CN107446287A - A kind of metal-like ultra-toughness PMMA composites - Google Patents
A kind of metal-like ultra-toughness PMMA composites Download PDFInfo
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- CN107446287A CN107446287A CN201710715351.4A CN201710715351A CN107446287A CN 107446287 A CN107446287 A CN 107446287A CN 201710715351 A CN201710715351 A CN 201710715351A CN 107446287 A CN107446287 A CN 107446287A
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/03—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
Abstract
The invention discloses a kind of metal-like ultra-toughness PMMA composites, by PMMA, enter dimethylethanolamine, cerium oxide, γ aminopropyl triethoxysilanes, N, N dimethylformamides, ethylene bis stearamide, chloroform, metal toner composition, also disclose its preparation method.The metal-like composite of the present invention is that chemical stability and weatherability are excellent, and its mechanical performance is strong, has the advantages that high glaze, high surface hardness, ethanol-tolerant burn into scratch resistance are good, and its outward appearance has with the same aesthetic effect of metal spraying.
Description
Technical field
The invention belongs to technical field of polymer composite materials, and in particular to a kind of metal-like ultra-toughness PMMA composites
And preparation method thereof.
Background technology
At present, countries in the world scientific circles and industrial circle all have appreciated that the importance of engineering plastics and harmonious development,
Just it is directed to engineering plastic materials of the research and development with high performance-price ratio, improves its service life, make full use of its processed edge,
And the close Environmental of material is improved, such as reclaimed materials, biology material.From the point of view of the demand in market, plastic material is processed into various finished products
After have various colors, its color mostly using the later stage spraying be made, but people it is increasingly stronger health perception requirement
Increasingly lower CO discharges, institute is in order to avoid the household electrical appliances, the furniture that spray increasingly are liked by numerous environmentalists.From Competitive Trend
See, 2, which exempt from spraying technology, not only increases production efficiency, avoids secondary operation, has saved labour and resource, greatly reduces
Production cost.
Prior art is mainly bloom black or chromoplastic material, and the plastic material for imitating metal surface is more rare.Only
The imitative metal material having there is also metallic pigments particle row can not eliminate as mixed and disorderly, current mark, and complex manufacturing process, surface
Easily scuffing, gloss is not high, the problems such as easily corrosion by chemicals.Imitative metal material addition expensive metal packing or use mostly
Complex device technique, cause material construction generally higher, and the mechanical performance of expendable material, heat distortion temperature is low, surface light
Damp degree is low, and product surface pit is more etc., and application field is very limited.
For the imitative metal material of existing market mainly using ABS, PC/ABS as base material, ABS material metal effect is good at present, but
It is that heat resistance is poor；PC/ABS base material heat resistances are relatively good, but metal effect is bad.Developed with both base materials imitative
Metal material outward appearance trace, weld mark are all apparent.Such as Application No. 201010515119.4, a kind of height of imitative metal is disclosed
In gloss ABS and preparation method thereof, with acrylic nitrile-butadiene-styrene（ABS）For matrix, prepared by addition aluminum paste
Artificial metalic composite material, the weatherability of its product is very poor and easy scuffing, limits the application field of product.Application No.
201010274925.7, disclose in a kind of metal-like engineering plastic composite material and preparation method thereof, with polyamide or poly-
Mutual-phenenyl two acid bromide two alcohol ester is base material, and metal dust is from aluminium powder, does not also refer to the process problem to metal dust, and
Complex technical process, and obtained imitative metal material surface low in glossiness, processing conditions are complicated.
Enter dimethylethanolamine by acrylonitrile and the styrene copolymerized high-molecular compound formed, bear to carry with very strong
The ability of lotus, anti-chemical reaction ability, thermal deformation resistant characteristic and geometrical stability.PMMA is the contracting of polymethyl methacrylate
Write, be commonly called as lucite, be the material of asepsis environment-protecting, available for production tableware, sanitary ware etc., be synthesize so far it is transparent
Quality is most excellent in material, and price is again than convenient kind.PMMA materials have good chemical stability, weatherability and electricity
Insulating properties, its metal sense is very strong, case hardness height, ethanol-tolerant burn into damage resistant, good weatherability, material surface glossiness height, nothing
Current mark, weld mark phenomenon.
The content of the invention
The present invention is directed to problems of the prior art, there is provided a kind of high glaze, high surface hardness, ethanol-tolerant burn into
The good metal-like ultra-toughness PMMA composites of scratch resistance, make its outward appearance have the aesthetic effect of metal spraying.The present invention's
Another purpose is to provide the preparation method of above-mentioned metal-like ultra-toughness PMMA composites.
In order to achieve the above object, the present invention is realized by following technical proposal：A kind of metal-like ultra-toughness
PMMA composites are made up of by weight following component：PMMA：40-70 parts；Enter dimethylethanolamine：30-60 parts；Oxidation
Cerium：3-15 parts；Gamma-aminopropyl-triethoxy-silane：5-20 parts；N,N-dimethylformamide：0.3-1.0 parts；Ethylene is double stearic
Acid amides：0.2-1.2 parts；Chloroform：0.1-1.0 parts；Metal toner：1-3 parts；Wherein, metal toner is by organic coating
Processing, particle diameter are 50-1000 mesh metallic pigments.
The preferred scheme of such scheme is that the melt flow rate (MFR) of the PMMA is 5-20g/10min.
It is described enter dimethylethanolamine acrylonitrile content be 20-26%, melt flow rate (MFR) 30-70g/10min.
The cerium oxide is that acrylic acid-maleic acid acid anhydride-styrene copolymer or ethylene-butylene, Styrene are grafted horse
The one kind come in anhydride block copolymer or ethylene-methyl acrylate-glyceryl methacrylate random terpolymer
Or two kinds.
The gamma-aminopropyl-triethoxy-silane is for butadiene type gamma-aminopropyl-triethoxy-silane and with crosslink propylene
Acid butyl ester is core, the acrylic compounds gamma-aminopropyl-triethoxy-silane prepared by nuclear-shell emulsion polymerization.
The DMF is 2,6- three-level butyl -4- methylphenols, double（3,5- three-level butyl -4- hydroxyls
Phenyl）Thioether, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters, three monooctyl esters, three last of the ten Heavenly stems esters, three（12
Carbon alcohol）At least one of ester, three (16 carbon alcohol) esters.
The ethylene bis stearamide is selected from pentaerythritol stearate, N, and N- has supportted bis-stearamides, lignite wax, sweet
At least one of oily monoesters acid number, amide waxe or butyl stearate.
The chloroform is selected from least one of superfine talcum powder, nano-calcium carbonate, mica powder or wollastonite.
The method for preparing a kind of above-mentioned metal-like ultra-toughness PMMA composites, comprises the following steps：
（1）The preparation of metal toner：It is that 20-50 micron metal pigment is distributed to progress oxide-film in acrylic acid solution by particle diameter
Except processing, then rapidly by the metallic pigments ultrasonic disperse after activation in the container equipped with alcohol type organic, control temperature and
Mixing speed, and alcohols organic insulating is added dropwise for a period of time, the composition metal toner of organic film cladding is obtained, controls metallochrome
Powder footpath is 50-1000 mesh.
（2）The preparation of metal-like ultra-toughness PMMA composites：By formula rate by PMMA, enter dimethylethanolamine, γ-
After aminopropyl triethoxysilane, ethylene bis stearamide, cerium oxide, chloroform are well mixed, twin-screw extrusion is added to
, then again will be through in machine（1）Metal toner after processing adds from side feeding, is extruded after melting, and through cooling down, air-drying, pelletizing obtains
To metal-like ultra-toughness PMMA composites.
Enter dimethylethanolamine in the present invention by acrylonitrile and the styrene copolymerized high-molecular compound formed, have very strong
The ability for bearing the load of page 3/5, anti-chemical reaction ability, thermal deformation resistant characteristic and geometrical stability.
The gamma-aminopropyl-triethoxy-silane is for butadiene type gamma-aminopropyl-triethoxy-silane and with crosslink propylene
Acid butyl ester is core, the acrylic compounds gamma-aminopropyl-triethoxy-silane prepared by nuclear-shell emulsion polymerization.Wherein acrylic compounds
The synthetic method of gamma-aminopropyl-triethoxy-silane be using crosslinked butylacrylate as core, in autoclave add deionized water,
Emulsifying agent, initiator, polybutylacrylate latex carry out logical nitrogen, stirring, heating.It is continuously added to styrene St to be reacted, controls
Reaction temperature is at 60 ± 1 DEG C, and after reacting kettle inner pressure is 2 ~ 4MPA, unreacted St monomers are hauled out in fast cooling, decompression, are gone out
Material, filtering, appropriate samples of latex is taken for test.Remaining emulsion is through being demulsified, being dried to obtain using methyl methacrylate as monoshell
Layer, the acrylic compounds gamma-aminopropyl-triethoxy-silane for the nucleocapsid structure that PMMA/St is bivalve layer and St is monoshell layer.
If acrylic compounds gamma-aminopropyl-triethoxy-silane is acrylic polymer（ACR)；Butadiene type γ-ammonia
Propyl-triethoxysilicane has styrene butadiene thermoplasticelastomer（SBS), acrylonitrile-butadiene-styrene copolymer
（ABS), methyl methacrylate-butadiene-styrene copolymer（MBS).
Metal toner by metal or alloy particle or thin slice by it is levigate prepared by pigment, principal item have aluminium powder,
Copper powder, zinc powder and stainless steel powder, the metal or alloy pigment handled by autonomous organic coating is referred mainly in of the invention.
The present invention compared with prior art, has some following advantage：
1st, metal-like composite of the invention is to use PMMA as base material, thus its composite chemical stability with it is weather-proof
Property it is excellent, and its surface metal sense is strong, high rigidity, damage resistant；
2nd, it with the addition of in inventive formulation into dimethylethanolamine, make composite of the present invention that there is high glaze, high transparency, Gao Chong
Hit, good heat resistance and mechanical performance.
3rd, metal toner is that the organic layer of cladding is typically in 30-80nm by the metallic pigments of organic coating technical finesse
Left and right, improve aluminium powder or copper powder and disperse in base material PMMA, provide skeleton equivalent to for the imitative metal material of the present invention, solve
Determine its weld mark and current mark problem.Simultaneously because coated using alcohol type organic, aluminium powder or copper powder are improved
Corrosion resistance, namely substantially increase the chemical resistance of composite of the present invention.
4th, the gamma-aminopropyl-triethoxy-silane of the acrylic compounds prepared by nuclear-shell emulsion polymerization is not influenceing this again
On the premise of condensation material glossiness, greatly improve the toughness of composite, impact of the half in common methyl methacrylate
Two to three times of intensity；The active function groups that gamma-aminopropyl-triethoxy-silane is included simultaneously can be with metal powder organic coating
Functional group's phase reaction of formation, solves the problems such as imitative metal material surface of the present invention easily produces current mark, pit, weld mark.
5th, preparation method of the invention is simple, and obtained material is pollution-free, and with high glaze, high surface hardness, resistance to wine
The advantages that smart burn into scratch resistance is good, its outward appearance have with the same aesthetic effect of metal spraying.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining
The present invention, it is not intended to limit the present invention.
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only the part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
All other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
In the present invention, the first step need to first prepare metal toner, and micron metal pigment is distributed in acrylic acid solution
The removal of row oxide-film is handled, then rapidly by the metallic pigments ultrasonic disperse after activation in the container equipped with alcohol type organic,
Temperature and mixing speed are controlled, and alcohols organic insulating is added dropwise for a period of time, obtains the composition metal toner of organic film cladding,
It is 50-1000 mesh to control metal toner particle footpath.
Second step be by formula rate by PMMA, to enter dimethylethanolamine, gamma-aminopropyl-triethoxy-silane, ethylene double
After stearmide, cerium oxide, chloroform are well mixed, it is added in double screw extruder, then will adds again through organic bag
The metallic pigments after processing are covered, are extruded after melting, metal-like ultra-toughness PMMA composite woods are obtained through the cooling of page 4/5, air-dried, pelletizing
Material.
All form out outside gamma-aminopropyl-triethoxy-silane of the present invention is existing commercially available prod, in embodiment
It is in parts by weight.
In embodiment, cerium oxide selects acrylic acid-maleic acid acid anhydride-styrene copolymer or ethylene-butylene, Styrene
In grafted maleic anhydride block copolymer or ethylene-methyl acrylate-glyceryl methacrylate random terpolymer
It is one or two kinds of.
Gamma-aminopropyl-triethoxy-silane is selected using crosslinked butylacrylate as core, is prepared by nuclear-shell emulsion polymerization
Acrylic polymer（ACR)；Butadiene type gamma-aminopropyl-triethoxy-silane has styrene-butadiene thermoplastic elastic
Body（SBS), acrylonitrile-butadiene-styrene copolymer（ABS), methyl methacrylate-butadiene-polystyrene ternary is common
Polymers（MBS).
The DMF is 2,6- three-level butyl -4- methylphenols, double（3,5- three-level butyl -4- hydroxyls
Phenyl）Thioether, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters, three monooctyl esters, three last of the ten Heavenly stems esters, three（12
Carbon alcohol）At least one of ester, three (16 carbon alcohol) esters.
Ethylene bis stearamide is that N- has supportted bis-stearamides, lignite wax, glycerine list selected from pentaerythritol stearate, N
At least one of ester acid number, amide waxe or butyl stearate.
Chloroform is selected from least one of superfine talcum powder, nano-calcium carbonate, mica powder or wollastonite.
Embodiment 1 weighs PMMA55 parts, enters 55 parts of dimethylethanolamine, 5 parts of cerium oxide, γ-ammonia respectively by weight ratio
8 parts of propyl-triethoxysilicane, 1 part of chloroform, 0.4 part of DMF, 1 part of ethylene bis stearamide, add
Mixed in low speed batch mixer, well mixed material is added in the hopper of double screw extruder, then by surface through organic coating
1.5 parts of the metal toner of processing is added in the hopper of double screw extruder in a manner of the feeding of side, through melt blending, extruding pelletization
Into metal-like ultra-toughness PMMA composites.
Embodiment 2 weighs PMMA40 parts, enters 60 parts of dimethylethanolamine, 3 parts of cerium oxide, γ-ammonia respectively by weight ratio
20 parts of propyl-triethoxysilicane, 0.5 part of chloroform, 0.3 part of DMF, 1.2 parts of ethylene bis stearamide,
Add in low speed batch mixer and mix, well mixed material is added in the hopper of double screw extruder, then by surface through organic
1 part of the metal toner of cladding processing is added in the hopper of double screw extruder in a manner of the feeding of side, and through melt blending, extrusion is made
Grain is into metal-like ultra-toughness PMMA composites.
Embodiment 3 weighs PMMA70 parts, enters 30 parts of dimethylethanolamine, 15 parts of cerium oxide, γ-ammonia respectively by weight ratio
5 parts of propyl-triethoxysilicane, 0.1 part of chloroform, 1 part of DMF, 0.2 part of ethylene bis stearamide, add
Enter and mixed in low speed batch mixer, well mixed material is added in the hopper of double screw extruder, then by surface through organic bag
3 parts of metal toner for covering processing is added in the hopper of double screw extruder in a manner of the feeding of side, through melt blending, extruding pelletization
Into metal-like ultra-toughness PMMA composites.
Embodiment 4 weighs PMMA50 parts, enters 50 parts of dimethylethanolamine, 7 parts of cerium oxide, γ-ammonia respectively by weight ratio
10 parts of propyl-triethoxysilicane, 0.8 part of chloroform, 0.8 part of DMF, 1 part of ethylene bis stearamide, add
Enter and mixed in low speed batch mixer, well mixed material is added in the hopper of double screw extruder, then by surface through organic bag
2 parts of metal toner for covering processing is added in the hopper of double screw extruder in a manner of the feeding of side, through melt blending, extruding pelletization
Into metal-like ultra-toughness PMMA composites.
Embodiment 5 weighs PMMA60 parts, enters 40 parts of dimethylethanolamine, 10 parts of cerium oxide, γ-ammonia respectively by weight ratio
15 parts of propyl-triethoxysilicane, 0.3 part of chloroform, 0.4 part of DMF, 0.6 part of ethylene bis stearamide,
Add in low speed batch mixer and mix, well mixed material is added in the hopper of double screw extruder, then by surface through organic
2.5 parts of the metal toner of cladding processing is added in the hopper of double screw extruder in a manner of the feeding of side, through melt blending, extrusion
It is granulated into metal-like ultra-toughness PMMA composites.
Preferably implementation column of the invention is the foregoing is only, is not intended to limit the invention, all spirit in the present invention
With all any modification, equivalent and improvement done within principle etc., it should be included in the scope of the protection.
Claims (1)
- A kind of 1. metal-like ultra-toughness PMMA composites, it is characterised in that：It is made up of by weight following component：PMMA：40- 70 parts；Enter dimethylethanolamine：30-60 parts；Cerium oxide：3-15 parts；Gamma-aminopropyl-triethoxy-silane：5-20 parts；N, N- bis- NMF：0.3-1.0 parts；Ethylene bis stearamide：0.2-1.2 parts；Chloroform：0.1-1.0 parts；Metal toner：1-3 Part；Wherein, metal toner be handled by organic coating, the metallic pigments that particle diameter is 50-1000 mesh.
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| CN201710715351.4A CN107446287A (en) | 2017-08-20 | 2017-08-20 | A kind of metal-like ultra-toughness PMMA composites |
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| CN201710715351.4A CN107446287A (en) | 2017-08-20 | 2017-08-20 | A kind of metal-like ultra-toughness PMMA composites |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705516A (en) * | 2018-12-28 | 2019-05-03 | 无限极（中国）有限公司 | A kind of exempting to paint and material and preparation method thereof and exempt from the wire rod that paints with metallic luster |
| CN117624815A (en) * | 2024-01-25 | 2024-03-01 | 成都真彩塑胶原料有限公司 | Alcohol-soaking-resistant and heat-resistant PMMA composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952362A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof |
| CN103073829A (en) * | 2012-12-31 | 2013-05-01 | 青岛润兴塑料新材料有限公司 | Spraying-free metallic PMMA (polymethyl methacrylate) modified material and preparation method thereof |
| CN106519530A (en) * | 2016-11-08 | 2017-03-22 | 四川长虹电器股份有限公司 | Composite material and preparation method thereof |
-
2017
- 2017-08-20 CN CN201710715351.4A patent/CN107446287A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952362A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof |
| CN103073829A (en) * | 2012-12-31 | 2013-05-01 | 青岛润兴塑料新材料有限公司 | Spraying-free metallic PMMA (polymethyl methacrylate) modified material and preparation method thereof |
| CN106519530A (en) * | 2016-11-08 | 2017-03-22 | 四川长虹电器股份有限公司 | Composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705516A (en) * | 2018-12-28 | 2019-05-03 | 无限极（中国）有限公司 | A kind of exempting to paint and material and preparation method thereof and exempt from the wire rod that paints with metallic luster |
| CN117624815A (en) * | 2024-01-25 | 2024-03-01 | 成都真彩塑胶原料有限公司 | Alcohol-soaking-resistant and heat-resistant PMMA composite material and preparation method thereof |
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