CN117209650A - Epoxy acrylate rubber with low brittleness temperature and manufacturing method thereof - Google Patents
Epoxy acrylate rubber with low brittleness temperature and manufacturing method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 118
- 239000005060 rubber Substances 0.000 title claims abstract description 118
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 126
- 239000002994 raw material Substances 0.000 claims abstract description 116
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 238000004073 vulcanization Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 238000006116 polymerization reaction Methods 0.000 claims description 50
- 239000000839 emulsion Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 22
- 150000002978 peroxides Chemical class 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 7
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 4
- RUZXDTHZHJTTRO-UHFFFAOYSA-N 7-amino-4h-1,4-benzoxazin-3-one Chemical compound N1C(=O)COC2=CC(N)=CC=C21 RUZXDTHZHJTTRO-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- -1 acrylic ester Chemical class 0.000 description 7
- 239000004033 plastic Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000013013 elastic material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010063 rubber manufacturing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses epoxy acrylate rubber with low brittleness temperature and a manufacturing method thereof, wherein the epoxy acrylate rubber comprises, by weight, 5 parts of epoxy vulcanization point monomer raw materials, 75-95 parts of functional monomer raw materials with low brittleness temperature, 3 parts of emulsifying agent and 250 parts of deionized water. According to the invention, the low-brittleness temperature functional monomer raw materials for improving the low-temperature resistance of the rubber material are added or added in the traditional manufacturing method, the brittleness temperatures of different copolymers are different, and the low-brittleness temperature functional monomer raw material copolymer for improving the low-temperature resistance of the rubber material has lower brittleness temperature, so that compared with the rubber which is not added in the traditional manufacturing method, the low-temperature resistance of the finally manufactured rubber is improved, the application field of the acrylate rubber is wider, and the special use requirement on the low-temperature resistance of the rubber can be met.
Description
Technical Field
The invention relates to the technical field of acrylic rubber manufacturing, in particular to epoxy acrylic rubber with low brittleness temperature and a manufacturing method thereof.
Background
Acrylate rubber (ACM) is an elastic material formed by copolymerizing acrylic ester and monomers with crosslinking reaction active groups, and the like, and the main chain of the elastic material is of a saturated structure, so that the elastic material has the performances of heat resistance, ultraviolet radiation resistance and ozone resistance; the side chain of the oil-resistant rubber contains polar ester groups, so that the oil-resistant rubber has excellent oil resistance. The main application of the acrylate rubber is to manufacture heat-resistant and oil-resistant sealing parts, oil pipes and the like, and is mainly used in the fields of automobiles, motorcycles, petroleum, chemical industry, machinery, power transformers and the like.
The ACM is used in combination with plastic to produce rubber-plastic alloy, and has some advantages combined with plastic to raise toughness and improve some performance defects and shortcomings of plastic.
The physical and mechanical properties of acrylate rubbers are affected by a number of factors, including: the structure of the rubber (the raw material ratio of the polymer), the molecular weight of the rubber, the compounding processing technology of the rubber, and the like.
Acrylate rubbers are of different types, and are classified according to the types of vulcanization point monomers, and are more commonly used at present: active chlorine type, carboxylic acid type, epoxy type, double/multiple crosslinking point type, and the like. According to different temperature resistant grades of the sizing materials, the sizing materials can be divided into: standard type, cold-resistant modified type, heat-resistant modified type, etc.
Different types of acrylate rubber have different matched processing technologies, and different types of acrylate rubber have different mechanical properties, advantages and disadvantages and different suitable application fields.
The epoxy rubber can be used in the field of common heat-resistant and oil-resistant sealing parts, and the epoxy rubber does not contain chlorine element in the rubber structure, so that the epoxy rubber can be also suitable for the field (such as the electronic field) with contraindication to chlorine. In addition, the epoxy group is contained in the epoxy type rubber structure, so that the grafting reaction is convenient, favorable conditions are created for modification and subsequent processing of materials, and the preparation of rubber-plastic alloy is facilitated, so that the epoxy type rubber has good application prospect.
The acrylic rubber has the characteristics of high temperature resistance and oil resistance, can be used for a long time in hot oil at 150 ℃, and has a short time temperature resistance of 200 ℃ (about 10 hours).
The low temperature resistance of the existing acrylate rubber is not very good. The brittleness temperature of the standard rubber is about-10 to-15 ℃, the cold resistance is about-20 ℃, the cold resistance is improved to about-30 ℃, and the super cold resistance is about-35 to-40 ℃.
With the development of technology, the low temperature resistance requirements of rubber are gradually increased in some use processes, particularly in some fields of rubber and plastic combined use, the low temperature resistance requirements of rubber are higher, the existing varieties are difficult to meet, and in order to make the application field of epoxy acrylate rubber wider and meet the requirements of more use scenes, the invention provides the epoxy acrylate rubber with low brittleness temperature and a manufacturing method thereof.
Disclosure of Invention
The invention aims to provide epoxy acrylate rubber with low brittleness temperature and a manufacturing method thereof.
The invention adopts the following technical scheme to realize the aim:
the epoxy acrylate rubber with low brittleness temperature in the technical scheme comprises, by weight, 5 parts of epoxy vulcanization point monomer raw materials, 75-95 parts of low brittleness temperature functional monomer raw materials, 3 parts of emulsifying agent and 250 parts of deionized water.
In the above technical solution, preferably, the method further comprises up to 20 parts of basic acrylate monomer raw materials.
In the above technical solution, preferably, the epoxy cure site monomer raw material includes at least one of glycidyl acrylate, glycidyl methacrylate and glycidyl acrylate; the low brittleness temperature functional monomer raw material comprises at least one of ethoxyethyl acrylate, 2-ethylhexyl acrylate, n-sunflower methacrylate, n-dodecyl methacrylate and cinnamyl methacrylate.
In the above technical solution, preferably, the base acrylate monomer raw material includes at least one of ethyl acrylate and methoxyethyl acrylate.
In the above technical solution, preferably, the emulsifier is sodium dodecyl sulfate.
The manufacturing method of the epoxy acrylate rubber with low brittleness temperature in the technical scheme comprises the following steps:
s1, adding rubber raw material components into a mixing tank, and uniformly stirring and mixing to prepare mixed monomer raw materials;
s2, adding deionized water and an emulsifying agent into a reaction kettle, and stirring to prepare an emulsion;
s3, introducing nitrogen into the reaction kettle to exchange air;
s4, adding one third of mixed monomer raw materials into the reaction kettle for the first time, and stirring for 10 minutes to prepare monomer aqueous emulsion; adding a peroxide initiator solution with the concentration of 0.02% into the reaction kettle to initiate a first polymerization reaction; after the reaction starts, the temperature of the monomer aqueous emulsion is raised to 50-70 ℃ by the heat released by the polymerization reaction; after the first polymerization reaction is completed, the temperature of the water emulsion stops to rise, cooling water is introduced into a jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃;
s5, adding one third of mixed monomer raw materials into the reaction kettle for the second time, and stirring for 10 minutes; adding peroxide initiator solution with the concentration of 0.02% into the reaction kettle for the second time to initiate the second polymerization reaction; after the second polymerization reaction is completed, cooling water is introduced into the jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃;
s6, adding one third of mixed monomer raw materials into the reaction kettle for the third time, and stirring for 10 minutes; thirdly, adding a peroxide initiator solution with the concentration of 0.02% into the reaction kettle to initiate a third polymerization reaction;
s7, heating the rubber emulsion in the reaction kettle to 80 ℃ after the third polymerization reaction is completed, and preserving heat for 1 hour at 80 ℃;
s8, after heat preservation, the rubber emulsion is subjected to coagulation, colloidal particle cleaning and drying, and a rubber product is prepared.
In the above technical scheme, the rubber raw material component preferably comprises an epoxy type vulcanization point monomer raw material and a functional monomer raw material with low brittleness temperature or a basic acrylate monomer raw material, and an epoxy type vulcanization point monomer raw material and a functional monomer raw material with low brittleness temperature.
In the above technical scheme, preferably, the emulsification time in the step S2 is 10min, and the emulsification process is heated to 30-40 ℃.
In the above technical scheme, preferably, the polymerization reaction in S4, S5 and S6 is carried out at 30-70 ℃.
In the above technical solution, preferably, the peroxide is ammonium persulfate.
Compared with the prior art, the epoxy acrylate rubber with low brittleness temperature and the manufacturing method thereof provided by the invention have the following beneficial effects:
according to the invention, the low-brittleness temperature functional monomer raw materials for improving the low-temperature resistance of the rubber material are added or added in the traditional manufacturing method, the brittleness temperatures of different copolymers are different, and the copolymers of the low-brittleness temperature functional monomer raw materials have lower brittleness temperatures, so that compared with the rubber which is not added in the traditional manufacturing method, the low-temperature resistance of the finally manufactured rubber is improved, the application field of the acrylate rubber is wider, and the special use requirement on the low-temperature resistance of the rubber can be met.
Detailed Description
The epoxy acrylate rubber with low brittleness temperature provided by the embodiment of the invention comprises, by weight, 5 parts of epoxy vulcanization point monomer raw materials, 75-95 parts of low brittleness temperature functional monomer raw materials, 3 parts of emulsifying agent and 250 parts of deionized water.
In order to better implement the invention, in the present embodiment, the epoxy-type vulcanization point monomer raw material includes at least one of glycidyl acrylate, glycidyl methacrylate, and glycidyl acrylate; the epoxy type vulcanization point monomer raw material is used for realizing vulcanization processing in the rubber manufacturing process.
The low brittleness temperature functional monomer raw material comprises at least one of ethoxyethyl acrylate, 2-ethylhexyl acrylate, n-sunflower methacrylate, n-dodecyl methacrylate and cinnamyl methacrylate. The low brittleness temperature functional monomer material forms copolymer during rubber producing process, such as 2-ethylhexyl polyacrylate with brittleness temperature of-85 deg.c, and the brittleness temperature of the rubber product is lowered through adding the low brittleness temperature functional monomer material.
In order to better implement the present invention, in this embodiment, the base acrylate monomer raw material includes at least one of ethyl acrylate and methoxyethyl acrylate.
To better practice the invention, in this example, the emulsifier is sodium dodecyl sulfate.
To better practice the invention, this example also includes up to 20 parts of a base acrylate monomer feed.
The embodiment of the invention provides a manufacturing method of epoxy acrylate rubber with low brittleness temperature, which comprises the following steps:
s1, adding rubber raw material components into a mixing tank, and uniformly stirring and mixing to prepare mixed monomer raw materials; wherein the rubber raw material component comprises an epoxy type vulcanization point monomer raw material and a functional monomer raw material with low brittleness temperature or a basic acrylate monomer raw material, and an epoxy type vulcanization point monomer raw material and a functional monomer raw material with low brittleness temperature;
s2, adding deionized water and an emulsifying agent into a reaction kettle, and stirring to prepare an emulsion;
s3, introducing nitrogen into the reaction kettle to exchange air;
s4, adding one third of mixed monomer raw materials into the reaction kettle for the first time, and stirring for 10 minutes to prepare monomer aqueous emulsion; adding a peroxide initiator solution with the concentration of 0.02% into a reaction kettle to initiate a first polymerization reaction, wherein the first polymerization reaction is carried out at the temperature of 30-70 ℃; after the reaction starts, the temperature of the monomer aqueous emulsion is raised to 50-70 ℃ by the heat released by the polymerization reaction; after the first polymerization reaction is completed, the temperature of the water emulsion stops to rise, cooling water is introduced into a jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃;
s5, adding one third of mixed monomer raw materials into the reaction kettle for the second time, and stirring for 10 minutes; adding a peroxide initiator solution with the concentration of 0.02% into the reaction kettle for the second time to initiate a second polymerization reaction, wherein the second polymerization reaction is carried out at the temperature of 30-70 ℃; after the second polymerization reaction is completed, cooling water is introduced into the jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃; the second polymerization reaction is carried out so that the molecular weight of the polymer produced by the first polymerization reaction is increased;
s6, adding one third of mixed monomer raw materials into the reaction kettle for the third time, and stirring for 10 minutes; thirdly, adding a peroxide initiator solution with the concentration of 0.02 percent into the reaction kettle to initiate a third polymerization reaction, wherein the third polymerization reaction is carried out at the temperature of 30-70 ℃; the third polymerization reaction continues to increase the molecular weight of the polymer to achieve the expected target requirement;
s7, heating the rubber emulsion in the reaction kettle to 80 ℃ after the third polymerization reaction is finished, and preserving the heat at 80 ℃ for 1 hour, so that the residual monomer raw materials in the rubber emulsion can be ensured to be forcedly reacted at high temperature, and the residual monomer raw materials are reduced;
s8, after heat preservation, the rubber emulsion is subjected to coagulation, colloidal particle cleaning and drying, and a rubber product is prepared.
In order to better implement the invention, in the embodiment, the emulsification time in the step S2 is 10min, and the emulsification process is heated to 30-40 ℃.
To better practice the invention, in this example, the peroxide is ammonium persulfate.
Through the three batch polymerization reactions, the continuous increase of the molecular weight of the polymer is realized, the three feeds are more convenient for production operation compared with the one-time feeds, the one-time feeds have too high control requirement on the dripping speed, if the one-time feeds are improperly controlled, the temperature rise is too high or the polymerization reaction is interrupted, the three batch polymerization reactions are more convenient for controlling the reaction temperature, the polymerization reaction carried out among the whole monomer raw materials can be more sufficient, the residues of unreacted monomer raw materials are reduced, and the quality of rubber products is affected.
The chemical structural formula of the monomer raw material contains double bonds, under the action of free radicals of an initiator, the double bonds are opened to form crosslinking points, when the crosslinking points among acrylate monomers are mutually linked, macromolecular polymers are formed, polymer molecules are larger and larger in the reaction process until reaching a target value, and meanwhile, the functional monomer raw material with low brittleness temperature becomes a part of the polymers, so that the low temperature resistance of the formed rubber is improved.
Example 1
The epoxy acrylate rubber with low brittleness temperature provided by the embodiment of the invention comprises, by weight, 20 parts of a basic acrylate monomer raw material, 5 parts of an epoxy vulcanization point monomer raw material, 75 parts of a functional monomer raw material with low brittleness temperature, 3 parts of an emulsifier and 250 parts of deionized water.
Wherein the basic acrylic ester monomer raw material is 20 parts of ethyl acrylate;
the epoxy type vulcanizing point monomer raw material is 5 parts of glycidyl acrylate;
the functional monomer raw material with low brittleness temperature is 75 parts of 2-ethylhexyl acrylate;
the emulsifier is sodium dodecyl sulfate.
The embodiment of the invention provides a manufacturing method of epoxy acrylate rubber with low brittleness temperature, which comprises the following steps:
s1, adding 20 parts of ethyl acrylate, 5 parts of glycidyl acrylate and 75 parts of 2-ethylhexyl acrylate into a mixing tank, and uniformly stirring and mixing to prepare a mixed monomer raw material;
s2, adding deionized water and an emulsifying agent into a reaction kettle, and stirring to prepare an emulsion;
s3, introducing nitrogen into the reaction kettle to exchange air;
s4, adding one third of mixed monomer raw materials into the reaction kettle for the first time, and stirring for 10 minutes to prepare monomer aqueous emulsion; adding a peroxide initiator solution with the concentration of 0.02% into a reaction kettle to initiate a first polymerization reaction, wherein the first polymerization reaction is carried out at the temperature of 30-70 ℃; after the reaction starts, the temperature of the monomer aqueous emulsion is raised to 50-70 ℃ by the heat released by the polymerization reaction; after the first polymerization reaction is completed, the temperature of the water emulsion stops to rise, cooling water is introduced into a jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃;
s5, adding one third of mixed monomer raw materials into the reaction kettle for the second time, stirring for 10 minutes, and enabling the mixed monomer raw materials to enter into the micelle of the monomer water emulsion to form the micelle containing the polymer and the mixed monomer raw materials; adding a peroxide initiator solution with the concentration of 0.02% into the reaction kettle for the second time to initiate a second polymerization reaction, wherein the second polymerization reaction is carried out at the temperature of 30-70 ℃; after the second polymerization reaction is completed, cooling water is introduced into the jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃; the second polymerization reaction is carried out so that the molecular weight of the polymer produced by the first polymerization reaction is increased;
s6, adding one third of mixed monomer raw materials into the reaction kettle for the third time, and stirring for 10 minutes; thirdly, adding a peroxide initiator solution with the concentration of 0.02 percent into the reaction kettle to initiate a third polymerization reaction, wherein the third polymerization reaction is carried out at the temperature of 30-70 ℃; the third polymerization reaction continues to increase the molecular weight of the polymer to achieve the expected target requirement;
s7, heating the rubber emulsion in the reaction kettle to 80 ℃ after the third polymerization reaction is finished, and preserving the heat at 80 ℃ for 1 hour, so that the residual monomer raw materials in the rubber emulsion can be ensured to be forcedly reacted at high temperature, and the residual monomer raw materials are reduced;
s8, after heat preservation, the rubber emulsion is subjected to coagulation, colloidal particle cleaning and drying, and a rubber product is prepared.
In order to better implement the invention, in the embodiment, the emulsification time in the step S2 is 10min, and the emulsification process is heated to 30-40 ℃.
To better practice the invention, in this example, the peroxide is ammonium persulfate.
Example 2
The epoxy acrylate rubber with low brittleness temperature provided by the embodiment of the invention comprises, by weight, 10 parts of a basic acrylate monomer raw material, 5 parts of an epoxy vulcanization point monomer raw material, 85 parts of a functional monomer raw material with low brittleness temperature, 3 parts of an emulsifier and 250 parts of deionized water.
Wherein, the basic acrylic ester monomer raw material is 10 parts of methoxyethyl acrylate;
the epoxy type vulcanizing point monomer raw material is 5 parts of glycidyl acrylate;
the functional monomer raw material with low brittleness temperature is 85 parts of n-sunflower methacrylate;
the emulsifier is sodium dodecyl sulfate.
The method for producing the epoxy acrylate rubber with low brittleness temperature provided in example 2 of the present invention is the same as in example 1.
Example 3
The epoxy acrylate rubber with low brittleness temperature provided by the embodiment of the invention comprises, by weight, 5 parts of a basic acrylate monomer raw material, 5 parts of an epoxy vulcanization point monomer raw material, 90 parts of a functional monomer raw material with low brittleness temperature, 3 parts of an emulsifier and 250 parts of deionized water.
Wherein the basic acrylic ester monomer raw material is 5 parts of ethyl acrylate;
the epoxy type vulcanization point monomer raw material is 5 parts of glycidyl methacrylate;
the functional monomer raw material with low brittleness temperature is 90 parts of n-dodecyl methacrylate;
the emulsifier is sodium dodecyl sulfate.
The method for producing the epoxy acrylate rubber with low brittleness temperature according to example 3 of the present invention is the same as that of example 1.
Example 4
The epoxy acrylate rubber with low brittleness temperature provided by the embodiment of the invention comprises, by weight, 5 parts of a basic acrylate monomer raw material, 5 parts of an epoxy vulcanization point monomer raw material, 90 parts of a functional monomer raw material with low brittleness temperature, 3 parts of an emulsifier and 250 parts of deionized water.
Wherein the basic acrylic ester monomer raw material is 5 parts of ethyl acrylate;
the epoxy type vulcanization point monomer raw material is 5 parts of glycidyl methacrylate;
the functional monomer raw material with low brittleness temperature is 90 parts of cinnamyl methacrylate;
the emulsifier is sodium dodecyl sulfate.
The method for producing the epoxy acrylate rubber with low brittleness temperature according to example 4 of the present invention is the same as that of example 1.
Example 5
The epoxy acrylate rubber with low brittleness temperature provided by the embodiment of the invention comprises, by weight, 5 parts of epoxy vulcanization point monomer raw materials, 95 parts of low brittleness temperature functional monomer raw materials, 3 parts of emulsifying agent and 250 parts of deionized water.
Wherein, the raw material of the epoxy vulcanization point monomer is 5 parts of glycidyl methacrylate;
the functional monomer raw material with low brittleness temperature is 60 parts of ethoxyethyl acrylate and 35 parts of 2-ethylhexyl acrylate;
the emulsifier is sodium dodecyl sulfate.
The method for producing the epoxy acrylate rubber with low brittleness temperature according to example 5 of the present invention is the same as that of example 1.
In this example 5, the base acrylate monomer material was not added, and since the brittleness temperature of the polymer of ethyl acrylate was high, the brittleness temperature of the rubber was less advantageously lowered after the addition of ethyl acrylate. Although the latex coagulation time of the rubber produced is prolonged without adding the base acrylate monomer raw material, the low temperature resistance of the rubber and the use of the rubber are not affected as a whole.
In example 1, the amount of ethyl acrylate added was 20 parts as compared with example 5, because the brittleness temperature of the polymer of 2-ethylhexyl acrylate was-85℃and, after both were added to the rubber preparation raw material, the brittleness temperature of both examples 1 and 5 could reach about-50℃with a uniform brittleness temperature.
In order to ensure that the brittleness temperature meets the practical use situation of the rubber, but too low brittleness temperature can also have certain influence on other characteristics of the rubber, so that in the practical production process, the brittleness temperature value of the rubber can be adjusted by adding different monomer raw material components and monomer raw material types.
Comparative example 1
The adhesive comprises, by weight, 75 parts of ethyl acrylate as an acrylate monomer raw material, 20 parts of n-butyl acrylate, 5 parts of glycidyl methacrylate as an epoxy monomer raw material, 3 parts of an emulsifier and 250 parts of deionized water.
This comparative example 1 provides a method for producing an epoxy acrylate rubber in accordance with example 1.
Comparative example 2
The adhesive comprises, by weight, 45 parts of acrylic ester monomer raw materials, 25 parts of n-butyl acrylate, 25 parts of methoxyethyl acrylate, 5 parts of glycidyl methacrylate, 3 parts of emulsifying agent and 250 parts of deionized water.
This comparative example 2 provides a method for producing an epoxy acrylate rubber in accordance with example 1.
Brittle temperature performance tests were performed on examples 1 to 5 and comparative examples 1 to 2 as shown in Table 1.
TABLE 1
| Brittle temperature, DEG C | |
| Example 1 | -58 |
| Example 2 | -56 |
| Example 3 | -49 |
| Example 4 | -48 |
| Example 5 | -50 |
| Comparative example 1 | -21 |
| Comparative example 2 | -28 |
From Table 1, it can be seen that the rubbers prepared by adding the low brittleness temperature functional monomer materials for improving the low temperature resistance of the rubber materials in examples 1 to 5 have lower brittleness temperatures than the rubbers prepared in comparative examples 1 to 2, i.e., the low temperature resistance of the rubbers is improved.
In summary, the invention provides a low temperature resistant epoxy acrylate rubber and a manufacturing method thereof, which comprises the steps of adding or adding functional monomer raw materials with low brittleness temperature, mixing and stirring the rubber raw materials to prepare mixed monomer raw materials, heating emulsion prepared by mixing deionized water and an emulsifying agent to 30-40 ℃, adding one third of the mixed monomer raw materials into the emulsion under the condition of filling nitrogen to remove air in a reaction kettle, adding ammonium persulfate with the concentration of 0.02% to initiate a first polymerization reaction in the reaction kettle, and when the emulsion reaches the temperature of 50-70 ℃, indicating that the reaction is basically completed if the temperature does not continuously rise. The temperature of the emulsion is reduced to 35-40 ℃, one third of the mixed monomer raw materials are added for stirring and mixing for 10 minutes, and initiator solution with the concentration of 0.02% is added for the second time to initiate the second polymerization reaction, so that the molecular chain of the polymer grows up. Then, a third polymerization was initiated in the same manner. After the third polymerization reaction is finished, the temperature of the rubber emulsion is directly increased to 80 ℃ without reducing the temperature, the temperature is kept for 1 hour, residual monomers in the emulsion are forced to react at high temperature, the residual amount of monomer raw materials is reduced, the rubber product is prepared after the temperature is kept, the functional monomer raw materials with low brittleness temperature, epoxy vulcanization point monomer raw materials and basic acrylate monomer raw materials are polymerized to form a polymer, and the polymer is formed by the added functional monomer raw materials with low brittleness temperature for improving the low temperature resistance of the rubber material, so that the brittleness temperature of the rubber is reduced, and the low temperature resistance of the final rubber product is improved.
In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention. It will be apparent that the described embodiments are merely some, but not all, embodiments of the invention. Based on these embodiments, all other embodiments that may be obtained by one of ordinary skill in the art without inventive effort are within the scope of the invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art may still combine, add or delete features of the embodiments of the present invention or make other adjustments according to circumstances without any conflict, so as to obtain different technical solutions without substantially departing from the spirit of the present invention, which also falls within the scope of the present invention.
Claims (10)
1. The epoxy acrylate rubber with low brittleness temperature is characterized by comprising, by weight, 5 parts of epoxy vulcanization point monomer raw materials, 75-95 parts of low brittleness temperature functional monomer raw materials, 3 parts of emulsifying agents and 250 parts of deionized water.
2. The low brittleness temperature epoxy acrylate rubber according to claim 1, further comprising up to 20 parts of a base acrylate monomer raw material.
3. The low brittleness temperature epoxy acrylate rubber of claim 1, wherein said epoxy cure site monomer feed comprises at least one of glycidyl acrylate, glycidyl methacrylate, and glycidyl acrylate;
the low brittleness temperature functional monomer raw material comprises at least one of ethoxyethyl acrylate, 2-ethylhexyl acrylate, n-sunflower methacrylate, n-dodecyl methacrylate and cinnamyl methacrylate.
4. The low brittleness temperature epoxy acrylate rubber according to claim 2, wherein said base acrylate monomer raw material comprises at least one of ethyl acrylate and methoxyethyl acrylate.
5. The low brittleness temperature epoxy acrylate rubber according to claim 1, wherein said emulsifier is sodium dodecyl sulfate.
6. A process for producing the low-brittleness-temperature epoxy acrylate rubber according to any one of claims 1 to 5, comprising the steps of:
s1, adding rubber raw material components into a mixing tank, and uniformly stirring and mixing to prepare mixed monomer raw materials;
s2, adding deionized water and an emulsifying agent into a reaction kettle, and stirring to prepare an emulsion;
s3, introducing nitrogen into the reaction kettle to exchange air;
s4, adding one third of mixed monomer raw materials into the reaction kettle for the first time, and stirring for 10 minutes to prepare monomer aqueous emulsion; adding a peroxide initiator solution with the concentration of 0.02% into the reaction kettle to initiate a first polymerization reaction; after the reaction starts, the temperature of the monomer aqueous emulsion is raised to 50-70 ℃ by the heat released by the polymerization reaction; after the first polymerization reaction is completed, the temperature of the water emulsion stops to rise, cooling water is introduced into a jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃;
s5, adding one third of mixed monomer raw materials into the reaction kettle for the second time, and stirring for 10 minutes; adding peroxide initiator solution with the concentration of 0.02% into the reaction kettle for the second time to initiate the second polymerization reaction; after the second polymerization reaction is completed, cooling water is introduced into the jacket of the reaction kettle, and the temperature of the rubber emulsion is reduced to 35-40 ℃;
s6, adding one third of mixed monomer raw materials into the reaction kettle for the third time, and stirring for 10 minutes; thirdly, adding a peroxide initiator solution with the concentration of 0.02% into the reaction kettle to initiate a third polymerization reaction;
s7, heating the rubber emulsion in the reaction kettle to 80 ℃ after the third polymerization reaction is completed, and preserving heat for 1 hour at 80 ℃;
s8, after heat preservation, the rubber emulsion is subjected to coagulation, colloidal particle cleaning and drying, and a rubber product is prepared.
7. The method for producing an epoxy acrylate rubber having a low brittleness temperature according to claim 6 wherein said rubber raw material component comprises an epoxy cure site monomer raw material and a functional monomer raw material having a low brittleness temperature or a base acrylate monomer raw material, an epoxy cure site monomer raw material and a functional monomer raw material having a low brittleness temperature.
8. The method for producing an epoxy acrylate rubber having a low brittleness temperature according to claim 6, wherein the emulsification time in S2 is 10min and the emulsification process is raised to 30 to 40 ℃.
9. The method for producing an epoxy acrylate rubber having a low brittleness temperature according to claim 6, wherein the polymerization reaction in S4, S5, S6 is performed at 30 to 70 ℃.
10. The method for producing an epoxy acrylate rubber having a low brittleness temperature according to claim 6, wherein said peroxide is ammonium persulfate.
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