CN106749870B - A kind of acetoacetate type acrylic rubber and preparation method thereof - Google Patents
A kind of acetoacetate type acrylic rubber and preparation method thereof Download PDFInfo
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- CN106749870B CN106749870B CN201611167963.6A CN201611167963A CN106749870B CN 106749870 B CN106749870 B CN 106749870B CN 201611167963 A CN201611167963 A CN 201611167963A CN 106749870 B CN106749870 B CN 106749870B
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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 acrylic rubber and preparation method thereof.The acetoacetate type acrylic rubber includes that the following monomer polymerization being calculated by mass percentage obtains: alkyl acrylate monomer 65%~95%；Oil resistant low temperature resistant monomer 0%~30%；Cure site monomer containing acetoacetyl 3%~8%；Assist curable monomer 0.5 ~ 1%.The acetoacetate type acrylic rubber that the present invention synthesizes is the novel acrylic ester rubber using acetoacetate structure as active crosslinking points preparation, optimizing processing performance on the basis of remaining acrylic rubber low compression set rate, oil resistant reduces curing temperature raising productivity, and raising is heat-resisting for a long time to use temperature.Rubber product after present invention vulcanization is suitable for needing the rubber components, pipeline, container lining and the cable contacted for a long time with oil and the rubber part for being exposed to ozone, hot environment of long-term heat-resisting oil resistant.
Description
Technical field
The present invention relates to rubber materials, more particularly, to a kind of acetoacetate type acrylic rubber and its preparation side
Method.
Background technique
Acrylic rubber (hereinafter referred to as ACM) is elastomer obtained by being copolymerized using acrylate as main monomer, master
Chain is saturated carbon chains, and side group is polar ester groups, and the dience rubber than having double bond on main chain is stablized.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 sealing elements of automobile, such as oil sealing, gasket.Acrylic rubber is widely applied
In various sealing rings, washer, liner and tubing, wherein exceed 90% application field it is related to auto industry.In recent years, by
In the high speed development of automobile industry, greatly improves whole market to the demand of high-performance rubber sealing material, pushed third
The exploitation of olefin(e) acid ester rubber.In the R&D process of Hyundai Motor, the size of engine is reduced 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.
As a result, being that the operating temperature of engine room climbs up and up caused by above-mentioned variation.Therefore, to organic material associated there
The heat resistance of acrylic rubber also has higher requirement, and automobile ACM has to have the same duration of good mechanical property
Phase heat resisting temperature will reach 180 DEG C or more.Meet this requirement, promoting ACM heat aging property is grinding for acrylic rubber
Study carefully exploitation hot spot.
Additionally while acrylic rubber has many excellent properties, but ACM rubber processing performance is led also by denouncing
Show as that easy adhesion, easy incipient scorch, vulcanization time be long, temperature height leads to glue physical performance decline, production process low with production efficiency
Safety coefficient is lower, not environmentally the disadvantages of.Therefore, it need be modified.The processing of usual ACM need to select specific vulcanization
System and by add additional processing auxiliary agent improve its processing performance, some drawbacks can be improved, but reduce glue
Physical property and increase manufacturing cost.For the processing performance disadvantage for preferably overcoming ACM current, carry out into one both at home and abroad
The research of step.In domestic novel peroxide cure acrylic rubber of 102643382 A of patent CN and preparation method thereof,
By be introduced into main rubber can with it is any one in the cure site monomer vinyl chloride, bromopropene, bromobutene of peroxide reactions
Kind, to improve rate of cure, have many advantages, such as not corrode mold, processability and good physical performance, but rubber contains halogen, vulcanization
Toxic gas may be discharged, and polymerized monomer risk is big.
For another example mention in a kind of preparation method of vulcanizing-free acrylic ester rubber of patent CN101812180A with acrylic acid
Esters monomer, styrene and the monomer of functional group containing tertiary amine and function monomer containing chlorine are raw material, prepare self-crosslinking acrylic ester
Rubber can avoid vulcanization, and direct moulding by casting is rubber, but it cannot add filler reinforcement, not with current conventional fabrication process
Together, molding mode is single, it is difficult to promote.
Summary of the invention
The present invention is directed to overcome the defect of the above-mentioned prior art, a kind of acetoacetate type acrylic rubber is provided, it is described
Acetoacetate type acrylic rubber has more high heat resistance, and (performance change can conform under 185 DEG C × 72h of hot air aging
Ask), moderate curingprocess rate, can room temperature vulcanization, and vulcanize productivity height.
Another object of the present invention is to provide the preparation methods of the acetoacetate type acrylic rubber.
Goal of the invention of the invention is achieved by the following technical programs:
A kind of acetoacetate type acrylic rubber is obtained by the following monomer polymerization being calculated by mass percentage:
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 is contained referring to mentioned component and ratio by remaining monomer and dosage
Each monomer is polymerize to obtain oh type acrylic rubber by the monomer of ethylenic bond insatiable hunger key and hydroxyl, then with diketene or
Acetoacetic ester reaction preparation.
Preferably, the acetoacetate type acrylic rubber passes through the following monomer polymerization being calculated by mass percentage
It obtains:
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 is contained referring to mentioned component and ratio by remaining monomer and dosage
Each monomer is polymerize to obtain oh type acrylic rubber by the monomer of ethylenic bond insatiable hunger key and hydroxyl, then with diketene or
Acetoacetic ester reaction preparation.The acetoacetyl reactivity of acetoacetate type acrylic rubber of the present invention is high, will
It is introduced into acrylic rubber system, can react with cyanamide class, isocyanates.Since acetoacetyl reactivity height will
Superior performance can be brought to ACM, such as room temperature curing (with the reacting of diamines, michael reaction).Its structure or reaction are former
Manage as follows: acetoacetate based structures are as follows:
Acetoacetate based structures
1. with reacting for cyanamide class
2. with reacting for isocyanates
In addition acetoacetic acid group can not only exist in the form of ketone, can also exist in the form of its isomers enol,
It can directly be reacted with conventional Diamines vulcanizing agent, reaction equation is as follows:
3. with reacting for diamines
4. michael reaction
The present invention is that active crosslinking points realize that room temperature vulcanization improves production efficiency with acetoacetate structure, improves processability
Can, raising is heat-resisting for a long time to use temperature.Inventor passes through various trials, and discovery is using the acetoacetate with the structure
Based structures are as cure site monomer, by, with the use of that can control curingprocess rate well, avoiding coke with suitable vulcanizing agent
It burns, stick the negative issues such as roller, processing performance is excellent, and is able to achieve room temperature vulcanization, and vulcanization crosslinking is abundant；Furthermore acetyl second
Acidic group and the distinctive cross-bond mode of vulcanizing agent can be improved the heat resistance of acrylic rubber, guarantee that vulcanization assembly adhesive exists
185 DEG C of long-time services.Therefore acetoacetate type acrylic rubber can remain acrylic rubber low compression set
Optimizing processing performance on the basis of rate, oil resistant reduces curing temperature raising productivity, and raising is heat-resisting for a long time to use temperature.
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 acrylic rubber reacts preparation second with diketene or methyl acetoacetate or ethyl acetoacetate
Ethyl acetoacetic acid type acrylic rubber, reaction equation are 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 bond 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 the two of carbon-carbon double bonds
First carboxylic acid monoalkyl ester monomer can play acid monomer and thiosynergistic, and since the property of monomer monoesters improves rubber
Glue resists cold effect, while the negative issues such as incipient scorch, glutinous Kun are avoided that in sulfidation.
The dicarboxylic acids monoalkyl ester monomer of the carbon-carbon double bonds, it is 6~10 that wherein ester group, which preferably has carbon atom number,
Ether alcohol formed, maleic acid monoethylene glycol only son ether-ether, maleic acid monopropylene glycol 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 monopropylene glycol 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 function and 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 rise auxiliary sulfurization, while carbon atom number be 6~10 ether alcohol structure presence can suitable control rate of cure, protect
It holds high crosslinking 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 the carbon-carbon double bonds can by the dicarboxylic acids of corresponding carbon-carbon double bonds/
The alkyl ether alcohol reaction with same mole that acid anhydrides is 6~10 with carbon atom number is prepared, such as maleic acid monoethylene glycol only son's ether-ether
It is prepared by maleic anhydride and ethylene glycol monobutyl ether that molar ratio is 1:1 through esterification.Other raw materials can refer to this
Method synthesis.
Arrcostab is the Arrcostab formed by the fatty alcohol with carbon atom number 1~8 in the alkyl acrylate monomer.
The alkyl acrylate is as specific enumerable 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
For one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate.According to the needs of performance, can use several
Kind alkyl acrylate carries out compounding adjustment.
Preferably, the low temperature oil resistant monomer be acrylic acid alcohol ethers monomer, specific enumerable methoxyethyl acrylate,
Ethoxyethyl acrylate, methoxyethyl butyl ester, ethioxy butyl ester, acrylic acid diethylene glycol monomethyl ether, diethyl
At least one of oxygroup ethyl acrylate.
It is highly preferred that the acrylic acid alcohol ethers monomer is methoxyethyl acrylate, ethoxyethyl acrylate, propylene
At least one of acid diethylene glycol monomethyl ether.
The present invention, which is also optionally added, to be copolymerized with alkyl acrylate monomer, oil resistant low temperature resistant monomer
Monomer, the specific enumerable conjugate diene monomer of these monomers, non-conjugated diene monomers, aromatic vinyl monomer, unsaturated nitrile
Monomer, unsaturated acyl amine monomer, multi-functional acrylate's class monomer etc..Normally, the additional amount of these monomers is no more than
The 2% of acetoacetate type acrylic rubber gross mass.
The acetoacetate type acrylic rubber carries out free radical polymerization by monomer and obtains.As polymerisation process,
The progress of the methods of emulsion polymerization, suspension polymerization, mass polymerization and solution polymerization process can be used.It is steady in view of technique
Qualitative and feasibility, it is preferred to use emulsion polymerization carries out.
As a kind of optional method, the preparation method of the acetoacetate type acrylic rubber by emulsion polymerization into
Row, includes the following steps:
S1. deionized water, emulsifier, part initiator are added in reaction kettle to be mixed, water solution A is made；
S2. by alkyl acrylate monomer, oil resistant low temperature resistant monomer, cure site monomer, auxiliary curable monomer, molecular weight tune
After saving agent, remaining initiator mixing, monomer mixed phase B is obtained；
S3. logical nitrogen protection is carried out to water solution A, is warming up to 20~80 DEG C；
S4. water solution A in reaction kettle is added in 1/5 mixed phase B, stirred under nitrogen atmosphere temperature control is reacted；
S5. exothermic heat of reaction finishes and after temperature drops back to temperature control range, and residual monomer mixed phase B is added in a manner of being added dropwise
Enter in system described in S4, be added dropwise in 1~4h, maintain 20~80 DEG C, 2~5h of thermotonus is maintained after being added dropwise, is obtained
To acrylic rubber lotion；
S6. the lotion obtained S5 under the conditions of 70 DEG C~90 DEG C is demulsified, object to be polymerized agglomerate completely after by gained
Flocculate is washed, is dehydrated, being dried to water content less than 0.5% to get acetoacetate type acrylic rubber life
Glue or hydroxy acryl acid ester rubber raw rubber.
If obtaining hydroxy acryl acid ester rubber raw rubber, also need and appropriate diketene or methyl acetoacetate, ethyl ester mixing
After uniformly, through extruder at a temperature of 90~120 DEG C, extrusion molding prepares acetoacetate type acrylic rubber raw rubber.
Emulsifier can be polyoxyethylene alkyl ether, polyoxyethylated alkyl phenol, polyethenoxy sorbitan Arrcostab
The equal advanced fatty alcohol sulfonate anionoid such as nonionic surfactants or dodecane sulfonate, dodecyl benzene sulfonate
At least one of surfactant.More preferably dodecane sulfonate.
Preferably, the usage amount of the emulsifier is the 0.5~4% of polymerized monomer total weight.
Initiator can be 2,2- azodiisobutyronitrile, two -2- methylbutyronitrile of 2,2- azo, two -2,4- two of 2,2- azo
Methyl valeronitrile, two -4- methoxyl group -2,4- methyl pentane nitrile of 2,2- azo, 2,2- azo two (2 Methylpropionic acid methyl esters), 2,2- are even
The azo-compounds such as nitrogen two (2- methyl-prop amidine) -2- hydrochloride；Cumene hydroperoxide (CHP), di-t-butyl peroxide, peroxidating
Bis- (tert-butyl peroxide) hexanes of diisopropylbenzene (DIPB), benzoyl peroxide (BPO), lauroyl peroxide (LPO), dimethyl, dimethyl are double
(tert-butyl peroxide) -3- hexin, bis- (t-butylperoxyisopropyl) benzene, bis- (tert-butyl peroxide) trimethyl-cyclohexanes,
Bis- (tert-butyl peroxide) valerates of butyl-, peroxide -2-ethyl hexanoic acid tert-butyl, dibenzoyl peroxide, terpane peroxidating
The organic peroxides such as hydrogen and peroxidized t-butyl perbenzoate；The inorganic persulfuric acid such as ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate
At least one of salt.Peroxide initiator can also be used with reducing agent with redox system is combined into, such as be cooperated
Ferrous sulfate, cuprous naphthenate, sodium sulfoxylate formaldehyde etc..
Preferably, the usage amount of the initiator is the 0.1~0.5% of polymerized monomer total 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 are the 0.01~0.2% of polymerized monomer total weight.
Preferably, the dosage of the water is 1.5~3 times of polymerized monomer total weight.
Preferably, the demulsification is added in the aqueous solution containing flocculating agent and flocculant for the lotion for obtaining S6.It is described
Flocculating agent can be the metal salts such as sodium chloride, calcium chloride, aluminium chloride, sodium sulphate, and it is inorganic can also to form acid-with hydrochloric acid, sulfuric acid etc.
Salt system is used as cohesion.The flocculant is added to prevent rubber agglomeration to be difficult to agglomerate, can be used Sodium Polyacrylate,
Polyvinyl alcohol etc..
A kind of vulcanized rubber composition, by acetoacetate type acrylic rubber through over cure in the vulcanized rubber composition
Change is made.The vulcanizing system can be cyanamide since acetoacetate type high reaction activity, the selection of vulcanizing agent have diversity
Class, isocyanates, more (methyl) esters of acrylic acid, common Polyamine Type, amino silicone alkanes vulcanizing agent.
Preferably, Polyamine Type vulcanizing agent, end are added in the sulfidation of the acetoacetate type acrylic rubber raw rubber
Amido silicon oil and vulcanization accelerator.If necessary, reinforcing agent, antioxidant, release 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 vulcanized rubber composition, includes the following steps:
Acetoacetate type acrylic rubber is entered into two-roll mill and carries out raw rubber pressing, addition processing aid, vulcanization promotees
Into agent, filler is then added, filler is made to be mixed into raw rubber substantially, adds vulcanizing agent, triangle bag 5 times are beaten in double roller, Bao Tong 3
Secondary, blanking, slice temperature is at 40~45 DEG C；Subcooled water, cold wind dry up slice in short-term；It places 24 hours, the vulcanization rubber is made
Glue composition.
A method of improve vulcanized rubber composition heat resistance and resistance to low temperature, the vulcanized rubber composition by
Acetoacetate type acrylic rubber is made through vulcanization, and the acetoacetate type acrylic rubber by pressing quality percentage below
Monomer polymerization than calculating obtains:
Alkyl acrylate monomer 65%~85%；
Oil resistant low temperature resistant monomer 10%~30%；
Cure site monomer containing acetoacetyl 3%~8%；
Assist curable monomer 0.5~1%；
Or
The cure site monomer containing acetoacetyl is changed into and is contained referring to mentioned component and ratio by remaining monomer and dosage
Each monomer is polymerize to obtain oh type acrylic rubber by the monomer of ethylenic bond insatiable hunger key and hydroxyl, then with diketene or
Acetoacetic ester reaction preparation；
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 atom number 1~8 in body.
Compared with prior art, the invention has the following beneficial effects:
The present invention is using methacrylic acid ethyl acetoacetate or acrylic acid ethyl acetoacetate isoreactivity monomer and (first
Base) crylic acid hydroxy ester hydroxyl by reaction generate acetoacetyl, the vulcanization as acetoacetate type acrylic rubber
Point cooperates different vulcanizing agents co-vulcanized；It, which vulcanizes assembly adhesive, has suitable curingprocess rate, avoids incipient scorch, glutinous roller；Realize room
Temperature vulcanization is not required to post vulcanization, improves production efficiency；It improves long-term heat-resisting using temperature and to remain acrylic rubber resistance to
Oil, cold-resistant advantage, gained acrylate vulcanizate composition is suitable for the rubber components, long-term for needing long-term high temperature resistant oil resistant
It is lubricated with oily pipeline, container lining and the cable contacted and the rubber part for being exposed to ozone, hot environment, such as automobile hydraulic
The fields such as sealing, hydraulic oil transmission sebific duct, cable cover(ing), the oil-resistant pipe of oil sealing, liner, running part and bearing.
Specific embodiment
Explanation is further expalined to the present invention combined with specific embodiments below, the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention, as long as the form using equivalent substitution or equivalent transformation is obtained
The technical solution obtained should all include within the scope of protection of the claims of the present invention.
In following embodiment, raw material used is commercial goods.
Embodiment 1
S1. emulsion tank is added in 150 parts of deionized waters, 3 parts of dodecyl sodium sulfates, 0.3 part of ammonium persulfate is then added
It is dissolved through mechanical stirring and water solution A is made；
S2. by 60 parts of ethyl acrylates, 25 parts of butyl acrylates, 12 parts of methoxyethyl acrylates, 0.5 part of maleic acid list
Ethylene glycol monobutyl ether ester, 2.5 parts of methacrylic acid ethyl acetoacetates and 0.05 part of n-dodecyl mercaptan after mixing, obtain
Obtain monomer mixed phase B；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up to 60 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Start to react within the scope of 60 DEG C；
S5. after reaction kettle reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 1.5h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 60 DEG C；Thermotonus is maintained after being added dropwise
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
It being sufficiently stirred during entering, object to be polymerized agglomerates completely, gained precipitate is washed with water 3~5 times, after extrusion dehydration,
It is placed in extrusion expansion drying box and dries to water content less than 0.5% to get the production of acetoacetate type acrylic rubber raw rubber
Product.
Note: 1 rubber compounding vulcanizing agent of embodiment is methyl diphenylene diisocyanate in the following table 1 vulcanization of rubber formula.
Embodiment 2
S1. emulsion tank is added in 200 parts of deionized waters, 3 parts of dodecyl sodium sulfates, 0.3 part of ammonium persulfate is then added
It is dissolved through mechanical stirring and water solution A is made；
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
Alcohol after mixing, obtains monomer mixed phase B；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 70 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Degree starts to react within the scope of 70 DEG C；
S5. after reaction kettle reacts 30 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 2h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 70 DEG C；Thermotonus is maintained after being added dropwise
4h obtains acetoacetate type acrylic rubber lotion；
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
It being sufficiently stirred during entering, object to be polymerized agglomerates completely, gained flocculate is washed with water 3~5 times, after extrusion dehydration,
It is placed in extrusion expansion drying box and dries to water content less than 0.5% to get the life of acetoacetate type acrylic rubber lotion
Glue product.
Note: 2 rubber compounding vulcanizing agent of embodiment is hexa methoxy melamine in the following table 1 vulcanization of rubber formula.
Embodiment 3
S1. emulsion tank is added in 200 parts of deionized waters, 2 parts of neopelexes, 0.3 part of persulfuric acid is then added
Potassium is dissolved through mechanical stirring is made water solution A；
S2. by 42 parts of ethyl acrylates, 20 parts of butyl acrylates, 30 parts of methoxyethyl acrylates, 0.6 part of maleic acid list
Diethylene glycol monobutyl ether ester, 8 parts of methacrylic acid ethyl acetoacetates and 0.08 part of n-dodecyl mercaptan after mixing, obtain
Obtain monomer mixed phase B；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 75 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Degree starts to react within the scope of 75 DEG C；
S5. after reaction kettle reacts 30 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 3h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 75 DEG C；Thermotonus is maintained after being added dropwise
5h obtains acetoacetate type acrylic acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 800 parts of water for containing 40 parts of sodium chloride and 4 parts of polyvinyl alcohol
It being demulsified in solution, is sufficiently stirred during the addition process, object to be polymerized agglomerates completely, gained flocculate is washed with water 3~5 times,
After extrusion dehydration, it is placed in extrusion expansion drying box and dries to water content less than 0.5% to get acetoacetate type propylene
Acid esters rubber raw rubber product.
Note: 3 rubber compounding vulcanizing agent of embodiment is hexamethylene diamine in the following table 1 vulcanization of rubber formula.
Embodiment 4
S1. emulsion tank is added in 250 parts of deionized waters, 2 parts of dodecyl sodium sulfates and 2 parts of polyoxyethylene alkane is then added
Base phenolic ether, 0.005 part of ferrous sulfate, 0.2 part of sodium sulfoxylate formaldehyde are dissolved through mechanical stirring is made water solution A；
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 uniformly mixed
Afterwards, monomer mixed phase B is obtained；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 40 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Degree starts to react within the scope of 40 DEG C；
S5. after reaction kettle reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 1.5h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 40 DEG C；Thermotonus is maintained after being added dropwise
4h obtains oh type acrylic acid ester emulsion；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 700 parts of aqueous solutions containing 20 parts of calcium chloride, 15 parts of hydrochloric acid
Middle demulsification, is sufficiently stirred during the addition process, and object to be polymerized agglomerates 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% to get the life of hydroxy acrylate rubber
Glue product；
S7. after mixing by S6 hydroxy acryl acid ester rubber raw rubber and 4 parts of diketenes, pass through extruder 90~120
DEG C extrusion molding prepares acetoacetate type acrylic rubber raw rubber.
Note: it is 100CPS Amino End Group silicone oil that 4 rubber compounding vulcanizing agent of embodiment, which is viscosity, in the following table 1 vulcanization of rubber formula.
Embodiment 5
S1. emulsion tank is added in 220 parts of deionized waters, 3 parts of neopelexes and 1 part of polyoxyethylene is then added
Alkyl sorbitol dehydration ester, 0.003 ferrous sulfate, 0.15 part of sodium sulfoxylate formaldehyde are dissolved through mechanical stirring is made water solution A；
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. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 50 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Degree starts to react within the scope of 50 DEG C；
S5. after reaction kettle reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 2.5h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 50 DEG C；Thermotonus is maintained after being added dropwise
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 aqueous solution, is sufficiently stirred during the addition process, object to be polymerized agglomerates completely, and gained flocculate is washed with water 3~5
It is secondary, after extrusion dehydration, it is placed in extrusion expansion drying box and dries to water content less than 0.5% to get oh type propylene
Acid esters rubber raw rubber product；
S7. after S6 hydroxy acryl acid ester rubber raw rubber and 6 parts of methyl acetoacetates being closed uniformly, by extruder 90~
120 DEG C are extruded into acetoacetate type acrylic rubber raw rubber.
Note: 5 rubber compounding vulcanizing agent of embodiment is end aminopropyltriethoxy trimethoxy silicon in the following table 1 vulcanization of rubber formula
Alkane.
Embodiment 6
S1. emulsion tank is added in 300 parts of deionized waters, 3 parts of dodecyl sodium sulfates and 1 part of polyoxyethylene alkane is then added
Base phenolic ether and 0.006 ferrous sulfate, 0.3 part of sodium sulfoxylate formaldehyde dissolve the water solution A that emulsifier is made through mechanical stirring；
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
Body after mixing, obtains monomer mixed phase B；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 40 DEG C；；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Start to react within the scope of 40 DEG C；
S5. after reaction kettle reacts 30 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, and maintains stirred under nitrogen atmosphere reaction within the scope of 40 DEG C during about dropwise addition 2h；Thermotonus 4h is maintained after being added dropwise,
Obtain hydroxy acryl acid ester lotion；
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 during the addition process, object to be polymerized agglomerates completely, and gained flocculate is washed with water
It washs 3~5 times, after extrusion dehydration, is placed in extrusion expansion drying box and dries to water content less than 0.5% to get containing hydroxyl
Base acrylic acid ester emulsion rubber raw rubber product；
S7. after S6 hydroxy acryl acid ester rubber raw rubber and 8 parts of ethyl acetoacetates being closed uniformly, by extruder 90~
120 DEG C are extruded into acetoacetate type acrylic rubber raw rubber.
Note: 6 rubber compounding vulcanizing agent of embodiment is ethylene glycol diacrylate in the following table 1 vulcanization of rubber formula.
Embodiment 7
S1. emulsion tank is added in 200 parts of deionized waters, 3 parts of dodecyl sodium sulfates is then added and are dissolved through mechanical stirring
The water solution A of emulsifier is made；
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 uniformly mixed
Afterwards, monomer mixed phase B is obtained；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 60 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Start to react within the scope of 60 DEG C；
S5. after reaction kettle reacts 20 minutes stabilizations, residual monomer mixed phase B is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 1.5h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 60 DEG C；Thermotonus is maintained after being added dropwise
4h obtains hydroxy acryl acid ester lotion；
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
It being sufficiently stirred during entering, object to be polymerized agglomerates completely, gained flocculate is washed with water 3~5 times, after extrusion dehydration,
It is placed in extrusion expansion drying box and dries to water content less than 0.5% to get the production of hydroxy acryl acid ester emulsion rubber raw rubber
Product；
S7. after closing S6 hydroxy acryl acid ester rubber raw rubber and 5 parts of diketenes uniformly, pass through 90~120 DEG C of extruder
It is extruded into acetoacetate type acrylic rubber raw rubber.
Note: 7 rubber compounding vulcanizing agent of embodiment is diacrylate -1,6-HD ester in the following table 1 vulcanization of rubber formula.
Embodiment 8
S1. emulsion tank is added in 300 parts of deionized waters, 4 parts of dodecyl sodium sulfates is then added and 0.004 sulfuric acid is sub-
Iron, 0.15 part of sodium sulfoxylate formaldehyde dissolve the water solution A that emulsifier is made through mechanical stirring；
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
Cumyl peroxide and 0.05 part of n-dodecyl mercaptan after mixing, obtain monomer mixed phase B；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 30 DEG C；
S4. the acquisition monomer mixed phase B of 1/5 parts by weight is added in reaction kettle, under nitrogen protection, maintains emulsion system
Temperature starts to react within the scope of 30 DEG C；
S5. after reaction kettle reacts 20 minutes stabilizations, residue is obtained into monomer mixed phase B and is transferred to reaction kettle, and is started past
Reaction kettle is added dropwise, about dropwise addition 3h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 30 DEG C；Maintain temperature anti-after being added dropwise
5h is answered, hydroxy acryl acid ester lotion is obtained；
S6. under the conditions of 80 DEG C, polymer emulsion is added to 800 parts of water for containing 40 parts of calcium chloride and 3 parts of polyvinyl alcohol
It being demulsified in solution, is sufficiently stirred during the addition process, object to be polymerized agglomerates completely, gained flocculate is washed with water 3~5 times,
After extrusion dehydration, it is placed in extrusion expansion drying box and dries to water content less than 0.5% to get hydroxy acryl acid ester
Rubber raw rubber product；
S7. after mixing by S6 hydroxy acryl acid ester rubber raw rubber and 9 parts of methyl acetoacetates and a small amount of acetic acid, lead to
It crosses 90~120 DEG C of extruder and is extruded into acetoacetate type acrylic rubber raw rubber.
Note: 8 rubber compounding vulcanizing agent of embodiment is hexamethylene diamine in the following table 1 vulcanization of rubber formula.
Embodiment 9
S1. emulsion tank is added in 250 parts of deionized waters, 2 parts of dodecyl sodium sulfates is then added, 2 parts of polyoxyethylene are de-
Water sorbierite Arrcostab and 0.3 part of ammonium persulfate dissolve the water solution A that emulsifier is made through mechanical stirring；
S2. by 50 parts of ethyl acrylates, 20 parts of butyl acrylates, 24 parts of methoxyethyl acrylates, 1 part of maleic acid list second
Glycol monobutyl ether ester, 5.0 parts of methacrylic acid ethyl acetoacetates and 0.03 part of n-dodecyl mercaptan after mixing, obtain
Monomer mixed phase B；
S3. water solution A is added in reaction kettle, is maintained under nitrogen protection, stirring is warming up within the scope of 60 DEG C；
S4. the monomer mixed phase B of 1/5 parts by weight is transferred in reaction kettle, under nitrogen protection, maintains emulsion system temperature
Degree starts to react within the scope of 60 DEG C；
S5. after reaction kettle reacts 20 minutes stabilizations, remaining mixture lotion C is transferred to reaction kettle, and is started toward reaction
Kettle is added dropwise, about dropwise addition 1.5h, during which maintains stirred under nitrogen atmosphere reaction within the scope of 60 DEG C；Thermotonus is maintained after being added dropwise
4h obtains acetoacetate type acrylic rubber lotion；
S6. under the conditions of 80 DEG C, polymer emulsion is added in 600 parts of aqueous solutions containing 30 parts of magnesium sulfate and is demulsified,
Be sufficiently stirred in adition process, object to be polymerized agglomerates completely, gained flocculate is 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% to get acetoacetate type acrylic rubber raw rubber
Product.
Note: 9 rubber compounding vulcanizing agent of embodiment is diacrylate 1,6-HD ester in the following table 1 vulcanization of rubber formula.
Embodiment 10
Fumaric acid list diethylene glycol monobutyl ether in embodiment 7 is replaced using monomethyl ester, other monomers and technique
Step and embodiment 7 are consistent.
Embodiment 11
Maleic acid list diethylene glycol monobutyl ether ester in embodiment 8 is replaced using ethyl maleate, other monomers and work
Skill step and embodiment 8 are consistent.
Embodiment 12
Maleic acid monoethylene glycol only son's ether-ether in embodiment 9 is replaced using ethyl maleate, other monomers and technique
Step and embodiment 9 are consistent.
Vulcanized rubber embodiment:
It is formulated (in parts by weight) by table 1, rubber mixing mill is added in 1 to 12 rubber raw rubber of embodiment, benefit is added portionwise
The mixture of filler, inert filler, stearic acid, anti-aging agent, wax and plasticizer by force, 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
Methyltrimethoxysilane etc.；Polyfunctionality acrylic or methacrylic acid ester such as ethylene glycol diacrylate etc.) and vulcanization rush
Into the mixture of agent (diphenylguanidine, cumyl peroxide, potassium stearate etc.), bottom sheet after 4 triangle bags is made a call to, parks 12 in room temperature
Hour, later by rubber compound at room temperature vulcanization 24 hours.
Vulcanizing agent used in comparative example A R-840 (four two (pentamethylene) thiurams of vulcanization), vulcanization accelerator (stearic acid
Potassium), sulphur.It is formulated (in parts by weight) by table 1, rubber mixing mill is added in comparative example A's R-840 rubber raw rubber, benefit is added portionwise
The mixture of filler, inert filler, stearic acid, anti-aging agent, wax and plasticizer by force, waits all mixtures to be mixed into rubber
Afterwards, it is eventually adding the mixture of vulcanizing agent and vulcanization accelerator, makes a call to bottom sheet after 4 triangle bags, parks 5min at 180 DEG C, later
By rubber compound 170 DEG C post-cure 4 hours.
Following performance test is carried out to embodiment 1~12 and comparative example A R-840:
1, Mooney viscosity is tested
The Mooney viscosity of rubber compound is according to GB/T 1232.1-2000 first part: the measurement of Mooney viscosity is tested,
Experimental temperature is 100 DEG C, preheating time 1min, testing time 4min.
2, Mooney scorch time is tested
Mooney scorch time (t10) tests 120 DEG C of sizing material time of scorch according to national standard GB/T1233-92, and t10 value is bigger,
Anti- incipient scorch is more excellent, and machinability is more preferable.
3, hardness test
The shore a hardness of ACM vulcanizate is according to GB/T 531.1-2008 part 1: Shore durometer method (Shao Er hardness)
It is tested.
4, Mechanics Performance Testing
The universal testing machine produced with Shenzhen new SANS measurement technology Co., Ltd is surveyed according to GB/T 528-2009
Try the tensile property of vulcanizate；According to the tearing strength of GB/T 529-2008 test vulcanizate, sample is square；According to GB/
T7759-1996 (B method) tests ACM vulcanizate compression set value, test condition are as follows: and 150 DEG C of test temperature, standing time
70h, precompressed shrinkage are 25%.
5, heat aging property is tested
ACM vulcanizate heat-resistant air aging property is tested according to GB/T 3512-2001, and test temperature is 185 DEG C, aging
Time is 72h.
6, oil resistance is tested
The oil resistance of ACM vulcanizate is tested according to GB/T 1690-2006, and test temperature is 150 DEG C, and soaking time is
72h, test liquid are IRM903# oil.
7, brittleness temperature is tested
According to the brittleness temperature (Tb) of GB/T 1682-1994 (single specimen method) test ACM vulcanizate.
1 vulcanization of rubber formula of table
2 embodiment vulcanising composition performance test of table
During being processed into vulcanized rubber, inventor has found rubber good fluidity of the invention, combines sulfurizing formula
Roller not incipient scorch is not sticked in mixed process；Realize room temperature vulcanization, high production efficiency.In conjunction with 2 test result of table it is found that the present invention is implemented
For vulcanized rubber t10, t50, t90 prepared by example in safely controllable range, anti-incipient scorch ability is strong, and process safety is high.This
Outside, vulcanized rubber mechanical performance prepared by the present invention and oil resistance are very good, 185 DEG C × 72h of hot air aging performance
Long-term heat resistance can be protruded especially.In addition from the embodiment 10,11,12 of the corresponding replacement auxiliary curable monomer of embodiment 7,8,9
Rubber comparison it is found that the currently preferred more conventional curable monomer of auxiliary curable monomer in cryogenic property and processing performance
More advantage assists the replacement of curable monomer to bring apparent influence to black brittleness.Comparative example A R-840 can not achieve room temperature
Vulcanization needs conventional high temperature to vulcanize (vulcanizing agent, the auxiliary curing agent of use are different from embodiment), and conventional physical property is close, oil resistant
Heat resistance is suitable, and compression set rubber protected than this patent is slightly worse.
Therefore, acetoacetate type acrylic rubber of the present invention can overcome in existing acrylic rubber processing and performance
It is insufficient, it can be achieved that room temperature vulcanization, have it is higher it is long-term it is heat-resisting use temperature, acrylate vulcanizate composition is suitable for needing
The rubber components of long-term high temperature resistant oil resistant, pipeline, container lining and the cable contacted for a long time with oil and it is exposed to ozone, high temperature
The rubber part of environment, as the sealing of automobile hydraulic lubrication oil seal, liner, running part and bearing, hydraulic oil transmit sebific duct, electricity
The fields such as cable sheath, oil-resistant pipe use.
Claims (7)
1. a kind of acetoacetate type acrylic rubber, which is characterized in that poly- by the following monomer being calculated by mass percentage
Conjunction obtains:
Alkyl acrylate monomer 65%~95%；
Oil resistant low temperature resistant monomer 0%~30%；
Cure site monomer containing acetoacetyl 3%~8%；
Assist curable monomer 0.5 ~ 1%；
Or
Remaining monomer and dosage change the cure site monomer containing acetoacetyl containing ethylene linkage into referring to mentioned component and ratio
Each monomer is polymerize to obtain oh type acrylic rubber by the monomer of formula insatiable hunger key and hydroxyl, then with diketene or acetyl
Acetic acid esters reaction preparation；
The auxiliary curable monomer is the dicarboxylic acids monoalkyl ester monomer of carbon-carbon double bonds；
Ester group in the dicarboxylic acids monoalkyl ester monomer of the carbon-carbon double bonds is formed by the ether alcohol with carbon atom number 6 ~ 10.
2. acetoacetate type acrylic rubber according to claim 1, which is characterized in that described to vulcanize containing acetoacetyl
Point monomer is methacrylic acid ethyl acetoacetate and/or acrylic acid ethyl acetoacetate.
3. acetoacetate type acrylic rubber according to claim 1, which is characterized in that the key of insatiable hunger containing ethylenic bond and
The monomer of hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
4. acetoacetate type acrylic rubber according to claim 1, which is characterized in that the alkyl acrylate monomer
Middle Arrcostab is the Arrcostab formed by the fatty alcohol with carbon atom number 1 ~ 8.
5. acetoacetate type acrylic rubber according to claim 1, which is characterized in that the oil resistant low temperature resistant monomer is
Acrylic acid alcohol ethers monomer.
6. according to claim 1 to acetoacetate type acrylic rubber described in any one of 5 claims, which is characterized in that institute
It states acetoacetate type acrylic rubber and is made by the monomer through free radical polymerization.
7. a kind of vulcanized rubber composition, which is characterized in that the acetoacetate as described in any one of claim 1 to 6 claim
Type acrylic rubber is made through vulcanization.
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