is solved.
(2) The anti-hydrolytic polylactic acid fiber composite material provided by the invention modifies the nucleating agent, improves the compatibility of the nucleating agent and the polylactic acid, and improves the comprehensive performance of the polylactic acid. Firstly, talcum powder and carbon nano tubes are soaked in hydrogen peroxide solution to enable the surfaces of the talcum powder and the carbon nano tubes to be activated and oxidized, so that subsequent reaction is facilitated, then, cetyl trimethyl ammonium bromide is added to react with hydrotalcite, so that the hydrotalcite smoothly enters hydrotalcite layers, hydrotalcite with a partially stripped structure can be generated, the modified hydrotalcite is changed from oleophobic hydrophilicity to hydrophobic lipophilicity, the compatibility with non-polar polymers is improved, meanwhile, as the distance between the hydrotalcite layers is obviously enlarged, the surface energy is obviously reduced, the lipophilic hydrotalcite enables polylactic acid to be inserted into hydrotalcite layer layers, and finally, the hydrotalcite is uniformly dispersed in a polylactic acid matrix, and the particle size of mixed particles is smaller, the higher the crystallinity of the polylactic acid is, and the better heterogeneous nucleation effect is; and the gamma-glycidoxypropyltrimethoxysilane is covered on the surface of the mixed particle to organize the surface of the mixed particle, so that the bonding strength between the mixed particle and the polylactic acid is improved, and the mechanical property of the polylactic acid is improved.
(3) Compared with the traditional micromolecular hydrolysis resistant agent, the hydrolysis resistant agent for the hydrolysis resistant polylactic acid fiber composite material provided by the invention not only can improve the hydrolysis stability of polylactic acid, but also can be used as a compatibilizer to improve the compatibility of the polylactic acid and inorganic powder; meanwhile, the mechanical property of the polylactic acid fiber can be effectively improved by matching with the modified nucleating agent; hydrotalcite layered silicate in the modified nucleating agent is used as a nucleating point of heterogeneous nucleation in polylactic acid, so that the crystallization nucleation density of the polylactic acid is improved, and the polylactic acid melt is subjected to heterogeneous nucleation at a higher temperature, so that the crystallization performance of the polylactic acid is improved; meanwhile, due to the existence of the hydrotalcite and the carbon nano tube, spherulites generated when the polylactic acid melt is cooled are small and many, have small size, uniform distribution and high crystallization speed, are beneficial to processing polylactic acid products, have higher crystallinity and better hydrolysis resistance, and further improve the hydrolysis resistance of the polylactic acid.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The polylactic acid has the mark of 6201D, the weight-average molecular weight is 80-100 ten thousand, and the polylactic acid is produced by American Nature Works company; the poly (butylene succinate) is purchased from Virginia plastic raw material Co., ltd, and is of a brand FZ91PM; the ethylene-vinyl acetate copolymer is purchased from Shanghai Luwanghao new material science and technology limited, and has the trade mark of VS430 and the VA content of 19 percent; the epoxy chain extender SAG-008 Nautongri polymer new molecular material science and technology company is a styrene (St) -Acrylonitrile (AN) -glycidyl methacrylate ternary (GMA) copolymer, the GMA content is 8%, and the weight average molecular weight is 90000; the epoxy chain extender MSA-7200 is purchased from Xinyuxiang new material science and technology limited company in Dongying city, and the number average molecular weight is 3200 +/-200; the hyperbranched polyester is purchased from high star novel carbon material Changzhou limited company, the average hydroxyl number is 6, and the molecular weight is 900; the hydrotalcite is purchased from environmental protection science and technology Limited of Rene, jiangsu, and the mesh number is 800 meshes; the carbon nano tube is purchased from Zhongke jin Jiang (Beijing) science and technology Limited company, the tube diameter is 10-20nm, and the length is 10-20 mu m; the carboxymethyl cellulose was purchased from Gallery Changlin cellulose, inc. under the model number CLHG-005.
Example 1
A preparation method of a hydrolysis-resistant polylactic acid fiber composite material comprises the following steps:
weighing raw materials according to a formula, drying 950g of polylactic resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of composite hydrolysis resistant agent and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder, and granulating and drying, wherein the temperature of each zone of the double-screw extruder is 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the rotating speed of a screw is 200rpm, so as to obtain master batches; and (3) carrying out melt spinning, winding and drafting on the master batch through a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process comprises the steps of carrying out 90 ℃ on the drafting temperature of a first hot roller, carrying out 110 ℃ on the drafting temperature of a second hot roller and carrying out 3 times of drafting multiplying power to obtain the anti-hydrolytic polylactic acid composite fiber.
The preparation method of the composite hydrolysis-resistant agent comprises the following steps:
(1) Adding 20g of dicyclohexylcarbodiimide and 10g of succinic anhydride into 200mL of toluene, then adding 0.08g of 4-dimethylaminopyridine, stirring and reacting for 4 hours at 90 ℃, and evaporating to remove the toluene after the reaction is finished to obtain a product A;
(2) And (2) uniformly mixing the product A (30 g) in the step (1) and 100g of hyperbranched polyester, adding 18g of aminopropyltrimethoxysilane and 3g of p-toluenesulfonic acid, reacting for 6 hours at 80 ℃, and obtaining the composite hydrolysis resistant agent after the reaction is finished.
The preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 30g of carbon nano tube, adding 500mL of hydrogen peroxide solution with the mass concentration of 20% for soaking for 8 hours, and filtering and drying after soaking to obtain mixed powder;
s2, adding the mixed powder (100 g) in the step S1 into 600mL of ethanol, then adding 15g of hexadecyl trimethyl ammonium bromide, reacting for 3h at 60 ℃, adding 6g of gamma-glycidyl ether oxypropyl trimethoxy silane and 4g of carboxymethyl cellulose after the reaction is finished, reacting for 4h at a constant temperature of 70 ℃, cooling, filtering, drying, ball-milling and sieving with a 600-mesh sieve after the reaction is finished, thus obtaining the modified nucleating agent.
Example 2
A preparation method of a hydrolysis-resistant polylactic acid fiber composite material comprises the following steps:
weighing raw materials according to a formula, drying 900g of polylactic resin, adding 50g of ethylene-vinyl acetate copolymer, 5g of diphenylmethane diisocyanate, 1g of composite hydrolysis resistant agent and 10g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder, granulating and drying, wherein the temperature of each zone of the double-screw extruder is 170, 180, 190, 200 and 210 ℃, the head temperature is 195 ℃ and the screw rotation speed is 150rpm, and obtaining master batches; carrying out melt spinning, winding and drafting on the master batch by a spinning machine, wherein the melt spinning temperature is 200 ℃, the winding speed is 1000m/min, and the drafting process comprises the following steps: the drafting temperature of the first hot roller is 70 ℃, the drafting temperature of the second hot roller is 90 ℃, and the drafting multiplying power is 2 times, so that the hydrolysis-resistant polylactic acid composite fiber is obtained.
The preparation method of the composite hydrolysis-resistant agent comprises the following steps:
(1) Adding 20g of dicyclohexylcarbodiimide and 10g of succinic anhydride into 200mL of toluene, then adding 0.05g of 4-dimethylaminopyridine, stirring and reacting at 80 ℃ for 5 hours, and evaporating to remove the toluene after the reaction is finished to obtain a product A;
(2) And (2) uniformly mixing the product A (30 g) in the step (1) and 80g of hyperbranched polyester, adding 15g of aminopropyltrimethoxysilane and 2g of p-toluenesulfonic acid, reacting for 8 hours at 70 ℃, and obtaining the composite hydrolysis resistant agent after the reaction is finished.
The preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 20g of carbon nano tubes, adding 500mL of hydrogen peroxide solution with the mass concentration of 15% for soaking for 10 hours, and filtering and drying after soaking to obtain mixed powder;
s2, adding the mixed powder (100 g) in the step S1 into 600mL of ethanol, then adding 10g of hexadecyl trimethyl ammonium bromide, reacting for 3h at 60 ℃, adding 4g of gamma-glycidyl ether oxypropyl trimethoxy silane and 2g of carboxymethyl cellulose after the reaction is finished, reacting for 5h at a constant temperature at 60 ℃, cooling, filtering, drying, ball-milling and sieving with a 600-mesh sieve after the reaction is finished, thus obtaining the modified nucleating agent.
Example 3
A preparation method of a hydrolysis-resistant polylactic acid fiber composite material comprises the following steps:
weighing raw materials according to a formula, drying 1000g of polylactic resin, adding 100g of polybutylene succinate, 20g of epoxy chain extender SAG-008, 5g of composite hydrolysis resistant agent and 30g of modified nucleating agent into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, granulating and drying, wherein the temperature of each zone of the double-screw extruder is 170, 180, 190, 200 and 210 ℃, the head temperature is 195 ℃ and the screw rotation speed is 300rpm, and obtaining master batches; and (3) carrying out melt spinning, winding and drafting on the master batch through a spinning machine, wherein the melt spinning temperature is 250 ℃, the winding speed is 1500m/min, and the drafting process comprises the steps of carrying out 110 ℃ on a first hot roll, carrying out 130 ℃ on a second hot roll and carrying out 4 times of drafting multiplying power to obtain the anti-hydrolytic polylactic acid composite fiber.
The preparation method of the composite hydrolysis-resistant agent comprises the following steps:
(1) Adding 20g of dicyclohexylcarbodiimide and 10g of succinic anhydride into 200mL of toluene, then adding 0.1g of 4-dimethylaminopyridine, stirring at 100 ℃ for reaction for 3 hours, and evaporating to remove the toluene after the reaction is finished to obtain a product A;
(2) And (2) uniformly mixing the product A (30 g) obtained in the step (1) with 120g of hyperbranched polyester, then adding 20g of aminopropyl trimethoxy silane and 4g of p-toluenesulfonic acid, reacting for 4 hours at 90 ℃, and obtaining the composite hydrolysis resistant agent after the reaction is finished.
The preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 40g of carbon nano tubes, adding 500mL of 20% hydrogen peroxide solution for impregnation for 5 hours, and filtering and drying after the impregnation is finished to obtain mixed powder;
s2, adding the mixed powder (100 g) obtained in the step S1 into 600mL of ethanol, then adding 20g of hexadecyl trimethyl ammonium bromide, reacting at 60 ℃ for 3h, adding 8g of gamma-glycidyl ether oxypropyl trimethoxy silane and 5g of carboxymethyl cellulose after the reaction is finished, reacting at 75 ℃ for 3h at constant temperature, cooling, filtering, drying, ball-milling and sieving with a 600-mesh sieve after the reaction is finished, thus obtaining the modified nucleating agent.
Comparative example 1
A preparation method of a hydrolysis-resistant polylactic acid fiber composite material comprises the following steps:
weighing raw materials according to a formula, drying 950g of polylactic resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of composite hydrolysis resistant agent and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder, granulating and drying, wherein the temperature of each area of the double-screw extruder is 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the rotating speed of a screw is 200rpm, so as to obtain master batches; and (2) carrying out melt spinning, winding and drafting on the master batch through a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process comprises the steps of carrying out first hot roller drafting at 90 ℃, carrying out second hot roller drafting at 110 ℃ and carrying out drafting multiplying power by 3 times to obtain the polylactic acid composite fiber.
The preparation method of the composite hydrolysis-resistant agent comprises the following steps:
(1) Adding 20g of dicyclohexylcarbodiimide and 10g of succinic anhydride into 200mL of toluene, then adding 0.08g of 4-dimethylaminopyridine, stirring and reacting for 4 hours at 90 ℃, and evaporating to remove the toluene after the reaction is finished to obtain a product A;
(2) And (2) uniformly mixing the product A (30 g) in the step (1) and 100g of hyperbranched polyester, adding 18g of aminopropyltrimethoxysilane and 3g of p-toluenesulfonic acid, reacting for 6 hours at 80 ℃, and obtaining the composite hydrolysis resistant agent after the reaction is finished.
The preparation method of the modified nucleating agent comprises the following steps:
and uniformly mixing 100g of hydrotalcite and 30g of carbon nano tube to obtain the modified nucleating agent.
Comparative example 2
A preparation method of a hydrolysis-resistant polylactic acid fiber composite material comprises the following steps:
weighing raw materials according to a formula, drying 950g of polylactic resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of anti-hydrolysis agent and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder, granulating and drying, wherein the temperature of each area of the double-screw extruder is 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the rotating speed of a screw is 200rpm, so as to obtain master batches; and (3) carrying out melt spinning, winding and drafting on the master batch through a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process comprises the steps of carrying out 90 ℃ on the drafting temperature of a first hot roller, carrying out 110 ℃ on the drafting temperature of a second hot roller and carrying out 3 times of drafting multiplying power to obtain the anti-hydrolytic polylactic acid composite fiber.
Wherein the hydrolysis-resistant agent is dicyclohexylcarbodiimide;
the preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 30g of carbon nano tubes, adding 500mL of 20% hydrogen peroxide solution for soaking for 8 hours, and filtering and drying after soaking to obtain mixed powder;
s2, adding the mixed powder (100 g) obtained in the step S1 into 600mL of ethanol, then adding 15g of hexadecyl trimethyl ammonium bromide, reacting for 3 hours at 60 ℃, adding 6g of gamma-glycidyl ether oxypropyl trimethoxy silane and 4g of carboxymethyl cellulose after the reaction is finished, reacting for 4 hours at a constant temperature at 70 ℃, cooling, filtering, drying, ball-milling and sieving with a 600-mesh sieve after the reaction is finished, thus obtaining the modified nucleating agent.
Comparative example 3
A preparation method of a hydrolysis-resistant polylactic acid fiber composite material comprises the following steps:
weighing raw materials according to a formula, drying 950g of polylactic resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of anti-hydrolysis agent and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder, granulating and drying, wherein the temperature of each area of the double-screw extruder is 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the rotating speed of a screw is 200rpm, so as to obtain master batches; and (3) carrying out melt spinning, winding and drafting on the master batch through a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process comprises the steps of carrying out 90 ℃ on the drafting temperature of a first hot roller, carrying out 110 ℃ on the drafting temperature of a second hot roller and carrying out 3 times of drafting multiplying power to obtain the anti-hydrolytic polylactic acid composite fiber.
Wherein the anti-hydrolysis agent is dicyclohexylcarbodiimide;
the preparation method of the modified nucleating agent comprises the following steps:
and uniformly mixing 100g of hydrotalcite and 30g of carbon nano tube to obtain the modified nucleating agent. The hydrolysis-resistant polylactic acid composite fibers prepared in the examples 1 to 3 and the comparative examples 1 to 3 are subjected to performance tests, wherein the tensile strength and the elongation at break are tested according to the standard GB/T14337-2008 < method for testing the tensile performance of chemical fiber short fibers >, the fiber strength is tested at a tensile speed of 20mm/min, the fiber clamping length is 20mm, and each group of test results is calculated by the arithmetic average value of 20 fibers; hydrolysis resistance evaluation method: placing the sample in a constant temperature and humidity box with the temperature of 60 ℃ and the relative humidity of 95% for treatment for 144h, after the treatment is finished, testing the tensile strength and the elongation at break of the sample after the sample is dried, wherein the strength retention rate is the tensile strength after the treatment/the tensile strength before the treatment multiplied by 100%, the elongation at break retention rate is the elongation at break after the treatment/the elongation at break before the treatment multiplied by 100%, and the test results are as shown in the following table 1:
TABLE 1
| Tensile strength cN/dtex | Elongation at break% | Strength retention ratio | Retention of elongation at break | |
| Example 1 | 3.53 | 54.7 | 93.7 | 91.5 |
| Example 2 | 3.39 | 57.2 | 91.2 | 90.4 |
| Example 3 | 3.45 | 52.9 | 92.6 | 91.8 |
| Comparative example 1 | 3.22 | 46.3 | 75.3 | 71.6 |
| Comparative example 2 | 3.14 | 41.5 | 81.4 | 74.3 |
| Comparative example 3 | 2.93 | 40.6 | 70.8 | 67.2 |
As can be seen from the above table 1, the polylactic acid composite fiber prepared by the invention has greatly improved hydrolysis resistance and good application prospect.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The hydrolysis-resistant polylactic acid fiber composite material is characterized by comprising the following raw materials in parts by weight:
90-100 parts of polylactic acid, 5-10 parts of toughening agent, 0.5-2 parts of compatilizer, 0.1-0.5 part of composite hydrolysis resistant agent and 1-3 parts of modified nucleating agent.
2. The anti-hydrolytic polylactic acid fiber composite material as claimed in claim 1, wherein the weight average molecular weight of the polylactic acid is 40 to 100 ten thousand.
3. The anti-hydrolysis polylactic acid fiber composite material as claimed in claim 1, wherein the toughening agent is one or more of polybutylene succinate and ethylene-vinyl acetate copolymer; the compatilizer is one or more of maleic anhydride, diphenylmethane diisocyanate or epoxy chain extender.
4. The composite material of claim 1, wherein the preparation method of the composite hydrolysis-resistant agent comprises the following steps:
(1) Adding dicyclohexylcarbodiimide and succinic anhydride into toluene, then adding 4-dimethylaminopyridine, carrying out stirring reaction, and evaporating to remove toluene after the reaction is finished to obtain a product A;
(2) And (2) uniformly mixing the product A obtained in the step (1) and hyperbranched polyester, then adding aminopropyl trimethoxy silane and p-toluenesulfonic acid, heating for reaction, and obtaining the composite hydrolysis-resistant agent after the reaction is completed.
5. The anti-hydrolytic polylactic acid fiber composite material as claimed in claim 4, wherein the mass ratio of dicyclohexylcarbodiimide, succinic anhydride and 4-dimethylaminopyridine in step (1) is 20:10:0.05-0.1; the stirring reaction temperature is 80-100 ℃, and the reaction time is 3-5h.
6. The anti-hydrolysis polylactic acid fiber composite material as claimed in claim 4, wherein the mass ratio of the product A, the hyperbranched polyester, the aminopropyltrimethoxysilane and the p-toluenesulfonic acid in the step (2) is 30:80-120:15-20:2-4; the heating reaction temperature is 70-90 ℃, and the reaction time is 4-8h.
7. The anti-hydrolysis polylactic acid fiber composite material as claimed in claim 1, wherein the preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing hydrotalcite and carbon nano tubes, adding a hydrogen peroxide solution for impregnation, and filtering and drying after the impregnation is finished to obtain mixed powder;
and S2, adding the mixed powder in the step S1 into ethanol, then adding hexadecyl trimethyl ammonium bromide, reacting for 3 hours at 60 ℃, adding gamma-glycidyl ether oxypropyl trimethoxy silane and carboxymethyl cellulose after the reaction is finished, carrying out constant temperature reaction, and cooling, filtering, drying and ball-milling after the reaction is finished to obtain the modified nucleating agent.
8. The anti-hydrolytic polylactic acid fiber composite material as claimed in claim 7, wherein the mass ratio of the hydrotalcite to the carbon nanotubes in step S1 is 10:2-4, wherein the mass concentration of the hydrogen peroxide solution is 15-20%, and the dipping time is 5-10h; in the step S2, the mass ratio of the mixed powder, cetyl trimethyl ammonium bromide, gamma-glycidoxypropyltrimethoxysilane and carboxymethyl cellulose is 100:10-20:4-8:2-5, wherein the constant temperature reaction is carried out at 60-75 ℃ for 3-5h.
9. A method of preparing a hydrolysis resistant polylactic acid fiber composite according to any of claims 1 to 8, comprising the steps of:
weighing the raw materials according to a formula, drying the polylactic resin, adding the dried polylactic resin, a toughening agent, a compatilizer, a composite hydrolysis resistant agent and a modified nucleating agent into a high-speed mixer, uniformly mixing, and then adding the mixture into a double-screw extruder for granulation and drying to obtain master batches; and carrying out melt spinning, winding and drafting on the master batch through a spinning machine to obtain the hydrolysis-resistant polylactic acid fiber composite material.
10. The method as claimed in claim 9, wherein the temperature of each zone of the twin-screw extruder is 170 to 210 ℃ and the screw rotation speed is 150 to 300rpm; the melt spinning temperature is 190-250 ℃, and the winding speed is 1000-1500m/min; the drafting process comprises the following steps: the drawing temperature of the first hot roll is 70-110 ℃, the drawing temperature of the second hot roll is 90-130 ℃, and the drawing multiplying power is 2-4 times.
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