CN101445620A - Multi-functional rubber additive and method for preparing same - Google Patents
Multi-functional rubber additive and method for preparing same Download PDFInfo
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- CN101445620A CN101445620A CNA2008102203217A CN200810220321A CN101445620A CN 101445620 A CN101445620 A CN 101445620A CN A2008102203217 A CNA2008102203217 A CN A2008102203217A CN 200810220321 A CN200810220321 A CN 200810220321A CN 101445620 A CN101445620 A CN 101445620A
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Abstract
The invention provides a multi-functional rubber additive and a method for preparing same. The multi-functional rubber additive has an abovementioned molecular structural formula; wherein, the left side of the formula is provided with a benzothiazolyl radical; R1 is methylene, ethylidene or propylidene; R2 is cymene or ethyl; R3 is ethylidene, propylidene, methoxy or ethoxy. The preparation method comprises the steps as follows: 2-mercaptobenzothiazole (accelerant M) and alkali are dissolved in organic solvent; subsequently, chlorocarbon silane is added and reacts for 0.5-24 hours at the temperature of 20-120 DEG C under the mixing condition; the reaction products are filtrated, washed, and distilled by pressure-reduction so as to gain viscous liquid-shaped target products finally. The multi-functional rubber additive has multi-functions such as plasticizing, dispersing, promoting, reinforcing, and the like, simple preparation flow, high yield and simple separation process.
Description
Technical field
The present invention relates to the synthetic and filler reinforcement rubber materials of rubber ingredients, specifically be meant a kind of multifunctional rubber chemicals and preparation method.
Background technology
Rubber ingredients mainly comprise processing aid, promote vulcanizing agent, strengthening agent and anti-aging agent etc.Wherein processing aid comprises softening agent, dispersion agent, tenderizer and tackifier etc. again.In recent years, rubber ingredients develop to the high efficiency and multi-function direction, refer to that efficiently addition is few, and multipotency refers to that a kind of auxiliary agent has multiple function concurrently.Use multifunctional rubber chemicals, can reduce the cooperation component number in the prescription, to simplify prescription.The multi-functional of auxiliary agent can be realized by chemical synthesis process, promptly introduces multiple functional group in the auxiliary agent structure.As introduce carboxyl with tackify; Introduce alkyl and increase affine with rubber; Introduce hydroxyl so that reactive behavior and reinforcing effect to be provided.
Thiofide can impel the vulcanizing agent activation after being meant and adding rubber size, thereby the crosslinking reaction between accelerated cure agent and rubber molecule reaches the material that shortens curing time, reduces the curing temperature effect.Vulcanization accelerator comprises kinds such as thiazoles, sulfenamide, thiurams, dithiocarbamate(s), guanidine class, xanthogenic acid salt.The thiazole accelerator time of scorch is shorter, and vulcanization rate is slower.Thiurams, dithiocarbamate(s), guanidine class and secondary amine class sulphenamide react with airborne oxynitrides in the Rubber processing process, are easy to generate nitrosamine, with the DNA alkylation, have and finally bring out carcinogenic possibility.Replace secondary amine class (NOBS) with primary amine class sulphenamide (NS, TBSI etc.) in the rubber industry in recent years, but because its production technique is comparatively complicated, consumption is little at home.The developing direction of following promotor: 1. the exploitation vulcanization rate is fast, the efficient promotor that curing temperature is low, cured properties is good.2. time of scorch is long, operational safety, nontoxic, odorless, pollution-free green promotor.3. the multi-functional promotor of having both effects such as sulfuration, activation, promotion, anti-scorch and reinforcement.
Be extensive use of various fillers such as carbon black, white carbon black, potter's clay, lime carbonate, talcum powder, halloysite, magnesium hydroxide, aluminium hydroxide etc. in the rubber compounding, wherein carbon black, white carbon black etc. belong to the reinforcement filler, and potter's clay, lime carbonate, talcum powder, halloysite, magnesium hydroxide, aluminium hydroxide etc. belong to non-reinforcement filler.Studies show that the interaction of reinforcement filler and rubber cross network can improve the reinforcing effect of filler effectively.Even be non-reinforcement filler, through suitable surface modification make its with rubber network between form strong combining, also can produce the different strengthening action of degree.
Traditional rubber ingredients function singleness is difficult to satisfy the requirement of rubber industry.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, a kind of multifunctional rubber chemicals and preparation method thereof is provided.
The molecular structural formula of described multifunctional rubber chemicals is as follows:
The left side is the benzothiazole group in the formula, R
1Be methylene radical, ethylidene or propylidene, R
2Be methyl or ethyl, R
3Be methyl, ethyl, methoxy or ethoxy.
The preparation method of multifunctional rubber chemicals: 2-benzothiazolyl mercaptan joined to be made into mass concentration in the organic solvent be 5～30% solution; adding mole number is the alkali of 1～1.5 times of 2-benzothiazolyl mercaptan; adding mole number again is the chlorocarbon base silane of 1～1.5 times of 2-benzothiazolyl mercaptan; then under nitrogen protection 20～80 ℃ the reaction 0.5～24 hour; the sediment of the product that obtains is filtered; underpressure distillation obtains the aqueous product of thickness.
Among the preparation method of above-mentioned multifunctional rubber chemicals, described alkali is one or more mixtures in sodium methylate, sodium ethylate, the sodium hydroxide.Organic solvent is chloroform, ether, butyl ether, sherwood oil, ethanol, benzene, toluene, normal hexane or hexanaphthene.Chlorocarbon base silane compound is the chloromethyl Trimethoxy silane, β-chloroethyl Trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, chloromethyl-methyl-dimethylsilane, β-chloroethyl methyl dimethoxysilane, gamma-chloropropylmethyldimethoxysilane, chloromethyl ethyl dimethoxy silane, β-chloroethyl ethyl dimethoxy silane, γ-chloropropyl ethyl dimethoxy silane, the chloromethyl triethoxyl silane, β-chloroethyl triethoxyl silane, γ-chloropropyl triethoxysilane, the chloromethyl methyldiethoxysilane, β-chloroethyl methyldiethoxysilane, γ-chloropropyl methyldiethoxysilane, chloromethyl ethyl diethoxy silane, β-chloroethyl ethyl diethoxy silane or γ-chloropropyl ethyl diethoxy silane.
The present invention has synthesized and has had multi-functional above-mentioned new type rubber auxiliary agents such as integrating plasticising, dispersion, promotion, reinforcement.This multifunctional rubber chemicals can react with rubber molecular chain and filler simultaneously, improves reinforcing effect, improves the dispersion of filler in rubber matrix, improves the mechanical property and the dynamic properties of filler filling and vulcanization glue greatly.Multifunctional rubber chemicals can improve the processing characteristics of filler loaded compound, and has the promotion sulfuration, and time of scorch is long, operational safety, and vulcanization rate is fast, can improve the curability of sizing material greatly.Compared with prior art, the present invention also has following advantage:
1) utilizes 2-benzothiazolyl mercaptan and chlorocarbon base silane compound under nitrogen protection, to react, will promote that group takes in the molecular structure, thereby obtain having multi-functional rubber ingredients.
2) end of multifunctional rubber chemicals molecule has alkoxyl group, the surface hydroxyl generation alcoholysis reaction of fillers such as energy and white carbon black, clay, lime carbonate, halloysite, magnesium hydroxide in sulfidation, the benzothiazole sulfenyl of its other end has the sulfurized of promotion effect and while and rubber molecule chain reaction, make filler produce firm combining with rubber molecular chain, improve reinforcing effect, can also improve dynamic properties and other performances of cross-linked rubber.
3) benzothiazole sulphur-carbon bond is more stable in the multifunctional rubber chemicals molecule, does not decompose substantially under the compounding rubber processing temperature, is difficult for causing the rubber incipient scorch, and its time of scorch is long, and vulcanization rate is fast, can improve the curability of sizing material greatly.
4) multifunctional rubber chemicals can improve dispersion and the distribution of filler in rubber matrix, and rubber is had plastification, improves the processing characteristics of filler loaded compound greatly, reduces power consumption of polymer processing.
5) do not produce toxic substance in its building-up process of multifunctional rubber chemicals, it does not contain the secondary amine structure, and not generate nitrosamines in Rubber processing is green non-poisonous, can not cause environmental pollution.
6) preparation flow of multifunctional rubber chemicals provided by the invention is simple, the productive rate height, and separating technology is simple, is easy to promote.
Embodiment
Embodiment 1
Take by weighing 0.1mol (16.7g) 2-benzothiazolyl mercaptan and 250g toluene, place flask with three necks,round bottom, add the sodium methylate of 0.1mol (5.4g), stir, mixed solution is heated to 120 ℃, and from a side mouth of there-necked flask with 0.1m
3The speed of/h feeds nitrogen; again 0.1mol (28.86g) γ-chloropropyl triethoxysilane is joined in the above-mentioned solution; then under nitrogen protection 120 ℃ the reaction 18 hours; with the product that obtains; sediment is filtered; low boiler cut is removed in underpressure distillation, obtains the aqueous product of yellow thickness, yield 93.5%.
Resultant product is 3-benzothiazolethio-1-propyl group-triethoxyl silane, called after Silane-M.Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show that institute's synthetic product is target product Silane-M.
(unit: weight part), corresponding rubber unvulcanizate curing parameter sees Table 2 (phr in the table is a umber, i.e. the used amount of Silane-M in 100 parts the rubber) to see Table 1 with the basic recipe of the styrene-butadiene rubber(SBR)/white carbon black composite material of product S ilane-M preparation.From table 2, as seen, multifunctional rubber chemicals Silane-M is joined in the matrix material rubber unvulcanizate, obviously reduced sulfurizing time t
C90, the sizing material time of scorch then remains unchanged substantially, has the good characteristic that inductive phase is long, vulcanization rate is fast.And Silane-M has the plastifying effect, has improved the flowability of silica compound, makes minimal torque M
LReduce.
Table 3 is mechanical properties of styrene-butadiene rubber(SBR)/white carbon black composite material made from multifunctional rubber chemicals Silane-M.As can be seen, significantly improve, be significantly higher than the cross-linked rubber that does not add Silane-M, and permanentset and elongation at break are decreased with mechanical properties such as the stress at definite elongation of the matrix material of multifunctional rubber chemicals Silane-M preparation, tensile strength, tear strengths.Table 4 is the dynamic propertiess with the styrene-butadiene rubber(SBR)/white carbon black composite material of Silane-M preparation.Silane-M can improve the dynamic fatigue property and the wear resisting property of styrene-butadiene rubber(SBR)/white carbon black composite material greatly, improves the anti-slippery of styrene-butadiene rubber(SBR)/white carbon black composite material as tread rubber, reduces rolling resistance.
Table 1
Table 2
Table 3
Table 4
Embodiment 2
Take by weighing 1mol (167g) 2-benzothiazolyl mercaptan and 1.2kg ethanol; place stainless steel vessel; the sodium ethylate that adds 1.5mol (87g); stir; again 1.5mol (336.8g) γ-chloropropyl ethyl diethoxy silane is joined in the above-mentioned solution; then under nitrogen protection 60 ℃ the reaction 0.5 hour; with the product that obtains; sediment is filtered; low boiler cut is removed in underpressure distillation; obtain the aqueous product 3-benzothiazolethio of yellow thickness-1-propyl group-ethyl diethoxy silane, called after Silane-H, yield 76.2%.
Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show that institute's synthetic product is target product Silane-H.
The basic recipe of filling the butadiene-styrene rubber green compound with the white carbon black of product S ilane-H preparation sees Table 5, and (unit: weight part), the mooney viscosity of corresponding rubber unvulcanizate sees Table 6.As seen, multifunctional rubber chemicals Silane-H is joined white carbon black fill in the butadiene-styrene rubber rubber unvulcanizate from table 6, its compound viscosity sharply reduces, and improves the processing characteristics of sizing material greatly, reduces power consumption of polymer processing.
Table 5
Table 6
(unit: weight part), the mechanical property of corresponding matrix material sees Table 8 to see Table 7 with the basic recipe of the natural rubber/halloysite matrix material of product S ilane-H preparation.As seen, multifunctional rubber chemicals Silane-H is joined in natural rubber/halloysite matrix material from table 8, its stress at definite elongation, stretching and tear strength improve a lot.
Table 7
Table 8
Embodiment 3
Take by weighing 0.5mol (83.5g) 2-benzothiazolyl mercaptan and 0.2kg chloroform; place there-necked flask; the sodium hydroxide that adds 0.75mol (30g); be heated to 80 ℃; stir; and feeding nitrogen; again 0.5mol (85.25g) chloromethyl Trimethoxy silane is joined in the above-mentioned solution; then under nitrogen protection 80 ℃ the reaction 6 hours; with the product that obtains, sediment to be filtered, low boiler cut is removed in underpressure distillation; obtain yellow liquid product 3-benzothiazolethio methyltrimethoxy silane, yield 83.7%.
Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show that institute's synthetic product is a target product.
Embodiment 4
Take by weighing 0.2mol (33.4g) 2-benzothiazolyl mercaptan and 150g sherwood oil; place there-necked flask; the sodium hydroxide that adds 0.3mol (12g); stir; and feeding nitrogen; again 0.25mol (49.13g) chloropropyl ethyl dimethoxy silane is joined in the above-mentioned solution; under nitrogen protection, reacted 24 hours under the room temperature condition then; with the product that obtains; sediment is filtered; low boiler cut is removed in underpressure distillation, obtains yellow liquid product 3-benzothiazolethio-1-propyl group ethyl dimethoxy silane, yield 72.9%.
Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show that institute's synthetic product is a target product.
Embodiment 5～6
With 2-benzothiazolyl mercaptan, sodium hydroxide and chloropropyl ethyl dimethoxy silane is the method for feedstock production 3-benzothiazolethio-1-propyl group ethyl dimethoxy silane, may further comprise the steps:
With chloroform, ethanol is solvent, and all the other conditions are with embodiment 4.
Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show that institute's synthetic product is a target product.
Embodiment 7～8
2-benzothiazolyl mercaptan and chloromethyl Trimethoxy silane and β-chloroethyl methyldiethoxysilane prepares benzothiazolethio methyltrimethoxy silane and 2-[4-morpholinodithio thio-ethyl methyldiethoxysilane respectively, and all the other conditions are with embodiment 1.
Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show that institute's synthetic product is a target product.
Claims (5)
1, a kind of multifunctional rubber chemicals is characterized in that, it has following molecular structural formula:
The left side group is the benzothiazole group in the formula, R
1Be methylene radical, ethylidene or propylidene, R
2Be methyl or ethyl, R
3Be methyl, ethyl, methoxy or ethoxy.
2, the preparation method of the described a kind of multifunctional rubber chemicals of claim 1; it is characterized in that; 2-benzothiazolyl mercaptan joined to be made into mass concentration in the organic solvent be 5～30% solution; the adding mole number is equivalent to the alkali of 1～1.5 times of 2-benzothiazolyl mercaptan; add mole number again and be equivalent to the chlorocarbon base silane of 1～1.5 times of 2-benzothiazolyl mercaptan; then under nitrogen protection 20～120 ℃ the reaction 0.5～24 hour; sediment in the product that obtains is filtered; underpressure distillation; obtain the aqueous target product of thickness, promptly described multifunctional rubber chemicals.
3. the preparation method of a kind of multifunctional rubber chemicals according to claim 2 is characterized in that, described alkali is one or more mixtures in sodium hydroxide, sodium methylate, the sodium ethylate.
4, the preparation method of a kind of multifunctional rubber chemicals according to claim 2 is characterized in that, described organic solvent is chloroform, ether, butyl ether, sherwood oil, methyl alcohol, ethanol, benzene, toluene, normal hexane or hexanaphthene.
5, preparation method according to each described a kind of multifunctional rubber chemicals in the claim 2～4, it is characterized in that described chlorocarbon base silane compound is the chloromethyl Trimethoxy silane, β-chloroethyl Trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, chloromethyl-methyl-dimethylsilane, β-chloroethyl methyl dimethoxysilane, gamma-chloropropylmethyldimethoxysilane, chloromethyl ethyl dimethoxy silane, β-chloroethyl ethyl dimethoxy silane, γ-chloropropyl ethyl dimethoxy silane, the chloromethyl triethoxyl silane, β-chloroethyl triethoxyl silane, γ-chloropropyl triethoxysilane, the chloromethyl methyldiethoxysilane, β-chloroethyl methyldiethoxysilane, γ-chloropropyl methyldiethoxysilane, chloromethyl ethyl diethoxy silane, β-chloroethyl ethyl diethoxy silane or γ-chloropropyl ethyl diethoxy silane.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344462A (en) * | 2011-07-20 | 2012-02-08 | 江苏麒祥高新材料有限公司 | Low-volatility benzothiazolyl mercaptosilanes and preparation method thereof |
| CN104045664A (en) * | 2011-07-20 | 2014-09-17 | 江苏麒祥高新材料有限公司 | Benzothiazole thiol silane prepared from 2-thiol benzothiazole and chloropropyl triethoxysilane |
| CN105061808A (en) * | 2015-08-29 | 2015-11-18 | 江苏麒祥高新材料有限公司 | Rubber antioxidant preparing method |
| CN108101935A (en) * | 2017-12-29 | 2018-06-01 | 烟台大学 | Silane of one kind structure containing benzimidazole and preparation method thereof |
| CN108218911A (en) * | 2017-12-29 | 2018-06-29 | 烟台大学 | Silane of one kind structure containing benzothiazole and preparation method thereof |
| CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
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2008
- 2008-12-23 CN CNA2008102203217A patent/CN101445620A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344462A (en) * | 2011-07-20 | 2012-02-08 | 江苏麒祥高新材料有限公司 | Low-volatility benzothiazolyl mercaptosilanes and preparation method thereof |
| CN103923115A (en) * | 2011-07-20 | 2014-07-16 | 江苏麒祥高新材料有限公司 | Benzothiazole thiol silane prepared through 2-mercaptobenzothiazole and chloroethyl ethyl dimethyldiethoxylsilane and preparation method thereof |
| CN104045664A (en) * | 2011-07-20 | 2014-09-17 | 江苏麒祥高新材料有限公司 | Benzothiazole thiol silane prepared from 2-thiol benzothiazole and chloropropyl triethoxysilane |
| CN103923115B (en) * | 2011-07-20 | 2016-03-30 | 江苏麒祥高新材料有限公司 | Benzothiazole hydrosulphonyl silane prepared by 2-benzothiazolyl mercaptan and chloroethylethyl diethoxy silane and preparation method |
| CN104045664B (en) * | 2011-07-20 | 2016-07-06 | 江苏麒祥高新材料有限公司 | Benzothiazole hydrosulphonyl silane prepared by 2-benzothiazolyl mercaptan and chloropropyl triethoxysilane |
| CN105061808A (en) * | 2015-08-29 | 2015-11-18 | 江苏麒祥高新材料有限公司 | Rubber antioxidant preparing method |
| CN105061808B (en) * | 2015-08-29 | 2018-02-23 | 江苏麒祥高新材料有限公司 | A kind of preparation method of rubber antioxidant |
| CN108101935A (en) * | 2017-12-29 | 2018-06-01 | 烟台大学 | Silane of one kind structure containing benzimidazole and preparation method thereof |
| CN108218911A (en) * | 2017-12-29 | 2018-06-29 | 烟台大学 | Silane of one kind structure containing benzothiazole and preparation method thereof |
| CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
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