CN108276519A - Acrylic ester polymerization reaction retarder and its acrylate composition - Google Patents
Acrylic ester polymerization reaction retarder and its acrylate composition Download PDFInfo
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- CN108276519A CN108276519A CN201810101687.6A CN201810101687A CN108276519A CN 108276519 A CN108276519 A CN 108276519A CN 201810101687 A CN201810101687 A CN 201810101687A CN 108276519 A CN108276519 A CN 108276519A
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- Prior art keywords
- acrylate
- retarder
- composition
- acrylic ester
- acrylate composition
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of acrylic ester polymerization reaction retarder and its acrylate composition, retarder uses the tert-butyl alcohol and triethylamine by weight for 2:1 ratio composition, can inhibit the polymerization rate of acrylic ester monomer raw material, and it is at the uniform velocity, so that reaction heat discharges in time, and can be adjusted the PH of polymerisation environment, to stablize being smoothed out for polymerisation to make polymerization rate.
Description
Technical field
The present invention relates to rubber synthesis technical field, more particularly to a kind of acrylic ester polymerization reaction retarder and its third
Alkene acid ester composite.
Background technology
Acrylic rubber (abbreviation ACM), be by alkyl acrylate or its gather with alkoxyalkyl acrylate
It closes and obtains, have many advantages, such as that the cold resistance, the oil resistivity that meet use environment are especially oil resistivity at high temperature.Therefore, third
Olefin(e) acid ester rubber is increasing as its demand such as conveyer belt built in the hose of automobile, oil sealing, 0 type circle, device/machinery.It is existing
Some acrylic rubber are utilized in generation polymerisation in emulsifier aqueous solution and are made, but acrylate in the prior art
The speed of polymerisation occurs for each raw material monomer of rubber, and such reaction is exothermic reaction, can be produced during the reaction
Raw a large amount of reaction heat, when polymerisation is too fast, reaction heat can not discharge in time, influence the performance of final rubber product.
Invention content
In view of this, a kind of acrylic ester polymerization reaction retarder of present invention offer and its acrylate composition,
The polymerization rate of acrylic ester monomer raw material can not only be inhibited, it is at the uniform velocity Er Qieke to make polymerization rate
The PH of polymerisation environment is adjusted.
The acrylic ester polymerization reaction retarder of the present invention, retarder are 2 by weight by the tert-butyl alcohol and triethylamine:
1 ratio composition.
The invention also discloses a kind of acrylate composition with the retarder, acrylate composition contains
The retarder.
Further, acrylate composition includes following component by weight percentage：Ethyl acrylate 10% -60%, third
Olefin(e) acid butyl ester 10%-50%, methoxyethyl acrylate 10%-50% and crosslinking points monomer 2%-5%, retarder 0.1-
0.5%.
Further, acrylate composition includes following component by weight percentage：Ethyl acrylate 30% -50%, third
Olefin(e) acid butyl ester 20%-35%, methoxyethyl acrylate 25%-35% and crosslinking points monomer 2%-4%, retarder 0.2-
0.4%.
Further, acrylate composition includes following component by weight percentage：Ethyl acrylate 45%, acrylic acid fourth
Ester 24%, methoxyethyl acrylate 28% and crosslinking points monomer 2.7%, retarder 0.3%.
Further, crosslinking points monomer has carboxyl, epoxy group or active cl radical.
Beneficial effects of the present invention：The acrylic ester polymerization reaction retarder of the present invention, uses the tert-butyl alcohol and three second
Amine is 2 by weight:1 ratio composition, can inhibit the polymerization rate of acrylic ester monomer raw material, make to gather
It is at the uniform velocity, so that reaction heat discharges in time, and can be adjusted the PH of polymerisation environment, to stablize to close reaction speed
Polymerisation is smoothed out.
The acrylate composition of the present invention, due to using above-mentioned retarder, in bulk polymerization reaction process, speed can
It remains a constant speed, the reaction heat generated in polymerization process can discharge in time, and the pH value of whole polymerisation environment can
In the state of maintaining reliably, the performance and quality of rubber product made from the acrylate composition are improved.
Specific implementation mode
Clear, complete description is carried out to technical scheme of the present invention below in conjunction with the embodiment of the present invention, it is clear that retouched
The embodiment stated is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, originally
The every other embodiment that field those of ordinary skill is obtained without making creative work, belongs to the present invention
The range of protection.
It is to be appreciated that the technical solution between each embodiment can be combined with each other, but must be common with this field
Technical staff can be implemented as basis, will be understood that this skill when the combination of technical solution appearance is conflicting or cannot achieve
The combination of art scheme is not present, also not the present invention claims protection domain in.
The present invention proposes a kind of acrylic ester polymerization reaction retarder, retarder by the tert-butyl alcohol and triethylamine by weight
Than being 2:1 ratio composition.According to the specific weight of actual needs the selection tert-butyl alcohol and triethylamine of retarder, the tert-butyl alcohol is utilized
The reaction speed of acrylic ester polymerization reaction is adjusted jointly with the catalytic and inhibition property of triethylamine, keeps its holding even
Speed so that reaction heat discharges in time, prevents a large amount of aggregations of heat in reaction kettle from causing safety accident, and retarder accounts for acrylic acid
Ester composition total quality 0.1-0.5%, ensure make polymerization rate at the uniform velocity under the premise of, can be by polymerisation environment
PH values be adjusted to 7.5-8.
The invention also discloses a kind of acrylate composition containing above-mentioned retarder, the acrylate composition
Embodiment one：The polyacrylate composition of the present embodiment, by mass percentage content be made of following components：Ethyl acrylate
60%, butyl acrylate 10%, methoxyethyl acrylate 28%, crosslinking points monomer 1.9% and retarder 0.1%.
Embodiment two, the polyacrylate composition of the present embodiment of acrylate composition, by mass percentage content
It is made of following components：Ethyl acrylate 49.8%, butyl acrylate 10%, methoxyethyl acrylate 38%, crosslinking points list
Body 2% and retarder 0.2%.
Embodiment three, the polyacrylate composition of the present embodiment of acrylate composition, by mass percentage content
It is made of following components：Ethyl acrylate 40%, butyl acrylate 11.8%, methoxyethyl acrylate 45%, crosslinking points list
Body 3% and retarder 0.2%.
The example IV of acrylate composition, the polyacrylate composition of the present embodiment, by mass percentage content
It is made of following components：Ethyl acrylate 30%, butyl acrylate 17%, methoxyethyl acrylate 49.6%, crosslinking points list
Body 3% and retarder 0.4%.
Embodiment five, the polyacrylate composition of the present embodiment of acrylate composition, by mass percentage content
It is made of following components：Ethyl acrylate 11%, butyl acrylate 35%, methoxyethyl acrylate 50%, crosslinking points monomer
3.5% and retarder 0.5%.
Embodiment six, the polyacrylate composition of the present embodiment of acrylate composition, by mass percentage content
It is made of following components：Ethyl acrylate 10%, butyl acrylate 50%, methoxyethyl acrylate 35%, crosslinking points monomer
4.5% and retarder 0.5%.
Embodiment seven, the polyacrylate composition of the present embodiment of acrylate composition, by mass percentage content
It is made of following components：Ethyl acrylate 44.7%, butyl acrylate 24%, methoxyethyl acrylate 28%, crosslinking points list
Body 3% and retarder 0.3%.
The method that the polyacrylate composition of the various embodiments described above prepares rubber is, by composition acrylic rubber combination
The various raw material monomers and conditioning agent of object are added in emulsifier aqueous solution, under nitrogen protection, it is anti-to cause combined polymerization by free radical
It answers, after the completion of copolymerization, adds reducing agent and post-processed, finally add flocculating agent demulsification, rinsed through clear water, taken off
Water obtains composition product.Wherein, conditioning agent be n- dodecyl mereaptan, tert-dodecyl mercaptan and one kind in two different benzene xanthates,
Two or three, it is used for being the 0-0.2% of various raw material monomer total weights；Water in emulsifier aqueous solution is deionization
Water, dosage can be the 150-500% of various raw material monomer total weights；Emulsifier can be dodecyl sodium sulfate, dodecane
Any one in base benzene sulfonic acid sodium salt, lauryl sodium sulfate, disproportionated rosin soap or two kinds, concentration can be 2-10%；Freely
Base is decomposed by free radical donor and is provided, and dosage is a ten thousandth of various raw material monomer total weights to 2/1000ths, the freedom
Base donor can be that two isobutyl of azo is fine, two different heptan of azo is fine, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide
It is any one in formyl, cumyl peroxide, di-t-butyl peroxide, ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate
Kind:And the polymeric reaction temperature that free radical donor is used alone is 50-100 DEG C, the polymerisation temperature being used in conjunction with reducing agent
Degree is 5-50 DEG C；The reducing agent can be sodium sulfite, sodium thiosulfate, sodium hydrogensulfite, sodium dithionite, burnt sulfurous
Any one in sour sodium, sodium formaldehyde sulphoxylate or ferrous sulfate；The flocculating agent is dilute sulfuric acid, dilute hydrochloric acid, chlorination
In sodium, magnesium chloride, calcium chloride, alchlor, poly-ferric chloride, aluminium polychloride, polyacrylamide, ethyl alcohol any one or
Several, dosage is the 1-5% of various raw material monomer total weights.
It in the above embodiment of the present invention, is obtained by experimental test, when ethyl acrylate unit and acrylic acid methoxy
When the content of base ethyl ester is excessive, the hydrolytic resistance of obtained acrylic rubber composition deteriorates, that is, influences whether acrylic rubber
The hydrolytic resistance of composition entirety, and when the content of methoxyethyl acrylate is very few, obtained acrylic rubber composition
Oil resistivity deteriorate, that is, influence whether the oil resistivity of acrylic rubber composition entirety, and when crosslinking points monomer is excessive, obtain
Acrylic rubber composition be hardened, when crosslinking points monomer is very few, the intensity of obtained acrylic rubber composition is insufficient；
In the various embodiments described above, ethyl acrylate, butyl acrylate, methoxyethyl acrylate and crosslinking points monomer content obtain
Appropriate proportioning does not interfere with the hydrolytic resistance of acrylic rubber composition entirety not only, but also with preferable resistance to
Low temperature properties, while can guarantee oil resistivity, wherein especially with the 7th embodiment best results, and analyzed through differential scanning calorimetry,
Glass transition temperature is relatively low, minimum reachable -30 DEG C, and oil resistivity is preferable.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (6)
1. a kind of acrylic ester polymerization reaction retarder, it is characterised in that：The retarder is by the tert-butyl alcohol and triethylamine by weight
It is 2 that amount part, which is compared,:1 ratio composition.
2. a kind of acrylate composition with retarder described in claim 1, it is characterised in that：The acrylate group
It closes object and contains the retarder.
3. acrylate composition according to claim 2, it is characterised in that：The acrylate composition by weight hundred
It includes following component to divide ratio：Ethyl acrylate 10%-60%, butyl acrylate 10%-50%, methoxyethyl acrylate
10%-50% and crosslinking points monomer 1%-5%, retarder 0.1-0.5%.
4. acrylate composition according to claim 3, it is characterised in that：The acrylate composition by weight hundred
It includes following component to divide ratio：Ethyl acrylate 30%-50%, butyl acrylate 20%-35%, methoxyethyl acrylate
25%-35% and crosslinking points monomer 2%-4%, retarder 0.2-0.4%.
5. acrylate composition according to claim 4, it is characterised in that：The acrylate composition by weight hundred
It includes following component to divide ratio：Ethyl acrylate 45%, butyl acrylate 24%, methoxyethyl acrylate 28% and crosslinking points list
Body 2.7%, retarder 0.3%.
6. acrylate composition according to claim 5, it is characterised in that：The crosslinking points monomer has carboxyl, ring
Oxygroup or active cl radical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810101687.6A CN108276519A (en) | 2018-02-01 | 2018-02-01 | Acrylic ester polymerization reaction retarder and its acrylate composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810101687.6A CN108276519A (en) | 2018-02-01 | 2018-02-01 | Acrylic ester polymerization reaction retarder and its acrylate composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108276519A true CN108276519A (en) | 2018-07-13 |
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ID=62807353
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810101687.6A Pending CN108276519A (en) | 2018-02-01 | 2018-02-01 | Acrylic ester polymerization reaction retarder and its acrylate composition |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050234207A1 (en) * | 2004-04-20 | 2005-10-20 | Moutinho Marcus Tadeu M | Preparation process of acrylic rubber, acrylic rubber, composition of the acrylic rubber and articles cured thereof |
| CN101993511A (en) * | 2009-08-28 | 2011-03-30 | 袁文阳 | Cold-resistant acrylate rubber as well as preparation and application thereof |
| CN103467664A (en) * | 2013-09-13 | 2013-12-25 | 四川凯本新材料科技有限公司 | Preparation method of flame-retardant, impact-resistant and high-fluidity chloroethylene-based special resin |
| CN103467647A (en) * | 2012-06-06 | 2013-12-25 | 袁洪庆 | Cold resistant acrylic rubber, and preparation and application thereof |
| CN104016821A (en) * | 2014-06-10 | 2014-09-03 | 中国科学院过程工程研究所 | Polymerization inhibitor and polymerization inhibiting method for (methyl) acrolein, (methyl) acrylic acid and esters thereof |
| CN106554460A (en) * | 2016-12-01 | 2017-04-05 | 重庆金茂达特种橡胶有限公司 | Low temperature resistant polyacrylate composition and preparation method thereof |
-
2018
- 2018-02-01 CN CN201810101687.6A patent/CN108276519A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050234207A1 (en) * | 2004-04-20 | 2005-10-20 | Moutinho Marcus Tadeu M | Preparation process of acrylic rubber, acrylic rubber, composition of the acrylic rubber and articles cured thereof |
| CN101993511A (en) * | 2009-08-28 | 2011-03-30 | 袁文阳 | Cold-resistant acrylate rubber as well as preparation and application thereof |
| CN103467647A (en) * | 2012-06-06 | 2013-12-25 | 袁洪庆 | Cold resistant acrylic rubber, and preparation and application thereof |
| CN103467664A (en) * | 2013-09-13 | 2013-12-25 | 四川凯本新材料科技有限公司 | Preparation method of flame-retardant, impact-resistant and high-fluidity chloroethylene-based special resin |
| CN104016821A (en) * | 2014-06-10 | 2014-09-03 | 中国科学院过程工程研究所 | Polymerization inhibitor and polymerization inhibiting method for (methyl) acrolein, (methyl) acrylic acid and esters thereof |
| CN106554460A (en) * | 2016-12-01 | 2017-04-05 | 重庆金茂达特种橡胶有限公司 | Low temperature resistant polyacrylate composition and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《化工百科全书》编辑部: "《化工百科全书 第9卷》", 30 June 1995 * |
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