CN101168531A - Method for synthesizing rubber accelerator DZ - Google Patents
Method for synthesizing rubber accelerator DZ Download PDFInfo
- Publication number
- CN101168531A CN101168531A CNA2007101906460A CN200710190646A CN101168531A CN 101168531 A CN101168531 A CN 101168531A CN A2007101906460 A CNA2007101906460 A CN A2007101906460A CN 200710190646 A CN200710190646 A CN 200710190646A CN 101168531 A CN101168531 A CN 101168531A
- Authority
- CN
- China
- Prior art keywords
- rubber accelerator
- dicyclohexyl amine
- synthetic method
- weight
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229920001971 elastomer Polymers 0.000 title claims abstract description 13
- 239000005060 rubber Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 15
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical class C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000006210 lotion Substances 0.000 claims description 6
- FDBSRZMPVJHVAC-UHFFFAOYSA-N n-chloro-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(Cl)C1CCCCC1 FDBSRZMPVJHVAC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- -1 chloro dicyclohexyl amine Chemical compound 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new method for synthesizing rubber accelerator DZ, and adopts ammonia gas to replace the present usual deacid reagent. The invention comprises the following steps: accelerator DM, N-iorine-substituted dicyclohexylamine and dicyclohexylamine are filled in a reactor; absolute methanol is added to be agitated evenly and then heated; the ammonia gas is blown into the solution; gas blowing is stopped, the solution is agitated to continuously react; the solution is cooled and filtered to obtain a DZ crude product; the DZ crude product is washed for two times with carbinol and washed for two times with cold water; the DZ crude product is dried to obtain a DZ product. The invention uses the ammonia gas as the deacid reagent, the price of the ammonia gas is cheap, the using quantity is few, the reaction rate is quick, and the product quality is high, thus the invention is suitable for the industrialization 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 0721946 Al 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. the synthetic method of a rubber accelerator DZ is characterized in that may further comprise the steps:
A) with altax, 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.
2. the synthetic method of rubber accelerator DZ according to claim 1, it is characterized in that: steps A), the weight of N-chloro dicyclohexyl amine is 1.2 times of DM; The weight of dicyclohexyl amine is 1.2 times of DM.
3. the synthetic method of rubber accelerator DZ according to claim 1 and 2, it is characterized in that: step B), the weight of anhydrous methanol is 6 times of DM.
4. the synthetic method of rubber accelerator DZ according to claim 1 and 2, it is characterized in that: step C), reaction pressure is 0.1 ~ 5MPa, and temperature of reaction is 20 ~ 65 ℃.
5. the synthetic method of rubber accelerator DZ according to claim 1 and 2, it is characterized in that: step e), cooling temperature is 0 ~ 20 ℃.
6. the synthetic method of rubber accelerator DZ according to claim 1 is characterized in that: with step e) in the Recycling Mother Solution that obtains apply mechanically.
7. the synthetic method of rubber accelerator DZ according to claim 1 is characterized in that: with step F) in the pure washing lotion recycled that obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101906460A CN100551917C (en) | 2007-11-27 | 2007-11-27 | A kind of synthetic method of rubber accelerator DZ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101906460A CN100551917C (en) | 2007-11-27 | 2007-11-27 | A kind of synthetic method of rubber accelerator DZ |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101168531A true CN101168531A (en) | 2008-04-30 |
| CN100551917C CN100551917C (en) | 2009-10-21 |
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ID=39389321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101906460A Expired - Fee Related CN100551917C (en) | 2007-11-27 | 2007-11-27 | A kind of synthetic method of rubber accelerator DZ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100551917C (en) |
Cited By (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) |
| 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 |
| 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 |
| 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 |
-
2007
- 2007-11-27 CN CNB2007101906460A patent/CN100551917C/en not_active Expired - Fee Related
Cited By (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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| Publication number | Publication date |
|---|---|
| CN100551917C (en) | 2009-10-21 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
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Granted publication date: 20091021 Termination date: 20101127 |