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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- CN105367790A CN105367790A CN201510889001.0A CN201510889001A CN105367790A CN 105367790 A CN105367790 A CN 105367790A CN 201510889001 A CN201510889001 A CN 201510889001A CN 105367790 A CN105367790 A CN 105367790A
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- castor oil
- cyclic carbonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 239000012948 isocyanate Substances 0.000 title claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 24
- 239000004359 castor oil Substances 0.000 title claims abstract description 10
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 10
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 10
- 150000005676 cyclic carbonates Chemical class 0.000 title abstract 7
- 229960001777 castor oil Drugs 0.000 title abstract 6
- -1 thiol cyclic carbonate Chemical class 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 77
- 235000004443 Ricinus communis Nutrition 0.000 claims description 74
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 229960002703 undecylenic acid Drugs 0.000 claims description 12
- 235000013311 vegetables Nutrition 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 235000019198 oils Nutrition 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 7
- 229960001701 chloroform Drugs 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 238000012650 click reaction Methods 0.000 claims description 4
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical class SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 4
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical class CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 2
- TYZFMFVWHZKYSE-UHFFFAOYSA-N 3-mercaptohexanol Chemical compound CCCC(S)CCO TYZFMFVWHZKYSE-UHFFFAOYSA-N 0.000 claims description 2
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- FYUIDMFERMDYKI-UHFFFAOYSA-N CC1(C(C=CC=C1)C(=O)C(=O)C1=CC=CC=C1)C Chemical compound CC1(C(C=CC=C1)C(=O)C(=O)C1=CC=CC=C1)C FYUIDMFERMDYKI-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000008158 vegetable oil Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000010773 plant oil Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 150000004651 carbonic acid esters Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G71/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Cosmetics (AREA)
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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