CN1092207C - Solvent-resisting thermostable shockproof polystyrene resin and its preparation process - Google Patents
Solvent-resisting thermostable shockproof polystyrene resin and its preparation process Download PDFInfo
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- CN1092207C CN1092207C CN99109421A CN99109421A CN1092207C CN 1092207 C CN1092207 C CN 1092207C CN 99109421 A CN99109421 A CN 99109421A CN 99109421 A CN99109421 A CN 99109421A CN 1092207 C CN1092207 C CN 1092207C
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- resisting
- polystyrene resin
- solvent
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- toughner
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
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Abstract
The present invention relates to solvent resisting heat stable shock resisting polystyrene resin and a preparation method thereof, which uses phenylethylene as a monomer and epoxidation polybutadiene rubber or epoxidation butadiene and styrene copolymer rubber or the mixture of a plurality of kinds of epoxidation rubber as a toughening agent, and the solvent resisting heat stable shock resisting polystyrene resin is obtained by a free radical polymerization method. The epoxy value of the epoxidation rubber is from 5 to 50% (percentage by weight), the use level of the toughening agent is from 3% to 20% (percentage by weight), and a free radical polymerization reaction can be initiated by heat or an initiating agent.
Description
Technical field
Impact-resistant polystyrene resin is a toughner with the polybutadiene rubber of classics or divinyl, styrol copolymer rubber normally, according to certain ratio toughner is dissolved in the vinylbenzene, adopts method preparation that thermal initiation or initiator cause.After adding rubber toughening agent, greatly improved the shock resistance of polystyrene resin, but the solvent resistance of polystyrene resin, thermal stability remain in tangible deficiency, limited the use of impact-resistant polystyrene resin to a certain extent, for example in industries such as household electrical appliances, packings to these two demands for higher performance.How the present report of no data still improves the solvent resistance and the thermal stability of impact-resistant polystyrene resin effectively.
Summary of the invention
The objective of the invention is to adopt the mixture of epoxidised polybutadiene rubber or epoxidised divinyl, styrol copolymer rubber or several epoxidezed rubbers to do toughner and prepare solvent-resisting thermostable shockproof polystyrene resin, products obtained therefrom is compared with common impact-resistant polystyrene resin, and its solvent resistance, thermal stability all are significantly improved.Key of the present invention is to adopt functionalized rubber to replace general rubber, that is: at first adopt classical epoxidizing method that polybutadiene rubber or divinyl, styrol copolymer rubber are carried out epoxidation reaction, the epoxidation value of toughner rubber is controlled in certain scope, be dissolved in the vinylbenzene by certain proportioning then, prepare solvent-resisting thermostable shockproof polystyrene resin by free radical reaction.
Solvent-resisting thermostable shockproof polystyrene resin involved in the present invention, it is characterized in that this resin is is monomer with vinylbenzene, mixture with epoxidised polybutadiene rubber or epoxidised divinyl, styrol copolymer rubber or several epoxidezed rubbers is a toughner, adopts free radical polymerisation process to prepare.Above-mentioned solvent-resisting thermostable shockproof polystyrene resin, wherein the styrene content general range is 80%-97% (weight percent, down together), and the butadiene content general range is 3%-20%, the styrene content optimum range is 90%-95%, and the butadiene content optimum range is 5%-10%.Above-mentioned solvent-resisting thermostable shockproof polystyrene resin, its microscopic pattern is similar to general impact-resistant polystyrene resin to have tangible island structure feature, and its number-average molecular weight scope is generally 5 * 10
4-50 * 10
4, optimum range is 15 * 10
4-35 * 10
4
The preparation method of solvent-resisting thermostable shockproof polystyrene resin involved in the present invention is as follows: by monomer ratio vinylbenzene, toughner are added in the reactor, toughner consumption general range is a 3%-20% (weight percent, as follows), toughner consumption optimum range is 5%-10%; The initiation reaction temperature is 60 ℃-180 ℃, the method that adopts free radical to cause is carried out polymerization, reaction finishes the back and adds anti-aging agent (Hinered phenols or and the mixture of phosphorous acid esters), adopts traditional method that polymkeric substance is carried out aftertreatment, carries out analytical test after the product drying granulation.The radical polymerization initiating method can adopt thermal initiation or initiator to cause.The consumption of radical initiator is generally 150ppm-600ppm when adopting radical initiator to cause, radical initiator is selected from the mixture of a kind of radical initiator or several radical initiators, transformation period is not more than 60 minutes usually in the time of 110 ℃, radical initiator generally is selected from thermolysis type initiator, and this class initiator is generally superoxide and the two nitriles of azo.
Radical initiator involved in the present invention is selected from the mixture of a kind of radical initiator or several radical initiators, generally be selected from thermolysis type initiator, this class initiator is generally superoxide and the two nitriles of azo, superoxide is generally peroxidation two acyl (as: dibenzoyl peroxide, peroxidation two o-methyl-benzene formyls, acetyl peroxide isobutyryl etc.), peroxy dicarbonate (as: peroxy dicarbonate two different lactones, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate di-t-butyl cyclohexyl etc.), peroxycarboxylic acid esters (as: the peroxidation trimethylacetic acid tert-butyl ester, peroxidized t-butyl perbenzoate etc.), alkyl peroxide (as: tertbutyl peroxide, isopropyl benzene hydroperoxide etc.), peroxidation two alkane (as: dicumyl peroxide etc.), the two nitriles of azo are generally Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
Toughner used in the present invention is the mixture of epoxidised polybutadiene rubber or epoxidised divinyl, styrol copolymer rubber or several epoxidezed rubbers, and its oxirane value scope is generally 5%-50%, and optimum range is 15%-35%.Toughner number-average molecular weight general range is 50000-300000, and the number-average molecular weight optimum range is 100000-250000.
The preparation of solvent-resisting thermostable shockproof polystyrene resin involved in the present invention is general adopts following operational path to implement: substance law, body-suspension method, solution method, suspension method, continuous bulk are best implementing process route.
Further specify the present invention below in conjunction with embodiment, Comparative Examples, but and the scope of unrestricted claim protection of the present invention.
Embodiment
Embodiment 1
In having 2 liters of stainless steel cauldrons of stirring, at first add 1302 gram vinylbenzene, add epoxidised polybutadiene rubber 98 grams of toughner again, the epoxidation value of toughner is 17%, opens to stir toughner is dissolved in the vinylbenzene fully, and the toughner consumption is 7% (weight percent), the initiation reaction temperature is 110 ℃, the method that adopts radical initiator to cause is carried out polymerization, and initiator adopts 1.1-two (tert-butyl peroxide) hexanaphthene, and initiator amount is 400ppm.Reaction finishes the back and adopts traditional method that polymkeric substance is carried out aftertreatment, anti-aging agent B215 (vapour Ba-Jia Ji company product) consumption is 1% of a product, carry out analytical test behind the product drying, adopt classical way specimen performance, the result is as follows: Izod shock strength 130J/m, tensile strength 27.9MPa, flexural strength 39.9Mpa; The thermal weight loss initial temperature is 425.01 ℃.The product batten immerses in the normal hexane, and the mass percent of swelling weightening finish in 24 hours is 5.45%.
Embodiment 2
Polymerization process and processing condition are with embodiment 1, and just the epoxidation value of toughner epoxidized polybutadiene rubber is 31%, and the properties of sample test result is as follows: Izod shock strength 110J/m, tensile strength 34.7MPa, flexural strength 53.1Mpa; The thermal weight loss initial temperature is 426.74 ℃.The product batten immerses in the normal hexane, the mass percent of swelling weightening finish in 7 hours, 24 hours, 48 hours is respectively 0.39%, 1.35%, 2.70%, compare with embodiment 1, increase along with polybutadiene rubber epoxidation value, the mass percent of the swelling weightening finish of impact-resistant polystyrene resin significantly reduces, and the solvent resistance of resin significantly improves.Comparative Examples
Polymerization process and processing condition are with embodiment 1, and just toughner is the polybutadiene rubber before the epoxidation reaction of using among embodiment 1, the embodiment 2.The properties of sample test result is as follows: Izod shock strength 89J/m, tensile strength 31.8MPa, flexural strength 41.6MPa; The thermal weight loss initial temperature is 416.83 ℃, compares with embodiment 2 with embodiment 1, and epoxidized polybutadiene rubber has improved the thermal weight loss initial temperature of impact-resistant polystyrene resin significantly, and the thermal stability of resin significantly improves.The product batten immerses in the normal hexane, the mass percent of swelling weightening finish in 7 hours, 24 hours, 48 hours is respectively 4.84%, 6.72%, 8.70%, compare with embodiment 2 with embodiment 1, epoxidized polybutadiene rubber has reduced the mass percent of the swelling weightening finish of impact-resistant polystyrene resin significantly, and the solvent resistance of resin significantly improves.Annotate 1: product mechanical property Izod shock strength adopts ASTM D256, tensile strength to adopt ASTM D638, flexural strength to adopt ASTM D790 standard testing; Solvent resistance adopts ISO175-1981 (E) standard testing; The thermal weight loss initial temperature adopts thermogravimetric analyzer TGA test, and heat-up rate is 10 ℃/min.Annotate 2: employed toughner polybutadiene rubber is the commercially available prod Asaprene760A rubber that Japanese Asahi company produces in the Comparative Examples, and employed toughner is the epoxidation glue of above-mentioned Asaprene760A rubber among embodiment 1, the embodiment 2.Annotate 3: the epoxidation reaction of rubber is pressed the classical way operation, the epoxidation reaction condition of Asaprene760A rubber: 45 ℃ of temperature of reaction, 4 hours reaction times, the mol ratio of hydrogen peroxide and formic acid is 3, the weight percent of toluene and rubber is 9, and the weight percent of hydrogen peroxide and rubber is decided on the size of final oxirane value.The oxirane value of product is pressed document Jay R R, Direct Titration of Epoxy Compounds and Aziridines, AnalChem, 1964,36 (3): the method test in 667.
Claims (18)
1. a solvent-resisting thermostable shockproof polystyrene resin is characterized in that this resin is is monomer with vinylbenzene, is toughner with epoxidised polybutadiene rubber, adopts free radical polymerisation process to prepare.
2. solvent-resisting thermostable shockproof polystyrene resin according to claim 1, wherein styrene content is 80%-97% (weight percent), butadiene content is 3%-20% (weight percent).
3. solvent-resisting thermostable shockproof polystyrene resin according to claim 2, wherein styrene content is 90%-95% (weight percent), butadiene content is 5%-10% (weight percent).
4. solvent-resisting thermostable shockproof polystyrene resin according to claim 1, wherein the toughner consumption is 3%-20% (weight percent).
5. solvent-resisting thermostable shockproof polystyrene resin according to claim 4, wherein the toughner consumption is 5%-10% (weight percent).
6. solvent-resisting thermostable shockproof polystyrene resin according to claim 1, its number-average molecular weight are 5 * 10
4-50 * 10
4
7. solvent-resisting thermostable shockproof polystyrene resin according to claim 6, its number-average molecular weight are 15 * 10
4-35 * 10
4
8. the preparation method of a solvent-resisting thermostable shockproof polystyrene resin, it is characterized in that: this solvent-resisting thermostable shockproof polystyrene resin prepares by free radical polymerisation process, at first the epoxidised polybutadiene rubber of toughner is dissolved in the vinylbenzene, the content of toughner in vinylbenzene is 3%-20% (weight percent), the method that adopts free radical to cause is carried out polymerization, and reaction finishes the back and adopts traditional method that polymkeric substance is carried out aftertreatment.
9. method according to Claim 8, wherein the radical polymerization initiating method can adopt thermal initiation or initiator to cause.
10. according to the method for claim 9, wherein radical initiator is selected from the mixture of a kind of radical initiator or several radical initiators.
11. according to the method for claim 10, wherein radical initiator is selected from thermolysis type initiator, this class initiator is a superoxide, is selected from peroxidation two acyls, peroxy dicarbonate, peroxycarboxylic acid esters, alkyl peroxide, peroxidation two alkane.
12. method according to claim 11, wherein peroxide initiator is selected from one or more the mixture in the following material: dibenzoyl peroxide, peroxidation two o-methyl-benzene formyls, acetyl peroxide isobutyryl, peroxy dicarbonate two different lactones, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate di-t-butyl cyclohexyl, the peroxidation trimethylacetic acid tert-butyl ester, peroxidized t-butyl perbenzoate, tertbutyl peroxide, isopropyl benzene hydroperoxide, 1,1-two (tert-butyl peroxide) hexanaphthene, dicumyl peroxide.
13. method according to Claim 8, wherein the oxirane value of toughner epoxidezed rubber is 5%-50% (weight percent).
14. according to the method for claim 13, wherein the oxirane value of toughner epoxidezed rubber is 15%-35% (weight percent).
15. method according to Claim 8, wherein the number-average molecular weight of toughner epoxidezed rubber is 50000-300000.
16. according to the method for claim 15, wherein the number-average molecular weight of toughner epoxidezed rubber is 100000-250000.
17. method according to Claim 8, wherein the preparation of solvent-resisting thermostable shockproof polystyrene resin can adopt following operational path to implement: substance law, body-suspension method, solution method, suspension method.
18. according to the method for claim 17, wherein the preparation were established of solvent-resisting thermostable shockproof polystyrene resin is a continuous bulk.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109421A CN1092207C (en) | 1999-06-30 | 1999-06-30 | Solvent-resisting thermostable shockproof polystyrene resin and its preparation process |
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|---|---|---|---|
| CN99109421A CN1092207C (en) | 1999-06-30 | 1999-06-30 | Solvent-resisting thermostable shockproof polystyrene resin and its preparation process |
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|---|---|
| CN1239720A CN1239720A (en) | 1999-12-29 |
| CN1092207C true CN1092207C (en) | 2002-10-09 |
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| CN99109421A Expired - Fee Related CN1092207C (en) | 1999-06-30 | 1999-06-30 | Solvent-resisting thermostable shockproof polystyrene resin and its preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030742B (en) * | 2011-09-29 | 2015-04-08 | 中国石油化工股份有限公司 | Preparation method of anti-impact ABS (acrylonitrile butadiene styrene) resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521569A (en) * | 1979-03-29 | 1985-06-04 | The Dow Chemical Company | Impact styrene polymer |
| US5177115A (en) * | 1990-11-29 | 1993-01-05 | Basf Aktiengesellschaft | Oil-resistant, expandable styrene polymers |
-
1999
- 1999-06-30 CN CN99109421A patent/CN1092207C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521569A (en) * | 1979-03-29 | 1985-06-04 | The Dow Chemical Company | Impact styrene polymer |
| US5177115A (en) * | 1990-11-29 | 1993-01-05 | Basf Aktiengesellschaft | Oil-resistant, expandable styrene polymers |
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| CN1239720A (en) | 1999-12-29 |
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