CN108752513A - A kind of preparation of acrylate-olefin copolymers containing cross-linking double bond and vulcanization process - Google Patents
A kind of preparation of acrylate-olefin copolymers containing cross-linking double bond and vulcanization process Download PDFInfo
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- CN108752513A CN108752513A CN201810500035.XA CN201810500035A CN108752513A CN 108752513 A CN108752513 A CN 108752513A CN 201810500035 A CN201810500035 A CN 201810500035A CN 108752513 A CN108752513 A CN 108752513A
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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Abstract
The preparation method of the acrylate-olefin copolymers containing cross-linking double bond being prepared using Louis (Lewis) acid catalyst catalysis acrylate, alkene and polyfunctional monomer copolymerization disclosure sets forth a kind of, and the method further vulcanized using vulcanizing agent.Polyfunctional monomer reactable group can partly be retained as the crosslinking points of polymer further processing during the reaction.Specific aim vulcanizing agent is selected according to crosslinkable functionality different on the polymer molecular chain of generation, prepares elastomeric material.
Description
Technical field
The present invention relates to a kind of methods for realizing the alkene containing cross-linking double bond and acrylic ester copolymer and vulcanization, belong to poly-
Close object synthesis and manufacture field.
Background technology
Acrylate and olefin copolymer(AEM)Both it can overcome polyolefin(Non-polar polymer)Bonding, dyeing, printing
It is difficult with being blended, and polyacrylate can be solved(Polar polymer)Low temperature resistant, oil resistant contradiction is a kind of with unique applications
Chemical products.With neoprene (CR), chlorosulfonated polyethylene rubber(Hypalon), ethylene propylene diene rubber(EPDM), chlorination it is poly-
Ethylene rubber(CPE)And epichlorohydrin rubber(ECO)Etc. elastomer phases ratio, it increases significantly in terms of heat-resisting, oil resistivity;And
Compared with fluoroelastomer, fluorine silicone rubber and hydrogenated nitrile-butadiene rubber, its price is then much lower, and it is neutral to be suitable for production auto industry
The more demanding rubber components of energy.It is used for the various seal members and hose of automobile engine and transmission system, so that portion
Part has good comprehensive performance and reliability, such as resistant of high or low temperature and oil resistivity.Applications of the AEM in dynamical system seal member
Example has:Valve mechanism cover(Cavaera housing)Gasket, CMPS Camshaft Position Sensor sealing ring, spark plug sealing ring, Pcv valve are close
Seal, VVT oil circuit sealing rings piston seal, food tray gasket and various O-rings etc..
AEM copolymers will meet its performance requirement in automobile engine and transmission system, it is necessary at over cure processing
Reason.And its vulcanization after the most important determinant of performance be in its molecular structure can vulcanization unit type, quantity and selection
Vulcanizing system.
At present on international market AEM elastomeric materials by E.I.Du Pont Company's simple monopoly, trade mark Vamac@, it is divided into and does not contain
The dual products of vulcanization unit and containing can vulcanization unit ternary product.Containing can the ternary product of vulcanization unit its active group
Group is chlorine element, thus the series of products will produce environmental pollution gas under the cooperation of its vulcanizing agent polyamine in sulfidation
Hydrogen chloride has certain injury to processing staff's body and has carcinogenic risk.
The present invention is in view of the above problems, provide a kind of polyfunctionality list introducing the unit containing double bond during monomer polymerization
The method of body replaces the introducing of E.I.Du Pont Company's monomer containing chlorine type, avoids environmental pollution of the AEM elastomers in vulcanizing process
With personnel's actual bodily harm.
Invention content
The polyfunctional monomer of the unit of the present invention containing double bond, double bond is not complete participates in instead in the course of the polymerization process
It answers but partly retains or selectively retain, the double bond retained during polymer sulfuration plays crosslinking points.
Double bond part retain monomer include:Conjugated diene(Including:1,3- butadiene, 1,3- pentadienes, 1,3- oneself two
Alkene, 1,3- heptadiene, 1,3- octadienes, 1,3- nonadienes, 1,3- decadinene, 2- methyl-1s, 3- butadiene, 2,3- dimethyl-
1,3-butadiene etc., but not limited to this), non-conjugated diene hydrocarbon(Including:3- methyl-1s, 2- butadiene, 1,4- pentadienes, 1,5-
Hexadiene, 1,6- heptadiene, 1,7- octadienes, 1,8- nonadienes, 1,9- decadinene etc., but not limited to this).The system is very suitable
Conjunction prepares the polymer that strand is in branching pattern, and polymer molecular weight distribution is wide, has good processing performance.But it should
, it is noted that the double bond of the type has same reactivity, copolyreaction, thus double bond part conservative list can participate in
Body conversion ratio of feed ratio and copolymerization system monomer in being copolymerized formula system has upper limit requirement, otherwise can lead to copolymer
Gel occurs during the reaction for system.
The monomer that double bond selectively retains mainly has:Allyl acrylate, allyl methacrylate and ring
Oxygroup allyl ether(Including:Allyl glycidyl ether), but not limited to this.The characteristics of the type monomer is to contain double bond
Liang Zhong functional groups activity it is different, epoxy group and acrylic double bond belong to high activity group, and double bond is opened in polymerization process
It is connected to the part that copolymer chain is formed on macromolecular radical, and allyl belongs to inertia group, it can be in polymerization process
It is effectively maintained.But the common such as epoxy acrylate of the monomer containing functional group of acrylate elastomer(Including:Propylene
Acid glycidyl ester and glycidyl methacrylate)Then be not suitable for the copolymerization system, because of two kinds of officials of the type monomer
Energy group activity is all very high, is involved in polymerisation, and double bond cannot be retained in copolymer structure.
Polymer of the present invention can be used a variety of vulcanizing systems and carry out vulcanization crosslinking, including sulphur system, peroxidating
Objects system(Including di-tert-butyl peroxide(DBP), cumyl peroxide(DCP), 2,5- dimethyl -2,5(Di-t-butyl
Peroxide)Hexane(AD), 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane(3M)Deng, but not limited to this), diacyl
Peroxide(Including benzoyl peroxide(BPO), t-butyl perbenzoate(TPB)Deng, but not limited to this), naphthoquinone derivatives body
System(Including benzoquinones dioxime(GMF), dibenzoyl p quinone dioxime(DBGMF)Deng, but not limited to this)With maleimide amine system
(Such as meta-phenylene bismaleimide)Deng.Curing temperature:100-200 DEG C, vulcanization time:3-30min specifically regards copolymer
Depending on middle double bond type and selected vulcanizing system.
Advantage of the present invention:
1. the present invention provides a kind of method replacement Du for the polyfunctional monomer introducing the unit containing double bond during monomer polymerization
The introducing of company of nation monomer containing chlorine type avoids environmental pollution and personnel actual bodily harm of the AEM elastomers in vulcanizing process.
2. the molar content containing cross-linking double bond monomer in the polymer that the present invention synthesizes arbitrarily may be used in 0-30% range
It adjusts, the material of the low elongation at break of high tensile can be prepared by coordinating vulcanizing system of the present invention both, can also be prepared
The material of low tensile strength high elongation at tear can also be accomplished between tensile strength and elongation at break according to actual needs
The two balances.
Attached drawing and subordinate list explanation
Fig. 1 copolymer number-average molecular weights(Mn)And molecular weight distribution (PDI) figure
Fig. 2 copolymer nuclear magnetic resonance spectroscopy phenograms
Fig. 3 copolymer nuclear magnetic resonance spectroscopy phenograms
Fig. 4 copolymer nuclear resounce magnetic hydrogen composes phenogram
Fig. 5 copolymer nuclear magnetic resonance spectroscopy phenograms
Fig. 6 elastomeric material mechanical property figures
1. copolymer material processing formula table of table
Specific implementation mode:
The present invention is specifically addressed below by embodiment, it must further be noted that the present embodiment is to of the invention into one
Step explanation, must not believe that the scope of the present invention is only limitted to this, person skilled in art can be according to the content of foregoing invention
Make some immaterial modifications and adaptations.
Embodiment 1.
Methyl acrylate 4mL, 1- octene 5mL, allyl glycidyl ether 1mL, alchlor 3.68g, azobisisoheptonitrile
0.1g, dichloromethane 50mL, 40 DEG C of reaction 7h of water-bath, obtain sticky polymers solution, by this under conditions of sealing and having stirring
Solution, which pours into, obtains polymer in methanol hydrochloride solution, which, which is dissolved in acetone methanol hydrochloride solution, precipitates 2 times, must purify
Polymer.Polymer is dissolved in tetrahydrofuran(THF), polymer molecular weight and its distribution are characterized using gel permeation chromatography (GPC),
The results are shown in Figure 1;Polymer is dissolved in deuterochloroform, and characterizing copolymerization units in polymer using nuclear magnetic resonance spectroscopy forms, knot
Fruit is as shown in Figure 2.Polymer is mixed into corresponding filler and vulcanizing agent(Such as table 1), 160 DEG C vulcanize 9 minutes, material tensile property
As shown in Figure 6.
Embodiment 2.
Methyl acrylate 4.6mL, 1- octene 5mL, allyl glycidyl ether 0.4mL, alchlor 3.68g, two different heptan of azo
Nitrile 0.1g, dichloromethane 50mL, 40 DEG C of reaction 7h of water-bath, obtain sticky polymers solution under conditions of sealing and having stirring, will
The solution, which pours into, obtains polymer in methanol hydrochloride solution, which, which is dissolved in acetone methanol hydrochloride solution, precipitates 2 times, must carry
Straight polymer.Polymer is dissolved in tetrahydrofuran(THF), characterize polymer molecular weight using gel permeation chromatography (GPC) and its divide
Cloth, data are as shown in Figure 1;Polymer is dissolved in deuterochloroform, and characterizing copolymerization units in polymer using nuclear magnetic resonance spectroscopy forms,
Data are as shown in Figure 3.
Embodiment 3.
Methyl acrylate 4mL, 1- octene 6.5mL, 1,7- octadiene 0.3mL, alchlor 2.94g, azobisisoheptonitrile 0.1g,
Dichloromethane 50mL, 40 DEG C of reaction 7h of water-bath, obtain sticky polymers solution, which are fallen under conditions of sealing and having stirring
Enter and obtain polymer in methanol hydrochloride solution, which, which is dissolved in acetone methanol hydrochloride solution, precipitates 2 times, must purify polymerization
Object.Polymer is dissolved in tetrahydrofuran(THF), polymer molecular weight and its distribution, data are characterized using gel permeation chromatography (GPC)
As shown in Figure 1;Polymer is dissolved in deuterochloroform, and characterizing copolymerization units in polymer using nuclear magnetic resonance spectroscopy forms, and data are such as
Shown in Fig. 4.Polymer is mixed into corresponding filler and vulcanizing agent(Such as table 1), 160 DEG C vulcanize 9 minutes, and material tensile property is as schemed
Shown in 6.
Embodiment 4.
Methyl acrylate 4mL, 1- octene 8mL, allyl methacrylate 1 mL, alchlor 3.47g, azodiisobutyronitrile
0.1g, dichloromethane 50mL are sealed with 40 DEG C of reaction 7h of water-bath under conditions of stirring, sticky polymers solution are obtained, by the solution
It pours into and obtains polymer in methanol hydrochloride solution, which, which is dissolved in acetone methanol hydrochloride solution, precipitates 2 times, must purify polymerization
Object.Polymer is dissolved in tetrahydrofuran(THF), polymer molecular weight and its distribution, data are characterized using gel permeation chromatography (GPC)
As shown in Figure 1;Polymer is dissolved in deuterochloroform, and characterizing copolymerization units in polymer using nuclear magnetic resonance spectroscopy forms, and data are such as
Shown in Fig. 5.
Table 1
CBS:N- cyclohexyls -2-[4-morpholinodithio sulfenamide;M:2- benzothiazolyl mercaptans.
Claims (6)
1. preparation and the vulcanization process of a kind of acrylate-olefin copolymers containing cross-linking double bond, in lewis acid catalyst
Under the conditions of existing, acrylate, alkene and the monomer radical solution polymerization process preparation containing cross-linking double bond contain can be into one
The acrylate-olefin copolymers of step reaction double bond.
2. matched filler, vulcanizing agent and accelerating agent can be selected in the copolymer, carries out vulcanization and prepare elastomeric material.
3. including containing cross-linking double bond monomer described in claim 1:Conjugated diene(Including:1,3- butadiene, 1,3- penta 2
Alkene, 1,3- hexadienes, 1,3- heptadiene, 1,3- octadienes, 1,3- nonadienes, 1,3- decadinene, 2- methyl-1s, 3- butadiene,
2,3- dimethyl -1,3-butadiene etc., but not limited to this), non-conjugated diene hydrocarbon(Including:3- methyl-1s, 2- butadiene, 1,4-
Pentadiene, 1,5- hexadienes, 1,6- heptadiene, 1,7- octadienes, 1,8- nonadienes, 1,9- decadinene etc., but not limited to this),
Epoxy acrylate(Including:Glycidyl acrylate and glycidyl methacrylate), epoxy group allyl ether(Packet
It includes:Allyl glycidyl ether)And two or more mixtures.
4. molar fraction is 0-30% to bifunctional monomer's unit described in claim 1 in the polymer.
5. the copolymer number-average molecular weight 20000-500000, preferably 50000-200000 described in claim 1, polydispersion refers to
Number(PDI) 1.5-10.0, preferably 2.0-5.0.
6. polymer sulfuration system described in claim 2 includes sulphur system, peroxide systems(Including di-tert-butyl peroxide
Object(DBP), cumyl peroxide(DCP), 2,5- dimethyl -2,5(Di-t-butyl peroxide)Hexane(AD), 1,1- di-t-butyls
Peroxy -3,3,5- trimethyl-cyclohexanes(3M)Deng, but not limited to this), diacyl peroxide(Including benzoyl peroxide
(BPO), t-butyl perbenzoate(TPB)Deng, but not limited to this), naphthoquinone derivatives system(Including benzoquinones dioxime(GMF), hexichol
Formyl parabenzoquinone dioxime(DBGMF)Deng, but not limited to this)With maleimide amine system(Such as meta-phenylene bismaleimide)
Deng.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN116655943A (en) * | 2023-05-16 | 2023-08-29 | 深圳市嘉卓成科技发展有限公司 | Preparation method of antibacterial and antiviral water-based hydroxy acrylate emulsion |
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CN102498137A (en) * | 2009-08-28 | 2012-06-13 | 国立大学法人东京大学 | Production method of copolymer of allyl monomer containing polar group |
CN103665241A (en) * | 2012-09-11 | 2014-03-26 | 中国石油化工集团公司 | Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof |
WO2017118544A1 (en) * | 2016-01-05 | 2017-07-13 | Sabic Global Technologies B.V. | Method for preparing ethylene copolymer |
CN107075024A (en) * | 2014-10-30 | 2017-08-18 | 阿朗新科德国有限责任公司 | Include the curable compositions of the EVAc containing epoxy radicals |
CN107501464A (en) * | 2017-07-24 | 2017-12-22 | 四川大学 | A kind of preparation method of olefin-acrylate copolymer |
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Patent Citations (5)
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CN102498137A (en) * | 2009-08-28 | 2012-06-13 | 国立大学法人东京大学 | Production method of copolymer of allyl monomer containing polar group |
CN103665241A (en) * | 2012-09-11 | 2014-03-26 | 中国石油化工集团公司 | Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof |
CN107075024A (en) * | 2014-10-30 | 2017-08-18 | 阿朗新科德国有限责任公司 | Include the curable compositions of the EVAc containing epoxy radicals |
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CN107501464A (en) * | 2017-07-24 | 2017-12-22 | 四川大学 | A kind of preparation method of olefin-acrylate copolymer |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN116655943A (en) * | 2023-05-16 | 2023-08-29 | 深圳市嘉卓成科技发展有限公司 | Preparation method of antibacterial and antiviral water-based hydroxy acrylate emulsion |
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