CN103242199A - Method for preparing dimer fatty acid diisocyanate by using dimer fatty acid diamine - Google Patents
Method for preparing dimer fatty acid diisocyanate by using dimer fatty acid diamine Download PDFInfo
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- CN103242199A CN103242199A CN2013101975517A CN201310197551A CN103242199A CN 103242199 A CN103242199 A CN 103242199A CN 2013101975517 A CN2013101975517 A CN 2013101975517A CN 201310197551 A CN201310197551 A CN 201310197551A CN 103242199 A CN103242199 A CN 103242199A
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- fatty acid
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Abstract
The invention discloses a method for preparing dimer fatty acid diisocyanate by using dimer fatty acid diamine. The method comprises the following steps of: mixing 50-120 parts by weight of hydrocarbon solvents, 6 parts by weight of triphosgene and 0-1 part by weight of catalysts in a reactor, and increasing temperature to 60-100 DEG C to obtain a mixed solution; adding 5 parts by weight of the dimer fatty acid diamine to 30-60 parts by weight of the hydrocarbon solvents, and dropwise adding into the mixed solution to carry out condensation reaction for 3-10 hours; carrying out distillation treatment on condensation reaction liquid obtained by adding no catalyst in the condensation reaction, and removing the hydrocarbon solvents to directly obtain a product, namely the dimer fatty acid diisocyanate; carrying out the distillation treatment on the condensation reaction liquid obtained by adding the catalysts in the condensation reaction; after the hydrocarbon solvents are removed, carrying out extraction treatment by using an extracting agent; and then removing the extracting agent through reduced pressure distillation to obtain the dimer fatty acid diisocyanate.
Description
Technical field
The present invention relates to the preparation method of a kind of dimer (fatty acid) yl diisocyanate (DDI), particularly a kind of dimer (fatty acid) yl diamines (DDAm) belongs to the materials chemistry synthesis technical field as the raw material of synthetic dimer (fatty acid) yl diisocyanate and its preparation method.
Background technology
Dimer (fatty acid) yl diisocyanate (DDI) is a kind of long carbochain vulcabond, and the N=C=O functional group reactions is active in its molecular structure reduces, and is the medium aliphatic diisocyanate of speed of response that a kind of molecular weight is big, toxicity is low.
About the application of DDI, " document dimer (fatty acid) yl diisocyanate and application thereof " ([J], Push Technology, 1988, seen comprehensive summary in 4:55-61).DDI is applied to be expected in the hydroxyl terminated polybutadiene propellant, HTPB propellant to provide the favorable manufacturability energy, good mechanical performance, and can prolong Composite Propellant Slurry working life as propellant curing agent.The advantage water-fast except having, that toxicity is low, side chain on the DDI molecule can play self-plasticizing action in the propelling agent network, thereby the polarity effect between the reduction macromolecular chain, and then weaken the cohesive action of matrix material under the low temperature, thus the cryogenic mechanics performance that improves material can be provided.
Carbamide paint by the DDI preparation is a kind of good outdoor coating, and it has good weather resistance, high-elongation, resistance to abrasion and the cementability good to metal, is applicable to aircraft, guided missile coating.
The vinylformic acid tetramethylolmethane of DDI and hydroxyl still contains hydroxyl in the tamanori that 65 ℃ of reactions obtain in the presence of catalyzer, the novel ink that cooperates benzidine Huang, trihydroxymethyl propane, triacrylate, softening agent, benzophenone and polyethylene wax etc. to make, per hour number to be printed can reach 8000 pages.
Before the present invention makes, patent documentation MARWAN RASIM KAMAL and EDGAR ROBERT ROGIER. Polyisocyanates and Derivatives([P] GB1023390, the technical scheme that a kind of Cirtius of employing rearrangement method prepares DDI is disclosed 1965,2).Cirtius rearrangement method technology is that dimer (fatty acid) yl is made the dimerization fat acyl chloride earlier, and further azide makes the dimer (fatty acid) yl carbonyl azide, and pyrolysis obtains dimer (fatty acid) yl diisocyanate in solvent at last.This method productive rate is higher, but owing to experience dimer (fatty acid) yl carbonyl azide is that unsettled intermediate is difficult for the realization suitability for industrialized production, and is 36 carbon vulcabond through the DDI that the Cirtius rearrangement method makes.
Summary of the invention
The objective of the invention is the deficiency at the prior art existence, a kind of can be used for preparing the raw material dimer (fatty acid) yl diamines of the synthetic usefulness of dimer (fatty acid) yl diisocyanate and its preparation method are provided, and provide a kind of reaction conditions gentleness, technology simple and feasible, be fit to the preparation method of the dimer (fatty acid) yl diisocyanate of suitability for industrialized production.
For achieving the above object, the technical solution used in the present invention is: a kind of dimer (fatty acid) yl diamines is provided, 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 "=-.
The invention provides a kind of preparation method of dimer (fatty acid) yl diamines, comprise the steps:
(1) by weight, after mixing under the ice-water bath condition, temperature rising reflux reduction reaction 12～50 hours obtains the muddy reaction solution of deep yellow with 30～80 parts of ethers reaction mediums, 4～8 parts of metal hydride reducing agents and 5 parts of dimer (fatty acid) yl diamide;
(2) with after the cooling of above-mentioned reaction solution, extract again, washing and drying treatment;
(3) add activated carbon in the extraction liquid after drying treatment, the decolouring of carrying out 10～30 minutes is handled; Again after filtration, remove activated carbon and siccative; Filtrate is carried out underpressure distillation handle, make the dimer (fatty acid) yl diamines after removing extraction agent wherein.
Among the preparation method of above-mentioned dimer (fatty acid) yl diamines, described ethers reaction medium is a kind of in tetrahydrofuran (THF), ether or the dioxane; Described metal hydride reducing agent is a kind of in sodium borohydride, POTASSIUM BOROHYDRIDE or the lithium aluminum hydride; Extraction treatment technology described in the step (2) is: with extraction agent extraction 3～4 times; Combining extraction liquid is washed 1～2 time extraction liquid under the normal temperature; Described extraction agent is a kind of in methylene dichloride, ethylene dichloride or the chloroform; The input amount of each extraction agent and the weight ratio of dimer (fatty acid) yl diamide are 3～6:1; Water consumption during each washing the and the weight ratio of dimer (fatty acid) yl diamide are 2～4:1.
It is a kind of with the method for dimer (fatty acid) yl diamines for the preparation of dimer (fatty acid) yl diisocyanate that the present invention also provides, and comprises the steps:
(1) by weight, 50～120 parts of varsols, 6 parts of triphosgene and 0～1 part of catalyzer are mixed in reactor, be warming up to 60～100 ℃, obtain mixing solutions; By weight, in 30～60 parts of varsols, add 5 parts of dimer (fatty acid) yl diamines, be added drop-wise to the condensation reaction of carrying out in the above-mentioned mixing solutions 3～10 hours; The structural formula of described dimer (fatty acid) yl diamines is:
Wherein, m=3, n=3, R=-, R '=-CH=CH-, R "=-CH=CH-; Or m=5, n=4, R=-CH
2-, R '=-, R "=-;
(2) do not distill processing in condensation reaction, adding the resulting condensation reaction solution of catalyzer, remove varsol, directly obtain the product dimer (fatty acid) yl diisocyanate; Distill processing in condensation reaction, adding the resulting condensation reaction solution of catalyzer, remove varsol after, carry out extraction treatment with extraction agent, remove extraction agent through underpressure distillation again, obtain dimer (fatty acid) yl diisocyanate.
Above-mentioned with the method for dimer (fatty acid) yl diamines for the preparation of dimer (fatty acid) yl diisocyanate in, described varsol is a kind of in toluene, dimethylbenzene or the ethyl acetate; Described catalyzer is a kind of in pyridine or the triethylamine; Extraction agent described in the step (2) is a kind of in normal heptane or the normal hexane.
Because technique scheme is used, the present invention compared with prior art has following advantage:
The present invention makes the dimer (fatty acid) yl diamines by amide dimer reduction, and reaction yield height, product are pure.Again dimer (fatty acid) yl diamines and phosgene or triphosgene reaction can directly be made DDI.Compare with existing DDI technology of preparing, preparation process reaction conditions gentleness of the present invention, technology are simple and feasible, easy to implement, and the synthetic method of product is suitable for suitability for industrialized production.
The DDI for preparing by technical solution of the present invention is 38 carbon vulcabond, because generated isocyanate group by the carbonyl reaction in the triphosgene molecule.And Cirtius rearrangement rule becomes isocyanate group by the azidocarbonyl pyrolysis in the dimeracid molecular structure.Therefore, the DDI carbochain that the present invention makes is longer, can more give full play to the performance advantage of long carbochain vulcabond.
Description of drawings
Fig. 1 is the fourier transform infrared spectroscopy figure of a kind of dimer (fatty acid) yl diamines of providing of the embodiment of the invention;
Fig. 2 is the fourier transform infrared spectroscopy figure of a kind of dimer (fatty acid) yl diisocyanate of providing of the embodiment of the invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
Preparation dimer (fatty acid) yl diamines:
Bathe under the cooling conditions at cryosel, in reaction flask, add 60g ethers reaction medium ether, 3.7g metal hydride reducing agent sodium borohydride and 5.6g dimer (fatty acid) yl diamide.Mix the water-bath of recession deicing, change heated water bath into, reaction mixture is warming up to backflow stage by stage, reacted 30 hours.With dichloromethane extraction 4 times, use the 20g methylene dichloride at every turn, extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 20g when washing at every turn.With 5g anhydrous sodium sulfate drying 3 hours.Adding the 5g decolorizing with activated carbon then handled 15 minutes.At last, underpressure distillation is except methylene dichloride, and vacuum distillation temperature is 40 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 40 minutes again, stops distillation.Get weak yellow liquid product dimer (fatty acid) yl diamines, the product productive rate is 78.6%.
The structural formula of products therefrom is:
Wherein, m=3, n=3, R=-, R '=-CH=CH-, R "=-CH=CH-.
Product test hydrogen nuclear magnetic resonance spectrum (solvent DCCl
3): δ 0.84～0.88,1.28,3.30～3.32,5.65,7.27 ppm.
Product test fourier transform infrared spectroscopy: ν 3415.3 (amino), 2923.5,2852.6(methylene radical) cm
-1
Referring to accompanying drawing 1, it is the fourier transform infrared spectroscopy figure by the dimer (fatty acid) yl diamines of present embodiment technical scheme preparation; Among the figure, ν 3415.3 cm
-1Be amino absorption peak, 2923.5 and 2852.6cm
-1Be the hydrocarbon absorption peak of long carbochain methylene radical.Lose the carbonylic stretching vibration peak of dimer (fatty acid) yl diamide in the infrared absorption curve, illustrate that reduction reaction is complete, the dimer (fatty acid) yl diamide changes the dimer (fatty acid) yl diamines into fully through reduction reaction.
To be applied to prepare dimer (fatty acid) yl diisocyanate by the dimer (fatty acid) yl diamines that technique scheme prepares:
In the 250ml there-necked flask, add 100g varsol toluene, 6.0g triphosgene and 0.6g catalyzer pyridine.After being warming up to 90 ℃, slowly Dropwise 5 .3g dimer (fatty acid) yl diamines is dissolved in the solution in the 50g toluene.
Dropwised the back insulation reaction 5 hours, directly underpressure distillation is except toluene, and vacuum distillation temperature is 65 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation.Residue uses the 30g normal heptane with normal heptane extraction 4 times at every turn, and extraction finishes the back combining extraction liquid.
The extraction liquid that merges adds the 3g decolorizing with activated carbon to be handled 15 minutes.Last underpressure distillation gets dimer (fatty acid) yl diisocyanate except normal heptane, and product yield is 75.8%.Vacuum distillation temperature is 65 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation, obtains dimer (fatty acid) yl diisocyanate.
Referring to accompanying drawing 2, it is the fourier transform infrared spectroscopy figure by the dimer (fatty acid) yl diisocyanate of above-mentioned steps preparation; Product test fourier transform infrared spectroscopy: ν 2925.4,2850.2(methylene radical C-H); 2271.7(-N=C=O) cm
-1Among Fig. 2, ν 2925.4 and 2850.2 cm
-1Be the hydrocarbon absorption peak of long carbochain methylene radical.The amino that loses the dimer (fatty acid) yl diamines in the infrared absorption curve absorbs, and at 2271.7cm
-1The new distinctive absorption peak of isocyanate group occurs, illustrate that the dimer (fatty acid) yl diamines has changed dimer (fatty acid) yl diisocyanate into fully through condensation reaction.
Embodiment two:
Bathe under the cooling at cryosel, in reaction flask, add 60g tetrahydrofuran (THF), 3.8g lithium aluminum hydride and 5.6g dimer (fatty acid) yl diamide.The reinforced recession deicing water-bath that finishes changes heated water bath into, and reaction mixture is warming up to backflow stage by stage, reacts 48 hours.With ethylene dichloride extraction 4 times, use the 20g ethylene dichloride at every turn, extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 20g when washing at every turn.With 5g anhydrous sodium sulfate drying 3 hours.Adding the 5g decolorizing with activated carbon then handled 15 minutes.Last underpressure distillation gets the dimer (fatty acid) yl diamines except ethylene dichloride, and vacuum distillation temperature is 50 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation.Get weak yellow liquid product dimer (fatty acid) yl diamines, the product productive rate is 70.2%.
To be applied to prepare dimer (fatty acid) yl diisocyanate by the dimer (fatty acid) yl diamines that technique scheme prepares:
In the 250ml there-necked flask, add 50g ethyl acetate and 6.0g triphosgene.After being warming up to 78 ℃, slowly Dropwise 5 .3g dimer (fatty acid) yl diamines is dissolved in the solution in the 40g ethyl acetate.
Dropwised the back insulation reaction 6 hours.Stopped reaction adds the 3g decolorizing with activated carbon after reaction solution is cooled to 50 ℃ and handled 15 minutes.Last underpressure distillation gets dimer (fatty acid) yl diisocyanate except ethyl acetate, and product yield is 79.1%.Vacuum distillation temperature is 55 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation, obtains dimer (fatty acid) yl diisocyanate.
Embodiment three:
Bathe under the cooling at cryosel, in reaction flask, add 60g tetrahydrofuran (THF), 5.3g POTASSIUM BOROHYDRIDE and 5.6g dimer (fatty acid) yl diamide.The reinforced recession deicing water-bath that finishes changes heated water bath into, and reaction mixture is warming up to backflow stage by stage, reacts 48 hours.With chloroform extraction 4 times, use the 20g chloroform at every turn, extraction finishes the back combining extraction liquid.
The extraction liquid washing that merges 2 times, water consumption is 20g when washing at every turn.With 5g anhydrous sodium sulfate drying 3 hours.Adding the 5g decolorizing with activated carbon then handled 15 minutes.Last underpressure distillation gets the dimer (fatty acid) yl diamines except chloroform, and vacuum distillation temperature is 50 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation.Get weak yellow liquid product dimer (fatty acid) yl diamines, the product productive rate is 72.9%.
To be applied to prepare dimer (fatty acid) yl diisocyanate by the dimer (fatty acid) yl diamines that technique scheme prepares:
In the 250ml there-necked flask, add 60g ethyl acetate, 0.5g triethylamine and 6.0g triphosgene.After being warming up to 78 ℃, slowly Dropwise 5 .3g dimer (fatty acid) yl diamines is dissolved in the solution in the 50g ethyl acetate.
Dropwised the back insulation reaction 4 hours, stopped reaction, directly underpressure distillation is except ethyl acetate, and vacuum distillation temperature is 55 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation.Residue uses the 30g normal hexane with n-hexane extraction 4 times at every turn, and extraction finishes the back combining extraction liquid.
The extraction liquid that merges adds the 3g decolorizing with activated carbon to be handled 15 minutes.Last underpressure distillation gets dimer (fatty acid) yl diisocyanate except normal hexane, and product yield is 82.5%.Vacuum distillation temperature is 55 ℃, and vacuum tightness is 10mmHg, and distilling does not have solvent to distillate after 50 minutes again, stops distillation, obtains dimer (fatty acid) yl diisocyanate.
Claims (4)
1. a dimer (fatty acid) yl diamines is characterized in that comprising the steps: for the preparation of the method for dimer (fatty acid) yl diisocyanate
(1) by weight, 50～120 parts of varsols, 6 parts of triphosgene and 0～1 part of catalyzer are mixed in reactor, be warming up to 60～100 ℃, obtain mixing solutions; By weight, in 30～60 parts of varsols, add 5 parts of dimer (fatty acid) yl diamines, be added drop-wise to the condensation reaction of carrying out in the above-mentioned mixing solutions 3～10 hours; The structural formula of described dimer (fatty acid) yl diamines is:
Wherein, m=3, n=3, R=-, R '=-CH=CH-, R "=-CH=CH-;
Or m=5, n=4, R=-CH
2-, R '=-, R "=-;
(2) do not distill processing in condensation reaction, adding the resulting condensation reaction solution of catalyzer, remove varsol, directly obtain the product dimer (fatty acid) yl diisocyanate; Distill processing in condensation reaction, adding the resulting condensation reaction solution of catalyzer, remove varsol after, carry out extraction treatment with extraction agent, remove extraction agent through underpressure distillation again, obtain dimer (fatty acid) yl diisocyanate.
2. dimer (fatty acid) yl diamines according to claim 1 is characterized in that for the preparation of the method for dimer (fatty acid) yl diisocyanate: described varsol is a kind of in toluene, dimethylbenzene or the ethyl acetate.
3. dimer (fatty acid) yl diamines according to claim 1 is characterized in that for the preparation of the method for dimer (fatty acid) yl diisocyanate: described catalyzer is a kind of in pyridine or the triethylamine.
4. dimer (fatty acid) yl diamines according to claim 1 is characterized in that for the preparation of the method for dimer (fatty acid) yl diisocyanate: the extraction agent described in the step (2) is a kind of in normal heptane or the normal hexane.
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| US1023390A (en) * | 1912-01-02 | 1912-04-16 | Spencer Lens Co | Nose-piece for microscopes. |
| GB1023390A (en) * | 1965-02-01 | 1966-03-23 | Gen Mills Inc | Polyisocyanates and derivatives |
| US3799965A (en) * | 1972-08-21 | 1974-03-26 | Gen Mills Chem | Alicyclic diisocyanates |
| CN1046522A (en) * | 1989-04-21 | 1990-10-31 | 三井东压化学株式会社 | Alicyclic diamine and vulcabond of alicyclic ring and polyisocyanate root close isocyanuric acid ester and preparation method thereof |
| CN101234998A (en) * | 2006-12-23 | 2008-08-06 | 赢创德固赛有限责任公司 | Process for the continuous preparation of (cyclo) aliphatic diisocyanates |
| CN101648885A (en) * | 2009-09-10 | 2010-02-17 | 苏州大学 | Amide dimer and preparation method thereof |
-
2010
- 2010-05-28 CN CN2013101975517A patent/CN103242199A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1023390A (en) * | 1912-01-02 | 1912-04-16 | Spencer Lens Co | Nose-piece for microscopes. |
| GB1023390A (en) * | 1965-02-01 | 1966-03-23 | Gen Mills Inc | Polyisocyanates and derivatives |
| US3799965A (en) * | 1972-08-21 | 1974-03-26 | Gen Mills Chem | Alicyclic diisocyanates |
| CN1046522A (en) * | 1989-04-21 | 1990-10-31 | 三井东压化学株式会社 | Alicyclic diamine and vulcabond of alicyclic ring and polyisocyanate root close isocyanuric acid ester and preparation method thereof |
| CN101234998A (en) * | 2006-12-23 | 2008-08-06 | 赢创德固赛有限责任公司 | Process for the continuous preparation of (cyclo) aliphatic diisocyanates |
| CN101648885A (en) * | 2009-09-10 | 2010-02-17 | 苏州大学 | Amide dimer and preparation method thereof |
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| 季宝等: "三光气的反应机理和应用", 《科技情报开发与经济》 * |
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Application publication date: 20130814 |