CN105367790B - A kind of preparation method of the branched more membered ring carbonates of castor oil-base and its non-isocyanate polyurethane - Google Patents
A kind of preparation method of the branched more membered ring carbonates of castor oil-base and its non-isocyanate polyurethane Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of branched more membered ring carbonates of castor oil-base and its non-isocyanate polyurethane.The branched polyenoid prepolymer of castor oil-base that this method is modified using 10 undecenoic acids, sulfydryl cyclic carbonate ester is raw materials, chloroform is solvent, in the presence of photoinitiators, ultraviolet light irradiation reacts 6~15h and obtains the polynary branched cyclic carbonate ester prepolymer of castor oil-base, and prepolymer further prepares castor oil-base non-isocyanate polyurethane with amine compound reaction.The preparation of cyclic carbonate ester is without HTHP and catalyst in the present invention, and can access number of the control ring carbonate group in vegetable oil well；The cyclic carbonate ester of preparation has branched structure and relatively low viscosity, longer interval base between vegetable oil tie point be present so that the cyclic carbonate ester group in end position has very high reactivity.Gained polyurethane based on castor oil material has the advantages that biodegradable, renewable carbon content are high, can be used as the renewable polyurethane resin of coating.
Description
Technical field
The invention discloses the preparation side of a kind of branched more membered ring carbonates of castor oil-base and its non-isocyanate polyurethane
Method, and in particular to the branched more membered ring carbonate prepolymers of castor oil-base and its non-isocyanate that a kind of 10 hendecenoic acid is modified
The preparation method of polyurethane.
Background technology
Non-isocyanate polyurethane (NIPU) is prepared by the copolyreaction of more membered ring carbonate prepolymers and polyamine, its
Compared with polyisocyanic acid ester polyurethane, the use of the larger isocyanates of toxicity is not only avoided, remains conventional urethane material
The excellent mechanical property of material, and due to amino-formate bond being not present on its backbone structure, so as to be made up from molecular structure
Deficiency of traditional polyisocyanic acid ester polyurethane in terms of hydrolytic stability, anti-permeability performance, it has excellent chemical resistance
Property, water resistance and permeability resistance.During preparation NIPU is raw materials used, polyamine is generally industrial goods, and cyclic carbonate ester prepolymer is set
Prepared by meter then turn into the main research for preparing NIPU.
Vegetable oil source extensively, it is cheap, be easy to get, with vegetable oil prepare vegetable oil basic ring carbonic ester have it is nontoxic, can biology
The advantages of degraded.Isocyanates production polyurethane is replaced with vegetable oil basic ring carbonic ester, it is safer, environmentally friendly, while can reduce
Dependence to petroleum resources, realize industrial economy sustainable development.
The current method for preparing vegetable oil basic ring carbonic ester is mainly carbon dioxide insertion epoxy method, i.e., first by vegetable oil
Unsaturated double-bond epoxidation, then will carbon dioxide insert vegetable oil basic ring oxygen in formed vegetable oil basic ring carbonic ester.This side
It is 100% that method, which prepares gained vegetable oil basic ring carbonic ester renewable carbon content, but need in special reactor, high temperature,
Long-time reaction is carried out in the presence of high pressure and catalyst, simultaneously because the oxidable unsaturated double-bond of vegetable oil is located at unsaturated lipid
In fat acid chain, the epoxide group after epoxidation is in the identical position with double bond, because steric effect causes carbon dioxide
Insertion rate is not high, and so as to cause the cyclic carbonate ester number of access relatively low, and such method can not design control ring carbonic acid well
Access number of the ester group in vegetable oil；Cyclic carbonate ester group obtained by preparing is joined directly together with vegetable fatty acids chain not to be deposited
In interval base, easily coated by aliphatic acid long-chain and tangle and reduce its reactivity as polyurethane for prepolymer.
The present invention is directed to the deficiency in existing vegetable oil basic ring polycarbonate prepolymer thing technology of preparing, there is provided a kind of simple easy
OK, the preparation side for the branched more membered ring carbonate prepolymers of castor oil-base that cyclic carbonate ester group number is controllable and reactivity is high
Method.The double bond on the branched polynary alkene of castor oil being modified by 10 hendecenoic acid can be carried out efficiently with sulfydryl, single-minded sulfydryl-alkene
Click-reaction, the present invention is by controlling the when ultraviolet lighting time that feeds intake of sulfydryl cyclic carbonate ester and castor oil-base multiolefin to control
The access number of cyclic carbonate ester group processed, by introducing 10 hendecenoic acid in cyclic carbonate ester group and Castor Oil Fatty Acid interchain
Long fatty carbon chain to improve the pliability of the reactivity of end-link carbonic acid ester group and castor oil-base non-isocyanate polyurethane,
The renewable resin of coating can be used as.
The content of the invention
The purpose of the present invention is overcome the shortcomings of in existing vegetable oil basic ring polycarbonate prepolymer thing preparation method, there is provided a kind of
Simple and easy prepares the branched more membered ring carbonate pre-polymerizations of plant oil base that cyclic carbonate ester group number is controllable and reactivity is high
The method of thing, and 10 hendecenoic acid Long carbon chain is introduced into non-isocyanate polyurethane main chain, improve the non-isocyanic acid of castor oil-base
The pliability and water resistance of ester polyurethane.
To achieve the above object, the present invention prepares the branched more membered ring carbonates of castor oil-base using sulfydryl-alkene click-reaction
Prepolymer：The branched polynary alkene of castor oil-base, sulfydryl cyclic carbonate ester, the light trigger that 10 hendecenoic acid is modified are added to reaction
In device, solvent is done with chloroform, under ultraviolet light irradiation, 6~15h is reacted at 0~40 DEG C, revolving removes solvent and obtains castor oil
The branched more membered ring carbonates of base；The cyclic carbonate ester average functionality of the branched more membered ring carbonates of castor oil-base is 2~8.7；
The non-isocyanate polyurethane is prepared by the following method：By the branched more membered ring carbonate prepolymers of castor oil-base
After being mixed in proportion at room temperature with polyhydric amine compounds, coated in polytetrafluoroethylene (PTFE) template, being placed in 50-150 DEG C of baking oven scala media
Section heating response 5~48 hours, obtains castor oil-base non-isocyanate polyurethane.
In the present invention, the branched polynary alkene of described castor oil-base is prepared by the following method：By castor oil-base polyalcohol, three
Ethamine, ethyl acetate are added in reaction bulb, and ice bath stirring is lower to instill 10- hendecene acyl chlorides, after ice bath reaction 2h, remove ice bath after
12~24h of continuous reaction, filtering, organic layer alkali liquid washing, anhydrous magnesium sulfate are dried, and revolving removes solvent, obtains 10 hendecenoic acid and changes
The branched polynary alkene of castor oil-base of property；The carbon-carbon double bond average functionality of the branched polynary alkene of modified castor oil base be 5.7~
8.7。
In the present invention, described castor oil-base polyalcohol is prepared by sulfydryl-alkene click-reaction：By castor oil, containing sulfydryl
Alcohol compound, light trigger, dichloromethane add reaction bulb in, at 0~40 DEG C ultra violet lamp react 5~10h, spend from
Sub- water washing removes excessive alcohol, and organic layer is dried with anhydrous magnesium sulfate, and it is polynary that revolving removing dichloromethane obtains castor oil-base
Alcohol；The hydroxyl average functionality of described castor oil-base polyalcohol is 5.7~8.7.
In the present invention, described alcohol compound containing sulfydryl includes 2 mercapto ethanol, 3- sulfydryls -1,2-PD, 3- mercaptos
It is one or more kinds of mixed in base -2- butanol, 3- sulfydryl -2- methyl anyl alcohols, 6- sulfydryl -1- hexanols, 3- sulfydryl -1- hexanols
Compound.
In the present invention, described light trigger includes dimethoxybenzoin, 2- hydroxy-2-methyl -1- phenylacetones, 2,4,
6- trimethylbenzoy-diphenies phosphine oxide, 1- hydroxycyclohexyl phenyl ketones, 2,2- dimethyl benzil ketals, 2,2-
One or more kinds of mixtures in diethoxy acetophenone.The dosage of light trigger for reactant gross mass 1%~
3%.
In the present invention, the branched more membered ring carbonates of described castor oil-base are in castor oil aliphatic chain and cyclic carbonate ester functional group
Between introduce the long-chain of 10 hendecenoic acid, cyclocarbonate radical cumularsharolith assigns cyclic carbonate ester in the end position of 10 hendecenoic acid long-chain
Higher reactivity.
In the present invention, described polyhydric amine compounds be ethylenediamine, propane diamine, hexamethylene diamine, m-xylene diamine, certain herbaceous plants with big flowers diamines,
Mixture more than one or both of IPD, polyethylene polyamine and polyetheramine.
In the present invention, castor oil is replaced as initiation material using the vegetable oil containing unsaturated carbon-carbon double bond, according to this hair
Bright disclosed method can prepare the branched more membered ring carbonates of other plant oil base, and described vegetable oil includes rapeseed oil, olive
Mixture more than one or both of oil, linseed oil, tung oil, grape-kernel oil.
The preparation method of cyclic carbonate ester is without HTHP and catalyst in the present invention, and can design control ring carbon well
Access number of the acid esters group in vegetable oil；The cyclic carbonate ester for preparing gained has branched structure, has relatively low viscosity, with
Longer interval base between vegetable oil tie point be present so that there is the cyclic carbonate ester group in end position very high reaction to live
Property.Preparing gained polyurethane based on castor oil material has the advantages that biodegradable, renewable carbon content are high, coating can be used as to use
Renewable polyurethane resin.
Brief description of the drawings
Fig. 1 is the synthetic route chart for the more membered ring carbonates of castor oil-base that cyclic carbonate ester average functionality is 5.7.
Embodiment
In order to preferably explain the present invention, below in conjunction with specific embodiment, the present invention is described in further detail, but
They do not form to the present invention and limited.
Embodiment 1
1) preparation of sulfydryl cyclic carbonate ester
11.8g glycerine cyclic carbonate esters, 13g 3- mercaptopropionic acids, 1.24g p-methyl benzenesulfonic acid, 40ml dichloromethane are added anti-
Answer in bottle, back flow reaction 8h at 80 DEG C.After deionized water in three times wash solution, dried with anhydrous magnesium sulfate, revolving is removed
Solvent, obtain 16.27g sulfydryl cyclic carbonate esters, yield 79%.Its nuclear magnetic resonance data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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).
13C NMR(100MHz,CDCl3, δ ppm) and 171.18 (OC=O), 154.56 (OC (O) O), 73.82 (CH), 65.19
(CH2),63.24(CH2),38.09(CH2),19.45(CH2)。
2) hydroxyl average functionality is the preparation of 8.7 castor oil-base polyalcohol
By castor oil 9g, 3- sulfydryl -1,2- propane diols 5g, light trigger 2- hydroxy-2-methyl -1- phenylacetones 0.24g
And dichloromethane 20ml is added in reactor, ultraviolet lighting reaction 8h, makes to be washed with deionized removing excessively at room temperature
3- sulfydryls -1,2-PD, organic layer dried with anhydrous magnesium sulfate, and revolving removes dichloromethane, obtains 11.55g hydroxyls and puts down
The castor oil-base polyalcohol that equal degree of functionality is 8.7, determine that double bond reaction is complete by NMR technology, yield 95.7%.
3) carbon-carbon double bond average functionality is the preparation of the 8.7 branched multiolefin of castor oil-base
10 hendecenoic acid 10g, thionyl chloride 30g and dichloromethane 20ml are added in reactor, stirred at 50 DEG C
5h, revolving remove dichloromethane and thionyl chloride, obtain 11g 10- hendecene acyl chlorides.It is 8.7 by hydroxyl average functionality
Castor oil-base polyalcohol 4g, triethylamine 5.67g and ethyl acetate 30ml are added in reactor, by 10- hendecenes under ice bath
Acyl chlorides 11.37g is added dropwise in solution in 0.5h, is continued after reacting 2h, is removed ice bath and react 12h at room temperature, filters, take organic
Layer, is washed three times with 1wt% NaOH solution, is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate, obtains 7.8g double bonds and puts down
The branched multiolefin of castor oil-base that equal degree of functionality is 8.7, yield 96%.Its nuclear magnetic resonance data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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).
13C NMR(101MHz,CDCl3, δ ppm) and 179.60 (C=O), 139.16 (C=C), 114.16 (C=C), 77.51
(CH),73.51(CH),68.38(CH),63.47(CH2),62.32(CH2),42.87(CH),38.14(CH2),34.77
(CH2),33.80(CH2),31.83(CH2),29.55(CH2),29.14(CH2),26.71(CH2),25.83-25.21(CH2),
24.92(CH2),22.57(CH2),19.42(CH2),18.38(CH2),14.05(CH3)。
4) cyclic carbonate ester average functionality is the preparation of the 8.7 polynary branched cyclic carbonate ester of castor oil-base
The branched polynary alkene 6.6g of castor oil-base, the mercapto that the 10 hendecenoic acid that carbon-carbon double bond average functionality is 8.7 is modified
Basic ring carbonic ester 4.5g, dimethoxybenzoin 0.16g and chloroform 10ml are added in reactor, at room temperature ultraviolet lighting
12h is reacted, revolving removes solvent, obtains the branched polynary ring carbon acid of castor oil-base that 11.02g cyclic carbonate esters average functionality is 8.7
Ester.Its nuclear magnetic resonance data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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).
13C NMR(101MHz,CDCl3, δ ppm) and 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(CH2),65.07(CH2),63.27(CH2),61.69
(CH2),42.80(CH),34.43(CH2),33.93(CH2),33.83-33.69(CH2),32.60(CH2),31.72(s),
30.26-28.73(CH2),28.73-27.98(CH2),26.92(CH2,26.60-26.19(CH2),25.13(CH2),24.87
(CH2),24.63(CH2),23.87(CH2),22.54(CH2),14.04(CH3)。
Embodiment 2
1) hydroxyl average functionality is the preparation of 5.7 castor oil-base polyalcohol
By castor oil 9g, 2 mercapto ethanol 3.78g, light trigger 2,2- diethoxy acetophenones 0.20g and dichloromethane
20ml is added in reactor, at room temperature ultraviolet lighting reaction 8h, makes the 2- sulfydryl second for removing excess is washed with deionized
Alcohol, organic layer are dried using anhydrous magnesium sulfate, and revolving removes dichloromethane and obtains the castor that 9.77g hydroxyls average functionality is 5.7
Sesame oil polylol, determine that double bond reaction is complete by NMR technology, yield 87.1%.
2) carbon-carbon double bond average functionality is the preparation of the 5.7 branched multiolefin of castor oil-base
Castor oil-base polyalcohol 4g, triethylamine 3.44g and ethyl acetate 30ml that hydroxyl average functionality is 5.7 are added
Into reactor, 10- hendecene acyl chlorides 7g is added dropwise in solution in 0.5h under ice bath, continues to react 2h, then in room
The lower reaction 12h of temperature, filtering, takes organic layer, is washed three times with 1wt% NaOH solution, dried with anhydrous magnesium sulfate, revolving removes
Ethyl acetate, obtain the castor oil-base multiolefin that 6.5g carbon-carbon double bonds average functionality is 5.7, yield 95%.Its nuclear-magnetism
Resonance data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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).
13C NMR(101MHz,CDCl3, δ ppm) and 179.40 (C=O), 139.17 (C=C), 114.16 (C=C), 73.52
(C-OH),68.73(CH),63.44(CH2),62.15(CH2),42.82(CH),38.04(CH2),34.75(CH2),33.90
(CH2),31.87(CH2),29.51(CH2),29.18(CH2),26.73(CH2),25.82-25.23(CH2),24.89(CH2),
22.54(CH2),19.47(CH2),18.36(CH2),14.02(CH3)。
3) cyclic carbonate ester average functionality is the preparation of the 5.7 polynary branched cyclic carbonate ester of castor oil-base
By carbon-carbon double bond average functionality be 5.7 the branched multiolefin 5.7g of castor oil-base, sulfydryl cyclic carbonate ester 3.5g,
1- hydroxycyclohexyl phenyl ketones 0.08g and chloroform 8ml are added in reactor, at room temperature ultraviolet lighting reaction 12h,
Revolving removes solvent, obtains the branched more membered ring carbonates of castor oil-base that 9.02g cyclic carbonate esters average functionality is 5.7.Its core
MR data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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).
13C NMR(101MHz,CDCl3, δ ppm) and 178.88 (C=O), 173.72 (C=O), 155.26 (OC (O) O),
73.67(CH),70.11(CH),66.04(CH),65.62(CH2),65.45(CH2),63.27(CH2),61.67(CH2),
42.79(CH),34.31(CH2),33.91(CH2),33.71(CH2),32.19(CH2),31.70(s),30.23-28.35
(CH2),27.08(CH2),26.76(CH2,25.12(CH2),24.87(CH2),24.69(CH2),23.76(CH2),22.53
(CH2),14.04(CH3)。
Embodiment 3
Cyclic carbonate ester average functionality is the preparation of the 6.8 polynary branched cyclic carbonate ester of castor oil-base：
By castor oil-base branched multiolefin 7.48g of the carbon-carbon double bond average functionality for 8.7, sulfydryl cyclic carbonate ester
3.5g, 2- hydroxy-2-methyl -1- phenylacetones 0.15g and chloroform 10ml are added in reactor, at room temperature ultraviolet light
According to reaction 12h, revolving removes solvent, obtains the more cyclic carbonate esters of castor oil-base that 10.98g cyclic carbonate esters average functionality is 6.8.
Its nuclear magnetic resonance data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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).
13C NMR(101MHz,CDCl3, δ ppm) and 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 (CH2),
65.05(CH2),63.25(CH2),61.62(CH2),42.81(CH),34.43(CH2),33.95(CH2),33.84-33.65
(CH2),32.62(CH2),31.74(s),30.24-28.72(CH2),28.72-27.97(CH2),26.96(CH2,26.62-
26.15(CH2),25.14(CH2),24.86(CH2),24.61(CH2),23.89(CH2),22.55(CH2),14.03(CH3)。
Embodiment 4
Cyclic carbonate ester average functionality is the 2 more cyclic carbonate esters of castor oil-base：
By carbon-carbon double bond average functionality be 5.7 the branched polynary alkene 5.7g of castor oil-base, sulfydryl cyclic carbonate ester 1.15g,
2,2- dimethyl benzil ketals 0.08g and chloroform 8ml are added in reactor, at room temperature ultraviolet lighting reaction 12h,
Revolving removes solvent, obtains the more membered ring carbonates of castor oil-base that 6.85g cyclic carbonate esters average functionality is 2.Its nuclear magnetic resonance
Data are as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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)。
13C NMR(101MHz,CDCl3, δ ppm) and 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 (CH2),65.41(CH2),
63.25(CH2),61.68(CH2),42.77(CH),34.32(CH2),33.95(CH2),33.76(CH2),32.14(CH2),
31.72(s),30.25-28.36(CH2),27.09(CH2),26.77(CH2,25.18(CH2),24.86(CH2),24.68
(CH2),23.75(CH2),22.52(CH2),14.03(CH3)。
Embodiment 5
Cyclic carbonate ester average functionality is the preparation of the 5 more cyclic carbonate esters of castor oil-base
By carbon-carbon double bond average functionality be 5.7 the branched polynary alkene 5.7g of castor oil-base, sulfydryl cyclic carbonate ester 3.5g, 2,
4,6- trimethylbenzoy-dipheny phosphine oxide 0.08g and chloroform 8ml are added in reactor, ultraviolet at room temperature
Illumination reaction 8h, revolving remove solvent, obtain the more membered ring carbonates of castor oil-base that 8g cyclic carbonate esters average functionality is 5.Its
Nuclear magnetic resonance data is as follows：
1H NMR(400MHz,CDCl3, δ ppm) and 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)。
13C NMR(101MHz,CDCl3, δ ppm) and 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 (CH2),
65.13(CH2),63.25(CH2),61.64(CH2),42.86(CH),34.45(CH2),33.94(CH2),33.85-33.68
(CH2),32.65(CH2),31.74(s),30.28-28.66(CH2),28.76-27.85(CH2),26.88(CH2,26.62-
26.16(CH2),25.13(CH2),24.85(CH2),24.64(CH2),23.89(CH2),22.54(CH2),14.04(CH3)。
Embodiment 6
Average functional group's degree of 2g in Example 2 is the more cyclic carbonate esters of 8.7 castor oil-bases and 0.225g 1,2- second two
Amine is well mixed at room temperature, is subsequently poured into tetrafluoroethene template, is placed in 8h in 70 DEG C of baking ovens, then be warming up to 100 DEG C
2h is toasted, cyclic carbonate ester is in 1780cm in infrared spectrum-1The characteristic absorption peak at place disappears, and the castor oil-base for obtaining light brown is non-different
Cyanate polyurethane coating film.
Embodiment 7
Average functional group's degree of 2g in Example 2 be the more cyclic carbonate esters of 8.7 castor oil-bases and 0.434g 1,6- oneself two
Amine is well mixed at room temperature, is subsequently poured into tetrafluoroethene template, is placed in 8h in 70 DEG C of baking ovens, then be warming up to 100 DEG C
2h is toasted, cyclic carbonate ester is in 1780cm in infrared spectrum-1The characteristic absorption peak at place disappears, and the castor oil-base for obtaining light brown is non-different
Cyanate polyurethane coating film.
Embodiment 8
Average functional group's degree of 2g in Example 3 is the more cyclic carbonate esters of 5.7 castor oil-bases and 0.587g different Fo Er
Ketone diamines is well mixed at room temperature, is subsequently poured into tetrafluoroethene template, is placed in 8h in 70 DEG C of baking ovens, then be warming up to
100 DEG C are toasted 2h, and cyclic carbonate ester is in 1780cm in infrared spectrum-1The characteristic absorption peak at place disappears, and obtains the castor oil of light brown
Base non-isocyanate polyurethane film.
Embodiment 9
Average functional group's degree of 2g in Example 3 is the more cyclic carbonate esters of 5.7 castor oil-bases and 0.469g isophthalic two
Methylamine (NIPU8) is well mixed at room temperature, is subsequently poured into tetrafluoroethene template, is placed in 8h in 70 DEG C of baking ovens, then rise
Warm to 100 DEG C are toasted 2h, and cyclic carbonate ester is in 1780cm in infrared spectrum-1The characteristic absorption peak at place disappears, and obtains the castor of light brown
Sesame oil base non-isocyanate polyurethane film.
Claims (5)
- A kind of 1. preparation method of castor oil-base non-isocyanate polyurethane, it is characterised in that：By the branched more yuan of rings of castor oil-base After polycarbonate prepolymer thing mixes in proportion at room temperature with polyhydric amine compounds, coated in polytetrafluoroethylene (PTFE) template, be placed in 50~ Stage heating response 5~48 hours, obtains castor oil-base non-isocyanate polyurethane in 150 DEG C of baking ovens；The preparation method of the branched more membered ring carbonate prepolymers of castor oil-base is：The castor oil that 10 hendecenoic acid is modified The branched polynary alkene of base, sulfydryl cyclic carbonate ester, light trigger are added in reactor, solvent are made with chloroform, in ultraviolet light spoke According under, 6~15h is reacted at 0~40 DEG C, revolving removes solvent and obtains the branched more membered ring carbonates of castor oil-base；The castor oil-base The cyclic carbonate ester average functionality of branched more membered ring carbonates is 2~8.7；The branched polynary alkene of castor oil-base is prepared by the following method：Castor oil-base polyalcohol, triethylamine, ethyl acetate are added Entering in reaction bulb, ice bath stirring is lower to instill 10- hendecene acyl chlorides, and after ice bath reacts 2h, removing ice bath continues 12~24h of reaction, Filtering, organic layer alkali liquid washing, anhydrous magnesium sulfate are dried, and revolving removes solvent, obtain the castor oil-base branch of 10 hendecenoic acid modification Change polynary alkene；The carbon-carbon double bond average functionality of the branched polynary alkene of modified castor oil base is 5.7~8.7；The castor oil-base polyalcohol is prepared by sulfydryl-alkene click-reaction：Castor oil, alcohol compound containing sulfydryl, light are drawn Send out in agent, dichloromethane addition reaction bulb, ultra violet lamp reacts 5~10h at 0~40 DEG C, is washed with deionized and removed The alcohol of amount, organic layer are dried with anhydrous magnesium sulfate, and revolving removes dichloromethane and obtains castor oil-base polyalcohol；Described castor oil The hydroxyl average functionality of polylol is 5.7~8.7.
- A kind of 2. preparation method of castor oil-base non-isocyanate polyurethane as claimed in claim 1, it is characterised in that：It is described Polyhydric amine compounds be ethylenediamine, propane diamine, hexamethylene diamine, m-xylene diamine, decamethylene diamine, IPD, more ethene it is more Mixture more than one or both of amine and polyetheramine.
- A kind of 3. preparation method of castor oil-base non-isocyanate polyurethane as claimed in claim 1, it is characterised in that：Castor-oil plant Oil using containing unsaturated carbon-carbon double bond vegetable oil replace, described vegetable oil include rapeseed oil, olive oil, linseed oil, tung oil, Mixture more than one or both of grape-kernel oil.
- A kind of 4. preparation method of castor oil-base non-isocyanate polyurethane as claimed in claim 1, it is characterised in that：It is described Alcohol compound containing sulfydryl include 2 mercapto ethanol, 3- sulfydryl -1,2- propane diols, 3- sulfydryl -2- butanol, 3- sulfydryl -2- first One or more kinds of mixtures in base amylalcohol, 6- sulfydryl -1- hexanols, 3- sulfydryl -1- hexanols.
- A kind of 5. preparation method of castor oil-base non-isocyanate polyurethane as claimed in claim 1, it is characterised in that：It is described Light trigger include dimethoxybenzoin, 2- hydroxy-2-methyl -1- phenylacetones, 2,4,6- trimethylbenzoyls-hexichol Base phosphine oxide, 1- hydroxycyclohexyl phenyl ketones, 2,2- dimethyl benzil ketals, one kind in 2,2- diethoxy acetophenones Or more than one mixture；The dosage of light trigger is the 1%~3% of reactant gross mass.
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| CN113336949B (en) * | 2021-06-21 | 2023-03-28 | 岭南师范学院 | Amino organic silicon-based pentaerythritol cyclic carbonate and preparation method and application thereof |
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