CN101648885A - Amide dimer and preparation method thereof - Google Patents
Amide dimer and preparation method thereof Download PDFInfo
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- CN101648885A CN101648885A CN 200910034857 CN200910034857A CN101648885A CN 101648885 A CN101648885 A CN 101648885A CN 200910034857 CN200910034857 CN 200910034857 CN 200910034857 A CN200910034857 A CN 200910034857A CN 101648885 A CN101648885 A CN 101648885A
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Abstract
The invention relates to a raw material for preparing dimer(fatty acid)yl diisocyanate (DDI), in particular to amide dimer (DDA) and a preparation method thereof. The preparation method comprises thefollowing steps: adding 10 parts of dimer acid and 1-3 parts of urea in a reaction container by weight, heating to 140-150 DEG C and reacting for 10-20min, keeping temperature at 170-200 DEG C for 2-8h to obtain deep yellow reaction solution and finally preparing DDA by extracting and decoloring. The invention has the advantage of simple process, easy operation and capability for industrialized production.
Description
Technical field
The present invention relates to a kind of raw material that can be used for preparing dimer acid diisocyanate (DDI), particularly a kind of amide dimer (DDA) and preparation method thereof belongs to the materials chemistry synthesis technical field.
Background technology
Composite solidpropellant is that multiple chemical raw material is controlled the matrix material that chemical reaction generated by strictness, and the quality of its mechanical property is determined by multiple factor.Wherein, tamanori performance quality is one of most important deciding factor, and the quality of curing system is the key factor that affects the mechanical properties.
In hydroxy-terminated polybutadienes tamanori (HTPB), select for use the low vulcabond of reactive behavior can make curing reaction more steady, thereby prolong the working life of propellant charge.Dimer acid diisocyanate (DDI) is a kind of long-chain vulcabond, and the N=C=O functional group reactions is active in the molecular structure reduces, and is the solidifying agent kind that a kind of molecular weight is big, toxicity is low.Be applied to be expected in the hydroxyl terminated polybutadiene propellant, HTPB propellant to provide the favorable manufacturability energy, prolong Composite Propellant Slurry working life.And the advantage that DDI has is water-fast, toxicity is low.
Before the present invention makes, about the synthesis technique of DDI, in document " dimer (fatty acid) yl diisocyanate and application thereof " ([J] Push Technology, 1988, appear in the newspapers 4:55-61), what it adopted is dimeracid carbonyl azide thing rearrangement method and two polyamine phosgenations.Dimeracid carbonyl azide thing rearrangement method is that dimeracid is made dimeracid carbonyl azide thing earlier, then in solvent under certain temperature thermal degradation generate isocyanic ester, discharge nitrogen.This method productive rate is higher, but is difficult for realizing suitability for industrialized production.Two polyamine phosgenations described in the prior art mainly comprise the dintrile method, and it is to be raw material with the dimeracid, earlier generate two polynitriles with ammonia gas react, again with two polynitriles under Raney's nickel catalyst catalysis, pressure hydration obtains two polyamine.Two polyamine and phosgene or triphosgene reaction can directly obtain dimer (fatty acid) yl diisocyanate DDI.Though the dintrile method is the DDI product of synthesis of high purity directly, prepare two polyamine severe reaction conditions by two polynitriles pressure hydrations, also be difficult for realizing suitability for industrialized production.
Summary of the invention
At the deficiency that prior art exists, the purpose of this invention is to provide and a kind ofly can be used as the raw material that is used to prepare dimer acid diisocyanate, and synthesis technique simple, be applicable to amide dimer of suitability for industrialized production and preparation method thereof.
Technical scheme of the present invention provides a kind of amide dimer, and its structural formula is:
Wherein, m=3, n=3, R=-, R '=-CH=CH-, R "=-CH=CH-; Or m=5, n=4, R=-CH
2-, R '=-, R "=-.
A kind of preparation method of amide dimer comprises the steps:
(1) amidate action
By weight, the urea of 10 parts dimeracids and 1～3 part is joined in the reactor, be warming up to 140～150 ℃, react after 10～20 minutes, insulation reaction 2～8 hours under 170～200 ℃ temperature condition obtains deep yellow transparent reaction liquid again;
(2) extraction and drying treatment
Above-mentioned deep yellow transparent reaction liquid is cooled to 100～120 ℃, under agitation condition, add aqueous sodium carbonate, be extraction agent with organic solvent ethyl acetate, methylene dichloride, toluene, sherwood oil, Skellysolve A, normal hexane or normal heptane again, carry out 3～4 times extraction; Combining extraction liquid is washed 1～2 time extraction liquid under the normal temperature; Add siccative anhydrous sodium sulphate or anhydrous magnesium sulfate in the extraction liquid after washing, carry out drying treatment;
(3) decolouring and distillation are handled
Add activated carbon in the extraction liquid after drying treatment, the decolouring of carrying out 15～30 minutes is handled; Again after filtration, remove activated carbon and siccative; Filtrate is carried out underpressure distillation handle, make amide dimer after wherein extraction agent is distillated.
Described dimeracid is dimerization linolenic acid or dimerization eleostearic acid.
In the described step (2), the weight ratio of the water consumption when at every turn washing and the input amount of dimeracid is 1～3: 1; The input amount of extraction agent and the weight ratio of dimeracid are 3～10: 1; The add-on of siccative and the weight ratio of dimeracid are 0.1～0.3: 1, and the drying treatment time is 1～10 hour.
In the described step (3), the add-on of activated carbon and the weight ratio of dimeracid are 0.1～0.3: 1; The temperature that underpressure distillation is handled is 20～80 ℃, and vacuum tightness is 0.5～20mmHg.
DDA by the technical solution of the present invention preparation, through hoffman degradation reaction (" organic chemistry ", Beijing: Higher Education Publishing House, 1999 (3 editions): p396), can prepare two polyamine, can directly make DDI with the reaction of phosgene or triphosgene, its building-up reactions productive rate height, product are pure, can be preparation of industrialization DDI and supply raw materials.
Compared with prior art, the inventive method is simple, and is easy to implement, and the synthetic method of product is suitable for suitability for industrialized production, and the amide dimer that provides can be used as the raw material of DDI green production.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
The 250ml there-necked flask is equipped with stirring, oil bath heating and thermometer.Add 56g dimerization linolenic acid and 12g urea.Be warming up to 150 ℃, the fierce generation of reaction also continues several minutes, then at 180 ℃ of insulation reaction 4h, obtains deep yellow transparent reaction liquid.Reaction solution is cooled to 110 ℃, adds 5% aqueous sodium carbonate 40mL under the high degree of agitation, with ethyl acetate extraction 4 times, uses the 100g ethyl acetate at every turn, and extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 60g when washing at every turn.With 7g anhydrous sodium sulfate drying 3h.Add the 7g decolorizing with activated carbon then and handle 15min.Last underpressure distillation removes ethyl acetate and gets amide dimer, and vacuum distillation temperature is 45 ℃, and vacuum tightness is 10mmHg, does not have solvent to distillate again behind the distillation 40min, stops distillation.Get weak yellow liquid shape amide dimer, the product productive rate is 80.5%.The structural formula of products therefrom is:
Product is done hydrogen nuclear magnetic resonance,
1HNMR (δ): 0.86～0.89,1.260,3.26～3.30,7.27ppm.FT-IR (γ): 3352.2,3176.5 (amide group), 2924.1,2856.2 (methylene radical), 1641.2 (carbonyl) cm
-1Ultimate analysis C
36H
72N
2O
2Theoretical value (measured value): C 76.59 (76.34); H 12.80 (12.62); N4.96 (4.98).
Press the DDA of present embodiment technical scheme preparation, through hoffman degradation reaction, can prepare raw material two polyamine of preparation of industrialization DDI, two polyamine and phosgene or triphosgene reaction can directly make high purity DDI by high yield.
Embodiment 2
The 250ml there-necked flask is equipped with stirring, oil bath heating and thermometer.Add 56g dimerization eleostearic acid and 15g urea.Be warming up to 150 ℃, the fierce generation of reaction also continues several minutes, then at 180 ℃ of insulation reaction 4h, obtains deep yellow transparent reaction liquid.Reaction solution is cooled to 110 ℃, adds 5% aqueous sodium carbonate 40mL under the high degree of agitation, with petroleum ether extraction 4 times, uses the 100g sherwood oil at every turn, and extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 60g when washing at every turn.With 7g anhydrous sodium sulfate drying 3h.Add the 7g decolorizing with activated carbon then and handle 15min.Last underpressure distillation removes sherwood oil and gets amide dimer, and vacuum distillation temperature is 45 ℃, and vacuum tightness is 10mmHg, does not have solvent to distillate again behind the distillation 40min, stops distillation.Get the weak yellow liquid amide dimer, the product productive rate is 82.9%.The structural formula of products therefrom is:
Product is made hydrogen nuclear magnetic resonance,
1HNMR (δ): 0.85～0.93,1.26～1.30,3.16～3.10,6.88～7.04ppm.FT-IR (γ): 3351.1,3188.4 (amide group), 2923.1,2860.5 (methylene radical), 1640.9 (carbonyl) cm
-1Ultimate analysis C
36H
72N
2O
2Theoretical value (measured value): C 76.59 (76.55); H 12.80 (12.78); N4.96 (5.02).
Embodiment 3
The 250ml there-necked flask is equipped with stirring, oil bath heating and thermometer.Add 56g dimerization linolenic acid and 18g urea.Be warming up to 150 ℃, the fierce generation of reaction also continues several minutes, then at 180 ℃ of insulation reaction 6h, obtains deep yellow transparent reaction liquid.Reaction solution is cooled to 110 ℃, adds 5% aqueous sodium carbonate 40mL under the high degree of agitation, with n-hexane extraction 4 times, uses the 100g normal hexane at every turn, and extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 60g when washing at every turn.With 7g anhydrous magnesium sulfate drying 4h.Add the 7g decolorizing with activated carbon then and handle 15min.Last underpressure distillation removes normal hexane and gets amide dimer, and vacuum distillation temperature is 45 ℃, and vacuum tightness is 10mmHg, does not have solvent to distillate again behind the distillation 40min, stops distillation.Get deep yellow liquid amide dimer, the product productive rate is 86.5%.Ultimate analysis C
36H
72N
2O
2Theoretical value (measured value): C 76.59 (76.18); H 12.80 (12.71); N4.96 (4.88).
Embodiment 4
The 250ml there-necked flask is equipped with stirring, oil bath heating and thermometer.Add 56g dimeracid dimerization linolenic acid and 18g urea.Be warming up to 150 ℃, the fierce generation of reaction also continues several minutes, then at 170 ℃ of insulation reaction 4.5h, obtains deep yellow transparent reaction liquid.Reaction solution is cooled to 110 ℃, adds 5% aqueous sodium carbonate 40mL under the high degree of agitation, with n-hexane extraction 4 times, uses the 100g normal hexane at every turn, and extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 60g when washing at every turn.With 7g anhydrous magnesium sulfate drying 3h.Add the 7g decolorizing with activated carbon then and handle 15min.Last underpressure distillation removes normal hexane and gets amide dimer, and vacuum distillation temperature is 45 ℃, and vacuum tightness is 10mmHg, does not have solvent to distillate again behind the distillation 40min, stops distillation.Get the yellow liquid amide dimer, the product productive rate is 85.1%.Ultimate analysis C
36H
72N
2O
2Theoretical value (measured value): C 76.59 (76.63); H 12.80 (12.88); N4.96 (5.10).
Claims (5)
1. amide dimer is characterized in that its structural formula is:
Wherein, m=3, n=3, R=-, R '=-CH=CH-, R "=-CH=CH-; Or m=5, n=4, R=-CH
2-, R '=-, R "=-.
2. the preparation method of an amide dimer is characterized in that comprising the steps:
(1) amidate action
By weight, the urea of 10 parts dimeracids and 1～3 part is joined in the reactor, be warming up to 140～150 ℃, react after 10～20 minutes, insulation reaction 2～8 hours under 170～200 ℃ temperature condition obtains deep yellow transparent reaction liquid again;
(2) extraction and drying treatment
Above-mentioned deep yellow transparent reaction liquid is cooled to 100～120 ℃, under agitation condition, add aqueous sodium carbonate, be extraction agent with organic solvent ethyl acetate, methylene dichloride, toluene, sherwood oil, Skellysolve A, normal hexane or normal heptane again, carry out 3～4 times extraction; Combining extraction liquid is washed 1～2 time extraction liquid under the normal temperature; Add siccative anhydrous sodium sulphate or anhydrous magnesium sulfate in the extraction liquid after washing, carry out drying treatment;
(3) decolouring and distillation are handled
Add activated carbon in the extraction liquid after drying treatment, the decolouring of carrying out 15～30 minutes is handled; Again after filtration, remove activated carbon and siccative; Filtrate is carried out underpressure distillation handle, make amide dimer after wherein extraction agent is distillated.
3. the preparation method of a kind of amide dimer according to claim 2, it is characterized in that: described dimeracid is dimerization linolenic acid or dimerization eleostearic acid.
4. the preparation method of a kind of amide dimer according to claim 2, it is characterized in that: in the described step (2), the weight ratio of the water consumption when at every turn washing and the input amount of dimeracid is 1～3: 1; The input amount of extraction agent and the weight ratio of dimeracid are 3～10: 1; The add-on of siccative and the weight ratio of dimeracid are 0.1～0.3: 1, and the drying treatment time is 1～10 hour.
5. the preparation method of a kind of amide dimer according to claim 2, it is characterized in that: in the described step (3), the add-on of activated carbon and the weight ratio of dimeracid are 0.1～0.3: 1; The temperature that underpressure distillation is handled is 20～80 ℃, and vacuum tightness is 0.5～20mmHg.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844988A (en) * | 2010-05-28 | 2010-09-29 | 苏州大学 | Dimeric fatty acid diamine, preparation method and method for preparing dimeric fatty acid diisocyanate |
| CN103242199A (en) * | 2010-05-28 | 2013-08-14 | 苏州大学 | Method for preparing dimer fatty acid diisocyanate by using dimer fatty acid diamine |
| CN104193641A (en) * | 2014-07-25 | 2014-12-10 | 南通大学 | Normal pressure synthesis method of oleamide |
| CN104981286B (en) * | 2013-02-11 | 2017-06-23 | 禾大公司 | dispersant |
| CN107090064A (en) * | 2017-05-24 | 2017-08-25 | 万华化学集团股份有限公司 | A kind of macromonomer with many alkyl structures, preparation method and the method that polymer polyatomic alcohol is prepared using it |
| CN107337614A (en) * | 2017-08-29 | 2017-11-10 | 湖北工程学院 | Chromatographically pure N, N dimethyl acetamide and preparation method thereof, production system |
| CN109880532A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of dimeric dibasic acid and its preparation method and application |
| CN109880531A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of dimer (fatty acid) yl and preparation method thereof |
| CN112457190A (en) * | 2020-10-27 | 2021-03-09 | 航天材料及工艺研究所 | Dimer acid modified polyether polyamine compound, preparation method and application thereof |
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2009
- 2009-09-10 CN CN2009100348574A patent/CN101648885B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844988A (en) * | 2010-05-28 | 2010-09-29 | 苏州大学 | Dimeric fatty acid diamine, preparation method and method for preparing dimeric fatty acid diisocyanate |
| CN103242199A (en) * | 2010-05-28 | 2013-08-14 | 苏州大学 | Method for preparing dimer fatty acid diisocyanate by using dimer fatty acid diamine |
| CN101844988B (en) * | 2010-05-28 | 2014-07-02 | 苏州大学 | Dimeric fatty acid diamine, preparation method and method for preparing dimeric fatty acid diisocyanate |
| CN104981286B (en) * | 2013-02-11 | 2017-06-23 | 禾大公司 | dispersant |
| CN104193641A (en) * | 2014-07-25 | 2014-12-10 | 南通大学 | Normal pressure synthesis method of oleamide |
| CN104193641B (en) * | 2014-07-25 | 2016-05-04 | 南通大学 | The atmospheric synthesizing method of oleamide |
| CN107090064A (en) * | 2017-05-24 | 2017-08-25 | 万华化学集团股份有限公司 | A kind of macromonomer with many alkyl structures, preparation method and the method that polymer polyatomic alcohol is prepared using it |
| CN107090064B (en) * | 2017-05-24 | 2019-04-23 | 万华化学集团股份有限公司 | A method of macromonomer, preparation method with more alkyl structures and polymer polyatomic alcohol is prepared using it |
| CN107337614A (en) * | 2017-08-29 | 2017-11-10 | 湖北工程学院 | Chromatographically pure N, N dimethyl acetamide and preparation method thereof, production system |
| CN109880532A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of dimeric dibasic acid and its preparation method and application |
| CN109880531A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of dimer (fatty acid) yl and preparation method thereof |
| CN109880532B (en) * | 2017-12-06 | 2021-11-09 | 中国石油化工股份有限公司 | Dimer acid and preparation method and application thereof |
| CN112457190A (en) * | 2020-10-27 | 2021-03-09 | 航天材料及工艺研究所 | Dimer acid modified polyether polyamine compound, preparation method and application thereof |
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