CN102585294B - Compound rubber bonding promoting agent and preparation method thereof - Google Patents
Compound rubber bonding promoting agent and preparation method thereof Download PDFInfo
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- CN102585294B CN102585294B CN 201210008913 CN201210008913A CN102585294B CN 102585294 B CN102585294 B CN 102585294B CN 201210008913 CN201210008913 CN 201210008913 CN 201210008913 A CN201210008913 A CN 201210008913A CN 102585294 B CN102585294 B CN 102585294B
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Abstract
The invention relates to a compound rubber bonding promoting agent and a preparation method thereof. The compound rubber bonding promoting agent consists of the following ingredients in parts by mass: 25 to 43 parts of cobalt salts, 25 to 40 parts of terephthalic acid metal salts, 5 to 8 parts of silane coupling agents, 25 to 35 parts of paraffin and 1 to 3 parts of stearic acid. The surface hydrophilicity of terephthalic acid metal salt powder becomes the surface lipophilicity after the treatment by activating agents of stearic acid, then, the silane coupling agents and the cobalt salts are added, the materials are uniformly mixed and stirred in a stirring kettle, the paraffin is finally added and is stirred for 10 to 15 minutes at 140 DEG C to 165 DEG C, and the compound rubber bonding promoting agent is prepared through granulation. The thickening agent has the advantages that the existence of transitional metal ions such as the cobalt salts is effectively reduced, meanwhile, active additives with stabilization and modification effects are also used, the bonding effect is not influenced, and meanwhile, the rubber-metal bonding stability can be effectively improved.
Description
Technical field
The present invention relates to a kind of compound rubber bound promotor and preparation method thereof.
Background technology
Strengthen rubber item industries such as travelling belt, Rubber Hose Braided With Steel Wire at all steel or semi-steel radial tire, steel wire, need elastomerics such as rubber and metallic framework material to have high-intensity bonding.Because steel wire cord has intensity height (can carry big portative power), modulus is higher, fatigue lifetime is long, low, the high especially many advantages of weather resistance of elongation.But because physics and chemical property change greatly, bonding between rubber and steel wire cord is very difficult.And this class rubber item in use, owing to operate under high temperature and high loading, will inevitably cause the aging of rubber, thereby make the separating of rubber and metallic framework material, and causes the tire delamination, quality phenomenon such as broken line in conveying belt or the sebific duct.
Improving the effective means of rubber-metal framework material bond strength is to add special Synergist S-421 95 in rubber, i.e. so-called adhesionpromoter.At present, the normal employing added cobalt salt as tackiness agent, with performances such as the long-term high-strength adhesive power that guarantees elastomerics such as rubber and metallic framework and high anti-aging, heat-resisting oxygen, moisture-proof, salt water resistance corrosion.
The actual tackifier that use mainly are the organic salt of variable valency metal at present, at first are organic cobalt salts.But use variable valency metal organic salt cost height on the one hand, negative impact is arranged on the other hand, when being higher than 0.1%～0.3% (in atoms metal) when the tackifier consumption, the catalyzed oxidation that can accelerate rubber matrix, the easy incipient scorch of sizing material, sulfide cross-linked bond is easily degraded.In addition, sulfur consumption must increase in the sizing compound formula that has increased tackifier, and the thermostability of cross-linked rubber is descended.
Technology contents
The technical problem to be solved in the present invention is that existing rubber bound promotor cost height, thickening property, thermostability are undesirable.The invention provides a kind of compound rubber bound promotor, these tackifier have namely effectively reduced the existence of variable valency metal ionses such as cobalt salt, used simultaneously the active additive with stable and modifying function again, when not influencing bond effect, can effectively improve the adhesion stability of rubber-metal.
The technical solution used in the present invention is:
A kind of compound rubber bound promotor is made up of the raw material of following mass parts: cobalt salt 25-43 part, terephthaldehyde's acid metal salt 25-40 part, silane coupling agent 5-8 part, paraffin 25-35 part, stearic acid 1-3 part.
Described cobalt salt is preferably one or more of cobalt boracylate, cobalt stearate, cobalt naphthenate, capric acid cobalt.
Described terephthaldehyde's acid metal salt is preferably one or more of terephthalic acid calcium, terephthalic acid magnesium, terephthalic acid zinc, potassium terephthalate, para-phthalic sodium, terephthalic acid barium, terephthalic acid aluminium, terephthalic acid iron.
Described silane coupling agent is preferably γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl methyl diethoxy γ base silane, two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, two (the silica-based propyl group of triethoxy) disulphide, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-aminopropyl methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, 17 fluorine decyl Trimethoxy silanes, 17 fluoro decyltrichlorosilanes, methyltrimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, one or more of vinyl trimethoxysilane oligomer.
The present invention at first carries out the activation of powder, and being about to becomes surperficial oleophylic after terephthalic acid metal-salt powder is handled by activated dose of stearic acid of surface hydrophilic.Concrete grammar activates 15-20min down in 200 ℃-300 ℃ afterwards for terephthaldehyde's acid metal salt and stearic acid are added mixing and stirring in the stirring tank jointly.Add silane coupling agent and cobalt salt again, in the stirring tank mixing and stirring, add paraffin at last, stir 10-15min down at 140 ℃-165 ℃, granulation makes.
The technique effect of the invention: effectively reduced the existence of variable valency metal ionses such as cobalt salt in the tackiness agent, therefore the catalyzed oxidation that can not accelerate rubber matrix uses this product gained sizing material to be difficult for incipient scorch.Simultaneously, owing to used the active additive with stable and modifying function, not only do not influence bond effect, also effectively improve the adhesion stability of rubber-metal.The present invention has improved the quality of product, has reduced user's production cost simultaneously.
Embodiment
Embodiment 1: 40 parts of terephthalic acid calcium and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 20min down in 300 ℃ afterwards.Add 5 parts of γ-r-chloropropyl trimethoxyl silanes and 25 parts of cobalt boracylates again, in the stirring tank mixing and stirring, add 27 parts of paraffin at last, stir 15min down at 150 ℃, granulation makes bind enhancer No. 1.
Embodiment 2: 25 parts of terephthalic acid magnesium and 2 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 15min down in 200 ℃ afterwards.Add 5 parts of γ-chloropropyl triethoxysilanes and 43 parts of cobalt stearates again, in the stirring tank mixing and stirring, add 25 parts of paraffin at last, stir 10min down at 140 ℃, granulation makes: No. 2 bind enhancers.
Embodiment 3: 25 parts of terephthalic acid zinc and 1 part of stearic acid are added the stirring tank mixing and stirring jointly, activate 15min down in 250 ℃ afterwards.Add 8 parts of gamma-chloropropylmethyldimethoxysilanes and 40 parts of cobalt naphthenates again, in the stirring tank mixing and stirring, add 26 parts of paraffin at last, stir 12min down at 165 ℃, granulation makes bind enhancer No. 3.
Embodiment 4: 30 parts of terephthalic acid iron and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 16min down in 200 ℃ afterwards.Add 5 parts of γ-chloropropyl methyl diethoxy γ base silane and 27 parts of capric acid cobalts again, in the stirring tank mixing and stirring, add 35 parts of paraffin at last, stir 11min down at 150 ℃, granulation makes bind enhancer No. 4.
Embodiment 5: 25 parts of terephthalic acid aluminium and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 20min down in 300 ℃ afterwards.Add 7 parts of two-(the silica-based propyl group of γ-triethoxy) tetrasulfide and 35 parts of cobalt boracylates again, in the stirring tank mixing and stirring, add 30 parts of paraffin at last, stir 15min down at 155 ℃, granulation makes bind enhancer No. 5.
Embodiment 6: 30 parts of potassium terephthalates and 2 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 15min down in 300 ℃ afterwards.Add 6 parts of two (the silica-based propyl group of triethoxy) disulphide and 30 parts of cobalt stearates again, in the stirring tank mixing and stirring, add 32 parts of paraffin at last, stir 10min down at 150 ℃, granulation makes bind enhancer No. 6.
Embodiment 7: 28 parts of para-phthalic sodiums and 1 part of stearic acid are added the stirring tank mixing and stirring jointly, activate 20min down in 300 ℃ afterwards.Add 8 parts of γ-mercaptopropyl trimethoxysilanes and 28 parts of cobalt naphthenates again, in the stirring tank mixing and stirring, add 35 parts of paraffin at last, stir 15min down at 160 ℃, granulation makes bind enhancer No. 7.
Embodiment 8: 27 parts of terephthalic acid barium and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 20min down in 200 ℃ afterwards.Add 7 parts of gamma-mercaptopropyltriethoxysilanes and 33 parts of capric acid cobalts again, in the stirring tank mixing and stirring, add 30 parts of paraffin at last, stir 10min down at 145 ℃, granulation makes bind enhancer No. 8.
Embodiment 9:40 part terephthalic acid calcium and 5 parts of γ-r-chloropropyl trimethoxyl silanes, 25 parts of cobalt boracylates in the stirring tank mixing and stirring, add 27 parts of paraffin at last, stir 15min down at 150 ℃, and granulation makes bind enhancer No. 9.
Embodiment 10: 40 parts of terephthalic acid calcium and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 20min down in 300 ℃ afterwards.Add 25 parts of cobalt boracylates again, in the stirring tank mixing and stirring, add 27 parts of paraffin at last, stir 15min down at 150 ℃, granulation makes bind enhancer No. 10.
Embodiment 11: 40 parts of terephthalic acid calcium and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly, activate 20min down in 300 ℃ afterwards.Add 5 parts of γ-r-chloropropyl trimethoxyl silanes again, in the stirring tank mixing and stirring, add 27 parts of paraffin at last, stir 15min down at 150 ℃, granulation makes bind enhancer No. 11.
Embodiment 12: with 3 parts of stearic acid, 5 parts of γ-r-chloropropyl trimethoxyl silanes and 25 parts of cobalt boracylates, in the stirring tank mixing and stirring, add 27 parts of paraffin at last, stir 15min down at 150 ℃, granulation makes bind enhancer No. 12.
Embodiment 13: 40 parts of phthalic acid calcium and 3 parts of stearic acid are added the stirring tank mixing and stirring jointly.Add 5 parts of γ-r-chloropropyl trimethoxyl silanes and 25 parts of cobalt boracylates again, in the stirring tank mixing and stirring, add 27 parts of paraffin at last, stir 15min down at 150 ℃, granulation makes bind enhancer No. 13.
Embodiment 14: add sizing material and various Synergist S-421 95 respectively by prescription in mill, it is mixing to mould white silk according to common process, and with the rubber unvulcanizate of last gained by the tabletting machine slice, be cut into the film of 100mm * 150mm, the gained mixed sheet vulcanizes at vulcanizing press, and curing temperature is 143 ℃.After being cooled to normal temperature.Film is applied certain pressure to it equably, carry out the film stripping test after parking 4h and 24h.
Sizing material is undertaken mixing by following proportioning, be mass parts:
100 parts of natural gums (NR);
20 parts of cis-butadiene cements (BR);
50 parts of butadiene-styrene rubbers (SBR);
Carbon black N33030 part;
Carbon black N66010 part;
5 parts in zinc oxide;
2.2 parts in sulphur (S);
1.0 parts of accelerator TBBSs;
5 parts of aromatic hydrocarbon oil;
5 parts of rubber adhesion promotors;
Wherein the 1-13 sizing material is respectively and has added the made sizing material of 1-13 bind enhancer in the sizing material; No. 14 sizing material bind enhancers all are cobalt boracylate; No. 15 sizing material does not add bind enhancer.
Cure test: measure 143 ℃ of temperature, 1 ° of rotor pivot angle, time 40min at vulkameter.The RlA of rubber unvulcanizate analyzes: mix frequency and the temperature scanning analysis that glitters glue at the RPA analyser, 100 ℃ of frequency sweeping experiment control temperature, frequency 0～1200ttz, temperature scanning experiment controlled frequency 100cDm, 40～160 ℃ of temperature.
Physical and mechanical properties: the detection of shore a hardness (adopting GB/T531-1999); The detection of 300% stress at definite elongation (adopting GB/T 8656); The detection of tensile strength and tensile yield (adopting GB/T 8656); The detection of tensile yield (adopting GB/T 8656); The detection of tension set (adopting GB/T7759-1996); The detection of tear strength (adopting GB/T529-2008); Detection (adopting GB/T 16586-1996) with the H extraction method cohesive strength of steel wire line.
Table 1
From the table as can be known, added the formulated rubber material vulkameter data of gained adhesionpromoter of the present invention in the test and do not added the gained sizing material and be more or less the same, illustrate and use gained rubber adhesion promotor of the present invention that the rubber vulcanization characteristic is had no adverse effect, use the extraction intensity of adhesionpromoter gained sizing material of the present invention and steel wire line obviously to improve, and strength property and extraction performance after aging also be improved, and can match in excellence or beauty with the rubber strength of whole employing organic cobalt salts as the tackiness agent gained.Behind long senile experiment, from stability factor as can be seen, the stability factor of gained adhesionpromoter of the present invention is higher, to the end properties of tire etc. and certain effect is arranged work-ing life.
Terephthaldehyde's acid metal salt of embodiment 9 is without the perstearic acid modification, embodiment 10 does not add silane coupling agent, embodiment 11 does not add cobalt salt, embodiment 12 does not add terephthaldehyde's acid metal salt, the terephthalic acid of embodiment 13 only is simple the mixing with stearic acid, terephthalic acid does not obtain effective modification, and table 1 result shows that embodiment 9-12 gained adhesionpromoter thickening property is undesirable, and stability is not good enough yet.
Be enlightenment with above-mentioned foundation desirable embodiment of the present invention, by above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification sheets, must determine its technical scope according to the claim scope.
Claims (6)
1. a compound rubber bound promotor is made up of the raw material of following mass parts: cobalt salt 25-43 part, terephthaldehyde's acid metal salt 25-40 part, silane coupling agent 5-8 part, paraffin 25-35 part, stearic acid 1-3 part.
2. the described compound rubber bound promotor of claim 1 is characterized in that cobalt salt is preferably one or more of cobalt boracylate, cobalt stearate, cobalt naphthenate, capric acid cobalt.
3. the described compound rubber bound promotor of claim 1 is characterized in that described terephthaldehyde's acid metal salt is preferably one or more of terephthalic acid calcium, terephthalic acid magnesium, terephthalic acid zinc, potassium terephthalate, para-phthalic sodium, terephthalic acid barium, terephthalic acid aluminium, terephthalic acid iron.
4. the described compound rubber bound promotor of claim 1, it is characterized in that silane coupling agent is preferably γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, gamma-chloropropylmethyldimethoxysilane, two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, two (the silica-based propyl group of triethoxy) disulphide, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-aminopropyl methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, 17 fluorine decyl Trimethoxy silanes, 17 fluoro decyltrichlorosilanes, methyltrimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, one or more of vinyl trimethoxysilane oligomer.
5. the preparation method of the described compound rubber bound promotor of claim 1, become surperficial oleophylic after it is characterized in that terephthalic acid metal-salt powder handled by activated dose of stearic acid of surface hydrophilic, add silane coupling agent and cobalt salt again, in the stirring tank mixing and stirring, add paraffin at last, stir 10-15min down at 140 ℃-165 ℃, granulation makes.
6. the preparation method of the described compound rubber bound promotor of claim 5, it is characterized in that becoming surperficial oleophylic concrete grammar after terephthalic acid metal-salt powder is handled by activated dose of stearic acid of surface hydrophilic is: terephthaldehyde's acid metal salt and stearic acid are added mixing and stirring in the stirring tank jointly, activate 15-20min down in 200 ℃-300 ℃ afterwards.
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| CN 201210008913 CN102585294B (en) | 2012-01-12 | 2012-01-12 | Compound rubber bonding promoting agent and preparation method thereof |
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| CN102585294B true CN102585294B (en) | 2013-08-14 |
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| CN103030838A (en) * | 2013-01-16 | 2013-04-10 | 江苏爱特恩高分子材料有限公司 | Silane coupling agent and preparation thereof |
| CN104311983B (en) * | 2014-10-28 | 2016-10-19 | 河北科技大学 | A kind of expansion plate with high adhesion force and controllable expansion ratio and preparation method thereof |
| CN110529671B (en) * | 2019-08-05 | 2020-06-19 | 大庆市普庆密封材料配件有限公司 | Carbon silica gel high-pressure steel wire woven hose for oil well |
| KR102652167B1 (en) * | 2019-09-11 | 2024-03-27 | 주식회사 엘지화학 | Method for preparing acrylic processing aid, acrylic processing aid produced by the method and vinyl chloride resin composition comprising the acrylic processig aid |
| KR102721861B1 (en) * | 2019-09-25 | 2024-10-23 | 주식회사 엘지화학 | Method for preparing core-shell copolymer, core-shell copolymer produced by the method and resin composition comprising the copolymer |
| CN119220198A (en) * | 2024-11-27 | 2024-12-31 | 朝阳市征和化工有限公司 | A method for preparing a cobalt salt type adhesion promoter |
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| GB9015150D0 (en) * | 1990-07-10 | 1990-08-29 | Manchem Ltd | Metal-organic composition |
| US5994434A (en) * | 1996-06-26 | 1999-11-30 | Bridgestone Corporation | Adhesion promoter composition and adherent rubber composition containing the same |
| CN100475827C (en) * | 2006-08-24 | 2009-04-08 | 朝阳市征和化工有限公司 | Method for preparing composite metal salt adhesion improver |
| CN101130674A (en) * | 2006-08-24 | 2008-02-27 | 朝阳市征和化工有限公司 | Adhesion promotion agent of composite metal stearate |
| CN101768287A (en) * | 2008-12-29 | 2010-07-07 | 冯星起 | Rubber adhesion accelerating agent |
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