CN103288681A - Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method - Google Patents
Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method Download PDFInfo
- Publication number
- CN103288681A CN103288681A CN2013102784324A CN201310278432A CN103288681A CN 103288681 A CN103288681 A CN 103288681A CN 2013102784324 A CN2013102784324 A CN 2013102784324A CN 201310278432 A CN201310278432 A CN 201310278432A CN 103288681 A CN103288681 A CN 103288681A
- Authority
- CN
- China
- Prior art keywords
- carbodiimide
- diisopropyl
- produced
- thiocarbamide
- technology
- 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
- 0 *c(cc1*)cc(*)c1N=C=Nc1c(*)cc(*)cc1* Chemical compound *c(cc1*)cc(*)c1N=C=Nc1c(*)cc(*)cc1* 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N CC(C)N=C=NC(C)C Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- PBMIETCUUSQZCG-UHFFFAOYSA-N N=C=NC1CCCCC1 Chemical compound N=C=NC1CCCCC1 PBMIETCUUSQZCG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for producing N, N'-diisopropylbenzene carbodiimide by a thiourea method. Firstly, 2, 6-diisopropyl phenylamine and carbon disulfide are synthesized in a water medium to form N, N'-diisopropyl phenylthiourea, the N, N'-diisopropyl phenylthiourea is filtered and washed and then directly added into a reactor sequentially together with auxiliaries and solvents without drying, the temperature is increased to 70 DEG C, pre-allocated sodium hypochlorite solution with 6-10% concentration of oxidizing agents is dripped up in 30 minutes, the mixture reacts for 1.5 hours at the same temperature and is static for 15 minutes, a lower aqueous phase is discarded, secondary oxidation is performed under the same condition, sodium hydroxide aqueous solution with 20-40% concentration of desulfurizing agents is added, the temperature is increased to 80 DEG C, the mixture reacts for 1 hour, an aqueous layer is separated by washing, methylbenzene is evaporated out, and ethanol is added to obtain the white N, N'-diisopropylbenzene carbodiimide by crystallization. The process has the advantages that raw materials are easily obtained, the process is simple to operate, and the produced N, N'-diisopropylbenzene carbodiimide is high in purity, fine in color and easy to industrialize.
Description
Technical field
The present invention relates to N, N '-carbodiimide preparation method technical field, particularly a kind of thiocarbamide method is produced anti-hydrolysis stabilizer N, the technology of N '-diisopropyl benzene carbodiimide.
Background technology
N, N '-two replaces carbodiimide, general molecular formula (I)
R-N＝C＝N-R
1 (I)
Comprise (II), (III) or (IV).
Wherein R, R1-R6 are alkyl or the hydrogen atoms of C1-4, can be identical or different.Be mainly used in the anti-hydrolysis stabilizer of polyester polymer.
The thiocarbamide method is produced N, the technology that N '-two replaces carbodiimide mainly contains: among the CN101096349A, N, N '-dicyclohexyl carbodiimide is reacted in xylene solution by hexahydroaniline and dithiocarbonic anhydride and generates dicyclohexyl thiourea and sodium sulphite earlier, and dicyclohexyl thiourea generates through clorox secondary oxidation depriving hydrogen sulphide.Being the sodium sulphite that generates with the first step reaction removes wherein sulphur with sulfur reaction in the oxidation organic phase afterwards; In " the Shandong chemical industry " 2006 (3), N, the synthetic method of N '-DIC is raw material with industrial Isopropylamine, dithiocarbonic anhydride, and reflux removes the hydrogen sulfide of a part, synthesized N, N '-di-isopropyl thiourea is oxygenant with the chloro diethylamine again, the hydrogen sulfide of another molecule of oxidation removal, prepared N, N '-DIC.Among the CN101628882A, N, N '-two (2, the 6-diisopropyl phenyl) production technique of carbodiimide is to generate N with 2,6-diisopropyl aniline and thiocarbamide condensation, N '-two (2,6-diisopropyl phenyl) thiocarbamide, crystallization obtains after the hydrogen peroxide oxidation of cupric chloride catalysis.These methods respectively have relative merits, but because the difference of the character of starting raw material own, all can not obtain the N of high yield according to preceding two kinds of methods, N '-diisopropyl phenyl thiocarbamide, then a kind of method adopts copper catalyst can bring the problem that product is painted and metal ion is residual.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of thiocarbamide method and produce N, the technology of N '-diisopropyl benzene carbodiimide.
The technical solution adopted in the present invention is: a kind of thiocarbamide method is produced N, and the technology of N '-diisopropyl benzene carbodiimide may further comprise the steps:
A: in water medium, synthesize N, N '-diisopropyl phenyl thiocarbamide with 2,6-diisopropyl aniline and dithiocarbonic anhydride earlier;
B: carry out the once oxidation reaction, with N, N '-diisopropyl phenyl thiocarbamide adds in the reactor together with auxiliary agent, solvent after washing after filtration successively, be warming up to 70 ℃, dripped the chlorine bleach liquor of pre-configured oxygenant 6-10% concentration at 30 minutes, reacted 1.5 hours down at 70 ℃, static 15 minutes, discard lower floor's water;
C: carry out the secondary oxidation reaction, under the condition of step B, carry out secondary oxidation;
D: carry out desulfurization and handle, add the aqueous sodium hydroxide solution of sweetening agent 20-40% concentration in the solution after the step C oxidation, be warming up to 80-90 ℃, reacted 0.5-1.5 hour;
E: the washing branch vibration layer, steam toluene, add alcohol crystal and obtain white N, N '-diisopropyl benzene carbodiimide.
As preferably, the solvent among the described step B is the toluene aromatic solvent, and density is less than 1000Kg/m
3
As preferably, the auxiliary agent among the described step B is polyoxyethylene glycol.
As preferably, described oxygenant chlorine bleach liquor is 6-10%.
As preferably, the concentration of described sweetening agent aqueous sodium hydroxide solution is 33%.
As preferably, the desulfurization reaction temperature of described step D is 80 ℃.
As preferably, the desulphurization reaction time of described step D is 1 hour.
As preferably, described steps A reaction product does not need drying directly to carry out the B step reaction.
Compared with prior art, the invention has the beneficial effects as follows: the producing and manufacturing technique raw material is easy to get, technological operation is simple, products obtained therefrom purity height, color are good, be easy to industrialization.
Embodiment
In order more to be expressly understood technical scheme of the present invention, below the present invention is further described.
Embodiment 1
In the 500m1 reaction flask that has stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant voltage feeding device, add 80ml water and 88.5g2, the 6-diisopropyl aniline, unlatching is stirred in 10-20 ℃ and is dripped 22.5g dithiocarbonic anhydride down, stirring at room 1hr, slowly being warming up to backflow (about 80 ℃) reaction 6hr does not overflow to there being hydrogen sulfide, the hydrogen sulfide that generates with the aqueous sodium hydroxide solution absorption reaction in the process, then cooling, suction filtration, wash intermediate N, N '-two (2,6-diisopropyl phenyl) thiocarbamide.
Add above-mentioned intermediate 118g (moisture 20%), 9g poly(oxyethylene glycol) 400,400ml toluene in the reactor successively, be warming up to 70 ℃, dripped 6% chlorine bleach liquor 220ml in 30 minutes, synthermal reaction down 1.5 hours, static 15 minutes, discard lower floor's water.Add the 4.5g poly(oxyethylene glycol) 400 again, the chlorine bleach liquor 180ml in dropping 6% in 30 minutes under 70 ℃ carries out secondary oxidation.In the toluene solution of thick product, add the aqueous sodium hydroxide solution 27g of 33% concentration of metering then, be warming up to 80 ℃, reacted 1 hour, wash the toluene solution that obtains product for three times.Distillation at last removes solvent toluene, is cooled to 60 ℃, adds 180ml ethanol crystallisation by cooling, the dry white crystals thing 73g of getting of filtration washing.Fusing point 48-50 ℃, efficient liquid phase chromatographic analysis purity 98.96%.
Embodiment 2
In the 30L reactor that has stirring, thermometer, reflux condensation mode device for absorbing tail gas and constant voltage feeding device, add 7L water and 7.36Kg industry 2,6-diisopropyl aniline (96%), unlatching is stirred in 10-20 ℃ and is dripped 1.8Kg dithiocarbonic anhydride down, stirring at room 1hr, slowly being warming up to backflow (about 80 ℃) reaction 6hr does not overflow to there being hydrogen sulfide, the hydrogen sulfide that generates with the aqueous sodium hydroxide solution absorption reaction in the process, cooling then, suction filtration, washing and drying get intermediate N, N '-two (2,6-diisopropyl phenyl) thiocarbamide 7.6Kg.
Above-mentioned intermediate 3Kg, 300g poly(oxyethylene glycol) 400,12.5L toluene are added in the reactor successively, be warming up to 70 ℃, in the chlorine bleach liquor 10L of 30 minutes Dropwise 5 %, synthermal reaction down 1.5 hours static 15 minutes, discards lower floor's water.Add the 150g poly(oxyethylene glycol) 400 again, the chlorine bleach liquor 9L in 30 minutes Dropwise 5 % under 70 ℃ carries out secondary oxidation.In the toluene solution of thick product, add the aqueous sodium hydroxide solution 900g of 33% concentration of metering then, be warming up to 80 ℃, reacted 1 hour, wash the toluene solution that obtains product for three times.Distillation at last removes solvent toluene, is cooled to 60 ℃, adds 5L ethanol crystallisation by cooling, the dry white crystals thing 2.5Kg of getting of filtration washing.Fusing point 48-50 ℃, efficient liquid phase chromatographic analysis purity 99.36%.
Comparative example
Intermediate 40g, 4g poly(oxyethylene glycol) 400,180ml toluene are added in the reactor successively, be warming up to 70 ℃, dripped 6% chlorine bleach liquor 100ml in 30 minutes, synthermal reaction down 1.5 hours static 15 minutes, discards lower floor's water.Add the 2g poly(oxyethylene glycol) 400 again, the chlorine bleach liquor 80ml in dropping 6% in 30 minutes under 70 ℃ carries out secondary oxidation.Wash the toluene solution that obtains product for three times.Distillation at last removes solvent toluene, is cooled to 60 ℃, adds 80ml ethanol crystallisation by cooling, the dry faint yellow crystallisate 36g of getting of filtration washing.Efficient liquid phase chromatographic analysis purity 95.96%.
The said products has all been determined structure through infrared spectra, nuclear-magnetism and efficient liquid phase chromatographic analysis, tries out in nylon, poly(lactic acid) and obtains effect preferably.
The above only is preferred embodiments of the present invention, so all equivalences of doing according to the described structure of patent claim of the present invention, feature and principle change or modify, is included in the patent claim of the present invention.
Claims (8)
1. a thiocarbamide method is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: may further comprise the steps:
A: in water medium, synthesize N, N '-diisopropyl phenyl thiocarbamide with 2,6-diisopropyl aniline and dithiocarbonic anhydride earlier;
B: carry out the once oxidation reaction, with N, N '-diisopropyl phenyl thiocarbamide adds in the reactor together with auxiliary agent, solvent after washing after filtration successively, be warming up to 70 ℃, dripped the chlorine bleach liquor of pre-configured oxygenant 6-10% concentration at 30 minutes, reacted 1.5 hours down at 70 ℃, static 15 minutes, discard lower floor's water;
C: carry out the secondary oxidation reaction, under the condition of step B, carry out secondary oxidation;
D: carry out desulfurization and handle, add the aqueous sodium hydroxide solution of sweetening agent 20-40% concentration in the solution after the step C oxidation, be warming up to 80-90 ℃, reacted 0.5-1.5 hour;
E: the washing branch vibration layer, steam toluene, add alcohol crystal and obtain white N, N '-diisopropyl benzene carbodiimide.
2. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: the solvent among the described step B is the toluene aromatic solvent, and density is less than 1000Kg/m
3
3. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: the auxiliary agent among the described step B is polyoxyethylene glycol.
4. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: described oxygenant chlorine bleach liquor is 6-10%.
5. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: the concentration of described sweetening agent aqueous sodium hydroxide solution is 33%.
6. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: the desulfurization reaction temperature of described step D is 80 ℃.
7. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: the desulphurization reaction time of described step D is 1 hour.
8. thiocarbamide method according to claim 1 is produced N, and the technology of N '-diisopropyl benzene carbodiimide is characterized in that: described steps A reaction product does not need drying directly to carry out the B step reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102784324A CN103288681A (en) | 2013-07-04 | 2013-07-04 | Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102784324A CN103288681A (en) | 2013-07-04 | 2013-07-04 | Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103288681A true CN103288681A (en) | 2013-09-11 |
Family
ID=49090283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102784324A Pending CN103288681A (en) | 2013-07-04 | 2013-07-04 | Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103288681A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193653A (en) * | 2014-08-07 | 2014-12-10 | 山东汇海医药化工有限公司 | Novel synthesis method of N, N'-dicyclohexylcarbo-diimide |
| CN108084055A (en) * | 2017-12-27 | 2018-05-29 | 山东汇海医药化工有限公司 | A kind of method of N, N '-di-isopropyl thiourea oxidative synthesis N, N '-diisopropylcarbodiimide |
| CN109485583A (en) * | 2018-10-09 | 2019-03-19 | 淄博天堂山化工有限公司 | The preparation method of N, N '-diisopropylcarbodiimide |
| CN111978227A (en) * | 2020-09-04 | 2020-11-24 | 山西省化工研究所（有限公司） | Synthetic method of thiourea |
| CN113200866A (en) * | 2021-03-29 | 2021-08-03 | 龙曦宁（上海）医药科技有限公司 | Synthetic method of diafenthiuron impurity D |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502722A (en) * | 1960-05-24 | 1970-03-24 | Bayer Ag | Carbodiimides |
| JPH054957A (en) * | 1991-05-17 | 1993-01-14 | Kawaguchi Kagaku Kogyo Kk | Production of 2,6-diisopropylphenylcarbodiimide |
| US5532414A (en) * | 1992-11-11 | 1996-07-02 | Basf Aktiengesellschaft | 4-substituted bis(2,6-diisopropylphenyl)-carbodiimides, their preparation, their use, and 4-substituted 2,6-diisopropylphenyl isocyanates which can be used for their preparation |
| CN101096349A (en) * | 2006-06-26 | 2008-01-02 | 山东金城医药化工有限公司 | Production technique of N,N'-dicyclo hexylcar bodiimide |
| CN101538225A (en) * | 2009-05-08 | 2009-09-23 | 池州万维化工有限公司 | Dual-carbodiimide class and preparation as well as anti-hydrolysis application thereof |
| CN101628882A (en) * | 2009-08-05 | 2010-01-20 | 池州万维化工有限公司 | Production process of N, N'-2 (2,6-2-phenyl-isopropyl) carbodiimide |
-
2013
- 2013-07-04 CN CN2013102784324A patent/CN103288681A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502722A (en) * | 1960-05-24 | 1970-03-24 | Bayer Ag | Carbodiimides |
| JPH054957A (en) * | 1991-05-17 | 1993-01-14 | Kawaguchi Kagaku Kogyo Kk | Production of 2,6-diisopropylphenylcarbodiimide |
| US5532414A (en) * | 1992-11-11 | 1996-07-02 | Basf Aktiengesellschaft | 4-substituted bis(2,6-diisopropylphenyl)-carbodiimides, their preparation, their use, and 4-substituted 2,6-diisopropylphenyl isocyanates which can be used for their preparation |
| CN101096349A (en) * | 2006-06-26 | 2008-01-02 | 山东金城医药化工有限公司 | Production technique of N,N'-dicyclo hexylcar bodiimide |
| CN101538225A (en) * | 2009-05-08 | 2009-09-23 | 池州万维化工有限公司 | Dual-carbodiimide class and preparation as well as anti-hydrolysis application thereof |
| CN101628882A (en) * | 2009-08-05 | 2010-01-20 | 池州万维化工有限公司 | Production process of N, N'-2 (2,6-2-phenyl-isopropyl) carbodiimide |
Non-Patent Citations (2)
| Title |
|---|
| MICHAEL FINDLATER等: "Synthesis and structure of two new (guanidinate)boron dichlorides and their attempted conversion to boron(I) derivatives", 《DALTON TRANSACTIONS》 * |
| 叶德勇: "2，6-二异丙基苯碳二亚胺的合成研究", 《中国优秀硕士学位论文 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193653A (en) * | 2014-08-07 | 2014-12-10 | 山东汇海医药化工有限公司 | Novel synthesis method of N, N'-dicyclohexylcarbo-diimide |
| CN108084055A (en) * | 2017-12-27 | 2018-05-29 | 山东汇海医药化工有限公司 | A kind of method of N, N '-di-isopropyl thiourea oxidative synthesis N, N '-diisopropylcarbodiimide |
| CN109485583A (en) * | 2018-10-09 | 2019-03-19 | 淄博天堂山化工有限公司 | The preparation method of N, N '-diisopropylcarbodiimide |
| CN111978227A (en) * | 2020-09-04 | 2020-11-24 | 山西省化工研究所（有限公司） | Synthetic method of thiourea |
| CN113200866A (en) * | 2021-03-29 | 2021-08-03 | 龙曦宁（上海）医药科技有限公司 | Synthetic method of diafenthiuron impurity D |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100434416C (en) | Production technique of N,N'-dicyclo hexylcar bodiimide | |
| CN103288681A (en) | Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method | |
| CN107056727A (en) | A kind of oxadiazole compound of 5 arylseleno of 2 aryl 1,3,4 and preparation method | |
| JP5724366B2 (en) | Method for producing cyclic disulfonic acid ester compound | |
| CN101260118B (en) | Water-phase synthesis method for di-[(triethoxylsilicon)propyl]-bisulfide | |
| CN105949018A (en) | Sulfocompound selective catalytic oxidation reaction system in aqueous phase | |
| CN102887840A (en) | Method for preparing low-water-content solid methyl disulfonic acid through taking methylene chloride as raw material | |
| CN102558004B (en) | Chemical synthesis method for S-(4-tolyl)benzene sulfonate | |
| CN102875435B (en) | Organic thiosulfuric acid derivative preparation method | |
| CN112079748A (en) | Method for preparing dicyclohexylcarbodiimide by using vilsmeier reagent | |
| CN102924354A (en) | Synthetic method of methomyl | |
| CN103408427A (en) | 9-fluorenylmethyl chloroformate preparation method | |
| CN102993114B (en) | A kind of production method of 1H-TETRAZOLE-5-acetic acid | |
| CN106946753A (en) | The synthesis technique of sodium polydithio-dipropyl sulfonate | |
| CN101805327A (en) | Rabeprazole sodium compound and novel preparation method thereof | |
| CN106083679A (en) | A kind of preparation method of dialkoxy xanthate polysulfide | |
| CN110337434A (en) | The method for preparing 2- cyanoimidazole compound | |
| CN103626695B (en) | New method for preparing fluazinam by using mixed solvent as medium | |
| CN112830892A (en) | Synthesis method of pyridine-3-sulfonyl chloride | |
| CN111892553A (en) | Method for synthesizing ammonium acetate mediated benzothiazole compound | |
| CN102295591A (en) | Novel preparation method of 4, 4-dichlorodiphenyl sulfone | |
| CN111187193B (en) | Preparation method of rubber additive 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane | |
| CN111704591A (en) | Synthesis method of copper-catalyzed thio-naphthothiazolone compound | |
| CN114539081B (en) | Method for separating and purifying glycine by utilizing N, N-dibutyl ethanolamine | |
| CN104558065A (en) | Preparation method of L-rhamnose bis(dodecyl)mercaptal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130911 |