CN104558810A - Low-gloss polypropylene composite and preparation method thereof - Google Patents
Low-gloss polypropylene composite and preparation method thereof Download PDFInfo
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- CN104558810A CN104558810A CN201410843440.3A CN201410843440A CN104558810A CN 104558810 A CN104558810 A CN 104558810A CN 201410843440 A CN201410843440 A CN 201410843440A CN 104558810 A CN104558810 A CN 104558810A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
Abstract
The invention provides a low-gloss polypropylene composite and a preparation method thereof. Modified polypropylene has low gloss while maintaining excellent mechanical properties. The low-gloss polypropylene composite comprises components in parts by mass as follows: 40-90 parts of polypropylene resin, 5-30 parts of inorganic filler, 5-30 parts of a matting agent and 0.2-0.4 parts of an antioxidant. The modified polypropylene prepared by blending and extruding the components has low gloss and excellent mechanical properties, and can be widely used as a material for automobiles and electronics.
Description
One. technical field:
The present invention relates to a kind of preparation method of modified polypropene, specifically a kind of low-luster polypropylene matrix material and preparation method thereof.
Two. background technology:
The advantages such as polypropylene (PP) has that density is low, mechanical property is more excellent, also has good proof stress be full of cracks, antifatigue surrender and chemical resistance and has low price, easily machine-shaping, reclaim, reusable edible, obtain a wide range of applications, particularly continue to increase in the application of automotive industry, household electrical appliances and mechanical field.But because polypropylene material resistance to low temperature is poor, rigidity is lower, the service requirements for inner and outer decorative parts of automobile can not be reached, therefore for modification must be carried out to it.The modification of the main method of modifying of polypropylene flexible body tenacity-increased profax; The modification of Inorganic Fillers Filled Reinforced Polypropylene; And utilize polypropylene, mineral filler, elastomerics three acting in conjunction touchened reinforced polypropylene study on the modification.
Along with the development of automobile industry, people have higher requirement to automobile: light-duty, energy-conservation, attractive in appearance, safety, environmental protection etc., also more and more higher to the requirement of driving indoor comfort.If the glossiness of cab inside gadget is higher, just have stronger light reflection, thus affect the comfortableness of navigating mate.Therefore, automotive upholstery needs lower glossiness.
The method being eliminated gloss by embossed surface is applied to practice, but requires independent step, add cost, and abrasion subsequently also can remove the lacklustre surface of embossing, thus gloss is reproduced.
Also can obtain low-luster additionally by product surface spray dumb light paint, but its production cost is higher, and sometimes can not meets service requirements, along with the prolongation of production time, may need again to process.
There are some researches show and added filler in small, broken bits, as silicon-dioxide, silicate, aluminate or other mineral filler can reduce the glossiness of polypropylene composite material, but mineral filler addition is less, and glossiness reduces not obvious, does not reach service requirements; Add the reduction that can cause again too much goods physicals, especially the reduction of shock strength is more remarkable, also has the reduction of corresponding heat-drawn wire, the reduction of welded seam intensity, thermal ageing and photoaging deficiency in addition.
Three. summary of the invention:
The invention reside in and obtain low-luster polypropylene matrix material by adding matting agent, this modified polypropene not only has lower glossiness, and excellent in mechanical performance.
A kind of low-luster polypropylene matrix material, its feature is as follows: its component comprises: acrylic resin 40 ~ 90 mass parts; Mineral filler 5 ~ 30; Matting agent 5 ~ 30 mass parts; Oxidation inhibitor 0.2 ~ 0.4 mass parts.
Described acrylic resin 50 ~ 80 mass parts; Described mineral filler 10 ~ 25; Described matting agent 10 ~ 25 mass parts.
Use matting agent for band epoxy functional polymer graft rubber.
Described band epoxy functional polymer graft rubber, its grafting is mutually for being with the polymkeric substance of epoxy-functional monomers's molecule or being with epoxy-functional monomers's molecule and the multipolymer not with epoxy-functional monomers's molecule, and its rubber matrix is any one in diene, ethylene-octene, Ethylene/Butylene, paracril and silicon rubber.
Described band epoxy-functional monomers is any one in glycidyl acrylate, glycidyl methacrylate and alkyl glycidyl ether; Described is not any one in ethene, propylene with epoxy-functional monomers.Described matting agent is acrylate-glycidyl ester grafted ethene-octene rubber: divide Ethylene-octene rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 30 mass parts acrylate-glycidyl esters, 70 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product;
Or matting agent is glycidyl methacrylate graft silicon rubber: divide silicone rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 10 mass parts glycidyl methacrylate, 90 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product;
Matting agent 3 is alkyl glycidyl ether grafting paracril: divide paracril matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 10 mass parts alkyl glycidyl ethers, 90 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
The particle diameter of described rubber matrix is 0.05 micron to 30 microns.
The particle diameter of described rubber matrix is 0.05 micron to 10 microns.
The ratio of described grafting phase and rubber matrix is 1:10 to 20:10.
A kind of preparation method of low-luster polypropylene matrix material, it is characterized in that acrylic resin 40 ~ 90 mass parts, mineral filler 5 ~ 30, matting agent 5 ~ 30 mass parts, oxidation inhibitor 0.2 ~ 0.4 mass parts, under the processing temperature of 160 DEG C ~ 230 DEG C, blended melting is extruded.
Low-luster polypropylene matrix material of the present invention can also carry out modification by typical additives, comprises toughener (glass fibre and carbon fiber etc.), toughner, softening agent, mobility properties-correcting agent, thermo-stabilizer, releasing agent, fire retardant, tinting material and other thermoplastic resin etc.
Beneficial effect:
1, the present invention is preferred, and matting agent addition causes gloss reduction amplitude less compared with I haven't seen you for ages, and do not reach delustring requirement, matting agent addition can increase cost more at most, and can reduce the physicals of polypropylene composite material.Core element of the present invention is matting agent 1-3, and it has remarkable delustring compared with commercially available matting agent, and simultaneously the physicals such as impelling strength, modulus in flexure, tensile strength is well kept.
2, the low-luster polypropylene matrix material gloss obtained by the present invention is soft.
3, the low-luster polypropylene matrix material extinction effect obtained by the present invention is given prominence to, and the physicalies such as impelling strength, modulus in flexure, tensile strength are well kept, and can be widely used in the field such as automobile, electronic apparatus.
Four. embodiment:
Better the present invention can be described by following examples, but be not limited to these embodiments.
In the examples below, polypropylene is the K8003 that Yanshan Petrochemical is produced; Inorganic rigid particle is the talcum powder that Haicheng City Ai Hai talcum company limited of Liaoning Province produces, and antioxidant is the antioxidant 1010 that Yantai rising star's chemical article company limited produces; POE is the LG170 of Korea S LG chemical production; Matting agent 1 is acrylate-glycidyl ester grafting Afpol; Matting agent 2 is glycidyl methacrylate graft silicon rubber; Matting agent 3 is alkyl glycidyl ether grafting Afpol.
Test bending property according to GB/T9341-2000, GB/T1843-1996 tests impact property, GB1040-92 tests tensile property, GB/T3682-2000 tests melt flow rate, measures gloss at normal temperatures with Konica Minolta multi gloss 268 Grossmeters (60 °).
Graft process:
Matting agent 1 (acrylate-glycidyl ester grafted ethene-octene rubber): divide Ethylene-octene rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 30 mass parts acrylate-glycidyl esters, 70 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
Matting agent 2 (glycidyl methacrylate graft silicon rubber): divide silicone rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 10 mass parts glycidyl methacrylate, 90 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
Matting agent 3 (alkyl glycidyl ether grafting paracril): divide paracril matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 10 mass parts alkyl glycidyl ethers, 90 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
Matting agent as a comparison:
Matting agent 4 (acrylate-glycidyl ester grafted ethene-octene rubber): divide Ethylene-octene rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 20 mass parts acrylate-glycidyl esters, 80 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
Matting agent 5 (glycidyl methacrylate graft silicon rubber): divide silicone rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 2 mass parts to press down linking agent triphenyl phosphite 5 mass parts glycidyl methacrylate, 95 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
Matting agent 6 (alkyl glycidyl ether grafting paracril): divide paracril matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 5 mass parts alkyl glycidyl ethers, 95 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
Embodiment 1:
(1) technical recipe
(2) complete processing
By the oxidation inhibitor of the acrylic resin of 75 mass parts, 20 mass parts talcum powder, 5 mass parts matting agents 1 (acrylate-glycidyl ester grafting Afpol), 0.3 mass parts in high-speed mixer 80 ~ 90 DEG C mixing 5 minutes, then extruding pelletization on the twin screw extruder, the temperature of forcing machine is: 190 DEG C, an interval, two, 195 DEG C, three interval, four, 200 DEG C, five, six, seven, eight interval, nine 195 DEG C, intervals, through extrusion moulding low-luster polypropylene matrix material.
Low-luster polypropylene matrix material is obtained by this technique.Its performance is in table 1.
Embodiment 2:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Embodiment 3:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Embodiment 4:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Embodiment 5:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Embodiment 6:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Embodiment 7:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Comparative example 1:
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 1.
Comparative example 2 (comparing with embodiment 1)
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 2.
Comparative example 3 (embodiment 6 compares)
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 2.
Comparative example 4 (comparing with embodiment 7)
Technical recipe
Above-mentioned formula is shaping according to embodiment 1 complete processing, obtained low-luster polypropylene matrix material.Its performance is in table 2.
Table 1: performance data.
Paper examines index of the present invention is glossiness, and its numerical value lower explanation glossiness is lower, and effect is better; All will lower than comparative example 1 by the glossiness can finding out embodiment 1-7 in table 1, and embodiment 5 glossiness is minimum, is only 1/7th of comparative example 1.
Whether prepare matting agent to affect the mechanical properties performance for investigating different ratios, namely adopt embodiment 2, embodiment 6, embodiment 7 with comparative example 1 compared with, its other components are the same, just matting agent difference.Result table 1.Find notched Izod impact strength by table 1, flexural strength, modulus in flexure and comparative example 1 are more or less the same, but eliminate optical property is widely different, embodiment 2, embodiment 6, embodiment 7 is all 15, and comparative example 1 is 35, illustrate that matting agent of the present invention can ensure original mechanical property, delustring is remarkable again.
Ratio whether key factor is prepared for investigating whether matting agent of the present invention further, contriver adopts and uses embodiment 2 and comparative example 2 respectively, embodiment 6 and comparative example 3, embodiment 7 is compared with embodiment 4: as table 2: result display comparison example 2-4 indices is worse than the present invention, particularly dullness.Therefore matting agent 1-3 specified proportion of the present invention ensures its delustring important factor.
Table 2: performance data.
Claims (9)
1. a low-luster polypropylene matrix material, its feature is as follows: its component comprises: acrylic resin 40 ~ 90 mass parts; Mineral filler 5 ~ 30; Matting agent 5 ~ 30 mass parts; Oxidation inhibitor 0.2 ~ 0.4 mass parts.
2. a kind of low-luster polypropylene matrix material according to claim 1, is characterized in that, described acrylic resin 50 ~ 80 mass parts; Mineral filler 10 ~ 25; Matting agent 10 ~ 25 mass parts.
3. a kind of low-luster polypropylene matrix material according to any one of claim 1-2, is characterized in that: described matting agent is band epoxy functional polymer graft rubber.
4. a kind of low-luster polypropylene matrix material according to claim 4, it is characterized in that: described band epoxy functional polymer graft rubber, its grafting is mutually for being with the polymkeric substance of epoxy-functional monomers's molecule or being with epoxy-functional monomers's molecule and the multipolymer not with epoxy-functional monomers's molecule, and its rubber matrix is any one in diene, ethylene-octene, Ethylene/Butylene, paracril and silicon rubber.
5. a kind of low-luster polypropylene matrix material according to claim 5, is characterized in that: described band epoxy-functional monomers is any one in glycidyl acrylate, glycidyl methacrylate and alkyl glycidyl ether; Described is not any one in ethene, propylene with epoxy-functional monomers.
6. according to claim 3 low-luster polypropylene matrix material, described matting agent is acrylate-glycidyl ester grafted ethene-octene rubber: divide Ethylene-octene rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 30 mass parts acrylate-glycidyl esters, 70 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product;
Or matting agent is glycidyl methacrylate graft silicon rubber: divide silicone rubber matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 10 mass parts glycidyl methacrylate, 90 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product;
Matting agent 3 is alkyl glycidyl ether grafting paracril: divide paracril matrix, 0.3 mass parts initiator dicumyl peroxide, 3 quality to divide cografting monomer styrene, 1 mass parts to press down linking agent triphenyl phosphite 10 mass parts alkyl glycidyl ethers, 90 quality, after fully mixing, under the processing temperature of 160 DEG C ~ 200 DEG C, extrude pelletizing by twin screw extruder obtain graft product.
7. a kind of low-luster polypropylene matrix material according to claim 6, is characterized in that, the particle diameter of described rubber matrix is 0.05 micron to 30 microns.
8. a kind of low-luster polypropylene matrix material according to claim 7, is characterized in that, the particle diameter of described rubber matrix is 0.05 micron to 10 microns.
9. the preparation method of a kind of low-luster polypropylene matrix material as described in claim 1-8, is characterized in that acrylic resin 40 ~ 90 mass parts; Mineral filler 5 ~ 30; Matting agent 5 ~ 30 mass parts; Oxidation inhibitor 0.2 ~ 0.4 mass parts, under the processing temperature of 160 DEG C ~ 230 DEG C, blended melting is extruded.
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| CN201410843440.3A CN104558810A (en) | 2014-12-30 | 2014-12-30 | Low-gloss polypropylene composite and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610985A (en) * | 2016-12-16 | 2018-10-02 | 远东新世纪股份有限公司 | Low-gloss sheet and molded article thereof |
| CN115011032A (en) * | 2022-05-20 | 2022-09-06 | 南京金杉汽车工程塑料有限责任公司 | Preparation method of polypropylene composite material with low glossiness and high toughness |
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| US20070049682A1 (en) * | 2005-09-01 | 2007-03-01 | Walsh David J | Soft polymer compositions having improved high temperature properties |
| CN102532774A (en) * | 2010-12-16 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Low-gloss polypropylene composite material and preparation method thereof |
| CN102786768A (en) * | 2012-08-09 | 2012-11-21 | 南京金杉汽车工程塑料有限责任公司 | Low-glossiness ABS (acrylonitrile butadiene styrene) resin and preparation method of low-glossiness ABS resin |
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Patent Citations (4)
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| CN1678682A (en) * | 2002-08-01 | 2005-10-05 | 兰科瑟斯公司 | Thermoplastic composition having low gloss appearance |
| US20070049682A1 (en) * | 2005-09-01 | 2007-03-01 | Walsh David J | Soft polymer compositions having improved high temperature properties |
| CN102532774A (en) * | 2010-12-16 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Low-gloss polypropylene composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108610985A (en) * | 2016-12-16 | 2018-10-02 | 远东新世纪股份有限公司 | Low-gloss sheet and molded article thereof |
| CN108610985B (en) * | 2016-12-16 | 2020-06-16 | 远东新世纪股份有限公司 | Low-gloss sheet and molded article thereof |
| CN115011032A (en) * | 2022-05-20 | 2022-09-06 | 南京金杉汽车工程塑料有限责任公司 | Preparation method of polypropylene composite material with low glossiness and high toughness |
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