CN100551917C - A kind of synthetic method of rubber accelerator DZ - Google Patents
A kind of synthetic method of rubber accelerator DZ Download PDFInfo
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- CN100551917C CN100551917C CNB2007101906460A CN200710190646A CN100551917C CN 100551917 C CN100551917 C CN 100551917C CN B2007101906460 A CNB2007101906460 A CN B2007101906460A CN 200710190646 A CN200710190646 A CN 200710190646A CN 100551917 C CN100551917 C CN 100551917C
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- dicyclohexyl amine
- ammonia
- synthetic method
- rubber accelerator
- dithio
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Abstract
The present invention discloses a kind of novel method of synthetic rubber accelerator DZ, and it adopts ammonia to replace acid binding agent commonly used at present, may further comprise the steps: with altax, and N-chloro dicyclohexyl amine, dicyclohexyl amine is packed in the reactor; Add anhydrous methanol, stirring and evenly mixing, heating; In above-mentioned solution, blast ammonia, react; Stop air-blowing, stir and continue reaction down; Cooling, suction filtration obtains the DZ crude product; Wash twice with methyl alcohol, twice of cold wash; Drying obtains the DZ product.This invention uses ammonia as acid binding agent, the low price of ammonia, and consumption is few, and speed of response is fast, and the quality product height is fit to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of method of synthetic rubber accelerator DZ, a kind of specifically method that adopts ammonia as the synthetic DZ of acid binding agent.
Background technology
(molecular formula is C to rubber accelerator DZ for N, N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide
19H
26N
2S
2) be a kind of good late effect property time sulphonyl class promotor, be applicable in the sizing material of high reactivity strengthening agent large usage quantity to have mechanical property and dynamic property preferably.At present, its production technology adopts highly basic such as sodium hydroxide or sodium methylate as acid binding agent usually, the cost of acid binding agent raw material is higher, need dissolving and dissolution rate slow, long reaction time, often have water to generate, abraum salt is difficult to flush away, and quality product fusing point (melting range＞3 ℃) and yield (＜70%) are difficult to reach requirement.For example European patent EP 0721946A1 discloses the synthetic method of a kind of DZ on (open day December 27 nineteen ninety-five), it has just adopted sodium hydroxide as acid binding agent, this method has that sodium hydroxide need dissolve and dissolution rate is slow, long reaction time, reaction has water to generate, and abraum salt is difficult to shortcomings such as flush away.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic method of new rubber accelerator DZ, it adopts ammonia as acid binding agent, the low price of ammonia, and consumption is few, and speed of response is fast, and the quality product height of producing, and is fit to suitability for industrialized production.
The synthetic method of rubber accelerator DZ of the present invention is characterized in that may further comprise the steps:
A) with altax (2,2 '-dithio-bis-benzothiazole), N-chloro dicyclohexyl amine, dicyclohexyl amine is packed in the reactor; The weight of N-chloro dicyclohexyl amine is 0.5 ~ 2 times of DM, and the weight of dicyclohexyl amine is 0.5 ~ 2 times of DM;
B) add anhydrous methanol, the weight of anhydrous methanol is 5 ~ 30 times of DM, and stirring and evenly mixing is heated to and boils;
C) in above-mentioned solution, blast ammonia, with ammonia as acid binding agent;
D) stop air-blowing, stirring and refluxing;
E) cooling, suction filtration obtains the DZ crude product;
F) washing again after the washed with methanol;
G) drying obtains the DZ product.
F) wash twice with methyl alcohol, twice of cold wash; The pure washing lotion that obtains can recycled.
G) drying obtains the DZ product.
Above-mentioned steps A) in, N-chloro dicyclohexyl amine and dicyclohexyl amine weight preferably all be 1.2 times of DM.
Above-mentioned steps B) in, the weight of anhydrous methanol is preferably 6 times of DM.
Above-mentioned steps C) in, reaction pressure is preferably 0.1 ~ 5MPa, and temperature of reaction is 20 ~ 65 ℃.
Above-mentioned steps E) in, cooling temperature is preferably 0 ~ 20 ℃.
Step e) and the mother liquor that obtains F) and pure washing lotion all can recycled.
Technical scheme of the present invention can be represented by following equation:
The present invention adopts ammonia as acid binding agent, the low price of ammonia, and molecular weight is little, and consumption is also few, and speed of response is exceedingly fast, and can reduce raw materials cost and process cost greatly; Ammonia is purer, does not introduce solid impurity, the quality product height; And ammonia solubleness in methyl alcohol is big, and dissolution rate is fast, has solved acid binding agent and dissolve this difficult problem of difficulty in solvent, has deducted acid binding agent dissolution process in the suitability for industrialized production, has reduced investment cost and has improved throughput; Doing acid binding agent reaction with sodium hydroxide has water to generate, and water causes quality product to descend to reacting unfavorable, and then raw materials cost is too high with sodium methylate and other acid binding agent; Product of the present invention need not other recrystallization or other purification operations; By-product NH
4Cl can be used as chemical fertilizer, further reduces cost; Synthetic method is simple and easy to control, and mother liquor that obtains and pure washing lotion can recycleds, and total recovery can be near 100%.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Below be described further with specific embodiment.
Embodiment one:
As the represented flow process that goes out in the accompanying drawing: with DM16.6g, dicyclohexyl amine 10.9g, chloro dicyclohexyl amine 13.1g joins in the four-hole boiling flask, adds the dissolving of 120ml anhydrous methanol, stirring and evenly mixing.Heating feeds ammonia under normal pressure, keep 60 ~ 65 ℃ of reactions 5 ~ 10 minutes.Stop logical ammonia, continue reaction 30 minutes, be cooled to 5 ℃.Suction filtration washes twice with 25ml methyl alcohol, twice of 150ml washing.Vacuum-drying gets DZ product 18.1g, and once through yield is 52.3%, and melting range is 99 ~ 101 ℃.
Embodiment two:
With DM16.6g, dicyclohexyl amine 10.9g, chloro dicyclohexyl amine 13.8g joins in the four-hole boiling flask, adds the dissolving of 150ml anhydrous methanol, stirring and evenly mixing.Heating feeds ammonia under normal pressure, keep 40 ~ 45 ℃ of reactions 10 ~ 20 minutes.Stop logical ammonia, continue reaction 30 minutes, be cooled to 10 ℃.Suction filtration washes twice with 25ml methyl alcohol, twice of 200ml washing.Vacuum-drying gets DZ product 16.9g, and once through yield is 48.8%, and melting range is 100 ~ 102 ℃.
Embodiment three:
With DM16.6g, dicyclohexyl amine 18.2g, chloro dicyclohexyl amine 21.8g joins in the four-hole boiling flask, adds the dissolving of 150ml anhydrous methanol, stirring and evenly mixing.Heating feeds ammonia under normal pressure, keep 60 ~ 65 ℃ of reactions 5 ~ 10 minutes.Stop logical ammonia, continue reaction 30 minutes, be cooled to 10 ℃.Suction filtration washes twice with 25ml methyl alcohol, twice of 150ml washing.Vacuum-drying gets DZ product 17.1g, and once through yield is 49.4%, and melting range is 98 ~ 101 ℃.
Embodiment four:
With DM16.6g, dicyclohexyl amine 4.6g, chloro dicyclohexyl amine 5.5g joins in the four-hole boiling flask, adds the dissolving of 150ml anhydrous methanol, stirring and evenly mixing.Heating feeds ammonia under normal pressure, keep 60 ~ 65 ℃ of reactions 5 ~ 10 minutes.Stop logical ammonia, continue reaction 30 minutes, be cooled to 10 ℃.Suction filtration washes twice with 25ml methyl alcohol, twice of 150ml washing.Vacuum-drying gets DZ product 9.0g, and once through yield is 26.0%, and melting range is 93 ~ 98 ℃.
Embodiment five:
With DM16.6g, dicyclohexyl amine 10.9g, chloro dicyclohexyl amine 13.1g joins in the four-hole boiling flask, adds the dissolving of embodiment two gained reaction mother liquors and once pure washing lotion (adding a small amount of solvent to 150ml), stirring and evenly mixing.Heating feeds ammonia under normal pressure, keep 60 ~ 65 ℃ of reactions 5 ~ 10 minutes.Stop logical ammonia, continue reaction 30 minutes, be cooled to 5 ℃.Suction filtration is washed once with embodiment two gained secondaries alcohol washing lotion, and 25ml methyl alcohol is washed once.Wash once with embodiment two gained secondary water washing liquid, 200ml washes once again.Vacuum-drying gets DZ product 34.0g, and yield is 98.2%, and melting range is 97 ~ 100 ℃.
Claims (7)
1, a kind of rubber accelerator N, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that may further comprise the steps:
A) with promotor 2,2 '-dithio-bis-benzothiazole, N-chloro dicyclohexyl amine, dicyclohexyl amine is packed in the reactor; The weight of N-chloro dicyclohexyl amine is 2,0.5 ~ 2 times of 2 '-dithio-bis-benzothiazole, and the weight of dicyclohexyl amine is 2,0.5 ~ 2 times of 2 '-dithio-bis-benzothiazole;
B) add anhydrous methanol, the weight of anhydrous methanol is 2,5 ~ 30 times of 2 '-dithio-bis-benzothiazole, and stirring and evenly mixing is heated to and boils;
C) in above-mentioned solution, blast ammonia, with ammonia as acid binding agent;
D) stop air-blowing, stirring and refluxing;
E) cooling, suction filtration obtains N, N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide crude product;
F) washing again after the washed with methanol;
G) drying obtains N, N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide product.
2, rubber accelerator N according to claim 1, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that: steps A), the weight of N-chloro dicyclohexyl amine is 2,1.2 times of 2 '-dithio-bis-benzothiazole; The weight of dicyclohexyl amine is 2,1.2 times of 2 '-dithio-bis-benzothiazole.
3, rubber accelerator N according to claim 1 and 2, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that: step B), the weight of anhydrous methanol is 2,6 times of 2 '-dithio-bis-benzothiazole.
4, rubber accelerator N according to claim 1 and 2, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that: step C), reaction pressure is 0.1 ~ 5MPa, and temperature of reaction is 20 ~ 65 ℃.
5, rubber accelerator N according to claim 1 and 2, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that: step e), cooling temperature is 0 ~ 20 ℃.
6, rubber accelerator N according to claim 1, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that: with step e) in the Recycling Mother Solution that obtains apply mechanically.
7, rubber accelerator N according to claim 1, the synthetic method of N-dicyclohexyl amine-2-[4-morpholinodithio sulphenamide is characterized in that: with step F) in the pure washing lotion recycled that obtains.
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| CNB2007101906460A CN100551917C (en) | 2007-11-27 | 2007-11-27 | A kind of synthetic method of rubber accelerator DZ |
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| CNB2007101906460A CN100551917C (en) | 2007-11-27 | 2007-11-27 | A kind of synthetic method of rubber accelerator DZ |
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| CN100551917C true CN100551917C (en) | 2009-10-21 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382077A (en) * | 2011-09-20 | 2012-03-21 | 科迈化工股份有限公司 | Method for preparing pharmaceutical grade DM (accelerator) with industrial grade DM |
| CN103102327A (en) * | 2012-11-16 | 2013-05-15 | 江苏国立化工科技有限公司 | Preparation method of rubber accelerator DZ (N,N-Dicyclohexyl-2-benzothiazolsulfene amide) |
| CN103626719A (en) * | 2013-09-14 | 2014-03-12 | 东营万通橡胶助剂有限公司 | Method of washing rubber vulcanization accelerator CBS by virtue of sub concentration-process |
| CN103508978A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ with two-dropping method |
| CN105837482A (en) * | 2016-04-06 | 2016-08-10 | 衢州信步化工科技有限公司 | Preparation method for reducing production cost of alpha-dimethylbutyryl-S-methyl propionate |
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2007
- 2007-11-27 CN CNB2007101906460A patent/CN100551917C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 橡胶硫化促进剂DZ合成工艺探讨. 刘怡志.合成化学，第8卷第4期. 2000 |
| 橡胶硫化促进剂DZ合成工艺探讨. 刘怡志.合成化学，第8卷第4期. 2000 * |
| 次磺酰胺类橡胶硫化促进剂的生产与合成工艺现状. 吴沫，姚丽年.精细石油化工，第6期. 1990 |
| 次磺酰胺类橡胶硫化促进剂的生产与合成工艺现状. 吴沫，姚丽年.精细石油化工，第6期. 1990 * |
| 用粗M合成橡胶硫化促进剂DZ. 张越，李小云，李建军.化学推进剂与高分子材料，第4期. 1999 |
| 用粗M合成橡胶硫化促进剂DZ. 张越，李小云，李建军.化学推进剂与高分子材料，第4期. 1999 * |
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