CN117071105B - Heat-resistant polylactic acid fiber composite material and preparation method thereof - Google Patents
Heat-resistant polylactic acid fiber composite material and preparation method thereof Download PDFInfo
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- CN117071105B CN117071105B CN202311335331.6A CN202311335331A CN117071105B CN 117071105 B CN117071105 B CN 117071105B CN 202311335331 A CN202311335331 A CN 202311335331A CN 117071105 B CN117071105 B CN 117071105B
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 94
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 93
- 239000000835 fiber Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000011787 zinc oxide Substances 0.000 claims abstract description 49
- 239000002667 nucleating agent Substances 0.000 claims abstract description 43
- 239000010451 perlite Substances 0.000 claims abstract description 43
- 235000019362 perlite Nutrition 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012745 toughening agent Substances 0.000 claims abstract description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 238000002074 melt spinning Methods 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000004804 winding Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 241000196324 Embryophyta Species 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- -1 polybutylene succinate Polymers 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 239000002025 wood fiber Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The application relates to the technical field of polylactic acid fibers, and particularly discloses a heat-resistant polylactic acid fiber composite material and a preparation method thereof. The polylactic acid fiber comprises the following raw materials in parts by weight: 50-75 parts of polylactic resin, 10-25 parts of toughening agent, 1-5 parts of compatilizer, 1-3 parts of antioxidant, 5-12 parts of composite nucleating agent and 6-15 parts of plant fiber; wherein the composite nucleating agent is formed by compounding nano zinc oxide and perlite; the preparation method comprises the following steps: mixing polylactic acid resin and a composite nucleating agent, adding a toughening agent, a compatilizer, an antioxidant, plant fibers and cerium oxide, uniformly mixing, melting, extruding and granulating, and then melt spinning, winding and drawing to obtain the polylactic acid fiber composite material. The polylactic acid fiber composite material has the advantage of improving the heat resistance of the polylactic acid fiber composite material through the synergistic effect among the raw materials.
Description
Technical Field
The application relates to the technical field of polylactic acid fibers, in particular to a heat-resistant polylactic acid fiber composite material and a preparation method thereof.
Background
Polylactic acid, also called polylactide, is obtained by taking starch extracted from plant resources as a raw material to obtain lactic acid, and then synthesizing the lactic acid by a chemical method, and can be completely degraded into carbon dioxide and water, so that films, sheets, fibers and the like can be prepared. Polylactic acid has good biocompatibility, is nontoxic and nonirritating, and is applied to packaging, medical and health products, daily necessities and the like.
The polylactic acid melt-blown non-woven fabric is a non-woven fabric material prepared by taking polylactic acid fibers as raw materials through processes such as water jet, and the like, has simple preparation process, does not need to additionally add chemical substances, and has the characteristics of environmental protection and degradability.
Polylactic acid is a crystalline polymer, but only one methylene carbon atom exists between ester groups on a molecular main chain, the molecular chain is in a spiral structure, the movement of the molecular chain is limited, the crystallization speed is very slow, and the polylactic acid fiber is not resistant to high temperature, so that the preparation of the heat-resistant polylactic acid fiber composite material is a great difficulty which needs to be solved rapidly at present.
Disclosure of Invention
In order to improve the heat resistance of the polylactic acid fiber composite material, the application provides a heat-resistant polylactic acid fiber composite material and a preparation method thereof.
In a first aspect, the present application provides a heat-resistant polylactic acid fiber composite material, which adopts the following technical scheme:
the heat-resistant polylactic acid fiber composite material comprises the following raw materials in parts by weight: 50-75 parts of polylactic resin, 10-25 parts of toughening agent, 1-5 parts of compatilizer, 1-3 parts of antioxidant, 5-12 parts of composite nucleating agent and 6-15 parts of plant fiber; wherein the composite nucleating agent is formed by compounding nano zinc oxide and perlite;
the composite nucleating agent is prepared by the following method: adding nano zinc oxide and perlite into water, adding hexadecyl trimethyl ammonium bromide, uniformly mixing, stirring for a period of time under the water bath condition, carrying out suction filtration, and drying to obtain the composite nucleating agent.
Further, the composite nucleating agent is prepared by the following method: adding nano zinc oxide and perlite into water, adding hexadecyl trimethyl ammonium bromide, uniformly mixing, heating to 60-80 ℃ in water bath, stirring for 1-3h, carrying out suction filtration and drying to obtain a composite nucleating agent;
wherein, the weight ratio of perlite to cetyl trimethyl ammonium bromide is 1: (0.4-0.6), the addition amount of water in each 1g perlite is 3-5mL.
By adopting the technical scheme, the heat-resistant polylactic acid fiber composite material can keep good mechanical properties such as tensile strength and the like and improve the heat resistance of the polylactic acid fiber composite material through the synergistic effect among the raw materials, wherein the tensile strength is 0.90-0.93MPa, the longitudinal hot water shrinkage ratio is 2-16%, and the transverse hot water shrinkage ratio is 5-19%.
The polylactic acid resin is a main component, the toughening agent can improve the toughness of the polylactic acid fiber, the compatilizer can improve the compatibility of various raw materials and the polylactic acid resin, the antioxidant can improve the oxidation resistance of the polylactic acid resin, the stability of the polylactic acid resin is improved, and the plant fiber is added into the raw materials of the polylactic acid fiber composite material, so that the tensile strength of the polylactic acid fiber composite material can be improved.
The nucleating agent can promote the crystallization of the polylactic acid resin, improve the crystallization rate and improve the crystallinity, so the heat resistance of the polylactic acid fiber composite material can be improved. The composite nucleating agent is formed by compounding nano zinc oxide and perlite, wherein the nano zinc oxide has high temperature resistance, the perlite is an inorganic material with very low heat conductivity and high heat stability, the nano zinc oxide is loaded on the perlite to form the inorganic nucleating agent, so that polylactic acid has an amorphous state and a crystalline state structure at the same time, the crystalline state area is like a matrix, the amorphous state areas are connected together, the crystallinity is further improved, and the crystallization rate is also improved by adding the composite nucleating agent, so that the heat resistance of the polylactic acid fiber composite material is improved.
And the preparation method is used for preparing the composite nucleating agent, so that the raw materials are convenient to mix better and play a role, and the heat resistance of the polylactic acid fiber composite material is improved.
As preferable: the weight ratio of the nano zinc oxide to the perlite is (0.6-0.8): 1.
the addition amount of the nano zinc oxide is too small, so that the effect of the composite nucleating agent is poor, and the performance of the polylactic acid fiber is affected; the excessive addition of nano zinc oxide can cause agglomeration due to larger surface energy of nano zinc oxide, so that nano zinc oxide cannot be loaded on perlite better, and the formation of the composite nucleating agent is affected. By adopting the technical scheme, when the addition amount of the nano zinc oxide and the perlite is in the range, the composite nucleating agent can be better formed, and the heat resistance of the polylactic acid fiber composite material can be better improved.
As preferable: the nano zinc oxide is pretreated by the following method before use: and (3) placing the silane coupling agent into an ethanol solution, adding nano zinc oxide, performing ultrasonic dispersion, heating, stirring while heating, filtering, washing and drying after a period of time to obtain the pretreated nano zinc oxide.
Further, the nano zinc oxide is pretreated before use by adopting the following method: adding a silane coupling agent into an ethanol solution, adding nano zinc oxide, performing ultrasonic dispersion for 20-40min, heating to 30-50 ℃, stirring while heating, filtering after 1-2h, washing with water for 3-5 times, and drying to obtain pretreated nano zinc oxide;
wherein, the weight ratio of the nano zinc oxide to the silane coupling agent is 1: (0.3-0.5), the addition amount of the ethanol solution in each 1g of nano zinc oxide is 2-4mL, and the mass fraction of the ethanol solution is 40%.
By adopting the technical scheme, the specific surface energy of the nano zinc oxide is large, self agglomeration is easy to generate, the dispersibility is influenced, the silane coupling agent is used for preprocessing the nano zinc oxide, the specific surface energy of the nano zinc oxide can be reduced, the dispersibility is improved, the nano zinc oxide is convenient to load on perlite better, the composite nucleating agent is convenient to play a role, and the heat resistance of the polylactic acid fiber composite material is convenient to improve.
As preferable: the perlite is pretreated prior to use by the following method: and (3) putting the perlite into a sodium hydroxide solution, heating in a water bath for a period of time, filtering, washing and drying to obtain the pretreated perlite.
Further, the perlite is pre-treated prior to use by the following method: placing perlite into sodium hydroxide solution, heating in water bath at 60-80deg.C for 30-50min, filtering, washing with hydrochloric acid solution to neutrality, and oven drying to obtain pretreated perlite;
wherein, the adding amount of the sodium hydroxide solution in each 1g of perlite is 2-4mL, the mass fraction of the sodium hydroxide solution is 30%, and the mass fraction of the hydrochloric acid solution is 30%.
By adopting the technical scheme, the sodium hydroxide solution is utilized to pretreat the perlite, so that other impurities on the perlite can be removed, the surface area of the perlite can be increased, the perlite can be conveniently and better loaded with nano zinc oxide, and the heat resistance of the polylactic acid fiber composite material can be conveniently improved.
As preferable: the polylactic acid fiber composite material also comprises 2-5 parts by weight of cerium oxide.
By adopting the technical scheme, the cerium oxide can improve the crystallization rate of the polylactic acid resin and greatly improve the crystallinity, so that the heat resistance of the polylactic acid fiber composite material can be improved.
As preferable: the plant fiber is one or more of wood fiber, fibrilia and bamboo fiber.
As preferable: the toughening agent is one or more of polybutylene succinate, polycaprolactone and polyhydroxyalkanoate; the compatilizer is one or more of maleic anhydride and diphenylmethane diisocyanate; the antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants.
By adopting the technical scheme, the types of the plant fiber, the toughening agent, the compatilizer and the antioxidant are limited, so that the raw materials can play a role better, and the polylactic acid fiber composite material can keep good mechanical properties such as toughness and the like.
In a second aspect, the present application provides a method for preparing a heat-resistant polylactic acid fiber composite material, which adopts the following technical scheme:
a preparation method of a heat-resistant polylactic acid fiber composite material comprises the following steps:
mixing polylactic acid resin and a composite nucleating agent, adding a toughening agent, a compatilizer, an antioxidant, plant fibers and cerium oxide, uniformly mixing, melting, extruding and granulating, and then melt spinning, winding and drawing to obtain the polylactic acid fiber composite material.
Through adopting above-mentioned technical scheme, mix polylactic acid resin and compound nucleating agent at first, help compound nucleating agent to carry out the modification to polylactic acid resin, improve polylactic acid resin's crystallization rate, help improving polylactic acid fiber composite's heat resistance, then add other raw materials, be convenient for each raw materials misce bene.
In summary, the present application includes at least one of the following beneficial technical effects:
1. because the nano zinc oxide and perlite are compounded to serve as the composite nucleating agent, the crystallization rate and the crystallization degree of the polylactic acid resin are improved through the synergistic effect between the nano zinc oxide and the perlite, so that the heat resistance of the polylactic acid fiber composite material is improved, the tensile strength can reach 0.93MPa, the longitudinal hot water shrinkage ratio is reduced to 2%, and the transverse hot water shrinkage ratio is reduced to 5%;
2. in the present application, it is preferable to use cerium oxide as a raw material of the polylactic acid fiber composite material, and cerium oxide can increase the crystallization rate of the polylactic acid resin and can greatly increase the crystallinity, and therefore, the heat resistance of the polylactic acid fiber composite material can be improved.
Detailed Description
The present application is described in further detail below in conjunction with the detailed description.
Raw materials
The starting materials in this application are all commercially available.
The toughening agent is poly butylene succinate and has a molecular weight of 516; the compatilizer is diphenylmethane diisocyanate; the antioxidant is antioxidant 1010; the plant fiber is wood fiber; the silane coupling agent is KH550.
Preparation example
Preparation example 1
A composite nucleating agent, which is prepared by the following method:
adding 1.2kg of nano zinc oxide and 2kg of perlite into 8L of water, adding 0.8kg of cetyltrimethylammonium bromide, uniformly mixing, heating to 70 ℃ in a water bath, stirring for 2h, carrying out suction filtration, and drying to obtain the composite nucleating agent.
Preparation example 2
A composite nucleating agent is different from that of preparation example 1 in that the addition amount of nano zinc oxide is different, and the addition amount of nano zinc oxide in preparation example 2 is 1.4kg.
Preparation example 3
A composite nucleating agent is different from that of preparation example 1 in that the addition amount of nano zinc oxide is different, and the addition amount of nano zinc oxide in preparation example 3 is 1.6kg.
Examples
Example 1
The raw material proportion of the heat-resistant polylactic acid fiber composite material is shown in table 1.
A preparation method of a heat-resistant polylactic acid fiber composite material comprises the following steps:
mixing polylactic acid resin and the composite nucleating agent prepared by adopting the preparation example 1, adding the toughening agent, the compatilizer, the antioxidant, the plant fiber and the cerium oxide, uniformly mixing, melting, extruding and granulating, and then carrying out melt spinning, winding and drawing to obtain the polylactic acid fiber composite material.
Examples 2 to 5
The difference between the heat-resistant polylactic acid fiber composite material and the embodiment 1 is that the raw material ratio of the polylactic acid fiber composite material is different, and the raw material ratio is shown in the table 1.
Example 6
A heat-resistant polylactic acid fiber composite material is different from example 4 in that the source of the composite nucleating agent in the polylactic acid fiber composite material is different, and the composite nucleating agent in example 6 is prepared by adopting the preparation example 2.
Example 7
A heat-resistant polylactic acid fiber composite material is different from example 4 in that the source of the composite nucleating agent in the polylactic acid fiber composite material is different, and the composite nucleating agent in example 7 is prepared by adopting the preparation example 3.
Example 8
A heat resistant polylactic acid fiber composite material, which differs from example 6 in that the nano zinc oxide in the composite nucleating agent of the polylactic acid fiber composite material is pretreated prior to use by the following method: adding a silane coupling agent into an ethanol solution with the mass fraction of 40%, adding nano zinc oxide, performing ultrasonic dispersion for 30min, heating to 40 ℃, stirring while heating, filtering after 1.5h, washing with water for 5 times, and drying to obtain pretreated nano zinc oxide; wherein, the weight ratio of the nano zinc oxide to the silane coupling agent is 1:0.4, the addition amount of the ethanol solution in each 1g of nano zinc oxide is 3mL.
Example 9
A heat resistant polylactic acid fiber composite material, which differs from example 6 in that perlite in the composite nucleating agent of the polylactic acid fiber composite material is pretreated prior to use by the following method: placing perlite into 30% sodium hydroxide solution by mass fraction, heating in water bath at 70deg.C for 40min, filtering, washing with 30% hydrochloric acid solution by mass fraction to neutrality, and oven drying to obtain pretreated perlite; wherein, the addition amount of the sodium hydroxide solution in each 1g of perlite is 3mL.
Comparative example
Comparative example 1
A heat-resistant polylactic acid fiber composite material is different from example 1 in that a composite nucleating agent is not added to the raw material of the polylactic acid fiber composite material.
Comparative example 2
A heat resistant polylactic acid fiber composite material, which differs from example 1 in that the composite nucleating agent of the polylactic acid fiber composite material is replaced with nano zinc oxide in equal amount.
Comparative example 3
A heat resistant polylactic acid fiber composite material is different from example 1 in that the composite nucleating agent of the polylactic acid fiber composite material is replaced with perlite in equal amount.
Performance test
The polylactic acid fiber composites in examples 1 to 9 and comparative examples 1 to 3 were subjected to the following performance tests:
tensile strength: determination of tensile Properties of plastics according to GB/T1040.1-2018 section 1: the tensile strength of the polylactic acid fiber composite material was measured in general rules, and the measurement results are shown in table 2.
Hot water shrinkage ratio: and testing the hot water shrinkage proportion of the irradiated polylactic acid fiber composite material by adopting an electron beam with the irradiation dose of 200 kGy.
As can be seen from Table 2, the heat-resistant polylactic acid fiber composite material of the present application can not only maintain good mechanical properties such as tensile strength, but also improve the heat resistance of polylactic acid by the synergistic effect between the raw materials, wherein the tensile strength is 0.90-0.93MPa, the longitudinal hot water shrinkage ratio is 2% -16%, and the transverse hot water shrinkage ratio is 5% -19%.
As can be seen from the combination of examples 1 and comparative examples 1 to 3, the tensile strength in example 1 is 0.90MPa, the longitudinal hot water shrinkage ratio is 16%, and the transverse hot water shrinkage ratio is 19%, which is superior to comparative examples 1 to 3, and shows that the composite nucleating agent is more suitable for polylactic acid, and the heat resistance is improved.
As can be seen from the combination of examples 4 and examples 6 to 7, the tensile strength in example 6 is 0.92MPa, the longitudinal hot water shrinkage ratio is 4%, and the transverse hot water shrinkage ratio is 6%, which is superior to other examples, and shows that the composite nucleating agent is more suitable to be prepared by adopting the preparation example 2, and the heat resistance is improved.
As can be seen from the combination of examples 6 and 8, the tensile strength in example 8 is 0.92MPa, the longitudinal hot water shrinkage ratio is 3%, and the transverse hot water shrinkage ratio is 6%, which is superior to example 6, and shows that the nano zinc oxide is more suitable for pretreatment before use, and can improve the dispersibility thereof, thereby facilitating the function and further improving the heat resistance of the polylactic acid fiber composite material.
As can be seen from the combination of examples 8 and 9, the tensile strength in example 9 is 0.93MPa, the longitudinal hot water shrinkage ratio is 2%, and the transverse hot water shrinkage ratio is 5%, which is superior to that in example 8, and shows that the perlite is more suitable for pretreatment before use, can remove other impurities on the perlite, can also increase the surface area of the perlite, is convenient for the perlite to better load nano zinc oxide, and is convenient for improving the heat resistance of the polylactic acid fiber composite material.
The foregoing embodiments are all preferred examples of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (4)
1. A heat-resistant polylactic acid fiber composite material is characterized in that: a heat-resistant polylactic acid fiber composite material is characterized in that: the material comprises the following raw materials in parts by weight: 50-75 parts of polylactic resin, 10-25 parts of toughening agent, 1-5 parts of compatilizer, 1-3 parts of antioxidant, 5-12 parts of composite nucleating agent and 6-15 parts of plant fiber; wherein the composite nucleating agent is formed by compounding nano zinc oxide and perlite;
the composite nucleating agent is prepared by the following method: adding nano zinc oxide and perlite into water, adding hexadecyl trimethyl ammonium bromide, uniformly mixing, stirring for 1-3h under the water bath condition, carrying out suction filtration and drying to obtain a composite nucleating agent;
the weight ratio of the nano zinc oxide to the perlite is (0.6-0.8): 1, a step of;
the nano zinc oxide is pretreated by the following method before use: adding a silane coupling agent into an ethanol solution, adding nano zinc oxide, performing ultrasonic dispersion for 20-40min, heating to 30-50 ℃, stirring while heating, filtering after 1-2h, washing with water for 3-5 times, and drying to obtain pretreated nano zinc oxide;
wherein, the weight ratio of the nano zinc oxide to the silane coupling agent is 1: (0.3-0.5), wherein the addition amount of the ethanol solution in each 1g of nano zinc oxide is 2-4mL, and the mass fraction of the ethanol solution is 40%;
the perlite is pretreated prior to use by the following method: placing perlite into sodium hydroxide solution, heating in water bath at 60-80deg.C for 30-50min, filtering, washing with hydrochloric acid solution to neutrality, and oven drying to obtain pretreated perlite;
wherein, the adding amount of the sodium hydroxide solution in each 1g of perlite is 2-4mL, the mass fraction of the sodium hydroxide solution is 30%, and the mass fraction of the hydrochloric acid solution is 30%;
the polylactic acid fiber composite material also comprises 2-5 parts by weight of cerium oxide.
2. The heat resistant polylactic acid fiber composite material according to claim 1, wherein: the plant fiber is one or more of wood fiber, fibrilia and bamboo fiber.
3. The heat resistant polylactic acid fiber composite material according to claim 1, wherein: the toughening agent is one or more of polybutylene succinate, polycaprolactone and polyhydroxyalkanoate; the compatilizer is one or more of maleic anhydride and diphenylmethane diisocyanate; the antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants.
4. A method for preparing the heat-resistant polylactic acid fiber composite material according to any one of claims 1 to 3, comprising the steps of: mixing polylactic acid resin and a composite nucleating agent, adding a toughening agent, a compatilizer, an antioxidant, plant fibers and cerium oxide, uniformly mixing, melting, extruding and granulating, and then melt spinning, winding and drawing to obtain the polylactic acid fiber composite material.
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