CN112409746A - High-weather-resistance scratch-resistant marble-imitated ABS material and preparation method thereof - Google Patents
High-weather-resistance scratch-resistant marble-imitated ABS material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 74
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 73
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 73
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 73
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 71
- 239000000956 alloy Substances 0.000 claims abstract description 69
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 69
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 48
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 43
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 41
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 20
- 229920005604 random copolymer Polymers 0.000 claims abstract description 20
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 238000001746 injection moulding Methods 0.000 claims abstract description 17
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 7
- IUWLKCUMIZASAL-UHFFFAOYSA-N C1(C=C/C(=O)O1)=O.C=CC1=CC=CC=C1.C=CC=C.C(C=C)#N Chemical compound C1(C=C/C(=O)O1)=O.C=CC1=CC=CC=C1.C=CC=C.C(C=C)#N IUWLKCUMIZASAL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 14
- 239000012463 white pigment Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000004579 marble Substances 0.000 abstract description 11
- 230000006750 UV protection Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 description 5
- 239000006028 limestone Substances 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 239000004595 color masterbatch Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A high weather-resistant scratch-resistant marble-imitated ABS material and a preparation method thereof belong to the technical field of high polymer materials. The material is formed by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch, wherein the PMMA/ABS alloy base stock comprises: 50-70 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 30-50 parts of polymethyl methacrylate, 0.5-1 part of anti-UV agent and 0.2-2 parts of silicone powder; the PET/PBT alloy master batch comprises: 1-4 parts of polyethylene terephthalate, 1-4 parts of polybutylene terephthalate, 0.1-2 parts of pigment powder, 0.02-0.1 part of styrene-butadiene-acrylonitrile-maleic anhydride random copolymer and 0.02-0.1 part of dispersing agent. The modified material has higher hardness and scratch resistance, simultaneously has higher UV resistance effect and has marble texture.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-weather-resistance scratch-resistant marble-imitated ABS material and a preparation method thereof.
Background
Marble, also called marble, is recrystallized limestone with main component of CaCO3Limestone becomes soft at high temperature and high pressure and is recrystallized to form marble when mineral substances in the limestone change, and the limestone has various colors, obvious patterns and good texture. Meanwhile, the high-hardness high-rigidity high-strength. Due to the advantages of texture and appearance, more and more household plastic products also pursue marble grains to improve the style and grade of the products, such as washbasins, dining tables, stool chairs and the like on the market at present, but at present, the products are mainly formed by coating films after plastic products are molded, or the marble stripe appearance is realized by a water transfer printing process. However, the two processes have requirements on the structure and the appearance of the product, the laminating cost is high, the waste is large, the water transfer printing technology cost is high, the printing ink is also wasted, and meanwhile, certain pollution is caused to the environment. The direct injection molding process of producing marble stripe is simple and low in cost, and the product with marble stripe may be produced in only one step.
The ABS material has excellent performance and good texture, so the ABS material is widely applied to various industries, is used for replacing metal parts, can be recycled and is popular with various plastic product manufacturers. However, the components of the ABS material contain rubber, so that the surface hardness of the ABS material is not high, the product is easily scratched in a long-time use process, and the attractiveness of the product is influenced, so that the improvement of the surface hardness of the ABS material and the scratch resistance of the material are also great demands of the current market.
Patent document (publication No. CN 105482351B) discloses an ABS material with marble-like decorative effect, which comprises filler resin, ABS resin, compatibilizer, flow modifier, and color masterbatch, and improves mechanical properties and impact strength of the material by adding the compatibilizer.
Patent document (publication No. CN 107163491B) discloses a modified ABS material, which comprises synthetic ABS resin and marble stripe color master batch, and can be used to prepare marble stripe effect material.
However, the two materials do not improve or have limited effect on the weather resistance and scratch resistance of the ABS material, and cannot meet the high requirements of the marble-imitated ABS material on hardness, impact strength and scratch resistance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a high-weather-resistance scratch-resistant marble-imitated ABS material and a preparation method thereof.
A high weather-resistant scratch-resistant marble-imitated ABS material is characterized by being formed by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch;
the PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 50-70 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 30-50 parts of polymethyl methacrylate, 0.5-1 part of anti-UV agent and 0.2-2 parts of silicone powder;
the PET/PBT alloy master batch comprises the following raw materials in parts by weight: 1-4 parts of polyethylene terephthalate, 1-4 parts of polybutylene terephthalate, 0.1-2 parts of pigment powder, 0.02-0.1 part of styrene-butadiene-acrylonitrile-maleic anhydride random copolymer and 0.02-0.1 part of dispersing agent.
The high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that the melt index of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer is 15-35 g/10min under the test conditions of 220 ℃ and 10 Kg.
The high-weather-resistance scratch-resistant marble-imitated ABS material and the preparation method thereof are characterized in that the melt index of the polymethyl methacrylate is 2-20 g/10min under the test conditions of 230 ℃ and 3.8 Kg.
The high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that the viscosity of the polyethylene glycol terephthalate is 0.6-0.8 dl/g, and the viscosity of the polybutylene terephthalate is 0.7-0.9 dl/g.
The high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that the pigment powder is one or a mixture of more than two of white pigment, carbon black, transparent blue, transparent yellow and transparent red.
The high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that the UV resistant agent is one or a mixture of more than two of 511G, 770, 328 and UV-P.
The preparation method of the high-weather-resistance scratch-resistant marble-imitated ABS material is characterized by comprising the following steps of:
1) preparing PET/PBT alloy master batch, drying for 3H in a drying oven at 80 ℃, and cooling to normal temperature for later use;
2) respectively pre-drying methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and polymethyl methacrylate in a drying box at the temperature of 80 ℃ for 4 hours, mixing, premixing for 5 minutes in a low-speed stirrer, adding an anti-UV agent and silicone powder, premixing for 5 minutes, discharging, extruding and granulating by a double-screw extruder, and uniformly mixing for later use;
3) and (3) adding 100 parts by weight of the uniformly mixed material obtained in the step 2) and 3-5 parts by weight of the PET/PBT alloy master batch obtained in the step 1) into a stirrer, stirring for 3 minutes, uniformly mixing, adding into an injection molding machine, and performing injection molding to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
The preparation method of the high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that the preparation method of the PET/PBT alloy master batch in the step 1) comprises the following steps: adding 1-4 parts of polyethylene terephthalate, 1-4 parts of polybutylene terephthalate, 0.1-2 parts of pigment powder, 0.02-0.1 part of styrene-butadiene-acrylonitrile-maleic anhydride random copolymer and 0.02-0.1 part of dispersing agent into a stirrer, stirring and mixing for 10-20min, taking out, adding into a double-screw extruder, melting and mixing, extruding, air-drying and granulating to obtain the PET/PBT alloy master batch, wherein the pigment powder is one or a mixture of more than two of white pigment, carbon black, transparent blue, transparent yellow and transparent red.
The preparation method of the high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that 50-70 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 30-50 parts of polymethyl methacrylate, 0.5-1 part of UV resistant agent and 0.2-2 parts of silicone powder in the step 2), wherein the UV resistant agent is one or a mixture of more than two of 511G, 770, 328 and UV-P.
The preparation method of the high-weather-resistance scratch-resistant marble-imitated ABS material is characterized in that the injection molding process in the step 2) has the following requirements: setting the back pressure to be 0 at the beginning, adjusting the temperature of each heating zone, wherein the adjustment requires to be increased every 5 ℃, the PET/PBT alloy master batch is increased by 5 ℃ when being granular, and the dispersion effect of the stripes is adjusted according to the adjustment of the injection molding speed when being completely melted, wherein the temperature of each heating zone is as follows: the first zone is 180 ℃, the second zone is 185 ℃, the third zone is 190 ℃, the fourth zone is 200 ℃ and the fifth zone is 220 ℃.
The invention has the following beneficial effects: (1) the surface hardness of the ABS material is improved by modifying the polymethyl methacrylate alloy, and the surface hardness of the material is improved by compounding with silicone powder and is improved to 2H from the original HB. (2) By adding PET/PBT alloy color master batches, the dispersibility of the master batches with different colors is uneven to form flow lines according to the difference of the melting points of the materials. The modified material has higher hardness and scratch resistance, simultaneously has higher UV resistance effect and has marble texture.
Detailed Description
The present invention will be further illustrated by the following specific examples. In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1:
1. a high-weather-resistance scratch-resistant marble-imitated ABS material is prepared by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch.
The PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 70 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 30 parts of polymethyl methacrylate, 0.8 part of UV resistant agent and 0.5 part of silicone powder.
The PET/PBT alloy master batch comprises the following raw materials in parts by weight: 3 parts of polyethylene terephthalate, 3 parts of polybutylene terephthalate, 0.8 part of white pigment, 0.4 part of carbon black, 0.1 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.06 part of dispersant.
2. The preparation method of the PET/PBT alloy master batch comprises the following steps:
1) 3 parts of polyethylene terephthalate, 3 parts of polybutylene terephthalate, 0.8 part of white pigment, 0.1 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.06 part of dispersant are added into a stirrer and stirred for 10-20 minutes.
2) And adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the PET/PBT alloy white master batch.
3) According to the formula weight, 3 parts of polyethylene terephthalate, 3 parts of polybutylene terephthalate, 0.4 part of carbon black, 0.1 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.06 part of dispersing agent are added into a stirrer together and stirred for 10-20 minutes, and the mixture is melted and mixed by a double-screw extruder, extruded, air-dried and granulated to obtain the PET/PBT alloy black master batch.
3. The preparation method of the high weather-resistant scratch-resistant marble-imitated ABS material comprises the following steps:
ABS and PMMA are respectively pre-dried in a drying box at the temperature of 80 ℃ for 4 hours, 70 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 30 parts of polymethyl methacrylate are mixed, premixed for 5 minutes in a low-speed stirrer, added with 0.8 part of UV resistant agent and 0.5 part of silicone powder, premixed for 5 minutes, discharged, extruded and granulated through a double-screw extruder, and uniformly mixed for later use. And uniformly mixing 100 parts of uniformly mixed material, 2 parts of PET/PBT alloy white master batch and 1 part of PET/PBT alloy black master batch to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
Example 2:
1. a high-weather-resistance scratch-resistant marble-imitated ABS material is prepared by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch.
The PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 60 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 40 parts of polymethyl methacrylate, 0.5 part of UV resistant agent and 1.0 part of silicone powder.
The PET/PBT alloy master batch comprises the following raw materials in parts by weight: 4 parts of polyethylene terephthalate, 4 parts of polybutylene terephthalate, 1.2 parts of white pigment, 0.8 part of carbon black, 0.05 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.1 part of dispersant.
2. The preparation method of the PET/PBT alloy master batch comprises the following steps:
1) adding 4 parts of polyethylene terephthalate, 4 parts of polybutylene terephthalate, 1.2 parts of white pigment, 0.05 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.1 part of dispersing agent into a stirrer and stirring for 10-20 minutes;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the PET/PBT alloy white master batch.
3) According to the formula weight, 4 parts of polyethylene terephthalate, 4 parts of polybutylene terephthalate, 0.8 part of carbon black, 0.05 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.1 part of dispersant are added into a stirrer together and stirred for 10-20 minutes, and the mixture is melted and mixed by a double-screw extruder, extruded and air-dried and granulated to obtain PET/PBT alloy black master batches;
3. the preparation method of the high weather-resistant scratch-resistant marble-imitated ABS material comprises the following steps:
ABS and PMMA are respectively pre-dried in a drying box at the temperature of 80 ℃ for 4 hours, 60 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 40 parts of polymethyl methacrylate are mixed, premixed for 5 minutes in a low-speed stirrer, added with 0.5 part of UV resistant agent and 1.0 part of silicone powder, premixed for 5 minutes, discharged, extruded and granulated through a double-screw extruder, and uniformly mixed for later use. And uniformly mixing 100 parts of uniformly mixed material, 3 parts of PET/PBT alloy white master batch and 2 parts of PET/PBT alloy black master batch to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
Example 3:
1. a high-weather-resistance scratch-resistant marble-imitated ABS material is prepared by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch.
The PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 50 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 50 parts of polymethyl methacrylate, 1.0 part of UV resistant agent and 2.0 parts of silicone powder.
The PET/PBT alloy master batch comprises the following raw materials in parts by weight: 2 parts of polyethylene terephthalate, 2 parts of polybutylene terephthalate, 0.8 part of white pigment, 0.8 part of carbon black, 0.02 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.08 part of dispersant.
2. The preparation method of the PET/PBT alloy master batch comprises the following steps:
1) adding 2 parts of polyethylene terephthalate, 2 parts of polybutylene terephthalate, 0.8 part of white pigment, 0.02 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.08 part of dispersing agent into a stirrer and stirring for 10-20 minutes;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the PET/PBT alloy white master batch.
3) According to the formula weight, 2 parts of polyethylene terephthalate, 2 parts of polybutylene terephthalate, 0.8 part of carbon black, 0.02 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.08 part of dispersing agent are added into a stirrer together and stirred for 10-20 minutes, and the mixture is melted and mixed by a double-screw extruder, extruded and air-dried and granulated to obtain PET/PBT alloy black master batches;
3. the preparation method of the high weather-resistant scratch-resistant marble-imitated ABS material comprises the following steps:
ABS and PMMA are respectively pre-dried in a drying box at the temperature of 80 ℃ for 4H, 50 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 50 parts of polymethyl methacrylate are mixed, premixed for 5 minutes in a low-speed stirrer, added with 1.0 part of UV resistant agent and 2.0 parts of silicone powder, premixed for 5 minutes, discharged, extruded and granulated through a double-screw extruder, and uniformly mixed for later use. And uniformly mixing 100 parts of uniformly mixed material, 2 parts of PET/PBT alloy white master batch and 2 parts of PET/PBT alloy black master batch to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
Example 4:
1. a high-weather-resistance scratch-resistant marble-imitated ABS material is prepared by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch.
The PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 55 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 45 parts of polymethyl methacrylate, 0.6 part of anti-UV agent and 0.2 part of silicone powder.
The PET/PBT alloy master batch comprises the following raw materials in parts by weight: 4 parts of polyethylene terephthalate, 4 parts of polybutylene terephthalate, 0.8 part of white pigment, 1.2 parts of carbon black, 0.04 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.1 part of dispersant.
2. The preparation method of the PET/PBT alloy master batch comprises the following steps:
1) adding 4 parts of polyethylene terephthalate, 4 parts of polybutylene terephthalate, 0.8 part of white pigment, 0.04 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.1 part of dispersing agent into a stirrer and stirring for 10-20 minutes;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the PET/PBT alloy white master batch.
3) According to the formula weight, 4 parts of polyethylene terephthalate, 4 parts of polybutylene terephthalate, 1.2 parts of carbon black, 0.04 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.1 part of dispersant are added into a stirrer together to be stirred for 10-20 minutes, and the mixture is melted and mixed by a double-screw extruder, extruded, air-dried and granulated to obtain the PET/PBT alloy black master batch.
3. The preparation method of the high weather-resistant scratch-resistant marble-imitated ABS material comprises the following steps:
ABS and PMMA are respectively pre-dried in a drying box at the temperature of 80 ℃ for 4 hours, 55 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 45 parts of polymethyl methacrylate are mixed, a low-speed stirrer is premixed for 5 minutes, 0.6 part of UV resistant agent and 0.2 part of silicone powder are added, premixed for 5 minutes and discharged, extruded and granulated through a double-screw extruder, and uniformly mixed for later use. And uniformly mixing 100 parts of uniformly mixed material, 2 parts of PET/PBT alloy white master batch and 2 parts of PET/PBT alloy black master batch to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
Example 5:
1. a high-weather-resistance scratch-resistant marble-imitated ABS material is prepared by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch.
The PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 55 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 45 parts of polymethyl methacrylate, 0.6 part of anti-UV agent and 0.2 part of silicone powder.
The PET/PBT alloy master batch comprises the following raw materials in parts by weight: 1 part of polyethylene terephthalate, 1 part of polybutylene terephthalate, 0.4 part of white pigment, 0.8 part of carbon black, 0.06 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.06 part of dispersant.
2. The preparation method of the PET/PBT alloy master batch comprises the following steps:
1) adding 1 part of polyethylene terephthalate, 1 part of polybutylene terephthalate, 0.4 part of white pigment, 0.06 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.06 part of dispersant into a stirrer and stirring for 10-20 minutes;
2) and adding the mixed material into a double-screw extruder, and carrying out melt mixing, extrusion, air drying and grain cutting to obtain the PET/PBT alloy white master batch.
3) According to the formula weight, 1 part of polyethylene terephthalate, 1 part of polybutylene terephthalate, 0.8 part of carbon black, 0.06 part of styrene-nitrile rubber-maleic anhydride random copolymer and 0.06 part of dispersant are added into a stirrer together and stirred for 10-20 minutes, and the mixture is melted and mixed by a double-screw extruder, extruded, air-dried and granulated to obtain PET/PBT alloy black master batches;
3. the preparation method of the high weather-resistant scratch-resistant marble-imitated ABS material comprises the following steps:
ABS and PMMA are respectively pre-dried in a drying box at the temperature of 80 ℃ for 4 hours, 55 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 45 parts of polymethyl methacrylate are mixed, premixed for 5 minutes in a low-speed stirrer, added with 0.6 part of UV resistant agent and 0.2 part of silicone powder, premixed for 5 minutes, discharged, extruded and granulated through a double-screw extruder, and uniformly mixed for later use. And uniformly mixing 100 parts of uniformly mixed material, 1 part of PET/PBT alloy white master batch and 2 parts of PET/PBT alloy black master batch to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
Comparative example:
the comparison was made with a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer as a comparative example, without any addition of auxiliaries. Comparative examples and examples 1-5 performance tests were performed on the following table 1:
table 1 example sample performance testing
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A high weather-resistant scratch-resistant marble-imitated ABS material is characterized by being formed by injection molding of PMMA/ABS alloy base stock and PET/PBT alloy master batch;
the PMMA/ABS alloy base material comprises the following raw materials in parts by weight: 50-70 parts of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, 30-50 parts of polymethyl methacrylate, 0.5-1 part of anti-UV agent and 0.2-2 parts of silicone powder;
the PET/PBT alloy master batch comprises the following raw materials in parts by weight: 1-4 parts of polyethylene terephthalate, 1-4 parts of polybutylene terephthalate, 0.1-2 parts of pigment powder, 0.02-0.1 part of styrene-butadiene-acrylonitrile-maleic anhydride random copolymer and 0.02-0.1 part of dispersing agent.
2. The marble-like ABS material according to claim 1, wherein the melt index of the methylmethacrylate-acrylonitrile-butadiene-styrene copolymer is 15-35 g/10min at 220 ℃ under 10Kg test condition.
3. The marble-imitated ABS material with high weather resistance and scratch resistance as claimed in claim 1, wherein the polymethyl methacrylate has a melt index of 2-20 g/10min at 230 ℃ and 3.8 Kg.
4. The marble-like ABS material with high weather and scratch resistance as claimed in claim 1, wherein the viscosity of the polyethylene terephthalate is 0.6 to 0.8dl/g, and the viscosity of the polybutylene terephthalate is 0.7 to 0.9 dl/g.
5. The marble-like ABS material according to claim 1, wherein the pigment powder is a mixture of one or more of white pigment, carbon black, transparent blue, transparent yellow and transparent red.
6. The marble-like ABS material of claim 1 wherein the UV resistant agent is one or a mixture of more than two of 511G, 770, 328, UV-P.
7. The method for preparing the marble-imitated ABS material with high weather resistance and scratch resistance as claimed in claim 1, which comprises the following steps:
1) preparing PET/PBT alloy master batch, drying for 3H in a drying oven at 80 ℃, and cooling to normal temperature for later use;
2) respectively pre-drying methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and polymethyl methacrylate in a drying box at the temperature of 80 ℃ for 4 hours, mixing, premixing for 5 minutes in a low-speed stirrer, adding an anti-UV agent and silicone powder, premixing for 5 minutes, discharging, extruding and granulating by a double-screw extruder, and uniformly mixing for later use;
3) and (3) adding 100 parts by weight of the uniformly mixed material obtained in the step 2) and 3-5 parts by weight of the PET/PBT alloy master batch obtained in the step 1) into a stirrer, stirring for 3 minutes, uniformly mixing, adding into an injection molding machine, and performing injection molding to obtain the high-weather-resistance scratch-resistant marble-imitated ABS material.
8. The method for preparing the marble-imitated ABS material with high weather resistance and scratch resistance as claimed in claim 7, wherein the preparation method of the PET/PBT alloy master batch in the step 1) comprises the following steps: adding 1-4 parts of polyethylene terephthalate, 1-4 parts of polybutylene terephthalate, 0.1-2 parts of pigment powder, 0.02-0.1 part of styrene-butadiene-acrylonitrile-maleic anhydride random copolymer and 0.02-0.1 part of dispersing agent into a stirrer, stirring and mixing for 10-20min, taking out, adding into a double-screw extruder, melting and mixing, extruding, air-drying and granulating to obtain the PET/PBT alloy master batch, wherein the pigment powder is one or a mixture of more than two of white pigment, carbon black, transparent blue, transparent yellow and transparent red.
9. The method for preparing the marble-like ABS material with high weather resistance and scratch resistance as claimed in claim 7, wherein the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer in step 2) is 50-70 parts, the polymethyl methacrylate is 30-50 parts, the UV resistant agent is 0.5-1 part, and the silicone powder is 0.2-2 parts, wherein the UV resistant agent is one or a mixture of more than two of 511G, 770, 328 and UV-P.
10. The method for preparing the marble-imitated ABS material with high weather resistance and scratch resistance as claimed in claim 7, wherein the process requirements of the injection molding in the step 2) are as follows: setting the back pressure to be 0 at the beginning, adjusting the temperature of each heating zone, wherein the adjustment requires to be increased every 5 ℃, the PET/PBT alloy master batch is increased by 5 ℃ when being granular, and the dispersion effect of the stripes is adjusted according to the adjustment of the injection molding speed when being completely melted, wherein the temperature of each heating zone is as follows: the first zone is 180 ℃, the second zone is 185 ℃, the third zone is 190 ℃, the fourth zone is 200 ℃ and the fifth zone is 220 ℃.
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