CN105367790A - Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof - Google Patents
Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof Download PDFInfo
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- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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Abstract
The present invention discloses a preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof. The method is as below: raw materials of 10-undecylenic acid modified castor-oil base branched polyenoid prepolymer and thiol cyclic carbonate and a solvent chloroform are subjected to UV radiation reaction in the presence of a photoinitiator for 6-15 h to obtain a castor-oil base polybasic branched cyclic carbonate prepolymer; and the prepolymer further reacts with an amino compound to prepare the castor-oil base non-isocyanate polyurethane. The preparation of the cyclic carbonate does not require high temperature, high pressure or catalyst, and can well control the graft number of cyclic carbonate groups in the vegetable oil; and the prepared cyclic carbonate has branched structure and lower viscosity, and has long space group from a vegetable oil connection point, so that the cyclic carbonate group at the end has very high reactivity. The castor-oil base polyurethane material has the advantages of biodegradability and high content of renewable carbon, and can be used as renewable polyurethane resin for paint.
Description
Technical field
The invention discloses the preparation method of the polynary cyclic carbonate ester of a kind of castor oil-base branching and non-isocyanate polyurethane thereof, be specifically related to a kind of polynary cyclic carbonate ester prepolymer of castor oil-base branching of 10 hendecenoic acid modification and the preparation method of non-isocyanate polyurethane thereof.
Background technology
Non-isocyanate polyurethane (NIPU) is prepared by the copolyreaction of polynary cyclic carbonate ester prepolymer and polyamine, it is compared with polyisocyanic acid ester polyurethane, not only avoid the use of the larger isocyanic ester of toxicity, remain the excellent mechanical property of conventional urethane material, and due to its backbone structure not existing amino-formate bond, thus compensate for the deficiency of traditional polyisocyanic acid ester polyurethane in stability to hydrolysis, anti-permeability performance from molecular structure, it has excellent chemical resistance, water tolerance and permeability resistance.During preparation NIPU is raw materials used, polyamine is generally industrial goods, and the design preparation of cyclic carbonate ester prepolymer then becomes the main research of preparation NIPU.
Vegetable oil source extensively, cheap, be easy to get, prepare plant oil based cyclic carbonate ester with vegetables oil and there is nontoxic, biodegradable advantage.Replace isocyanic ester to produce urethane, safer, environmental protection with plant oil based cyclic carbonate ester, the dependence to petroleum resources can be reduced simultaneously, realize industrial economy Sustainable development.
The method of the plant oil based cyclic carbonate ester of current preparation is mainly carbonic acid gas and inserts epoxy method, namely first by the unsaturated double-bond epoxidation in vegetables oil, then is inserted in plant oil based epoxy by carbonic acid gas and forms plant oil based cyclic carbonate ester.It is 100% that this method prepares gained plant oil based cyclic carbonate ester renewable carbon content, but need to react for a long time in special reactor, under high temperature, high pressure and catalyzer exist, simultaneously because the oxidable unsaturated double-bond of vegetables oil is arranged in unsaturated fatty acids chain, epoxide group after epoxidation is in the identical position with double bond, because steric effect causes the insertion rate of carbonic acid gas not high, thus cause the cyclic carbonate ester number that accesses on the low side, and these class methods can not the access number of design con-trol cyclic carbonate ester group in vegetables oil well; The cyclic carbonate ester group preparing gained is directly connected with vegetable fatty acids chain and there is not spacer, is easily reduced it as the reactive behavior of polyurethane for prepolymer by the coated entanglement of lipid acid long-chain.
The present invention is directed to the deficiency in existing plant oil based cyclic carbonate ester prepolymer technology of preparing, provide a kind of simple, the controlled and preparation method of the polynary cyclic carbonate ester prepolymer of the castor oil-base branching that reactive behavior is high of cyclic carbonate ester group number.Because the double bond on the polynary alkene of Viscotrol C branching of 10 hendecenoic acid modification and sulfydryl can carry out efficiently, single-minded sulfydryl-alkene click-reaction, the present invention is by controlling the access number of the when ultraviolet lighting time controling cyclic carbonate ester group of feeding intake of sulfydryl cyclic carbonate ester and castor oil-base multiolefin, by introducing the long fatty carbon chain of 10 hendecenoic acid at cyclic carbonate ester group and Castor Oil Fatty Acid interchain with the snappiness of the reactive behavior and castor oil-base non-isocyanate polyurethane that improve end-link carbonic acid ester group, can be used as the renewable resin of coating.
Summary of the invention
The object of the invention is to overcome the deficiency in existing plant oil based cyclic carbonate ester prepolymer preparation method, there is provided a kind of and simple prepare the controlled and method of the polynary cyclic carbonate ester prepolymer of reactive behavior is high plant oil based branching of cyclic carbonate ester group number, and 10 hendecenoic acid Long carbon chain is introduced in non-isocyanate polyurethane main chain, improve snappiness and the water tolerance of castor oil-base non-isocyanate polyurethane.
For achieving the above object, the present invention adopts sulfydryl-alkene click-reaction to prepare castor oil-base branching polynary cyclic carbonate ester prepolymer: join in reactor by the polynary alkene of castor oil-base branching of 10 hendecenoic acid modification, sulfydryl cyclic carbonate ester, light trigger, solvent is made with trichloromethane, under ultraviolet light irradiation, react 6 ~ 15h at 0 ~ 40 DEG C, revolve and steam except desolventizing obtains the polynary cyclic carbonate ester of castor oil-base branching; The cyclic carbonate ester average functionality of the polynary cyclic carbonate ester of described castor oil-base branching is 2 ~ 8.7;
Described non-isocyanate polyurethane is prepared by the following method: after being mixed in proportion under polynary for castor oil-base branching cyclic carbonate ester prepolymer and polyhydric amine compounds room temperature, be coated in tetrafluoroethylene template, be placed in 50-150 DEG C of baking oven stage reacting by heating 5 ~ 48 hours, obtain castor oil-base non-isocyanate polyurethane.
In the present invention, the described polynary alkene of castor oil-base branching is prepared by the following method: add in reaction flask by castor oil-base polyvalent alcohol, triethylamine, ethyl acetate, ice bath stirs lower instillation 10-hendecene acyl chlorides, after ice bath reaction 2h, remove ice bath and continue reaction 12 ~ 24h, filter, organic layer alkali liquid washing, anhydrous magnesium sulfate drying, revolves steaming and desolventizes, and obtains the polynary alkene of castor oil-base branching of 10 hendecenoic acid modification; The carbon-carbon double bond average functionality of the polynary alkene of described modified castor oil base branching is 5.7 ~ 8.7.
In the present invention, described castor oil-base polyvalent alcohol is by sulfydryl-alkene click-reaction preparation: by Viscotrol C, add in reaction flask containing mercaptoalcohol compounds, light trigger, methylene dichloride, ultra violet lamp reaction 5 ~ 10h at 0 ~ 40 DEG C, excessive alcohol is removed with deionized water wash, organic over anhydrous dried over mgso, revolves steaming removing methylene dichloride and obtains castor oil-base polyvalent alcohol; The hydroxyl average functionality of described castor oil-base polyvalent alcohol is 5.7 ~ 8.7.
In the present invention, described one or more the mixture comprised containing mercaptoalcohol compounds in 2 mercapto ethanol, 3-Mercapto-1，2-propanediol, 3-sulfydryl-2-butanols, 3-sulfydryl-2-methyl amyl alcohol, 6-sulfydryl-1-hexanol, 3-sulfydryl-1-hexanol.
In the present invention; described light trigger comprises dimethoxybenzoin, 2-hydroxy-2-methyl-1-phenyl-acetone, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2; 2-dimethyl benzil ketals; one or more mixture in 2,2-diethoxy acetophenone.The consumption of light trigger is 1% ~ 3% of reactant total mass.
In the present invention, the described polynary cyclic carbonate ester of castor oil-base branching introduces the long-chain of 10 hendecenoic acid between Viscotrol C aliphatic chain and cyclic carbonate ester functional group, cyclocarbonate radical cumularsharolith, in the end position of 10 hendecenoic acid long-chain, gives the reactive behavior that cyclic carbonate ester is higher.
In the present invention, described polyhydric amine compounds is one or more the mixture in quadrol, propylene diamine, hexanediamine, m-xylene diamine, certain herbaceous plants with big flowers diamines, isophorone diamine, polyethylene polyamine and polyetheramine.
In the present invention, the vegetables oil containing unsaturated carbon-carbon double bond is adopted to replace Viscotrol C as starting raw material, all can prepare the polynary cyclic carbonate ester of other plant oil base branching according to method disclosed by the invention, described vegetables oil comprises one or more the mixture in rapeseed oil, sweet oil, oleum lini, tung oil, raisin seed oil.
In the present invention, the preparation method of cyclic carbonate ester is without the need to High Temperature High Pressure and catalyzer, and can the access number of design con-trol cyclic carbonate ester group in vegetables oil well; The cyclic carbonate ester preparing gained has branched structure, has lower viscosity, and there is longer spacer between vegetables oil tie point, makes the cyclic carbonate ester group being in end position have very high reactive behavior.Prepare gained polyurethane based on castor oil material and there is biodegradable, renewable carbon content advantages of higher, can be used as the renewable urethane resin of coating.
Accompanying drawing explanation
The synthetic route chart of Fig. 1 to be cyclic carbonate ester average functionality be polynary cyclic carbonate ester of castor oil-base of 5.7.
Embodiment
In order to explain the present invention better, below in conjunction with specific embodiment, the present invention is described in further detail, but they do not form restriction to the present invention.
Embodiment 1
1) preparation of sulfydryl cyclic carbonate ester
By 11.8g glycerine cyclic carbonate ester, 13g3-thiohydracrylic acid, 1.24g tosic acid, 40ml methylene dichloride adds in reaction flask, back flow reaction 8h at 80 DEG C.After dividing three washing solns with deionized water, with anhydrous magnesium sulfate drying, revolve and boil off solvent, obtain 16.27g sulfydryl cyclic carbonate ester, productive rate 79%.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)4.95(ddd,J＝9.1,6.1,3.8Hz,1H),4.58(t,J＝8.6Hz,1H),4.43(dd,J＝12.6,3.3Hz,1H),4.35(dd,J＝5.2,2.6Hz,1H),4.32(d,J＝5.3Hz,1H),2.81(td,J＝7.9,4.0Hz,2H),2.74(dd,J＝10.2,3.9Hz,2H),1.71-1.61(m,1H)。
13CNMR(100MHz,CDCl
3,δppm)171.18(OC＝O),154.56(OC(O)O),73.82(CH),65.19(CH
2),63.24(CH
2),38.09(CH
2),19.45(CH
2)。
2) hydroxyl average functionality is the preparation of the castor oil-base polyvalent alcohol of 8.7
By Viscotrol C 9g, 3-sulfydryl-1,2-propylene glycol 5g, light trigger 2-hydroxy-2-methyl-1-phenyl-acetone 0.24g and methylene dichloride 20ml join in reactor, at room temperature ultraviolet lighting reaction 8h, deionized water wash is used to remove excessive 3-Mercapto-1，2-propanediol, organic over anhydrous dried over mgso, revolve and steam removing methylene dichloride, obtain the castor oil-base polyvalent alcohol that 11.55g hydroxyl average functionality is 8.7, reacted completely by NMR technology determination double bond, productive rate is 95.7%.
3) carbon-carbon double bond average functionality is the preparation of the castor oil-base branching multiolefin of 8.7
10 hendecenoic acid 10g, thionyl chloride 30g and methylene dichloride 20ml are added in reactor, at 50 DEG C, stirs 5h, revolve and steam removing methylene dichloride and thionyl chloride, obtain the 10-hendecene acyl chlorides of 11g.By hydroxyl average functionality be 8.7 castor oil-base polyvalent alcohol 4g, triethylamine 5.67g and ethyl acetate 30ml join in reactor, under ice bath, 10-hendecene acyl chlorides 11.37g is added dropwise in solution in 0.5h, after continuing reaction 2h, remove ice bath and at room temperature react 12h, filter, get organic layer, three times are washed by the NaOH solution of 1wt%, with anhydrous magnesium sulfate drying, revolve and steam removing ethyl acetate, obtain the castor oil-base branching multiolefin that 7.8g double bond average functionality is 8.7, productive rate is 96%.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.83(td,J＝16.6,6.6Hz,8.7H),5.27(s,1H),5.11(s,1H),4.98(dd,J＝24.6,13.7Hz,18H),4.92–4.81(m,1H),4.71(t,J＝7.8Hz,1H),4.44–4.06(m,7H),3.96(t,J＝7.0Hz,2H),2.67(d,J＝6.5Hz,5H),2.46(t,J＝7.4Hz,5H),2.31(dd,J＝24.7,17.2Hz,14H),2.10(ddd,J＝20.6,14.2,7.3Hz,23H),1.85–1.47(m,43H),1.47–1.09(m,139H),0.89(d,J＝7.0Hz,9H)。
13CNMR(101MHz,CDCl
3，δppm)179.60(C＝O),139.16(C＝C),114.16(C＝C),77.51(CH),73.51(CH),68.38(CH),63.47(CH
2),62.32(CH
2),42.87(CH),38.14(CH
2),34.77(CH
2),33.80(CH
2),31.83(CH2),29.55(CH
2),29.14(CH
2),26.71(CH
2),25.83-25.21(CH
2),24.92(CH
2),22.57(CH
2),19.42(CH
2),18.38(CH
2),14.05(CH
3)。
4) cyclic carbonate ester average functionality is the preparation of the polynary branching cyclic carbonate ester of castor oil-base of 8.7
Be that the polynary alkene 6.6g of castor oil-base branching of the 10 hendecenoic acid modification of 8.7, sulfydryl cyclic carbonate ester 4.5g, dimethoxybenzoin 0.16g and trichloromethane 10ml join in reactor by carbon-carbon double bond average functionality, at room temperature ultraviolet lighting reaction 12h, revolve and steam except desolventizing, obtain the polynary cyclic carbonate ester of castor oil-base branching that 11.02g cyclic carbonate ester average functionality is 8.7.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.16(s,1H),5.00(d,J＝19.4Hz,8.7H),4.65(dt,J＝17.1,8.2Hz,8H),4.49-4.10(m,33H),4.01-3.82(m,2H),2.98(dd,J＝20.1,13.3Hz,6H),2.78(ddt,J＝26.7,14.3,7.0Hz,42H),2.54(t,J＝7.3Hz,14H),2.42-2.23(m,17H),2.19-1.99(m,6H),1.87-1.73(m,5H),1.72-1.46(m,44H),1.27(dd,J＝14.4,6.2Hz,145H),0.88(d,J＝6.9Hz,9H)。
13CNMR(101MHz,CDCl
3，δppm)179.00(C＝O),176.74(C＝O),155.22(OC(O)O),76.75(CH),71.96(CH),70.29(CH),70.02(CH),66.05(CH
2),65.07(CH
2),63.27(CH
2),61.69(CH
2),42.80(CH),34.43(CH
2),33.93(CH
2),33.83-33.69(CH
2),32.60(CH
2),31.72(s),30.26-28.73(CH
2),28.73-27.98(CH
2),26.92(CH
2,26.60-26.19(CH
2),25.13(CH
2),24.87(CH
2),24.63(CH
2),23.87(CH
2),22.54(CH
2),14.04(CH
3)。
Embodiment 2
1) hydroxyl average functionality is the preparation of the castor oil-base polyvalent alcohol of 5.7
By Viscotrol C 9g, 2 mercapto ethanol 3.78g, light trigger 2,2-diethoxy acetophenone 0.20g and methylene dichloride 20ml joins in reactor, at room temperature ultraviolet lighting reaction 8h, deionized water wash is used to remove excessive 2 mercapto ethanol, organic layer uses anhydrous magnesium sulfate drying, revolve steaming removing methylene dichloride and obtain the castor oil-base polyvalent alcohol that 9.77g hydroxyl average functionality is 5.7, reacted completely by NMR technology determination double bond, productive rate is 87.1%.
2) carbon-carbon double bond average functionality is the preparation of the castor oil-base branching multiolefin of 5.7
By hydroxyl average functionality be 5.7 castor oil-base polyvalent alcohol 4g, triethylamine 3.44g and ethyl acetate 30ml join in reactor, under ice bath, 10-hendecene acyl chlorides 7g is added dropwise in solution in 0.5h, continue reaction 2h, then at room temperature react 12h, filter, get organic layer, wash three times by the NaOH solution of 1wt%, with anhydrous magnesium sulfate drying, revolve and steam removing ethyl acetate, obtain the castor oil-base multiolefin that 6.5g carbon-carbon double bond average functionality is 5.7, productive rate is 95%.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.80(td,J＝16.9,6.7Hz,5.7H),5.26(s,1H),4.95(dd,J＝24.2,13.5Hz,12H),4.86(s,1H),4.68(t,J＝7.4Hz,1H),4.43-4.23(m,2H),4.22-4.06(m,5H),3.93(t,J＝7.0Hz,2H),2.79-2.50(m,5H),2.48-2.18(m,14H),2.18-1.92(m,17H),1.76(dd,J＝15.0,7.8Hz,3H),1.55(d,J＝32.8Hz,28H),1.32(d,J＝32.2Hz,105H),0.86(d,J＝6.7Hz,9H)。
13CNMR(101MHz,CDCl
3，δppm)179.40(C＝O),139.17(C＝C),114.16(C＝C),73.52(C-OH),68.73(CH),63.44(CH
2),62.15(CH
2),42.82(CH),38.04(CH
2),34.75(CH
2),33.90(CH
2),31.87(CH2),29.51(CH
2),29.18(CH
2),26.73(CH
2),25.82-25.23(CH
2),24.89(CH
2),22.54(CH
2),19.47(CH
2),18.36(CH
2),14.02(CH
3)。
3) cyclic carbonate ester average functionality is the preparation of the polynary branching cyclic carbonate ester of castor oil-base of 5.7
By carbon-carbon double bond average functionality be 5.7 castor oil-base branching multiolefin 5.7g, sulfydryl cyclic carbonate ester 3.5g, 1-hydroxycyclohexyl phenyl ketone 0.08g and trichloromethane 8ml join in reactor, at room temperature ultraviolet lighting reaction 12h, revolve and steam except desolventizing, obtain the polynary cyclic carbonate ester of castor oil-base branching that 9.02g cyclic carbonate ester average functionality is 5.7.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.25(s,1H),4.95(s,5.7H),4.57(t,J＝8.5Hz,5H),4.35(ddd,J＝16.8,12.6,6.8Hz,18H),4.23-4.03(m,7H),2.99-2.74(m,16H),2.69(t,J＝7.0Hz,15H),2.53(t,J＝7.3Hz,11H),2.41-2.18(m,14H),2.18-1.88(m,7H),1.84-1.47(m,42H),1.28(s,115H),0.87(d,J＝6.9Hz,9H)。
13CNMR(101MHz,CDCl
3，δppm)178.88(C＝O),173.72(C＝O),155.26(OC(O)O),73.67(CH),70.11(CH),66.04(CH),65.62(CH
2),65.45(CH
2),63.27(CH
2),61.67(CH
2),42.79(CH),34.31(CH
2),33.91(CH
2),33.71(CH
2),32.19(CH
2),31.70(s),30.23-28.35(CH
2),27.08(CH
2),26.76(CH
2,25.12(CH
2),24.87(CH
2),24.69(CH
2),23.76(CH
2),22.53(CH
2),14.04(CH
3)。
Embodiment 3
Cyclic carbonate ester average functionality is the preparation of the polynary branching cyclic carbonate ester of castor oil-base of 6.8:
Be the castor oil-base branching multiolefin 7.48g of 8.7 by carbon-carbon double bond average functionality, sulfydryl cyclic carbonate ester 3.5g, 2-hydroxy-2-methyl-1-phenyl-acetone 0.15g and trichloromethane 10ml joins in reactor, at room temperature ultraviolet lighting reaction 12h, revolve and steam except desolventizing, obtain the many cyclic carbonate esters of castor oil-base that 10.98g cyclic carbonate ester average functionality is 6.8.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.82(td,J＝14.3,6.2Hz,2.7H),5.20(s,1H),5.02(dd,J＝18.4,12.3Hz,12H),4.65(dt,J＝15.4,7.7Hz,6H),4.48-4.15(m,25H),4.03-3.85(m,2H),2.97(dd,J＝20.1,13.3Hz,6H),2.78(ddt,J＝24.6,12.6,6.0Hz,36H),2.54(t,J＝7.3Hz,14H),2.42-2.23(m,17H),2.19-1.99(m,6H),1.87-1.73(m,5H),1.72-1.46(m,37H),1.27(dd,J＝14.4,6.2Hz,145H),0.88(d,J＝6.9Hz,9H)。
13CNMR(101MHz,CDCl
3，δppm)179.01(C＝O),176.75(C＝O),155.23(OC(O)O),139.15(C＝C),114.14(C＝C),76.76(CH),71.93(CH),70.28(CH),70.03(CH),66.04(CH
2),65.05(CH
2),63.25(CH
2),61.62(CH
2),42.81(CH),34.43(CH
2),33.95(CH
2),33.84-33.65(CH
2),32.62(CH
2),31.74(s),30.24-28.72(CH
2),28.72-27.97(CH
2),26.96(CH
2,26.62-26.15(CH
2),25.14(CH
2),24.86(CH
2),24.61(CH
2),23.89(CH
2),22.55(CH
2),14.03(CH
3)。
Embodiment 4
Cyclic carbonate ester average functionality is the many cyclic carbonate esters of castor oil-base of 2:
Be the polynary alkene 5.7g of castor oil-base branching, the sulfydryl cyclic carbonate ester 1.15g, 2 of 5.7 by carbon-carbon double bond average functionality, 2-dimethyl benzil ketals 0.08g and trichloromethane 8ml joins in reactor, at room temperature ultraviolet lighting reaction 12h, revolve and steam except desolventizing, obtain the polynary cyclic carbonate ester of castor oil-base that 6.85g cyclic carbonate ester average functionality is 2.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.82(td,J＝5.6,3.7Hz,1.7H),5.26(s,1H),4.98(dd,J＝18.4,11.2Hz,8H),4.57(t,J＝8.5Hz,4H),4.35(ddd,J＝14.8,10.6,6.2Hz,16H),4.20-4.01(m,6H),2.96-2.72(m,15H),2.65(t,J＝7.0Hz,14H),2.54(t,J＝7.3Hz,10H),2.45-2.16(m,14H),2.17-1.86(m,7H),1.82-1.49(m,42H),1.25(s,116H),0.88(d,J＝6.9Hz,9H)。
13CNMR(101MHz,CDCl
3，δppm)178.86(C＝O),173.78(C＝O),155.25(OC(O)O),139.18(C＝C),114.17(C＝C),73.65(CH),70.16(CH),66.05(CH),65.63(CH
2),65.41(CH
2),63.25(CH
2),61.68(CH
2),42.77(CH),34.32(CH
2),33.95(CH
2),33.76(CH
2),32.14(CH
2),31.72(s),30.25-28.36(CH
2),27.09(CH
2),26.77(CH
2,25.18(CH
2),24.86(CH
2),24.68(CH
2),23.75(CH
2),22.52(CH
2),14.03(CH
3)。
Embodiment 5
Cyclic carbonate ester average functionality is the preparation of the many cyclic carbonate esters of castor oil-base of 5
Be the polynary alkene 5.7g of castor oil-base branching, the sulfydryl cyclic carbonate ester 3.5g, 2 of 5.7 by carbon-carbon double bond average functionality; 4; 6-trimethylbenzoy-dipheny phosphine oxide 0.08g and trichloromethane 8ml joins in reactor; at room temperature ultraviolet lighting reaction 8h; revolve and steam except desolventizing, obtain the polynary cyclic carbonate ester of castor oil-base that 8g cyclic carbonate ester average functionality is 5.Its nuclear magnetic resonance data is as follows:
1HNMR(400MHz,CDCl
3，δppm)5.82(td,J＝3.6,3.5Hz,0.7H),5.26(s,1H),4.98(dd,J＝16.4,10.8Hz,7H),4.58(t,J＝8.6Hz,5H),4.33(ddd,J＝16.2,11.6,6.5Hz,18H),4.23-4.05(m,6H),2.98-2.74(m,16H),2.67(t,J＝7.0Hz,15H),2.53(t,J＝7.3Hz,10H),2.46-2.15(m,14H),2.18-1.85(m,7H),1.85-1.48(m,42H),1.26(s,116H),0.89(d,J＝6.9Hz,9H)。
13CNMR(101MHz,CDCl
3,δppm)179.03(C＝O),176.74(C＝O),155.25(OC(O)O),139.16(C＝C),114.17(C＝C),76.78(CH),71.95(CH),70.22(CH),70.03(CH),66.15(CH
2),65.13(CH
2),63.25(CH
2),61.64(CH
2),42.86(CH),34.45(CH
2),33.94(CH
2),33.85-33.68(CH
2),32.65(CH
2),31.74(s),30.28-28.66(CH
2),28.76-27.85(CH
2),26.88(CH
2,26.62-26.16(CH
2),25.13(CH
2),24.85(CH
2),24.64(CH
2),23.89(CH
2),22.54(CH
2),14.04(CH
3)。
Embodiment 6
The average functional group degree of the 2g in Example 2 is the many cyclic carbonate esters of 8.7 castor oil-base and 0.225g1,2-quadrol at room temperature mixes, and then pours in tetrafluoroethylene template, is placed in 70 DEG C of baking oven 8h, be warming up to 100 DEG C of baking 2h again, in infrared spectra, cyclic carbonate ester is at 1780cm
-1the charateristic avsorption band at place disappears, and obtains the castor oil-base non-isocyanate polyurethane film of light brown.
Embodiment 7
The average functional group degree of the 2g in Example 2 is the many cyclic carbonate esters of 8.7 castor oil-base and 0.434g1,6-hexanediamine at room temperature mixes, and then pours in tetrafluoroethylene template, is placed in 70 DEG C of baking oven 8h, be warming up to 100 DEG C of baking 2h again, in infrared spectra, cyclic carbonate ester is at 1780cm
-1the charateristic avsorption band at place disappears, and obtains the castor oil-base non-isocyanate polyurethane film of light brown.
Embodiment 8
The average functional group degree of the 2g in Example 3 is that the many cyclic carbonate esters of 5.7 castor oil-base at room temperature mix with the isophorone diamine of 0.587g, then pour in tetrafluoroethylene template, be placed in 70 DEG C of baking oven 8h, be warming up to 100 DEG C of baking 2h again, in infrared spectra, cyclic carbonate ester is at 1780cm
-1the charateristic avsorption band at place disappears, and obtains the castor oil-base non-isocyanate polyurethane film of light brown.
Embodiment 9
The average functional group degree of the 2g in Example 3 is that the many cyclic carbonate esters of 5.7 castor oil-base at room temperature mix with the m-xylene diamine (NIPU8) of 0.469g, then pour in tetrafluoroethylene template, be placed in 70 DEG C of baking oven 8h, be warming up to 100 DEG C of baking 2h again, in infrared spectra, cyclic carbonate ester is at 1780cm
-1the charateristic avsorption band at place disappears, and obtains the castor oil-base non-isocyanate polyurethane film of light brown.
Claims (8)
1. the preparation method of a castor oil-base non-isocyanate polyurethane, it is characterized in that: after being mixed in proportion under polynary for castor oil-base branching cyclic carbonate ester prepolymer and polyhydric amine compounds room temperature, be coated in tetrafluoroethylene template, be placed in 50 ~ 150 DEG C of baking oven stage reacting by heating 5 ~ 48 hours, obtain castor oil-base non-isocyanate polyurethane.
2. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as claimed in claim 1, it is characterized in that: the preparation method of castor oil-base branching polynary cyclic carbonate ester prepolymer is: the polynary alkene of castor oil-base branching of 10 hendecenoic acid modification, sulfydryl cyclic carbonate ester, light trigger are joined in reactor, solvent is made with trichloromethane, under ultraviolet light irradiation, react 6 ~ 15h at 0 ~ 40 DEG C, revolve and steam except desolventizing obtains the polynary cyclic carbonate ester of castor oil-base branching; The cyclic carbonate ester average functionality of the polynary cyclic carbonate ester of described castor oil-base branching is 2 ~ 8.7.
3. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as claimed in claim 1, is characterized in that: described polyhydric amine compounds is one or more the mixture in quadrol, propylene diamine, hexanediamine, m-xylene diamine, certain herbaceous plants with big flowers diamines, isophorone diamine, polyethylene polyamine and polyetheramine.
4. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as claimed in claim 2, it is characterized in that: the polynary alkene of castor oil-base branching is prepared by the following method: castor oil-base polyvalent alcohol, triethylamine, ethyl acetate are added in reaction flask, ice bath stirs lower instillation 10-hendecene acyl chlorides, after ice bath reaction 2h, remove ice bath and continue reaction 12 ~ 24h, filter, organic layer alkali liquid washing, anhydrous magnesium sulfate drying, revolve steaming to desolventize, obtain the polynary alkene of castor oil-base branching of 10 hendecenoic acid modification; The carbon-carbon double bond average functionality of the polynary alkene of described modified castor oil base branching is 5.7 ~ 8.7.
5. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as claimed in claim 4, it is characterized in that: castor oil-base polyvalent alcohol is by sulfydryl-alkene click-reaction preparation: by Viscotrol C, add in reaction flask containing mercaptoalcohol compounds, light trigger, methylene dichloride, ultra violet lamp reaction 5 ~ 10h at 0 ~ 40 DEG C, excessive alcohol is removed with deionized water wash, organic over anhydrous dried over mgso, revolves steaming removing methylene dichloride and obtains castor oil-base polyvalent alcohol; The hydroxyl average functionality of described castor oil-base polyvalent alcohol is 5.7 ~ 8.7.
6. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as claimed in claim 5, it is characterized in that: Viscotrol C can adopt the vegetables oil containing unsaturated carbon-carbon double bond to replace, and described vegetables oil comprises one or more the mixture in rapeseed oil, sweet oil, oleum lini, tung oil, raisin seed oil.
7. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as claimed in claim 5, it is characterized in that: described one or more the mixture comprised containing mercaptoalcohol compounds in 2 mercapto ethanol, 3-Mercapto-1，2-propanediol, 3-sulfydryl-2-butanols, 3-sulfydryl-2-methyl amyl alcohol, 6-sulfydryl-1-hexanol, 3-sulfydryl-1-hexanol.
8. the preparation method of a kind of castor oil-base non-isocyanate polyurethane as described in claim 2 or 5, it is characterized in that: described light trigger comprises dimethoxybenzoin, 2-hydroxy-2-methyl-1-phenyl-acetone, 2,4,6-trimethylbenzoy-dipheny phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethyl benzil ketals, one or more mixture in 2,2-diethoxy acetophenone; The consumption of light trigger is 1% ~ 3% of reactant total mass.
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