CN1490352A - Composition containing phenylethylene-maleic anhydride random copolymer - Google Patents
Composition containing phenylethylene-maleic anhydride random copolymer Download PDFInfo
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- CN1490352A CN1490352A CNA021374503A CN02137450A CN1490352A CN 1490352 A CN1490352 A CN 1490352A CN A021374503 A CNA021374503 A CN A021374503A CN 02137450 A CN02137450 A CN 02137450A CN 1490352 A CN1490352 A CN 1490352A
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Abstract
A composition containing atactic styrene-maleic acid anhydride copolymer is prepared from SMA, impact improver, coloring mother particles of plastics and glass fibre. Said impact improver is chosen from SBS, MBS and ACR. Its advantages are high strength and high impact strength for notch.
Description
Technical field
The present invention relates to a kind of composition that contains atactic styrene-maleic anhydride copolymer, particularly about the composition of glass fibre reinforced styrene-maleic anhydride random copolymer of containing pigment.
Background technology
Glass fibre reinforced styrene-copolymer-maleic anhydride (glass strengthens the SMA resin) makes it become possibility as structural timber owing to significantly improved mechanical strength, thermotolerance, the dimensional stability of SMA resin, and, be widely used in automotive industry and make structured materials such as air-conditioning grid as instrument board framework, household electrical appliances industry owing to the raw material good strong rival who becomes polycarbonate (PC), polyphenylene oxide engineering plastics such as (PPO) of processing fluidity easy to manufacture that is easy to get.
Styrene-maleic anhydride copolymer is because the rigidity of molecular structure is big, shock resistance is very poor, though strengthening the back resistance to impact shock through glass fibre increases, use but still can not satisfy industrial some, so the glass fibre reinforced styrene-copolymer-maleic anhydride that uses as structural timber is meant that generally glass fibre strengthens the SMA resin of toughening modifying.Toughness reinforcing SMA resin can obtain by SMA resin and (impact modifying agent) blend of some thermoplastic elastomer or with some rubber copolymerized method.
From angle attractive in appearance, usually also need glass to strengthen the SMA resin in actual applications and have various colors, therefore strengthening the SMA resin at the preparation glass also needs to add a certain amount of pigment.The method of coloring plastic has pigment dry mix, aqueous tinting material method, pasty state tinting material method and Masterbatch staining method etc.Before in the several method since pigment be condensed into bigger particle easily or in some crystalline resin, play the nucleator effect; so the adding of pigment usually can reduce some performance such as shock strength, the heat-drawn wire etc. of plastics, and shortcomings such as dust, pollution are arranged.The Masterbatch staining method is because superior, easy to use, no dust of coloring effect and pollution, use the most extensive, but the Masterbatch of different carriers resin is bigger to the impact property influence of some plastics, particularly notch-sensitive glass filament reinforced plastics such as glass fibre is strengthened the SMA resin.
World patent WO9115543 has described composition and the manufacture method thereof that a kind of glass fibre strengthens the SMA resin complexes, this method has adopted the impact modifying agent of the ABS resin (the SAN resin can be selected to add) of high rubber content as the SMA resin, it requires the ratio of maleic anhydride weight content of the glass fibre weight content of whole mixture and SMA resin between 0.62～1.40, therefore the SMA resin that only is suitable for maleic anhydride weight content higher (22～40%), there is the low shortcoming of shock strength in the SMA of the glass fibre of preparation enhancing simultaneously resin complexes, and for example 20% glass fibre of their preparation enhancing (SMA40 weight part+ABS50 weight part+SAN10 weight part) composite I zod parallel direction shock strength is 9.8 kilojoule/rice
2And the vertical direction shock strength only is 8.8 kilojoule/rice
2, the non-notched Izod impact strength of Charpy only is 18.6 kilojoule/rice
2Japanese patent laid-open 4-345645 has also reported a kind of manufacture method that glass fibre that fascia uses strengthens the SMA resin complexes of doing, this method is to adopt the impact modifying agent of thermoplastic elastomers such as SBS or MBS as the SMA resin, but owing to need prepare the SMA masterbatch of high content of glass fiber with special equipment, so technology is complicated.Preceding method does not all solve pigment strengthens the influence of SMA resin complexes shock strength to glass fibre problem.
Summary of the invention
Technical problem to be solved by this invention is to solve to exist the composition mechanical strength of the glass fibre reinforced styrene-maleic anhydride random copolymer that contains the pigment component for preparing low in the conventional art, shock strength is low, the problem of notched Izod impact strength difference provides a kind of new composition that contains atactic styrene-maleic anhydride copolymer.It is good that said composition has mechanical property, the characteristics that notched Izod impact strength is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of composition that contains atactic styrene-maleic anhydride copolymer comprises following component in parts by weight:
A) random copolymers of phenylethylene-maleic anhydride (SMA) is 40～85 parts, and wherein maleic anhydride content is 5～35% by weight percentage;
B) impact modifying agent is 10～25 parts, wherein rubber constituent is 50～90% by weight percentage, and impact modifying agent is selected from styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene graft copolymer (MBS) or acrylate nucleocapsid multipolymer (ACR) and composition thereof;
C) the plastic color master grain is 0.1～10 part, wherein by weight percentage in the plastic color master grain pigment be 20～50%;
D) glass fibre is 1～40 part.
In the technique scheme, be 55～75 parts in random copolymers (SMA) the consumption preferable range of parts by weight phenylethylene-maleic anhydride, the maleic anhydride content preferable range is 15～25% by weight percentage.The molecular weight of atactic styrene-maleic anhydride copolymer is 10～300,000 in addition, and preferable range is 15～250,000.The impact modifying agent preferred version is selected from methyl methacrylate-butadiene-styrene graft copolymer (MBS), and the rubber constituent preferable range is 70～90% in the impact modifying agent by weight percentage.In parts by weight, plastic color master grain consumption preferable range is 1～5 part, wherein by weight percentage in the plastic color master grain amount of pigment preferable range be 30～50%; Plastic color master grain preferred version is for being carrier with ABS resin or EVA resin and composition thereof, and the carrier consumption is 40～70% of a plastic color master grain weight; Also can contain auxiliary agents such as paucidisperse agent, coupling agent, oxidation inhibitor, static inhibitor or brightening agent in the plastic color master grain, its consumption is generally 0.1～10% of plastic color master grain weight.Glass fibre is in parts by weight, and the consumption preferable range is 10～30 parts, and the glass fibre preferred version is an alkali free glass fibre, and form can be a continuous fiber, also staple fibre.The most handy silane coupling agent of fiberglass surfacing is handled.Silane coupling agent commonly used has triethoxyl silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloyl propyl trimethoxy silicane, N-β-(aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-aminopropyl triethoxysilane or γ-Racemic glycidol propyl ether Trimethoxy silane coupling agent treatment.
Glass of the present invention strengthens the SMA resin combination except above-mentioned main component, also can add additives such as filler, oxidation inhibitor, ultra-violet stabilizer, does not describe in detail one by one at this.
The preparation method of the present composition can use Banbury (Banbury) Banbury mixer, single screw rod or twin screw extruder, and is wherein the most frequently used with twin screw extruder.Resin alloy and glass fibre strengthen and can divide secondary to finish also can once to finish.Secondary processes strengthens aforementioned blend with glass fibre more for the second time and obtains promptly earlier all resins and additive melt blending granulation in proportion under molten state.One-time process is that resin, additive and glass fibre obtain through a melt blending granulation.Take one-time process and secondary processes to depend primarily on processing units, more more economical from the energy consumption one-time process than secondary processes.Processing temperature generally can change between 200～300 ℃, but with best between 220～260 ℃.
Raw material more particularly of the present invention and testing method are as follows:
Raw material
The SMA resin: Shanghai Petroleum Chemical Engineering Institute produces, maleic anhydride quality percentage composition 16～25%.
The MBS resin: Japanese clock deep pool chemical company produces, and wherein rubber constituent is 70～90 weight %.
Carbon black: the trade mark DL-430 of Shanghai Cabot chemical industry company limited.
Polyvinyl resin base carbon black Masterbatch (carbon black+PE Masterbatch): the trade mark PE2705 of Shanghai Cabot chemical industry company limited
ABS resin base carbon black Masterbatch (30 weight % carbon blacks+70 weight %ABS Masterbatchs): Shanghai plastics 21 factories, the trade mark 5070.
Phthalocyanine blue and EVA resin base phthalocyanine blue Masterbatch (50 weight % phthalocyanine blues+50 weight %EVA resin Masterbatchs): auspicious Dehua, Shanghai worker's pigment business department.
Antioxidant 1010: Shanghai Gaoqiao-vapour clings to chemical company limited and produces.
Alkali free glass fibre: huge strong glass fibre company limited of Tongxiang, Zhejiang megalith group, RP986, diameter 13 μ.
Testing method
Calcination remnants press ASTM D2584.
Tensile strength is pressed ASTM D638, I class sample, draw speed 5.1 mm/min.
Bending property is pressed ASTM D790,3.2 mm thick samples.
The Izod shock strength is pressed ASTM D256A, 3.2 mm thick samples.
Heat-drawn wire (HDT) is pressed ASTM D648,1.82MPa load, 6.4 mm thick specimen sizes.
Owing to selected suitable impact modifying agent and plastic color master grain, make the composition mechanical property for preparing obtain bigger raising among the present invention, notched Izod impact strength has also obtained improving by a relatively large margin simultaneously, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[comparative example 1～2 and embodiment 1]
Mixing in a container in back adding twin screw extruder first feeder (being fit to the pellet feeding) by proportion of composing in the table one through exsiccant SMA resin (wherein the maleic anhydride weight percent content is 18%) and carbon black (or carbon black+ABS Masterbatch), MBS resin (wherein rubber constituent is 70 weight %) mixes the back with 1010 oxidation inhibitor and adds in twin screw extruder second feeder (suitable powder feeding).Twin screw extruder (German Leistritz company, screw diameter Φ=27 millimeter, length-to-diameter ratio L/D=36) each section temperature (from charging opening to head) is set at 200 ℃ respectively, and 220 ℃, 230 ℃, 235 ℃, 240 ℃.Aforementioned component adds the twin screw extruder from first feeder and second feeder by the speed of prior calibration respectively simultaneously, alkali free glass fibre is introduced continuously from forcing machine middle part charging opening, the extruder screw rotating speed is 100～150 rev/mins, be extruded into bar-shaped sample and strengthen the SMA resin complexes, promptly contain the composition of atactic styrene-maleic anhydride copolymer through the glass fibre that the water-cooled pelletizing promptly obtains black.
Above-mentioned resin complexes is used plastic-injection moulding machine (model SZ-68/400 85 ℃ of dryings after 2 hours, China Liuzhou plastics machinery head factory Shanghai subsidiary factory) is injection molded into ASTM standard batten, injecting condition is 250 ℃ of injection temperatures, injection pressure 9MPa (gauge pressure), injection cycle 60 seconds.Batten carries out performance measurement after room temperature is placed at least 24 hours.The content of glass fiber of glass fibre enhancing SMA resin complexes can directly get granulated samples or the injection moulding batten is measured by ignition test.
Table one contains the composition and performance of the glass fibre enhancing SMA resin complexes of pigment
| Numbering | Comparative example 1 | Comparative example 2 | Embodiment 1 |
| Form (parts by weight) SMA MBS antioxidant 1010 carbon black carbon black+PE Masterbatch carbon black+ABS Masterbatch alkali-free glass fibre, % | ????84 ????16 ????0.5 ????1 ? ? ????17 | ????84 ????16 ????0.5 ? ????2 ? ????19 | ????84 ????16 ????0.5 ? ? ????2 ????18.4 |
| The performance tensile strength, the MPa flexural strength, the MPa bending elastic modulus, MPa Izod shock strength, joules per meter HDT (1.82MPa), ℃ | ? ????81.4 ????130 ????5034 ????82 ????127 | ? ????79.9 ????134 ????5230 ????73 ????129 | ? ????81.3 ????140 ????5612 ????94 ????128 |
Can find out from the result of last table, it is all lower to adopt the glass fibre that directly adds carbon black (comparative example 1) and add polyvinyl resin base carbon black Masterbatch (comparative example 2) preparation to strengthen SMA resin complexes shock strength, and adopts method of the present invention with the glass fibre enhancing SMA resin complexes that ABS resin base carbon black Masterbatch (embodiment 1) prepares high impulse strength and mechanical property to be arranged.
[comparative example 3 and embodiment 2～3]
The operational path identical with Comparative Examples 1 and embodiment 1, just pigment adopts phthalocyanine blue and EVA resin base phthalocyanine blue Masterbatch respectively, SMA resin (wherein MA content is 24 weight %) is 80: 20 and 70: 30 with the ratio of the quality of MBS resin (wherein rubber constituent is 90 weight %), and the gained glass fibre strengthens SMA resin complexes performance such as table two.
Table two contains the composition and performance of the glass fibre enhancing SMA resin complexes of pigment
| Numbering | Comparative Examples 3 | Embodiment 2 | Embodiment 3 |
| Form (parts by weight) SMA MBS antioxidant 1010 phthalocyanine blue phthalocyanine blue+EVA Masterbatch alkali free glass fibre, % | ? ????80 ????20 ????0.5 ????1 ? ????15 | ? ????80 ????20 ????0.5 ? ????2 ????15 | ? ????70 ????30 ????0.5 ? ????4 ????14 |
| The performance tensile strength, the MPa flexural strength, the MPa bending elastic modulus, MPa Izod shock strength, joules per meter HDT (1.82MPa), ℃ | ? ????71.9 ????109 ????4622 ????86 ????127 | ? ????73.2 ????110 ????4699 ????109 ????126 | ? ????62.8 ????86 ????4018 ????126.1 ????120 |
Can find out that from the result of last table adopting the glass fibre enhancing SMA resin complexes ratio that adds the preparation of EVA resin base phthalocyanine blue Masterbatch directly to add the blue glass fibre enhancing SMA resin complexes for preparing of monastral blue has high impulse strength.
The present invention adopts the resin-based glass fibre that contains the preparation of pigment colour master batch of ABS resin or EVA to strengthen the SMA resin complexes preferably that shock strength and mechanical property are because ABS resin or EVA resin have consistency preferably with the SMA resin, make pigment glass fibre strengthen in the SMA resin dispersion more even due to.
Claims (8)
1, a kind of composition that contains atactic styrene-maleic anhydride copolymer comprises following component in parts by weight:
A) random copolymers of phenylethylene-maleic anhydride is 40～85 parts, and wherein maleic anhydride content is 5～35% by weight percentage;
B) impact modifying agent is 10～25 parts, wherein rubber constituent is 50～90% by weight percentage, and impact modifying agent is selected from styrene-butadiene-styrene block copolymer, methyl methacrylate-butadiene-styrene graft copolymer or acrylate nucleocapsid multipolymer and composition thereof;
C) the plastic color master grain is 0.1～10 part, wherein by weight percentage in the plastic color master grain pigment be 20～50%;
D) glass fibre is 1～40 part.
2,, it is characterized in that maleic anhydride content is 15～25% by weight percentage in 55～75 parts of the random copolymerss of parts by weight phenylethylene-maleic anhydride according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1.
3,, it is characterized in that impact modifying agent is selected from methyl methacrylate-butadiene-styrene graft copolymer according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1.
4,, it is characterized in that rubber constituent is 70～90% by weight percentage in the impact modifying agent according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1.
5, according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1, it is characterized in that in parts by weight plastic color master grain be 1～5 part, wherein by weight percentage in the plastic color master grain pigment be 30～50%.
6, according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1, it is characterized in that the plastic color master grain is a carrier with ABS resin or EVA resin and composition thereof, the carrier consumption is 40～70% of a plastic color master grain weight.
7,, it is characterized in that glass fibre is an alkali free glass fibre according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1.
8,, it is characterized in that glass fibre counts 10～30 parts with parts by weight according to the described composition that contains atactic styrene-maleic anhydride copolymer of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA021374503A CN1490352A (en) | 2002-10-16 | 2002-10-16 | Composition containing phenylethylene-maleic anhydride random copolymer |
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| CNA021374503A CN1490352A (en) | 2002-10-16 | 2002-10-16 | Composition containing phenylethylene-maleic anhydride random copolymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352666B (en) * | 2007-07-26 | 2010-08-25 | 中国石油化工股份有限公司 | Compound demulsifying agent and method of use thereof |
| CN101864117A (en) * | 2010-03-05 | 2010-10-20 | 上海锦湖日丽塑料有限公司 | Glass fiber reinforced styrene resin blends with good appearance and mechanical property and preparation method thereof |
| CN102493016A (en) * | 2011-12-21 | 2012-06-13 | 苏州大学 | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof |
| CN114621553A (en) * | 2022-03-09 | 2022-06-14 | 金发科技股份有限公司 | Styrene maleic anhydride copolymer composite material and preparation method and application thereof |
-
2002
- 2002-10-16 CN CNA021374503A patent/CN1490352A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352666B (en) * | 2007-07-26 | 2010-08-25 | 中国石油化工股份有限公司 | Compound demulsifying agent and method of use thereof |
| CN101864117A (en) * | 2010-03-05 | 2010-10-20 | 上海锦湖日丽塑料有限公司 | Glass fiber reinforced styrene resin blends with good appearance and mechanical property and preparation method thereof |
| CN101864117B (en) * | 2010-03-05 | 2013-03-13 | 上海锦湖日丽塑料有限公司 | Glass fiber reinforced styrene resin blends with good appearance and mechanical property and preparation method thereof |
| CN102493016A (en) * | 2011-12-21 | 2012-06-13 | 苏州大学 | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof |
| CN102493016B (en) * | 2011-12-21 | 2014-08-20 | 苏州大学 | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof |
| CN114621553A (en) * | 2022-03-09 | 2022-06-14 | 金发科技股份有限公司 | Styrene maleic anhydride copolymer composite material and preparation method and application thereof |
| CN114621553B (en) * | 2022-03-09 | 2023-09-26 | 金发科技股份有限公司 | Styrene maleic anhydride copolymer composite material and preparation method and application thereof |
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