Method for preparing plant oil-based cyclic carbonate prepolymer through thiol-ene click reaction

A cyclocarbonate and vegetable oil-based technology, which is applied in the field of preparation of vegetable oil-based cyclocarbonate prepolymers, can solve the problem of not being able to design and control the number of cyclocarbonate group connections, unfavorable safety production, and reduced reactivity, etc. problem, achieving highly reproducible, method-simple, and highly reactive results

Active Publication Date: 2015-09-02
JIANGXI SCI & TECH NORMAL UNIV
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  • Summary
  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The preparation method of the existing vegetable oil-based cyclocarbonate prepolymer is mainly the epoxy-carbon dioxide insertion method, that is, the carbon-carbon double bond of the vegetable oil is first epoxidized, and then carbon dioxide is inserted into the epoxy under high temperature, high pressure and the presence of a catalyst. Preparation of vegetable oil-based cyclocarbonate prepolymer from vegetable oil, this preparation method requires high equipment and is not conducive to safe production; and this type of method cannot be well designed to control the number of access of cyclocarbonate groups in vegetable oil; preparation The resulting cyclic carbonate group is directly connected to the vegetable oil fatty acid chain without a spacer, and is easily covered and entangled by the long chain of fatty acid to reduce its reactivity with the amine group

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1) the preparation method that contains mercapto ring carbonate:

[0020] Add 5.4g of glycerol cyclocarbonate, 5.8g of 3-mercaptopropionic acid, 0.56g of p-toluenesulfonic acid, and 20ml of dichloromethane into the reaction flask in turn, and reflux at 80°C for 8h; wash the solution three times with deionized water , and then dried with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain 3.6 g of mercapto-containing ring carbonate with a yield of 67%.

[0021] 1 H NMR (400MHz, 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).

[0022] 13 C NMR (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 ).

[0023] FTIR(KBr)ν:2954,2571(SH),1794(OC(O)O),1740(OC=O),1400,1097,1057,772,708cm -1 .

[0024] 2) T...

Embodiment 2

[0046] The mercapto-containing ring carbonate that 1.36g embodiment 1 makes, 1.9g castor oil, 0.097g 2-hydroxyl-2-methyl-1-phenylacetone, 3ml trichloromethane are added in reaction flask successively, at 2.0 mw / cm 2 Under ultraviolet light irradiation, react at 35° C. for 10 h; remove the solvent to obtain a castor oil-based cyclocarbonate prepolymer with an average functional group number of cyclocarbonate of 2.9, and the yield is 100%.

[0047] 1 H NMR (400MHz, CDCl 3,δppm) 5.27(d, J=20.4Hz, 1H), 4.96(s, 3H), 4.57(t, J=8.4Hz, 3H), 4.50–4.23(m, 10H), 4.14(dd, J=11.8, 5.9Hz, 3H), 3.68(dt, J=47.9, 23.9Hz, 3H), 3.05–2.47(m, 20H), 2.44–2.22(m, 6H), 1.84–1.05(m, 77H), 0.87(d ,J=6.7Hz,9H).

[0048] 13 C NMR (100MHz, CDCl 3, δppm) 173.17(OC=O), 171.32(OC=O), 154.25(OC(O)O), 73.70(CH), 71.86(CH), 68.91(CH), 65.96(CH 2 ), 63.19 (CH 2 ),62.05(CH 2 ), 46.15 (CH 2 ), 37.76 (CH 2 ),37.56(CH 2 ), 34.33 (CH 2 ), 33.89–33.20 (CH 2 ), 32.68–32.60 (CH 2 ), 30.53 (CH 2 ), 26.80–...

Embodiment 3

[0050] Add 1.48g of the mercapto-containing ring carbonate prepared in Example 1, 1.9g of olive oil, 0.1g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 3ml of chloroform into the reaction flask at 1.4mw / cm 2 Under ultraviolet light irradiation, react at 30° C. for 16 h; remove the solvent to obtain an olive oil-based cyclocarbonate prepolymer with an average functional group number of 3 cyclocarbonates, and the yield is 100%.

[0051] 1 H NMR (400MHz, CDCl 3, δppm)5.25(s,1H),4.95(s,3H),4.58(td,J=8.6,3.5Hz,3H),4.35(ddt,J=21.6,19.0,9.2Hz,10H),4.14(dd, J=11.8, 5.7Hz, 2H), 3.03–2.47(m, 15H), 2.33(dd, J=20.7, 13.6Hz, 6H), 1.77–1.11(m, 75H), 0.87(t, J=6.5Hz ,9H).

[0052] 13 C NMR (100MHz, CDCl 3, δppm) 173.14(OC=O), 171.48(OC=O), 154.25(OC(O)O), 73.64(CH), 68.90(CH), 66.03(CH 2 ), 63.14 (CH 2 ), 62.08 (CH 2 ), 58.46(CH), 46.39(CH 2 ),37.77(CH 2 ),34.75(CH 2 ), 33.87 (CH 2 ), 3.89 (CH 2 ), 29.79-29.383 (CH 2 ), 29.21 (CH 2 ), 26.8078 (CH 2 ),25.15(CH 2 ),2...

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Abstract

The invention discloses a method for preparing plant oil-based cyclic carbonate prepolymer through thiol-ene click reaction. Glycerol carbonate, thiol-containing organic acid and catalysts are mixed; dichloromethane is used as a solvent; reaction is carried out at 60 to 120 DEG C for 6 to 12h to obtain thiol-containing cyclic carbonates; next, vegetable oil, the thiol-containing cyclic carbonates and photoinitiators are added into a reactor; trichloromethane is used as a solvent; under the ultraviolet light irradiation, the reaction is carried out at -5DEG C to 40 DEG C for 8 to 48h; rotary evaporation is carried out to obtain plant oil-based cyclic carbonate prepolymers. The method has the advantages that high temperature, high pressure and catalysts are not needed; in addition, the connecting number of cyclic carbonate groups in the vegetable oil can be better designed and controlled; separation radicals exist between the prepared cyclic carbonate groups and vegetable oil fatty acid chains, so that the cyclic carbonate groups positioned at the end site have higher reaction activity. The method has the advantages that the preparing method is simple, the reaction condition is mild, the selectivity is high, and the product yield is high.

Description

technical field [0001] The invention relates to a preparation method of a vegetable oil-based cyclocarbonate prepolymer, in particular to a method for preparing a vegetable oil-based cyclocarbonate prepolymer by adopting a mercapto-ene click reaction. Background technique [0002] Polyurethane is a kind of polymer material with wide application and excellent performance, which is mainly prepared by the reaction of polyisocyanate and polyol prepolymer. Polyisocyanate is highly toxic to the human body, and the traditional polyisocyanate production process using phosgene as a raw material is also highly toxic. In order to avoid the use of highly toxic polyisocyanate, coupled with the promotion of "clean production process", non-isocyanate polyurethane came into being. Non-isocyanate polyurethanes are mainly prepared by reacting cyclocarbonate prepolymers with primary aliphatic amines. The preparation methods of cyclic carbonate mainly include the carbon dioxide insertion epox...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G64/30
Inventor 付长清申亮李文才
Owner JIANGXI SCI & TECH NORMAL UNIV
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