CN104558613A - Method for synthesizing sulfur-containing silane copolymer with low VOC (volatile organic compounds) emission - Google Patents
Method for synthesizing sulfur-containing silane copolymer with low VOC (volatile organic compounds) emission Download PDFInfo
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Abstract
The invention relates to a method for synthesizing a sulfur-containing silane copolymer with low VOC (volatile organic compounds) emission, belonging to the field of silane coupling agent production. The method comprises the steps of based on 3-mercaptopropyltriethoxysilane and terminated sulfur-containing silane as raw materials, adding a small amount of hydrochloric acid catalyst, deionized water and a ethanol mixture according to a proportion under the stirring and heating conditions through adoption of a hydrolysis copolycondensation process to react; and after reaction, carrying out reduced pressure distillation at the distillation temperature of 60 DEG C under the vacuum of -0.09MPa to remove components having low boiling points from the reaction system, thereby obtaining the sulfur-containing silane copolymer product with low VOC emission. The method has the characteristics of simplicity, low production cost and good product stability, so the method is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of sulfuric silane multipolymer of low VOC discharge, belong to silane coupling agent production field.
Background technology
At present, in radial tyre production technology, white carbon black usage quantity in tyre wire belt adhesive glue formula is larger, to sizing material mixing, to extrude and the operation such as calendering brings serious processing problems, Mooney viscosity as rubber unvulcanizate is high, white carbon black bad dispersibility, sizing material heat-dissipating are fast, and it is mixing to need to carry out segmentation, this have impact on the performance of belt adhesive glue to a certain extent, adds the tooling cost of sizing material.
3-mercaptopropyltriethoxysilane is sulfuric silane, this type of coupling agent is mainly used in rubber and plastics industry for the treatment of mineral filler, its effect is better than vinyltriethoxysilane, but due to its bad smell and higher reactive behavior (-SH), use range is subject to certain restrictions in some fields.End-blocking sulfuric silane (3-Octanoylthio-1-propyl-triethoxysilicane) is as a kind of novel silane coupler product; the large tread glue formula of white carbon black consumption and steel wire adhesive formula can be applied to; effectively can reduce the mooney viscosity of sizing material when not carrying out any adjustment to original formulation, reduce mixing hop count, reduce the hysteresis loss of sizing material; overcoming with Si69 and Si75 for representing the incipient scorch phenomenon of silane coupling agent product in mixing middle appearance, the bond properties of sizing material and steel wire can also be improved simultaneously.
Along with people are more and more stronger to environmental protection consciousness, to volatile organic compounds (VOC) content in material, require low as far as possible or do not have.But, due to the triethoxy functional group in end-blocking sulfuric silane molecule there is intermolecular condensation when high temperature time, have the discharge of low molecule organic matter, be unfavorable for environmental protection.In addition, 3-mercaptopropyltriethoxysilane molecular weight, flash-point only has 88 DEG C, lower, therefore restricted to temperature in application process, and there is certain potential safety hazard.
Low in order to solve flash-point, and in application process, reduce the discharge of VOC, synthesis sulfuric silane multipolymer is best solution, compared with monomolecular sulfuric silane, this multipolymer is owing to being polymerized in advance, eliminate low molecule ethanol, improve molecular weight, boiling point and flash-point, there is following significant advantage:
(1) low volatilization, high flash point, applies safer;
(2) good stability, the shelf lives is longer;
(3) VOC quantity discharged is few, applies more environmental protection.
The synthetic method of the silane low polymer of current report is hydrolytie polycondensation technique, namely silane coupling agent is adopted to be raw material, under the conditions such as hydrocarbon solvent, catalyzer, heating, stirring, add a certain proportion of water to be hydrolyzed polycondensation, then carry out distilling out coproduct ethanol and hydrocarbon solvent, then neutralize, filter after obtain the silane low polymer product of certain polymerization degree.Its deficiency is complex process, and production cost is higher, is not suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is to: provide a kind of technique simple, production cost is low, be applicable to the synthetic method of the sulfuric silane multipolymer of the low VOC discharge of suitability for industrialized production.
Technical scheme of the present invention is:
A synthetic method for the sulfuric silane multipolymer of low VOC discharge, is characterized in that: it comprises the steps:
1), 3-mercaptopropyltriethoxysilane and end-blocking sulfuric silane are joined in the glass reaction flask with induction stirring, thermometer, oil bath heating and reflux exchanger, wherein oil bath computer heating control is at 30-100 DEG C, and reflux exchanger temperature of cooling water controls at 5-10 DEG C;
2) join in glass constant pressure funnel after, hydrochloric acid, deionized water and ethanol being mixed by the mass ratio of 1 ︰ 72 ︰ 400.
3), stirring is opened, induction stirring speed is set to per minute 80-300 and turns, be added drop-wise in flask by the mixture of hydrochloric acid, deionized water and ethanol under 30-100 DEG C of temperature condition and react, time for adding is 0.1-4 hour, drips rear continuation reaction 0.1-2 hour;
4), after completion of the reaction, product thick in glass reaction flask is carried out underpressure distillation, and distillation temperature controls, at 60 DEG C, vacuum tightness-0.09MPa, low boiling component in reaction mass to be taken off, must the sulfuric silane copolymer product of low VOC discharge, product appearance is light yellow clear liquid.
Sulfuric silane copolymer product chemical structural formula is:
The present invention compares the VOC quantity discharged of silane coupler containing sulfur in table one:
Table one:
As shown in Table 1, containing less volatility ethoxy group in oligopolymer, therefore, the reduction of VOC can reach more than 80%.The sharply minimizing of VOC discharge contributes to the disposal of pollutants controlling mixing process, can meet the demand of environmentally friendly type product.
The invention has the advantages that:
The present invention adopts 3-mercaptopropyltriethoxysilane and end-blocking sulfuric silane to be raw material, reacts with aqueous ethanol, and then underpressure distillation must the sulfuric silane multipolymer of low VOC discharge; Compare with synthetic technology with currently available products, patent of the present invention has the following advantages:
1, VOC quantity discharged reduces more than 80%, applies environmental protection more;
2, the oligopolymer obtained after prepolymerization, the shelf lives of product is longer;
3, flash-point is higher than 100 DEG C, uses safer;
4, with sulfuric silane and aqueous ethanol for raw material, single step reaction can obtain product, and technique is simple, and production cost is low, is applicable to suitability for industrialized production;
5, prior art needs to add the catalyzer such as metal complex or the vitriol oil, and be hydrolyzed reaction under hydrocarbon solvent exists, and needs neutralization, filtration treatment after having reacted; The present invention directly utilizes salt acid as catalyst, to be hydrolyzed polycondensation under ethanol exists, and not only technique is simple, and cost is lower, and does not bring metal ion into, product quality and security better.
Embodiment
Embodiment 1:
The 3-mercaptopropyltriethoxysilane of 536g, the end-blocking sulfuric silane of 1003g are joined together in the glass reaction flask of 3000ml with induction stirring, thermometer, oil bath heating and reflux exchanger; Wherein oil bath computer heating control is at 90 DEG C, and reflux exchanger temperature of cooling water controls at 10 DEG C; Then join in 500ml glass constant pressure funnel after 1g hydrochloric acid, 72g deionized water and 400g ethanol being mixed.Open and stir, arranging stirring velocity is per minute 300 turns, hydrochloric acid, deionized water and alcohol mixture is added drop-wise in flask and reacts, within 4 hours, dropwise, drip rear continuation reaction 2 hours under 60 DEG C of temperature condition.
After completion of the reaction, material in glass reaction flask is carried out underpressure distillation, distillation temperature arranges 60 DEG C, vacuum tightness setting-0.09MPa, low boiling component in reaction mass is taken off, obtain low VOC sulfuric silane copolymer product finished product 1225g, finished product is light yellow clear liquid, detects through rotational viscosimeter, the viscosity (25 DEG C) of finished product is 22cps, SiO
2content is 23.5%.
Embodiment 2:
The 3-mercaptopropyltriethoxysilane of 536g, the end-blocking sulfuric silane of 1003g are joined together in the glass reaction flask of 3000ml with induction stirring, thermometer, oil bath heating and reflux exchanger, wherein oil bath computer heating control is at 95 DEG C, and reflux exchanger temperature of cooling water controls 9 DEG C.Then join in 500ml glass constant pressure funnel after 1g hydrochloric acid, 72g deionized water and 400g ethanol being mixed.Open and stir, arranging stirring velocity is per minute 290 turns, hydrochloric acid, deionized water and alcohol mixture is added drop-wise in flask and reacts, within 3 hours, dropwise, drip rear continuation reaction 1.5 hours under 70 DEG C of temperature condition.
After completion of the reaction, material in glass reaction flask is carried out underpressure distillation, distillation temperature arranges 60 DEG C, vacuum tightness setting-0.09MPa, low boiling component in reaction mass is taken off, must low VOC sulfuric silane copolymer product finished product 1237g, finished product is light yellow clear liquid, detects through rotational viscosimeter, finished product viscosity (25 DEG C) is 23.4cps, SiO
2content is 23.9%.
Embodiment 3:
The 3-mercaptopropyltriethoxysilane of 536g, the end-blocking sulfuric silane of 1003g are joined together in the glass reaction flask of 3000ml with induction stirring, thermometer, oil bath heating and reflux exchanger, wherein oil bath computer heating control is at 100 DEG C, and reflux exchanger temperature of cooling water controls 8 DEG C.Then join in 500ml glass constant pressure funnel after 1g hydrochloric acid, 72g deionized water and 400g ethanol being mixed.Open and stir, arranging stirring velocity is per minute 250 turns, hydrochloric acid, deionized water and alcohol mixture is added drop-wise in flask and reacts, within 3.5 hours, dropwise, drip rear continuation reaction 1 hour under 90 DEG C of temperature condition.
After completion of the reaction, material in glass reaction flask is carried out underpressure distillation, distillation temperature arranges 60 DEG C, vacuum tightness setting-0.09MPa, low boiling component in reaction mass is taken off, must low VOC sulfuric silane copolymer product finished product 1228g, finished product is light yellow clear liquid, detects through rotational viscosimeter, the viscosity (25 DEG C) of finished product is 24cps, SiO
2content is 24.1%.
Claims (2)
1. a synthetic method for the sulfuric silane multipolymer of low VOC discharge, is characterized in that: it comprises the steps:
1), 3-mercaptopropyltriethoxysilane and end-blocking sulfuric silane are joined in the glass reaction flask with induction stirring, thermometer, oil bath heating and reflux exchanger, wherein oil bath computer heating control is at 30-100 DEG C, and reflux exchanger temperature of cooling water controls at 5-10 DEG C;
2) join in glass constant pressure funnel after, hydrochloric acid, deionized water and ethanol being mixed by the mass ratio of 1 ︰ 72 ︰ 400;
3), stirring is opened, induction stirring speed is set to per minute 80-300 and turns, be added drop-wise in flask by the mixture of hydrochloric acid, deionized water and ethanol under 30-100 DEG C of temperature condition and react, time for adding is 0.1-4 hour, drips rear continuation reaction 0.1-2 hour;
4), after completion of the reaction, product thick in glass reaction flask is carried out underpressure distillation, and distillation temperature controls, at 60 DEG C, vacuum tightness-0.09MPa, low boiling component in reaction mass to be taken off, must the sulfuric silane copolymer product of low VOC discharge, product appearance is light yellow clear liquid.
2. the synthetic method of the sulfuric silane multipolymer of a kind of low VOC discharge according to claim 1, is characterized in that: described sulfuric silane copolymer product chemical structural formula is:
Table one: the VOC theoretical discharge amount of silane coupler containing sulfur
Containing less volatility ethoxy group in oligopolymer, therefore, the reduction of VOC can reach more than 80%;
The sharply minimizing of VOC discharge contributes to the disposal of pollutants controlling mixing process, can meet the demand of environmentally friendly type product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037413A (en) * | 2015-08-07 | 2015-11-11 | 荆州市江汉精细化工有限公司 | Sulfur-containing silane copolymer and preparation method thereof |
| CN108609634A (en) * | 2018-06-07 | 2018-10-02 | 南京曙光精细化工有限公司 | Continuous production purifies the device of polysulfide silanes coupling agent by-product brine |
| CN114409901A (en) * | 2022-01-05 | 2022-04-29 | 湖北江瀚新材料股份有限公司 | Environment-friendly end-capped mercaptosilane and mercaptosilane copolymer and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037413A (en) * | 2015-08-07 | 2015-11-11 | 荆州市江汉精细化工有限公司 | Sulfur-containing silane copolymer and preparation method thereof |
| CN105037413B (en) * | 2015-08-07 | 2017-10-03 | 荆州市江汉精细化工有限公司 | A kind of sulfuric silane copolymer and preparation method thereof |
| CN108609634A (en) * | 2018-06-07 | 2018-10-02 | 南京曙光精细化工有限公司 | Continuous production purifies the device of polysulfide silanes coupling agent by-product brine |
| CN108609634B (en) * | 2018-06-07 | 2023-11-03 | 南京曙光新材料有限公司 | Device for purifying byproduct brine of polysulfide silane coupling agent in continuous production |
| CN114409901A (en) * | 2022-01-05 | 2022-04-29 | 湖北江瀚新材料股份有限公司 | Environment-friendly end-capped mercaptosilane and mercaptosilane copolymer and preparation method thereof |
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