CN102952362B - Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof - Google Patents

Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof Download PDF

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CN102952362B
CN102952362B CN201210458184.7A CN201210458184A CN102952362B CN 102952362 B CN102952362 B CN 102952362B CN 201210458184 A CN201210458184 A CN 201210458184A CN 102952362 B CN102952362 B CN 102952362B
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metal
pmma
powder
toughner
matrix
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CN102952362A (en
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杨亚娣
任东方
李荣群
姚其海
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Orinko Advanced Plastics Co Ltd
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HEFEI ORINKO PLASTICS GROUP CO Ltd
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Abstract

The invention discloses a metallic super-toughened PMMA (polymethyl methacrylate) composite material which consists of PMMA, AS (acrylonitrile) resin, a compatilizer, a flexibilizer, an antioxidant, a lubricant, a reinforcing agent and metal powder. The invention also discloses a preparation method of the metallic super-toughened PMMA composite material. The metallic composite material disclosed by the invention has excellent chemical stability and weather resistance, has a strong mechanical performance and has the advantages of high gloss, high surface hardness, resistance to alcohol corrosion, good scraping resistance and the like; and the appearance of the metallic super-toughened PMMA composite material has the same aesthetic effect with that formed by metal spraying.

Description

Super tough PMMA matrix material of a kind of metal-like and preparation method thereof
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to super tough PMMA matrix material of a kind of metal-like and preparation method thereof.
technical background
At present, countries in the world scientific circles and industrial community have all been recognized the importance of engineering plastics and harmonious development, just be devoted to the engineering plastic materials that research and development have high performance-price ratio, improve its work-ing life, make full use of its processed edge, and improve the close environment of material, as reclaimed materials, biological material.From the demand in market, plastic material has various colors after being processed into various finished products, and its color adopts later stage spraying to make mostly, but the more and more stronger health perception of people requires more and more lower CO 2discharge, institute in case the household electrical appliances, the furniture that spray more and more by numerous environmentalists, liked.From Competitive Trend, exempt from spraying technology and not only improved production efficiency, avoided secondary processing, saved labor force and resource, greatly reduce production cost.
Prior art is mainly high light black or colored plastic material, and the plastic material of imitative metallic surface is more rare.The metallic pigment particle row that only imitative metallic substance also exists cannot eliminate as mixed and disorderly, current mark, and complex manufacturing process, and surface easily scratches, gloss is not high, easily by problems such as chemical corrosion.Mostly imitative metallic substance adds expensive metallic stuffing or adopts complex apparatus technique, causes material cost generally higher, and the mechanical property of expendable material, heat-drawn wire is low, surface gloss is low, and product surface pit is many etc., and Application Areas is very limited.
The imitative metallic substance of existing market is mainly to take ABS, PC/ABS as base material at present, and ABS material metal is effective, but thermotolerance is poor; PC/ABS base material thermotolerance is relatively good, but metal effect is bad.The imitative metallic substance outward appearance trace developing with these two kinds of base materials, weld mark are all clearly.If application number is 201010515119.4, disclose in a kind of high gloss ABS Alloy And Preparation Method of imitative metal, the acrylic nitrile-butadiene-styrene (ABS) of take is matrix, add aluminium-silver slurry and prepare artificial metalic composite material, the weathering resistance of its product is very poor and easily scratch, and has limited the Application Areas of product.Application number is 201010274925.7, disclose in a kind of metal-like engineering plastic composite material and preparation method thereof, take polymeric amide or polybutylene terephthalate as base material, metal-powder is for selecting aluminium powder, do not mention the processing problem to metal-powder yet, and complex technical process, and the imitative metal material surface low in glossiness making, processing conditions is complicated.
AS resin, by vinyl cyanide and the styrene copolymerized macromolecular compound forming, has the ability of very strong carry load, anti-chemical reaction ability, thermal deformation resistant characteristic and geometrical stability.PMMA is the abbreviation of polymethylmethacrylate, is commonly called as synthetic glass, is the material of asepsis environment-protecting, can be used for producing tableware, sanitary ware etc., is that to synthesize up to now in transparent material quality the most excellent, and price is more suitable kind again.PMMA material has good chemical stability, weathering resistance and electrical insulating property, and its metal sense is very strong, surface hardness is high, ethanol-tolerant burn into damage resistant, good weatherability, and material surface glossiness is high, without current mark, weld mark phenomenon.
Summary of the invention
The present invention is directed to problems of the prior art, a kind of high gloss, high surface hardness, the super tough PMMA matrix material of metal-like that ethanol-tolerant burn into scratch resistance is good are provided, make its outward appearance there is the aesthetic effect of metal spraying.Another object of the present invention is to provide the preparation method of the super tough PMMA matrix material of above-mentioned metal-like.
In order to achieve the above object, the present invention realizes by following technical proposal:
The super tough PMMA matrix material of a kind of metal-like consists of by weight following component:
PMMA:40-70 part;
AS resin: 30-60 part;
Compatilizer: 3-15 part;
Toughner: 5-20 part;
Oxidation inhibitor: 0.3-1.0 part;
Lubricant: 0.2-1.2 part;
Toughener: 0.1-1.0 part;
Metal toner: 1-3 part;
Wherein, metal toner is for process organic coating is processed, particle diameter is 50-1000 order metallic pigment.
The preferred version of such scheme is that the melt flow rate (MFR) of described PMMA is 5-20 g/10min.
The acrylonitrile content of described AS resin is that 20-26%, melt flow rate (MFR) are 30-70 g/10min.
Described compatilizer is a kind of in vinylformic acid-maleic anhydride-styrene terpolymer or ethene-butylene-styrene grafted maleic anhydride segmented copolymer or ethylene-methyl acrylate-glyceryl methacrylate random terpolymer or two kinds.
Described toughner is butadiene type toughner and take crosslink propylene acid butyl ester as core, the acrylic acid or the like toughner prepared by nuclear-shell emulsion polymerization.
Described oxidation inhibitor is 2, tri-grades of butyl-4-methylphenols of 6-, two (3, tri-grades of butyl-4-hydroxy phenyls of 5-) in thioether, four (β-(tri-grades of butyl-4-hydroxy phenyls of 3,5-) propionic acid) pentaerythritol ester, three monooctyl esters, three last of the ten Heavenly stems ester, three (Lauryl Alcohol) ester, three (16 carbon alcohol) esters at least one.
Described lubricant is for being selected from pentaerythritol stearate, N, and N-has supportted at least one in bis-stearamides, montanin wax, monoglyceride acid number, amide waxe or butyl stearate.
Described toughener is for being selected from least one in superfine talcum powder, nano-calcium carbonate, mica powder or wollastonite.
The method of preparing the super tough PMMA matrix material of above-mentioned a kind of metal-like, comprises the following steps:
(1) preparation of metal toner:
By particle diameter, be that 20-50 micron metal colo(u)rant dispersion is carried out oxide film Transformatin in acrylic acid solution, then rapidly ultrasonic being dispersed in of metallic pigment after activation is equipped with in the organic container of alcohols, control temperature and stirring velocity, and drip alcohols organic insulating for some time, obtain the coated composition metal toner of organic membrane, controlling metallic color powder footpath is 50-1000 order.
2) preparation of the super tough PMMA matrix material of metal-like:
After PMMA, AS resin, toughner, lubricant, compatilizer, toughener being mixed by formula rate, join in twin screw extruder, and then the metal toner after process (1) is added from side feeding, after melting, extrude, through cooling, air-dry, pelletizing, obtain the super tough PMMA matrix material of metal-like.
In the present invention, AS resin, by vinyl cyanide and the styrene copolymerized macromolecular compound forming, has the ability of very strong carry load, anti-chemical reaction ability, thermal deformation resistant characteristic and geometrical stability.
Described toughner is butadiene type toughner and take crosslink propylene acid butyl ester as core, the acrylic acid or the like toughner prepared by nuclear-shell emulsion polymerization.Wherein the synthetic method of acrylic acid or the like toughner is to take crosslink propylene acid butyl ester as core, adds deionized water, emulsifying agent, initiator, polybutylacrylate latex to lead to nitrogen, stirring, intensification in autoclave.Add continuously vinylbenzene St to react, control temperature of reaction at 60 ± 1 ℃, after reacting kettle inner pressure is 2 ~ 4MPA, fast cooling, unreacted St monomer is hauled out in step-down, and discharging, filtration are got appropriate samples of latex for test.All the other emulsions through breakdown of emulsion, dry obtain take methyl methacrylate as monoshell layer, PMMA/St as bivalve layer and acrylic acid or the like toughner that St is the nucleocapsid structure of monoshell layer.
If acrylic acid or the like toughner is acrylic polymer (ACR); Butadiene type toughner has styrene butadiene thermoplasticelastomer (SBS), acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-divinyl-styrene copolymer (MBS).
Metal toner passes through pigment levigate and that make by particle or the thin slice of metal or alloy, and principal item has aluminium powder, copper powder, zinc powder and Stainless Steel Powder, mainly refers to metal or the alloy pigment through autonomous organic coating, processed in the present invention.
The present invention compared with prior art, has following some advantage:
1, metal-like matrix material of the present invention is that to adopt PMMA be base material, so its matrix material chemical stability and weathering resistance are good, and its surface metal sense strongly, high rigidity, damage resistant;
2, in the present invention formula, added AS resin, made matrix material of the present invention there is high gloss, high transparent, HI high impact, good thermotolerance and mechanical property.
3, metal toner is the metallic pigment through organic coating technical finesse, coated organic layer is generally in 30-80nm left and right, improved the dispersion in base material PMMA of aluminium powder or copper powder, be equivalent to, for the imitative metallic substance of the present invention provides skeleton, solve its weld mark and current mark problem.Due to what adopt, be that alcohol type organic is coated simultaneously, improved the corrosion resistance of aluminium powder or copper powder, also greatly improved the chemical resistant properties of matrix material of the present invention.
The toughner of the acrylic acid or the like of 4, preparing by nuclear-shell emulsion polymerization is not affecting under the prerequisite of this matrix material glossiness, and the toughness of matrix material is improved greatly, two to three times of half shock strength at common methyl methacrylate; Functional group's phase reaction that the active function groups that toughner comprises simultaneously can form with metal powder organic coating, has solved the imitative metal material surface of the present invention and has easily produced the problems such as current mark, pit, weld mark.
5, preparation method of the present invention is simple, and the material making is pollution-free, and has the advantages such as high gloss, high surface hardness, ethanol-tolerant burn into scratch resistance be good, and its outward appearance has the same aesthetic effect of same metal spraying.
embodiment:
Provide embodiment below so that the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field some nonessential improvement that content is made the present invention according to the present invention and adjustment still belong to protection scope of the present invention.
In the present invention, the first step need first be prepared metal toner, micron metal colo(u)rant dispersion is carried out to oxide film Transformatin in acrylic acid solution, then rapidly ultrasonic being dispersed in of metallic pigment after activation is equipped with in the organic container of alcohols, control temperature and stirring velocity, and drip alcohols organic insulating for some time, and obtain the coated composition metal toner of organic membrane, controlling metallic color powder footpath is 50-1000 order.
Second step is after PMMA, AS resin, toughner, lubricant, compatilizer, toughener being mixed by formula rate, join in twin screw extruder, and then by the metallic pigment that add after organic coating is processed, after melting, extrude, through cooling, air-dry, pelletizing, obtain the super tough PMMA matrix material of metal-like.
Of the present inventionly allly form toughner and be existing commercially available prod outward, in embodiment all in weight part.
In embodiment, compatilizer is selected a kind of in vinylformic acid-maleic anhydride-styrene terpolymer or ethene-butylene-styrene grafted maleic anhydride segmented copolymer or ethylene-methyl acrylate-glyceryl methacrylate random terpolymer or two kinds.
Toughner is selected and be take crosslink propylene acid butyl ester as core, the acrylic polymer of preparing by nuclear-shell emulsion polymerization (ACR); Butadiene type toughner has styrene butadiene thermoplasticelastomer (SBS), acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-divinyl-styrene copolymer (MBS).
Described oxidation inhibitor is 2, tri-grades of butyl-4-methylphenols of 6-, two (3, tri-grades of butyl-4-hydroxy phenyls of 5-) in thioether, four (β-(tri-grades of butyl-4-hydroxy phenyls of 3,5-) propionic acid) pentaerythritol ester, three monooctyl esters, three last of the ten Heavenly stems ester, three (Lauryl Alcohol) ester, three (16 carbon alcohol) esters at least one.
Lubricant is for being selected from pentaerythritol stearate, N, and N-has supportted at least one in bis-stearamides, montanin wax, monoglyceride acid number, amide waxe or butyl stearate.
Toughener is for being selected from least one in superfine talcum powder, nano-calcium carbonate, mica powder or wollastonite.
embodiment 1
Take respectively by weight ratio 55 parts of PMMA, 55 parts of AS resins, 5 parts of compatilizers, 8 parts of toughner, 1 part of toughener, 0.4 part, oxidation inhibitor, 1 part of lubricant, add in low speed mixer and mix, the material mixing is added in the hopper of twin screw extruder, 1.5 parts of the metal toners again surface processed through the organic coating mode with side feeding adds in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes the super tough PMMA matrix material of metal-like.
embodiment 2
Take respectively by weight ratio 40 parts of PMMA, 60 parts of AS resins, 3 parts of compatilizers, 20 parts of toughner, 0.5 part of toughener, 0.3 part, oxidation inhibitor, 1.2 parts of lubricants, add in low speed mixer and mix, the material mixing is added in the hopper of twin screw extruder, 1 part of the metal toner again surface processed through the organic coating mode with side feeding adds in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes the super tough PMMA matrix material of metal-like.
embodiment 3
Take respectively by weight ratio 70 parts of PMMA, 30 parts of AS resins, 15 parts of compatilizers, 5 parts of toughner, 0.1 part of toughener, 1 part, oxidation inhibitor, 0.2 part of lubricant, add in low speed mixer and mix, the material mixing is added in the hopper of twin screw extruder, 3 parts of the metal toners again surface processed through the organic coating mode with side feeding adds in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes the super tough PMMA matrix material of metal-like.
embodiment 4
Take respectively by weight ratio 50 parts of PMMA, 50 parts of AS resins, 7 parts of compatilizers, 10 parts of toughner, 0.8 part of toughener, 0.8 part, oxidation inhibitor, 1 part of lubricant, add in low speed mixer and mix, the material mixing is added in the hopper of twin screw extruder, 2 parts of the metal toners again surface processed through the organic coating mode with side feeding adds in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes the super tough PMMA matrix material of metal-like.
embodiment 5
Take respectively by weight ratio 60 parts of PMMA, 40 parts of AS resins, 10 parts of compatilizers, 15 parts of toughner, 0.3 part of toughener, 0.4 part, oxidation inhibitor, 0.6 part of lubricant, add in low speed mixer and mix, the material mixing is added in the hopper of twin screw extruder, 2.5 parts of the metal toners again surface processed through the organic coating mode with side feeding adds in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes the super tough PMMA matrix material of metal-like.
Sample in above-described embodiment 1-5 is injection molded into GB batten according to unified technique, according to testing standard and condition, it is carried out respectively to measuring mechanical property, its test data is as shown in the table.
Table: the main physical index of the super tough PMMA matrix material of metal-like:
As can be seen from the above table, metal-like matrix material of the present invention is that chemical stability and weathering resistance are good, and its mechanical property is strong, there is the advantages such as high gloss, high surface hardness, ethanol-tolerant burn into scratch resistance be good, its outward appearance has the same aesthetic effect of same metal spraying.
The foregoing is only the better implementation column of the present invention, not in order to limit the present invention, all any modifications of making within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (6)

1. the super tough PMMA matrix material of metal-like, is characterized in that: following component, consist of by weight:
PMMA:40-70 part;
AS resin: 30-60 part;
Compatilizer: 3-15 part;
Toughner: 5-20 part;
Oxidation inhibitor: 0.3-1.0 part;
Lubricant: 0.2-1.2 part;
Toughener: 0.1-1.0 part;
Metal toner: 1-3 part;
Wherein, described toughner is to take crosslink propylene acid butyl ester as core, the acrylic acid or the like toughner prepared by nuclear-shell emulsion polymerization;
Described compatilizer is a kind of in vinylformic acid-maleic anhydride-styrene terpolymer, ethene-butylene-styrene grafted maleic anhydride segmented copolymer or two kinds;
Described lubricant is for being selected from N, and N-has supportted at least one in bis-stearamides, montanin wax, amide waxe or butyl stearate;
Described metal toner is to obtain by method organic coating processing below: by particle diameter, be that 20-50 micron metal colo(u)rant dispersion is carried out oxide film Transformatin in acrylic acid solution, then rapidly ultrasonic being dispersed in of metallic pigment after activation is equipped with in the organic container of alcohols, control temperature and stirring velocity, and drip alcohols organic insulating for some time, obtain the coated composition metal toner of organic membrane, controlling metallic color powder footpath is 50-1000 order;
Above-mentioned matrix material is after first PMMA, AS resin, toughner, lubricant, compatilizer, toughener being mixed, join in twin screw extruder, and then metal toner is added from its side feeding, after melting, extrude, through cooling, air-dry, pelletizing is resulting.
2. the super tough PMMA matrix material of a kind of metal-like according to claim 1, is characterized in that: the melt flow rate (MFR) of described PMMA is 5-20 g/10min.
3. the super tough PMMA matrix material of a kind of metal-like according to claim 1, is characterized in that: the acrylonitrile content of described AS resin is that 20-26%, melt flow rate (MFR) are 30-70 g/10min.
4. the super tough PMMA matrix material of a kind of metal-like according to claim 1, it is characterized in that: described oxidation inhibitor is 2,6-di-tert-butyl-4-methy phenol, two (3,5-di-tert-butyl-hydroxy phenyl) in thioether, four [β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, three monooctyl esters, three last of the ten Heavenly stems ester, three (Lauryl Alcohol) ester, three (16 carbon alcohol) esters at least one.
5. the super tough PMMA matrix material of a kind of metal-like according to claim 1, is characterized in that: described toughener is for being selected from least one in superfine talcum powder, nano-calcium carbonate, mica powder or wollastonite.
6. the super tough PMMA matrix material of a kind of metal-like according to claim 1; it is characterized in that: described metal toner is particle or the levigate pigment of making of thin slice process of metal or alloy; through organic coating, process metallic particles aluminium powder, copper powder, zinc powder and the Stainless Steel Powder of use.
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