CN112175339A - Polymer material and preparation method thereof - Google Patents
Polymer material and preparation method thereof Download PDFInfo
- Publication number
- CN112175339A CN112175339A CN202011030530.2A CN202011030530A CN112175339A CN 112175339 A CN112175339 A CN 112175339A CN 202011030530 A CN202011030530 A CN 202011030530A CN 112175339 A CN112175339 A CN 112175339A
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- China
- Prior art keywords
- polymer
- parts
- polymer material
- antioxidant
- expandable microspheres
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- 239000002861 polymer material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000103 Expandable microsphere Polymers 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000011256 inorganic filler Substances 0.000 claims abstract description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 17
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000001746 injection moulding Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims description 34
- 239000004743 Polypropylene Substances 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000005187 foaming Methods 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 239000004793 Polystyrene Substances 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 10
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound 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 4
- 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 4
- 239000000843 powder Substances 0.000 claims description 4
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 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 compound 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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 229920005669 high impact polystyrene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 239000004797 high-impact polystyrene Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229940083159 ethylene distearamide Drugs 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000011056 performance test Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000013585 weight reducing agent 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C08J9/0028—Use of organic additives containing nitrogen
-
- 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
- C08J9/0038—Use of organic additives containing phosphorus
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/0066—Use of inorganic 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a polymer material and a preparation method thereof. The polymer material comprises polymer material particles, expandable microspheres, inorganic filler and the like. The preparation method comprises the following steps: uniformly mixing polymer material particles, inorganic filler, compatilizer, interface modifier, lubricant and antioxidant in proportion, and extruding and drawing the mixture by a double-screw extruder to obtain modified polymer master batches; the modified polymer particles and the expandable microspheres are blended, and a single-screw injection molding machine is utilized to prepare the low-density sprayable polymer composite material. Under the condition of ensuring the strength of the polymer material, the invention effectively improves the buckling deformation of the polymer material and the density of the polymer material, and leads the surface of the material to be rougher, thereby improving the wetting ability and enhancing the sprayability. The surface of the expandable microsphere has more active groups, and the hyperbranched interface modification auxiliary agent is combined, so that the polarity of the surface of the polymer is increased, and the sprayability of the polymer is improved.
Description
Technical Field
The invention relates to a low-density sprayable polymer material and a preparation method thereof, belonging to the field of plastic modification.
Background
At present, many polymer materials have good physical properties, such as polypropylene, polyethylene, polystyrene, and the like, and are widely used in various industries such as household appliances, automobiles, garden furniture, and the like.
However, it is known that these polymer materials are all nonpolar materials, and the adhesion of these polymer materials to polar materials such as paint and coating is very poor, and when these products are coated, it is usually necessary to treat the surface of the product with dichloroethane, plasma, flame, super strong water, etc. to make the surface of the product polar, so as to improve the adhesion of the coating and paint, but these methods all have certain limitations, such as easy pollution, high equipment cost, low efficiency, etc.
The expandable microsphere is a novel physical foaming agent, is shaped like a balloon, and consists of a thermoplastic shell and a volatile gas solvent, wherein the shell is usually made of an acrylic copolymer and an acrylonitrile copolymer, and the volatile gas solvent is mainly made of hydrocarbons such as isobutane or isopentane and the like. After heating, the internal solvent is strongly gasified, so that the volume of the polymer shell is severely expanded to 80-100 times, and the polymer shell can be solidified after low-temperature cooling, and is the only dense-pore expanding agent in the world. The additive is widely used in different fields of soles, plasticine, wallpaper printing, paint and the like at present, but is not used in modified plastics in a large scale, products are continuously updated along with the development of expandable microsphere technology at present, the temperature resistance of the product can reach more than 265 ℃ at most aiming at different temperature-resistant products with different foaming ratios at present, CN108912384A discloses an ultrahigh-temperature expandable thermoplastic microsphere and a preparation method and application thereof, the ultrahigh-temperature expandable thermoplastic microsphere comprises a thermoplastic shell and an expandable substance wrapped in the thermoplastic shell, the thermoplastic shell comprises a polymer which is obtained by the following monomer polymerization reaction and adopts a surface treating agent and is subjected to surface treatment: (1) acrylate, (2) nitrile monomer, (3) carboxyl-containing active monomer with polymerizable double bond, (4) active monomer with amido and (5) active monomer with hydroxyl. The invention has high initial temperature (180210 ℃), high maximum foaming temperature (250280 ℃) and excellent heat resistance and gas barrier property, has excellent foaming performance at high temperature and can meet the application requirements of related fields.
In recent years, it has been reported that the polarity of such polymers is improved by adding one or more polar materials to achieve the sprayability of the polymer materials, for example, EP0481789a2, CN1235989A, CN101735511A, and the like, the polar materials are maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, hydroxyl terminated polybutadiene, polyurethane elastomer, hydroxybutyl vinyl acrylate, and the like to enhance the polarity of the polymer materials. However, most of the polar materials reported so far have poor compatibility with the elastomer component with toughening effect in the grafted and modified polyolefin obtained by grafting a polar monomer with polyolefin, thereby leading to the unsatisfactory performance of the composite material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prior polymer material with low polarity has the technical problems of poor surface adhesion and poor spraying performance.
In order to solve the technical problem, the invention provides a polymer material which is characterized by comprising 70-90 parts of polymer material particles, 1-8 parts of expandable microspheres and 5-40 parts of inorganic filler by weight.
Preferably, the polymer material particles include at least one of Polyethylene (PE), polypropylene (PP), Polystyrene (PS), and styrene thermoplastic elastomer (SBS).
More preferably, the polyethylene is at least one of Low Density Polyethylene (LDPE) and High Density Polyethylene (HDPE), and the melt flow rate is between 1 and 50g/10min under the test condition of 190 ℃/2.16 kg; the polypropylene is one or more of homopolymerized polypropylene and copolymerized polypropylene, and the melt flow rate is between 1 and 60g/10min under the test condition of 230 ℃/2.16 kg; the polystyrene is at least one of common Polystyrene (PS) and High Impact Polystyrene (HIPS), and the melt flow rate is between 1 and 100g/10min under the test condition of 230 ℃/1.2 kg; the styrene thermoplastic elastomer has the mass fraction of styrene of 30-45% and the relative molecular mass of 10-30 ten thousand.
Preferably, the expandable microspheres are selected according to the processing temperature of the polymer material, the expandable microspheres corresponding to the foaming temperature are selected, and the polymer material particles are molten and do not decompose within the interval between the initial foaming temperature and the foaming peak temperature of the expandable microspheres.
Preferably, the inorganic filler is one or more of calcium carbonate, talcum powder, barium sulfate and quartz powder.
Preferably, the polymer material further comprises an auxiliary agent: 0-10 parts of compatilizer, 0-5 parts of interface modifier, 0-3 parts of lubricant and 0-3 parts of antioxidant.
More preferably, the compatilizer is any one or more of polypropylene PP-g-MAH grafted by maleic anhydride, polyethylene PE-g-MAH grafted by maleic anhydride, POE grafted by maleic anhydride and PS grafted by maleic anhydride.
More preferably, the interfacial modifier is at least one of a hydroxyl-terminated "hyperbranched" polyolefin and a carboxyl-terminated "hyperbranched" polyolefin.
More preferably, the lubricant is any one or more of stearate, polyethylene wax, ethylene bisstearamide (ERS) and erucamide.
More preferably, the antioxidant is any one or more of antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ], antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite), antioxidant 1076 (n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant 1790(1,3, 5-tris (tert-butyl-3-hydrocarbyl-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (lH,3H,5H) -trione), and antioxidant 412S (pentaerythritol tetrakis 3-laurylthiopropionate).
The invention also provides a preparation method of the polymer material, which is characterized by comprising the following steps:
step 1): uniformly mixing polymer material particles, inorganic filler and an auxiliary agent added according to needs in proportion, and extruding and bracing the mixture by a double-screw extruder to obtain modified polymer master batches;
step 2): the modified polymer particles and the expandable microspheres are blended, and a single-screw injection molding machine is utilized to prepare the low-density sprayable polymer composite material.
Preferably, the modified polymer particles in step 2) are directly blended with the expandable microspheres, or the expandable microspheres are firstly prepared into expandable microsphere master batches and then mixed with the modified polymer particles, so that the modified polymer particles can be conveniently mixed and injected for injection molding.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, by adding micropores generated by heating and foaming expandable microspheres, on one hand, under the condition of ensuring the strength of the polymer material, the buckling deformation of the polymer material and the density of the polymer material are effectively improved, and on the other hand, the surface of the material is rougher, so that the wetting capacity is improved, and the sprayability is enhanced. In addition, the surface of the expandable microsphere has more active groups, and the hyperbranched interface modification auxiliary agent is combined, so that the polarity of the surface of the polymer is increased, and the sprayability of the polymer is improved.
(2) According to the invention, the polymer particles and the auxiliary agent are blended to prepare the modified master batch, and the modified master batch and the expandable microspheres are blended for injection molding, so that the problems of microsphere damage, complex operation process and the like caused by processing are reduced, the maximization of the expansion ratio of the microspheres is effectively ensured, the advantages of the expandable microspheres are fully exerted, the density of the material is reduced, the sprayability of the material is improved, and the like.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
The materials used in examples 1 to 4 and comparative examples 1 to 5 are all commercially available products. The proportions of the raw materials are indicated by weight parts unless otherwise specified.
In examples 1 to 4: the particle size range of the expandable microspheres 1 is 25-45 μm, the initial foaming temperature is between 120-145 ℃, the foaming peak temperature is between 190-200 ℃, and the minimum foaming density is lower than 15kg/m3(ii) a The particle size range of the expandable microspheres 2 is 25-35 μm, the initial foaming temperature is between 180 ℃ and 200 ℃, the foaming peak temperature is between 220 ℃ and 230 ℃, and the minimum foaming density is lower than 15kg/m3(ii) a The particle size range of the expandable microspheres 3 is 8-15 μm, the initial foaming temperature is 200-220 ℃, the foaming peak temperature is 255-265 ℃, and the minimum foaming density is lower than 30kg/m3。
Example 1
A preparation method of a modified styrene thermoplastic elastomer material comprises the following steps:
uniformly mixing 75 parts by mass of styrene thermoplastic elastomer resin, 5 parts by mass of inorganic filler calcium carbonate, 8 parts by mass of compatilizer maleic anhydride grafted polypropylene PP-g-MAH, 3 parts by mass of interface modifier terminal hydroxyl hyperbranched polyolefin, 0.5 part by mass of lubricant polyethylene wax and 0.5 part by mass of antioxidant 1010, adding the mixture into a feed port of a double-screw extruder, and controlling the temperature of the extruder to be between 120 ℃ and 160 ℃ to prepare the styrene thermoplastic elastomer resin modified master batch. And (3) blending and injection molding 4 parts of expandable microspheres 1 and the master batch to obtain the expandable microsphere modified styrene thermoplastic elastomer material. The material is injection molded into products within the range of 160-180 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 2
A preparation method of a modified polystyrene material comprises the following steps:
uniformly mixing 75 parts of polystyrene resin, 5 parts of inorganic filler quartz powder, 8 parts of compatilizer maleic anhydride grafted PS, 3 parts of interface modifier carboxyl-terminated hyperbranched polyolefin, 0.5 part of lubricant ERS and 0.5 part of antioxidant 168, adding the mixture into a feed inlet of a double-screw extruder, controlling the temperature of the extruder to be 120-180 ℃, preparing polystyrene modified master batches, and blending and injecting 2 parts of expandable microspheres 1 and 2 parts of expandable microspheres 2 and the master batches to obtain the expandable microsphere modified polystyrene material. The material is injection molded into a product within the temperature range of 160-190 ℃, and the relevant performance test results of the product are shown in Table 1.
Example 3
A preparation method of a modified polyethylene material comprises the following steps:
after 75 parts of polyethylene resin, 5 parts of inorganic filler talcum powder, 8 parts of compatilizer maleic anhydride grafted polyethylene PE-g-MAH, 3 parts of interface modifier hydroxyl-terminated hyperbranched polyolefin, 0.5 part of lubricant erucamide and 0.5 part of antioxidant 1076 are uniformly mixed, the mixture is added into a feeding port of a double-screw extruder, and the temperature of the extruder is controlled between 120 ℃ and 180 ℃, so that the polyethylene modified master batch is prepared. And 2 parts of expandable microspheres 1 and 2 parts of expandable microspheres 2 are mixed with the master batch for injection molding, so that the expandable microsphere modified polyethylene material can be obtained. The material is injection molded into products within the temperature range of 160-220 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 4
A preparation method of a modified polypropylene material comprises the following steps:
after 75 parts of polypropylene resin, 5 parts of inorganic filler barium sulfate, 8 parts of compatilizer maleic anhydride grafted POE, 3 parts of interface modifier carboxyl-terminated hyperbranched polyolefin, 0.5 part of lubricant calcium stearate and 0.5 part of antioxidant 1790 are uniformly mixed, the mixture is added into a feeding port of a double-screw extruder, and the temperature of the extruder is controlled to be 180-230 ℃, so that the polypropylene modified master batch is prepared. And (3) blending 2 parts of expandable microspheres 2 and 2 parts of expandable microspheres 3 with the master batch for injection molding to obtain the expandable microsphere modified polypropylene material. The material is injection molded into products within the temperature range of 210 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 1
After 75 parts of styrene thermoplastic elastomer resin, 5 parts of inorganic filler, 8 parts of compatilizer, 3 parts of interface modifier, 0.5 part of lubricant and 0.5 part of antioxidant are uniformly mixed, the mixture is added into a main feeding port of a double-screw extruder, and the temperature of the extruder is controlled to be between 120 ℃ and 160 ℃, so that the styrene thermoplastic elastomer material can be obtained. The material is injection molded into products within the range of 160-180 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 2
After 75 parts of polystyrene resin, 5 parts of inorganic filler, 8 parts of compatilizer, 3 parts of interface modifier, 0.5 part of lubricant and 0.5 part of antioxidant are uniformly mixed, the mixture is added into a feeding port of a double-screw extruder, and the temperature of the extruder is controlled to be between 120 ℃ and 180 ℃, so that the polystyrene material can be obtained. The material is injection molded into a product within the temperature range of 160-190 ℃, and the relevant performance test results of the product are shown in Table 1.
Comparative example 3
After 75 parts of polyethylene resin, 5 parts of inorganic filler, 8 parts of compatilizer, 3 parts of interface modifier, 0.5 part of lubricant and 0.5 part of antioxidant are uniformly mixed, the mixture is added into a feeding port of a double-screw extruder, and the temperature of the extruder is controlled to be between 120 ℃ and 180 ℃, so that the polyethylene material can be obtained. The material is injection molded into products within the temperature range of 160-220 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 4
After 75 parts of polypropylene resin, 5 parts of inorganic filler, 8 parts of compatilizer, 3 parts of interface modifier, 0.5 part of lubricant and 0.5 part of antioxidant are uniformly mixed, the mixture is added into a feeding port of a double-screw extruder, and the temperature of the extruder is controlled between 180 ℃ and 230 ℃, so that the polypropylene material can be obtained. The material is injection molded into products within the temperature range of 210 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 5
Uniformly mixing 75 parts of polypropylene resin, 2 parts of expandable microspheres 2, 2 parts of expandable microspheres 3,5 parts of inorganic filler, 8 parts of compatilizer, 3 parts of interface modifier, 0.5 part of lubricant and 0.5 part of antioxidant, and adding the mixture into a single-screw injection molding machine to obtain the expandable microsphere modified polypropylene material. The material is injection molded into products within the temperature range of 210 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Performance test evaluation mode:
density test standard: ISO1183-1:2004, immersion method, temperature 23 ℃, immersion liquid: water;
tensile test standard: ISO527, tensile speed 10 mm/min;
bending test standard: ISO178, speed: 2 mm/min;
and (3) testing the adhesion of the coating: ISO2409, test spacing 2mm, stipulate grade 0 or grade 1 as acceptable.
TABLE 1
As shown in Table 1, the density of the system was greatly reduced by adding expandable microspheres, and the density was 0.8481, 0.8527, 8257 and 0.8343g/cm in the SBS resin, the PS resin, the PE resin and the PP resin, respectively3The density is reduced by about 10-20%, the adhesive force grade of the coating is changed from 5 grade to 0 grade, the qualified level is reached, and the requirements of various vehicle plastics and household plastic products are met. In addition, through the comparison of mechanical properties, although the mechanical properties are reduced, the expandable microspheres have the shells and belong to closed holes, so that the material still maintains good mechanical properties.
As can be seen from the data of example 4 and comparative examples 4-5, when the microspheres were blended with resin powder and other adjuvants and fed into an injection molding machine, the resulting material had a density of exactly 0.967g/cm3And the mechanical property is seriously reduced, which shows the dispersion effect of the single-screw injection molding machineIs not preferred. In comparative example 5, the adhesion of the coating was also relatively poor, indicating that the cavities formed on the surface of the microspheres and the introduced active functional groups were not uniformly dispersed on the surface of the polymer, thereby reducing the sprayability of the polymer material.
Therefore, by combining the above cases, the expandable microspheres are added into the polymer modified material, so that the weight reduction and the spraying property of the finished piece can be effectively realized, and the mechanical property of the material is ensured. The method effectively reduces the complex flow of the modern spraying process and can meet the requirements of various products.
Claims (9)
1. The polymer material is characterized by comprising 70-90 parts of polymer material particles, 1-8 parts of expandable microspheres and 5-40 parts of inorganic filler by weight.
2. The polymeric material of claim 1, wherein the polymeric material particles comprise at least one of polyethylene, polypropylene, polystyrene, and styrene thermoplastic elastomer.
3. The polymeric material of claim 2, wherein the polyethylene is at least one of a low density polyethylene and a high density polyethylene: the test condition is 190 ℃/2.16kg, the melt flow rate is between 1 and 50g/10 min; the polypropylene is one or more of homopolymerized polypropylene and copolymerized polypropylene: the melt flow rate is between 1 and 60g/10min under the test condition of 230 ℃/2.16 kg; the polystyrene is at least one of common polystyrene and high impact polystyrene, and the melt flow rate is between 1 and 100g/10min under the test condition of 230 ℃/1.2 kg; the styrene thermoplastic elastomer has the mass fraction of styrene of 30-45% and the relative molecular mass of 10-30 ten thousand.
4. The polymer material of claim 1, wherein the expandable microspheres are selected according to the processing temperature of the polymer material, and the expandable microspheres have an initial foaming temperature and a foaming peak temperature, and the polymer material particles are molten and do not decompose.
5. The polymer material according to claim 1, wherein the inorganic filler is one or more of calcium carbonate, talc, barium sulfate and quartz powder.
6. The polymeric material of claim 1, further comprising an auxiliary agent: 0-10 parts of compatilizer, 0-5 parts of interface modifier, 0-3 parts of lubricant and 0-3 parts of antioxidant.
7. The polymer material of claim 6, wherein the compatibilizer is one or more of polypropylene PP-g-MAH grafted with maleic anhydride, polyethylene PE-g-MAH grafted with maleic anhydride, POE grafted with maleic anhydride, and PS grafted with maleic anhydride; the interface modifier is at least one of hydroxyl-terminated hyperbranched polyolefin and carboxyl-terminated hyperbranched polyolefin; the lubricant is any one or more of stearate, polyethylene wax, ethylene distearamide and erucamide; the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 1790 and antioxidant 412S.
8. A method of preparing a polymeric material according to any of claims 1 to 7, comprising the steps of:
step 1): uniformly mixing polymer material particles, inorganic filler and an auxiliary agent added according to needs in proportion, and extruding and bracing the mixture by a double-screw extruder to obtain modified polymer master batches;
step 2): the modified polymer particles and the expandable microspheres are blended, and a single-screw injection molding machine is utilized to prepare the low-density sprayable polymer composite material.
9. The method of claim 8, wherein the modified polymer particles of step 2) are directly blended with the expandable microspheres, or the expandable microspheres are first prepared into expandable microsphere masterbatch and then mixed with the modified polymer particles.
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| CN113174120A (en) * | 2021-03-03 | 2021-07-27 | 快思瑞科技(上海)有限公司 | Light glass fiber reinforced ABS composite board material and board preparation method |
| CN113347814A (en) * | 2021-05-31 | 2021-09-03 | Oppo广东移动通信有限公司 | Shell, preparation method thereof and electronic equipment |
| CN113372652A (en) * | 2021-07-30 | 2021-09-10 | 无锡会通轻质材料股份有限公司 | Special material for mould pressing high temperature resistant forming for EPP foaming |
| CN114213702A (en) * | 2021-11-23 | 2022-03-22 | 快思瑞科技(上海)有限公司 | Polypropylene plate and preparation method thereof |
| CN114316311A (en) * | 2021-11-23 | 2022-04-12 | 快思瑞科技(上海)有限公司 | Foamed composite material and preparation method thereof |
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| CN113174120A (en) * | 2021-03-03 | 2021-07-27 | 快思瑞科技(上海)有限公司 | Light glass fiber reinforced ABS composite board material and board preparation method |
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| CN114213702A (en) * | 2021-11-23 | 2022-03-22 | 快思瑞科技(上海)有限公司 | Polypropylene plate and preparation method thereof |
| CN114316311A (en) * | 2021-11-23 | 2022-04-12 | 快思瑞科技(上海)有限公司 | Foamed composite material and preparation method thereof |
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