CN106749870A - A kind of acetoacetate type ACM and preparation method thereof - Google Patents
A kind of acetoacetate type ACM and preparation method thereof Download PDFInfo
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- CN106749870A CN106749870A CN201611167963.6A CN201611167963A CN106749870A CN 106749870 A CN106749870 A CN 106749870A CN 201611167963 A CN201611167963 A CN 201611167963A CN 106749870 A CN106749870 A CN 106749870A
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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
- C08F220/12—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
Abstract
The invention discloses a kind of acetoacetate type ACM and preparation method thereof.The acetoacetate type ACM includes that the following monomer polymerization calculated by mass percentage is obtained：Alkyl acrylate monomer 65%~95%；Oil resistant low temperature resistant monomer 0%~30%；Cure site monomer containing acetoacetyl 3%~8%；Auxiliary curable monomer 0.5 ~ 1%.The acetoacetate type ACM of present invention synthesis is the novel acrylic ester rubber prepared as active crosslinking points using acetoacetate structure, optimize processing characteristics reduction curing temperature on the basis of ACM low compression set rate, oil resistant is remained and improve productivity ratio, improve long-term heat-resisting temperature in use.Rubber after present invention vulcanization is applied to the rubber components for needing long-term heat-resisting oil resistant, pipeline, container lining and the cable for being contacted with oil for a long time and exposed to ozone, the rubber part of hot environment.
Description
Technical field
The present invention relates to rubber materials, more particularly, to a kind of acetoacetate type ACM and its preparation side
Method.
Background technology
It with acrylate is main monomer through elastomer obtained by copolymerization that ACM (hereinafter referred to as ACM) is, its master
Chain is saturated carbon chains, and side base is polar ester groups, than the dience rubber stabilization with double bond on main chain.Above-mentioned special construction is assigned
Give its many excellent properties, such as low temperature resistant, ageing-resistant, oil resistant, resistance to ozone, uvioresistant.Simultaneously because with excellent resistance to
High-temperature oil resistance performance, is widely used in the various seals of automobile, such as oil sealing, pad.ACM is widely applied
In various sealing rings, packing ring, pad and tubing, wherein the application field for exceeding 90% is related to auto industry.In recent years, by
In the high speed development of automobile industry, whole market is greatly improved the demand of high-performance rubber encapsulant, promote third
The exploitation of olefin(e) acid ester rubber.In the R＆D process of Hyundai Motor, the size of engine reduces constantly, and power is not
Increase disconnectedly.On the other hand, extra pressure is provided by turbo charge system so that the design of engine room is more compact.
Result caused by above-mentioned change, is that the operating temperature of engine room climbs up and up.Therefore, to organic material associated there
The heat resistance of ACM there has also been requirement higher, and automobile ACM is had to the good same duration of mechanical property
Phase heat resisting temperature will reach more than 180 DEG C.Meet this requirement, lifting ACM heat aging properties are grinding for ACM
Study carefully exploitation focus.
Additionally while ACM has many excellent properties, but ACM rubber processings performance is also extensively denounced, main
Show as easy adhesion, easy incipient scorch, cure time is long, temperature is high causes the decline of glue physical performance and low production efficiency, production process
Safety coefficient is relatively low, not environmentally the shortcomings of.Therefore, it need be modified.The processing of usual ACM need to select specific vulcanization
System and improve its processing characteristics by adding additional processing auxiliary agent, its some drawbacks can be improved, but reduce glue
Physical property and increase manufacturing cost.For the processing characteristics shortcoming for preferably overcoming ACM current, carry out entering one both at home and abroad
The research of step.In domestic new peroxide cure ACMs of A of patent CN 102643382 and preparation method thereof,
By be introduced into main rubber can be in cure site monomer vinyl chloride, bromopropene, the bromobutene with peroxide reactions it is any one
Kind, so as to improve rate of cure, the advantages of with mould, processability and good physical performance is not corroded, but rubber contains halogen, vulcanization
Toxic gas may be discharged, and polymerized monomer is dangerous big.
And for example mentioned with acrylic acid in a kind of preparation methods of vulcanizing-free acrylic ester rubber of patent CN101812180A
Esters monomer, styrene and functional group containing tertiary amine monomer and chloride function monomer are raw material, prepare self-crosslinking acrylic ester
Rubber, can avoid vulcanization, and direct moulding by casting is rubber, but it can not add filler reinforcement, with current conventional fabrication process not
Together, molding mode is single, it is difficult to promote.
The content of the invention
It is described it is contemplated that overcoming the defect of above-mentioned prior art, there is provided a kind of acetoacetate type ACM
Acetoacetate type ACM has more high-fire resistance energy, and (performance change can be conformed under 185 DEG C × 72h of hot air aging
Ask), moderate curingprocess rate, can room temperature vulcanization, and it is high to vulcanize productivity ratio.
Preparation method another object of the present invention is to provide the acetoacetate type ACM.
Goal of the invention of the invention is achieved by the following technical programs：
A kind of acetoacetate type ACM, is polymerized by the following monomer calculated by mass percentage and obtained：
Alkyl acrylate monomer 65%~95%；
Oil resistant low temperature resistant monomer 0%~30%；
Cure site monomer containing acetoacetyl 3%~8%；
Auxiliary curable monomer：0.5~1%；
Or
The cure site monomer containing acetoacetyl is changed into and contained by remaining monomer and consumption with reference to mentioned component and ratio
The monomer of ethylenic insatiable hunger key and hydroxyl, each monomer be polymerized obtains oh type ACM, then with diketene or
It is prepared by acetoacetic ester reaction.
Preferably, the acetoacetate type ACM, is polymerized by the following monomer calculated by mass percentage
Obtain：
Alkyl acrylate monomer 75%~85%；
Oil resistant low temperature resistant monomer 10%~20%；
Cure site monomer containing acetoacetyl 3%~8%；
Auxiliary curable monomer：0.5~1%；
Or
The cure site monomer containing acetoacetyl is changed into and contained by remaining monomer and consumption with reference to mentioned component and ratio
The monomer of ethylenic insatiable hunger key and hydroxyl, each monomer be polymerized obtains oh type ACM, then with diketene or
It is prepared by acetoacetic ester reaction.The acetoacetyl reactivity of acetoacetate type ACM of the present invention is high, will
It is introduced into ACM system, can be reacted with cyanamide class, isocyanates.Be tod because acetoacetyl reactivity is high
More excellent performance, such as cold curing (reaction, michael reaction with diamines) can be brought to ACM.Its structure or reaction are former
Reason is as follows：Acetoacetate based structures are as follows：
Acetoacetate based structures
1. with the reaction of cyanamide class
2. with the reaction of isocyanates
Other acetoacetic acid group can not only exist in the form of ketone, can also exist in the form of its isomers enol, its
Can directly be reacted with conventional Diamines vulcanizing agent, reaction equation is as follows：
3. with the reaction of diamines
4. michael reaction
The present invention realizes room temperature vulcanization improve production efficiency by active crosslinking points of acetoacetate structure, improves processability
Can, improve long-term heat-resisting temperature in use.Inventor is had found using the acetoacetate with the structure by many trials
Based structures can well control curingprocess rate as cure site monomer by being used cooperatively with suitable vulcanizing agent, it is to avoid burnt
Burn, stick the negative issues such as roller, processing characteristics is excellent, and can realize room temperature vulcanization, and vulcanization crosslinking is abundant；Furthermore acetyl second
Acidic group and the distinctive cross-bond mode of vulcanizing agent, it is possible to increase the heat resistance of ACM, it is ensured that vulcanization assembly adhesive exists
185 DEG C of long-term uses.Therefore acetoacetate type ACM can remain ACM low compression set
Optimize processing characteristics reduction curing temperature on the basis of rate, oil resistant and improve productivity ratio, improve long-term heat-resisting temperature in use.
The cure site monomer containing acetoacetyl is methacrylic acid ethyl acetoacetate, also known as acetoacetate ylmethyl
Ethyl acrylate, and/or acrylic acid ethyl acetoacetate, also known as acetoacetyl ethyl acrylate.
The oh type ACM prepares second with diketene or methyl acetoacetate or ethyl acetoacetate reaction
Ethyl acetoacetic acid type ACM, its reaction equation is as follows：
R is-CH3When, it is methyl acetoacetate.
R is-C2H5When, it is ethyl acetoacetate.
The monomer of the key of insatiable hunger containing ethylenic and hydroxyl is hydroxyethyl methacrylate, hydroxy propyl methacrylate, third
Olefin(e) acid hydroxyl ethyl ester or hydroxypropyl acrylate.
Preferably, it is described help curable monomer be the ethylenically unsaturated monomers containing carboxylic group be carbon-carbon double bonds two
First carboxylic acid monoalkyl ester monomer, can play acid monomer and thiosynergistic, and because the property of monomer monoesters improves rubber
Glue resists cold effect, while being avoided that the negative issues such as incipient scorch, glutinous Kun in sulfidation.
It is 6~10 that the dicarboxylic acids monoalkyl ester monomer of the carbon-carbon double bonds, wherein ester group preferably have carbon number
Ether alcohol formed, maleic acid monoethylene glycol only son ether-ether, maleic acid MPG only son ether-ether, maleic acid list diethyl can be exemplified as
2-ethoxyethanol ester, maleic acid monoethylene glycol only son ether-ether, maleic acid MPG only son ether-ether, fumaric acid monoethylene glycol only son
Ether-ether, fumaric acid list diethylene glycol monoethyl ether ester, fumaric acid list diethylene glycol monobutyl ether ester etc..
According to the preferred maleic acid monoethylene glycol only son ether-ether of action effect, maleic acid list diethylene glycol monobutyl ether ester, rich horse
Sour monoethylene glycol only son ether-ether, fumaric acid list diethylene glycol monobutyl ether.The dicarboxylic acids monoalkyl ester list of the carbon-carbon double bonds
Body, can play auxiliary sulfurization, while the presence that carbon number is 6~10 ether alcohol structure can suitable control rate of cure, guarantor
Crosslinking high is held while avoiding the negative issues such as incipient scorch, glutinous Kun, moreover it is possible to improve rubber cold resistance.
The dicarboxylic acids monoalkyl ester of described carbon-carbon double bonds can by the dicarboxylic acids of corresponding carbon-carbon double bonds/
Acid anhydrides is prepared with the alkyl ether alcohol reaction with same mole that carbon number is 6~10, such as maleic acid monoethylene glycol only son ether-ether
It is 1 by mol ratio：1 maleic anhydride is prepared with ethylene glycol monobutyl ether through esterification.Other raw materials may be referred to this
Method synthesizes.
Arrcostab is the Arrcostab formed by the fatty alcohol with carbon number 1~8 in the alkyl acrylate monomer.
The alkyl acrylate is used as can specifically enumerate methyl acrylate, ethyl acrylate, n-propyl, propylene
Acid esters N-butyl, isobutyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite or Isooctyl acrylate monomer.More preferably
It is one or more in methyl acrylate, ethyl acrylate, n-butyl acrylate.The need for according to performance, can use several
Planting alkyl acrylate carries out compounding adjustment.
Preferably, the low temperature oil resistant monomer be acrylic acid alcohol ethers monomer, can specifically enumerate methoxyethyl acrylate,
Ethoxyethyl acrylate, methoxyethyl butyl ester, ethioxy butyl ester, acrylic acid diethylene glycol monomethyl ether, diethyl
At least one in epoxide ethyl acrylate.
It is highly preferred that the acrylic acid alcohol ethers monomer is methoxyethyl acrylate, ethoxyethyl acrylate, propylene
At least one in acid diethylene glycol monomethyl ether.
The present invention is also optionally added can be copolymerized with alkyl acrylate monomer, oil resistant low temperature resistant monomer
Monomer, these monomers can specifically enumerate conjugate diene monomer, non-conjugated diene monomers, aromatic vinyl monomer, unsaturated nitrile
Monomer, unsaturated acyl amine monomer, multi-functional acrylate's class monomer etc..Normally, the addition of these monomers is no more than
The 2% of acetoacetate type ACM gross mass.
The acetoacetate type ACM carries out radical polymerization and obtains by monomer.As polymerisation process,
Can be carried out using methods such as emulsion polymerization, suspension polymerization, mass polymerization and solution polymerization process.In view of the steady of technique
Qualitative and feasibility, it is preferred to use emulsion polymerization is carried out.
Used as a kind of alternative, the preparation method of the acetoacetate type ACM is entered by emulsion polymerization
OK, comprise the following steps：
S1. add deionized water, emulsifying agent, part initiator to mix in reactor, water solution A is obtained；
S2. alkyl acrylate monomer, oil resistant low temperature resistant monomer, cure site monomer, auxiliary curable monomer, molecular weight are adjusted
After section agent, remaining initiator mixing, monomer mixed phase B is obtained；
S3. logical nitrogen protection is carried out to water solution A, 20~80 DEG C are warming up to；
S4. by water solution A in 1/5 mixed phase B addition reactors, stirred under nitrogen atmosphere temperature control is reacted；
S5. exothermic heat of reaction is finished and after temperature drops back to temperature control scope, and residual monomer mixed phase B is added in the way of being added dropwise
Enter in system described in S4, the completion of dropping in 1~4h maintains 20~80 DEG C, and 2~5h of thermotonus is maintained after completion of dropping, obtains
To ACM emulsion；
S6. the emulsion that S5 is obtained is demulsified under the conditions of 70 DEG C~90 DEG C, thing to be polymerized condense completely after by gained
Flocculate is washed, is dehydrated, being dried to water content less than 0.5%, obtains final product the acetoacetate type ACM life
Glue or hydroxy acryl acid ester rubber raw rubber.
If obtaining hydroxy acryl acid ester rubber raw rubber, also need to mix with appropriate diketene or methyl acetoacetate, ethyl ester
After uniform, by extruder at a temperature of 90~120 DEG C, extrusion molding prepares acetoacetate type ACM rubber.
Emulsifying agent can be polyoxyethylene alkyl ether, polyoxyethylated alkyl phenol, polyethenoxy sorbitan Arrcostab
Deng the senior fatty alcohol sulfonate anionoid such as nonionic surfactant or dodecane sulfonate, dodecyl benzene sulfonate
At least one in surfactant.More preferably dodecane sulfonate.
Preferably, the usage amount of the emulsifying agent is the 0.5~4% of polymerized monomer gross weight.
Initiator can be 2,2- the azodiisobutyronitriles, -2- methylbutyronitriles of 2,2- the azos two, -2,4- two of 2,2- azos two
Methyl the valeronitrile, -4- methoxyl group -2,4- methyl pentane nitriles of 2,2- azos two, 2,2- azos two (2 Methylpropionic acid methyl esters), 2,2- idols
The azo-compounds such as nitrogen two (2- methyl-props amidine) -2- hydrochlorides；Cumene hydroperoxide (CHP), di-t-butyl peroxide, peroxidating
Double (tert-butyl peroxide) hexanes of diisopropylbenzene (DIPB), benzoyl peroxide (BPO), lauroyl peroxide (LPO), dimethyl, dimethyl are double
(tert-butyl peroxide) -3- hexins, double (t-butylperoxyisopropyl) benzene, double (tert-butyl peroxide) trimethyl-cyclohexanes,
Butyl-bis- (tert-butyl peroxide) valerate, peroxide -2-ethyl hexanoic acid tert-butyl, dibenzoyl peroxide, terpane peroxidating
The organic peroxide such as hydrogen and peroxidized t-butyl perbenzoate；The inorganic persulfuric acid such as ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate
At least one in salt.Peroxide initiator can also be used with being combined into redox system with reducing agent, for example, coordinate
Ferrous sulfate, cuprous naphthenate, sodium sulfoxylate formaldehyde etc..
Preferably, the usage amount of the initiator is the 0.1~0.5% of polymerized monomer gross weight.
Molecular weight regulator can be n-dodecyl mercaptan, tert-dodecylmercaotan or methyl styrene dimer body.It is excellent
Selection of land, the usage amount of the molecular weight regulator is the 0.01~0.2% of polymerized monomer gross weight.
Preferably, the consumption of the water is 1.5~3 times of polymerized monomer gross weight.
Preferably, the demulsification is during the emulsion that obtains S6 adds the aqueous solution containing flocculating agent and flocculant.It is described
Flocculating agent can be the slaine such as sodium chloride, calcium chloride, aluminium chloride, sodium sulphate, also can form acid-inorganic with hydrochloric acid, sulfuric acid etc.
Salt system is used as cohesion.The flocculant is added to prevent rubber from luming to be difficult to condense, can using Sodium Polyacrylate,
Polyvinyl alcohol etc..
A kind of vulcanizate compositions, by acetoacetate type ACM through over cure in the vulcanizate compositions
Change is made.The vulcanizing system has diversity due to acetoacetate type high reaction activity, the selection of vulcanizing agent, can be cyanamide
Class, isocyanates, many (methyl) esters of acrylic acids, conventional Polyamine Type, amino silicone alkanes vulcanizing agent.
Preferably, Polyamine Type vulcanizing agent, end are added in the sulfidation of the acetoacetate type ACM rubber
Amido silicon oil and vulcanization accelerator.If necessary, reinforcing agent, antioxidant, releasing agent can also be added.
It is highly preferred that the Polyamine Type vulcanizing agent is aliphatic diamine compounds.
Alternatively, the preparation method of the vulcanizate compositions, comprises the following steps：
Acetoacetate type ACM is entered into two-roll mill carries out rubber pressing, addition processing aid, and vulcanization promotees
Enter agent, be subsequently adding filler, filler is mixed into rubber substantially, add vulcanizing agent, triangle bag is beaten in double roller 5 times, it is thin by logical 3
It is secondary, blanking, slice temperature is at 40~45 DEG C；Slice subcooled water in short-term, cold wind drying；Place 24 hours, the vulcanization rubber is obtained
Glue composition.
A kind of method for improving vulcanizate compositions heat resistance and resistance to low temperature, the vulcanizate compositions by
Acetoacetate type ACM is made through vulcanization, and the acetoacetate type ACM is by following by quality percentage
Monomer polymerization than calculating is obtained：
Alkyl acrylate monomer 65%~85%；
Oil resistant low temperature resistant monomer 10%~30%；
Cure site monomer containing acetoacetyl 3%~8%；
Auxiliary curable monomer 0.5~1%；
Or
The cure site monomer containing acetoacetyl is changed into and contained by remaining monomer and consumption with reference to mentioned component and ratio
The monomer of ethylenic insatiable hunger key and hydroxyl, each monomer be polymerized obtains oh type ACM, then with diketene or
It is prepared by acetoacetic ester reaction；
The auxiliary curable monomer is the dicarboxylic acids monoalkyl ester monomer of carbon-carbon double bonds, the alkyl acrylate list
Arrcostab is the Arrcostab formed by the fatty alcohol with carbon number 1~8 in body.
Compared with prior art, the present invention has the advantages that：
The present invention uses methacrylic acid ethyl acetoacetate or acrylic acid ethyl acetoacetate isoreactivity monomer and (first
Base) crylic acid hydroxy ester hydroxyl by react generation acetoacetyl, as the vulcanization of acetoacetate type ACM
Point, coordinates different vulcanizing agents co-vulcanized；Its vulcanization assembly adhesive has suitable curingprocess rate, it is to avoid incipient scorch, glutinous roller；Realize room
Temperature vulcanization is not required to post vulcanization, improve production efficiency；Improve long-term heat-resisting temperature in use and to remain ACM resistance to
Oil, cold-resistant advantage, gained acrylate vulcanizate composition are suitable for needing the rubber components of long-term high temperature resistant oil resistant, long-term
With oily pipeline, container lining and the cable for contacting and exposed to ozone, the rubber part of hot environment, such as automobile hydraulic lubrication
The fields such as sealing, hydraulic oil transmission sebific duct, cable cover(ing), the oil-resistant pipe of oil sealing, pad, running part and bearing.
Specific embodiment
Explanation is further expalined to the present invention with reference to specific embodiment, its description is more specific and detailed, but
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as, as long as being obtained in the form of equivalent or equivalent transformation
The technical scheme for obtaining, all should be included within the protection domain of the claims in the present invention.
In following examples, raw material used is commercial goods.
Embodiment 1
S1. 150 parts of deionized waters are added into emulsion tank, is subsequently adding 3 parts of dodecyl sodium sulfates, 0.3 part of ammonium persulfate
Water solution A is obtained through mechanical agitation dissolving；
S2. by 60 parts of ethyl acrylates, 25 parts of butyl acrylates, 12 parts of methoxyethyl acrylates, 0.5 part of maleic acid list
After ethylene glycol monobutyl ether ester, 2.5 parts of methacrylic acid ethyl acetoacetates and 0.05 part of n-dodecyl mercaptan are well mixed, obtain
Obtain monomer mixed phase B；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up to 60 DEG C；
S4. by the monomer mixed phase B addition reactors of 1/5 weight portion, under nitrogen protection, emulsion system temperature is maintained
Start reaction in the range of 60 DEG C；
S5. after reactor reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 1.5h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 60 DEG C；Thermotonus is maintained after completion of dropping
4h, obtains acetoacetate type acrylic acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 500 parts containing being demulsified in 30 parts of calcium chloride waters, is being added
Be sufficiently stirred for during entering, thing to be polymerized condenses completely, gained precipitate washed with water 3~5 times, through extrusion dehydration after,
It is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product acetoacetate type ACM rubber product
Product.
Note：The rubber compounding vulcanizing agent of embodiment 1 is methyl diphenylene diisocyanate in table 1 below vulcanization of rubber formula.
Embodiment 2
S1. 200 parts of deionized waters are added into emulsion tank, is subsequently adding 3 parts of dodecyl sodium sulfates, 0.3 part of ammonium persulfate
Water solution A is obtained through mechanical agitation dissolving；
S2. by 5 parts of methyl acrylates, 45 parts of ethyl acrylates, 21 parts of butyl acrylates, 24 parts of methoxyethyl second
Ester, 1 part of maleic acid list diethylene glycol monobutyl ether ester, 4.0 parts of methacrylic acid ethyl acetoacetates and 0.1 part of dodecyl sulphur
After alcohol is well mixed, monomer mixed phase B is obtained；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 70 DEG C；
S4. the monomer mixed phase B of 1/5 weight portion is added in reactor, under nitrogen protection, maintains emulsion system temperature
Degree starts reaction in the range of 70 DEG C；
S5. after reactor reacts 30 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 2h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 70 DEG C；Thermotonus is maintained after completion of dropping
4h, obtains acetoacetate type ACM emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 600 parts containing being demulsified in 30 parts of aluminum chloride aqueous solutions, is being added
Be sufficiently stirred for during entering, thing to be polymerized condenses completely, gained flocculate washed with water 3~5 times, through extrusion dehydration after,
It is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product the life of acetoacetate type ACM emulsion
Glue product.
Note：The rubber compounding vulcanizing agent of embodiment 2 is hexa methoxy melamine in table 1 below vulcanization of rubber formula.
Embodiment 3
S1. 200 parts of deionized waters are added into emulsion tank, is subsequently adding 2 parts of neopelexes, 0.3 part of persulfuric acid
Potassium is obtained water solution A through mechanical agitation dissolving；
S2. by 42 parts of ethyl acrylates, 20 parts of butyl acrylates, 30 parts of methoxyethyl acrylates, 0.6 part of maleic acid list
After diethylene glycol monobutyl ether ester, 8 parts of methacrylic acid ethyl acetoacetates and 0.08 part of n-dodecyl mercaptan are well mixed, obtain
Obtain monomer mixed phase B；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 75 DEG C；
S4. the monomer mixed phase B of 1/5 weight portion is added in reactor, under nitrogen protection, maintains emulsion system temperature
Degree starts reaction in the range of 75 DEG C；
S5. after reactor reacts 30 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 3h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 75 DEG C；Thermotonus is maintained after completion of dropping
5h, obtains acetoacetate type acrylic acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 800 parts containing 40 parts of sodium chloride and 4 parts of water of polyvinyl alcohol
It is demulsified in solution, is sufficiently stirred in adition process, thing to be polymerized is condensed completely, and gained flocculate is washed with water 3~5 times,
After through extrusion dehydration, it is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product acetoacetate type propylene
Acid esters rubber raw rubber product.
Note：The rubber compounding vulcanizing agent of embodiment 3 is hexamethylene diamine in table 1 below vulcanization of rubber formula.
Embodiment 4
S1. 250 parts of deionized waters are added into emulsion tank, is subsequently adding 2 parts of dodecyl sodium sulfates and 2 parts of polyoxyethylene alkane
Base phenolic ether, 0.005 part of ferrous sulfate, 0.2 part of sodium sulfoxylate formaldehyde are obtained water solution A through mechanical agitation dissolving；
S2. by 10 parts of methyl acrylates, 50 parts of ethyl acrylates, 15 parts of butyl acrylates, 20 parts of ethioxy second
Ester, 4.5 parts of hydroxy-ethyl acrylates, 0.5 part of fumaric acid monoethylene glycol only son ether-ether and 0.2 part of cumyl peroxide are well mixed
Afterwards, monomer mixed phase B is obtained；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 40 DEG C；
S4. the monomer mixed phase B of 1/5 weight portion is added in reactor, under nitrogen protection, maintains emulsion system temperature
Degree starts reaction in the range of 40 DEG C；
S5. after reactor reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 1.5h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 40 DEG C；Thermotonus is maintained after completion of dropping
4h, obtains oh type acrylic acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 700 parts containing 20 parts of calcium chloride, 15 parts of salt aqueous acids
Middle demulsification, is sufficiently stirred in adition process, and thing to be polymerized condenses completely, and gained flocculate is washed with water 3~5 times, through squeezing
After press-dehydrating, it is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product the life of hydroxy acrylate rubber
Glue product；
S7. after being well mixed S6 hydroxy acryl acid ester rubber raw rubbers and 4 parts of diketenes, by extruder 90~120
DEG C extrusion molding prepares acetoacetate type ACM rubber.
Note：The rubber compounding vulcanizing agent of embodiment 4 is that viscosity is 100CPS Amino End Group silicone oil in table 1 below vulcanization of rubber formula.
Embodiment 5
S1. 220 parts of deionized waters are added into emulsion tank, is subsequently adding 3 parts of neopelexes and 1 part of polyoxyethylene
Alkyl sorbitol dehydration ester, 0.003 ferrous sulfate, 0.15 part of sodium sulfoxylate formaldehyde are obtained water solution A through mechanical agitation dissolving；
S2. by 15 parts of methyl acrylates, 50 parts of ethyl acrylates, 15 parts of butyl acrylates, 14 parts of propylene acid diethylene glycols
Monomethyl ether, 1 part of maleic acid list diethylene glycol monobutyl ether ester, 6 parts of hydroxy-ethyl acrylates and 0.1 part of cumyl peroxide mixing are equal
After even, monomer mixed phase B is obtained；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 50 DEG C；
S4. the monomer mixed phase B of 1/5 weight portion is added in reactor, under nitrogen protection, maintains emulsion system temperature
Degree starts reaction in the range of 50 DEG C；
S5. after reactor reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 2.5h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 50 DEG C；Thermotonus is maintained after completion of dropping
3h, obtains oh type acrylic acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 900 parts containing 30 parts of calcium chloride and 3 parts of Sodium Polyacrylates
It is demulsified in the aqueous solution, is sufficiently stirred in adition process, thing to be polymerized condenses completely, washes gained flocculate with water 3~5
It is secondary, through extrusion dehydration after, be placed in extrusion expansion drying box and dry to water content less than 0.5%, obtain final product oh type propylene
Acid esters rubber raw rubber product；
S7. by S6 hydroxy acryl acid ester rubber raw rubbers and 6 parts of methyl acetoacetates close it is uniform after, by extruder 90~
120 DEG C are extruded into acetoacetate type ACM rubber.
Note：The rubber compounding vulcanizing agent of embodiment 5 is end aminopropyltriethoxy trimethoxy silicon in table 1 below vulcanization of rubber formula
Alkane.
Embodiment 6
S1. 300 parts of deionized waters are added into emulsion tank, is subsequently adding 3 parts of dodecyl sodium sulfates and 1 part of polyoxyethylene alkane
The water solution A of emulsifying agent is obtained through mechanical agitation dissolving for base phenolic ether and 0.006 ferrous sulfate, 0.3 part of sodium sulfoxylate formaldehyde；
S2. by 60 parts of ethyl acrylates, 20 parts of butyl acrylates, 13 parts of ethoxyethyl acrylates, 0.5 part of maleic acid list
Diethylene glycol monobutyl ether ester, 6.5 parts of hydroxypropyl acrylates and 0.3 part of di-t-butyl peroxide and 0.02 part of methyl styrene dimer
After body is well mixed, monomer mixed phase B is obtained；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 40 DEG C；；
S4. the monomer mixed phase B of 1/5 weight portion is added in reactor, under nitrogen protection, maintains emulsion system temperature
Start reaction in the range of 40 DEG C；
S5. after reactor reacts 30 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and stirred under nitrogen atmosphere reaction in the range of 40 DEG C is maintained during 2h about is added dropwise；Thermotonus 4h is maintained after completion of dropping,
Obtain hydroxy acryl acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 800 parts containing 30 parts of calcium chloride, 10 parts of hydrochloric acid and 2 parts poly- third
It is demulsified in the aqueous solution of olefin(e) acid sodium, is sufficiently stirred in adition process, thing to be polymerized is condensed completely, and gained flocculate is washed with water
Wash 3~5 times, through extrusion dehydration after, be placed in extrusion expansion drying box and dry to water content less than 0.5%, obtain final product containing hydroxyl
Base acrylic acid ester emulsion rubber raw rubber product；
S7. by S6 hydroxy acryl acid ester rubber raw rubbers and 8 parts of ethyl acetoacetates close it is uniform after, by extruder 90~
120 DEG C are extruded into acetoacetate type ACM rubber.
Note：The rubber compounding vulcanizing agent of embodiment 6 is ethylene glycol diacrylate in table 1 below vulcanization of rubber formula.
Embodiment 7
S1. 200 parts of deionized waters are added into emulsion tank, is subsequently adding 3 parts of dodecyl sodium sulfates and is dissolved through mechanical agitation
The water solution A of emulsifying agent is obtained；
S2. by 15 parts of methyl acrylates, 45 parts of ethyl acrylates, 25 parts of butyl acrylates, 10 parts of methoxyethyl second
Ester, 4.4 parts of hydroxy-ethyl acrylates, 0.6 part of fumaric acid list diethylene glycol monobutyl ether and 1 part of 2,2- azodiisobutyronitrile are well mixed
Afterwards, monomer mixed phase B is obtained；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 60 DEG C；
S4. by the monomer mixed phase B addition reactors of 1/5 weight portion, under nitrogen protection, emulsion system temperature is maintained
Start reaction in the range of 60 DEG C；
S5. after reactor reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 1.5h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 60 DEG C；Thermotonus is maintained after completion of dropping
4h, obtains hydroxy acryl acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 600 parts containing being demulsified in 20 parts of calcium chloride waters, is being added
Be sufficiently stirred for during entering, thing to be polymerized condenses completely, gained flocculate washed with water 3~5 times, through extrusion dehydration after,
It is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product hydroxy acryl acid ester emulsion rubber rubber product
Product；
S7. by S6 hydroxy acryl acid ester rubber raw rubbers and 5 parts of diketenes close it is uniform after, by 90~120 DEG C of extruder
It is extruded into acetoacetate type ACM rubber.
Note：The rubber compounding vulcanizing agent of embodiment 7 is diacrylate -1,6-HD ester in table 1 below vulcanization of rubber formula.
Embodiment 8
S1. 300 parts of deionized waters are added into emulsion tank, is subsequently adding 4 parts of dodecyl sodium sulfates and 0.004 sulfuric acid is sub-
The water solution A of emulsifying agent is obtained through mechanical agitation dissolving for iron, 0.15 part of sodium sulfoxylate formaldehyde；
S2. by 10 parts of methyl acrylates, 45 parts of ethyl acrylates, 10 parts of butyl acrylates, 5 parts of acrylic acid 2- ethyl hexyls
Ester, 21.5 parts of methoxyethyl acrylates, 8 parts of hydroxy-ethyl acrylates, 0.5 part of maleic acid list diethylene glycol monobutyl ether ester, 0.1 part
After cumyl peroxide and 0.05 part of n-dodecyl mercaptan are well mixed, monomer mixed phase B is obtained；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 30 DEG C；
S4. by the acquisition monomer mixed phase B addition reactors of 1/5 weight portion, under nitrogen protection, emulsion system is maintained
Temperature starts reaction in the range of 30 DEG C；
S5. after reactor reacts 20 minutes stabilizations, residue is obtained into monomer mixed phase B and is transferred to reactor, and started past
Reactor is added dropwise, and 3h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 30 DEG C；Maintain temperature anti-after completion of dropping
5h is answered, hydroxy acryl acid ester emulsion is obtained；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 800 parts containing 40 parts of calcium chloride and 3 parts of water of polyvinyl alcohol
It is demulsified in solution, is sufficiently stirred in adition process, thing to be polymerized is condensed completely, and gained flocculate is washed with water 3~5 times,
After through extrusion dehydration, it is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product hydroxy acryl acid ester
Rubber raw rubber product；
S7. after being well mixed S6 hydroxy acryl acid ester rubber raw rubbers and 9 parts of methyl acetoacetates and a small amount of acetic acid, lead to
Cross 90~120 DEG C of extruder and be extruded into acetoacetate type ACM rubber.
Note：The rubber compounding vulcanizing agent of embodiment 8 is hexamethylene diamine in table 1 below vulcanization of rubber formula.
Embodiment 9
S1. 250 parts of deionized waters are added into emulsion tank, is subsequently adding 2 parts of dodecyl sodium sulfates, 2 parts of polyoxyethylene take off
The water solution A of emulsifying agent is obtained through mechanical agitation dissolving for water sorbierite Arrcostab and 0.3 part of ammonium persulfate；
S2. by 50 parts of ethyl acrylates, 20 parts of butyl acrylates, 24 parts of methoxyethyl acrylates, 1 part of maleic acid list second
After glycol monobutyl ether ester, 5.0 parts of methacrylic acid ethyl acetoacetates and 0.03 part of n-dodecyl mercaptan are well mixed, obtain
Monomer mixed phase B；
S3. by water solution A addition reactor, maintain under nitrogen protection, stirring is warming up in the range of 60 DEG C；
S4. the monomer mixed phase B of 1/5 weight portion is transferred in reactor, under nitrogen protection, maintains emulsion system temperature
Degree starts reaction in the range of 60 DEG C；
S5. after reactor reacts 20 minutes stabilizations, remaining mixture emulsion C is transferred to reactor, and start toward reaction
Kettle is added dropwise, and 1.5h is about added dropwise, and period maintains stirred under nitrogen atmosphere reaction in the range of 60 DEG C；Thermotonus is maintained after completion of dropping
4h, obtains acetoacetate type ACM emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added in 600 parts of aqueous solution containing 30 parts of magnesium sulfate and is demulsified,
Be sufficiently stirred in adition process, thing to be polymerized condenses completely, gained flocculate washed with water 3~5 times, through extrusion dehydration it
Afterwards, it is placed in extrusion expansion drying box and dries to water content less than 0.5%, obtains final product acetoacetate type ACM rubber
Product.
Note：The rubber compounding vulcanizing agent of embodiment 9 is diacrylate 1,6-HD ester in table 1 below vulcanization of rubber formula.
Embodiment 10
By fumaric acid list diethylene glycol monobutyl ether in embodiment 7 using monomethyl ester replacement, other monomers and technique
Step is consistent with embodiment 7.
Embodiment 11
By maleic acid list diethylene glycol monobutyl ether ester in embodiment 8 using ethyl maleate replacement, other monomers and work
Skill step is consistent with embodiment 8.
Embodiment 12
By maleic acid monoethylene glycol only son ether-ether in embodiment 9 using ethyl maleate replacement, other monomers and technique
Step is consistent with embodiment 9.
Vulcanized rubber embodiment：
(in parts by weight) is formulated by table 1, the rubber raw rubber of embodiment 1 to 12 is added into rubber mixing mill, be dividedly in some parts benefit
The mixture of strong filler, inert filler, stearic acid, age resistor, wax and plasticizer, waits all mixtures to be mixed into rubber
Afterwards, vulcanizing agent is eventually adding (according to the optional Diamines of this patent rubber activity, such as methylene dianiline (MDA), hexamethylene diamine；
Cyanamide class, isocyanates such as hexa methoxy melamine, methyl diphenylene diisocyanate etc.；Amino silicone class such as holds aminopropyl
MTMS etc.；Polyfunctionality acrylic or methacrylic acid esters such as ethylene glycol diacrylate etc.) and vulcanization rush
Enter the mixture of agent (diphenylguanidine, cumyl peroxide, potassium stearate etc.), make a call to bottom sheet after 4 triangle bags, 12 are parked in room temperature
Hour, afterwards by elastomeric compound in room temperature vulcanization 24 hours.
Vulcanizing agent (four two (pentamethylene) thiurams of vulcanization) used by comparative example A R-840, vulcanization accelerator (stearic acid
Potassium), sulphur.(in parts by weight) is formulated by table 1, comparative example A R-840 rubber raw rubbers are added into rubber mixing mill, be dividedly in some parts benefit
The mixture of strong filler, inert filler, stearic acid, age resistor, wax and plasticizer, waits all mixtures to be mixed into rubber
Afterwards, the mixture of vulcanizing agent and vulcanization accelerator is eventually adding, bottom sheet after 4 triangle bags is made a call to, 5min is parked at 180 DEG C, afterwards
By elastomeric compound in 170 DEG C of post-cures 4 hours.
Following performance test is carried out to embodiment 1~12 and comparative example A R-840：
1st, Mooney viscosity test
The Mooney viscosity of elastomeric compound is according to GB/T 1232.1-2000 Part I：The measure of Mooney viscosity is tested,
Experimental temperature is 100 DEG C, preheating time 1min, testing time 4min.
2nd, Mooney scorch time test
Mooney scorch time (t10), 120 DEG C of sizing material time of scorch are tested according to GB GB/T1233-92, and t10 values are bigger,
Anti- incipient scorch is more excellent, and machinability is more preferable.
3rd, hardness test
The shore a hardness of ACM vulcanizates is according to GB/T 531.1-2008 part 1s：Shore durometer method (Shao Er hardness)
Tested.
4th, Mechanics Performance Testing
The universal testing machine produced with the new SANS measurement technologies Co., Ltd in Shenzhen, surveys according to GB/T 528-2009
Try the tensile property of vulcanizate；The tearing strength of vulcanizate is tested according to GB/T 529-2008, sample is square；According to GB/
T7759-1996 (B methods) tests ACM vulcanizate compression set values, and test condition is：150 DEG C of test temperature, standing time
70h, precompressed shrinkage is 25%.
5th, heat aging property test
ACM vulcanizates heat-resistant air aging property is tested according to GB/T 3512-2001, and test temperature is 185 DEG C, aging
Time is 72h.
6th, oil resistance test
The oil resistance of ACM vulcanizates is tested according to GB/T 1690-2006, and test temperature is 150 DEG C, and soak time is
72h, test liquid is IRM903# oil.
7th, brittleness temperature test
The brittleness temperature (Tb) of ACM vulcanizates is tested according to GB/T 1682-1994 (single specimen method).
The vulcanization of rubber formula of table 1
The embodiment vulcanising composition performance test of table 2
During vulcanized rubber is processed into, inventor has found rubber good fluidity of the invention, combines sulfurizing formula
Roller not incipient scorch is not sticked in mixed process；Room temperature vulcanization is realized, production efficiency is high.Understood with reference to the test result of table 2, the present invention is implemented
In safely controllable scope, its anti-incipient scorch ability is strong, and process safety is high for vulcanized rubber t10, t50, t90 prepared by example.This
Outward, the vulcanized rubber mechanical performance and oil resistance that prepared by the present invention are very good, 185 DEG C × 72h of hot air aging performances
Long-term heat resistance can be protruded especially.In addition from embodiment 7,8, the 9 corresponding embodiments 10,11,12 for replacing auxiliary curable monomer
Rubber contrast understand that the currently preferred auxiliary more conventional curable monomer of curable monomer is in cryogenic property and processing characteristics
More advantage, aids in the replacement of curable monomer that obvious influence is brought on black brittleness.Comparative example A R-840 can not realize room temperature
, it is necessary to conventional high temperature vulcanization (vulcanizing agent of use, auxiliary curing agent are different from embodiment), conventional physical property is close, oil resistant for vulcanization
Quite, compression set protects rubber slightly worse to heat resistance than this patent.
Therefore, acetoacetate type ACM of the present invention can be overcome in existing ACM processing and performance
Deficiency, is capable of achieving room temperature vulcanization, and with long-term heat-resisting temperature in use higher, its acrylate vulcanizate composition is suitable for needing
The rubber components of long-term high temperature resistant oil resistant, pipeline, container lining and the cable for being contacted with oil for a long time and exposed to ozone, high temperature
The rubber part of environment, such as sealing of automobile hydraulic lubrication oil seal, pad, running part and bearing, hydraulic oil transmission sebific duct, electricity
The fields such as cable sheath, oil-resistant pipe use.
Claims (10)
1. a kind of acetoacetate type ACM, it is characterised in that poly- by the following monomer calculated by mass percentage
Conjunction is obtained：
Alkyl acrylate monomer 65%~95%；
Oil resistant low temperature resistant monomer 0%~30%；
Cure site monomer containing acetoacetyl 3%~8%；
Auxiliary curable monomer 0.5 ~ 1%；
Or
Remaining monomer and consumption are changed containing ethylene linkage the cure site monomer containing acetoacetyl into reference to mentioned component and ratio
The monomer of formula insatiable hunger key and hydroxyl, each monomer be polymerized obtains oh type ACM, then with diketene or acetyl
It is prepared by acetic acid esters reaction.
2. acetoacetate type ACM according to claim 1, it is characterised in that described containing acetoacetyl vulcanization
Point monomer is methacrylic acid ethyl acetoacetate and/or acrylic acid ethyl acetoacetate.
3. acetoacetate type ACM according to claim 1, it is characterised in that the key of insatiable hunger containing ethylenic and
The monomer of hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
4. acetoacetate type ACM according to claim 1, it is characterised in that the auxiliary curable monomer be containing
The dicarboxylic acids monoalkyl ester monomer of carbon-carbon double bond.
5. acetoacetate type ACM according to claim 5, it is characterised in that the binary of the carbon-carbon double bonds
Ester group in carboxylic acid monoalkyl ester monomer is formed by the ether alcohol with carbon number 6 ~ 10.
6. acetoacetate type ACM according to claim 1, it is characterised in that the alkyl acrylate monomer
Middle Arrcostab is the Arrcostab formed by the fatty alcohol with carbon number 1 ~ 8.
7. acetoacetate type ACM according to claim 1, it is characterised in that the oil resistant low temperature resistant monomer is
Acrylic acid alcohol ethers monomer.
8. the acetoacetate type ACM according to claim 1 to 7 any one claim, it is characterised in that institute
Acetoacetate type ACM is stated to be obtained through radical polymerization by the monomer.
9. a kind of vulcanizate compositions, it is characterised in that the acetoacetate as described in claim 1 to 8 any one claim
Type ACM is made through vulcanization.
10. a kind of method for improving vulcanizate compositions heat resistance and resistance to low temperature, it is characterised in that the vulcanization rubber
Glue composition is made up of acetoacetate type ACM through vulcanization, and the acetoacetate type ACM is by following
The monomer polymerization calculated by mass percentage is obtained：
Alkyl acrylate monomer 65%~95%；
Oil resistant low temperature resistant monomer 0%~30%；
Cure site monomer containing acetoacetyl 3%~8%；
Auxiliary curable monomer 0.5 ~ 1%；
Or
Remaining monomer and consumption are changed containing ethylene linkage the cure site monomer containing acetoacetyl into reference to mentioned component and ratio
The monomer of formula insatiable hunger key and hydroxyl, each monomer be polymerized obtains oh type ACM, then with diketene or acetyl
It is prepared by acetic acid esters reaction；
The auxiliary curable monomer is the dicarboxylic acids monoalkyl ester monomer of carbon-carbon double bonds, in the alkyl acrylate monomer
Arrcostab is the Arrcostab formed by the fatty alcohol with carbon number 1 ~ 8.
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|---|---|---|---|---|
| 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 |
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|---|---|---|---|---|
| JPS59136303A (en) * | 1983-01-25 | 1984-08-04 | Uchiyama Mfg Corp | Production of vulcanizable acrylic rubber |
| JPS60110728A (en) * | 1983-11-21 | 1985-06-17 | Uchiyama Mfg Corp | Production of vulcanizable acrylic rubber |
| JP2010270172A (en) * | 2009-05-19 | 2010-12-02 | Nakanishi Metal Works Co Ltd | Acrylic rubber composition and sealing material |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59136303A (en) * | 1983-01-25 | 1984-08-04 | Uchiyama Mfg Corp | Production of vulcanizable acrylic rubber |
| JPS60110728A (en) * | 1983-11-21 | 1985-06-17 | Uchiyama Mfg Corp | Production of vulcanizable acrylic rubber |
| JP2010270172A (en) * | 2009-05-19 | 2010-12-02 | Nakanishi Metal Works Co Ltd | Acrylic rubber composition and sealing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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