CN105968273A - Low-temperature resistant acrylate rubber and preparation method thereof - Google Patents
Low-temperature resistant acrylate rubber and preparation method thereof Download PDFInfo
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2421/00—Characterised by the use of unspecified rubbers
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Abstract
The invention relates to low-temperature resistant acrylate rubber and a preparation method thereof. The rubber is prepared from the following raw materials in parts by weight: 10-15 parts of n-butyl acrylate, 20-30 parts of 2-ethylhexyl acrylate, 3-5 parts of hydroxymethyl acrylamide, 20-30 parts of urethane acrylate, 10-15 parts of fluorinated acrylate, 15-25 parts of microcapsules, 10-18 parts of rubber microspheres, 3-5 parts of initiator, 30-60 parts of solvent and 1-2 parts of vulcanizing agent. The finally obtained acrylate rubber has excellent low-temperature resistance while the service life is prolonged.
Description
Technical field
The present invention relates to a kind of acrylate rubber, be specifically related to a kind of low temperature resistant acrylate rubber.
Background technology
Acrylate rubber is because of thermostability, resistance to ag(e)ing, weatherability, uvioresistant and the oil resistivity of its excellence, by extensively
It is applied to high temperature, oil-resistant sealing element industry.Its lower temperature resistance can generally achieve-25 DEG C--30 DEG C, conventional use can be met
Need, acrylate rubber (ACM) by its tolerance to cold difference be divided into standard type (brittleness temperature-12 DEG C), cold resisting type (-24 DEG C),
Super cold resistant type (-35 DEG C).Different types of ACM, on the one hand due to its backbone structure difference, physical property is respectively arranged with feature；Another
Aspect is close due to polarity, so the compatibility, intervulcanizability are preferable.For requiring heat-resisting, oil resistant and wanting low temperature resistant application to lead
Territory, such as the oil cooling pipe of automobile, the good combination property that different types of ACM blended rubber is had can meet its requirement.
Although ACM exists above-mentioned advantage, it is important a kind of industrial products, but existing product exists length in service life
Problem, meanwhile, prior art needs the acrylic rubber that lower temperature resistance is more excellent, and existing product has been difficult to meet higher
Requirement, therefore need the more excellent acrylic rubber of a kind of resistance to low temperature, and expect that service life can increase further.
Summary of the invention
Goal of the invention: the present invention provides a kind of acrylate rubber, it is desirable to provide a kind of resistance to low temperature is the most excellent
Acrylic rubber, it, by selecting soft monomer and the hard monomer of long-chain, adds urethane acrylate and fluorine-containing propene further
Acid esters carries out copolymerization, long chain acrylate and urethane acrylate and improves the pliability of acrylate rubber, has relatively low
Glass transition temperature, use the most again fluorinated acrylate to carry out copolymerization simultaneously, comprehensive various of monomer performance, obtain especially
The acrylate rubber of lower glass transition temperatures.Microcapsule and latex microspheres improve acrylate rubber by respective performance
Lower temperature resistance.
Present invention also offers the preparation method of a kind of low temperature resistant acrylate rubber, its each compositional selecting is specific add fashionable
Machine, obtains the low temperature resistant acrylate rubber of ad hoc structure.
The concrete technical scheme of the present invention: a kind of low temperature resistant acrylate rubber, rubber preparation use raw material be acrylic acid just
Butyl ester 10-15 weight portion, acrylic acid-2-ethyl caproite 20-30 weight portion, n-methylolacrylamide 3-5 weight portion, polyurethane third
Olefin(e) acid ester 20-30 weight portion, fluorinated acrylate 10-15 weight portion, microcapsule 15-25 weight portion, latex microspheres 10-18 weight
Part, initiator 3-5 weight portion, solvent 30-60 weight portion, vulcanizing agent 1-2 weight portion.
The present invention have selected concrete monomer, butyl acrylate Tg-56 DEG C, acrylic acid-2-ethyl caproite Tg-70 DEG C,
Its glass transition temperature obtained with other monomer copolymerizations is the lowest；Urethane acrylate has soft segment, and it can carry
The pliability of high acrylate rubber；The structure of fluorinated acrylate the most to a certain degree can reduce the Tg of acrylate rubber.
Summary monomer type and select, final acrylate rubber Tg is low, and pliability is good.
Described microcapsule coated liquid, described liquid is calcium chloride solution, sodium chloride solution, alcohol-water mixture or glycerol liquor
Mixture.The liquid of microcapsule coated has relatively low freezing point, and may remain under lower temperature is liquid, can improve soft
Toughness, even if reaching freezing point, liquid solidification heat release, also can keep pliability in a period of time.For the regulation of freezing point, chlorine
It is permissible that change calcium solution and sodium chloride solution can regulate freezing point, ethanol water mixture and glycerol liquor mixture by salinity
It is adjusted by the ratio of ethanol/water or glycerin/water.The present invention preferably prepares the microcapsule of different freezing point, during use not
It is used in mixed way with freezing point microcapsule, reaches to be released by heat under different temperatures, keep the activity of segment in acrylic rubber
Performance, improves pliability.
The most described solution is calcium chloride solution.Its freezing point can regulate that the lowest that high calcium chloride concentration is preferably used is molten
Liquid.In order to ensure the low temperature flexibility of microcapsule own material, the covering material of described microcapsule is polyurethane.
The rubber of described latex microspheres is polyurethane, nitrile rubber, EP rubbers, fluorubber or neoprene.This rubber
Microsphere can keep pliability under cryogenic with dispersive stress, in the case of matrix hardness improves, during by external force,
Latex microspheres can effective dispersive stress, improve its low temperature serviceability, a certain degree of have impact on its service life.
The particle diameter of described microcapsule is 50-80 micron.The particle diameter of described latex microspheres is 30-40 micron.Select suitably
Microcapsule and the particle size range of latex microspheres, when it is not the most in this scope, stress dispersive property is deteriorated, and closely can meet base
This performance requirement, it is difficult to meet higher demand.
The particle diameter of the most described rubber particle, less than the particle diameter of described microcapsule, makes latex microspheres can be interspersed in microcapsule
Between, when microcapsule reaches freezing point, becomes solid, latex microspheres can effective dispersive stress, it is to avoid solid structure is to third
The infringement of olefin(e) acid ester rubber.
Described initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide；Described solvent is diformazan
Benzene or ethyl acetate.
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps:
Step (1): take and the solvent of 15-30 weight portion is added reactor, be heated to 80-110 DEG C, then by n-butyl acrylate
10-15 weight portion, acrylic acid-2-ethyl caproite 20-30 weight portion, n-methylolacrylamide 3-5 weight portion and 1.2-2 weight portion
Initiator mix homogeneously, be at the uniform velocity added dropwise in reactor, dropping process completes at 1-1.5h, continue reaction 1h；
Step (2): by urethane acrylate 20-30 weight portion, fluorinated acrylate 10-15 weight portion, microcapsule 15-25 weight
Amount part, remaining 1.8-3 weight portion initiator and 15-30 parts by weight solvent mix homogeneously, at the uniform velocity add the reactor of step (1)
In, dropping process completes at 0.3-1h, continues reaction 0.5h；
Step (3): being added by latex microspheres 10-18 weight portion in the reactor of step (2), cooling obtains low temperature resistant acrylate
Rubber solutions, adds vulcanizing agent 1-2 weight portion further, adds heat cure and obtain low temperature resistant acrylate rubber.
The present invention uses the preparation method of routine all can prepare, and is not distinctly claimed.Preferably in preparation method, send out
Bright point is that the addition step in its preparation process, urethane acrylate and fluorochemical monomer add in (2nd) step, is in chain
The outside of section, can effectively control sub-chain motion each other, improves pliability.Microcapsule adds in (2nd) step, it is to avoid
Too early addition is wrapped up by acrylate segment, affects overall flexibility after microcapsule solidifies.Latex microspheres added in the later stage,
Become parcel, be uniformly dispersed, if together with encapsulation, disperseed uneven, it is difficult to effectively disperse, it is difficult to realized
Pliability.
Technique effect: present invention selection based on specific monomer, i.e. utilizes the glass transition temperature of monomer itself, segment
Length, substituent group performance, reduce the resistance to low temperature of matrix resin；Use again the microcapsule of cladding liquid, permissible not solidifying
As stress spaced point, when solidification, meeting heat release, lower temperature resistance can be improved；Using latex microspheres further, dispersion should
Power, and better prominent after microcapsule solidification at low temperatures.The selection of preparation method is also an inventive point place, its
Selecting monomer to add Quality Initiative segment structure on opportunity, add opportunity by controlling microcapsule and latex microspheres, controlling should under its low temperature
The scattered performance of power.Summary mechanism, the resistance to low temperature of the acrylate rubber finally given is excellent, prolongs service life
Long.
Detailed description of the invention
Embodiment 1:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 1
(-10 DEG C) 5 weight portion, microcapsule 2(-20 DEG C) 5 weight portions, microcapsule 3(-30 DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 5 weights
Amount part, the particle diameter of microcapsule 1-4 is each about 60 μm, remaining initiator 3 weight portion and the mixing of solvent xylene 40 weight portion all
Even, at the uniform velocity add in the reactor of step (1), dropping process completes at 0.5h, continues reaction 0.5h；Step (3): by 35 μm grains
Latex microspheres 15 weight portion in footpath adds in the reactor of step (2), and cooling obtains low temperature resistant acrylate rubber solution, enters one
Step adds vulcanizing agent 1 weight portion, adds heat cure and obtains low temperature resistant acrylate rubber.
Comparative example 1:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, n-octyl 25 weight portion, methylol
The initiator mix homogeneously of acrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process completes at 1h,
Continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 1(-10
DEG C) 5 weight portions, microcapsule 2(-20 DEG C) 5 weight portions, microcapsule 3(-30 DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 5 weight portions,
The particle diameter of microcapsule 1-4 is each about 60 μm, remaining initiator 3 weight portion and solvent xylene 40 weight portion mix homogeneously, even
Speed adds in the reactor of step (1), and dropping process completes at 0.5h, continues reaction 0.5h；Step (3): by micro-for 35 μm rubber
Ball 15 weight portion adds in the reactor of step (2), and cooling obtains low temperature resistant acrylate rubber solution, adds sulfuration further
Agent 1 weight portion, adds heat cure and obtains low temperature resistant acrylate rubber.
Comparative example 2:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 4
(-40 DEG C) 20 weight portion, remaining initiator 3 weight portion and solvent xylene 40 weight portion mix homogeneously, at the uniform velocity add step
(1) in reactor, dropping process completes at 0.5h, continues reaction 0.5h；Step (3): by the latex microspheres 15 of 35 μm particle diameters
Weight portion adds in the reactor of step (2), and cooling obtains low temperature resistant acrylate rubber solution, adds vulcanizing agent 1 further
Weight portion, adds heat cure and obtains low temperature resistant acrylate rubber.
Comparative example 3:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, remaining
Initiator 3 weight portion and solvent xylene 40 weight portion mix homogeneously, at the uniform velocity add in the reactor of step (1), drips process
Complete at 0.5h, continue reaction 0.5h；Step (3): latex microspheres 35 weight portion of 35 μm particle diameters is added the reaction of step (2)
In device, cooling obtains low temperature resistant acrylate rubber solution, adds vulcanizing agent 1 weight portion further, adds heat cure and obtain resistance to low
Temperature acrylate rubber.
Comparative example 4:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 1
(-10 DEG C) 10 weight portion, microcapsule 2(-20 DEG C) 10 weight portions, microcapsule 3(-30 DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 10
Weight portion, the particle diameter of microcapsule 1-4 is each about 60 μm, remaining initiator 3 weight portion and the mixing of solvent xylene 40 weight portion
Uniformly, at the uniform velocity adding in the reactor of step (1), dropping process completes at 0.5h, continues reaction 0.5h；Cooling obtains low temperature resistant
Acrylate rubber solution, adds vulcanizing agent 1 weight portion further, adds heat cure and obtain low temperature resistant acrylate rubber.
Comparative example 5:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule
(cladding water) 20 weight portions, remaining initiator 3 weight portion and solvent xylene 40 weight portion mix homogeneously, at the uniform velocity add step
(1) in reactor, dropping process completes at 0.5h, continues reaction 0.5h；Step (3): by the latex microspheres 15 of 35 μm particle diameters
Weight portion adds in the reactor of step (2), and cooling obtains low temperature resistant acrylate rubber solution, adds vulcanizing agent 1 further
Weight portion, adds heat cure and obtains low temperature resistant acrylate rubber.
Comparative example 6:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 1
(-10 DEG C) 5 weight portion, microcapsule 2(-20 DEG C) 5 weight portions, microcapsule 3(-30 DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 5 weights
Amount part, the particle diameter of microcapsule 1-4 is each about 60 μm, remaining initiator 3 weight portion and the mixing of solvent xylene 40 weight portion all
Even, at the uniform velocity add in the reactor of step (1), dropping process completes at 0.5h, continues reaction 0.5h；Step (3): by 60 μm grains
Latex microspheres 15 weight portion in footpath adds in the reactor of step (2), and cooling obtains low temperature resistant acrylate rubber solution, enters one
Step adds vulcanizing agent 1 weight portion, adds heat cure and obtains low temperature resistant acrylate rubber.
Comparative example 7:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 80 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
Methacrylamide 4 weight portion, urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 1(-10
DEG C) 5 weight portions, microcapsule 2(-20 DEG C) 5 weight portions, microcapsule 3(-30 DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 5 weight portions,
The particle diameter of microcapsule 1-4 is each about the initiator mixing of 60 μm, latex microspheres 15 weight portion of 35 μm particle diameters and 5 weight portions all
Even, at the uniform velocity it is added dropwise in reactor, stirs, react 2h；Cooling obtains low temperature resistant acrylate rubber solution, adds further
Enter vulcanizing agent 1 weight portion, add heat cure and obtain low temperature resistant acrylate rubber.
Comparative example 8:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
Methacrylamide 4 weight portion, microcapsule 1(-10 DEG C) 5 weight portions, microcapsule 2(-20 DEG C) 5 weight portions, microcapsule 3(-30
DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 5 weight portions, the particle diameter of microcapsule 1-4 be each about 60 μm and 2 weight portions initiator mix
Closing uniformly, be at the uniform velocity added dropwise in reactor, dropping process completes at 1h, continues reaction 1h；Step (2): by polyurethane acroleic acid
Ester 25 weight portion, fluorinated acrylate 12 weight portion, remaining initiator 3 weight portion and the mixing of solvent xylene 40 weight portion are all
Even, at the uniform velocity add in the reactor of step (1), dropping process completes at 0.5h, continues reaction 0.5h；Step (3): by 35 μm grains
Latex microspheres 15 weight portion in footpath adds in the reactor of step (2), and cooling obtains low temperature resistant acrylate rubber solution, enters one
Step adds vulcanizing agent 1 weight portion, adds heat cure and obtains low temperature resistant acrylate rubber.
Comparative example 9:
The preparation method of low temperature resistant acrylate rubber, concretely comprises the following steps: step (1): take the solvent xylene of 40 weight portions
Add reactor, be heated to 90 DEG C, then by n-butyl acrylate 12 weight portion, acrylic acid-2-ethyl caproite 25 weight portion, hydroxyl
The initiator mix homogeneously of Methacrylamide 4 weight portion and 2 weight portions, is at the uniform velocity added dropwise in reactor, and dropping process is at 1h
Complete, continue reaction 1h；Step (2): by urethane acrylate 25 weight portion, fluorinated acrylate 12 weight portion, microcapsule 1
(-10 DEG C) 5 weight portion, microcapsule 2(-20 DEG C) 5 weight portions, microcapsule 3(-30 DEG C) 5 weight portions, microcapsule 4(-40 DEG C) 5 weights
Amount part, the particle diameter of microcapsule 1-4 is each about 60 μm, latex microspheres 15 weight portion of 35 μm particle diameters, remaining initiator 3 weight portion
With solvent xylene 40 weight portion mix homogeneously, at the uniform velocity adding in the reactor of step (1), dropping process completes at 0.5h, continues
Continuous reaction 0.5h；Cooling obtains low temperature resistant acrylate rubber solution, adds vulcanizing agent 1 weight portion further, adds heat cure and obtain
To low temperature resistant acrylate rubber.
Concrete test data see table:
*, at-30 DEG C, recover after tensile elongation 100%, then stretch next time, tired in order to characterize stretch-proof under its low temperature
Property.
"---" represents and cannot measure.
Claims (10)
1. a low temperature resistant acrylate rubber, it is characterised in that: rubber preparation uses raw material to be n-butyl acrylate 10-15 weight
Amount part, acrylic acid-2-ethyl caproite 20-30 weight portion, n-methylolacrylamide 3-5 weight portion, urethane acrylate 20-30
Weight portion, fluorinated acrylate 10-15 weight portion, microcapsule 15-25 weight portion, latex microspheres 10-18 weight portion, initiator 3-
5 weight portions, solvent 30-60 weight portion, vulcanizing agent 1-2 weight portion.
Low temperature resistant acrylate rubber the most as claimed in claim 1, it is characterised in that: described microcapsule coated liquid, described
Liquid is calcium chloride solution, sodium chloride solution, ethanol/water mixture or glycerin/water mixture.
Low temperature resistant acrylate rubber the most as claimed in claim 2, it is characterised in that: described solution is calcium chloride solution.
4. the low temperature resistant acrylate rubber as according to any one of claim 1-3, it is characterised in that: the bag of described microcapsule
Covering material is polyurethane.
Low temperature resistant acrylate rubber the most as claimed in claim 1, it is characterised in that: the rubber of described latex microspheres is poly-ammonia
Ester, nitrile rubber, EP rubbers, fluorubber or neoprene.
Low temperature resistant acrylate rubber the most as claimed in claim 1, it is characterised in that: the particle diameter of described microcapsule is 50-80
Micron.
Low temperature resistant acrylate rubber the most as claimed in claim 1, it is characterised in that: the particle diameter of described latex microspheres is 30-
40 microns.
Low temperature resistant acrylate rubber the most as claimed in claim 1, it is characterised in that: the particle diameter of described rubber particle is less than institute
State the particle diameter of microcapsule.
Low temperature resistant acrylate rubber the most as claimed in claim 1, it is characterised in that: described initiator is azo two isobutyl
Nitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide；Described solvent is dimethylbenzene or ethyl acetate.
10. the preparation method of the low temperature resistant acrylate rubber of any one in a kind such as claim 1-9, it is characterised in that:
Step (1): the solvent taking 15-30 weight portion adds reactor, is heated to 80-110 DEG C, then by n-butyl acrylate
10-15 weight portion, acrylic acid-2-ethyl caproite 20-30 weight portion, n-methylolacrylamide 3-5 weight portion and 1.2-2 weight portion
Initiator mix homogeneously, be at the uniform velocity added dropwise in reactor, dropping process completes at 1-1.5h, continue reaction 1h；
Step (2): by urethane acrylate 20-30 weight portion, fluorinated acrylate 10-15 weight portion, microcapsule 15-25 weight
Amount part, remaining 1.8-3 weight portion initiator and the solvent mix homogeneously of 15-30 weight portion, at the uniform velocity add the reaction of step (1)
In device, dropping process completes at 0.3-1h, continues reaction 0.5h；
Step (3): being added by latex microspheres 10-18 weight portion in the reactor of step (2), cooling obtains low temperature resistant acrylate
Rubber solutions, adds vulcanizing agent 1-2 weight portion further, adds heat cure and obtain low temperature resistant acrylate rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610579988.0A CN105968273A (en) | 2016-07-22 | 2016-07-22 | Low-temperature resistant acrylate rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610579988.0A CN105968273A (en) | 2016-07-22 | 2016-07-22 | Low-temperature resistant acrylate rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105968273A true CN105968273A (en) | 2016-09-28 |
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Application publication date: 20160928 |