CN104804032A - Solvent method synthetic process of Si-75 - Google Patents

Abstract

The invention relates to a solvent method synthetic process of Si-75. Si-75 can be used for radial tyres and other rubber products and belongs to the technical field of coupling agents. The solvent method synthetic process comprises the following steps: adding sodium sulfide containing nine crystal water and powdered sulfur into methylbenzene, heating, dewatering, cooling, adding gamma-chloropropyl triethoxysilane and absolute ethyl alcohol, then adding ethylene glycol diethyl ether, heating, after the reaction, cooling to the room temperature, filtering inorganic salt and impurities for industrial salt application, transferring filtrate to a distiller, distilling solvent and foreshot under reduced pressure for recycling, and performing distillation to obtain the Si-75 when the vacuum degree is greater than or equal to 0.090 Mpa and the temperature is greater than or equal to 150 DEG C, wherein the molar ratio of the sodium sulfide to the powdered sulfur is 1:1, the weight ratio of the methylbenzene to the sodium sulfide is 1.6-2, the weight ratio of the gamma-chloropropyl triethoxysilane to the sodium sulfide is 2.00-2.06, the weight ratio of the absolute ethyl alcohol to the absolute ethyl alcohol is 1:1, and the weight ratio of the ethylene glycol diethyl ether to the methylbenzene is 0.3-0.6.

Description

A kind of curing is two-the solvent method synthesis technique of (γ-propyl-triethoxysilicane)

Technical field

The present invention relates to a kind of curing two-the solvent method synthesis technique of (γ-propyl-triethoxysilicane), curing is two-(γ-propyl-triethoxysilicane) can be used for, in radial tyre and other rubber item, belonging to coupling agent technical field.

Background technology

Curing is two-(γ-propyl-triethoxysilicane) trade name: and silicon-75 (Si-75) is a kind of multi-functional silane coupling agent that success uses in rubber industry, its application makes the physical and mechanical property of rubber improve, tensile strength, tearing toughness, wear resisting property, resistance to bending all can be improved significantly around be full of cracks performance etc., and permanent modification is minimized.Can also compound viscosity be reduced because it is more easily dispersed in rubber and plastic, improve processing characteristics.Being specially adapted to take silicon compound as the vulcanized rubber system of strengthening agent, and its filler be suitable for comprises carbon black, white carbon black, talcum powder, clay, mica powder, potter's clay etc.The polymkeric substance be suitable for comprises NR, IR, SBR, BR, NBR, EPDM etc.Be mainly used in the high-grade rubber item of tire, rubber soles, rubber roller, sealing member, string rubber etc., than tetra-sulfurized pair-(γ-propyl-triethoxysilicane) (Si-69), there is higher high-temperature stability, do not analyse sulphur, longer time of scorch is provided, have better coupling effect.

Curing is two-and (γ-propyl-triethoxysilicane) be also widely used in the high-grade concrete structure that bridge, motorway, port and pier, Hai Gong etc. use in severe environment.Application in metal surface anticorrosive process becomes study hotspot.

Curing is two-and (γ-propyl-triethoxysilicane), because the steric hindrance of two γ-propyl-triethoxysilicane base atomic group at disulfide bond two ends is comparatively large, comparatively tetrasulfide (Si-69) is difficult to synthesis.Its synthetic method, useful two-[γ-(triethoxysilicane) propyl group]-tetrasulfide (Si-69) slough under the effect of catalyzer two sulphur atoms obtain curing two-(γ-propyl-triethoxysilicane).But this method cost is higher, the bad assurance of reaction conditions.Also have United States Patent (USP) report Si-69 and Sodium sulphate anhydrous, 99min, γ-chloropropyl triethoxysilane reacts obtained Si-75 in alcohol solvent, but Sodium sulphate anhydrous, 99min is difficult to preparation and stores.Also useful siloxanes mercaptan is under oxygenant effect, and in aqueous phase, oxidation obtains Si-75, but more expensive containing the silane coupling agent of sulfydryl, and apply more, therefore this method does not have real economy to be worth.

Traditional production method is that the sodium sulphite and sulphur powder that contain crystal water are heated to more than 280 DEG C roast meltings, generate sodium polysulphide, γ-chloropropyl triethoxysilane reacting by heating is in organic solvent added again after cooling, obtained curing is two-(γ-propyl-triethoxysilicane).Because there being the irritant gass such as sulphur hydrogen, oxysulfide to produce in heat-processed, seriously polluted, operational difficulty, energy consumption is high.After have and use phase-transfer catalysis Aqueous phase, it is simple that method is comparatively gone up in the operation of this method, but increase because reaction system sulphur powder consumption reduces alkalescence, raw material γ-chloropropyl triethoxysilane and product facile hydrolysis, productive rate reduces, the short easy inefficacy of product shelf life, and because using more expensive catalyzer, the a large amount of sewage containing catalyzer produced need process, are unfavorable for environmental protection.

Summary of the invention

In order to overcome above-mentioned defect, the object of the present invention is to provide a kind of production operation processing method that is effective, simple, environmental protection.

To achieve these goals, the present invention adopts following technical scheme:

A, by containing the sodium sulphite of 9 crystal water and the sulphur powder with its equimolar ratio, put into the enamel reactor that agitator, reflux condensing tube, water trap and thermometer are housed;

B, add and be 1.6-2 toluene doubly containing 9 crystal water sodium sulphite weight ratios, be heated with stirring to 80-110 DEG C and start reflux dewatering, to the clarification of 110 DEG C of moisture content de-toluene to the greatest extent;

C, be cooled to less than 50 DEG C, add with sodium sulphite mol ratio is 2.00-2.06 γ-chloropropyl triethoxysilane doubly and the dehydrated alcohol with the weight ratio such as toluene, add toluene by weight 0.3-0.6 ethylene glycol diethyl ether doubly again, computer heating control temperature of reaction, at 95-100 DEG C, is reacted four-five hours;

D, reacted and be cooled to room temperature, cross and filter inorganic salt and impurity, rinse inorganic salt and impurity once or twice with toluene alcohol mixeding liquid, inorganic salt reclaim and do industrial salt; Filtrate moves to distiller, and ethanol, toluene and ethylene glycol diethyl ether are reclaimed in underpressure distillation and foreshot recycles; At vacuum tightness >=0.090Mpa, during temperature >=150 DEG C, distill to obtain product: curing is two-(γ-propyl-triethoxysilicane) (Si-75).

Synthetic process of the present invention adopts hypotoxic toluene to hold concurrently as solvent the method for dewatering agent azeotropic reflux dewatering, and the water in sodium sulphite raw material is deviate from.Add main solvent to hold concurrently protective material dehydrated alcohol; add a kind of high boiling solvent ethylene glycol diethyl ether and improve the steric hindrance potential energy that temperature of reaction overcomes sulphur sulfide linkage two ends atomic group; increase the solubleness of reaction system simultaneously, then add γ-chloropropyl triethoxysilane, heating anhydrous response.The product generated leaches inorganic salt after filtration and impurity does Industrial Salt use, filtrate steams ethanol, toluene and ethylene glycol diethyl ether and foreshot recycling use through underpressure distillation, then through underpressure distillation steam the curing that purity is high, color and luster good, the shelf lives is long two-(γ-propyl-triethoxysilicane) product.Do not use catalyzer in reaction process, do not produce sewage, solvent recovery cycle uses, and is beneficial to environmental protection, reduces costs.

Chemical equation:

2Cl(CH2)3Si(OCH2CH3)3﹢Na2S﹢S = S2〔(CH2)3Si(OCH2CH3)3〕2﹢2NaCl

Beneficial effect of the present invention:

Curing of the present invention is two-(γ-propyl-triethoxysilicane) synthesis technique in; toluene is adopted to hold concurrently solvent as dewatering agent; dehydrated alcohol to be held concurrently protective material as main solvent; add high boiling solvent ethylene glycol diethyl ether and improve temperature of reaction; avoid traditional technology baking heat method; produce a large amount of irritating sulphur hydrogen, oxysulfide flue gas, reduce atmospheric pollution, convenient operation.Compared with phase-transfer catalysis aqueous phase synthesis method, because not using catalyzer, raw material is cheap and easy to get, does not have more sewage to process discharge, reduce costs, be beneficial to environmental protection, and product shelf life is long.

Accompanying drawing explanation

Fig. 1 is process flow diagram of the present invention.

In Fig. 1: 1-nine water cure sodium, sulphur powder; 2-toluene test tank; 3-toluene tank; 4-alcohol meter measuring tank; 5-ethanol storage tank; 6--γ-chloropropyl triethoxysilane test tank; 7-reactor; 8-toluene, water separator; 9,15-toluene; 10-strainer; 11-inorganic salt and impurity; 12-filtrate; 13-distiller; 14-ethanol; 16-tank; 17-foreshot; 18-curing is two-and (γ-propyl-triethoxysilicane).

Embodiment

Describe the present invention below in conjunction with accompanying drawing:

Embodiment 1

A kind of curing is two-the solvent method synthesis technique of (Y-propyl-triethoxysilicane), and this technique comprises following processing step:

A, by containing the sodium sulphite of 9 crystal water and the sulphur powder with its equimolar ratio, put into the enamel reactor that agitator, reflux condensing tube, water trap and thermometer are housed; (can not iron class reactor be used because sulphur meets iron generation black iron sulphide)

B, add and be the toluene of 1.8 times containing 9 crystal water sodium sulphite weight ratios, be heated with stirring to 80 DEG C and start dehydration, to the clarification of 110 DEG C of moisture content de-toluene to the greatest extent;

C, be cooled to less than 50 DEG C, add with sodium sulphite mol ratio the dehydrated alcohol of the weight ratio such as Y-chloropropyl triethoxysilane and toluene being 2.03 times, add the ethylene glycol diethyl ether of toluene by weight 0.4 times again, computer heating control temperature of reaction, at 95-100 DEG C, is reacted four hours;

D, reacted and be cooled to room temperature, cross and filter inorganic salt and impurity, rinse inorganic salt and impurity first and second with toluene alcohol mixeding liquid, inorganic salt reclaim and do industrial salt; Filtrate moves to distiller, and ethanol, toluene and ethylene glycol diethyl ether are reclaimed in underpressure distillation and foreshot recycles; At vacuum tightness >=0.090Mpa, during temperature >=150 DEG C, distill to obtain product: curing is two-(γ-propyl-triethoxysilicane) (Si-75).

Add toluene and make solvent and dewatering agent pump around circuit dewaters, in anhydrous organic solvent, reacting by heating obtains curing two (γ-propyl-triethoxysilicane).

Add ethanol and make main solvent and protective material; its effect increases the solubleness to raw material and product of solvent in reaction process, protects the alkoxyl group in raw material γ-chloropropyl triethoxysilane and two (propyl-triethoxysilicane) molecule of product curing not decompose simultaneously.

Add ethylene glycol diethyl ether and improve temperature of reaction, increase the solubleness of reaction system simultaneously.

Embodiment 2

1, curing two-the solvent method synthesis technique of (γ-propyl-triethoxysilicane), this technique comprises following processing step:

A, by containing the sodium sulphite of 9 crystal water and the sulphur powder with its equimolar ratio, put into the enamel reactor that agitator, reflux condensing tube, water trap and thermometer are housed; (can not iron class reactor be used because sulphur meets iron generation black iron sulphide).

B, add and be the toluene of 1.6 times containing 9 crystal water sodium sulphite weight ratios, be heated with stirring to 90 DEG C and start reflux dewaterings, to the clarification of 110 DEG C of moisture content de-toluene to the greatest extent;

C, be cooled to less than 50 DEG C, add with sodium sulphite mol ratio is the γ-chloropropyl triethoxysilane of 2.00 times and the dehydrated alcohol with weight ratios such as toluene, add the ethylene glycol diethyl ether of toluene by weight 0.3 times again, computer heating control temperature of reaction, at 95-100 DEG C, is reacted four hours;

D, reacted and be cooled to room temperature, cross and filter inorganic salt and impurity, rinse inorganic salt and impurity once or twice with toluene alcohol mixeding liquid, inorganic salt reclaim and do industrial salt; Filtrate moves to distiller, and ethanol, toluene and ethylene glycol diethyl ether are reclaimed in underpressure distillation and foreshot recycles; At vacuum tightness >=0.090Mpa, during temperature >=150 DEG C, distill to obtain product: curing is two-(γ-propyl-triethoxysilicane) (Si-75).

Embodiment 3

1, curing two-the solvent method synthesis technique of (γ-propyl-triethoxysilicane), this technique comprises following processing step:

A, by containing the sodium sulphite of 9 crystal water and the sulphur powder with its equimolar ratio, put into the enamel reactor that agitator, reflux condensing tube, water trap and thermometer are housed; (can not iron class reactor be used because sulphur meets iron generation black iron sulphide)

B, add and be the toluene of 2 times containing 9 crystal water sodium sulphite weight ratios, be heated with stirring to 110 DEG C and start reflux dewaterings, to the clarification of 110 DEG C of moisture content de-toluene to the greatest extent;

C, be cooled to less than 50 DEG C, add with sodium sulphite mol ratio is the γ-chloropropyl triethoxysilane of 2.06 times and the dehydrated alcohol with weight ratios such as toluene, add the ethylene glycol diethyl ether of toluene by weight 0.6 times again, computer heating control temperature of reaction, at 95-100 DEG C, is reacted five hours;

D, reacted and be cooled to room temperature, cross and filter inorganic salt and impurity, rinse inorganic salt and impurity once or twice with toluene alcohol mixeding liquid, inorganic salt reclaim and do industrial salt; Filtrate moves to distiller, and ethanol, toluene and ethylene glycol diethyl ether are reclaimed in underpressure distillation and foreshot recycles; At vacuum tightness >=0.090Mpa, during temperature >=150 DEG C, distill to obtain product: curing is two-(γ-propyl-triethoxysilicane) (Si-75).

The description of symbols of Fig. 1 process flow diagram:

1-nine water cure sodium, sulphur powder; 2-toluene test tank; 3-toluene tank; 4-alcohol meter measuring tank; 5-ethanol storage tank; 6-Y-chloropropyl triethoxysilane test tank; 7-reactor; 8-toluene, water separator; 9,15-toluene; 10-strainer; 11-inorganic salt and impurity; 12-filtrate; 13-distiller; 14-ethanol; 16-tank; 17-ethylene glycol diethyl ether; 18-foreshot; 19-curing is two-and (Y-propyl-triethoxysilicane).

The equipment related in this technique is all prior art, and without the need to providing the accompanying drawing of equipment and equipment, those skilled in the art more can understand processing step of the present invention by FB(flow block).

Claims (1)

1. curing two-the solvent method synthesis technique of (γ-propyl-triethoxysilicane), it is characterized in that this technique comprises following processing step:

A, by containing the sodium sulphite of 9 crystal water and the sulphur powder with its equimolar ratio, put into the enamel reactor that agitator, reflux condensing tube, water trap and thermometer are housed;

B, add and be 1.6-2 toluene doubly containing 9 crystal water sodium sulphite weight ratios, be heated with stirring to 80-110 DEG C and start reflux dewatering, to the clarification of 110 DEG C of moisture content de-toluene to the greatest extent;

C, be cooled to less than 50 DEG C, add with sodium sulphite mol ratio is 2.00-2.06 γ-chloropropyl triethoxysilane doubly and the dehydrated alcohol with the weight ratio such as toluene, add toluene by weight 0.3-0.6 ethylene glycol diethyl ether doubly again, computer heating control temperature of reaction, at 95-100 DEG C, is reacted four-five hours;

D, reacted and be cooled to room temperature, cross and filter inorganic salt and impurity, rinse inorganic salt and impurity once or twice with toluene alcohol mixeding liquid, inorganic salt reclaim and do industrial salt; Filtrate moves to distiller, and ethanol, toluene and ethylene glycol diethyl ether are reclaimed in underpressure distillation and foreshot recycles; At vacuum tightness >=0.090Mpa, during temperature >=150 DEG C, distill to obtain product: curing is two-(γ-propyl-triethoxysilicane) (Si-75).