CN1834100A - Bisilane coupler contg. sulfur and nitrogen element and prepn. thereof - Google Patents
Bisilane coupler contg. sulfur and nitrogen element and prepn. thereof Download PDFInfo
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- CN1834100A CN1834100A CN 200510061528 CN200510061528A CN1834100A CN 1834100 A CN1834100 A CN 1834100A CN 200510061528 CN200510061528 CN 200510061528 CN 200510061528 A CN200510061528 A CN 200510061528A CN 1834100 A CN1834100 A CN 1834100A
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Abstract
This invention discloses a kind of sulphur- and nitrogen-containing silicone coupling reagent and its preparation method, that is, gamma-isocyanate propyl trialkoxyl silicane and dithiol compound react with each other at a mole ratio of 2:1 in organic solvent with the existence of organic catalyst. The mixture is then vacuum distilled to obtain a silicone coupling reagent that has two thiocarbamate units and six alkoxyls. This method has the advantages of simple technique flow, high yield and high practicability. The silicone coupling reagent based on this invention has good thermo stability and considerable coupling effect. It is a good substitution of conventional silicone coupling reagent and can be used in fumed silica-containing rubber so as to promote the comprehensive properties of vulcanized rubber.
Description
Technical field
The present invention relates to two silane coupling agents of a kind of sulfur-bearing and nitrogen element and preparation method thereof.
Background technology
Carbon black is widely used in comprising in the sizing material of tire as main strengthening agent, gives cross-linked rubber ideal mechanical property.Yet, only can not take into account or improve the wear resistance of tire tread glue, wet road surface traction property and rolling resistance simultaneously by changing carbon black grade and consumption.White carbon black has remarkable advantages aspect tread rubber wear resistance, wet road surface traction property and the rolling resistance as weighting agent taking into account, be used to the main strengthening agent of low-rolling-resistance of new generation, low oil consumption " green tire ", and the cross-linked rubber of superfine silicone dioxide reinforcement have advantages such as low-loss and the sliding property of moisture-proof.
The white carbon black particle surface contains a large amount of silanol bases, and the consistency between rubber is poor, and easily reunites in mixing process, thereby not surface treated white carbon black reinforcing effect is poor.The bifunctional silane coupling agent that contains element sulphur, as γ-mercaptopropyl trimethoxysilane, γ-thiocyanogen propyl-triethoxysilicane, two (the silica-based propyl group of 3-triethoxy) disulphide (TESPD) or two (the silica-based propyl group of 3-triethoxy) tetrasulfide (TESPT), when compounding rubber, can carry out surface modification to white carbon black, but the subparticipation vulcanization of rubber again when rubber-moulding makes the firm network structure of formation between white carbon black particle and the rubber matrix.
In tire tread glue, with white carbon black especially polymolecularity precipitated silica and coupling agent and usefulness, can improve tyre life (raising wear resistance) and security (raising anti-slippery) simultaneously, reduce fuel oil consumption (reduction rolling resistance).What tire industry used at present almost is silane coupler containing sulfur entirely, wherein multi-sulfur silane coupling agent TESPD and TESPT consumption maximum.In rubber mixing process, the multi-sulfur silane coupling agent needs long period and comparatively high temps fully to react with white carbon black.When melting temperature was higher than 160 ℃, the fracture of the polysulfidic bond of multi-sulfur silane coupling agent caused that sizing material incipient scorch, mooney viscosity increase, and are unfavorable for the dispersion of white carbon black particle in rubber.With the multi-sulfur silane acceptor modified white carbon black have also that mixing time is long, mixing hop count (3～6 sections) is many, the sizing material void content greatly, produce shortcoming such as substandard products because of incipient scorch.
At these problems of multi-sulfur silane coupling agent, Crompoton Osi company has developed silane coupling agent 3-capryloyl sulfo--1-propyl trimethoxy silicane (NXT)
Put on market in 2002.The tread rubber that NXT is used for the white carbon black filling can reduce compound viscosity, reduce mixing hop count, improve the sizing material processing characteristics, promote white carbon black to disperse, prolong sizing material time of scorch and shelf lives, reduce volatile content in the finished product, improve series of advantages (Joshi PG., Pickwell RJ. such as tread rubber ageing-resistant performance, Weller KJ., Hofstetter MH., Pohl ER., Stout ME., Osterholtz FD., Next-generation siliane coupling agent for silica/siliane reinforcement tire treadcompounds.Tire Tech.Int., 2002,80-84; Yan H., Sun K., Zhang Y., Zhang Y., FanY., Effects of silane coupling agents on the vulcanization characteristics of naturalrubber.J.Appl.Polym.Sci., 2004,94:1511-1518).
Summary of the invention
The purpose of this invention is to provide two silane coupling agents of a kind of sulfur-bearing and nitrogen element and preparation method thereof.
The molecular structural formula of two silane coupling agents of sulfur-bearing and nitrogen element is
R in the formula
1Be methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, R
2Be methyl or ethyl.
The preparation method of two silane coupling agents of sulfur-bearing and nitrogen element: γ-isocyanate group propyl trialkoxy silane is added in the organic solvent, be made into the solution that mass concentration is 5～20wt%, add mole number and be two mercaptan compounds of 0.5 times of γ-isocyanate group propyl trialkoxy silane, tertiary amine catalyst or the organotin catalysts that volumetric molar concentration is 0.5～15mmol/L, temperature of reaction is 40～100 ℃, under stirring and reflux conditions, react 5～24h, filtrate is carried out underpressure distillation remove low boiler cut, obtain the weak yellow liquid product.
In preparation method of the present invention:
γ-isocyanate group propyl trialkoxy silane is γ-isocyanate group propyl trimethoxy silicane or γ-isocyanate group propyl-triethoxysilicane; Two mercaptan compounds are 1,2-dimercaptopropane, 1,2-succinimide mercaptans, 1,2-pentane disulfide thioalcohol, 1,2-ethanthiol, 1,2-mercaptan in heptan two, 1, hot two mercaptan, 1 of 2-, 2-mercaptan in the ninth of the ten Heavenly Stems two or 1,2-mercaptan in the last of the ten Heavenly stems two; Organic solvent is benzene, toluene, ethylbenzene, n-proplbenzene, isopropyl benzene, o-Xylol, m-xylene or p-Xylol; Tertiary amine catalyst is triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethyl butylamine, N, N-diisopropylethylamine, N, accelerine, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine, N, N-Diethyl Aniline or dodecyl dimethyl amine; Organotin catalysts is tributyl stannic hydroxide, dibutyl tin acetate, dibutyl two butyric acid tin, dibutyl two caproic acid tin or dibutyl tin dilaurates.
Advantage of the present invention is:
1) under the effect of catalyzer, utilize the sulfydryl reaction of the isocyanate groups and two mercaptan compounds of γ-isocyanate group propyl trialkoxy silane, prepare two silane coupling agents of a kind of sulfur-bearing and nitrogen element, production technique is simple, productive rate height, product separate easily;
2) the two silane coupled agent molecule of sulfur-bearing and nitrogen element has 6 alkoxyl groups, coupling effect is obvious, and the carbonyl carbon-sulfide linkage in the molecule is stable, does not decompose substantially under the compounding rubber processing temperature, be difficult for causing the rubber incipient scorch, help the dispersion of white carbon black particle in rubber;
When 3) two silane coupling agents of sulfur-bearing and nitrogen element were used for the rubber of sulfur vulcanization, carbonyl carbon-sulfide linkage decomposed in the hot-forming process of rubber, and the free radical that is produced participates in the vulcanization of rubber, improved cross-linking density, improved mechanical properties of vulcanizate.
Embodiment
The present invention develops two silane coupling agents of a kind of sulfur-bearing and nitrogen element, and its molecule contains 2 thiocarbamate structural units and 6 alkoxyl groups.Except that the series of advantages with NXT, sulfur-bearing is stronger than NXT with thermostability with the coupling effect of two silane coupling agents of nitrogen element.When compounding rubber, the alkoxyl group of two silane coupling agents of sulfur-bearing and nitrogen element can play the surface modification effect to white carbon black, but the thiocarbamate structural unit do not decompose substantially, is difficult for causing the sizing material incipient scorch, helps the dispersion of white carbon black in rubber.In vulcanization of rubber process, carbonyl carbon-sulfide linkage ruptures in the thiocarbamate structural unit, the free radical that is produced participates in the vulcanization of rubber under the effect of vulcanizing agent and vulcanization accelerator, make the firm network structure of formation between white carbon black particle and the rubber matrix.
γ-isocyanate group propyl trialkoxy silane that the present invention uses is γ-isocyanate group propyl trimethoxy silicane or γ-isocyanate group propyl-triethoxysilicane.γ-isocyanate group propyl trimethoxy silicane and γ-isocyanate group propyl-triethoxysilicane can be selected from commercial silane coupling agent product, as buying the trade mark from U.S. Witco company is γ-isocyanate group propyl group trimethoxy silane of SilquestY-5187, and buying the trade mark from Japanese Shin-Etsu Chemial Co., Ltd is γ-isocyanate group propyl-triethoxysilicane of KBE-9007.
Two mercaptan compounds that use are 1,2-dimercaptopropane, 1,2-succinimide mercaptans, 1,2-pentane disulfide thioalcohol, 1,2-ethanthiol, 1,2-mercaptan in heptan two, 1, hot two mercaptan, 1 of 2-, 2-mercaptan in the ninth of the ten Heavenly Stems two or 1,2-mercaptan in the last of the ten Heavenly stems two.
The preparation of two silane coupling agents of sulfur-bearing and nitrogen element is to finish in a step, and γ-isocyanate group propyl trialkoxy silane and two mercaptan compounds were reacted in organic solvent in 2: 1 in molar ratio.Isocyanate groups is more active, at normal temperatures can with sulfhydryl compound generation chemical reaction, generate the Thiourethane compound.Under comparatively high temps, but adopt the catalyzer fast reaction speed.Suitable catalyzer can adopt tertiary amine compound (Dyer E., Glenn JF., The Kinetics of the reactions of phenyl isocyanate withcertain thiols.J.Am.Chem.Soc., 1957,79:366-369; Dyer E., Glenn JF., Lendrat EG., The kinetics of the reactions of phenyl isocyanate with thiols, J.Org.Chem., 1961,26:2919-2925), as triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethyl butylamine, N, N-diisopropylethylamine, N, accelerine, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine, N, N-Diethyl Aniline or dodecyl dimethyl amine.The inventor has found that, organotin (II) compound, as tributyl stannic hydroxide, dibutyl tin acetate, dibutyl two butyric acid tin, dibutyl two caproic acid tin or dibutyl tin laurates, also be the effective catalyst of γ-isocyanate group propyl trialkoxy silane and two mercaptan compounds reaction.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
With γ-isocyanate group propyl trimethoxy silicane, 1, the 2-dimercaptopropane is the method for two silane coupling agents of feedstock production sulfur-bearing and nitrogen element:
The adding of 7.80L benzene is equipped with in the reaction vessel of reflux condensing tube, agitator and thermometer, add 2mol (410g) γ-isocyanate group propyl trimethoxy silicane, being made into mass concentration is 5% solution, add 1mol (100g) 1,2-dimercaptopropane, 380mg triethylamine, controlled temperature are 40 ℃, under mechanical stirring and reflux conditions, react 24h, filtrate is carried out underpressure distillation remove low boiler cut, obtain the weak yellow liquid product, yield 75.6%.
Embodiment 2:
With γ-isocyanate group propyl-triethoxysilicane, 1, the 2-succinimide mercaptans is the method for two silane coupling agents of feedstock production sulfur-bearing and nitrogen element:
The adding of 99ml toluene is equipped with in the flask with three necks,round bottom of reflux condensing tube, agitator and thermometer, add 0.1mol (24.7g) γ-isocyanate group propyl-triethoxysilicane, being made into mass concentration is 20% solution, add 0.05mol (5.7g) 1,2-succinimide mercaptans, 280mg Tri-n-Propylamine, controlled temperature are 100 ℃, under mechanical stirring and reflux conditions, react 5h, filtrate is carried out underpressure distillation remove low boiler cut, obtain the weak yellow liquid product, yield 92.3%.
Embodiment 3:
With γ-isocyanate group propyl trimethoxy silicane, 1, the 2-pentane disulfide thioalcohol is the method for two silane coupling agents of feedstock production sulfur-bearing and nitrogen element:
The adding of 370ml ethylbenzene is equipped with in the flask with three necks,round bottom of reflux condensing tube, agitator and thermometer, add 0.2mol (41g) γ-isocyanate group propyl trimethoxy silicane, be made into mass concentration and be 10% solution, add 0.1mol (12.8g) 1,4-succinimide mercaptans, 130mg tributyl stannic hydroxide, controlled temperature is 80 ℃, under mechanical stirring and reflux conditions, react 15h, filtrate is carried out underpressure distillation remove low boiler cut, obtain the weak yellow liquid product, yield 84.7%.
Embodiment 4～8:
Respectively with 1,2-ethanthiol, 1,2-mercaptan in heptan two, 1, hot two mercaptan, 1 of 2-, 2-mercaptan in the ninth of the ten Heavenly Stems two or 1,2-mercaptan in the last of the ten Heavenly stems two replaces 1, the 2-succinimide mercaptans, two silane coupling agents of preparation sulfur-bearing and nitrogen element, all the other conditions are with embodiment 2.
Embodiment 9～13:
Replace toluene with n-proplbenzene, isopropyl benzene, o-Xylol, m-xylene or p-Xylol respectively, all the other conditions are with embodiment 2.
Embodiment 14～25
Respectively with tri-n-butylamine, N, N-dimethyl butylamine, N, N-diisopropylethylamine, N, accelerine, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine, N, N-Diethyl Aniline, dodecyl dimethyl amine, dibutyl tin acetate, dibutyl two butyric acid tin, dibutyl two caproic acid tin or dibutyl tin laurate replace the tributyl stannic hydroxide, and all the other conditions are with embodiment 3.
The invention provides two silane coupling agents of a kind of sulfur-bearing and nitrogen element and preparation method thereof.The preparation flow of two silane coupling agents of sulfur-bearing and nitrogen element is simple, the productive rate height, and product separates easily, is easy to promote.The two silane coupling agents that make based on the present invention have higher thermostability and stronger coupling effect, can replace the conventional silanes coupling agent, adopt known compounding process to add in the rubber combination that contains white carbon black, improve the over-all properties of cross-linked rubber.
Claims (7)
1. two silane coupling agents of sulfur-bearing and nitrogen element is characterized in that its molecular structural formula is
R in the formula
1Be methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, R
2Be methyl or ethyl.
2. the preparation method of two silane coupling agents of sulfur-bearing as claimed in claim 1 and nitrogen element, it is characterized in that, γ-isocyanate group propyl trialkoxy silane is added in the organic solvent, be made into the solution that mass concentration is 5～20wt%, add mole number and be two mercaptan compounds of 0.5 times of γ-isocyanate group propyl trialkoxy silane, volumetric molar concentration is tertiary amine catalyst or the organotin catalysts of 0.5～15mmol/L, temperature of reaction is 40～100 ℃, under stirring and reflux conditions, react 5～24h, filtrate is carried out underpressure distillation remove low boiler cut, obtain the weak yellow liquid product.
3. the preparation method of two silane coupling agents of a kind of sulfur-bearing according to claim 2 and nitrogen element, it is characterized in that described γ-isocyanate group propyl trialkoxy silane is γ-isocyanate group propyl trimethoxy silicane or γ-isocyanate group propyl-triethoxysilicane.
4. the preparation method of two silane coupling agents of a kind of sulfur-bearing according to claim 2 and nitrogen element, it is characterized in that, described two mercaptan compounds are 1,2-dimercaptopropane, 1,2-succinimide mercaptans, 1,2-pentane disulfide thioalcohol, 1,2-ethanthiol, 1,2-mercaptan in heptan two, 1, hot two mercaptan, 1 of 2-, 2-mercaptan in the ninth of the ten Heavenly Stems two or 1,2-mercaptan in the last of the ten Heavenly stems two.
5. the preparation method of two silane coupling agents of a kind of sulfur-bearing according to claim 2 and nitrogen element is characterized in that, described organic solvent is benzene, toluene, ethylbenzene, n-proplbenzene, isopropyl benzene, o-Xylol, m-xylene or p-Xylol.
6. the preparation method of two silane coupling agents of a kind of sulfur-bearing according to claim 2 and nitrogen element, it is characterized in that, described tertiary amine catalyst is triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethyl butylamine, N, N-diisopropylethylamine, N, accelerine, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine, N, N-Diethyl Aniline or dodecyl dimethyl amine.
7. the preparation method of two silane coupling agents of a kind of sulfur-bearing according to claim 2 and nitrogen element, it is characterized in that described organotin catalysts is tributyl stannic hydroxide, dibutyl tin acetate, dibutyl two butyric acid tin, dibutyl two caproic acid tin or dibutyl tin dilaurates.
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| JP2012240922A (en) * | 2011-05-16 | 2012-12-10 | Shin-Etsu Chemical Co Ltd | Organosilicon compound and method for producing the same, compounding agent for rubber, rubber composition, and tire |
| CN103254780A (en) * | 2013-04-08 | 2013-08-21 | 马鞍山拓锐金属表面技术有限公司 | Oilproof metal surface silane treatment agent and preparation method thereof |
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| CN111777874A (en) * | 2019-04-04 | 2020-10-16 | 深圳先进技术研究院 | Nano silicon dioxide and surface modification method thereof |
| CN112513166A (en) * | 2018-07-13 | 2021-03-16 | 大陆轮胎德国有限公司 | Sulfur-crosslinkable rubber mixture, vulcanized rubber and vehicle tire |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2199454T5 (en) * | 1997-08-21 | 2009-03-01 | Momentive Performance Materials Inc. | MERCAPTOSILANO COUPLING AGENTS BLOCKED FOR CAUCHOS WITH FILLING SUBSTANCE. |
| US6518335B2 (en) * | 2000-01-05 | 2003-02-11 | Crompton Corporation | Sulfur-containing silane coupling agents |
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- 2005-11-11 CN CNB2005100615280A patent/CN100387605C/en not_active Expired - Fee Related
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| CN103293904B (en) * | 2012-03-05 | 2017-03-01 | 富士施乐株式会社 | Roller member, charger, image processing system and handle box |
| CN103254780A (en) * | 2013-04-08 | 2013-08-21 | 马鞍山拓锐金属表面技术有限公司 | Oilproof metal surface silane treatment agent and preparation method thereof |
| CN103254781A (en) * | 2013-04-08 | 2013-08-21 | 马鞍山拓锐金属表面技术有限公司 | Metal surface silane treatment agent with high bending viscosity and preparation method thereof |
| CN103911861A (en) * | 2013-12-31 | 2014-07-09 | 上海宏和电子材料有限公司 | Electronic grade glass fiber cloth surface conditioning agent and silane coupling agent preparation method |
| CN103911861B (en) * | 2013-12-31 | 2016-01-13 | 上海宏和电子材料有限公司 | Electronic-grade glass fiber cloth surface conditioning agent and method |
| CN107022126B (en) * | 2017-04-25 | 2019-02-12 | 成都硅宝科技股份有限公司 | White carbon black filled rubber composite material and preparation method containing more sulfhydryl compounds |
| CN107022126A (en) * | 2017-04-25 | 2017-08-08 | 成都硅宝科技股份有限公司 | White carbon filled rubber composite containing many sulfhydryl compounds and preparation method thereof |
| CN112513166A (en) * | 2018-07-13 | 2021-03-16 | 大陆轮胎德国有限公司 | Sulfur-crosslinkable rubber mixture, vulcanized rubber and vehicle tire |
| CN112513166B (en) * | 2018-07-13 | 2023-03-17 | 大陆轮胎德国有限公司 | Sulfur-crosslinkable rubber mixture, vulcanized rubber and vehicle tire |
| US11739198B2 (en) | 2018-07-13 | 2023-08-29 | Continental Reifen Deutschland Gmbh | Sulfur-crosslinkable rubber mixture vulcanizate and vehicle tyre |
| CN108863865B (en) * | 2018-08-20 | 2020-08-11 | 铜仁学院 | Method for synthesizing butanedithiol |
| CN108863865A (en) * | 2018-08-20 | 2018-11-23 | 铜仁学院 | A kind of synthetic method of succinimide mercaptans |
| CN111777874A (en) * | 2019-04-04 | 2020-10-16 | 深圳先进技术研究院 | Nano silicon dioxide and surface modification method thereof |
| CN112662011A (en) * | 2020-12-09 | 2021-04-16 | 深圳先进技术研究院 | Modification method of silicon dioxide, silicon dioxide filler and epoxy resin composite material |
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