CN103289597A - Environment-friendly (methyl) acrylate modified rubber type adhesive and preparation process thereof - Google Patents
Environment-friendly (methyl) acrylate modified rubber type adhesive and preparation process thereof Download PDFInfo
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- CN103289597A CN103289597A CN2013102585208A CN201310258520A CN103289597A CN 103289597 A CN103289597 A CN 103289597A CN 2013102585208 A CN2013102585208 A CN 2013102585208A CN 201310258520 A CN201310258520 A CN 201310258520A CN 103289597 A CN103289597 A CN 103289597A
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- rubber
- tamanori
- methyl
- environment
- acrylate modified
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000853 adhesive Substances 0.000 title abstract description 8
- 230000001070 adhesive effect Effects 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 15
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 15
- 229920001194 natural rubber Polymers 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 17
- 239000004568 cement Substances 0.000 claims description 15
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000005061 synthetic rubber Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 150000001868 cobalt Chemical class 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- -1 zinc oxide metal oxides Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005270 abrasive blasting Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a preparation process and material composition of an environment-friendly (methyl) acrylate modified rubber type adhesive. A novel rubber-metal adhesive is prepared by carrying out reaction modification on high-molecule materials, such as natural rubber and the like, under the action of initiating agents, such as a hyperoxide and the like, by unsaturated carboxylic acid, such as acrylic acid and the like, or other polymerized monomers with second functional groups and substances, such as a metal oxide and the like which can be reacted with the polymerization monomers. The acrylate modified rubber type adhesive prepared through the process disclosed by the invention has the advantages of high adhesive strength, wide adhesive range, easiness and convenience for an adhesive process, no pollution of preparation and usage, and the like.
Description
Technical field
The preparation technology and the material that the present invention relates to a kind of environment-friendly type (methyl) acrylate modified rubber type tamanori are formed.
Background technology
Rubber and metal bind, comprehensively the high-modulus of the snappiness of rubber and metal; High performance rubber-metal composite members can be used for vehicle, boats and ships, machinofacture and aerospace field.
For rubber-metal composite products such as traditional rubber absorbers, reinforced seal parts, the indirect bonding method of the many employings of the bonding of metalwork and rubber.But this method has complex manufacturing, efficient is low, and environmental pollution is serious, and shortcoming such as bonding strength instability.
Directly the sulfuration adhesion process can partly be avoided above-mentioned shortcoming, as is widely used in the bonding system of radial tire undertread sizing material---Resorcinol/methylene radical donor/white carbon black system, and cobalt salt.But Resorcinol can distil when high-temperature mixing, contains the methylene radical donor of free formaldehyde, when mixing and be applied in the tire and also pollute the environment.For cobalt salt, there are three shortcomings.The one, dispersed bad in sizing material, if local content is excessive, can cause the generating rate of cuprous sulfide to be accelerated, and the resinifying reaction interval is spent deeply, cross-linking density is excessive, influences the cement properties of sizing material on the contrary.The 2nd, cobalt salt is a kind of pro-oxidant, and it can promote to wear out, and the cuprous layer of accelerated cure is degraded and caused bonding strength to descend.The 3rd, the cobalt salt price is higher, and price is very unstable.
In recent years, the metal-salt of acrylic or methacrylic acid is used to rubber-metal and binds promotor, and this auxiliary agent belongs to direct bonding method viscosity increaser, and is easy to use, but cement properties still remains to be improved.
Summary of the invention
The objective of the invention is a kind of novel (methyl) acrylate modified rubber type tamanori for the preparation of the rubber-metal bonding.With unsaturated carboxylic acids such as acrylic or methacrylic acid, the natural rubber (or synthetic rubber) that contains zinc oxide metal oxides such as (or) magnesium oxide, superoxide (as initiators such as dicumyl peroxides) and other rubber Synergist S-421 95 commonly used is carried out the reaction in modification, prepare a kind of free from extraneous odour, easy to store, outward appearance and the nondistinctive rubber unvulcanizate type of common rubber unvulcanizate tamanori, or further mix with benzene series, ketone system, oil system, ester series solvent or mixed solvent, prepare rubber cement type tamanori.Rubber unvulcanizate type tamanori can be used for directly vulcanizing adhesion process; Rubber cement type tamanori can be used for the indirect method adhesion process.The acrylate modified rubber type tamanori of the present invention's preparation has bonding strength height, bonding scope wide (can be used for the bonding of various metals and various rubber), adhesion process easy (directly bonding need not that metal is carried out sandblasting and can obtain high bonding strength), preparation, uses advantages such as pollution-free.
The present invention adopts following technical scheme to realize:
The first step, the component that will contain following four kinds of base substances mixes: 1. unsaturated carboxylic acid such as vinylformic acid or other have the polymerisable monomer 10-100 mass parts of second functional group, 2. metal oxide etc. can with 1. in the material 5-50 mass parts of monomer reaction, 3. initiator 0.5-5 mass parts such as superoxide, 4. macromolecular material such as natural rubber (gum or blend glue, contain the rubber unvulcanizate of other Synergist S-421 95 and latex or rubber cement) 100 mass parts.
Second step, said mixture to be handled, realization (methyl) acrylate is prepared a kind of new type rubber-metal-to-metal adhesive to the reaction modifying of macromolecular materials such as natural rubber.
Reaction principle of the present invention is: vinylformic acid, methacrylic acid (or other unsaturated carboxylic acid) and contain the rubber mix of metal oxide, superoxide after, can generate (methyl) acrylate, polymethyl acrylic acid, poly-methyl acrylate at a certain temperature, and when the vulcanization of rubber and rubber molecular chain react, simultaneously form firm surface adsorption with metal, thereby rubber and metal are sticked together.
What specify is:
1. the unsaturated carboxylic acids such as vinylformic acid in the above-mentioned the first step have the polymerisable monomer of second functional group except vinylformic acid, methacrylic acid also comprise other unsaturated carboxylic acid etc.
2. add in the rubber material with monomer reaction such as vinylformic acid in the above-mentioned the first step, be not limited to metal oxides such as zinc oxide, magnesium oxide, aluminum oxide, also comprise alkaline matters such as magnesium hydroxide, aluminium hydroxide.
3. the rubber in the above-mentioned the first step is not limited to natural rubber, also comprises macromolecular materials such as all synthetic rubber, thermoplastic elastomer and all performed polymers, monomer, latex, rubber cement that can polymerization.
4. be used in the above-mentioned the first step causing the material that modified monomer carries out polymerization, be not limited to superoxide, comprise that also other has the material that trigger monomer carries out polymerization.
5. the preparation technology in the above-mentioned the first step is not limited to earlier rubber and metal oxide, superoxide, other Synergist S-421 95 mixingly, and the process of reacting with vinylformic acid also comprises the process that above-mentioned five class materials are arranged in pairs or groups arbitrarily, mixed then.
6. mixing equipment and the technology in the above-mentioned the first step is not limited to equipment such as mill, Banbury mixer, screw extrusion press, high mixer, comprises that also all can mix raw-material equipment and technology in the above-mentioned the first step.
7. parking or thermal treatment in above-mentioned second step, the static state that is not limited under all temps is parked, and also comprises mold pressing under all temps, flows and process such as dynamic mechanically processing.
This tamanori can be used for directly sulfuration and binds, and also can be used as rubber cement and is used for the indirect method bonding.
The acrylate modified rubber type tamanori of the present invention's preparation has the following advantages:
1, bonding strength height: close with Chemlock, be better than other commercially available tamanori or viscosity increaser;
2, bonding scope is wide: can be used for the bonding of various metals and various rubber.
3, adhesion process is easy: can be used for directly sulfuration and bind, also can be used for indirect method and bind.Directly bind and need not to obtain high bonding strength to abrasive blasting.
4, prepare, use pollution-free: carry out airtight production, waste gas recovery during preparation, pollution-free substantially; All monomers polymerization during use, non-volatile gas.
Embodiment
The invention will be further described with embodiment below, and the present invention is not limited to this.
Embodiment 1
1. with the 100kg natural rubber, with 15kg zinc oxide, 2kg dicumyl peroxide, even by two roller mill mixings;
2. above-mentioned rubber unvulcanizate is processed into particulate state or other shape, mixes evenly with 35kg vinylformic acid then;
3. above-mentioned materials is placed in the encloses container, under 40-100 ℃, parked 24 hours, react completely to vinylformic acid and zinc oxide etc.;
4. above-mentioned materials is dried (40-100 ℃, 12-48 hour) or vacuum-drying (40-100 ℃, 2-12 hour), remove in the rubber unvulcanizate and may also reclaim by remaining vinylformic acid;
5. above-mentioned materials is even at the enterprising one-step melting of two roller mills, and be processed into sheet, particulate state, strip etc., the direct sulfuration that namely can be used for rubber and metal is binded.
6. with above-mentioned materials 100kg and toluene 30kg, ethyl acetate 125 kg, 120
#The mixed solvent that gasoline 125 kg form stirs, and mixes, and makes rubber cement, can be used for the metallic surface gluing, vulcanizes bonding with rubber then.
Rubber unvulcanizate type tamanori and the rubber cement type tamanori of present embodiment preparation are used for natural rubber and bind with not surface treated aluminium, 45# steel, stainless steel, and collapse mode is the natural rubber main body destruction.
Embodiment 2
1. with the 100kg natural rubber, with 15kg zinc oxide, 2kg dicumyl peroxide, mixing evenly by two roller mills or equipment such as Banbury mixer, screw extrusion press;
2. then on equipment such as mill, it is mixing evenly to add 40kg vinylformic acid in the above-mentioned materials, and above-mentioned rubber unvulcanizate is processed into particulate state, strip or other small size shape;
3. above-mentioned materials is placed in the encloses container, under 40-100 ℃, parked 24 hours, react completely to vinylformic acid and zinc oxide etc.;
4. above-mentioned materials is dried (40-100 ℃, 12-48 hour) or vacuum-drying (40-100 ℃, 2-12 hour), remove in the rubber unvulcanizate and may also reclaim by remaining vinylformic acid;
5. above-mentioned materials is even at the enterprising one-step melting of two roller mills, and be processed into sheet, particulate state, strip etc., the direct sulfuration that namely can be used for rubber and metal is binded.
6. above-mentioned materials 100kg and toluene 30kg, ethyl acetate 125 kg, 120# gasoline 125 kg are mixed, make rubber cement, can be used for the metallic surface gluing, vulcanize bonding with rubber.
Rubber unvulcanizate type tamanori and the rubber cement type tamanori of present embodiment preparation are used for natural rubber and bind with not surface treated aluminium, 45# steel, stainless steel, and collapse mode is the natural rubber main body destruction.
Embodiment 3
1. with the 100kg natural rubber, mixing evenly by two roller mills or equipment such as Banbury mixer, screw extrusion press with 15kg zinc oxide, 2kg dicumyl peroxide, and above-mentioned rubber unvulcanizate is processed into particulate state, strip or other small size shape;
2. above-mentioned materials 100kg and 45kg vinylformic acid and toluene 30kg, ethyl acetate 125 kg, 120# gasoline 125 kg are stirred to dissolving;
3. above-mentioned materials is placed in the encloses container, stirred 24 hours down at 40-100 ℃, react completely to vinylformic acid and zinc oxide etc.; Can be used for the metallic surface gluing, vulcanize bonding with rubber then.
The rubber cement type tamanori of present embodiment preparation is used for natural rubber and binds with not surface treated aluminium, 45# steel, stainless steel, and collapse mode is the natural rubber main body destruction.
Claims (9)
1. an environment-friendly type (methyl) acrylate modified rubber type tamanori, it is characterized in that, its prescription following (mass parts): 1. unsaturated carboxylic acid or other have the polymerisable monomer 10-100 mass parts of second functional group, 2. metal oxide or oxyhydroxide etc. can have the material 5-50 mass parts of the polymerisable monomer reaction of second functional group with above-mentioned unsaturated carboxylic acid or other, 3. initiator 0.5-5 mass parts such as superoxide, 4. rubber or other macromolecular material 100 mass parts.
2. a kind of environment-friendly type according to claim 1 (methyl) acrylate modified rubber type tamanori, it is characterized in that, described unsaturated carboxylic acid comprises vinylformic acid, methacrylic acid etc., and can with the polymerisable monomer with second functional group of described substance reaction in 2..
3. environment-friendly type according to claim 1 (methyl) acrylate modified rubber type tamanori, it is characterized in that: describedly can comprise metal oxides such as zinc oxide, magnesium oxide, aluminum oxide with the material that unsaturated carboxylic acid or other have a polymerisable monomer reaction of second functional group in 2., oxyhydroxide such as magnesium hydroxide, aluminium hydroxide, and can with the material of described monomer reaction in 1..
4. environment-friendly type according to claim 1 (methyl) acrylate modified rubber type tamanori, it is characterized in that: initiators such as described superoxide comprise dicumyl peroxide, benzoyl peroxide, and other can cause the material that described monomer in 1. carries out polyreaction.
5. environment-friendly type according to claim 1 (methyl) acrylate modified rubber type tamanori is characterized in that: the rubber that adopts or other macromolecular material comprise macromolecular materials such as natural rubber, all synthetic rubber, thermoplastic elastomer and all performed polymers, monomer, latex, rubber cement that can polymerization.
6. the preparation technology of environment-friendly type according to claim 1 (methyl) acrylate modified rubber type tamanori is characterized in that: employing method (1) or (2)
(1) earlier that elastomeric polymeric material and metal oxide, superoxide, other Synergist S-421 95 is mixing, react with unsaturated carboxylic acid then, make tamanori;
(2) above-mentioned formula materials is arranged in pairs or groups arbitrarily, mixed, and static state is at various temperatures parked or processes such as mold pressing and dynamic mechanically processing, makes tamanori.
7. the preparation technology of environment-friendly type according to claim 6 (methyl) acrylate modified rubber type tamanori, it is characterized in that: the tamanori that makes is rubber unvulcanizate type tamanori or rubber cement type tamanori.
8. the preparation technology of environment-friendly type according to claim 7 (methyl) acrylate modified rubber type tamanori, it is characterized in that: rubber unvulcanizate type tamanori comprises different shapes such as sheet, particulate state, strip.
9. the preparation technology of environment-friendly type according to claim 7 (methyl) acrylate modified rubber type tamanori is characterized in that: the solvent that rubber cement type tamanori adopts comprises that benzene series, ketone system, oil system, ester are equal solvent and mixed solvent thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310258520.8A CN103289597B (en) | 2013-06-26 | 2013-06-26 | A kind of environment-friendly type (methyl) acrylate-modified rubber-type adhesive and preparation technology |
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| CN201310258520.8A CN103289597B (en) | 2013-06-26 | 2013-06-26 | A kind of environment-friendly type (methyl) acrylate-modified rubber-type adhesive and preparation technology |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106432613A (en) * | 2015-08-10 | 2017-02-22 | 招远市鹏泰轮胎翻新有限公司 | Rubber cement used for modifying vulcanized rubber, and preparation method thereof |
| CN106752981A (en) * | 2016-12-06 | 2017-05-31 | 庄爱芹 | A kind of environment-friendly modified adhesive and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629239A (en) * | 2003-12-15 | 2005-06-22 | 韩国轮胎株式会社 | Adhesion rubber composition and adhesive thereof |
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2013
- 2013-06-26 CN CN201310258520.8A patent/CN103289597B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629239A (en) * | 2003-12-15 | 2005-06-22 | 韩国轮胎株式会社 | Adhesion rubber composition and adhesive thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106432613A (en) * | 2015-08-10 | 2017-02-22 | 招远市鹏泰轮胎翻新有限公司 | Rubber cement used for modifying vulcanized rubber, and preparation method thereof |
| CN106752981A (en) * | 2016-12-06 | 2017-05-31 | 庄爱芹 | A kind of environment-friendly modified adhesive and preparation method thereof |
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