CN104194697A - Adhesive and preparation method thereof - Google Patents
Adhesive and preparation method thereof Download PDFInfo
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- CN104194697A CN104194697A CN201410386760.0A CN201410386760A CN104194697A CN 104194697 A CN104194697 A CN 104194697A CN 201410386760 A CN201410386760 A CN 201410386760A CN 104194697 A CN104194697 A CN 104194697A
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- mercaptobenzothiazole
- adhesive
- reaction
- tert
- tackiness agent
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Abstract
The invention relates to a methylene donor adhesive in an improved adhesive system between rubber and a copper-plated steel cord framework material. The adhesive is characterized by being prepared in a manner of adding 2,6-di-tert-butyl phenoxy-methylene mercaptobenzothiazole to participate into reaction in the process of etherification reaction on hexamethylol melamine and ethyl alcohol, wherein resin molecules contain thiazole heterocyclic structures and tertiary butyl groups. An experiment shows that the adhesive binding force between the rubber material and the copper-plated steel cord framework material is significantly improved by the resin.
Description
Technical field
The present invention relates between a kind of improved rubber and copper plated steel cord framework material methylene radical donor tackiness agent in binding system, the tackiness agent methylene radical donor that especially a kind of bounding force is strong.
Background technology
Due to the development of automobile industry, the working conditions of tire product is more and more harsher.Such as the high speed of automobile and the demand of heavy haul transport, proposed more and more higher technical requirements to the use properties of tire.Wherein the bond properties between rubber and copper plated steel cord framework material also needs constantly to improve, because this bond properties is vital for the use properties of tire.
The method that improves the bond properties between rubber and the copper plated steel cord framework material at present m-first-Bai binding system of main employing is mixed and reaches among elastomeric material.In decades, methyl-etherified aminoresin is main methylene radical donor in m-first-Bai binding system always.In order to improve the contribution to m-first-Bai binding system bond properties of tackiness agent, people are by having carried out multiple modification to tackiness agent, and hope can improve its bond properties.
Such as improving methyl-etherified technique, manage to improve the degree of etherification of tackiness agent.
CN101045711B discloses a kind of method of improved hexamethylolmelamine etherificate, has adopted the catalyzer of Manganse Dioxide as etherificate, has improved degree of etherification.
CN101696258B discloses a kind of method of improved hexamethylolmelamine etherificate, has adopted methylal to participate in the method for ethanol etherificate, has improved degree of etherification.
These improvement can improve the quality of tackiness agent to a certain extent, but do not obtain significant raising for the bond properties of binding system, especially for the bond properties between elastomeric material and Coppered Steel Wire framework material, do not obtain substantial progress.This binding system has been used more than 40 years so far from exploitation, and changes not quite with coordinating of material of main part, can not meet the requirement of tyre industry development.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, a kind of tackiness agent that can significantly improve the bond properties between elastomeric material and copper plated steel cord framework material is provided.
The present invention's the first object realizes, main improvement is to carry out in the technological process of methyl-etherified at hexamethylol melamine, add a certain amount of 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole participates in reaction, make part methylol and 2, the reaction of 6-di-tert-butyl oxygen methylene mercaptobenzothiazole accesses part di-tert-butyl oxygen methylene mercaptobenzothiazole group on the molecule of methyl-etherified aminoresin, obtains a kind of new tackiness agent.In this tackiness agent, existing azoles heterocyclic group has again tertiary butyl group, there is fabulous bond properties, the bounding force of the m-first-Bai tackiness agent forming with this tackiness agent is very strong, can significantly improve the bounding force between elastomeric material and copper plated steel cord framework material, test shows bonding strength, steel wire extraction power, is all improved significantly.
Of the present invention 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole is reacted and prepares with 2-chloro methyl mercapto benzothiazole by 2,6 di t butyl phenol sodium in solvent.
Because improve 2 of use, 6-di-tert-butyl oxygen methylene mercaptobenzothiazole only has the activity of reacting with methylol on 4 of di-t-butyl phenyl ring, therefore in reaction, can not generate superpolymer, the viscosity of gained resin can be unobvious, can not affect normal use.
A kind of tackiness agent, by hexamethylolmelamine and ethanol, undertaken in the process of etherification reaction, add 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole jointly participates in reaction and makes, hexamethylolmelamine and 2, and the mol ratio of 6-di-tert-butyl oxygen methylene mercaptobenzothiazole is 1: 2-1: 0.01, in the process of etherificate, add 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole jointly to participate in reaction, reaction conditions is that PH is less than 5.
Below in conjunction with several embodiments, further illustrate the present invention.
Embodiment
Embodiment 1: in 1000ml reaction flask, add hexamethylolmelamine 250g and ethanol 500g, dilute sulphuric acid with 50% is transferred to 3 by the pH value of material, stirring is warming up to 50 ℃, and keep 50 ℃ to react, when material becomes clear substantially, add the ethanolic soln containing 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole 50g, continue to keep temperature to stir 100 minutes.Add again sodium hydroxide neutralization, make the pH value of material reach 7.5-8.5.Continue stirring 10 minutes, then rising temperature reclamation ethanol starts vacuum system and also continues to heat up after temperature arrives 90 ℃, and while arriving 110 ℃, filtered while hot when continuation is cooled to 90 ℃ after stirring and being incubated 30 minutes, just obtains wanted product 366g.Wherein non-volatile matter 98.7%, viscosity 2600cps/25 ℃, colourity (APHA) 23.
Embodiment 2: in 1000ml reaction flask, add hexamethylolmelamine 250g and ethanol 500g, dilute sulphuric acid with 50% is transferred to 3 by the pH value of material, stirring is warming up to 50 ℃, and keep 50 ℃ to react, when material becomes clear substantially, add the ethanolic soln containing 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole 40g, continue to keep temperature to stir 100 minutes.Add sodium hydroxide neutralization, make the pH value of material reach 7.5-8.5.Continue stirring 10 minutes, then rising temperature reclamation ethanol starts vacuum system and also continues to heat up after temperature arrives 90 ℃, and while arriving 110 ℃, filtered while hot when continuation is cooled to 90 ℃ after stirring and being incubated 30 minutes, just obtains wanted product 355g.Wherein non-volatile matter 98.8%, viscosity 2700cps/25 ℃, colourity (APHA) 22.
Embodiment 3: in 1000ml reaction flask, add hexamethylolmelamine 250g and ethanol 500g, dilute sulphuric acid with 50% is transferred to 3 by the pH value of material, stirring is warming up to 50 ℃, and keep 50 ℃ to react, when material becomes clear substantially, add the ethanolic soln containing 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole 30g, continue to keep temperature to stir 100 minutes.Add sodium hydroxide neutralization, make the pH value of material reach 7.5-8.5.Continue stirring 10 minutes, then rising temperature reclamation ethanol starts vacuum system and also continues to heat up after temperature arrives 90 ℃, and while arriving 110 ℃, filtered while hot when continuation is cooled to 90 ℃ after stirring and being incubated 30 minutes, just obtains wanted product 345g.Wherein non-volatile matter 98.6%, viscosity 2700cps/25 ℃, colourity (APHA) 20.
Resin of the present invention compares with contrast and bonding strength, steel wire are extracted power out, is all improved, and three embodiment resin property mean values are compared with the performance of comparative example resin, and steel wire extraction power has improved 33.7%, and bonding strength has improved 14.0%.
Claims (2)
1. the preparation method of a tackiness agent, it is characterized in that being undertaken in the process of etherification reaction by hexamethylolmelamine and ethanol, add 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole jointly participates in reaction and makes, hexamethylolmelamine and 2, the mol ratio of 6-di-tert-butyl oxygen methylene mercaptobenzothiazole is 1: 2-1: 0.01, in the process of etherificate, add 2,6-di-tert-butyl oxygen methylene mercaptobenzothiazole participates in reaction jointly, and reaction conditions is that PH is less than 5.
2. the preparation method of tackiness agent according to claim 1, is characterized in that etherification temperature is 20-70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410386760.0A CN104194697A (en) | 2014-08-07 | 2014-08-07 | Adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410386760.0A CN104194697A (en) | 2014-08-07 | 2014-08-07 | Adhesive and preparation method thereof |
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| CN104194697A true CN104194697A (en) | 2014-12-10 |
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| CN201410386760.0A Pending CN104194697A (en) | 2014-08-07 | 2014-08-07 | Adhesive and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305608A (en) * | 2019-06-17 | 2019-10-08 | 江苏国立化工科技有限公司 | A kind of preparation method of the modified adhesive for Tire production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059234A (en) * | 2008-09-01 | 2010-03-18 | Yokohama Rubber Co Ltd:The | Rubber composition for coating steel cord |
| CN101817913A (en) * | 2010-03-11 | 2010-09-01 | 浙江奥仕化学有限公司 | Preparation method of highly methyl etherified amino resin |
| WO2013069359A1 (en) * | 2011-11-08 | 2013-05-16 | 住友ゴム工業株式会社 | Rubber composition for tire cord coating, breaker edge strip, breaker cushion or cord-adjoining strip, and pneumatic tire |
| CN103739803A (en) * | 2013-12-25 | 2014-04-23 | 重庆建峰浩康化工有限公司 | Synthesis method of imino methylated amino resin |
-
2014
- 2014-08-07 CN CN201410386760.0A patent/CN104194697A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059234A (en) * | 2008-09-01 | 2010-03-18 | Yokohama Rubber Co Ltd:The | Rubber composition for coating steel cord |
| CN101817913A (en) * | 2010-03-11 | 2010-09-01 | 浙江奥仕化学有限公司 | Preparation method of highly methyl etherified amino resin |
| WO2013069359A1 (en) * | 2011-11-08 | 2013-05-16 | 住友ゴム工業株式会社 | Rubber composition for tire cord coating, breaker edge strip, breaker cushion or cord-adjoining strip, and pneumatic tire |
| CN103739803A (en) * | 2013-12-25 | 2014-04-23 | 重庆建峰浩康化工有限公司 | Synthesis method of imino methylated amino resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305608A (en) * | 2019-06-17 | 2019-10-08 | 江苏国立化工科技有限公司 | A kind of preparation method of the modified adhesive for Tire production |
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Application publication date: 20141210 |