CN1057832A - Preparation technique of diphenyl guanidine - Google Patents
Preparation technique of diphenyl guanidine Download PDFInfo
- Publication number
- CN1057832A CN1057832A CN 90105159 CN90105159A CN1057832A CN 1057832 A CN1057832 A CN 1057832A CN 90105159 CN90105159 CN 90105159 CN 90105159 A CN90105159 A CN 90105159A CN 1057832 A CN1057832 A CN 1057832A
- Authority
- CN
- China
- Prior art keywords
- reaction
- vulkacit
- diphenyl thiourea
- thiourea
- synthetic
- 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.)
- Pending
Links
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000003599 food sweetener Nutrition 0.000 claims abstract description 9
- 239000003765 sweetening agent Substances 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- MBEGFNBBAVRKLK-UHFFFAOYSA-N sodium;iminomethylideneazanide Chemical compound [Na+].[NH-]C#N MBEGFNBBAVRKLK-UHFFFAOYSA-N 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 claims 1
- 230000023556 desulfurization Effects 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 8
- 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 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 aryl thiourea Chemical compound 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The vulkacit D structural formula:
Vulkacit D is important thiofide, and the present invention is to be the synthetic diphenyl thiourea of raw material with aniline, dithiocarbonic anhydride, sulphur, again with Fe
2O
3As sweetening agent,, simultaneously the hydrogen sulfide waste gas of emitting in the above-mentioned reaction is fully utilized the combined preparation novel process of synthesizing thiourea by the synthetic vulkacit D of diphenyl thiourea.
Description
The invention belongs to thiofide.
The vulkacit D structural formula:
Vulkacit D is a kind of important thiofide, is used as plastics linking agent, thermally indicating material auxiliary agent in recent years again and connects building materials used additives etc.
The industrial production vulkacit D is existing historical for many years, u, s, p, and 2615045, Jiangsu chemical industry 1985, NO1, report is to adopt the mauguinite method among the P24, and mauguinite is hypertoxic gas, can cause that as equipment and pipe leakage the operator poisons, and be difficult to rescue.Domestic employing diphenyl thiourea method was once selected Pbo for use, ZnO, and Fe2O3 and oxygen-neutralized verdigris (O2-CuAc) are produced vulkacit D as sweetening agent.Reported the method for making sweetening agent with Pbo among the synthetic material auxiliary agent handbook P732 that Chemical Industry Press publishes, this method is to be recycled after Pbo is become Pbs.This method yield instability, the cost height, Lead contamination is serious, is difficult for industrialization.Reported zinc oxide method among the GerOffen481994,, the recycling problem of ZnS has been arranged also because ZnO is more expensive.Moreover synthetic vulkacit D need carry out two-step reaction, produces a large amount of hydrogen sulfide waste gas when generating the intermediate product diphenyl thiourea, and emit the SO2 contaminate environment when the recycling of ZnS.The spy opens among the clear 31-4673 and reports: in the presence of the ferric sesquichloride or oxidation high ferro of cheapness, make the method for vulkacit D with liquefied ammonia and aryl thiourea reaction, this method is used excessive liquefied ammonia, liquefied ammonia is promptly as reactant in reaction, also as solvent, its pressure is generally in the 0.7-1.5 MPa, and entire reaction course is to carry out under band pressure situation, brings many inconvenience to industrial production.
In order to solve to produce in the vulkacit D process environment is produced pollution problem, in order to reduce production costs special proposition the present invention.
The invention provides a new method of producing vulkacit D, this method is to synthesize vulkacit D with Fe2O3 as sweetening agent, the comprehensive utilization synthesizing thiourea of the H2S that emits during synthetic mesophase product diphenyl thiourea, not only solved the pollution problem of H2S to environment, and, paying and producing thiocarbamide is again important organic intermediate, can be used for the important intermediate of medicine, dyestuff, agricultural chemicals etc., also can be used as auxiliary agent in weaving, rubber, plastics industry.
The method applied in the present invention is: by aniline, dithiocarbonic anhydride, sulphur is the synthetic diphenyl thiourea of raw material, is the synthetic vulkacit D of sweetening agent again with Fe2O3, the H2S that emits when synthesizing diphenyl thiourea comprehensive utilization synthesizing thiourea.Method of the present invention has reduced the production cost of vulkacit D and thiocarbamide, has eliminated the pollution of H2S to environment.
Method principle of the present invention:
A, be the synthetic diphenyl thiourea of raw material with aniline, dithiocarbonic anhydride, sulphur
B, be sweetening agent with the oxidation high ferro, by the synthetic vulkacit D of diphenyl thiourea
C, the H2S that emits with a step reaction are the synthetic sulfuration of raw material urea
Reaction process of the present invention and condition:
1, synthetic diphenyl thiourea
Aniline and dithiocarbonic anhydride make diphenyl thiourea through washing, suction strainer, drying after condensation reaction under the pressure of 60-70 ℃ and 0.05 MPa, yield is more than 90%.
2, synthetic vulkacit D
In reactor, add diphenyl thiourea, be carried on Fe2O3 and ethanol on the r-Al2O3, logical liquefied ammonia in aforesaid liquid, press in making and reach 0.25 MPa, stop logical ammonia,, filter, add hydrochloric acid and make the vulkacit D hydrochloride 40-70 ℃ of reaction 6-10 hour, through neutralization, filtration, dry finished product vulkacit D, the yield 80% of getting.
3, by the hydrogen sulfide synthesizing thiourea
A, the H2S that will emit in the time of will synthesizing diphenyl thiourea purify (washing the organism of taking out of off) through aromatic hydrocarbons.
B, by solid: the liquor ratio value
※Be 1: the 2-5(weight ratio) add Ca(OH) 2 and water, under agitation add a part of CaCN2, absorb the H2S that emits among a slowly with negative pressure.
C, 20-50 ℃ of reaction 1 hour, add remainder CaCN2 again, continue reaction 3-5 hour at 60-90 ℃.
D, filtration, freezing, separate out the thiocarbamide crystal.
E, filtration, washing, the dry finished product thiocarbamide that gets, purity 〉=98%, yield are 80-90%.
※Solid-liquid ratio is elected smaller value as in this reaction, makes a gesture of measuring both to be beneficial to reaction and to carry out, and again can be directly freezingly from reaction solution goes out product, saves one step of evaporation operation than in the past.
Embodiment 1
A, synthetic diphenyl thiourea
In reaction flask, add 80 milliliters of aniline, 28 milliliters of dithiocarbonic anhydride, 108 ml waters, 0.1-0.4 restrains sulphur, is warmed up to 50-70 ℃, begins reaction, and emits H2S gas slowly.Reaction times is 5-6 hour, and reaction solution is after filtration, washing, drying make 91 gram diphenyl thioureas, 154-156 ℃ of product fusing point, and yield is more than 90%.
B, by the synthetic vulkacit D of diphenyl thiourea
In reaction flask, add 22,8 gram diphenyl thioureas, 100 gram Fe2O3 sweetening agents, 560 milliliters of dehydrated alcohols, logical ammonia, press in making and reach 0.25 MPa, stop logical ammonia, 40-70 ℃ of reaction ammonia excretion after 6-10 hour, steam ethanol, filter, add hydrochloric acid and regulate PH=2-5 and make the vulkacit D hydrochloride, neutralize, separate out vulkacit D with 10%NaOH, filtration, washing, dry 144-146 ℃ of the 17 gram vulkacit D fusing point that get.
C, synthesizing thiourea
To emit H2S gas among a, purify (removing the CS2 that does not have reaction) this arylamine by arylamine earlier and can select aniline, Tolylamine, xylidine etc. for use.
10 gram CaO are dissolved with 140 ml waters, add the CaCN2 of 30 grams 46.7%, feed H2S, 20-50 ℃ of reaction 1 hour, the CaCN2 that adds 20-40 gram again continues reaction 3-5 hour at 60-90 ℃, filters, with about 100 milliliters, 80 ℃ water washing filter cakes, filtrate is freezing with icy salt solution, separate out the thiocarbamide crystal, filtration, drying get thiocarbamide 21.3 grams, fusing point 175-176 ℃, purity is 98%.
Claims (3)
1, be that raw material is produced diphenyl thiourea by aniline and CS2, sulphur, produce diphenylguanidine through the sweetening agent desulfurization again, it is characterized in that selecting for use Fe2O3 to make H2S and the CaO aqueous solution and the CaCN2 reaction coproduction thiocarbamide of emitting when sweetening agent synthesizes diphenyl thiourea, the temperature of reaction of synthetic diphenyl thiourea is 50-70 ℃, reaction times is 5-6 hour, reaction pressure when synthesizing vulkacit D is 0.25 MPa, temperature of reaction is 40-70 ℃, emits H2S when synthesizing diphenyl thiourea and produce thiocarbamide after arylamine purifies (removing the CS2 that does not have reaction).
2, method according to claim 1 is characterized in that the optimal reaction temperature of synthetic diphenyl thiourea is 60-70 ℃.
3, method according to claim 1, the arylamine that the H2S that emits when it is characterized in that purifying diphenyl thiourea is used, the best can be aniline, monomethylaniline, xylidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105159 CN1057832A (en) | 1990-06-29 | 1990-06-29 | Preparation technique of diphenyl guanidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105159 CN1057832A (en) | 1990-06-29 | 1990-06-29 | Preparation technique of diphenyl guanidine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1057832A true CN1057832A (en) | 1992-01-15 |
Family
ID=4878992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90105159 Pending CN1057832A (en) | 1990-06-29 | 1990-06-29 | Preparation technique of diphenyl guanidine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1057832A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027000A (en) * | 2008-05-15 | 2011-04-20 | Ppg工业俄亥俄公司 | Method for producing bicyclic guanidines by use of a cyclic thiourea |
| CN102350349A (en) * | 2011-08-29 | 2012-02-15 | 科迈化工股份有限公司 | Catalyst for diphenylguanidine (DPG) serving as accelerating agent in oxygen oxidation synthesis production process, and preparation method thereof |
| CN102363601A (en) * | 2011-09-20 | 2012-02-29 | 科迈化工股份有限公司 | Method for producing rubber accelerator DGP by using hydrogen peroxide as oxidant |
| CN101602702B (en) * | 2009-07-22 | 2012-09-05 | 山东益丰生化环保股份有限公司 | Production technology for synthesizing thiourea by urea method |
| CN105348149A (en) * | 2015-12-15 | 2016-02-24 | 山东尚舜化工有限公司 | Method for improving quality of diphenylguanidine product |
| CN106316906A (en) * | 2016-08-23 | 2017-01-11 | 山东阳谷华泰化工股份有限公司 | Method for synthesizing accelerator DPTU |
| CN108586295A (en) * | 2018-05-23 | 2018-09-28 | 科迈化工股份有限公司 | A kind of continuous production method of accelerator D PG |
| CN109456241A (en) * | 2018-12-12 | 2019-03-12 | 北京彤程创展科技有限公司 | It is a kind of to prepare accelerant N, the system and method for N '-rhenocure CA |
-
1990
- 1990-06-29 CN CN 90105159 patent/CN1057832A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027000A (en) * | 2008-05-15 | 2011-04-20 | Ppg工业俄亥俄公司 | Method for producing bicyclic guanidines by use of a cyclic thiourea |
| CN103788099A (en) * | 2008-05-15 | 2014-05-14 | Ppg工业俄亥俄公司 | Method for producing bicyclic guanidines by use of a cyclic thiourea |
| CN102027000B (en) * | 2008-05-15 | 2015-06-17 | Ppg工业俄亥俄公司 | Method for producing bicyclic guanidines by use of a cyclic thiourea |
| CN101602702B (en) * | 2009-07-22 | 2012-09-05 | 山东益丰生化环保股份有限公司 | Production technology for synthesizing thiourea by urea method |
| CN102350349A (en) * | 2011-08-29 | 2012-02-15 | 科迈化工股份有限公司 | Catalyst for diphenylguanidine (DPG) serving as accelerating agent in oxygen oxidation synthesis production process, and preparation method thereof |
| CN102363601A (en) * | 2011-09-20 | 2012-02-29 | 科迈化工股份有限公司 | Method for producing rubber accelerator DGP by using hydrogen peroxide as oxidant |
| CN105348149A (en) * | 2015-12-15 | 2016-02-24 | 山东尚舜化工有限公司 | Method for improving quality of diphenylguanidine product |
| CN106316906A (en) * | 2016-08-23 | 2017-01-11 | 山东阳谷华泰化工股份有限公司 | Method for synthesizing accelerator DPTU |
| CN108586295A (en) * | 2018-05-23 | 2018-09-28 | 科迈化工股份有限公司 | A kind of continuous production method of accelerator D PG |
| CN108586295B (en) * | 2018-05-23 | 2021-12-10 | 科迈化工股份有限公司 | Continuous production method of vulcanization accelerator DPG |
| CN109456241A (en) * | 2018-12-12 | 2019-03-12 | 北京彤程创展科技有限公司 | It is a kind of to prepare accelerant N, the system and method for N '-rhenocure CA |
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