CN103289597B - A kind of environment-friendly type (methyl) acrylate-modified rubber-type adhesive and preparation technology - Google Patents
A kind of environment-friendly type (methyl) acrylate-modified rubber-type adhesive and preparation technology Download PDFInfo
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Abstract
The present invention relates to preparation technology and the material composition of a kind of environment-friendly type (methyl) acrylate-modified rubber-type adhesive, with the unsaturated carboxylic acids such as acrylic acid or other there is the polymerisable monomer of the second functional group, metal-oxides etc. can be with the material of above-mentioned monomer reaction, under the effect of the initiators such as peroxide, the macromolecular materials such as natural rubber are carried out reaction modifying, a kind of new type rubber-metal-to-metal adhesive of preparation；Acrylate-modified rubber-type adhesive prepared by the present invention has bonding strength height, bonding scope is wide, adhesion process is easy, prepare, use the advantages such as pollution-free.
Description
Technical field
The present invention relates to preparation technology and the material composition of a kind of environment-friendly type (methyl) acrylate-modified rubber-type adhesive.
Background technology
Rubber binds with metal, it is possible to the high resiliency of comprehensive rubber and the high-modulus of metal；High performance rubber-metal composite members, may be used for vehicle, boats and ships, machine-building and aerospace field.
For rubber-metal composite articles such as traditional rubber absorbers, skeleton sealing elements, metalwork uses, with the bonding of rubber, method of indirectly binding more.But it is low that the method has complex manufacturing, efficiency, environmental pollution is serious, and the shortcoming such as bonding strength is unstable.
Directly sulfuration adhesion process can partly avoid disadvantages mentioned above, as being widely used in the bonding system of radial tire undertread sizing material---resorcinol/methylene donor/white carbon system, and cobalt salt.But resorcinol can distil when high-temperature mixing, the methylene donor containing free formaldehyde, when mixing and apply and also pollute the environment in tire.For cobalt salt, there are three shortcomings.One is poor dispersion in sizing material, if local content is excessive, the generating rate of cuprous sulfide can be caused to accelerate, and resinification reaction interval is spent deeply, crosslink density is excessive, affects the cement properties of sizing material on the contrary.Two be cobalt salt be a kind of pro-oxidant, it can promote aging, the degraded of accelerated cure cuprous layer and cause bonding strength to decline.Three is that cobalt salt price is higher, and price is the most unstable.
In recent years, the slaine of acrylic or methacrylic acid is used for rubber-metal adhesion promoters, and this auxiliary agent belongs to directly bonding method tackifier, easy to use, but cement properties still has much room for improvement.
Summary of the invention
It is an object of the invention to prepare one novel (methyl) the acrylate-modified rubber-type adhesive binded for rubber-metal.With unsaturated carboxylic acids such as acrylic or methacrylic acid, the natural rubber (or synthetic rubber) commonly using compounding ingredient containing zinc oxide metal-oxides such as (or) magnesium oxide, peroxide (such as initiators such as cumyl peroxides) and other rubber is carried out reaction in-situ modified, prepare a kind of free from extraneous odour, easy to store, outward appearance and the nondistinctive mixing glue-type adhesive of common elastomeric compound, or mix with benzene series, ketone system, petroleum, ester series solvent or mixed solvent further, prepare rubber cement type adhesive.Mixing glue-type adhesive, can be used for directly vulcanizing adhesion process；Rubber cement type adhesive, can be used for indirect method adhesion process.Acrylate-modified rubber-type adhesive prepared by the present invention has that bonding strength is high, bonding scope wide (can be used for the bonding of various metal and various rubber), adhesion process are easy (directly bonding can obtain high bonding strength without metal is carried out blasting treatment), prepare, use the advantages such as pollution-free.
The present invention adopts the following technical scheme that realization:
The first step, component mix homogeneously by containing following four kinds of base substances: 1. the unsaturated carboxylic acid such as acrylic acid or other there is the polymerisable monomer 10-100 mass parts of the second functional group, 2. metal-oxide etc. can be with the material 5-50 mass parts of 1. middle monomer reaction, 3. the initiator 0.5-5 mass parts such as peroxide, 4. the macromolecular material such as natural rubber (gum or Blend rubber, elastomeric compound containing other compounding ingredient, and latex or rubber cement) 100 mass parts.
Second step, processes said mixture, it is achieved (methyl) acrylates reaction modifying to macromolecular materials such as natural rubbers, prepares a kind of new type rubber-metal-to-metal adhesive.
The reaction principle of the present invention is: acrylic acid, methacrylic acid (or other unsaturated carboxylic acid) with containing metal-oxide, peroxide rubber mix after, (methyl) acrylates, polymethylacrylic acid, poly-methyl acrylate can be generated at a certain temperature, and react with rubber molecular chain when the vulcanization of rubber, form firm surface adsorption with metal simultaneously, thus rubber is sticked together with metal.
Special instruction:
The unsaturated carboxylic acids such as the acrylic acid in the most above-mentioned first step, except acrylic acid, methacrylic acid also include that other unsaturated carboxylic acid etc. has the polymerisable monomer of the second functional group.
The most above-mentioned first step adds the material with the monomer reaction such as acrylic acid in rubber, is not limited to the metal-oxides such as zinc oxide, magnesium oxide, aluminium oxide, also includes the alkaline matter such as magnesium hydroxide, aluminium hydroxide.
Rubber in the most above-mentioned first step, is not limited to natural rubber, also includes macromolecular material and all performed polymers, the monomer that can be polymerized, latex, the rubber cements such as all of synthetic rubber, thermoplastic elastomer (TPE).
For causing modified monomer to carry out the material being polymerized in the most above-mentioned first step, it is not limited to peroxide, also includes that other has the material that trigger monomer carries out being polymerized.
Preparation technology in the most above-mentioned first step is not limited to first that rubber and metal-oxide, peroxide, other compounding ingredient is mixing, the process then reacted with acrylic acid, also includes the process that above-mentioned five class materials are arbitrarily arranged in pairs or groups, mixed.
Mixing apparatus in the most above-mentioned first step and technique, be not limited to the equipment such as mill, banbury, screw extruder, high mixer, also includes all to mix raw-material equipment and technology in the above-mentioned first step.
Parking or heat treatment in the most above-mentioned second step, the static state being not limited at various temperature is parked, and also includes the processes such as the mold pressing at various temperature, flowing and dynamic mechanically processing.
This adhesive can be used for directly vulcanizing bonding, it is possible to binds for indirect method as rubber cement.
Acrylate-modified rubber-type adhesive prepared by the present invention has the advantage that
1, bonding strength is high: close with Chemlock, is better than other commercially available adhesive or tackifier；
2, scope is binded wide: can be used for the bonding of various metal and various rubber.
3, adhesion process is easy: can be used for directly vulcanizing bonding it can also be used to indirect method is binded.Directly bind without abrasive blasting can be obtained high bonding strength.
4, prepare, use pollution-free: carry out airtight production, waste gas recovery during preparation, the most pollution-free；During use, all monomers are the most aggregated, non-volatile gas.
Detailed description of the invention
By embodiment, the invention will be further described below, and the present invention is not limited to this.
Embodiment 1
1. by 100kg natural rubber, and 15kg zinc oxide, 2kg cumyl peroxide, mixing uniformly by two-roll mill；
2. above-mentioned elastomeric compound is processed into graininess or other shape, then mixes uniformly with 35kg acrylic acid；
3. above-mentioned material is placed in hermetic container, parks at 40-100 DEG C 24 hours, react completely with zinc oxide etc. to acrylic acid；
4. above-mentioned material carries out drying (40-100 DEG C, 12-48 hour) or vacuum drying (40-100 DEG C, 2-12 hour), and removing in elastomeric compound may remaining acrylic acid reclaiming；
5. above-mentioned material is uniform at the enterprising one-step melting of two-roll mill, and be processed into lamellar, graininess, strip etc., i.e. can be used for rubber and metal directly vulcanizes bonding.
6. by above-mentioned material 100kg and toluene 30kg, ethyl acetate 125 kg, 120#The mixed solvent of gasoline 125 kg composition is stirred, and mix homogeneously makes rubber cement, can be used for metal surface gluing, then carries out sulfuration with rubber and binds.
Mixing glue-type adhesive prepared by the present embodiment and rubber cement type adhesive, bind with the most surface treated aluminum, 45# steel, rustless steel for natural rubber, and failure mode is natural rubber main body destruction.
Embodiment 2
1. by 100kg natural rubber, and 15kg zinc oxide, 2kg cumyl peroxide, mixing uniformly by two-roll mill or the equipment such as banbury, screw extruder；
The most then, on the equipment such as mill, in above-mentioned material, addition 40kg acrylic acid is mixing uniformly, and above-mentioned elastomeric compound is processed into graininess, strip or other small size shape；
3. above-mentioned material is placed in hermetic container, parks at 40-100 DEG C 24 hours, react completely with zinc oxide etc. to acrylic acid；
4. above-mentioned material carries out drying (40-100 DEG C, 12-48 hour) or vacuum drying (40-100 DEG C, 2-12 hour), and removing in elastomeric compound may remaining acrylic acid reclaiming；
5. above-mentioned material is uniform at the enterprising one-step melting of two-roll mill, and be processed into lamellar, graininess, strip etc., i.e. can be used for rubber and metal directly vulcanizes bonding.
6. by above-mentioned material 100kg and toluene 30kg, ethyl acetate 125 kg, 120# gasoline 125
Kg mix homogeneously, makes rubber cement, can be used for metal surface gluing, carries out sulfuration with rubber and binds.
Mixing glue-type adhesive prepared by the present embodiment and rubber cement type adhesive, bind with the most surface treated aluminum, 45# steel, rustless steel for natural rubber, and failure mode is natural rubber main body destruction.
Embodiment 3
1. by 100kg natural rubber, and 15kg zinc oxide, 2kg cumyl peroxide, mixing uniformly by two-roll mill or the equipment such as banbury, screw extruder, and above-mentioned elastomeric compound is processed into graininess, strip or other small size shape；
2. above-mentioned material 100kg is extremely dissolved with 45kg acrylic acid and toluene 30kg, ethyl acetate 125 kg, 120# gasoline 125 kg stirring；
3. above-mentioned material is placed in hermetic container, stirs 24 hours at 40-100 DEG C, react completely with zinc oxide etc. to acrylic acid；Can be used for metal surface gluing, then carry out sulfuration with rubber and bind.
Rubber cement type adhesive prepared by the present embodiment, binds with the most surface treated aluminum, 45# steel, rustless steel for natural rubber, and failure mode is natural rubber main body destruction.
Claims (6)
1. environment-friendly type (methyl) acrylate-modified rubber-type adhesive, it is characterised in that its formula is as follows, in terms of mass parts: 1. (methyl) acrylic acid 35-100 mass parts, 2. metal-oxide 5-15 mass parts, 3. peroxide initiator 2-5 mass parts, 4. rubber 100 mass parts；
The preparation technology of described environment-friendly type (methyl) acrylate-modified rubber-type adhesive, comprises the following steps:
First that rubber and metal-oxide, peroxide is mixing, then react with (methyl) acrylic acid, prepare adhesive.
Environment-friendly type the most according to claim 1 (methyl) acrylate-modified rubber-type adhesive, it is characterised in that: described 2. middle metal-oxide is the one in zinc oxide, magnesium oxide, aluminium oxide.
Environment-friendly type the most according to claim 1 (methyl) acrylate-modified rubber-type adhesive, it is characterised in that: described peroxide initiator is the one of cumyl peroxide, benzoyl peroxide.
Environment-friendly type the most according to claim 1 (methyl) acrylate-modified rubber-type adhesive, it is characterised in that: the adhesive prepared is mixing glue-type adhesive or rubber cement type adhesive.
Environment-friendly type the most according to claim 1 (methyl) acrylate-modified rubber-type adhesive, it is characterised in that: mixing glue-type adhesive is lamellar, graininess or strip.
Environment-friendly type the most according to claim 1 (methyl) acrylate-modified rubber-type adhesive, it is characterised in that: the solvent that rubber cement type adhesive is used is benzene series, ketone system, petroleum, ester series solvent and mixed solvent thereof.
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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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| 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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| CN1629239A (en) * | 2003-12-15 | 2005-06-22 | 韩国轮胎株式会社 | Adhesion rubber composition and adhesive thereof |
Non-Patent Citations (4)
| Title |
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| (甲基)丙烯酸原位溶胀改性天然橡胶和硫化胶粉的研究;翟俊学;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20051015(第6期);第15、20页 * |
| 原位生成甲基丙烯酸锌增强天然橡胶的结构和性能;陈玉坤等;《合成橡胶工业》;20050831;第28卷(第4期);第288-289页 * |
| 原位生成甲基丙烯酸锌对天然橡胶补强的研究;陈玉坤等;《现代化工》;20050430;第25卷(第4期);第39-42页 * |
| 溶胀法制备甲基丙烯酸锌增强天然橡胶;翟俊学等;《合成橡胶工业》;20071031;第30卷(第5期);第378-381页 * |
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Effective date of registration: 20190318 Address after: 226133 No. 168 Linjiang Avenue, Linjiang New District, Haimen City, Nantong City, Jiangsu Province Patentee after: Jiangsu Silicon Age Material Technology Co., Ltd. Address before: 266061 Qingdao University of Science and Technology, 69 Songling Road, Laoshan District, Qingdao City, Shandong Province Patentee before: Qingdao University of Science & Technology |
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