CN115679474B - 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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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 113
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 112
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 80
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 27
- 239000002667 nucleating agent Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 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 29
- 238000002156 mixing Methods 0.000 claims description 24
- 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 21
- 229960001545 hydrotalcite Drugs 0.000 claims description 20
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 20
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000004804 winding Methods 0.000 claims description 18
- 238000002074 melt spinning Methods 0.000 claims description 17
- 229920006150 hyperbranched polyester Polymers 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
- 239000003112 inhibitor Substances 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 11
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 11
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 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
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- -1 polybutylene succinate Polymers 0.000 claims description 8
- 229920002961 polybutylene succinate Polymers 0.000 claims description 8
- 239000004631 polybutylene succinate Substances 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
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- 238000005303 weighing Methods 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 6
- 239000004593 Epoxy Chemical group 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 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
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical group CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
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- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011159 matrix material Substances 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000655 anti-hydrolysis 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
- 230000007613 environmental effect Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test 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
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 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
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 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
- 150000003384 small molecules Chemical class 0.000 description 1
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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 resistance agent and 1-3 parts of modified nucleating agent. According to the polylactic acid fiber composite material, the polylactic acid raw material with high molecular weight is added, and meanwhile, the polymer hydrolysis resistance agent and the modified nucleating agent are added, so that the crystallization performance of the polylactic acid is modified, and the prepared polylactic acid fiber has high hydrolysis resistance, and meanwhile, 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 using lactic acid as a raw material, is colorless and nontoxic, has thermal properties similar to polystyrene, good biocompatibility, can be decomposed and absorbed by biology, and finally is degraded into carbon dioxide, and has wide application prospect. PLA is made from crops such as sugarcane, corn, sweet potato, etc., starch raw material is saccharified and then is converted into glucose, then is fermented into lactic acid by a certain strain, and is prepared into polylactic acid by a chemical synthesis method, and can be decomposed into H under the influence of environment and hydrolysis 2 O and CO 2 Is receiving close attention in environmental protection. Because of the relatively good biocompatibility and biodegradability of PLA, the PLA is widely applied in the fields of medical treatment, food packaging and the like.
Although abiotic hydrolysis of ester bonds on PLA segments is beneficial for assimilation and mineralization by microorganisms. And ester bonds are broken when PLA is hydrolyzed and degraded, so that a molecular chain is shortened, and the mechanical property is reduced. When the PLA material is used as an environment-friendly plastic bag or a non-biological application product, the PLA material is easy to hydrolyze in the storage and use processes, and the service life of the PLA product is seriously influenced especially in a high-temperature and high-humidity environment in summer, so that the PLA material has very important significance in toughening and hydrolysis-resistant modification. In the prior art, the method for solving the problem that the degradation speed of the polylactic acid resin is high mainly adopts crystallization and end capping at present.
Crystallization enables polylactic acid molecules to be orderly arranged, improves the hydrolysis resistance of the polylactic acid, but cannot thoroughly change the hydrolysis resistance problem of the polylactic acid. Inside the polylactic acid material, the crystallization part hydrolysis rate is slow, and the amorphous part hydrolysis rate is fast, so that the higher the crystallinity is, the stronger the hydrolysis resistance of the polylactic acid is. However, polylactic acid and polylactic acid homopolymers belong to semi-crystalline polymers. It is also difficult to obtain a homopolymer of polylactic acid, for example, so-called polylactic acid, which is actually a random copolymer having a certain amount of D-form, and the higher the D-form content, the slower the crystallization rate, and when the D-form exceeds 20%, the polylactic acid is in an amorphous state and cannot be crystallized. The polylactic acid resin has an excessively high crystallinity, which causes a problem of difficulty in feeding a screw during processing of the product, and a material having a low crystallinity is often required for realizing some properties of the polylactic acid product.
The Chinese patent application No. 201210096514.2 discloses a preparation method of hydrolysis-resistant modified polylactic acid fibers, 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 parts by weight, melt blending granulation is carried out after uniform mixing to obtain master batch, the obtained master batch is subjected to vacuum drying, melt spinning and winding to obtain winding wires, and finally drafting is carried out to obtain the modified polylactic acid fiber. Although the method can improve the hydrolysis resistance of the polylactic acid fiber, the polyfunctional compound reacts with carboxyl at the tail end of a polylactic acid molecular chain, so that gel points appear in a reaction system due to uneven dispersion of the hydrolysis resistance agent, and the quality of a modified polylactic acid product is affected. In addition, since the crystallization properties of the polylactic acid fibers are not modified, neither the mechanical properties nor the heat resistance of the polylactic acid fibers are improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the hydrolysis-resistant polylactic acid fiber composite material and the preparation method thereof, and the polylactic acid fiber material is prepared by adding a polylactic acid raw material with high molecular weight, and simultaneously adding a polymer hydrolysis-resistant agent and a modified nucleating agent to modify the crystallization property of polylactic acid, so that the prepared polylactic acid fiber has stronger hydrolysis resistance and good mechanical property and heat resistance.
In order to achieve the above purpose, the present invention provides the following technical solutions:
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 resistance agent and 1-3 parts of modified nucleating agent.
Preferably, the weight average molecular weight of the polylactic acid is 40-100 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 resistance agent comprises the following steps:
(1) Adding dicyclohexylcarbodiimide and succinic anhydride into toluene, then adding 4-dimethylaminopyridine, stirring for reaction, and evaporating to remove toluene after the reaction is completed to obtain a product A;
(2) And (3) uniformly mixing the product A obtained in the step (1) and hyperbranched polyester, then adding aminopropyl trimethoxy silane and p-toluenesulfonic acid, and carrying out a heating reaction to obtain the composite hydrolysis inhibitor after the reaction is completed.
Preferably, the mass ratio of dicyclohexylcarbodiimide, succinic anhydride and 4-dimethylaminopyridine in the step (1) is 20:10:0.05-0.1; the stirring reaction temperature is 80-100 ℃ and the reaction time is 3-5h.
Preferably, the mass ratio of the product A, hyperbranched polyester, aminopropyl trimethoxysilane and p-toluenesulfonic acid in the step (2) is 30:80-120:15-20:2-4; the temperature of the heating reaction 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 nanotubes, then adding hydrogen peroxide solution for soaking, and filtering and drying after the soaking is completed to obtain mixed powder;
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-glycidol ether oxypropyl trimethoxy silane and carboxymethyl cellulose after the reaction is finished, performing constant temperature reaction, and cooling, filtering, drying and ball milling after the reaction is finished to obtain the modified nucleating agent.
Preferably, in step S1, the mass ratio of hydrotalcite to carbon nanotubes is 10:2-4, wherein the mass concentration of the hydrogen peroxide solution is 15-20%, and the soaking time is 5-10h; the mass ratio of the mixed powder to the hexadecyl trimethyl ammonium bromide to the gamma-glycidyl ether oxypropyl trimethoxy silane to the carboxymethyl cellulose in the step S2 is 100:10-20:4-8:2-5, wherein the constant temperature reaction temperature is 60-75 ℃ and the reaction time is 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 polylactic acid resin, adding the polylactic acid resin, a toughening agent, a compatilizer, a composite hydrolysis resistance agent and a modified nucleating agent into a high-speed mixer, uniformly mixing, and then adding the mixture into a double-screw extruder for granulating and drying to obtain master batches; and carrying out melt spinning, winding and drawing on the master batch by a spinning machine to obtain the hydrolysis resistant polylactic acid fiber composite material.
Preferably, the temperature of each area 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 is that the drafting temperature of a first hot roller is 70-110 ℃, the drafting temperature of a second hot roller is 90-130 ℃, and the drafting multiplying power is 2-4 times. .
Compared with the prior art, the invention has the following beneficial effects:
(1) The hydrolysis resistant polylactic acid fiber composite material provided by the invention is characterized in that dicyclohexylcarbodiimide and succinic anhydride are reacted, a product A is obtained under the catalysis of 4-dimethylaminopyridine, then the product A and hyperbranched polyester are subjected to esterification reaction, the hyperbranched polyester contains a plurality of hydroxyl groups and can react with carboxyl groups in the product A, aminopropyl trimethoxysilane is added at the same time, the aminopropyl trimethoxysilane is introduced into the hyperbranched polyester to obtain a composite hydrolysis resistant agent, finally the hydrolysis resistant agent containing the hyperbranched polyester is introduced into polylactic acid, the residual hydroxyl groups in the hyperbranched polyester can seal carboxyl groups existing in the polylactic acid resin, the initial carboxyl group concentration is reduced, simultaneously the carboxyl groups continuously generated in the hydrolysis process are consumed, the carboxyl group concentration is kept at a lower level, so that the rate of the hydrolysis reaction is controlled, the service life of the material in a wet and hot working environment is prolonged, the hydrolysis resistant agent can also play a chain extension role to a certain extent, and the hydrolysis inhibition effect is better; and the polylactic acid molecules are introduced with hydrophobic siloxane-containing chain segments, the silicon-containing chain segments are easy to migrate to the surface, the surface energy and the surface tension of the system can be greatly reduced, and the hydrophobicity of the polylactic acid is improved, so that the hydrolytic stability of the material is improved. In addition, the added dicyclohexylcarbodiimide is introduced into the hyperbranched polyester in a grafting way, so that the dicyclohexylcarbodiimide can be uniformly distributed in the hyperbranched polyester, and the problem that gel points appear in a reaction system due to uneven dispersion of the hydrolysis resistance agent, so that the quality of a modified polylactic acid product is affected is solved.
(2) The hydrolysis-resistant polylactic acid fiber composite material provided by the invention modifies the nucleating agent, improves the compatibility of the nucleating agent and polylactic acid, and improves the comprehensive performance of the polylactic acid. Firstly, immersing talcum powder and carbon nano tubes in hydrogen peroxide solution to enable the surfaces of the talcum powder and the carbon nano tubes to be activated and oxidized, which is beneficial to the subsequent reaction, then adding hexadecyl trimethyl ammonium bromide to react with hydrotalcite to enable the hydrotalcite to smoothly enter the interlayer of the hydrotalcite, generating hydrotalcite with a partially peeled structure, changing the oleophobic hydrophilicity of the modified hydrotalcite into hydrophobic and oleophilic properties, improving the compatibility of a nonpolar polymer, simultaneously obviously reducing the surface energy due to obviously enlarged interlayer spacing of the hydrotalcite, leading the polylactic acid to be inserted between the hydrotalcite sheets, finally realizing that the hydrotalcite is uniformly dispersed in a polylactic acid matrix, and leading the smaller particle size of mixed particles to be higher, leading the crystallinity of the polylactic acid to be better; and finally, adding gamma-glycidyl ether oxypropyl trimethoxy silane and carboxymethyl cellulose, wherein the added carboxymethyl cellulose can be used as a nucleating agent and a toughening agent to be added into the polylactic acid matrix, so that the crystallization rate and the crystallization degree of the polylactic acid matrix can be greatly improved, the heat resistance of the polylactic acid matrix is improved, and the gamma-glycidyl ether oxypropyl trimethoxy silane covers the surfaces of mixed particle particles to enable the surfaces of the mixed particles to be organized, so that the bonding strength between the mixed particles and the polylactic acid is improved, and the mechanical property of the polylactic acid is improved.
(3) Compared with the traditional small-molecule hydrolysis inhibitor, the hydrolysis inhibitor of the polylactic acid fiber composite material can improve the hydrolysis stability of polylactic acid, can be used as a compatibilizer, and improves the compatibility of polylactic acid with inorganic powder; meanwhile, the mechanical properties 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 nucleation points for 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 hydrotalcite and carbon nanotubes, the polylactic acid melt generates small and more spherulites when being cooled, the spherulites have small size, even distribution and high crystallization speed, which is beneficial to the processing of polylactic acid products, and the higher the crystallization degree is, the better the hydrolysis resistance of the polylactic acid is, and the hydrolysis resistance of the polylactic acid is further improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The polylactic acid has the brand of 6201D and the weight average molecular weight of 80-100 ten thousand, and is produced by Nature Works company of America; the poly butylene succinate is purchased from Toguan city Weicai plastic raw material limited company, and the brand is FZ91PM; the ethylene-vinyl acetate copolymer is purchased from Shanghai and high-speed new material technology Co., ltd, and has the mark of VS430 and the VA content of 19%; the epoxy chain extender SAG-008 Nantong is a styrene (St) -Acrylonitrile (AN) -glycidyl methacrylate ternary (GMA) copolymer, the content of the GMA is 8%, and the weight average molecular weight is 90000; the epoxy chain extender MSA-7200 is purchased from the new material technology Co., ltd. Of Xinyuxiang in east Ying, and has the number average molecular weight of 3200+/-200; the hyperbranched polyester is purchased from the company of Changzhou carbon materials of the novel class of the Egypenum, the average hydroxyl number is 6, and the molecular weight is 900; the hydrotalcite is purchased from Jiangsu Leien environmental protection technology Co., ltd, and the mesh number is 800 mesh; the carbon nanotube is purchased from the scientific and technological Co.Ltd of the department of China Jin Yan (Beijing), the tube diameter is 10-20nm, and the length is 10-20 mu m; the carboxymethyl cellulose is purchased from gallery long forest cellulose limited company and is of the model of 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 acid resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of composite hydrolysis inhibitor and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder for granulating and drying, wherein the temperatures of all areas of the double-screw extruder are 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the screw speed is 200rpm to obtain master batches; and (3) carrying out melt spinning, winding and drafting on the master batch by a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process is that the drafting temperature of a first hot roller is 90 ℃, the drafting temperature of a second hot roller is 110 ℃, and the drafting multiplying power is 3 times, so as to obtain the hydrolysis-resistant polylactic acid composite fiber.
The preparation method of the composite hydrolysis resistance 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 at 90 ℃ for reaction for 4 hours, and evaporating to remove toluene after the reaction is completed to obtain a product A;
(2) Uniformly mixing the product A (30 g) obtained in the step (1) and 100g of hyperbranched polyester, then adding 18g of aminopropyl trimethoxy silane and 3g of p-toluenesulfonic acid, and reacting at 80 ℃ for 6 hours to obtain the composite hydrolysis inhibitor after the reaction is completed.
The preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 30g of carbon nano tubes, then adding 500mL of hydrogen peroxide solution with 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) 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 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 acid resin, adding 50g of ethylene-vinyl acetate copolymer, 5g of diphenylmethane diisocyanate, 1g of composite hydrolysis inhibitor and 10g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder for granulating and drying, wherein the temperatures of all areas of the double-screw extruder are 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the rotating speed of a screw is 150rpm, so as to obtain master batches; melt spinning, winding and drafting 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 temperature of the first hot roller is 70 ℃, the temperature of the second hot roller is 90 ℃, and the draft ratio is 2 times, so that the hydrolysis resistant polylactic acid composite fiber is obtained.
The preparation method of the composite hydrolysis resistance 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 at 80 ℃ for reaction for 5 hours, and evaporating to remove toluene after the reaction is completed to obtain a product A;
(2) Uniformly mixing the product A (30 g) obtained in the step (1) and 80g of hyperbranched polyester, then adding 15g of aminopropyl trimethoxy silane and 2g of p-toluenesulfonic acid, and reacting at 70 ℃ for 8 hours to obtain the composite hydrolysis inhibitor after the reaction is completed.
The preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 20g of carbon nanotubes, then adding 500mL of hydrogen peroxide solution with 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) obtained in the step S1 into 600mL of ethanol, then adding 10g of hexadecyl trimethyl ammonium bromide, reacting for 3 hours at 60 ℃, adding 4g of gamma-glycidyl ether oxypropyl trimethoxy silane and 2g of carboxymethyl cellulose after the reaction is finished, reacting for 5 hours at the constant temperature of 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 acid resin, adding 100g of polybutylene succinate, 20g of epoxy chain extender SAG-008, 5g of composite hydrolysis inhibitor and 30g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder for granulating and drying, wherein the temperatures of all areas of the double-screw extruder are 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the rotating speed of a screw is 300rpm, so as to obtain master batches; and (3) carrying out melt spinning, winding and drafting on the master batch by a spinning machine, wherein the melt spinning temperature is 250 ℃, the winding speed is 1500m/min, and the drafting process is that the drafting temperature of a first hot roller is 110 ℃, the drafting temperature of a second hot roller is 130 ℃, and the drafting multiplying power is 4 times, so as to obtain the hydrolysis-resistant polylactic acid composite fiber.
The preparation method of the composite hydrolysis resistance 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 toluene after the reaction is completed to obtain a product A;
(2) Uniformly mixing the product A (30 g) obtained in the step (1) and 120g of hyperbranched polyester, then adding 20g of aminopropyl trimethoxy silane and 4g of p-toluenesulfonic acid, and reacting at 90 ℃ for 4 hours to obtain the composite hydrolysis inhibitor after the reaction is completed.
The preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing 100g of hydrotalcite and 40g of carbon nano tubes, then adding 500mL of hydrogen peroxide solution with mass concentration of 20% for soaking for 5 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 20g of hexadecyl trimethyl ammonium bromide, reacting for 3 hours at 60 ℃, adding 8g of gamma-glycidyl ether oxypropyl trimethoxy silane and 5g of carboxymethyl cellulose after the reaction is finished, reacting for 3 hours at a constant temperature of 75 ℃, 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 acid resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of composite hydrolysis inhibitor and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder for granulating and drying, wherein the temperatures of all areas of the double-screw extruder are 170, 180, 190, 200 and 210 ℃, the temperature of a machine head is 195 ℃, and the screw speed is 200rpm to obtain master batches; and (3) carrying out melt spinning, winding and drafting on the master batch by a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process is that the drafting temperature of a first hot roller is 90 ℃, the drafting temperature of a second hot roller is 110 ℃, and the drafting multiplying power is 3 times, so as to obtain the hydrolysis-resistant polylactic acid composite fiber.
The preparation method of the composite hydrolysis resistance 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 at 90 ℃ for reaction for 4 hours, and evaporating to remove toluene after the reaction is completed to obtain a product A;
(2) Uniformly mixing the product A (30 g) obtained in the step (1) and 100g of hyperbranched polyester, then adding 18g of aminopropyl trimethoxy silane and 3g of p-toluenesulfonic acid, and reacting at 80 ℃ for 6 hours to obtain the composite hydrolysis inhibitor after the reaction is completed.
The preparation method of the modified nucleating agent comprises the following steps:
and uniformly mixing 100g of hydrotalcite and 30g of carbon nano tubes 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 acid resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of hydrolysis inhibitor and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder for granulating and drying, wherein the temperatures of all areas of the double-screw extruder are 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 by a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process is that the drafting temperature of a first hot roller is 90 ℃, the drafting temperature of a second hot roller is 110 ℃, and the drafting multiplying power is 3 times, so as to obtain the hydrolysis-resistant polylactic acid composite fiber.
Wherein the anti-hydrolysis 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, then adding 500mL of hydrogen peroxide solution with 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) 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 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.
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 acid resin, adding 80g of polybutylene succinate, 15g of maleic anhydride, 3g of hydrolysis inhibitor and 20g of modified nucleating agent into a high-speed mixer, uniformly mixing, then adding into a double-screw extruder for granulating and drying, wherein the temperatures of all areas of the double-screw extruder are 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 by a spinning machine, wherein the melt spinning temperature is 230 ℃, the winding speed is 1300m/min, and the drafting process is that the drafting temperature of a first hot roller is 90 ℃, the drafting temperature of a second hot roller is 110 ℃, and the drafting multiplying power is 3 times, so as to obtain the hydrolysis-resistant 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 tubes to obtain the modified nucleating agent. The hydrolysis resistant polylactic acid composite fibers prepared in examples 1-3 and comparative examples 1-3 were subjected to performance tests, wherein tensile strength and elongation at break were tested according to the standard GB/T14337-2008 "chemical fiber short fiber tensile Performance test method", fiber strength was tested at a tensile speed of 20mm/min, fiber clamping length was 20mm, and each set of test results was calculated as an arithmetic average value of 20 fibers; method for evaluating hydrolysis resistance: the samples were placed in a constant temperature and humidity cabinet at 60 c and 95% relative humidity for 144 hours, after the treatment was completed, the samples were tested for tensile strength and elongation at break after drying, the strength retention was the post-treatment tensile strength/pre-treatment tensile strength×100%, and the elongation at break retention was the post-treatment elongation at break/pre-treatment elongation at break×100%, with the test results shown in table 1 below:
TABLE 1
| Tensile strength cN/dtex | Elongation at break% | Strength retention rate | Elongation at break retention | |
| 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 table 1, the polylactic acid composite fiber prepared by the method has the advantages of greatly improved hydrolysis resistance and good application prospect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
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 resistance agent and 1-3 parts of modified nucleating agent;
the preparation method of the composite hydrolysis resistance agent comprises the following steps:
(1) Adding dicyclohexylcarbodiimide and succinic anhydride into toluene, then adding 4-dimethylaminopyridine, stirring for reaction, and evaporating to remove toluene after the reaction is completed to obtain a product A;
(2) Uniformly mixing the product A in the step (1) and hyperbranched polyester, then adding aminopropyl trimethoxy silane and p-toluenesulfonic acid, and carrying out heating reaction to obtain the composite hydrolysis inhibitor after the reaction is completed;
the mass ratio of dicyclohexylcarbodiimide, succinic anhydride and 4-dimethylaminopyridine in the step (1) is 20:10:0.05-0.1; the stirring reaction temperature is 80-100 ℃ and the reaction time is 3-5h;
the mass ratio of the product A to the hyperbranched polyester to the aminopropyl trimethoxysilane to the p-toluenesulfonic acid in the step (2) is 30:80-120:15-20:2-4; the temperature of the heating reaction is 70-90 ℃ and the reaction time is 4-8h;
the preparation method of the modified nucleating agent comprises the following steps:
s1, uniformly mixing hydrotalcite and carbon nanotubes, then adding hydrogen peroxide solution for soaking, and filtering and drying after the soaking is completed to obtain mixed powder;
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-glycidol ether oxypropyl trimethoxy silane and carboxymethyl cellulose after the reaction is finished, performing constant temperature reaction, and cooling, filtering, drying and ball milling after the reaction is finished to obtain the modified nucleating agent;
in the step S1, the mass ratio of hydrotalcite to carbon nano tube is 10:2-4, wherein the mass concentration of the hydrogen peroxide solution is 15-20%, and the soaking time is 5-10h; the mass ratio of the mixed powder to the hexadecyl trimethyl ammonium bromide to the gamma-glycidyl ether oxypropyl trimethoxy silane to the carboxymethyl cellulose in the step S2 is 100:10-20:4-8:2-5, wherein the constant temperature reaction temperature is 60-75 ℃ and the reaction time is 3-5h.
2. The hydrolysis resistant polylactic acid fiber composite material of claim 1, wherein the polylactic acid has a weight average molecular weight of 40-100 ten thousand.
3. The hydrolysis resistant polylactic acid fiber composite material according to 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; the epoxy chain extender is a styrene-acrylonitrile-glycidyl methacrylate terpolymer, the glycidyl methacrylate content is 8%, and the weight average molecular weight is 90000.
4. A process for the preparation of the hydrolysis resistant polylactic acid fiber composite material according to any one of claims 1 to 3, comprising the steps of:
weighing raw materials according to a formula, drying polylactic acid resin, adding the polylactic acid resin, a toughening agent, a compatilizer, a composite hydrolysis resistance agent and a modified nucleating agent into a high-speed mixer, uniformly mixing, and then adding the mixture into a double-screw extruder for granulating and drying to obtain master batches; and carrying out melt spinning, winding and drawing on the master batch by a spinning machine to obtain the hydrolysis resistant polylactic acid fiber composite material.
5. The process according to claim 4, wherein the twin-screw extruder has a temperature of 170-210℃in each zone and a screw speed of 150-300rpm; the melt spinning temperature is 190-250 ℃, and the winding speed is 1000-1500m/min; the drafting process comprises the following steps: the drafting temperature of the first hot roller is 70-110 ℃, the drafting temperature of the second hot roller is 90-130 ℃, and the drafting multiplying power is 2-4 times.
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