CN112126189A - Scratch-resistant acrylic material and preparation method thereof - Google Patents
Scratch-resistant acrylic material and preparation method thereof Download PDFInfo
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- CN112126189A CN112126189A CN202010991572.6A CN202010991572A CN112126189A CN 112126189 A CN112126189 A CN 112126189A CN 202010991572 A CN202010991572 A CN 202010991572A CN 112126189 A CN112126189 A CN 112126189A
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- resistant acrylic
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- 239000000463 material Substances 0.000 title claims abstract description 94
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 75
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 44
- -1 polysiloxane Polymers 0.000 claims abstract description 27
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 26
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 26
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 18
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 8
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 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 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 28
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 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 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- 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
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- 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
- C08J2423/08—Copolymers of ethene
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- 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
- C08J2425/00—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
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- C08J2427/00—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 a halogen; Derivatives of such polymers
- C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08J2435/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/06—Copolymers with vinyl aromatic monomers
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- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- 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
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- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2207/062—HDPE
Abstract
The application relates to the technical field of high polymer material modification, in particular to a scratch-resistant acrylic material and a preparation method thereof. The invention provides a scratch-resistant acrylic material, which takes polymethyl methacrylate and ABS resin as matrix resin through blending, and adds special silicone master batch and other components, wherein the silicone master batch forms a stable organizational structure through carrying polysiloxane and PTFE on a polyolefin resin carrier, so that the precipitation of the polysiloxane is effectively prevented, and in addition, under the action of a compatilizer, the silicone master batch and the scratch-resistant acrylic material form a stable dispersed structure. The abrasion resistance of the scratch-resistant acrylic material is greatly improved on the premise of not influencing the main mechanical property and appearance property of the material, and the problem of appearance abrasion or scratch of the acrylic material in long-term use can be effectively improved, so that the added value of the material is improved, namely the product competitiveness of the acrylic material is improved.
Description
Technical Field
The application relates to the technical field of high polymer material modification, in particular to a scratch-resistant acrylic material and a preparation method thereof.
Background
The acrylic material is also known as organic glass, has the chemical name of polymethyl methacrylate (PMMA), is a common high polymer material, is used as a transparent material, has the light transmittance of over 90 percent generally, and can be used as a substitute of glass. The acrylic material is made by polymerizing methyl methacrylate, and like other plastics, the overall weight of the acrylic material is light and is only about half of the weight of glass. The acrylic material has the advantages that the mechanical properties such as tensile resistance, impact resistance and the like are obviously better than those of common glass due to the long molecular chain structure of the acrylic material, the acrylic material can effectively bear larger impact without integral damage, in addition, the acrylic material is used as a conventional high polymer material, the production cost is lower, the acrylic material can be melted and formed at lower temperature, various shapes can be processed according to different molds, and the advantages are incomparable with common glass.
Generally, the impact performance of an acrylic material with a pure polymethyl methacrylate component is slightly poor, and in order to solve the problem, ABS (acrylonitrile-butadiene-styrene copolymer) is usually blended to a certain extent to improve the impact performance and low temperature performance of the acrylic material. The conventional acrylic material is usually an alloy material mixed by polymethyl methacrylate and ABS, the comprehensive performance of the material is excellent, and the material can meet most application scenes of daily life, but in actual application, the conventional acrylic material still has the problems of poor surface hardness and easy scratching, so that the appearance of an acrylic material member is influenced, and therefore, the development of the acrylic material which improves the scratch resistance and has high mechanical property is very necessary and can generate high economic benefit.
Disclosure of Invention
According to the requirements of an acrylic material on the premise of controllable cost, the scratch resistance of the acrylic material is improved, and the main mechanical property and appearance of the acrylic material are not affected basically, the invention provides the technical content of the first aspect, and specifically designs a scratch-resistant acrylic material which comprises, by weight, 330 parts of polymethyl methacrylate (PMMA) in 270-class, 650 parts of ABS in 550-class, 20-120 parts of auxiliary materials, 10-50 parts of a lubricant and 16-24 parts of a scratch-resistant agent, wherein the scratch-resistant agent is silicone master batch, and the lubricant is molybdenum disulfide.
Optionally, the auxiliary material comprises an antioxidant, and the antioxidant is one or a combination of an antioxidant 163 and an antioxidant 1010.
Optionally, the silicone master batch comprises, by weight, 6-10 parts of polysiloxane, 0.8-1.2 parts of PTFE, 8-10 parts of a polyolefin resin carrier, and 1.2-2.4 parts of a compatibilizer, and the molecular weight of the polysiloxane is not less than 100 ten thousand.
Optionally, the compatibilizer is a composition of, by mass, 0.3 to 0.6 part of an ethylene-butyl methacrylate-glycidyl acrylate copolymer (PWT), 0.3 to 0.6 part of a styrene-acrylonitrile copolymer (SAN), 0.2 to 0.4 part of styrene-maleic anhydride (SMA), and 0.4 to 0.8 part of polydimethylmethylvinylsiloxane.
Optionally, the polyolefin resin carrier is one or more of ethylene-vinyl acetate copolymer, high density polyethylene, and ethylene-vinyl acetate copolymer.
Optionally, the preparation method of the silicone master batch comprises the following steps:
1) weighing polysiloxane and polyolefin resin carrier, adding the polysiloxane and the polyolefin resin carrier into an internal mixer, and banburying for 3-5 minutes at the banburying temperature of 150-180 ℃;
2) weighing PTEF and a compatilizer, adding the PTEF and the compatilizer into an internal mixer, and continuously carrying out internal mixing for 3-5 minutes to obtain a semi-finished silicone master batch;
3) adding the semi-finished product of the silicone master batch into a double-screw extruder through a feeding device for extrusion, and granulating through a granulating device to obtain the silicone master batch, wherein the extrusion temperature of the double-screw extruder is 160-180 ℃.
The invention also provides technical contents of a second aspect, and specifically designs a preparation method of the scratch-resistant acrylic material according to any one of the technical contents of the first aspect, wherein a formula of the scratch-resistant acrylic material according to any one of the technical contents of the first aspect is adopted, and the preparation method comprises the following steps:
1) weighing polymethyl methacrylate, ABS, auxiliary materials, a lubricant and an anti-scratch agent, adding into a mixing device, and uniformly mixing to obtain a mixture;
2) feeding the mixture into a double-screw extruder through a feeding device and extruding to obtain an extruded material;
3) and granulating and homogenizing the extruded material by a post-treatment process to obtain the scratch-resistant acrylic material.
Optionally, firstly adding polymethyl methacrylate and ABS, setting the first-stage mixing process to be 400-600r/min, and mixing for 3-5 minutes; and then adding the rest materials, setting the second-stage mixing process to be 400-one and 600r/min, and mixing for 3-5 minutes to obtain the mixture after the second-stage mixing.
Optionally, in the step 2), the screw rotation speed of the twin-screw extruder is set to be 115-125r/min, and the temperatures of the sections in the extrusion direction are respectively as follows: the first section is 175-185 ℃, the second section is 205-215 ℃, the third section is 225-235 ℃, the fourth section is 225-235 ℃, the fifth section is 225-235 ℃, and the sixth section is 225-235 ℃, and in addition, the temperature of the machine head is 5 ℃ lower than that of the sixth section.
Optionally, the post-treatment process sequentially comprises water cooling, water blowing, granulation, screening and homogenization.
The invention provides a scratch-resistant acrylic material, which takes polymethyl methacrylate and ABS resin as matrix resin, and is added with special silicone master batch and other components, wherein polysiloxane and PTFE are carried on a polyolefin resin carrier by the silicone master batch, so that a stable organizational structure is formed, the precipitation of the polysiloxane is effectively prevented, and in addition, under the action of a compatilizer, the silicone master batch and the scratch-resistant acrylic material form a stably dispersed structure. The abrasion resistance of the scratch-resistant acrylic material is greatly improved on the premise of not influencing the main mechanical property and appearance property of the material, and the problem of appearance abrasion or scratch of the acrylic material in long-term use can be effectively improved, so that the added value of the material is improved, namely the product competitiveness of the acrylic material is improved.
Detailed Description
The present solution is explained below with reference to specific embodiments.
The invention provides a scratch-resistant acrylic material, which is characterized in that firstly, the acrylic material is usually organic glass, namely polymethyl methacrylate, actually, the acrylic material in practical significance is not limited to pure polymethyl methacrylate and a modifier thereof, but also comprises an alloy material containing polymethyl methacrylate and other polymers, the alloy material also has good light transmittance, the polymethyl methacrylate, the modifier thereof and the alloy material form the actual reference range of the acrylic material, namely, the acrylic material in the application refers to the acrylic alloy material under the condition of special description.
The scratch-resistant acrylic material comprises, by weight, 270-330 parts of polymethyl methacrylate, 550-650 parts of ABS, 20-120 parts of auxiliary materials, 10-50 parts of lubricant and 16-24 parts of scratch-resistant agent, wherein the scratch-resistant agent is silicone master batch, and the lubricant is molybdenum disulfide. The silicone master batch is a specially-made master batch material, is different from conventional silicone oil, can effectively solve the problem that the silicone oil is easy to separate out by a mode of carrying polysiloxane on a carrier, and in addition, the lubricant is molybdenum disulfide which is in a hexagonal system, and the bonding force of sulfur atoms among layers is very low, so that the interlaminar shear strength can be remarkably reduced, the friction factor is very small, the friction factors on the surface and inside of the material can be remarkably reduced, and the wear-resistant effect is achieved.
Experiments prove that in the acrylic alloy, the mass ratio of the polymethyl methacrylate to the ABS is 30: the main performances of the alloy material obtained by mixing the components in the proportion of 50-70, such as glossiness, hardness, mechanical property and the like, are comprehensive optimal levels, and in consideration of the adaptation effect with other components, the mass ratio of polymethyl methacrylate to ABS in the alloy material adopted by the invention adopts the proportion of 270-550-650.
The auxiliary materials are other materials commonly used in the conventional plastic modification technology, and can be fillers, dispersing agents, compatilizers or other modifiers with various functions according to requirements, the acrylic alloy material can have different characteristics through the use of different modifiers, the implementation method should be correspondingly set according to requirements, and for a person skilled in the art, the method belongs to a conventional implementation mode in the industry, so that although not described herein, the method still is a clear and complete technical means for the person skilled in the art. Considering the common use scene and the design life of the acrylic material, the auxiliary material at least comprises an antioxidant, the antioxidant is selected from one or more of an antioxidant 163 and an antioxidant 1010, and the antioxidant can obviously reduce the aging speed of the acrylic material, so that the use time is prolonged, and the practicability is enhanced.
Particularly, the silicone master batch comprises 6-10 parts of polysiloxane, 0.8-1.2 parts of PTFE (polytetrafluoroethylene), 8-10 parts of polyolefin resin carrier and 1.2-2.4 parts of compatilizer according to parts by weight, the molecular weight of the polysiloxane is not less than 100 ten thousand, and the ultrahigh molecular weight polysiloxane can further reduce the friction factor of the alloy material and improve the processability and glossiness of the alloy material, and is particularly suitable for the acrylic alloy material. The silicone master batch is added with a certain amount of PTFE on the basis of polysiloxane, wherein the PTFE is resin with excellent comprehensive performance, particularly has strong self-lubricating property and can assist in reducing the friction factor of the material. In order to improve the compatibility of the components, the invention provides a compound compatilizer, and particularly, in consideration of the components of the silicone master batch and the application mode of applying the silicone master batch to the acrylic alloy material, the compound compatilizer is a composition of 0.3-0.6 part of ethylene-butyl methacrylate-glycidyl acrylate copolymer (PWT), 0.3-0.6 part of styrene-acrylonitrile copolymer (SAN), 0.2-0.4 part of styrene-maleic anhydride (SMA) and 0.4-0.8 part of polydimethyl methyl vinyl siloxane. The polyolefin resin carrier is one or more of ethylene-vinyl acetate copolymer, high-density polyethylene and ethylene-vinyl acetate copolymer, and can be arranged in any proportion.
The silicone master batch can be mixed by adopting a plurality of mixing modes, wherein one preferred mode is to mix and blend by adopting an internal mixer. Specifically, the banburying process mainly comprises the following steps:
1) weighing a proper amount of polysiloxane and polyolefin resin, adding the polysiloxane and the polyolefin resin into an internal mixer, and internally mixing for 3-5 minutes, wherein the internally mixing temperature is set to be 150-180 ℃;
2) weighing PTEF and a compatilizer, adding the PTEF and the compatilizer into an internal mixer, and continuously carrying out internal mixing for 3-5 minutes to obtain a semi-finished silicone master batch;
3) adding the semi-finished product of the silicone master batch into a double-screw extruder through a feeding device for extrusion, and granulating through a granulating device to obtain the silicone master batch, wherein the extrusion temperature of the double-screw extruder is 160-180 ℃.
The silicone master batch matching the acrylic alloy material of the present invention can be prepared by the above internal mixing process, and after referring to the above internal mixing process, one skilled in the art can easily think of other production preparation methods of the silicone master batch, such as directly through a mixing-based process or using other similar blending methods, which are easily thought and do not depart from the spirit of the present invention, and therefore the above blending methods also fall within the protection scope of the present application.
The scratch-resistant acrylic material can be prepared after the silicone master batch is prepared. Generally, we directly prepare the acrylic material by means of basic blending. The adopted device at least comprises a mixing device, a feeding device, an extruder and a post-processing device, and the blending steps are as follows:
1) weighing proper amount of polymethyl methacrylate, ABS, auxiliary materials, lubricant and anti-scratching agent, namely silicone master batch, adding into a mixing device, and uniformly mixing to obtain a mixture;
2) feeding the mixture into a double-screw extruder through a feeding device and extruding to obtain an extruded material;
3) and granulating and homogenizing the extruded material by a post-treatment process to obtain the scratch-resistant acrylic material.
The post-treatment process comprises water cooling, water blowing, granulation, screening and homogenization in sequence, and the post-treatment device mainly comprises a water cooling tank, a water beater, a granulator, a vibrating screen and a homogenization tank according to the production sequence, and the device is used for cooling, water blowing, granulation, screening and homogenization of strips in sequence, and the scratch-resistant acrylic alloy particles are obtained after full homogenization.
Several embodiments of the acrylic material of the present invention and their performance effects are illustrated by specific examples below.
Example 1
The embodiment provides a scratch-resistant acrylic material, and the preparation method comprises the following steps:
1) weighing and mixing 0.3-0.6 part of ethylene-butyl methacrylate-glycidyl acrylate copolymer, 0.3-0.6 part of styrene-acrylonitrile copolymer, 0.2-0.4 part of styrene-maleic anhydride and 0.4-0.8 part of polydimethylmethylvinylsiloxane to obtain a compound compatilizer of silicone master batch;
2) weighing 6-10 parts of polysiloxane and 8-10 parts of polyolefin resin carrier, adding into a high-speed internal mixer, and internally mixing for 3-5 minutes at the temperature of 150-180 ℃, wherein the polyolefin resin is ethylene-vinyl acetate copolymer;
3) then adding 0.8-1.2 parts of PTFE and 1.2-2.4 parts of compound compatilizer, keeping the same temperature and continuously banburying for 3-5 minutes to obtain a semi-finished silicone product;
4) adding the semi-finished product of the silicone master batch into a double-screw extruder through a feeding device for extrusion, and granulating through a granulating device to obtain the silicone master batch, wherein the extrusion temperature of the double-screw extruder is 160-180 ℃;
5) weighing 300 parts of polymethyl methacrylate and 600 parts of ABS, placing the materials in a mixer, and setting the first-stage mixing process to be 400-600r/min for mixing for 3-5 minutes; then adding 40 parts of antioxidant 1010, 30 parts of molybdenum dioxide lubricant and 20 parts of silicone master batch obtained in the step 3), setting a second-stage mixing process to be 400-600r/min, mixing for 3-5 minutes, and obtaining the mixture after the second-stage mixing;
6) feeding the mixture into a double-screw extruder through a feeding device to be extruded to obtain an extruded material, setting the screw rotating speed of the double-screw extruder to be 115 and 125r/min, and respectively setting the temperature of each section according to the extrusion direction as follows: the first section is 175-185 ℃, the second section is 205-215 ℃, the third section is 225-235 ℃, the fourth section is 225-235 ℃, the fifth section is 225-235 ℃, and the sixth section is 225-235 ℃, in addition, the temperature of the machine head is 5 ℃ lower than that of the sixth section;
7) the extruded material is in a strip shape, and fully homogenized scratch-resistant acrylic alloy granules are obtained by sequentially passing through a water cooling tank, a water beater, a granulator, a vibrating screen and a homogenizing tank.
By adopting the above implementation method, the following group of acrylic alloy materials are prepared in this embodiment:
in the embodiment, except for special description, the compound compatilizer adopted by each implementation group and the comparative group is the same.
Comparative example 1 employed substantially the same production steps as example 5, except that comparative example 1 did not add a compatibilizer to the production of the silicone masterbatch, and comparative example 1 was otherwise identical to example 5. In addition, a comparison group 2 and a comparison group 3 are also provided, wherein the comparison group 2 adopts the production steps which are basically the same as those of the implementation group 5, the difference is that no silicone master batch scratch-resistant agent is adopted, and the rest production steps are the same as those of the implementation group 5; comparative group 3 employed substantially the same manufacturing procedure as comparative group 2, except that comparative group 3 did not employ molybdenum disulfide, the remaining manufacturing procedures were the same as comparative group 2, i.e., comparative group 3 did not employ either a silicone masterbatch anti-scratch agent or a molybdenum disulfide lubricant on the basis of example group 5, and the remaining manufacturing procedures were the same as example group 5.
Under the condition of fixing the dosage of polymethyl methacrylate, ABS, silicone master batch and the like, the influence of the composition of the silicone master batch on the acrylic alloy material is explained according to the implementation group and the comparison group.
The related acrylic alloy material is prepared by the composition design of the different groups of implementation groups and the comparison group, and the main performance of the acrylic alloy material obtained by each group is tested, and the method mainly comprises the following steps:
the test method of the impact strength is as follows: standard test specimens were prepared by injection molding and then notched impact strength was measured on a ZBC-25B plastic pendulum impact tester according to the GB1843-80 standard.
The tensile strength was tested in the following manner: standard test specimens were prepared by means of an injection molding machine and the tensile properties were measured on a CMT6104 universal electrical testing machine in accordance with the GB/T1040-92 standard.
The transmittance test mode is as follows: a standard test panel was prepared using an injection molding machine and the transmittance of the panel was measured using a ColorQuestXE optical tester according to the ASTM D1003 standard.
The method for testing the glossiness comprises the following steps: firstly, preparing a standard test sample by using an injection molding machine, and then testing the glossiness of the sample according to ASTM D2457-08 standard under the geometric condition of 60 DEG
The wear resistance test method comprises the following steps: preparing a standard test sample plate by using an injection molding machine, scraping the standard sample plate by using a common grid scraping method in a high polymer material according to a general GMW14688 standard by using an Erichsen scratch resistance tester, testing the color difference change of the scraping position before and after by using a Byk color difference tester, and qualitatively judging the wear resistance according to the color depth change rate (delta L) before and after, wherein the larger the value of the delta L is, the more obvious the color is whitish after scraping, the poorer the scratch resistance effect of the material is, and the poorer the scratch resistance performance is.
According to the above test method, the results are shown in the following table:
according to the comparison groups 2 and 3 and the implementation group 5, the scratch-resistant acrylic material can obviously improve the wear resistance under the condition of using silicone master batch modification and molybdenum disulfide lubricant, namely, the scratch resistance is obviously improved, and the mechanical property, the transmittance and other properties are basically not influenced. According to the comparison group 1 and the implementation group 5, the silicone master batch system disclosed by the invention has the effect of promoting compatibilization by using the compound compatilizer, so that the mechanical property, the appearance and the wear resistance of the acrylic alloy material are improved.
Example 2
The embodiment provides a scratch-resistant acrylic material, and the preparation method comprises the following steps:
1) weighing and mixing 0.45 part of ethylene-butyl methacrylate-glycidyl acrylate copolymer, 0.45 part of styrene-acrylonitrile copolymer, 0.45 part of styrene-maleic anhydride and 0.6 part of polydimethylmethylvinylsiloxane to obtain a compound compatilizer of silicone master batch;
2) weighing 8 parts of polysiloxane and 9 parts of polyolefin resin carrier, adding into a high-speed internal mixer, and internally mixing at the temperature of 150-180 ℃ for 3-5 minutes, wherein the polyolefin resin is high-density polyethylene;
3) then adding 1 part of PTFE and the compound compatilizer, keeping the same temperature, and continuously banburying for 3-5 minutes to obtain a silicone semi-finished product;
4) adding the semi-finished product of the silicone master batch into a double-screw extruder through a feeding device for extrusion, and granulating through a granulating device to obtain the silicone master batch, wherein the extrusion temperature of the double-screw extruder is 160-180 ℃;
5) weighing 330 parts of polymethyl methacrylate (PMMA) in a proportion of 270-; then adding 20 parts of an antioxidant 163 and 80 parts of talcum powder, 10-50 parts of molybdenum dioxide lubricant and 16-24 parts of silicone master batch obtained in the step 3), setting a second-stage mixing process to be at a rotating speed of 400-600r/min, and mixing for 3-5 minutes to obtain a mixture after second-stage mixing;
6) feeding the mixture into a double-screw extruder through a feeding device to be extruded to obtain an extruded material, setting the screw rotating speed of the double-screw extruder to be 115 and 125r/min, and respectively setting the temperature of each section according to the extrusion direction as follows: the first section is 175-185 ℃, the second section is 205-215 ℃, the third section is 225-235 ℃, the fourth section is 225-235 ℃, the fifth section is 225-235 ℃, and the sixth section is 225-235 ℃, in addition, the temperature of the machine head is 5 ℃ lower than that of the sixth section;
7) the extruded material is in a strip shape, and fully homogenized scratch-resistant acrylic alloy granules are obtained by sequentially passing through a water cooling tank, a water beater, a granulator, a vibrating screen and a homogenizing tank.
This example used the same starting materials as in example 1.
It should be noted that, in the present application, the same batch of silicone master batch is used as the anti-scratch agent, that is, the silicone master batch used in each embodiment or comparative group is the same, that is, 1 part by weight of the silicone master batch is not equal to 1 part by weight of the component used in the acrylic material, and this is used here for convenience of description, and a person of ordinary skill in the art should understand that.
By adopting the above implementation method, the following group of acrylic alloy materials are prepared in this embodiment
The performance test was performed on each of the test groups of this example in the same test method as in example 1, and the measured data are shown in the following table:
from the data, the impact performance of the acrylic alloy material is slightly reduced and the appearance is better along with the increase of the content of the polymethyl methacrylate in the acrylic alloy material, in addition, the content of the scratch-resistant agent silicone master batch is highly positively correlated with the wear resistance of the acrylic alloy, and the impact on the mechanical property and the appearance of the acrylic alloy is smaller. The above results show that the acrylic alloy material using the silicone master batch can significantly improve the scratch resistance under the condition that the mechanical property and the appearance are not affected basically.
The same and similar parts among the various embodiments in the specification of the present application may be referred to each other. In particular, for the system embodiment, since the method therein is substantially similar to the method embodiment, the description is simple, and the relevant points can be referred to the description in the method embodiment.
It should be noted that, in the present application, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. The term "comprising", without further limitation, means that the element so defined is not excluded from the group consisting of additional identical elements in the process, method, article, or apparatus that comprises the element.
Of course, the above description is not limited to the above examples, and technical features that are not described in this application may be implemented by or using the prior art, and are not described herein again; the above examples are only for illustrating the technical solutions of the present application and not for limiting the present application, and the present application is only described in detail with reference to the preferred embodiments, and those skilled in the art should understand that those skilled in the art should make changes, modifications, additions or substitutions within the spirit and scope of the present application without departing from the spirit of the present application and also fall within the scope of the claims of the present application.
Claims (10)
1. The scratch-resistant acrylic material is characterized by comprising, by weight, 270-330 parts of polymethyl methacrylate, 550-650 parts of ABS, 20-120 parts of auxiliary materials, 10-50 parts of lubricants and 16-24 parts of scratch-resistant agents, wherein the scratch-resistant agents are silicone master batches, and the lubricants are molybdenum disulfide.
2. The scratch-resistant acrylic material as claimed in claim 1, wherein the auxiliary material comprises an antioxidant, and the antioxidant is one or a combination of an antioxidant 163 and an antioxidant 1010.
3. The scratch-resistant acrylic material as claimed in claim 1, wherein the silicone master batch comprises, by weight, 6-10 parts of polysiloxane, 0.8-1.2 parts of PTFE, 8-10 parts of polyolefin resin carrier and 1.2-2.4 parts of compatilizer, and the molecular weight of the polysiloxane is not less than 100 ten thousand.
4. The scratch-resistant acrylic material as claimed in claim 3, wherein the compatibilizer is a composition of 0.3-0.6 parts by weight of ethylene-butyl methacrylate-glycidyl acrylate copolymer (PWT), 0.3-0.6 parts by weight of styrene-acrylonitrile copolymer (SAN), 0.2-0.4 parts by weight of styrene-maleic anhydride (SMA) and 0.4-0.8 parts by weight of polydimethylmethylvinylsiloxane.
5. The scratch-resistant acrylic material as claimed in claim 3, wherein the polyolefin resin carrier is one or more of ethylene-vinyl acetate copolymer, high density polyethylene and ethylene-vinyl acetate copolymer.
6. The scratch-resistant acrylic material according to claim 3, wherein the silicone master batch is prepared by the following steps:
1) weighing polysiloxane and polyolefin resin carrier, adding the polysiloxane and the polyolefin resin carrier into an internal mixer, and banburying for 3-5 minutes at the banburying temperature of 150-180 ℃;
2) weighing PTEF and a compatilizer, adding the PTEF and the compatilizer into an internal mixer, and continuously carrying out internal mixing for 3-5 minutes to obtain a semi-finished silicone master batch;
3) adding the semi-finished product of the silicone master batch into a double-screw extruder through a feeding device for extrusion, and granulating through a granulating device to obtain the silicone master batch, wherein the extrusion temperature of the double-screw extruder is 160-180 ℃.
7. A preparation method of a scratch-resistant acrylic material is characterized in that the formula of the scratch-resistant acrylic material as claimed in any one of claims 1 to 6 is adopted, and the preparation method comprises the following steps:
1) weighing polymethyl methacrylate, ABS, auxiliary materials, a lubricant and an anti-scratch agent, adding into a mixing device, and uniformly mixing to obtain a mixture;
2) feeding the mixture into a double-screw extruder through a feeding device and extruding to obtain an extruded material;
3) and granulating and homogenizing the extruded material by a post-treatment process to obtain the scratch-resistant acrylic material.
8. The preparation method as claimed in claim 7, wherein in the step 1), the polymethyl methacrylate and the ABS are added firstly, and the first-stage mixing process is set to a rotation speed of 400-600r/min for mixing for 3-5 minutes; and then adding the rest materials, setting the second-stage mixing process to be 400-one and 600r/min, and mixing for 3-5 minutes to obtain the mixture after the second-stage mixing.
9. The preparation method as claimed in claim 7, wherein in the step 2), the screw rotation speed of the twin-screw extruder is set to 115-125r/min, and the temperatures of the sections in the extrusion direction are respectively: the first section is 175-185 ℃, the second section is 205-215 ℃, the third section is 225-235 ℃, the fourth section is 225-235 ℃, the fifth section is 225-235 ℃, and the sixth section is 225-235 ℃, and in addition, the temperature of the machine head is 5 ℃ lower than that of the sixth section.
10. The method according to claim 7, wherein the post-treatment process comprises water cooling, water blowing, granulation, screening and homogenization in sequence.
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| CN108164912A (en) * | 2017-12-25 | 2018-06-15 | 天津科技大学 | A kind of low abrasion scratch-resistant ABS material and preparation method thereof |
| CN110157195A (en) * | 2019-06-09 | 2019-08-23 | 广州硅碳新材料有限公司 | A kind of dedicated wear-resisting silicone masterbatch of polyolefin and preparation method thereof |
| CN111154222A (en) * | 2020-01-19 | 2020-05-15 | 成都金发科技新材料有限公司 | ABS/PMMA alloy and preparation method thereof |
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| CN107778747A (en) * | 2017-11-15 | 2018-03-09 | 昆山飞奔塑胶模具有限公司 | A kind of high light wearable ABS/PMMA composites and preparation method thereof |
| CN108164912A (en) * | 2017-12-25 | 2018-06-15 | 天津科技大学 | A kind of low abrasion scratch-resistant ABS material and preparation method thereof |
| CN110157195A (en) * | 2019-06-09 | 2019-08-23 | 广州硅碳新材料有限公司 | A kind of dedicated wear-resisting silicone masterbatch of polyolefin and preparation method thereof |
| CN111154222A (en) * | 2020-01-19 | 2020-05-15 | 成都金发科技新材料有限公司 | ABS/PMMA alloy and preparation method thereof |
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