CN102050927A - Compound rubber modified styrene series resin composition and preparation method thereof - Google Patents
Compound rubber modified styrene series resin composition and preparation method thereof Download PDFInfo
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- CN102050927A CN102050927A CN2009102095486A CN200910209548A CN102050927A CN 102050927 A CN102050927 A CN 102050927A CN 2009102095486 A CN2009102095486 A CN 2009102095486A CN 200910209548 A CN200910209548 A CN 200910209548A CN 102050927 A CN102050927 A CN 102050927A
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Abstract
The invention discloses a rubber modified styrene series resin composition. The total content of rubber is 1 to 40 weight percent, and the rubber consists of superfine powder rubber and polybutadiene rubber. The composition is prepared by the following method of: adding styrene series polymer monomer or styrene series polymer monomer and unsaturated monomer, the superfine powder rubber and the polybutadiene rubber into a reaction kettle, stirring the mixture uniformly, and then performing polymerization. The prepared compound rubber modified styrene series composition has the advantages of insulation, easiness in forming and processing, low moisture absorption and the like, and has good tensile strength, cracking resistance and breakdown resistance.
Description
Technical field
The present invention relates to styrene resin composite of a kind of compounded rubber modification and preparation method thereof, more particularly, the present invention relates to a kind of ultra fine powder rubber and cis-1,4-polybutadiene rubber modified styrene resin composition and preparation method thereof.
Background technology
Polystyrene (PS) because of its abundant raw material, low price, be easy to forming process, water absorbability is little and transparent advantage such as good, has application widely in industry and civilian every field, is the very big a kind of general-purpose plastics of consumption.But polystyrene has determined shortcoming on its mechanical property as insufficient strength height, poor toughness etc., especially to show brittle behaviour because of the immanent structure of its molecular chain.This makes its range of application be restricted to a great extent.
More the method for traditional rubber toughened polystyrene adopts cis-1,4-polybutadiene rubber to be dissolved in and carries out graft polymerization in the styrene monomer, is the styrene resin that contains rubber of CN 1254722A and the method for preparation as patent publication No..Though but the rubber modified polystyrene polymkeric substance of this method preparation has good cantilever beam impact strength, hammer falling impact strength deficiency, the lower intensity of dropping hammer have then limited the ability of material puncture in transportation and use, and breakage rate is higher.
The rerum natura requirement of rubber modified polystyrene polymkeric substance, not only need to have high cantilever beam impact strength, tensile strength, also must possess good hammer falling impact strength, could not only satisfy rupture strength, the tensile strength of material but also have certain resistance and wear intensity.
In order to improve above-mentioned several rerum natura demand simultaneously, patent CN1536005A adopts three kinds of rubber toughened polystyrene polymkeric substance, these three kinds of rubber are respectively styrene-butadiene rubber(SBR), high along divinyl rubber and low along divinyl rubber, different rubber forms different rubber sizes and distributes, and makes the sum of the small particle size (0.05～0.4 μ m) in the polymkeric substance account for more than 80% of all particles sum.In order to make the rubber particles that forms the different-grain diameter size in the polymkeric substance, particle diameter control and polymerization technique are comparatively complicated in this patent.
Summary of the invention
The purpose of this invention is to provide a kind of rubber-modified styrene resin composition that has both high cantilever beam impact strength and hammer falling impact strength and preparation method thereof, preparation technology is simple for this styrene resin composite, can implement in the preparation high-impact polystyrene.
The total content of rubber is 1～40wt% in the described rubber-modified styrene resin composition, is preferably 3～30wt%, more preferably 5～25wt%, most preferably 5～10wt%.
Rubber in the described rubber-modified styrene resin composition by: ultra fine powder rubber and polybutadiene rubber are formed, and both weight ratios are 0.01: 1～1: 1, are preferably 0.05: 1～0.5: 1, more preferably 0.05: 1～0.2: 1.
The characteristics of described ultra fine powder rubber are less, the epigranulars of particle diameter, and its particle diameter is generally 20～500nm, is preferably 30～400nm, and more excellent is 50～300nm.Be characterized in that crosslinking degree is higher, the present invention adopts the method for the known mensuration gel content of the industry to characterize the crosslinking degree of rubber.The gel content of described powdered rubber generally is not less than 60wt%, preferably is not less than 70wt%, more preferably is not less than 90wt%.The swelling index of described powdered rubber is not more than 15, preferably is not more than 13.Each particulate in this powdered rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase, and it need not to add separant and gets final product unrestricted flow.
Kind for powdered rubber does not have any restriction, can be any in powder styrene butadiene rubber, powder natural rubber and the powder divinyl rubber, preferential choice of powder styrene-butadiene rubber(SBR), this rubber particle and preparation method thereof is disclosed among the Chinese patent CN1152082C, and its full content is introduced the present invention as a reference.
Described ultra fine powder rubber can prepare preceding 48 hours 0～100% adding mineral oil by powdered rubber weight at styrene resin composite, be preferably 0～50%, after treating after 48 hours that the powdered rubber part is oil-filled, help the dispersion of rubber particles in polystyrene substrate in the polymerization process.
Described polybutadiene rubber comprises that cis-rich polybutadiene rubber is (more than the cis-structure 90mol%, mooney viscosity 30～50ML100 ℃ 1+4, visual gel≤3) and low-cis-polybutadiene rubber (cis-structure 20～50mol%, mooney viscosity 30～60ML100 ℃ 1+4, visual gel≤3), preferentially select low-cis-polybutadiene rubber for use.
Rubber-modified styrene resin composition of the present invention be rubber particles by above-mentioned two kinds of rubber constituents as disperse phase, styrenic is formed as external phase.The rubber particles size distribution is between 0.05～2.0 μ m, and wherein ultra fine powder rubber forms the small particle size rubber particles of 0.05～0.3 μ m, and polybutadiene rubber then forms medium particle diameter of 0.3～2.0 μ m and big particle diameter rubber particles.Small particle size (0.05～0.3 μ m) rubber particles quantity accounts for more than 80% of rubber particles total amount.The face integration rate (rubber particles accounts for the face integration rate of resin combination in the unit surface of square section) that small particle size (0.05～0.3 μ m) rubber particles accounts for resin combination is 0.1%～4%, and more excellent is 0.5%～2%.
A specific embodiment for preparing ultra fine powder rubber of the present invention is:
With the synthesizing butadiene styrene rubber emulsion is raw material, adds linking agent and stirs one hour, adopts the high energy gamma source x ray irradiation x afterwards, makes rubber components crosslinked, gets cross-linking type butylbenzene rubber latex, and the gel content of emulsion should be not less than 60wt%, and swelling index should be not more than 15.Obtain powder styrene butadiene rubber after the drying.
The linking agent that adds is selected from (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, a kind of in Diethylene Glycol (methyl) acrylate, Vinylstyrene, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, preferential (methyl) Isooctyl acrylate monomer of selecting.Carry out the high energy gamma source ray that irradiation adopted and to comprise cobalt source, X-ray, ultraviolet ray and high-energy electron accelerator.Preferentially select for use the cobalt source to carry out irradiation, dosage is 2.5Mrad, and dose rate is 50Gy/min.Drying process can adopt spray-drying process or precipitation desiccating method, the preferably spray drying method, the inlet temperature of spray-dryer is 100 ℃～200 ℃, and temperature out is 20 ℃～80 ℃, collects dried ultra fine powder rubber particle with certain gel content in cyclonic separator.
Among the present invention, the employed monomer of styrenic is: vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl-dimethyl benzene, vinyl ethylbenzene etc., a kind of or two or more uses of above-mentioned monomer.Described styrenic also can be got with other unsaturated monomer copolymerization by above-mentioned monomer.Described unsaturated monomer is for example: vinyl cyanide, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc.Only adopt vinylbenzene as polymerization single polymerization monomer in the embodiment of the invention.
Radical polymerization is preferably adopted in polymerization of the present invention, and initiating method can adopt thermal initiation or initiator to cause.Initiator can use simple function group initiator or multifunctional initiator, and the simple function group initiator is as Potassium Persulphate, dicumyl peroxide, hydrogen phosphide cumene, dibenzoyl peroxide, peroxide di-t-butyl etc.Multifunctional initiator as: 1,1-cyclohexane di-tert-butyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane, di-tert-butyl peroxide-six hydrogen-terephthalate etc.The consumption of initiator is the 0.1wt%～2wt% of styrene monomer total amount.
Above-mentioned radical polymerization can add organic solvent, and described organic solvent preferably adopts 6～20 aromatic hydrocarbons, as benzene,toluene,xylene, ethylbenzene, pentane, octane, hexanaphthene, methylethylketone, acetone and methyl butyl ketone etc.The consumption of organic solvent is generally 0～60wt% of styrene monomer total amount, is preferably 10～30wt%.
The known some other auxiliary agent of the also available industry in above-mentioned radical polymerization process in addition, as anti-aging agent, antioxidant, concrete as: 2,2,4-trimethylammonium-1,2-dihydroquinoline polymer (RD); Four [3-(3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid] pentaerythritol ester (1010), three (2, the 4-di-t-butyl) phenyl phosphites (168), distearyl pentaerythritol diphosphite (618), CPPD N cyclohexyl N (4010), 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol (2246), 3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester (1076) etc.; Thermo-stabilizer, concrete as Zinic stearas, lead stearate, cadmium stearate.
Polymeric reaction temperature of the present invention is controlled at 50～250 ℃, is preferably 80～180 ℃.For controlling polymers molecular weight and raising monomer conversion, can adopt the form of stage feeding polymerization, promptly be chosen in the corresponding time of polymerization under the different polymeric temperature of reaction, for example polymerization temperature and corresponding time are: 100 ℃～130 ℃ following 4 hours, 130 ℃～140 ℃ were reacted 1 hour, and 140 ℃～170 ℃ were reacted 1 hour.Polymerization pressure is 0～3kg/cm
2
By conventional devolatilization, the drying and other steps of polymer melt process that obtains after the polyreaction, obtain the styrene resin composite of modified rubber of the present invention.
The styrene resin composite of modified rubber of the present invention, be on the basis of traditional rubber-modified styrene resin, introduced the rubber particles of this peculiar physical property of ultra fine powder rubber, has good consistency between itself and polystyrene substrate, in polystyrene substrate, formed homogeneous, nano level rubber particle, formed the reasonable distribution of rubber size in polystyrene substrate with polybutadiene rubber.The rubber modified polystyrene resin composition of gained not only has tensile strength, cantilever beam impact strength preferably, also has good hammer falling impact strength.Simultaneously, preparation method of the present invention is simple, does not have complicated technological processs such as particle diameter control, can implement on existing enhancing touthness of polyphenylethylene by adding device fully.
Compounded rubber modified phenylethylene system: compositions of the present invention not only have pure polystyrene insulation, be easy to advantages such as forming process, water absorbability be little, and have tensile strength, rupture strength and resistance preferably and wear intensity.Can be widely used in fields such as household electrical appliances, electronic apparatus industry and equipment industry, all occupy the very big market as meter case, lampshade, instrument part, telecommunication part, auto parts and medical facilities aspect.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment 1 sample.
Embodiment
The invention is further illustrated by the following examples, to deepen the understanding of the present invention.Below given embodiment be for better the explanation rather than the restriction the present invention.
Physical testing
1, gel content: press the GB/t18474-2001 test.
2, the mensuration of swelling index: with reference to Chinese patent CN1145662C Instructions Page 3 disclosed method.
3, socle girder notched Izod impact strength (kJ/m
2): test according to GB/T1843-1996.
4, tensile yield strength (Mpa): test according to GB/T1040-1992.
5, drop impact energy of perforation (J): according to ISO6603-2:2000
Embodiment 1
1, preparation styrene-butadiene rubber(SBR) powder:
Commercially available styrene-butadiene latex (Yanshan Petrochemical production, the trade mark: XSBRL-54B1) place a container, under agitation dropwise addition of acrylic acid isocaprylic acid 75g with solid content 50wt%, after being added dropwise to complete, continue to stir one hour, use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃～160 ℃, temperature out is 40 ℃～60 ℃, collects dried carboxylic styrene-butadiene rubber powder in cyclonic separator, obtains free flowable full sulfuration styrene-butadiene rubber(SBR) powder.The median size that records powdered rubber is about 150nm, and gel content is 92.6%, and swelling index is 7.6.
2, preparation polyphenylacetylene combination:
With the above-mentioned styrene-butadiene rubber(SBR) powder 11.7g that obtains, low-cis-polybutadiene rubber (A55AE, the Shanghai Gaoqiao petrochemical iy produced, cis-structure is less than 40mol%) 114.7g, vinylbenzene (Yanshan Petrochemical production) 1700g and anti-aging agent 10761.8g add in the 5L reactor, stir, swelling and dissolving 24 hours, add ethylbenzene 300g again, with nitrogen with air displacement in the still.Adopt the method polymerization of free radical mass polymerization, initiating method adopts thermal initiation.The polymeric kettle stir speed (S.S.) is 138rpm, and respectively 120～122 ℃ of following polymerizations 4 hours, 127～130 ℃ of following polymerizations 2 hours were 157～160 ℃ of following polymerizations 1.5 hours.The thickness body discharge of polymerization gained is fallen into 232 ℃ devolatilizer, and flash distillation rapidly removes unreacted monomer and solvent ethylbenzene under vacuum state.The polymerization resulting composition promptly gets sample through cooling, granulation, sample preparation, and rerum natura analysis is listed in table 1.
Fig. 1 is transmission electron microscope (TECNAI20 type, PHLIPS) figure of this sample.As we can see from the figure, cis-1,4-polybutadiene rubber forms the island rubber grain that contains polystyrene of 0.3～1.5 μ m size, powdered rubber then forms the following tiny solid rubber particle of 0.3 μ m, to particle diameter is that the area of the particle of 0.05～0.3 μ m is added up, and the face integration rate that draws small particle size (0.05～0.3 μ m) is 1.4%.
Comparative example 1
With the low-cis-polybutadiene rubber among cis-rich polybutadiene rubber (cis-structure is greater than 90mol% for BR9004, Yanshan Petrochemical production) the replacement embodiment 1, other conditions are identical with embodiment 1.The Physical Property Analysis of gained final composition is listed in table 1.
Embodiment 2
With in the styrene-butadiene rubber(SBR) powder of embodiment 1 preparation gained by mineral oil: the ratio adding mineral oil (63# of powdered rubber=0.2: 1, Yanshan Petrochemical is produced), stir with stirrer, place fully absorption in 24 hours, get the rubber 14.6g after oil-filled, other conditions are identical with embodiment 1.The Physical Property Analysis of gained final composition is listed in table 1.
With in the styrene-butadiene rubber(SBR) powder of embodiment 1 preparation gained by mineral oil: the ratio adding mineral oil (63# of powdered rubber=0.5: 1, Yanshan Petrochemical is produced), stir with stirrer, place fully absorption in 24 hours, get the rubber 17.6g after oil-filled, other conditions are identical with embodiment 1.The Physical Property Analysis of gained final composition is listed in table 1.
Embodiment 4
With in the styrene-butadiene rubber(SBR) powder of embodiment 1 preparation gained by mineral oil: the ratio adding mineral oil (63# of powdered rubber=0.8: 1, Yanshan Petrochemical is produced), stir with stirrer, place fully absorption in 24 hours, get the rubber 20.5g after oil-filled, other conditions are identical with embodiment 1.The Physical Property Analysis of gained final composition is listed in table 1.
Comparative example 2
Do not add the styrene-butadiene rubber(SBR) powder, only add cis-1,4-polybutadiene rubber (with embodiment 1) 126.4g, other condition is identical with embodiment 1.The Physical Property Analysis of gained final composition is listed in table 1.
Table 1
Claims (9)
1. rubber-modified styrene resin composition, wherein the total content of rubber is 1～40wt%, described rubber is made up of ultra fine powder rubber and polybutadiene rubber, both weight ratios are 0.01: 1～1: 1, the particle diameter of described ultra fine powder rubber is that 20～500nm, gel content are not less than 60wt%, swelling index is not more than 15, described polybutadiene rubber comprises cis-rich polybutadiene rubber and low-cis-polybutadiene rubber
Described rubber-modified styrene resin composition prepares by the following method: will stir in styrenic monomer or described monomer and unsaturated monomer, above-mentioned ultra fine powder rubber and the polybutadiene rubber adding reactor, polymerization pressure is 0～3kg/cm2, adopts the form of stage feeding polymerization to carry out polymerization in 50～250 ℃ of scopes.
2. rubber-modified styrene resin composition according to claim 1, wherein the total content of rubber is 3～30wt%, ultra fine powder rubber and polybutadiene rubber weight ratio are 0.05: 1～0.5: 1, and described polybutadiene rubber is a low-cis-polybutadiene rubber
Described rubber-modified styrene resin composition carries out polymerization by the form that adopts stage feeding polymerization in 80～180 ℃ of scopes and makes.
3. rubber-modified styrene resin composition according to claim 2, wherein the total content of rubber is 5～25wt%, ultra fine powder rubber and polybutadiene rubber weight ratio are 0.05: 1～0.2: 1, described ultra fine powder rubber is selected from any in powder styrene butadiene rubber, powder natural rubber and the powder divinyl rubber
Polymerization temperature and corresponding time are in the stage feeding polymerization process: 100 ℃～130 ℃ following 4 hours, 130 ℃～140 ℃ the reaction 1 hour, 140 ℃～170 ℃ the reaction 1 hour.
4. rubber-modified styrene resin composition according to claim 3, wherein the total content of rubber is 5～10wt%, described ultra fine powder rubber is a powder styrene butadiene rubber.
5. rubber-modified styrene resin composition according to claim 1, described ultra fine powder rubber prepares preceding 48 hours 0～100% adding mineral oil by powdered rubber weight at styrene resin composite.
6. rubber-modified styrene resin composition according to claim 5 is wherein pressed 0～50% of powdered rubber weight and is added mineral oil.
7. rubber-modified styrene resin composition according to claim 1, wherein said styrenic monomer is selected from: one or more in vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl-dimethyl benzene, the vinyl ethylbenzene; Described unsaturated monomer is selected from: vinyl cyanide, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate.
8. rubber-modified styrene resin composition according to claim 1 adopts radical polymerization, and initiating method adopts thermal initiation or initiator to cause.
9. rubber-modified styrene resin composition according to claim 8 adds various auxiliary agents in described radical polymerization process.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623133A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Biaxial oriented polystyrene composition, preparation method therefor and application of biaxial oriented polystyrene composition |
| CN108395505A (en) * | 2018-03-19 | 2018-08-14 | 星辉化学股份有限公司 | A kind of middle anti-impact polystyrene resin and preparation method thereof |
| CN109206560A (en) * | 2017-07-06 | 2019-01-15 | 中国石油天然气股份有限公司 | Yogurt cup sheet material and preparation method thereof |
| CN114106256A (en) * | 2022-01-28 | 2022-03-01 | 山东颐工材料科技股份有限公司 | Resin with core/shell structure and polymerization method thereof |
-
2009
- 2009-10-29 CN CN2009102095486A patent/CN102050927A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623133A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Biaxial oriented polystyrene composition, preparation method therefor and application of biaxial oriented polystyrene composition |
| CN105623133B (en) * | 2014-10-30 | 2018-12-28 | 中国石油化工股份有限公司 | Biaxially oriented polystyrene composition, preparation method and application |
| CN109206560A (en) * | 2017-07-06 | 2019-01-15 | 中国石油天然气股份有限公司 | Yogurt cup sheet material and preparation method thereof |
| CN108395505A (en) * | 2018-03-19 | 2018-08-14 | 星辉化学股份有限公司 | A kind of middle anti-impact polystyrene resin and preparation method thereof |
| CN108395505B (en) * | 2018-03-19 | 2020-08-07 | 星辉环保材料股份有限公司 | Medium-impact polystyrene resin and preparation method thereof |
| CN114106256A (en) * | 2022-01-28 | 2022-03-01 | 山东颐工材料科技股份有限公司 | Resin with core/shell structure and polymerization method thereof |
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Application publication date: 20110511 |