CN102391172A

CN102391172A - CPT (cytidine-5'-triphosphate) continuous synthesis process

Info

Publication number: CN102391172A
Application number: CN2011103137642A
Authority: CN
Inventors: 安敬尧; 姚红梅; 安鹏飞; 张秋印; 张开道
Original assignee: 张迎宾
Priority date: 2011-11-18
Filing date: 2011-11-18
Publication date: 2012-03-28

Abstract

The invention relates to a rubber antiscorching agent CTP (cytidine-5'-triphosphate) condensation reaction, in particular to a CTP continuous synthesis process. Cyclohexyl secondary sulfonyl chloride oil solution and phthalyl imine sodium water solution are injected into three to six sections of vertical pipeline static mixers connected in series for reaction in proportion; then mixed solution enters into a reaction stabilizer, phase transfer catalyst is added under a high speed stirring; later, the mixed solution enters into an oil-water separation device for temperature increment, so that generated CTP is dissolved into oil phase, and water phase is discharged out of the separation device; and low speed circulating temperature reduction is achieved, and CTP is formed through separation and crystallization. After the adoption of the invention, the reaction time is short, generally 30 minutes are enough; the mixture ratio is accurate and can be controlled accurately through a flow meter; since the reaction and the mixing are quick and sufficient, side reactions are less, the reaction yield ratio is higher than that in a conventional method, the product purity is high and generally higher than 98.5 percent; and crystalline particles are uniform, and the consumption of raw material resolvent is low.

Description

The continuous synthesis technique of a kind of CTP

Technical field

The present invention relates to a kind of rubber anti-chark agent CTP condensation reaction, the continuous synthesis technique of a kind of CTP.

Background technology

Anti-scorching agent CTP, (PVI); Molecular formula: C ₁₄H ₁₅O ₂NS; Structural formula:

Molecular weight: 261.34; CAS number: 17796-82-6; Physico-chemical property: white or faint yellow crystallization, be soluble in benzene, ether, acetone and vinyl acetic monomer are dissolved in the warm normal heptane and tetracol phenixin.Be slightly soluble in gasoline, be insoluble to kerosene and water.These article can be used for tree elastomer and viton, can prevent effectively that sizing material from incipient scorch taking place in the course of processing, enhance productivity.Simultaneously for standing Gao Re or having the sizing material of slight incipient scorch to have reactivation.

Phase-transfer catalyst (phase transfer catalyst) is called for short PTC, is in organic synthesis, to have used a kind of widely day by day new synthetic technology since the 70's of 20th century.The reaction of the phase-transfer catalysis that generally can adopt; All exist the aqueous solution and organic solvent two mutually, reaction of ionic type thing often dissolves in water, is insoluble to organic phase; Organic substrates then dissolves among the organic solvent, and two difficult mutually mixing mutually cause reaction to carry out very slowly.The existence of phase-transfer catalyst can combine with the ion of aqueous phase, and utilizes self affinity to organic solvent, in organic phase, impels reaction to take place the reactant transfer of aqueous phase.Phase-transfer catalyst kind commonly used is a lot, and the present invention adopts the quaternary phase-transfer catalyst.Quaternary ammonium salt commonly used has benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride etc.

The anti-scorching agent CTP building-up reactions all adopts the rhythmic reaction method; Because it is many more to make two kinds of raw material cyclohexyl time SULPHURYL CHLORIDE oil solution and the easy longer decomposition of decomposition-reaction times of phthalic imidine sodium water solution of CTP; During reaction; Reaction two mixes mutually and is difficult for fully, even, long reaction time, thereby can produce more side reaction, thereby causes yield, purity not high.It is that the jet of power is taken out the material mixing reactor with nitrogen that patent 200910017194.5 provides a kind of.Though raw materials mix is more preceding evenly,, can't guarantee that still two kinds of materials of synthetic CTP fully and with accurate ratio add and mix because its active force is centralized nitrogen jet (spirit is similar with the Venturi meter mixing tank).Therefore can not fundamentally solve the accurate and rapid thorough mixing reaction of inferior SULPHURYL CHLORIDE oil solution of two kinds of material cyclohexyl that synthesize CTP and phthalic imidine sodium water solution.Aforesaid method exist reaction time long, raw material decomposing phenomenon obviously, problem such as poor product quality, side reaction be bigger, have to be solved and improve.

Summary of the invention

The objective of the invention is to overcome the anti-scorching agent CTP building-up reactions and adopt the deficiency in the intermittent reaction, and adopt continuous synthesis technique.

The continuous synthesis technique of a kind of CTP with cyclohexyl time SULPHURYL CHLORIDE oil solution and phthalic imidine sodium water solution, injects 3～6 sections placed in-line riser static mixer reactions in proportion; Mixed solution gets into the stable reaction device subsequently, adds phase-transfer catalyst and fully reaction under high-speed stirring; Get into oily-water seperating equipment subsequently and heat up, the CTP of generation is dissolved in the oil phase fully, water is discharged tripping device; Cooling, Crystallization Separation goes out CTP; Temperature before said cyclohexyl time SULPHURYL CHLORIDE oil solution and the reaction of phthalic imidine sodium water solution all is controlled at below 0 ℃; Said cyclohexyl time SULPHURYL CHLORIDE oil solution; Be meant the cyclohexyl disulfide is dissolved in the aromatic hydrocarbon solvent oil; Chlorination generates cyclohexyl time SULPHURYL CHLORIDE oil solution, and its concentration is 10%～20%; Said phthalic imidine sodium water solution is meant the aqueous solution that phthalic imidine and dissolution of sodium hydroxide are processed in the water, and its concentration is 20%～30%; The mol ratio of cyclohexyl time SULPHURYL CHLORIDE and phthalic imidine sodium is 1:1～1.1, is preferably 1:1.02～1.05; Said phase-transfer catalyst is one of benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride or its combination.

Adopt the present invention, the reaction times is short, can accomplish with interior in general 30 minutes; Proportion speed is accurately controlled through under meter; Fully, side reaction is few because reaction mixes fast, and reaction yield is higher than existing method, and product purity is high, generally all greater than 98.5%; Crystalline particle is even, and the starting material solvent consumption is low.

Description of drawings

Accompanying drawing 1 is the continuous synthesis technique device of an a kind of CTP synoptic diagram;

Description of drawings: 1. cyclohexyl time SULPHURYL CHLORIDE oil solution still; 2. phthalic imidine sodium water solution still; 3. stable reaction still; 4. phase-splitting crystallization kettle; 5. cyclohexyl time SULPHURYL CHLORIDE pump; 6. phthalic imidine sodium pump; 7. crystal solution recycle pump; 8. phthalic imidine sodium under meter; 9. cyclohexyl time SULPHURYL CHLORIDE under meter; 10. series connection pipeline static mixer; 11. interchanger; 12. crystallization kettle water port; 13. crystallization kettle drain hole.

Embodiment

Explain with embodiment below and realize embodiment of the present invention:

With cyclohexyl time SULPHURYL CHLORIDE oil solution and phthalic imidine sodium water solution, inject 3～6 sections placed in-line riser static mixer reactions in proportion; Mixed solution gets into the stable reaction device subsequently, adds phase-transfer catalyst and fully reaction under high-speed stirring; Get into oily-water seperating equipment subsequently and heat up, the CTP of generation is dissolved in the oil phase, water is discharged tripping device; Cooling, Crystallization Separation goes out CTP; Temperature before said cyclohexyl time SULPHURYL CHLORIDE oil solution and the reaction of phthalic imidine sodium water solution all is controlled at below 0 ℃; Said cyclohexyl time SULPHURYL CHLORIDE oil solution; Be meant cyclohexyl time SULPHURYL CHLORIDE is dissolved in the aromatic hydrocarbon solvent oil that its concentration is 10%～20% oil solution; Said phthalic imidine sodium water solution is meant phthalic imidine sodium is dissolved in the water that its concentration is 20%～30% the aqueous solution; The mol ratio of cyclohexyl time SULPHURYL CHLORIDE and phthalic imidine sodium is 1:1～1.1, is preferably 1:1.02～1.05; Said phase-transfer catalyst is one of benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride or its combination.

Embodiment: temperature is controlled at the cyclohexyl time SULPHURYL CHLORIDE oil solution below 0 ℃ and is cooled to the phthalic imidine sodium water solution below 0 ℃, respectively through under meter, inject the reaction of upright multistage series connection pipeline static mixer from top with in-line pump; The pipeline static mixer outlet directly links to each other with the fluid inlet of stable reaction device through SV, and mixed reaction solution directly gets into the stopping reaction device and accomplishes reaction; Because the mixture of products C TP, raw material, oil phase, aqueous phase solvent can produce two and be separated; And the speed of response reason, only through the pipeline reactor several minutes, can't complete reaction; So will above-mentioned mixing solutions directly be put in the stable reaction device that is added with phase-transfer catalyst; Under high-speed stirring and phase-transfer catalyst effect, continue reaction, just can thoroughly accomplish reaction in general 10～30 minutes; In order to realize successive reaction, design stability still feed time is 10 minutes, stablizes 20 minutes still reaction times, implements four stable stills and switches circulating reaction; Below four stills switched circulating reaction once describe: first 10 minutes, first stablized still when being in the feed liquor state, and its outlet valve is in closing condition; The feed liquor valve of other stable stills is in closing condition, second stablize still outlet valve be in open mode, second 10 minutes; When second stable still is in the feed liquor state; Its outlet valve is in closing condition, and the feed liquor valve of other stable stills is in closing condition, the 3rd stablize still outlet valve be in open mode; The 3rd 10 minutes, when the 3rd stable still was in the feed liquor state, its outlet valve was in closing condition; The feed liquor valve of other stable stills is in closing condition, the 4th stablize still outlet valve be in open mode, the 4th 10 minutes; When the 4th stable still is in the feed liquor state; Its outlet valve is in closing condition, and the feed liquor valve of other stable stills is in closing condition, first stablize still outlet valve be in open mode; The 5th 10 minutes, first stablizes still when being in the feed liquor state, its outlet valve is in closing condition; The feed liquor valve of other stable stills is in closing condition; Second stablize still outlet valve be in open mode, begun next loop cycle, realized carrying out continuously of reaction.Stablize the reaction solution that the still reaction generates; Get into heat temperature raising phase-splitting crystallization kettle in turn continuously from top; Phase-splitting is carried out in heating continuously; With phase-splitting crystallization kettle drain outlet height is a plane, and this plane following phase-splitting still internal volume is stablized 30 minutes feed liquor volume of still greater than (equaling), and guarantees that with heating and reflux cooling level point (with the same horizontal plane of crystallization kettle drain hole) solution temperature is greater than 80 ℃ in the still; The bottom minimum point temperature is greater than 70 ℃, and can guarantee that CTP dissolves in oil phase fully this moment, guarantee also that the water oil phase separates fully and when feed liquor water can discharge outside the still continuously.When stable liquid stopped feed liquor after 30 minutes, the water of design phase-splitting still racks up just basically.(when drain no longer includes the water discharge, observe outlet at bottom pipe mesoscope, discharging tube is with the surplus water emptying from the bottom).

Continuous circulation decrease temperature crystalline: behind the emptying water, steam off valve, beginning nature decrease temperature crystalline; The outlet of unlatching oil reservoir; Extract upper strata fluid with pump and go into from the still rising pouring, make the still inner fluid form circulation and eluriate crystallization and the cooling that is deposited on the bottom through interchanger, with 2～4 ℃ of flow control cooling rates/time; When temperature is reduced to 40 ℃, open chilled brine between Tube Sheet of Heat Exchanger, 5～8 ℃ of control temperature drop speed/time. when oily temperature drop to 10 ℃, crystallization is accomplished; The water displacement is fuel-displaced; CTP delivers to solid-liquid separating machine in water and the water, tells product.

The ratio of cyclohexyl time SULPHURYL CHLORIDE and phthalic imidine sodium: 1: (1～1.1), preferred 1: (1.02～1.05).

(HG/T 20570,20-95) are meant: SV, SX, SL, SH, SK type, preferred SK type static mixer, multistage are meant 3～6 standard pipe static mixer series connection, at least three standard pipes to said pipeline static mixer.

Have numerous embodiment according to the method for the invention, change with interior method, all be regarded as protection scope of the present invention, repeat no more here as long as meet connotation of the present invention.

Claims

1. the continuous synthesis technique of CTP is characterized in that: with cyclohexyl time SULPHURYL CHLORIDE oil solution and phthalic imidine sodium water solution, inject 3～6 sections placed in-line riser static mixer reactions in proportion; Mixed solution gets into the stable reaction device subsequently, adds phase-transfer catalyst and fully reaction under high-speed stirring; Get into oily-water seperating equipment again and heat up, the CTP of generation is dissolved in the oil phase, water is discharged tripping device; Cooling, Crystallization Separation goes out CTP.

2. must ask the continuous synthesis technique of 1 described CTP according to power; It is characterized in that: the temperature before said cyclohexyl time SULPHURYL CHLORIDE oil solution and the reaction of phthalic imidine sodium water solution all is controlled at below 0 ℃; Said cyclohexyl time SULPHURYL CHLORIDE oil solution; Be meant cyclohexyl time SULPHURYL CHLORIDE is dissolved in the aromatic hydrocarbon solvent oil that its concentration is 10%～20% oil solution; Said phthalic imidine sodium water solution is meant phthalic imidine sodium is dissolved in the water that its concentration is 20%～30% the aqueous solution; The mol ratio of cyclohexyl time SULPHURYL CHLORIDE and phthalic imidine sodium is 1:1～1.1, is preferably 1:1.02～1.05; Said phase-transfer catalyst is one of benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride or its combination.