CN114806120A - Preparation method of heat-resistant polylactic acid foaming thermal forming body - Google Patents
Preparation method of heat-resistant polylactic acid foaming thermal forming body Download PDFInfo
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- CN114806120A CN114806120A CN202210672375.7A CN202210672375A CN114806120A CN 114806120 A CN114806120 A CN 114806120A CN 202210672375 A CN202210672375 A CN 202210672375A CN 114806120 A CN114806120 A CN 114806120A
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- polylactic acid
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- heat
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 115
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 114
- 238000005187 foaming Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004088 foaming agent Substances 0.000 claims abstract description 31
- 239000003365 glass fiber Substances 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 4
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000006260 foam Substances 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000005809 transesterification reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000005482 strain hardening Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0052—Organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a heat-resistant polylactic acid foaming thermal forming body; the material comprises 80-100 parts of polylactic acid, 1.5-3 parts of trimethylolpropane triacrylate, 0.3-0.8 part of nano zinc oxide, 5-20 parts of glass fiber, 0.5-2 parts of a silane coupling agent, 2-5 parts of a foaming agent, 0.1-0.3 part of a foaming promoter and 400-500 parts of N, N-dimethylformamide; carrying out transesterification reaction on trimethylolpropane triacrylate and a polylactic acid main chain, wherein the polylactic acid is converted into branched chain from a linear structure; the melt strength and the strain hardening strength of the glass fiber reinforced polylactic acid composite material; the silane coupling agent increases the compatibility and bonding capability of the glass fiber, the nano zinc oxide and the polylactic acid material; the foaming agent decomposes nitrogen, carbon dioxide and water under the conditions of a foaming promoter and heat to uniformly foam the polylactic acid, and the polylactic acid is thermoformed to form a foamed material with uniform and compact pore diameter, and has high thermal deformation temperature, good heat resistance and strength.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a heat-resistant polylactic acid foaming thermal forming body.
Background
Polylactic acid (PLA) is a linear aliphatic thermoplastic polyester, has good physical and mechanical properties, processability, biocompatibility and biodegradability, is similar to general plastics such as polyethylene, polypropylene, polyphenylenes and the like in many properties, has wide market prospect, can be developed from biomass raw materials, and is a renewable resource. In the era of the shortage of fossil energy, the replacement of the traditional plastic developed from fossil energy such as petroleum by renewable and degradable materials has positive significance. Although polylactic acid has many advantages, it is undeniable that polylactic acid is a slightly expensive raw material for industry, and in order to reduce the price of polylactic acid products, the function of polylactic acid in replacing traditional plastics is fully exerted, and the foaming treatment of polylactic acid is a feasible means, however, because the melt strength of PLA is low, pure PLA is difficult to maintain the shape of foam during the cell growth stage, and the cells are easy to collapse, so that large-scale production of PLA still has a great challenge.
Disclosure of Invention
The invention aims to provide a preparation method of a heat-resistant polylactic acid foaming thermal forming body, wherein polylactic acid is thermally formed to form a foaming material with uniform and compact pore diameter, the thermal deformation temperature is high, and the foaming material has better heat resistance and strength.
In order to achieve the purpose, the invention provides the following technical scheme:
a heat-resistant polylactic acid foaming thermal forming body comprises the following raw materials in parts by mass: 80-100 parts of polylactic acid, 1.5-3 parts of trimethylolpropane triacrylate, 0.3-0.8 part of nano zinc oxide, 5-20 parts of glass fiber, 0.5-2 parts of a silane coupling agent, 2-5 parts of a foaming agent, 0.1-0.3 part of a foaming promoter and 400-500 parts of N, N-dimethylformamide;
the preparation method of the heat-resistant polylactic acid foaming thermal forming body comprises the following steps:
the method comprises the following steps: taking a silane coupling agent in parts by mass, adding absolute ethyl alcohol which is 100-150 times of the mass of the silane coupling agent, ultrasonically dispersing for 3-15 min at the power of 400W, and averagely dividing the dispersed silane coupling agent-absolute ethyl alcohol mixed solution into two parts according to the same volume, wherein the two parts are respectively marked as group A and group B;
step two: adding nano zinc oxide in parts by mass into the mixed solution of the group A, adding glass fiber in parts by mass into the mixed solution of the group B, stirring the group A and the group B for 2-5 hours in a water bath at 50-60 ℃, filtering, washing for 2-3 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 5-8 hours to obtain surface-modified zinc oxide and surface-modified fiber;
step three: adding anhydrous ethanol with the mass 50-80 times of that of the foaming agent and deionized water with the mass 10-20 times of that of the foaming agent into the foaming agent and the foaming promoter in parts by mass, stirring at the speed of 80-120 r/min for 30-60 min, and carrying out 400W power ultrasonic treatment for 30-60 min to obtain a foaming mixed solution;
step four: taking the polylactic acid in parts by weight, adding the N, N-dimethylformamide in parts by weight, and stirring to fully dissolve the polylactic acid to form a polylactic acid solution; adding 50-80 times of absolute ethyl alcohol by mass of trimethylolpropane triacrylate into trimethylolpropane triacrylate in parts by mass, adding surface-modified zinc oxide, carrying out ultrasonic dispersion for 5-20 min, mixing with a polylactic acid solution, carrying out ultrasonic dispersion for 20-30 min again, adding a foaming mixed solution, carrying out oil bath heating at 80-90 ℃, stirring at the speed of 80-120 r/min, and reacting for 8-12 h to obtain a polylactic acid foaming base solution;
step five: pouring the polylactic acid foaming base liquid into a mold, rapidly heating the mold at a target heating temperature of 140-250 ℃ for 5-30 min, cooling to room temperature, and demolding to obtain the heat-resistant polylactic acid foaming thermal molding body.
More preferably, the glass fibers are chopped glass fibers.
More preferably, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and phenylaminomethyltriethoxysilane.
Further preferably, the foaming agent is diisopropyl azodicarboxylate, nano potassium carbonate and diethyl azodicarboxylate, and the foaming agent is diisopropyl azodicarboxylate according to the mass ratio: nano potassium carbonate: diethyl azodicarboxylate = 1: 0.8-1.5: 1-2. Diisopropyl azodicarboxylate is orange oily liquid, is still stable at 240 ℃ when being heated independently, but can be activated by using heat stabilizers such as organic tin compounds, cadmium soaps, zinc soaps and the like, the decomposition temperature is reduced, the gas evolution is 200-350 ml/g at 100-200 ℃, the diisopropyl azodicarboxylate is easy to disperse in plastics, the decomposition product is odorless, nontoxic, colorless and pollution-free, and the foaming pores are uniform and compact; the nano potassium carbonate is an inorganic foaming agent, the decomposition product is mainly carbon dioxide, the decomposition temperature is about 270 ℃, the gas yield is high, and when the nano potassium carbonate is used for foaming a plastic product, the foaming is rapid; the decomposition temperature of the azodicarbonic acid diethyl ester is 110-120 ℃, the gas forming amount is about 190ml/g, the decomposition can be promoted under the action of metal salt, and the decomposition product is nontoxic and pollution-free.
Further preferably, the foaming promoter is dibutyltin and zinc stearate soap according to a mass ratio of 1: 1 are mixed.
More preferably, in the fourth step, when the polylactic acid is dissolved using the N, N-dimethylformamide solvent, the stirring speed is 50 to 120 r/min.
Preferably, in the fifth step, the amount of the polylactic acid foaming base liquid poured into the mold is that, calculated by volume, the volume of the polylactic acid foaming base liquid is one third to one half of the volume of the mold each time, and the rapid heating rate is 10-40 ℃/min.
Under the action of nano zinc oxide, a main chain of polylactic acid and trimethylolpropane triacrylate undergo hydrolysis reaction to form polylactic acid and trimethylolpropane which take hydroxyl or carboxyl as end groups, and then under the promoting action of nano zinc oxide, the polylactic acid and the trimethylolpropane triacrylate undergo transesterification reaction, so that three-arm star-shaped polylactic acid long chains are generated, when two three-arm star-shaped polylactic acid long chains are simultaneously gathered around the nano zinc oxide, the two three-arm star-shaped polylactic acid long chains can be overlapped or connected together through coordination and complexation with the nano zinc oxide, and further a branched polylactic acid with more complex structure is formed, and the reaction is shown in the following reaction equation:
the invention has the beneficial effects that:
1. the method comprises the steps of carrying out transesterification reaction on trimethylolpropane triacrylate and a polylactic acid main chain to enable polylactic acid to be converted from a linear structure to a branched structure, simultaneously adding glass fiber to jointly enhance the melt strength and the strain hardening strength of the polylactic acid composite material, adding a silane coupling agent to increase the compatibility and the bonding capacity of the glass fiber, nano zinc oxide and the polylactic acid material, decomposing nitrogen, carbon dioxide or water under the conditions of a foaming promoter and heat by using a chemical foaming agent as the foaming agent to uniformly foam the polylactic acid, and preparing a polylactic acid foaming thermal forming body in a heating mode.
2. Trimethylolpropane triacrylate is a trifunctional reaction monomer, as with polylactic acid molecular chains, ester groups can be broken and recombined under the action of water, heat and an accelerant to generate an ester exchange reaction, the polylactic acid and the trimethylolpropane triacrylate generate the ester exchange reaction under the action of nano zinc oxide to generate a branched chain compound, hydrophilic groups on the surface of the nano zinc oxide enable the polylactic acid macromolecular chains and micromolecular polyester-trimethylolpropane triacrylate to tend to gather on the surface of the polylactic acid macromolecular chains and micromolecular polyester-trimethylolpropane triacrylate, and under the coordination complexing action, the long-chain branched polylactic acid with a three-arm topological structure is obtained, and the strength of the polylactic acid and the finished product of the polylactic acid is enhanced.
3. The silane coupling agent is used for processing the nano zinc oxide and the glass fiber to obtain the nano zinc oxide and the glass fiber with surface modification, so that the nano zinc oxide, the glass fiber and polylactic acid molecules have good compatibility in the preparation process, the nano zinc oxide, the glass fiber and the polylactic acid molecules can be uniformly dispersed in a polylactic acid material, basic conditions are provided for further performing ester exchange on the polylactic acid and uniformly compounding the polylactic acid and the glass fiber, and the strength of the polylactic acid is uniformly enhanced.
4. The foaming material is a chemical foaming agent, can be decomposed at a lower temperature under the action of heating and a foaming promoter to release gas for foaming, the decomposition products are nitrogen, carbon dioxide, water and the like, and the foaming material is non-toxic, colorless and pollution-free, the chemical foaming agent is uniformly mixed in the material to be foamed, and the foaming material with uniform and compact pore diameter can be formed by accurately controlling the temperature and the heating rate.
5. The polylactic acid foaming base liquid is poured into a mould, the mould is rapidly heated to decompose a foaming agent, gas is generated to foam a polylactic acid material, meanwhile, under the action of heat, the solvent is evaporated, the polylactic acid is thermoformed, the thermoforming and the thermal foaming are simultaneously carried out, the method and the operation are simple, complex production equipment is not needed, foamed products with different specifications can be produced by changing the mould, and the large-scale production is facilitated.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A heat-resistant polylactic acid foaming thermal forming body comprises the following raw materials in parts by mass: 100 parts of polylactic acid, 3 parts of trimethylolpropane triacrylate, 0.8 part of nano zinc oxide, 20 parts of glass fiber, 2 parts of a silane coupling agent, 5 parts of a foaming agent, 0.3 part of a foaming promoter and 500 parts of N, N-dimethylformamide;
the preparation method of the heat-resistant polylactic acid foaming thermal forming body comprises the following steps:
the method comprises the following steps: taking a silane coupling agent in parts by mass, adding absolute ethyl alcohol which is 150 times of the mass of the silane coupling agent, ultrasonically dispersing for 15min at the power of 400W, and averagely dividing the dispersed silane coupling agent-absolute ethyl alcohol mixed solution into two parts according to the same volume, wherein the two parts are respectively marked as a group A and a group B;
step two: adding nano zinc oxide in parts by mass into the mixed solution of the group A, adding glass fiber in parts by mass into the mixed solution of the group B, stirring the group A and the group B for 5 hours in a water bath at 60 ℃, filtering, washing for 3 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 8 hours to obtain surface-modified zinc oxide and surface-modified fiber;
step three: adding anhydrous ethanol and deionized water into a foaming agent and a foaming promoter in parts by weight, wherein the anhydrous ethanol is 80 times the mass of the foaming agent, and the deionized water is 20 times the mass of the foaming agent, stirring at a speed of 120r/min for 60min, and performing 400W power ultrasound for 60min to obtain a foaming mixed solution;
step four: taking the polylactic acid in parts by weight, adding the N, N-dimethylformamide in parts by weight, and stirring to fully dissolve the polylactic acid to form a polylactic acid solution; adding 80 times of absolute ethyl alcohol in mass of trimethylolpropane triacrylate into trimethylolpropane triacrylate in mass parts, adding surface-modified zinc oxide, carrying out ultrasonic dispersion for 20min, mixing with a polylactic acid solution, carrying out ultrasonic dispersion for 30min again, adding a foaming mixed solution, heating in an oil bath at 90 ℃, stirring at the speed of 120r/min, and reacting for 12h to obtain a polylactic acid foaming base solution;
step five: pouring the polylactic acid foaming base liquid into a mould, quickly heating the mould at the target heating temperature of 250 ℃ for 30min, cooling to room temperature, and demoulding to obtain the heat-resistant polylactic acid foaming thermal forming body.
Example 2
A heat-resistant polylactic acid foaming thermal forming body comprises the following raw materials in parts by mass: 80 parts of polylactic acid, 1.5 parts of trimethylolpropane triacrylate, 0.3 part of nano zinc oxide, 5 parts of glass fiber, 0.5 part of silane coupling agent, 2 parts of foaming agent, 0.1 part of foaming promoter and 400 parts of N, N-dimethylformamide;
the preparation method of the heat-resistant polylactic acid foaming thermal forming body comprises the following steps:
the method comprises the following steps: taking a silane coupling agent in parts by mass, adding absolute ethyl alcohol which is 100 times of the mass of the silane coupling agent, ultrasonically dispersing for 3min at the power of 400W, and averagely dividing the dispersed silane coupling agent-absolute ethyl alcohol mixed solution into two parts according to the same volume, wherein the two parts are respectively marked as a group A and a group B;
step two: adding nano zinc oxide in parts by mass into the mixed solution of the group A, adding glass fiber in parts by mass into the mixed solution of the group B, stirring the group A and the group B for 2 hours in a water bath at 50 ℃, filtering, washing for 2 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 5 hours to obtain surface-modified zinc oxide and surface-modified fiber;
step three: adding anhydrous ethanol 50 times the mass of the foaming agent and deionized water 10 times the mass of the foaming agent into the foaming agent and the foaming promoter in parts by mass, stirring at the speed of 80r/min for 30min, and carrying out ultrasonic treatment at the power of 400W for 30min to obtain a foaming mixed solution;
step four: taking the polylactic acid in parts by weight, adding the N, N-dimethylformamide in parts by weight, and stirring to fully dissolve the polylactic acid to form a polylactic acid solution; adding absolute ethyl alcohol with the mass 50 times that of trimethylolpropane triacrylate into trimethylolpropane triacrylate in parts by mass, adding surface-modified zinc oxide, carrying out ultrasonic dispersion for 5min, mixing with a polylactic acid solution, carrying out ultrasonic dispersion for 20min again, adding a foaming mixed solution, heating in an oil bath at 80 ℃, stirring at the speed of 80r/min, and reacting for 8h to obtain a polylactic acid foaming base solution;
step five: pouring the polylactic acid foaming base liquid into a mould, quickly heating the mould at the target heating temperature of 140 ℃ for 5min, cooling to room temperature, and demoulding to obtain the heat-resistant polylactic acid foaming thermal forming body.
Example 3
A heat-resistant polylactic acid foaming thermal forming body comprises the following raw materials in parts by mass: 90 parts of polylactic acid, 2 parts of trimethylolpropane triacrylate, 0.5 part of nano zinc oxide, 10 parts of glass fiber, 1 part of silane coupling agent, 3 parts of foaming agent, 0.2 part of foaming promoter and 450 parts of N, N-dimethylformamide;
the preparation method of the heat-resistant polylactic acid foaming thermal forming body comprises the following steps:
the method comprises the following steps: taking a silane coupling agent in parts by mass, adding absolute ethyl alcohol which is 120 times of the mass of the silane coupling agent, ultrasonically dispersing for 10min at the power of 400W, and averagely dividing the dispersed silane coupling agent-absolute ethyl alcohol mixed solution into two parts according to the same volume, wherein the two parts are respectively marked as a group A and a group B;
step two: adding nano zinc oxide in parts by mass into the mixed solution of the group A, adding glass fiber in parts by mass into the mixed solution of the group B, stirring the group A and the group B for 3 hours in a water bath at 55 ℃, filtering, washing for 3 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 6 hours to obtain surface-modified zinc oxide and surface-modified fiber;
step three: adding anhydrous ethanol 60 times the mass of the foaming agent and deionized water 15 times the mass of the foaming agent into the foaming agent and the foaming promoter in parts by mass, stirring at the speed of 100r/min for 50min, and performing ultrasonic treatment at the power of 400W for 40min to obtain a foaming mixed solution;
step four: taking the polylactic acid in parts by weight, adding the N, N-dimethylformamide in parts by weight, and stirring to fully dissolve the polylactic acid to form a polylactic acid solution; taking trimethylolpropane triacrylate in parts by mass, adding absolute ethyl alcohol in an amount which is 60 times that of the trimethylolpropane triacrylate, adding surface-modified zinc oxide, carrying out ultrasonic dispersion for 15min, then mixing with a polylactic acid solution, carrying out ultrasonic dispersion for 25min again, adding a foaming mixed solution, heating in an oil bath at 85 ℃, stirring at the speed of 100r/min, and reacting for 10h to obtain a polylactic acid foaming base solution;
step five: pouring the polylactic acid foaming base liquid into a mould, quickly heating the mould at the target heating temperature of 200 ℃ for 20min, cooling to room temperature, and demoulding to obtain the heat-resistant polylactic acid foaming thermal forming body.
The heat distortion temperature of the heat-resistant polylactic acid foaming thermal forming body prepared in the embodiment is detected according to the standard GB/T1633-2000, the thickness of a sample is 5mm, the side length is 10mm multiplied by 10mm, the force of 10N is used, and the heating speed is 120 ℃/h; the strength of the moulded body is tested for its compression resistance with reference to standard BB 0007-1995; average cell diameter the solid material pore size distribution and porosity was determined according to the standard GB/T21650.1-2008 mercury porosimetry and gas adsorption method part 1: the mercury intrusion test gave the results shown in the table:
| example 1 | Example 2 | Example 3 | |
| Heat distortion temperature (. degree. C.) | 112.3 | 117.5 | 115.6 |
| 1.5Kg load percent deformation (%) | 1.0 | 0.7 | 0.9 |
| Average pore diameter (μm) | 17.6 | 29.5 | 25.7 |
As shown in the table, the heat-resistant polylactic acid foaming thermal forming body prepared by the method has high thermal deformation temperature, small deformation percentage under the load of 1.5Kg, and better heat resistance and strength.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The heat-resistant polylactic acid foaming thermal forming body is characterized by comprising the following raw materials in parts by mass: 80-100 parts of polylactic acid, 1.5-3 parts of trimethylolpropane triacrylate, 0.3-0.8 part of nano zinc oxide, 5-20 parts of glass fiber, 0.5-2 parts of a silane coupling agent, 2-5 parts of a foaming agent, 0.1-0.3 part of a foaming promoter and 400-500 parts of N, N-dimethylformamide;
the preparation method of the heat-resistant polylactic acid foaming thermal forming body comprises the following steps:
the method comprises the following steps: taking a silane coupling agent in parts by mass, adding absolute ethyl alcohol which is 100-150 times of the mass of the silane coupling agent, ultrasonically dispersing for 3-15 min at the power of 400W, and averagely dividing the dispersed silane coupling agent-absolute ethyl alcohol mixed solution into two parts according to the same volume, wherein the two parts are respectively marked as group A and group B;
step two: adding nano zinc oxide in parts by mass into the mixed solution of the group A, adding glass fiber in parts by mass into the mixed solution of the group B, stirring the group A and the group B in a water bath at 50-60 ℃ for 2-5 hours, filtering, washing with absolute ethyl alcohol for 2-3 times, and drying in an oven at 80 ℃ for 5-8 hours to obtain surface-modified zinc oxide and surface-modified fiber;
step three: adding anhydrous ethanol with the mass 50-80 times of that of the foaming agent and deionized water with the mass 10-20 times of that of the foaming agent into the foaming agent and the foaming promoter in parts by mass, stirring at the speed of 80-120 r/min for 30-60 min, and carrying out 400W power ultrasonic treatment for 30-60 min to obtain a foaming mixed solution;
step four: taking the polylactic acid in parts by weight, adding the N, N-dimethylformamide in parts by weight, and stirring to fully dissolve the polylactic acid to form a polylactic acid solution; adding 50-80 times of absolute ethyl alcohol by mass of trimethylolpropane triacrylate into trimethylolpropane triacrylate in parts by mass, adding surface-modified zinc oxide, carrying out ultrasonic dispersion for 5-20 min, mixing with a polylactic acid solution, carrying out ultrasonic dispersion for 20-30 min again, adding a foaming mixed solution, carrying out oil bath heating at 80-90 ℃, stirring at the speed of 80-120 r/min, and reacting for 8-12 h to obtain a polylactic acid foaming base solution;
step five: pouring the polylactic acid foaming base liquid into a mold, rapidly heating the mold at a target heating temperature of 140-250 ℃ for 5-30 min, cooling to room temperature, and demolding to obtain the heat-resistant polylactic acid foaming thermal molding body.
2. The heat-resistant polylactic acid foamed thermal molded body according to claim 1, wherein: the glass fiber is chopped glass fiber.
3. The heat-resistant polylactic acid foamed thermal molded body according to claim 1, wherein the silane coupling agent is one or more of γ -aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, γ -methacryloxypropyltrimethoxysilane, and phenylaminomethyltriethoxysilane.
4. The heat-resistant polylactic acid foamed thermal molded body according to claim 1, wherein: the foaming agent is diisopropyl azodicarboxylate, nano potassium carbonate and diethyl azodicarboxylate which are mixed according to the mass ratio: nano potassium carbonate: diethyl azodicarboxylate = 1: 0.8-1.5: 1-2.
5. The heat-resistant polylactic acid foamed thermal molded body according to claim 1, wherein: the foaming accelerant is prepared from dibutyltin and zinc stearate soap according to a mass ratio of 1: 1 are mixed.
6. The heat-resistant polylactic acid foamed thermoformed article according to claim 1, wherein: in the fourth step, when the polylactic acid is dissolved by using the N, N-dimethylformamide solvent, the stirring speed is 50-120 r/min.
7. The heat-resistant polylactic acid foamed thermal molded body according to claim 1, wherein: in the fifth step, the amount of the polylactic acid foaming base liquid poured into the mold is that, according to the volume, the volume of the polylactic acid foaming base liquid is one third to one half of the volume of the mold each time, and the rapid heating rate is 10-40 ℃/min.
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| CN115490907A (en) * | 2022-11-02 | 2022-12-20 | 南宁斤美新材料科技有限公司 | Preparation method of high-temperature-resistant oil-stain-resistant composite plastic |
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| CN102408688A (en) * | 2010-09-26 | 2012-04-11 | 比亚迪股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN108341940A (en) * | 2018-02-12 | 2018-07-31 | 贵州大学 | A kind of preparation method of the efficiently long chain branching polylactic without gel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102408688A (en) * | 2010-09-26 | 2012-04-11 | 比亚迪股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN108341940A (en) * | 2018-02-12 | 2018-07-31 | 贵州大学 | A kind of preparation method of the efficiently long chain branching polylactic without gel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115490907A (en) * | 2022-11-02 | 2022-12-20 | 南宁斤美新材料科技有限公司 | Preparation method of high-temperature-resistant oil-stain-resistant composite plastic |
| CN115490907B (en) * | 2022-11-02 | 2023-07-28 | 揭阳市冠业塑料制品有限公司 | Preparation method of high Wen Fangyou dirt-resistant composite plastic |
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