CN1521195A - Method for preparation of acrylate rubber with double/ multicomponent vulcanization site monomer - Google Patents
Method for preparation of acrylate rubber with double/ multicomponent vulcanization site monomer Download PDFInfo
- Publication number
- CN1521195A CN1521195A CNA031172911A CN03117291A CN1521195A CN 1521195 A CN1521195 A CN 1521195A CN A031172911 A CNA031172911 A CN A031172911A CN 03117291 A CN03117291 A CN 03117291A CN 1521195 A CN1521195 A CN 1521195A
- Authority
- CN
- China
- Prior art keywords
- parts
- raw material
- preparation
- acrylic elastomer
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention is the preparation process of acrylic ester rubber with two or more sulfurizing agent components, and belongs to the field of synthesis of acrylic ester rubber. The acrylic ester rubber is copolymer produced with acrylic ester monomer and small amount of monomer with active cross-linking radical and through emulsion polymerization. The present invention features that the acrylic ester may be one or several of ethyl acrylate, butyl acrylate, methoxy ethyl acrylate and ethoxy ethyl acrylate; and the monomers with active cross-linking radical may be two or more selected from ethyl acetate monochloride, acrylonitrile, acrylic acid, acrylic glycidyl ether, acrylic glycidyl ester and ethylidene norbornene. The acrylic ester rubber has wide sulfurizing characteristic and may complete cross-linking sulfurization with partial or all the sulfurizing components.
Description
One, technical field
The present invention relates to synthetic rubber, particularly the manufacture method of esters of acrylic acid rubber.
Two, background technology
＜Chemicals handbook---Rubber ﹠ Rubber Products〉third edition (Liu Dengxiang chief editor, Chemical Industry Press, P167) illustrate: esters of acrylic acid rubber is to be the homopolymer or the multipolymer of principal monomer with the acrylate, because its major key is a saturated structures, have many polarity ester groups on the side switch simultaneously, thereby it have excellent heatproof, oil resistant, weathering resistance.Now industrial extensive application be multipolymer, it is by acrylate monomer and the monomeric multipolymer that has the crosslinking activity group on a small quantity.This multipolymer mainly is divided into two big classes, and the one, acrylic ester (ACM), the 2nd, ethene---acrylic ester (AEM), (according to the difference of cross-linking monomer, being divided into the chlorine type, reactive chlorine type, epoxy type, diene type and other type).Common esters of acrylic acid rubber belong to mostly copolymer as, the multipolymer of butyl acrylate and vinyl cyanide, the multipolymer of ethyl propenoate and 2 one chloroethyl vinyl ether etc.According to this book P168 record, the BJ that the Kaidi board of Jilin Chemical Industry Company and Beijing Chemical Research Institute produce is that acrylic elastomer all belongs to copolymer.＜rubber technology and manufacturing outline〉(Chen Shichao, Wang Yangdong write P57-58, Sinopec press) disclose: U.S. Goodrich company had released two kinds of esters of acrylic acid rubber in 1948, wherein a kind of is the copolymer of ethyl propenoate and 2-chloroethyl vinyl ether, and another kind is the copolymer of vinylformic acid fourth vinegar and acrylonitrile.The resistance toheat of acrylic rubber is higher than chloroprene rubber, paracril, is a kind of middle-grade heat-resisting oil-resistance specific synthetic rubber, and its technology trends is: further improve thermotolerance, making it is that better weather resistance and long lifetime are arranged; Further improve processing characteristics, its tackiness, corrodibility, mold fouling are improved; Make it have more excellent comprehensive performance; The ultra-high speed sulfuration makes it really not need post cure.
Say from vulcanization characteristics, present acrylic elastomer closes and makes with a kind of base monomer material copolymerizations such as a function monomer raw material and acrylate that vulcanize, selected sulfuration point function monomer raw material difference during polymerization, and make rubber have different vulcanization characteristicss, add man-hour, need put monomeric sizing material according to dissimilar sulfurations and select the different vulcanizing agent system that adapts separately for use, the range of choice of vulcanizing agent is narrow.And various vulcanizing agent system respectively have relative merits in application, and less range of choice is difficult to maximize favourable factors and minimize unfavourable ones.With other blend of glue kind and time spent, also can influence covulcanization because of vulcanization system is difficult to coupling, make different glue kind rubber also with being subjected to bigger restriction.If sizing material and vulcanizing agent mate badly, sizing material can not obtain good cure efficiency or good thing physical and mechanical properties.
Three, summary of the invention
The object of the present invention is to provide a kind of preparation method with two/monomeric acrylic elastomer of many component sulfuration points, make its corresponding product have vulcanization characteristics widely, to adapt to multiple vulcanizing agent system, solve existing to the comparatively narrow problem of the range of choice of vulcanizing agent.Above-mentioned purpose is realized by following technical scheme; A kind of preparation method with two/monomeric acrylic elastomer of many component sulfuration points, is raw material with acrylate monomer with the monomer that has the crosslinking activity gene on a small quantity, adopts emulsion polymerization, generates multipolymer, its feature is one of following kind or several in, described acrylate monomer raw material A:
Ethyl propenoate (EA), butyl acrylate (BA), vinylformic acid methoxyl group ethyl ester (MOEA), vinylformic acid ethoxy ethyl ester (EEA);
Described have the raw material monomer B of crosslinking activity group for to select two or more from the row kind;
Vinyl monochloroacetate (VCA), vinyl cyanide (AN), vinylformic acid (AA), vinylformic acid glycidyl ether (AGE), glycidyl acrylate (GA), ethylidene norbornene (ENB).
The 1-2% of above-mentioned raw materials B point total monomer raw material; Two or more monomeric consumptions can be identical among the raw material B, also can be inequality;
Above-mentioned polyreaction is to carry out under 50-70 ℃.
From technique scheme as seen, polymerization process of the present invention is an emulsion polymerization, can certainly be (pearl) polymerization that suspends.The post-treatment of the prepared esters of acrylic acid rubber of the present invention such as mixing, sulfuration etc., identical with the method for existing acrylic elastomer.Among the present invention, the sulfuration monomer component that contains two or more in the molecular structure of esters of acrylic acid rubber, they can add play man-hour crosslinked (sulfuration) effect, therefore, this sizing material vulcanizes applicable to a plurality of vulcanizing agent kinds, add man-hour, can utilize in the sizing material any sulfuration point monomer component crosslinking reaction to vulcanize, it is available to have more vulcanizing agent kind.Enlarged the range of choice of vulcanizing agent; Simultaneously, also help adopting with other glue kind blend such as viton, silicon rubber, chlorohydrin rubber.And, the monomer all crosslinked (sulfuration) that also available two groups of vulcanizing agent system make two kinds of cross-linking set in the sizing material; To improve the cross-linking density of sizing material, improve the physical and mechanical properties of cross-linked rubber.
Four, embodiment
Following embodiment is of the present invention specifying, but the present invention is not only limited to the following examples.
Embodiment 1
Ethyl propenoate: 90 parts; Vinyl cyanide: 8.5 parts; Vinyl monochloroacetate: 1.5 parts; Deionized water: 200 parts; Sodium laurylsulfonate: 3 parts; Potassium Persulphate, sodium bisulfite: an amount of.
Above-mentioned raw materials is packed in the reactor of the band whipping appts that nitrogen replacement is crossed, under 50-70 ℃ of condition, carry out polyreaction.The reaction finish after, through saltout, wash, drying, make desired product.Detailed process is: feed water vapor purging in latex solution, remove the residual monomer in the glue.Latex is condensed into micelle with calcium chloride or sodium chloride aqueous solution breakdown of emulsion, removes de-emulsifier, flocculation agent with hot wash, obtains rubber product through dewatered drying again.
Sizing material can vulcanize with two class vulcanization systems.
The first kind: available sodium stearate: 5 parts; Potassium stearate: 0.5 part; Sulphur: 0.5 part.This vulcanization system is to make the vinyl monochloroacetate sulfuration point monomer component in the glue play crosslinked action.
Second class: available triethylene tetramine: 2 parts; Sulfur: 1.25 parts.This vulcanization system is to make the vinyl cyanide cross-linking set monomer component in the glue play crosslinked action.
Also can vulcanize with above-mentioned two groups of vulcanizing agent system simultaneously, consumption is that separately half is to full consumption.
Embodiment 2
Ethyl propenoate: 35 parts; Butyl acrylate: 30 parts; Vinylformic acid methoxyl group ethyl ester: 30 parts; Glycidyl acrylate; 3.5 part; Vinyl monochloroacetate: 1.5 parts; Deionized water: 200 parts: sodium laurylsulfonate: 3 parts; Potassium Persulphate, sodium bisulfite: an amount of.
Make rubber product with the method identical with embodiment 1.
The sizing material available energy makes glycidyl acrylate carry out crosslinked promotor PZ (2 parts) to vulcanize, and also available energy makes vinyl monochloroacetate carry out crosslinked sodium stearate (5 parts), potassium stearate (0.5 part), and Sulfur (0.5 part) vulcanizes.Also can vulcanize with above-mentioned two groups of vulcanizing agent system simultaneously, the vulcanizing agent consumption be about each plant demand half to whole consumptions.
Embodiment 3
Ethyl propenoate: 45 parts; Butyl acrylate: 45 parts; Ethylidene norbornene: 8.5 parts; Vinyl monochloroacetate: 1.5 parts; Deionized water: 200 parts; Sodium laurylsulfonate: 3 parts; Potassium Persulphate, sodium bisulfite: an amount of.
Make rubber product with the method identical with embodiment 1.
The sizing material available energy makes ethylidene norbornene play the superoxide-d cp (2 parts) of crosslinked action, and additional crosslinker TIAC (2-4 part) vulcanizes; Also available energy makes vinyl monochloroacetate play the sodium stearate (5 parts) of crosslinked action, potassium stearate (0.5 part), Sulfur (0.5 part).Vulcanize.Also can vulcanize with above-mentioned two groups of vulcanizing agent system simultaneously, the vulcanizing agent consumption be about each plant demand half to whole consumptions.
Claims (9)
1, a kind of preparation method with two/monomeric acrylic elastomer of many component sulfuration points, is raw material with acrylate monomer with the monomer that has the crosslinking activity group on a small quantity, adopt emulsion polymerization, generate multipolymer, it is characterized in that described acrylate monomer raw material A is one of following kind or several:
Ethyl propenoate (EA), butyl acrylate (BA), vinylformic acid methoxyl group ethyl ester (MOEA), vinylformic acid ethoxy ethyl ester (EEA);
Described have the raw material monomer B of crosslinking activity group for to select two or more from the row kind;
Vinyl monochloroacetate (VCA), vinyl cyanide (AN), vinylformic acid (AA), vinylformic acid glycidyl ether (AGE), glycidyl acrylate (GA), ethylidene norbornene (ENB).
2, the preparation method of acrylic elastomer according to claim 1 is characterized in that, described raw material B accounts for the 1-20% of total monomer raw material; The monomeric consumption of among the raw material B two or more can be identical, also can be inequality.
3, the preparation method of acrylic elastomer according to claim 2 is characterized in that, described polyreaction is carried out under 50-70 ℃.
4, the preparation method of acrylic elastomer according to claim 1, it is characterized in that, described raw material A is an ethyl propenoate, raw material B is the fine and vinyl monochloroacetate of propylene, and with above-mentioned raw materials and deionized water, emulsifying agent, initiator are packed in the reactor of the band whipping appts that nitrogen replacement is crossed, and carry out polyreaction under 50-70 ℃ of condition; After reaction is finished, the product of isolating expectation and purifying.
5, the preparation method of acrylic elastomer according to claim 4 is characterized in that, described ethyl propenoate, 90 parts; Vinyl cyanide: 8.5 parts; Vinyl monochloroacetate: 1.5 parts; Deionized water: 200 parts; Emulsifying agent is a dodecyl semi-annular jade pendant acid sodium: 3 parts; Initiator is Potassium Persulphate, sodium bisulfite: an amount of.
6, the preparation method of acrylic elastomer according to claim 1 is characterized in that, described raw material A is an ethyl propenoate, three kinds of butyl acrylate and vinylformic acid methoxyl group esters; Raw material B be glycidyl acrylate and two kinds of vinyl monochloroacetates, the consumption of the two can be identical, also can be inequality.
7, the preparation method of acrylic elastomer according to claim 6 is characterized in that, described ethyl propenoate: 35 parts; 30 parts of butyl acrylates; Vinylformic acid methoxyl group ethyl ester: 30 parts; Propylene glycidyl ester: 3.5 parts; 1.5 parts of vinyl monochloroacetates; Deionized water: 200 parts; Emulsifying agent is a sodium laurylsulfonate: 3 parts; Initiator is Potassium Persulphate and sodium bisulfite: an amount of.
8, the preparation method of acrylic elastomer according to claim 1 is characterized in that, described raw material A is an ethyl propenoate, two kinds of butyl acrylates; Described raw material B is two kinds of ethylidene norbornene and vinyl monochloroacetates.
9, the preparation method of acrylic elastomer according to claim 8 is characterized in that, described ethyl propenoate: 45 parts; Butyl acrylate: 45 parts; Ethylidene norbornene: 8.5 parts; Emulsifying agent is a sodium laurylsulfonate: 3 parts; Initiator is Potassium Persulphate and sodium bisulfite: an amount of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117291 CN1226317C (en) | 2003-02-13 | 2003-02-13 | Method for preparation of acrylate rubber with double/ multicomponent vulcanization site monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117291 CN1226317C (en) | 2003-02-13 | 2003-02-13 | Method for preparation of acrylate rubber with double/ multicomponent vulcanization site monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1521195A true CN1521195A (en) | 2004-08-18 |
| CN1226317C CN1226317C (en) | 2005-11-09 |
Family
ID=34284668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03117291 Expired - Fee Related CN1226317C (en) | 2003-02-13 | 2003-02-13 | Method for preparation of acrylate rubber with double/ multicomponent vulcanization site monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1226317C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030862A (en) * | 2009-09-29 | 2011-04-27 | 九江世龙橡胶有限责任公司 | Cold-resistant acrylate rubber |
| CN102140150A (en) * | 2011-03-11 | 2011-08-03 | 安徽时代创新科技投资发展有限公司 | Preparation method for acrylic ester 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 |
| CN107663261A (en) * | 2016-07-27 | 2018-02-06 | 广州熵能创新材料股份有限公司 | A kind of double crosslinking points monomeric carboxylic acids type ACMs and preparation method thereof |
| CN111072846A (en) * | 2019-12-31 | 2020-04-28 | 山东海益橡胶科技有限公司 | Acrylate rubber capable of being directly vulcanized without washing and preparation method thereof |
| CN113563682A (en) * | 2021-08-25 | 2021-10-29 | 山东海益橡胶科技有限公司 | Modified carboxyl acrylate rubber without guanidine accelerator and preparation method thereof |
-
2003
- 2003-02-13 CN CN 03117291 patent/CN1226317C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030862A (en) * | 2009-09-29 | 2011-04-27 | 九江世龙橡胶有限责任公司 | Cold-resistant acrylate rubber |
| CN102140150A (en) * | 2011-03-11 | 2011-08-03 | 安徽时代创新科技投资发展有限公司 | Preparation method for acrylic ester rubber |
| 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 |
| CN104650275A (en) * | 2014-06-26 | 2015-05-27 | 柳州市够旺贸易有限公司 | Preparation method of acrylate rubber |
| CN107663261A (en) * | 2016-07-27 | 2018-02-06 | 广州熵能创新材料股份有限公司 | A kind of double crosslinking points monomeric carboxylic acids type ACMs and preparation method thereof |
| CN111072846A (en) * | 2019-12-31 | 2020-04-28 | 山东海益橡胶科技有限公司 | Acrylate rubber capable of being directly vulcanized without washing and preparation method thereof |
| CN113563682A (en) * | 2021-08-25 | 2021-10-29 | 山东海益橡胶科技有限公司 | Modified carboxyl acrylate rubber without guanidine accelerator and preparation method thereof |
| CN113563682B (en) * | 2021-08-25 | 2023-01-17 | 山东海益橡胶科技有限公司 | Modified carboxyl acrylate rubber without guanidine accelerator and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1226317C (en) | 2005-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3745196A (en) | Low-temperature and oil-resistant core-shell acrylic polymers | |
| EP1672027B1 (en) | Thermoplastic elastomer composition and formed article | |
| CN1081204C (en) | Thermoplastic elastomers having improved cure | |
| AU711182B2 (en) | Seed polymerized latex polymer having a gradient polymeric morphology and process for preparing the same | |
| CN101061157A (en) | Impact modified thermoplastic resin composition | |
| EP0924257A1 (en) | Fluorinated thermoplastic elastomers | |
| CN1440432A (en) | Antistatic polymers, blends and articles | |
| CN1861678A (en) | Preparation process of easy processing cold resisting type polyacrylate rubber | |
| CN1137167C (en) | Process for making polypropylene graft copolymers containing anhydride groups | |
| CN1800286A (en) | Polymer additives and adhesive compositions including them | |
| CN102498140A (en) | Nitrile rubbers and production thereof in organic solvents | |
| US3201373A (en) | Synthetic chlorine containing rubberacrylate type polymers | |
| CN108299583A (en) | A kind of cross-linking modified preparation method of special PVC resin | |
| JP3998159B2 (en) | Method for producing a gel-free ethylene / vinyl acetate copolymer having a high content of copolymerized vinyl acetate and a high Mooney viscosity | |
| CN1226317C (en) | Method for preparation of acrylate rubber with double/ multicomponent vulcanization site monomer | |
| KR950011900B1 (en) | Polyacetal resin composition | |
| KR950008477B1 (en) | Rubber composition | |
| CN1315940C (en) | Providing thermoplastic composition of luster less surface | |
| CN103080138A (en) | Rubber blends consisting of different nitrile rubbers | |
| CN1688655A (en) | Transparent and impact-resistant thermoplastic resin composition | |
| JP3395617B2 (en) | Method for producing (meth) acrylic polymer blend composition | |
| GB2044276A (en) | High nitrile impact resistant resins | |
| CN1281006A (en) | Composition with thermoplastic methacrylic acid (co) polymers as main component and shaping product obtained from said composition | |
| CN108517098A (en) | A kind of long-term thermoplastic dynamic vulcanized elastomer of high temperature resistant oil resistant and preparation method thereof | |
| CN106496466B (en) | A kind of Green Chemistry preparation method of vinyl chloride/butyl acrylate copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051109 Termination date: 20110213 |