CN101445575B - Heat-resistant acrylic ester rubber - Google Patents
Heat-resistant acrylic ester rubber Download PDFInfo
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- CN101445575B CN101445575B CN 200810136656 CN200810136656A CN101445575B CN 101445575 B CN101445575 B CN 101445575B CN 200810136656 CN200810136656 CN 200810136656 CN 200810136656 A CN200810136656 A CN 200810136656A CN 101445575 B CN101445575 B CN 101445575B
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- methyl acrylate
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Abstract
The invention relates to a heat-resistant acrylic ester rubber which is made by copolymerization of methyl acrylate, ethyl acrylate, vinyl monochloroacetate and regulating agent. Calculating by mass percentage, the detailed mixture ratio is: methyl acrylate, 5-40%; ethyl acrylate, 50-94%; vinyl monochloroacetate, 1-10%; and regulating agent, 0.0001-1%; batch process emulsion polymerization technique is used in the process of synthesis; the initiation temperature in the process of polymerization is 10-50 DEG C and the condensation temperature is 40-70 DEG C. The invention has very excellent physical and mechanical properties and post-processing property, thus meeting requirements of the motorcycles and oil-resistant and heat-resistant rubber tubes on material, the formed product of the invention has the advantages of excellent heat-resistance and oil resistance and high tensile-strength, the application of the product ranges from leakproof material of motorcycles, oil-resistant and heat-resistant tubes to protecting jackets and the like.
Description
Technical field
The present invention relates to a kind of heat-resistant acrylic ester rubber.
Background technology
Domestic acrylic elastomer is take ethyl propenoate, butyl acrylate etc. as principal monomer, the point monomer take the chloracetic acid vinyl acetate as sulfuration, the elastomerics that forms through letex polymerization, because its main chain is saturated [C-C] structure, therefore have the characteristics such as heat-resisting, oil resistant, resistance to oxidation, particularly heat resisting temperature can reach 200 ℃, so its temperature classification is only second to viton silicon rubber.And because of it to engine oil, gear oil, transformer wet goods good endurance, so be main various sealing members, liner in fields such as automobile, motorcycle, transformers, be widely used in flexible pipe.
At present, domestic acrylic elastomer uses comparatively extensive mainly take cold resisting type as main.Heat resistant type is to be polymerized take ethyl propenoate, vinyl cyanide etc. as principal monomer, and its rubber is harder, and tensile strength is not high, and the undesirable grade of post-treatment performance has restricted its application.The product of current use heat resistant type CALCIUM ACRYLATE rubber is substantially produced acrylic elastomer abroad and is captured.The domestic market needs a kind of characteristics such as heat-resisting, oil resistant, anti-ozone, high strength that have, and the domestic acrylic elastomer of post-treatment performance is preferably arranged again simultaneously.
Summary of the invention
Technical problem to be solved by this invention is, develops a kind of heat-resistant acrylic ester rubber for performance requriementss such as high strength, anti-machinery oil, heat-resisting, anti-ozone.Its main chain is saturated carbon-chain structure, thereby has heat-resisting, light, O
3Etc. characteristic, again because the alkyl number of methyl acrylate is minimum, thereby oil-proofness and larger tensile strength are preferably arranged.
Principle of work: adopt emulsion polymerization, select vinyl monochloroacetate as sulfuration point monomer, generate heat-resistant acrylic ester rubber by methyl acrylate, the synthetic copolymerization of ethyl propenoate.
The technical scheme that the present invention takes for achieving the above object is: a kind of heat resistant type CALCIUM ACRYLATE rubber, formed by methyl acrylate, ethyl propenoate, monochloroacetic acid hexenoic acid and mediator agent copolymerization, and by mass percentage, specifically prepare burden as follows:
Methyl acrylate: 5～40%
Ethyl propenoate: 50～94%
Vinyl monochloroacetate: 1～10%
Mediator agent: 0.0001～1%
Synthetic is to adopt the interrupter method emulsion polymerization technique, and the kick off temperature during polymerization is between 10～50 ℃, and condensation temperature is between 40～70 ℃.
Its making method and concrete steps are as follows:
1) adopt four kinds of basic monomer batchings
Methyl acrylate: 5～40%
Ethyl propenoate: 50～94%
Vinyl monochloroacetate: 1～10%
Mediator agent: 0.0001～1%
Above four kinds of basic monomers being mixed in proportion in the dry pre blend still, making hydrocarbon mutually standbyly, is that 1～10% emulsifier solution drops in reactor by a certain percentage with concentration, standby through fully being mixed and made into emulsion.
2) interrupter method polymerization: the hydrocarbon phase footpath metering that step 1 is prepared adds in reactor in proportion, fully stir, 10～50 ℃ this be that 0.0001～5% initiator carries out initiation reaction by adding concentration by a certain percentage, control its speed of response, more than repeating above operation secondary.
3) salt is poly-: it is that 2～20% flocculation agent salts solution mixes mutually with being pumped in collection surface with concentration that the reacted rubber cement of step 2 is added 0.001～5% stopper, breakdown of emulsion is condensed into the granular elastomer of white in the temperature of 40～70 ℃, through the washing, the oven dry product.
Beneficial effect of the present invention is:
Have the characteristics such as heat-resisting, oil resistant, anti-ozone, high strength, comprehensive physical is functional, and post-treatment is functional, simultaneously temperature limit of brittleness: between-11～-15 ℃, and maximum operation (service) temperature: between 180～200 ℃.Can satisfy motorcycle stopping property, oil pipe, liner etc. to the requirement of elastomeric material, its technology has reached leading domestic level.
The scope of application of this project: motorcycle sealing material; Heat-resisting, oil resisting rubber hose; Protecting jacket; Liner etc.
Embodiment
Heat-resistant acrylic ester rubber of the present invention, contain minimum alkyl on saturated main chain side group, it is methyl group, thereby its intensity is larger, oil-proofness is good, synthetic starting material are to be formed by methyl acrylate, ethyl propenoate, monochloroacetic acid hexenoic acid and mediator agent copolymerization, by mass percentage, specifically prepare burden as follows:
Methyl acrylate: 25%
Ethyl propenoate: 72%
Vinyl monochloroacetate: 3%
Mediator agent: 0.02%
Synthetic is to adopt the interrupter method emulsion polymerization technique, and the kick off temperature during polymerization is between 10～50 ℃, and condensation temperature is between 40～70 ℃.
Embodiment 1
1) adopt four kinds of basic monomer batchings
Methyl acrylate: 6%
Ethyl propenoate: 93%
Vinyl monochloroacetate: 1%
Mediator agent: 0.01%
Above four kinds of basic monomers being mixed in proportion in the dry pre blend still, making hydrocarbon mutually standbyly, is that 4% emulsifier solution drops in reactor by a certain percentage with concentration, standby through fully being mixed and made into emulsion.
2) interrupter method polymerization: the hydrocarbon phase footpath metering that step 1 is prepared adds in reactor in proportion, fully stir, 20 ℃ this be that 0.02% initiator carries out initiation reaction by adding concentration by a certain percentage, control its speed of response, more than repeating above operation secondary.
3) salt is poly-: it is that 7% flocculation agent salts solution mixes mutually with being pumped in collection surface with concentration that the reacted rubber cement of step 2 is added 1% stopper, and breakdown of emulsion is condensed into the granular elastomer of white in the temperature of 40 ℃ of left and right, through washing, oven dry product.
Embodiment 2
1) adopt four kinds of basic monomer batchings
Methyl acrylate: 25%
Ethyl propenoate: 72%
Vinyl monochloroacetate: 3%
Mediator agent: 0.02%
Above four kinds of basic monomers being mixed in proportion in the dry pre blend still, making hydrocarbon mutually standbyly, is that 4% emulsifier solution drops in reactor by a certain percentage with concentration, standby through fully being mixed and made into emulsion.
2) interrupter method polymerization: the hydrocarbon phase footpath metering that step 1 is prepared adds in reactor in proportion, fully stir, 35 ℃ this be that 0.02% initiator carries out initiation reaction by adding concentration by a certain percentage, control its speed of response, more than repeating above operation secondary.
3) salt is poly-: it is that 7% flocculation agent salts solution mixes mutually with being pumped in collection surface with concentration that the reacted rubber cement of step 2 is added 1% stopper, and breakdown of emulsion is condensed into the granular elastomer of white in the temperature of 45 ℃ of left and right, through washing, oven dry product.
Embodiment 3
1) adopt four kinds of basic monomer batchings
Methyl acrylate: 39%
Ethyl propenoate: 52%
Vinyl monochloroacetate: 9%
Mediator agent: 0.02%
Above four kinds of basic monomers being mixed in proportion in the dry pre blend still, making hydrocarbon mutually standbyly, is that 4% emulsifier solution drops in reactor by a certain percentage with concentration, standby through fully being mixed and made into emulsion.
2) interrupter method polymerization: the hydrocarbon phase footpath metering that step 1 is prepared adds in reactor in proportion, fully stir, 50 ℃ this be that 0.02% initiator carries out initiation reaction by adding concentration by a certain percentage, control its speed of response, more than repeating above operation secondary.
3) salt is poly-: it is that 7% flocculation agent salts solution mixes mutually with being pumped in collection surface with concentration that the reacted rubber cement of step 2 is added 1% stopper, and breakdown of emulsion is condensed into the granular elastomer of white in the temperature of 70 ℃ of left and right, through washing, oven dry product.
Claims (1)
1. the making method of a heat-resistant acrylic ester rubber, is characterized in that, concrete steps are as follows:
1) adopt four kinds of basic monomers batchings, by mass percentage and be no more than 100%:
Methyl acrylate: 5～40%
Ethyl propenoate: 50～94%
Vinyl monochloroacetate: 1～10%
Mediator agent: 0.0001～1%
Above four kinds of basic monomers being mixed in proportion in the dry pre blend still, making hydrocarbon mutually standbyly, is that 1～10% emulsifier solution drops in reactor by a certain percentage with concentration, standby through fully being mixed and made into emulsion;
2) interrupter method polymerization: with step 1 prepare hydrocarbon through the metering add in proportion in reactor, fully stir, be that 0.0001～5% initiator carries out initiation reaction by adding concentration by a certain percentage between 10～50 ℃, control its speed of response, more than repeating above operation secondary;
3) salt is poly-: it is that 2～20% flocculation agent salts solution mixes mutually with being pumped in collection surface with concentration that the reacted rubber cement of step 2 is added 0.001～5% stopper, breakdown of emulsion is condensed into the granular elastomer of white in the temperature of 40～70 ℃, through the washing, the oven dry product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810136656 CN101445575B (en) | 2008-12-31 | 2008-12-31 | Heat-resistant acrylic ester rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810136656 CN101445575B (en) | 2008-12-31 | 2008-12-31 | Heat-resistant acrylic ester rubber |
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| CN101445575A CN101445575A (en) | 2009-06-03 |
| CN101445575B true CN101445575B (en) | 2013-06-26 |
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| CN 200810136656 Expired - Fee Related CN101445575B (en) | 2008-12-31 | 2008-12-31 | Heat-resistant acrylic ester rubber |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102140150B (en) * | 2011-03-11 | 2013-11-20 | 安徽时代创新科技投资发展有限公司 | Preparation method for acrylic ester rubber |
| CN103588928A (en) * | 2013-11-08 | 2014-02-19 | 济南开发区星火科学技术研究院 | Preparation method for polyacrylate rubber |
| CN104650275A (en) * | 2014-06-26 | 2015-05-27 | 柳州市够旺贸易有限公司 | Preparation method of acrylate rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643055A (en) * | 2002-03-27 | 2005-07-20 | 日本油脂株式会社 | Olefinic thermoplastic elastomer and moldings thereof |
| CN1753965A (en) * | 2003-02-28 | 2006-03-29 | 综研化学株式会社 | Emulsion-type pressure sensitive adhesive and process for producing the same |
| EP1790689A1 (en) * | 2004-06-23 | 2007-05-30 | Zeon Corporation | Acrylic rubber composition and acrylic rubber crosslinked product |
| CN101218294A (en) * | 2005-08-08 | 2008-07-09 | 日油株式会社 | Thermoplastic elastomer composition |
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2008
- 2008-12-31 CN CN 200810136656 patent/CN101445575B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643055A (en) * | 2002-03-27 | 2005-07-20 | 日本油脂株式会社 | Olefinic thermoplastic elastomer and moldings thereof |
| CN1753965A (en) * | 2003-02-28 | 2006-03-29 | 综研化学株式会社 | Emulsion-type pressure sensitive adhesive and process for producing the same |
| EP1790689A1 (en) * | 2004-06-23 | 2007-05-30 | Zeon Corporation | Acrylic rubber composition and acrylic rubber crosslinked product |
| CN101218294A (en) * | 2005-08-08 | 2008-07-09 | 日油株式会社 | Thermoplastic elastomer composition |
Non-Patent Citations (2)
| Title |
|---|
| "丙烯酸甲酯/丙烯酸乙酯二元共聚物的红外光谱定量测定";董永春等;《天津纺织工学院学报》;19881231(第18期);第17-21页 * |
| 董永春等."丙烯酸甲酯/丙烯酸乙酯二元共聚物的红外光谱定量测定".《天津纺织工学院学报》.1988,(第18期),第17-21页. |
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| CN101445575A (en) | 2009-06-03 |
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