CN105085981A - Rubber adhesion promoter and preparation method and application thereof - Google Patents
Rubber adhesion promoter and preparation method and application thereof Download PDFInfo
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- CN105085981A CN105085981A CN201410201617.XA CN201410201617A CN105085981A CN 105085981 A CN105085981 A CN 105085981A CN 201410201617 A CN201410201617 A CN 201410201617A CN 105085981 A CN105085981 A CN 105085981A
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Abstract
The present invention discloses a multifunction rubber adhesion promoter as shown in formula (I), and the multifunction rubber adhesion promoter comprises 15% to 25% of metal ions and 0% to 9% of resorcinol. The present invention also discloses a preparation method and application of the multifunction rubber adhesion promoter in rubber products, the multifunction rubber adhesion promoter has the methylene acceptor and cobalt salt adhesion promoter function during use in rubber and framework material bonding, the dosage is reduced, and efficiency is improved.
Description
Technical field
The present invention relates to the synthesis field of multi-functional adhesion promotor, be specifically related to a kind of rubber adhesion promotor and its preparation method and application.
Background technology
The material that current rubber industry is used for rubber and framework material bonding is generally the systems such as m-first-cobalt that Resorcinol or resorcinol resin and the organic acid such as new cobalt decanoate or cobalt naphthenate cobalt form or m-first-Bai-cobalt.Because Resorcinol easily distils, in use often in air, discharge a large amount of poisonous volatile matter, bring harm to environment and workers ' health.Although resorcinol resin reduces the vapour pressure of Resorcinol, not easily distil, this production of resins technical difficulty is comparatively large, and there are certain requirements equipment, cost is higher.The use of rubber industry cobalt salt is transitioned into organic acid cobalt from inorganic cobalt, traditional organic acid cobalt salt is mentioned more in technical patent in the past, such as: Chinese patent CN200310105264.5 propose use organic acid directly and cobaltous dihydroxycarbonate react the technique preparing cobalt salt.Chinese patent CN201110189532.0 puts forward to use the mixed fatty acid such as Yatall MA, stearic acid and cobaltous hydroxide to react the method preparing cobalt salt.Chinese patent CN200710013046.7 proposes a kind of capric acid, mixing valeric acid, mixing second propionic acid etc. of using and reacts with cobaltous hydroxide the method preparing cobalt salt mixture.Chinese patent CN201110145768.4 proposes and utilizes the saponified method preparing promoter for binding cobalt salt with cobalt salt solution replacement(metathesis)reaction of organic acid.It is the method for Material synthesis ready denier oil acid cobalt that Chinese patent CN200910235112.4 proposes with floating oil fatty acid.US Patent No. 5021522 describes a kind of synthetic method of modification resorcinol formaldehyde resin.Chinese patent CN1726254A proposes the synthetic method of the resorcinol formaldehyde resin of a kind of phenol or modified by alkyl phenol.More than inventing is all the preparations for synthesis organic acid cobalt or resorcinol resin etc. with single performance material.All simple function can only be embodied in rubber applications.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, provides a kind of new rubber adhesion promotor, its structure such as formula shown in (I),
In formula (I), R is Co salt, Ni salt, Zn salt etc.
Rubber adhesion promotor of the present invention, the content 15% ~ 25% of its metal ion comprised, Resorcinol content is 0% ~ 9%.
Metal ion described in rubber adhesion promotor of the present invention is Co salt, Ni salt or Zn salt, and preferably, described metal ion is Co.Rubber adhesion promotor of the present invention has two Resorcinol type structure, has the methylene receptor of resorcinol resin and the adhesion promotion function of metal-salt simultaneously.Wherein, described metal-salt comprises cobalt salt, nickel salt, zinc salt etc.Preferably, cobalt salt refers to wherein one or more such as Cobaltous diacetate, rose vitriol, cobalt chloride cobalt.
Rubber adhesion promotor of the present invention is a kind of bisphenol type metal-salt, i.e. Resorcinol shaped metal salt, does not in use distil, no blooming, and has the dual-use function of adhesion promotion and methylene receptor simultaneously.In this adhesion promotor, the existence of divalent metal (comprising divalence cobalt etc.) can promote the generation of transition layer on the framework materials such as steel wire cord, well for the bonding of rubber and framework material.The existence of Resorcinol type structure can be used as methylene receptor equally, improves the cross-linking density of rubber, forms interpenetrating(polymer)networks, the bounding force of Reinforced Rubber and framework material with rubber.Thus play the double effects that existing two kinds of raw materials just have, substitute Resorcinol and resin thereof and organic acid cobalt salt, reduce raw material dosage, reduce costs.
Present invention also offers the preparation method of rubber adhesion promotor, comprise the following steps:
Step (one): raw material Resorcinol and sodium methylate, sodium ethylate, Potassium ethanoate etc. react and generate Resorcinol list phenates;
Step (two): aforementioned Resorcinol list phenates and metal-salt continue to react, prepares described rubber adhesion promotor.Described metal-salt comprises metal organic salt or metal inorganic salt.Described metal refers to divalent metal, comprises cobalt, nickel, zinc etc.
In a specific embodiments, raw material Resorcinol and sodium methylate react, the process of preparation method of the present invention is: Resorcinol and sodium methylate are obtained by reacting Resorcinol list phenates in a solvent, this product continues the precipitation being obtained by reacting target product with cobalt salt in a solvent, and washing is dried to neutrality and namely obtains this product.Its reaction formula is:
Wherein, R is Co salt, Ni salt, Zn salt.
In step (), metal inorganic salt comprises plumbic acetate, cobaltous carbonate, rose vitriol, zinc chloride.Preferably, metal inorganic salt is acetate.Preferably, metal-salt is cobalt salt.Cobalt salt refers to wherein one or more such as Cobaltous diacetate, rose vitriol, cobalt chloride.
In step (), the mol ratio of raw material Resorcinol and sodium methylate, sodium ethylate or Potassium ethanoate etc. is 1: 1 ~ 1: 1.1.
In step (), solvent is wherein one or more such as methyl alcohol, ethanol, toluene, dimethylbenzene, DMF.
In step (), pH=7 ~ 9 of reaction system; Temperature of reaction is 70 ~ 110 degrees Celsius.
In step (two), the mol ratio of intermediate product Resorcinol list phenates and metal-salt is 2: 1 ~ 5: 1.Preferably, the mol ratio of intermediate product Resorcinol list phenates and cobalt salt is 2: 1 ~ 3: 1.
In step (two), temperature of reaction is 80 ~ 150 degrees Celsius.
Present invention also offers another synthetic route of the preparation method of formula (I) rubber adhesion promotor, comprise the following steps:
Wherein, R is Co salt, Ni salt, Zn salt etc.
Wherein, metal-salt comprises plumbic acetate, cobaltous carbonate, rose vitriol, zinc chloride.Preferably, metal inorganic salt is acetate.Preferably, metal-salt is cobalt salt.Cobalt salt refers to wherein one or more such as Cobaltous diacetate, rose vitriol, cobalt chloride.
Present invention also offers the intermediate product dihydroxy-benzene list phenates shown in a kind of formula (II),
In formula (II), R is Na ion, K ion etc.
Present invention also offers Multifunctional rubber adhesion promotor shown in formula (I) and prepare the application in rubber product.Adhesion promotor of the present invention has methylene receptor and promoter for binding cobalt salt function in the bonding of rubber and framework material simultaneously, thus realizes consumption and reduce, and efficiency improves.
One or more in Raw Resorcinol of the present invention and oxide compound, oxyhydroxide, organic acid salt react and generate single phenates, are then generated a kind of two Resorcinol type cobalt salt or both mixtures of ad hoc structure by replacement(metathesis)reaction.Compared with prior art, in use of the present invention not easily distil, no blooming.Reduce consumption, improve efficiency, decrease the impact of X factor.In prior art rubber industry, m-first-cobalt system that the normally resorcinol-formaldehyde resin bonded for rubber and framework material and cobalt salt form, but above-mentioned substance in use only has simple function.And the synthetic method of Resorcinol shaped metal salt that the present invention proposes, the material prepared can have methylene receptor and promoter for binding cobalt salt function in the bonding of rubber with framework material simultaneously, thus alternative original m-first-cobalt system.
Accompanying drawing explanation
The synthetic route schematic diagram of Fig. 1 preparation method of the present invention.
Another synthetic route schematic diagram of Fig. 2 preparation method of the present invention.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Embodiment 1:
In the 500mL four-hole boiling flask having nitrogen protection, add 110 grams of Resorcinols, anhydrous methanol 300 grams, be warming up to 70 degree and entirely moltenly start stirring, 27 grams of sodium methylates slowly add.Add rear backflow 10 minutes, stratification, elimination solvent also washs to pH=6.5 ~ 7.Add anhydrous tetrahydro furan 200 grams and be warming up to 100 degree, more slowly add the 140 grams of anhydrous cobaltous sulfates pulverized, add rear maintenance stirring 30 minutes, normal pressure is sloughed solvent to 120 and is spent beginning underpressure distillation.Residuum vacuum-drying, is cooled to room temperature under nitrogen protection, obtains 151.9 grams, reddish brown powder.Through qualification, product is red-brown powder, has phenyl ring charateristic avsorption band (1500cm-1,1600cm-1) and phenolic hydroxyl group charateristic avsorption band (3200cm-1) to exist through infrared test.Through ultimate analysis, C:51.0%, H:3.3%, Co:20.1%, the i.e. chemical structure of this product:
Embodiment 2:
In the 500mL four-hole boiling flask having nitrogen protection, add 55 grams of Resorcinols, anhydrous tetrahydro furan 100 grams, heat up and start stirring, slowly add Potassium ethanoate 25 grams, continue reaction 30 minutes, leave standstill adjustment pH=6.5 ~ 7.This intermediate product and 62.5 grams of nickel acetates continue to react, and after separating out in a large number to salt, suction filtration also washs three times with anhydrous methanol.Vacuum-drying 0.5 hour, is cooled to room temperature under nitrogen protection, obtains product about 75 grams.Through qualification, product is grey powder, has phenyl ring charateristic avsorption band (1500cm-1,1600cm-1) and phenolic hydroxyl group charateristic avsorption band (3200cm-1) to exist through infrared test.Through ultimate analysis, C:51.9%, H:3.5%, Co:21.1%, the i.e. chemical structure of this product:
Embodiment 3:
55 grams of Resorcinols are added, dehydrated alcohol 100mL in the 500mL four-hole boiling flask having nitrogen protection.Start stirring be warming up to 70 degree entirely molten, slowly add the 60 grams of Cobaltous diacetates pulverized.Add rear maintenance 0.5 hour.Add strong aqua 300mL, 80 degree of maintenances 5 hours, filtering-depositing to neutral by washing with alcohol, be cooled to room temperature gradually under nitrogen protection, obtain product 73 grams.Through qualification, product is red-brown powder, has phenyl ring charateristic avsorption band (1500cm-1,1600cm-1) and phenolic hydroxyl group charateristic avsorption band (3200cm-1) to exist through infrared test.Through ultimate analysis, C:51.0%, H:3.3%, Co:21.0%, the i.e. chemical structure of this product:
Embodiment 4:
55 grams of Resorcinols are added, dehydrated alcohol 100mL in the 500mL four-hole boiling flask having nitrogen protection.Start stirring be warming up to 70 degree entirely molten, slowly add the 46 grams of zinc acetates pulverized.Add rear maintenance 0.5 hour.Add strong aqua 300mL, 80 degree of maintenances 5 hours, filtering-depositing to neutral by washing with alcohol, be cooled to room temperature gradually under nitrogen protection, obtain product 77.3 grams.Through qualification, product is grey powder, has phenyl ring charateristic avsorption band (1500cm-1,1600cm-1) and phenolic hydroxyl group charateristic avsorption band (3200cm-1) to exist through infrared test.Through ultimate analysis, C:50.1%, H:3.5%, Co:20.3%, the i.e. chemical structure of this product:
Embodiment 5
Utilize the product of embodiment 1 ~ 4, according to following table 1, natural rubber 100 parts, N32655 part, certain hour of beginning to pratise on the machine of beginning to pratise after the unclassified stores such as zinc oxide add successively, formula 1 uses CN20.5%0.5 part, Resorcinol 3 parts, formula 2 ~ 5 uses synthetic sample respectively.Preparation rubber testing formula 1 ~ 5.
Table 1 rubber testing formula
Detect the hot air aging (100 DEG C of 24h) of formula 1 ~ 5, the results are shown in shown in following table 2.
Table 2 performance difference per-cent (%)
| Test item | Formula 1 | Formula 2 | Formula 3 | Formula 4 | Formula 5 |
| 10% is fixed secondary | 100 | 104 | 110 | 106 | 95 |
| 30% is fixed secondary | 100 | 99 | 105 | 104 | 97 |
| 50% is fixed secondary | 100 | 98 | 100 | 105 | 103 |
| 100% is fixed secondary | 100 | 98 | 98 | 105 | 109 |
| Tensile strength at yield | 100 | 105 | 96 | 98 | 99 |
| Pull apart Zhongchang rate | 100 | 106 | 100 | 105 | 97 |
| Hardness | 100 | 103 | 101 | 100 | 108 |
Table 2 illustrates using standard recipe 1 as Calculation Basis, and synthetic product adds has certain performance high compared with the test result of standard recipe respectively afterwards, other test events more suitable than performance with standard recipe (within 5% error).
Detect the vulcanization characteristics of the sizing material of formula 1 ~ 5, become instrument RheometerMDR2000 without rotor sulphur, testing conditions 160 DEG C of 30min, the results are shown in shown in following table 3.
Table 3 performance difference per-cent (%)
| Glue number | Formula 1 | Formula 2 | Formula 3 | Formula 4 | Formula 5 |
| ML | 100 | 98 | 97 | 99 | 100 |
| MH | 100 | 102 | 99 | 100 | 100 |
| T10 | 100 | 98 | 92 | 96 | 100 |
| T50 | 100 | 101 | 94 | 98 | 99 |
| T90 | 100 | 101 | 106 | 103 | 96 |
| TS1 | 100 | 102 | 101 | 102 | 98 |
| TS2 | 100 | 103 | 100 | 103 | 97 |
Table 3 illustrates that sintetics is little on curing time impact, and other indexs are suitable.
Detect the sizing material coke burning performance of formula 1 ~ 5, Scorch127 DEG C, the results are shown in shown in following table 4.
Table 4 performance difference per-cent (%)
| Glue number | Formula 1 | Formula 2 | Formula 3 | Formula 4 | Formula 5 |
| Initial | 100 | 96 | 96 | 94 | 107 |
| Ts2 | 100 | 103 | 103 | 100 | 102 |
| Ts3 | 100 | 102 | 102 | 96 | 107 |
| Ts5 | 100 | 103 | 103 | 98 | 109 |
| Ts35 | 100 | 103 | 103 | 101 | 110 |
Table 4 illustrates synthetics, and comparatively standard recipe time of scorch is slightly long, effectively can guarantee the security in Rubber processing.
Detect steel wire cord bond properties (N) cure conditions of formula 1 ~ 5: 160 DEG C × 30min; Steel cord specification: 3+9+15*0.22+1, the results are shown in shown in following table 5.
Table 5 performance difference per-cent (%)
Table 5 illustrates in formula 2, and synthesis material has better performance in steam aging, also has this type of to embody in other formulas.Other test indexs are suitable with standard recipe test result.
Above-described embodiment, just in order to technical conceive of the present invention and feature are described, its object is to one of ordinary skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.The change of every equivalence done by the essence of content of the present invention or modification, all should be encompassed in protection scope of the present invention.
Claims (11)
1. a rubber adhesion promotor, is characterized in that, its structure such as formula shown in (I),
In formula (I), R is Co salt, Ni salt, Zn salt.
2. rubber adhesion promotor as claimed in claim 1, it is characterized in that, the content 15% ~ 25% of its metal ion comprised, Resorcinol content is 0% ~ 9%.
3. rubber adhesion promotor as claimed in claim 2, it is characterized in that, described metal ion is Co salt, Ni salt or Zn salt.
4. a preparation method for rubber adhesion promotor, is characterized in that, described preparation method comprises the following steps:
Step (one): raw material Resorcinol and sodium methylate, sodium ethylate or Potassium ethanoate react in a solvent and generate Resorcinol list phenates;
Step (two): this Resorcinol list phenates and metal-salt continue to react, prepares rubber adhesion promotor as claimed in claim 1.
5. preparation method as claimed in claim 4, it is characterized in that, in described step (), the mol ratio of described raw material Resorcinol and sodium methylate, sodium ethylate or Potassium ethanoate is 1: 1 ~ 1: 1.1.
6. preparation method as claimed in claim 4, is characterized in that, in described step (), described solvent is methyl alcohol, ethanol, toluene, dimethylbenzene, DMF, THF etc. wherein one or more.
7. preparation method as claimed in claim 4, it is characterized in that, in described step (two), the mol ratio of described Resorcinol list phenates and metal-salt is 2: 1 ~ 5: 1.
8. preparation method as claimed in claim 4, it is characterized in that, pH=7 ~ 9 in described step (), temperature of reaction is 70 ~ 110 degrees Celsius; Temperature of reaction in described step (two) is 80 ~ 150 degrees Celsius.
9. a preparation method for rubber adhesion promotor, is characterized in that, described preparation method is: continue to add ammoniacal liquor after Resorcinol and reacting metal salt and react, washing precipitation obtains rubber adhesion promotor as claimed in claim 1; Wherein, described metal-salt is Co salt, Ni salt or Zn salt; The reaction process of described preparation method is:
Wherein, R is Co salt, Ni salt, Zn salt.
10. the intermediate product Resorcinol list phenates shown in formula (II), is characterized in that,
In formula (II), R is Na ion, K ion.
11. formulas (I) rubber adhesion promotor is preparing the application in rubber product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105348459A (en) * | 2015-12-11 | 2016-02-24 | 彤程化学（中国）有限公司 | Rosin-modified resorcinol formaldehyde resin and preparation method and application thereof |
| CN107459614A (en) * | 2017-08-28 | 2017-12-12 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| CN108102354A (en) * | 2017-12-29 | 2018-06-01 | 中南大学 | A kind of well lid anticorrosion material and preparation method thereof |
| CN109575837A (en) * | 2018-11-28 | 2019-04-05 | 江苏麒祥高新材料有限公司 | Acylated salt adhesion promoter of no cobalt composition metal boron and preparation method thereof, application |
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| CN1680247A (en) * | 2005-01-12 | 2005-10-12 | 浙江工业大学 | Preparation of hydroresorcinol |
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| CN1680247A (en) * | 2005-01-12 | 2005-10-12 | 浙江工业大学 | Preparation of hydroresorcinol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348459A (en) * | 2015-12-11 | 2016-02-24 | 彤程化学（中国）有限公司 | Rosin-modified resorcinol formaldehyde resin and preparation method and application thereof |
| CN107459614A (en) * | 2017-08-28 | 2017-12-12 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| CN108102354A (en) * | 2017-12-29 | 2018-06-01 | 中南大学 | A kind of well lid anticorrosion material and preparation method thereof |
| CN109575837A (en) * | 2018-11-28 | 2019-04-05 | 江苏麒祥高新材料有限公司 | Acylated salt adhesion promoter of no cobalt composition metal boron and preparation method thereof, application |
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