CN112852131A - High-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and preparation method thereof - Google Patents
High-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN112852131A CN112852131A CN202110141221.0A CN202110141221A CN112852131A CN 112852131 A CN112852131 A CN 112852131A CN 202110141221 A CN202110141221 A CN 202110141221A CN 112852131 A CN112852131 A CN 112852131A
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- polylactic acid
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 80
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 80
- 159000000003 magnesium salts Chemical class 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 44
- 239000002667 nucleating agent Substances 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 27
- 239000003086 colorant Substances 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 239000011324 bead Substances 0.000 claims description 19
- -1 poly terephthalic acid-adipic acid-butanediol ester Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 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 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 3
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 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 claims description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical group CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- SXADIBFZNXBEGI-UHFFFAOYSA-N phosphoramidous acid Chemical compound NP(O)O SXADIBFZNXBEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 description 18
- 239000004033 plastic Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 7
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- ZLPOWNUXKJLCFE-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione hexanedioic acid terephthalic acid Chemical compound C1(C2=CC=C(C(=O)OCCCCO1)C=C2)=O.C(C2=CC=C(C(=O)O)C=C2)(=O)O.C(CCCCC(=O)O)(=O)O ZLPOWNUXKJLCFE-UHFFFAOYSA-N 0.000 description 1
- JQOQDMSGBHAUGS-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1.O=C1OCCCCOC(=O)C2=CC=C1C=C2 JQOQDMSGBHAUGS-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002699 waste material Substances 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
- 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
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and a preparation method thereof belong to the technical field of biodegradable plastics and preparation thereof. The method comprises the following steps: taking 40.9-79.1% of polylactic acid, 10-30% of magnesium salt whisker, 5-10% of hollow glass microsphere, 5-15% of toughening agent, 0.1-0.3% of nucleating agent, 0.2-0.8% of lubricant, 0.1-1% of auxiliary agent and 0.5-2% of coloring agent as raw materials, and drying the polylactic acid; putting the dried polylactic acid, the toughening agent, the nucleating agent, the lubricant, the auxiliary agent and the coloring agent into a high-speed mixer and stirring; and putting the obtained mixture into a double-screw extruder, and cooling and granulating after the mixture is extruded by the double-screw extruder to obtain a finished product. The material has ideal heat resistance, dimensional stability, strength, rigidity and degradability; the strength, rigidity and heat resistance of the polylactic acid are improved; the product has high surface quality and good effect; the product is lighter.
Description
Technical Field
The invention belongs to the technical field of biodegradable plastics and preparation thereof, and particularly relates to a high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and a preparation method thereof.
Background
The high surface quality mentioned above means: since the molded and manufactured product has an excellent smooth surface, the molded product can be directly used without surface coating treatment such as polishing and painting, however, in order to improve the rigidity and strength of the biodegradable material, the prior art is often reinforced by adding mineral materials such as glass fiber, etc., and the diameter ratio of the glass fiber is larger (in 10 μm or more), so that the appearance of the injection molded product is rough, and the injection molded product is difficult to directly use, and can only be used after the treatment such as polishing or painting. Plastics made of petrochemical raw materials are important basic materials and are widely applied in daily life, for example, with the increasing use amount of plastic packages, lunch boxes, expressages, cups, straws and the like, environmental pollution is more and more serious, particularly, marine environment pollution is more and more intensified, so that plastic wastes which are environmentally-friendly and cannot be naturally degraded become public hazards to natural environments including water areas.
In order to protect the environment where human beings rely on to live, biodegradable plastics such as polylactic acid derived from biological raw materials are gaining favor because the biodegradable plastics have properties close to those of common plastics, can be degraded into water and carbon dioxide again in natural environment, water area environment or composting environment after being discarded, can return to natural environment without causing secondary pollution, and can be widely used as degradable plastic bags, disposable plastic tableware, disposable plastic supplies of hotels and restaurants and express plastic packages in logistics industry.
However, when the polylactic acid plastic product is used as tableware such as chopsticks, problems such as insufficient rigidity and the glass fiber reinforcement which is the main method at present are exposed, but the glass fiber reinforcement is easy to warp and has rough surface, and the density of the final product is higher because the polylactic acid and the glass fiber are higher.
The Chinese patent CN106189136B recommends "a modified polylactic acid composite material and a manufacturing method and application thereof", the raw materials of the patent comprise: 15 to 30 parts of glass fiber, 5 to 15 parts of inorganic filler (hollow glass bead and/or hollow ceramic bead) and 48 to 78.6 parts of polylactic acid resin, and CN106433053B, wherein the patent is similar to the above-mentioned CN106189136B, the diameter of basalt fiber is more than 10 microns, which results in rough surface of the final product. In view of the foregoing, there is a need for improvement, and the technical solutions described below are made in this context.
Disclosure of Invention
The invention aims to provide a high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material with excellent flatness, toughness, strength and heat resistance, ideal rigidity and low density.
The invention also aims to provide a preparation method of the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material, which can ensure that the technical effect of the obtained high-surface-quality low-density magnesium salt whisker reinforced polylactic acid can be comprehensively embodied.
The invention is primarily aimed at completing the following tasks, and the magnesium salt whisker reinforced polylactic acid composite material with high surface quality and low density comprises the following raw materials in percentage by mass: 40.9-79.1% of polylactic acid, 10-30% of magnesium salt whisker, 5-10% of hollow glass microsphere, 5-15% of toughening agent, 0.1-0.3% of nucleating agent, 0.2-0.8% of lubricant, 0.1-1% of auxiliary agent and 0.5-2% of coloring agent.
A high surface quality low density magnesium salt whisker reinforced polylactic acid composite material, its raw materials make up according to the mass percent and match; 62% of polylactic acid, 20% of magnesium salt whisker, 5% of hollow glass microsphere, 10% of toughening agent, 0.1% of nucleating agent, 0.8% of lubricating agent, 0.1% of auxiliary agent and 2% of coloring agent.
A high surface quality low density magnesium salt whisker reinforced polylactic acid composite material, its raw materials make up according to the mass percent and match; 42.5 percent of polylactic acid, 30 percent of magnesium salt whisker, 10 percent of hollow glass microsphere, 15 percent of toughening agent, 0.3 percent of nucleating agent, 0.2 percent of lubricating agent, 1 percent of auxiliary agent and 1 percent of coloring agent.
A high surface quality low density magnesium salt whisker reinforced polylactic acid composite material, its raw materials make up according to the mass percent and match; 77.5 percent of polylactic acid, 10 percent of magnesium salt whisker, 6 percent of hollow glass microsphere, 5 percent of toughening agent, 0.2 percent of nucleating agent, 0.5 percent of lubricating agent, 0.3 percent of auxiliary agent and 0.5 percent of coloring agent.
In a specific embodiment of the invention, the polylactic acid has a melt index of 10-30g/10min, a purity of 98% or more and a density of 1.24g/cm3And the melting point is above 160 ℃.
In another specific embodiment of the invention, the magnesium salt whiskers are of the formula MgSO4 & 5Mg (OH)2 & 3H2O, the whiskers have an average diameter of less than 0.5 μm, an average length of 10-20 μm, and a density of 2.3g/cm3And a pH of 9; the toughening agent is poly terephthalic acid-adipic acid-butanediol ester (PBAT) and/or poly adipic acid-butanediol ester (PBS); the particle diameter D90 of the hollow glass bead is less than 50 mu m, and the density is less than 0.5g/cm3The compressive strength is more than 100MPa, and the wall thickness of the hollow glass bead is 1-2 μm; the melting index of the polybutylene terephthalate-adipate is 2-5g/10min and the melting point is 110-120 ℃, and the melting index of the polybutylene terephthalate-adipate is 4-20g/10min and the melting point is 110-120 ℃.
In another specific embodiment of the invention, the nucleating agent is one or a combination of more of superfine talcum powder with the diameter of less than 20 μm, sodium benzoate, sorbitol nucleating agent, organic sodium phosphate and potassium benzene sulfonate; the lubricant is pentaerythritol ester, fatty acid amide or alkane substance; the fatty acid amide is oleamide or ethylene bis stearamide, and the alkane substance is polyethylene wax; the auxiliary agent is a main antioxidant, an auxiliary antioxidant, hydroxybenzophenone, hydroxybenzotriazole or a metal ion passivator; the main antioxidant is an antioxidant 1010 or an antioxidant 1076; the secondary antioxidant is antioxidant 168 or phosphorous acid amide; the colorant is titanium dioxide, carbon black or carbon black master batch.
The invention also aims to complete the preparation method of the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material, which comprises the following steps:
A) preparing materials, namely taking the following raw materials in percentage by mass: 40.9-79.1% of polylactic acid, 10-30% of magnesium salt whisker, 5-10% of hollow glass microsphere, 5-15% of toughening agent, 0.1-0.3% of nucleating agent, 0.2-0.8% of lubricant, 0.1-1% of auxiliary agent and 0.5-2% of coloring agent, and drying the polylactic acid to obtain a raw material;
B) mixing, namely putting the dried polylactic acid, the toughening agent, the nucleating agent, the lubricant, the auxiliary agent and the coloring agent in the step A) into a high-speed mixer and stirring to obtain a mixture;
C) and (2) melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 40-44: 1 and the screw diameter of 65-75 mm, melt extrusion under the conditions of controlling the rotation speed and the extrusion temperature of the screw, feeding the magnesium salt whiskers in the step A) laterally in the fifth section of the double screw and feeding the hollow glass microspheres in the step A) laterally in the eighth section of the double screw in the melt extrusion process, and cooling and pelletizing the extruded mixture by the double-screw extruder to obtain the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material.
In another specific embodiment of the invention, the temperature of the drying in the step A) is 75-85 ℃, and the drying is carried out until the water content is less than 500 ppm; the stirring time in the step B) is 1-5 min.
In still another specific embodiment of the present invention, the screw rotation speed in step C) is controlled to 180-.
The technical scheme provided by the invention has the technical effects that: the polylactic acid, the magnesium salt whisker, the hollow glass bead, the flexibilizer, the nucleating agent, the lubricant and the auxiliary agentThe raw materials and the mass percentage of the colorant are reasonably selected, so that the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material can be ensured to be obtained, and the composite material also has ideal heat resistance, dimensional stability, strength, rigidity and degradability, and can meet the requirements of manufacturing products such as degradable chopsticks and degradable handles by an injection molding method; because the hollow glass beads are also inorganic substances, the strength, the rigidity and the heat resistance of the polylactic acid can be obviously improved; because the magnesium salt whisker is adopted, the problem of rough appearance caused by the introduction of glass fiber is solved, and the effect of high surface quality of the final product is fully reflected; meanwhile, the density of the hollow glass beads is less than 0.5g/cm3The density of the magnesium salt whisker is 2.3g/cm3The density of the polylactic acid is 1.24g/cm3Therefore, the density can be effectively reduced by adding the glass beads, and the product is lighter. The preparation method has simple process and no harsh process elements, and the obtained polylactic acid composite material can comprehensively embody the technical effects to meet the requirement of industrial scale-up production.
Detailed Description
Example 1:
A) preparing materials, namely preparing the following raw materials in percentage by mass (namely in percentage by mass): 62 percent of polylactic acid, 20 percent of magnesium salt whisker, 5 percent of hollow glass microsphere, 10 percent of toughening agent, 0.1 percent of nucleating agent, 0.8 percent of lubricating agent, 0.1 percent of auxiliary agent and 2 percent of coloring agent to obtain raw materials, wherein the polylactic acid in the step is the polylactic acid with the melt index of 10g/10min, the purity of more than 98 percent and the density of 1.24g/cm3And the melting point is above 160 ℃ and the injection molding grade L-lactide polylactic acid (PLLA) with the water content of less than 500ppm is dried at 85 ℃, the molecular formula of the magnesium salt whisker in the step is MgSO4 & 5Mg (OH)2 & 3H2O, the average diameter of the whisker is less than 0.5 μm, the average length is 15 μm, and the density is 2.3g/cm3The pH value is 9, the particle diameter D90 of the hollow glass bead in the step is less than 50 mu m, and the density is less than 0.5g/cm3The compressive strength is more than 100MPa, the wall thickness of the hollow glass bead is 1 mu m, and the toughening agent in the step has the melting index of 2-5g/10min and the melting pointThe lubricant is a mixture of 110-120 ℃ poly (butylene terephthalate-adipate-terephthalate) (PBAT) and 110-120 ℃ poly (butylene adipate-butylene terephthalate) (PBS) with the melt index of 4-20g/10min and the melting point of 110-120 ℃ which are mixed according to the same weight ratio, the nucleating agent in the step is a mixture of ultrafine talcum powder with the diameter of less than 20 mu m, sodium benzoate and sodium organophosphate which are mixed according to the same weight ratio, the lubricant in the step is pentaerythritol ester, the auxiliary agent in the step is a main antioxidant namely antioxidant 1010 (the antioxidant 1076 can also be used), and the colorant in the step is titanium dioxide;
B) mixing, namely putting the dried L-lactide polylactic acid (PLLA) obtained in the step A), a toughening agent, a nucleating agent, a lubricant, an auxiliary agent and a coloring agent into a high-speed mixer to be mixed for 5min to obtain a mixture;
C) melt extrusion (namely screw melt extrusion), putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 40: 1 and the diameter of 65mm, melt extrusion at the rotating speed of the screw of 600rpm and the extrusion temperature of 200 ℃, feeding the magnesium salt whisker obtained in the step A) into the double-screw extruder in the lateral direction in the fifth section (namely the five zone) of the double screw, feeding the hollow glass microsphere obtained in the step A) into the double-screw extruder in the lateral direction in the eighth section (namely the eight zone) of the double screw, cooling and granulating the mixture after melt extrusion by the double-screw extruder to obtain the magnesium salt whisker reinforced polylactic acid composite material (also called as plastic for short) with high surface quality and low density, wherein the magnesium salt whisker and the hollow glass microsphere are respectively fed into the fifth section and the eighth section of the double screw in the lateral direction in the step to avoid the breakage of the magnesium salt whisker, meanwhile, the hollow glass beads are added from the side direction, the spherical shape of the hollow glass can be easily kept in the molten plastic, and the phenomenon that the solid plastic particles are crushed to lose the advantage of hollow low density is avoided.
Example 2:
A) preparing materials, namely preparing the following raw materials in percentage by mass (namely in percentage by mass): 42.5 percent of polylactic acid, 30 percent of magnesium salt whisker, 10 percent of hollow glass microsphere, 15 percent of flexibilizer, 0.3 percent of nucleating agent, 0.2 percent of lubricant, 1 percent of auxiliary agent and 1 percent of colorant to obtain the raw materials, wherein in the stepThe polylactic acid has a melt index of 30g/10min, a purity of more than 98 percent and a density of 1.24g/cm3And the melting point is above 160 ℃ and the injection molding grade L-lactide polylactic acid (PLLA) with the water content of less than 500ppm is dried at 80 ℃, the molecular formula of the magnesium salt whisker in the step is MgSO4 & 5Mg (OH)2 & 3H2O, the average diameter of the whisker is less than 0.5 μm, the average length is 20 μm, and the density is 2.3g/cm3The pH value is 9, the particle diameter D90 of the hollow glass bead in the step is less than 50 mu m, and the density is less than 0.5g/cm3The compression strength is more than 100MPa, the wall thickness of the hollow glass beads is 2 microns, the toughening agent in the step is poly terephthalic acid-butylene adipate (PBAT) with the melting index of 2-5g/10min and the melting point of 110-120 ℃, the nucleating agent in the step is sorbitol nucleating agent with the diameter of less than 20 microns, the lubricant in the step is oleamide, the auxiliary agent in the step is antioxidant 168 (phosphite amide can also be used), and the colorant in the step is carbon black;
B) mixing, namely putting the dried L-lactide polylactic acid (PLLA) obtained in the step A), a toughening agent, a nucleating agent, a lubricant, an auxiliary agent and a coloring agent into a high-speed mixer to be mixed for 1min to obtain a mixture;
C) melt extrusion (namely screw melt extrusion), putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 44: 1 and the diameter of 70mm, melt extrusion at the rotating speed of 180rpm and the extrusion temperature of 220 ℃, feeding the magnesium salt whisker obtained in the step A) into the double-screw extruder in the lateral direction in the fifth section (namely the five zone) of the double screw, feeding the hollow glass microsphere obtained in the step A) into the double-screw extruder in the lateral direction in the eighth section (namely the eight zone) of the double screw, cooling and granulating the mixture after melt extrusion by the double-screw extruder to obtain the magnesium salt whisker reinforced polylactic acid composite material (also called as plastic for short) with high surface quality and low density, wherein the magnesium salt whisker and the hollow glass microsphere are respectively fed into the fifth section and the eighth section of the double screw in the lateral direction in the step to avoid the breakage of the magnesium salt whisker, meanwhile, the hollow glass beads are added from the side direction, the spherical shape of the hollow glass can be easily kept in the molten plastic, and the phenomenon that the solid plastic particles are crushed to lose the advantage of hollow low density is avoided.
Example 3:
A) preparing materials, namely preparing the following raw materials in percentage by mass (namely in percentage by mass): 77.5 percent of polylactic acid, 10 percent of magnesium salt whisker, 6 percent of hollow glass microsphere, 5 percent of flexibilizer, 0.2 percent of nucleating agent, 0.5 percent of lubricant, 0.3 percent of auxiliary agent and 0.5 percent of colorant to obtain the raw materials, wherein the polylactic acid in the step is the polylactic acid with the melt index of 20g/10min, the purity of more than 98 percent and the density of 1.24g/cm3And the melting point is above 160 ℃ and the injection molding grade L-lactide polylactic acid (PLLA) with the water content of less than 500ppm is dried at 75 ℃, the molecular formula of the magnesium salt whisker in the step is MgSO4 & 5Mg (OH)2 & 3H2O, the average diameter of the whisker is less than 0.5 μm, the average length is 10 μm, and the density is 2.3g/cm3The pH value is 9, the particle diameter D90 of the hollow glass bead in the step is less than 50 mu m, and the density is less than 0.5g/cm3The compression strength is more than 100MPa, the wall thickness of the hollow glass microspheres is 1.5 microns, the toughening agent in the step is poly (butylene adipate-co-glycol) (PBS) with the melting index of 4-20g/10min and the melting point of 110-120 ℃, the nucleating agent in the step is a mixture of potassium benzene sulfonate with the diameter of less than 20 microns and superfine talcum powder which are mixed according to the same weight ratio, the lubricating agent in the step is polyethylene wax, the auxiliary agent in the step is hydroxybenzotriazole (or phosphorous acid amide can be used), and the coloring agent in the step is carbon black master batch;
B) mixing, namely putting the dried L-lactide polylactic acid (PLLA) obtained in the step A), a toughening agent, a nucleating agent, a lubricant, an auxiliary agent and a coloring agent into a high-speed mixer to be mixed for 3min to obtain a mixture;
C) melt extrusion (namely screw melt extrusion), putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 42: 1 and the diameter of 75mm, melt extrusion at the rotating speed of 400rpm and the extrusion temperature of 160 ℃, feeding the magnesium salt whisker obtained in the step A) into the double-screw extruder in the lateral direction in the fifth section (namely the five zone) of the double screw, feeding the hollow glass microsphere obtained in the step A) into the double-screw extruder in the lateral direction in the eighth section (namely the eight zone) of the double screw, cooling and granulating the mixture after melt extrusion by the double-screw extruder to obtain the magnesium salt whisker reinforced polylactic acid composite material (also called as plastic for short) with high surface quality and low density, wherein the magnesium salt whisker and the hollow glass microsphere are respectively fed into the fifth section and the eighth section of the double screw in the lateral direction in the step to avoid the breakage of the magnesium salt whisker, meanwhile, the hollow glass beads are added from the side direction, the spherical shape of the hollow glass can be easily kept in the molten plastic, and the phenomenon that the solid plastic particles are crushed to lose the advantage of hollow low density is avoided.
Comparative example 1:
the glass fiber is produced and sold by China megalite glass fiber company Limited, and the model is 534A.
Comparative example 2:
the talcum powder is HYT-04C, has silicon content of above 60%, and average particle diameter of 0.75 μm.
The data obtained by comparing examples 1 to 3 with comparative examples 1 and 2 according to the invention are shown in the following table:
the evaluation method comprises the following steps:
drying the particles granulated by the double screw, drying for 4-8 hours under the drying condition of 80 ℃, then putting the particles into an injection molding machine, performing injection molding by adopting an ISO 294 standard mold, and simultaneously performing surface roughness evaluation by utilizing a flat plate, wherein the evaluation is divided into three grades of good, general and rough. Other mechanical and thermal test criteria are as follows:
| test items | Test method |
| Mechanical properties | |
| Tensile breaking strength | ISO 527-1/-2 |
| Elongation at tensile break | ISO 527-1/-2 |
| Bending strength | ISO 178 |
| Flexural modulus | ISO 178 |
| Notched izod impact strength 23 deg.c | ISO 180/1eA |
| Thermal performance | |
| Heat distortion temperature (0.45MPa) | ISO 75 |
| Others | |
| Density of | ISO 1183 |
Compared with the test data and the rough surface, the product added with the magnesium salt whisker and the hollow glass bead has higher bending modulus, lower density and good surface quality. The glass fiber product has the highest rigidity but has a rough surface. The talcum powder product has the best surface quality and is lack of rigidity. Therefore, the invention solves the problems of surface quality, rigidity, toughness, heat resistance and size stabilizer of polylactic acid products, so that the polylactic acid degradable plastic products can be fully applied to injection molding such as degradable chopsticks, degradable handles and the like, and the application range of the degradable polylactic acid plastic is greatly expanded. The manufacturing method of the invention has simple process.
Claims (10)
1. A high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material is characterized by comprising the following raw materials in percentage by mass: 40.9-79.1% of polylactic acid, 10-30% of magnesium salt whisker, 5-10% of hollow glass microsphere, 5-15% of toughening agent, 0.1-0.3% of nucleating agent, 0.2-0.8% of lubricant, 0.1-1% of auxiliary agent and 0.5-2% of coloring agent.
2. The high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material as claimed in claim 1, which is characterized in that the raw materials comprise the following components in percentage by mass; 62% of polylactic acid, 20% of magnesium salt whisker, 5% of hollow glass microsphere, 10% of toughening agent, 0.1% of nucleating agent, 0.8% of lubricating agent, 0.1% of auxiliary agent and 2% of coloring agent.
3. The high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material as claimed in claim 1, which is characterized in that the raw materials comprise the following components in percentage by mass; 42.5 percent of polylactic acid, 30 percent of magnesium salt whisker, 10 percent of hollow glass microsphere, 15 percent of toughening agent, 0.3 percent of nucleating agent, 0.2 percent of lubricating agent, 1 percent of auxiliary agent and 1 percent of coloring agent.
4. The high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material as claimed in claim 1, which is characterized in that the raw materials comprise the following components in percentage by mass; 77.5 percent of polylactic acid, 10 percent of magnesium salt whisker, 6 percent of hollow glass microsphere, 5 percent of toughening agent, 0.2 percent of nucleating agent, 0.5 percent of lubricating agent, 0.3 percent of auxiliary agent and 0.5 percent of coloring agent.
5. The high surface quality low density magnesium salt whisker reinforced polylactic acid composite material of any one of claims 1 to 4, wherein the polylactic acid has a melt index of 10-30g/10min, a purity of 98% or more, and a density of 1.24g/cm3And the melting point is above 160 ℃.
6. A high surface quality low density magnesium salt whisker reinforced polylactic acid composite material as claimed in any one of claims 1 to 4, wherein said magnesium salt whisker is of the formula MgSO4 seed 5Mg (OH)2 seed 3H2O, the whisker has an average diameter of less than 0.5 μm, an average length of 10 to 20 μm and a density of 2.3g/cm3And a pH of 9; the toughening agent is poly terephthalic acid-adipic acid-butanediol ester and/or poly adipic acid-butanediol ester; the particle diameter D90 of the hollow glass bead is less than 50 mu m, and the density is less than 0.5g/cm3The compressive strength is more than 100MPa, and the wall thickness of the hollow glass bead is 1-2 μm; the melting index of the polybutylene terephthalate-adipate is 2-5g/10min and the melting point is 110-120 ℃, and the melting index of the polybutylene terephthalate-adipate is 4-20g/10min and the melting point is 110-120 ℃.
7. The high surface quality low density magnesium salt whisker reinforced polylactic acid composite material of any one of claims 1 to 4, wherein the nucleating agent is one or a combination of more of superfine talcum powder with the diameter of less than 20 μm, sodium benzoate, sorbitol nucleating agent, organic sodium phosphate and potassium benzene sulfonate; the lubricant is pentaerythritol ester, fatty acid amide or alkane substance; the fatty acid amide is oleamide or ethylene bis stearamide, and the alkane substance is polyethylene wax; the auxiliary agent is a main antioxidant, an auxiliary antioxidant, hydroxybenzophenone, hydroxybenzotriazole or a metal ion passivator; the main antioxidant is an antioxidant 1010 or an antioxidant 1076; the secondary antioxidant is antioxidant 168 or phosphorous acid amide; the colorant is titanium dioxide, carbon black or carbon black master batch.
8. The preparation method of the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material as claimed in claim 1, characterized by comprising the following steps:
A) preparing materials, namely taking the following raw materials in percentage by mass: 40.9-79.1% of polylactic acid, 10-30% of magnesium salt whisker, 5-10% of hollow glass microsphere, 5-15% of toughening agent, 0.1-0.3% of nucleating agent, 0.2-0.8% of lubricant, 0.1-1% of auxiliary agent and 0.5-2% of coloring agent, and drying the polylactic acid to obtain a raw material;
B) mixing, namely putting the dried polylactic acid, the toughening agent, the nucleating agent, the lubricant, the auxiliary agent and the coloring agent in the step A) into a high-speed mixer and stirring to obtain a mixture;
C) and (2) melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 40-44: 1 and the screw diameter of 65-75 mm, melt extrusion under the conditions of controlling the rotation speed and the extrusion temperature of the screw, feeding the magnesium salt whiskers in the step A) laterally in the fifth section of the double screw and feeding the hollow glass microspheres in the step A) laterally in the eighth section of the double screw in the melt extrusion process, and cooling and pelletizing the extruded mixture by the double-screw extruder to obtain the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material.
9. The method for preparing the high-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material according to claim 8, wherein the drying temperature in the step A) is 75-85 ℃, and the drying is carried out until the water content is less than 500 ppm; the stirring time in the step B) is 1-5 min.
10. The method for preparing the magnesium salt whisker reinforced polylactic acid composite material with high surface quality and low density as claimed in claim 8, wherein the screw rotation speed is controlled to be 180-600rpm in step C), and the screw extrusion temperature is controlled to be 160-220 ℃.
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