CN102584634A - Polyurethane using vinyl ether as end group and synthesis method thereof - Google Patents
Polyurethane using vinyl ether as end group and synthesis method thereof Download PDFInfo
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- CN102584634A CN102584634A CN2011102211732A CN201110221173A CN102584634A CN 102584634 A CN102584634 A CN 102584634A CN 2011102211732 A CN2011102211732 A CN 2011102211732A CN 201110221173 A CN201110221173 A CN 201110221173A CN 102584634 A CN102584634 A CN 102584634A
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- vinyl ether
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- diisocyanate
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- RYROHOSJQGBCAZ-UHFFFAOYSA-N C=COCCCCOC(NCCCCCCNC(OCCCOC(NCCCCCCNC(OCCCCOC=C)=O)=O)=O)=O Chemical compound C=COCCCCOC(NCCCCCCNC(OCCCOC(NCCCCCCNC(OCCCCOC=C)=O)=O)=O)=O RYROHOSJQGBCAZ-UHFFFAOYSA-N 0.000 description 1
- DRHULWISRBOXRF-UHFFFAOYSA-N C=COCCCCOC(NCCCCCCNC(OCCOC(NCCCCCCNC(OCCCCOC=C)=O)=O)=O)=O Chemical compound C=COCCCCOC(NCCCCCCNC(OCCOC(NCCCCCCNC(OCCCCOC=C)=O)=O)=O)=O DRHULWISRBOXRF-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C(NCCCCCCNC(OCCCCOC=C)=O)=O)OCC*(C)OC(NCCCCCCNC(OCCCCOC=C)=O)=O Chemical compound CC(C(NCCCCCCNC(OCCCCOC=C)=O)=O)OCC*(C)OC(NCCCCCCNC(OCCCCOC=C)=O)=O 0.000 description 1
- BQCHHTUBYODYCE-UHFFFAOYSA-N Cc(ccc(NC(OCCCCOC(Nc1ccc(C)c(NC(OCC(CC2)CCC2OC=C)=O)c1)=O)=O)c1)c1NC(OCC1CCC(COC=C)CC1)=O Chemical compound Cc(ccc(NC(OCCCCOC(Nc1ccc(C)c(NC(OCC(CC2)CCC2OC=C)=O)c1)=O)=O)c1)c1NC(OCC1CCC(COC=C)CC1)=O BQCHHTUBYODYCE-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to polyurethane using vinyl ether as an end group. The polyurethane is characterized in that the polyurethane has a molecular structure general formula shown as the accompanying drawing, wherein R1, R2 and R3 are aliphatic hydrocarbon or aromatic hydrocarbon. A synthesis method comprises the steps that: in the anhydrous inert atmosphere, polylol is dripped into diisocyanate and is stirred, the temperature is controlled at 0 to 50 DEG C, and the reaction lasts 2 to 4 hours, wherein when the reaction activities of two -NCOs in the diisocyanate are different, the optimum reaction temperature is 0 DEG C, the optimum reaction time is 2.5 hours, catalysts are added after the reaction completion, in addition, the temperature is raised to 60 to 80 DEG C, hydroxyalkyl vinyl ether diluted by solvents is dripped, the materials are continuously stirred for reaction for 3 to 4 hours after the dripping completion, and products are finally obtained. The polyurethane has the advantages that the polymerization speed is high, the polymerization is not interfered by oxygen, the synthesis process is simple, toxicity is low, and odourlessness is realized, and the like. Therefore, good practical application values are realized in photocuring materials.
Description
Technical field
The present invention relates to the ultraviolet-curing paint technical field.
Background technology
From nineteen sixty-eight West Germany Beyer Co., Ltd deliver luminous energy is applied to the cured coating film technology since, the research and development of ultraviolet light polymerization (solidifying hereinafter to be referred as UV) tackiness agent is also developed rapidly.China begins one's study from early 1970s and develops the UV curing technology.UV is coating material solidified to have the incomparable advantage of many traditional coatings: capacity usage ratio is high, is suitable for heat-sensitive substrate material, and pollution-free, film forming speed is fast, and film quality is high, is the new generation of green Chemicals therefore.Wherein the cation photocuring technology is a kind of in the UV-curing technology; Advantages such as it has the influence that does not receive oxygen, and volumetric shrinkage is little, and adhesive power is strong; Therein ethylene base ether is one of active maximum monomer of cationoid polymerisation; And because that vinyl ethers compound has a polymerization velocity is fast, polymerization does not receive oxygen interference, low toxicity, advantage such as tasteless, so vinyl ethers compound has very practical using value in fields such as coating, tackiness agent, printing sensitization sheet material.The present invention has innovated a series of compounds that contain the urethane of vinyl ehter bond in view of these advantages, and the product that this method makes is not purified can be used as coating; And solvability is fine; Building-up process is simple, and condition is easy to control, and extraordinary actual application value is arranged.
Summary of the invention
The object of the invention is exactly that the advantage of very practical using value is arranged in fields such as coating, tackiness agent, printing sensitization sheet material in view of vinyl ethers compound, and invents a series of compounds that contain the urethane of vinyl ehter bond,
General formula of molecular structure of the present invention is:
R1 in the formula, R2, R3 are aliphatic hydrocarbon or aromatic hydrocarbon.
Compound method comprises: under the anhydrous inert atmosphere, in vulcabond, drip polyvalent alcohol and stirring, temperature is controlled at 0～50 ℃; Reaction 2～4h, wherein the two-NCO reactive behavior in the vulcabond not simultaneously, optimal reaction temperature is 0 ℃; Optimum reacting time is 2.5h, adds catalyzer after having reacted and is warming up to 60～80 ℃, drips the hydroxyalkyl vinyl ether with solvent cut; After dropwising, continue stirring reaction 3～4h, finally obtain product.
Employed catalyzer is a dibutyl tin laurate, and materials are the 0.2wt%～0.8wt% of vulcabond materials, and wherein best materials are 0.5wt%.
Vulcabond is aliphatic diisocyanate or alicyclic diisocyanate.Like isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), hexahydrotoluene two cyanates (HTDI), tetramethylxylylene diisocyanate (TMXDI) etc.
Polyvalent alcohol is aliphatic dihydroxy alcohol or divalent alcohol polyether compound.Like terepthaloyl moietie, Ucar 35, butyleneglycol, polyoxyethylene glycol, W 166 etc.
The hydroxyalkyl vinyl ether is hydroxyethyl vinyl ether, hydroxy butyl vinyl ether or hydroxyl cyclohexyl vinyl ether, preferred hydroxyethyl vinyl ether.The activity of hydroxyethyl vinyl ether better.
The molar ratio of vulcabond, polyvalent alcohol and hydroxyalkyl vinyl ether is about 2: 1: 2.Wherein the hydroxyalkyl vinyl ether is more excessive a little, reacts completely to guarantee isocyanate groups.
Employed solvent is THF, acetone, butanone, toluene, hexanaphthene, methylene dichloride, and weight consumption is 5～10 times of raw material.
Temperature of reaction is according to the difference of reactant and difference; When reactant is isophorone diisocyanate; Reaction beginning temperature is controlled at 0 ℃, is warming up to 60 ℃ afterwards, when reactant is tolylene diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate; Reaction beginning temperature is controlled at 50 ℃, is warming up to 80 ℃ afterwards.
Reaction needed is carried out under the condition of anhydrous and oxygen-free inflated with nitrogen protection, must purify before the solvent of use and the raw material reaction to dewater.The glassware that uses need be before reaction re-uses in 100～110 ℃ of oven dry half hours.
A series of monomeric compounds below having obtained via above step, concrete structure is following:
Monomer P-1 to P-45:
Advantage of the present invention is: it is the urethane of vinyl ether that the present invention has designed and synthesized some end groups.This monomer adds initiator cationoid polymerisation takes place under UV-light.Have that rate of polymerization is fast, polymerization does not receive that oxygen disturbs, synthesis technique is simple, low toxicity, advantage such as tasteless, therefore in photo-curing material, have good actual application and be worth.
Embodiment
Describe the present invention in detail with reference to embodiment below.
[embodiment 1]
The compound method of monomer P-1:
Toward in the four-hole bottle that whisking appliance, TM, tap funnel, reflux condensing tube are installed, adding IPDI (isophorone diisocyanate) 11.1115g (0.05mol), fill N in the bottle
2Protection adds PPG400 (W 166 400) 10.0000g (0.025mol) in tap funnel.Slowly drip, after dropwising, ice-water bath reaction 2.5h.Add DBTDL (dibutyl tin laurate) 0.2ml; React 10min at normal temperatures; Be increased to 60 ℃ to temperature then, slowly drip HBVE (4-hydroxy butyl vinyl ether) 6.0424g (0.052mol) that diluted with solvents tetrahydrofurane, wait to dropwise continued reaction 4h.Revolve after having reacted to steam and remove THF (THF), this product that finally obtains, this product are viscous liquid.
[embodiment 2]
The compound method of monomer P-2:
Spent glycol substitutes the W 166 in [embodiment 1], and all the other reagent and consumption are identical with [embodiment 1].
[embodiment 3]
The compound method of monomer P-6:
Substitute the 4-hydroxy butyl vinyl ether in [embodiment 1] with the hydroxyethyl vinyl ether, all the other reagent and consumption are identical with [embodiment 1].
[embodiment 4]
The compound method of monomer P-12:
Substitute the 4-hydroxy butyl vinyl ether in [embodiment 1], all the other reagent and consumption with the hydroxyl cyclohexyl vinyl ether
Identical with [embodiment 1].
[embodiment 5]
The compound method of monomer P-17:
Toward in the four-hole bottle that whisking appliance, TM, tap funnel, reflux condensing tube are installed, adding TDI (tolylene diisocyanate) 8.708g (0.05mol), fill N in the bottle
2Protection adds Ucar 35 1.9023g (0.025mol) in tap funnel.With about 60～65 ℃ of reactions of temperature control 3h.After having reacted, add DBTDL (dibutyl tin laurate) 0.2ml, be increased to 80 ℃ to temperature then, slowly drip HBVE (4-hydroxy butyl vinyl ether) 6.0424g (0.052mol) that diluted with solvents tetrahydrofurane, wait to dropwise continued reaction 4h.Revolve after having reacted to steam and remove THF and get final product.
[embodiment 6]
The compound method of monomer P-16:
Substitute the Ucar 35 in [embodiment 5] with W 166, all the other reagent and consumption are identical with [embodiment 5].
[embodiment 7]
The compound method of monomer P-23:
Use W 166 respectively, vinyl ethyl ether base ether substitutes Ucar 35, the 4-hydroxy butyl vinyl ether in [embodiment 5], and all the other reagent and consumption are identical with [embodiment 5].
[embodiment 8]
The compound method of monomer P-34:
Toward in the four-hole bottle that whisking appliance, TM, tap funnel, reflux condensing tube are installed, adding HMDI (hexamethylene diisocyanate) 8.41g (0.05mol), fill N in the bottle
2Protection adds PPG400 (W 166 400) 10.0000g (0.025mol) in tap funnel.Slowly drip, after dropwising, reaction 3h.Add DBTDL (dibutyl tin laurate) 0.2ml then, temperature is controlled at about 50 ℃ always, slowly drips HBVE (4-hydroxy butyl vinyl ether) 6.0424g (0.052mol) that diluted with solvents tetrahydrofurane again, dropwises afterreaction 4h.Revolve after having reacted to steam and remove THF and can obtain product.
[embodiment 9]
The compound method of monomer P-36:
Substitute the W 166 in [embodiment 8] with butyleneglycol, all the other reagent and consumption are identical with [embodiment 7].
[embodiment 10]
The compound method of monomer P-37:
Substitute the 4-hydroxy butyl vinyl ether in [embodiment 8] with vinyl ethyl ether base ether, all the other reagent and consumption are identical with [embodiment 8].
[embodiment 11]
The compound method of monomer P-44:
Substitute the 4-hydroxy butyl vinyl ether in [embodiment 8] with the hydroxyl cyclohexyl vinyl ether, all the other reagent and consumption are identical with [embodiment 8].
Claims (9)
1. urethane that end group is a vinyl ether, its special card is that its general formula of molecular structure is:
R1 in the formula, R2, R3 are aliphatic hydrocarbon or aromatic hydrocarbon.
2. urethane compound method that end group is a vinyl ether, its special card is that its compound method comprises: under the anhydrous inert atmosphere, in vulcabond, drip polyvalent alcohol and stirring; Temperature is controlled at 0～50 ℃, reaction 2～4h, and wherein the two-NCO reactive behavior in vulcabond is not simultaneously; Optimal reaction temperature is 0 ℃, and optimum reacting time is 2.5h, adds catalyzer after having reacted and is warming up to 60～80 ℃; Drip hydroxyalkyl vinyl ether with solvent cut; After dropwising, continue stirring reaction 3～4h, finally obtain product.
3. according to the said compound method of claim 2, it is characterized in that employed catalyzer is a dibutyl tin laurate, and materials are the 0.2wt%～0.8wt% of vulcabond materials, wherein best materials are 0.5wt%.
4. according to the said compound method of claim 2, it is characterized in that vulcabond is aliphatic diisocyanate or alicyclic diisocyanate.
5. according to the said compound method of claim 2, it is characterized in that polyvalent alcohol is aliphatic dihydroxy alcohol or divalent alcohol polyether compound.
6. according to the said compound method of claim 2, it is characterized in that the hydroxyalkyl vinyl ether is hydroxyethyl vinyl ether, hydroxy butyl vinyl ether or hydroxyl cyclohexyl vinyl ether, preferred hydroxyethyl vinyl ether.
7. according to the said compound method of claim 2, it is characterized in that the molar ratio of vulcabond, polyvalent alcohol and hydroxyalkyl vinyl ether is about 2: 1: 2.
8. according to the said compound method of claim 2, it is characterized in that employed solvent is THF, acetone, butanone, toluene, hexanaphthene, methylene dichloride, weight consumption is 5～10 times of raw material.
9. according to method described in the claim 1; It is characterized in that temperature of reaction according to the difference of reactant and difference, when reactant was isophorone diisocyanate, reaction beginning temperature was controlled at 0 ℃; Be warming up to 60 ℃ afterwards; When reactant was tolylene diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, reaction beginning temperature was controlled at 50 ℃, is warming up to 80 ℃ afterwards.
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| CN2011102211732A CN102584634B (en) | 2011-08-03 | 2011-08-03 | Polyurethane using vinyl ether as end group and synthesis method thereof |
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| CN2011102211732A CN102584634B (en) | 2011-08-03 | 2011-08-03 | Polyurethane using vinyl ether as end group and synthesis method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558491A (en) * | 2011-10-20 | 2012-07-11 | 湖北固润科技股份有限公司 | Polyurethane oligomer taking vinyl ether as end group and synthesis method |
| CN112646546A (en) * | 2020-12-22 | 2021-04-13 | 张学明 | Bridge deck waterproof material and preparation method thereof |
| CN115386334A (en) * | 2022-09-03 | 2022-11-25 | 烟台德邦科技股份有限公司 | UV (ultraviolet) moisture dual-curing organopolysiloxane composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4775732A (en) * | 1988-01-11 | 1988-10-04 | Allied-Signal Inc. | Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes |
| US5159098A (en) * | 1990-09-10 | 1992-10-27 | Isp Investments Inc. | Alk-1-enyloxy carbamates |
| EP0924234A1 (en) * | 1997-12-16 | 1999-06-23 | Morton International, Inc. | Solid vinyl ether terminated urethane curing agent |
| CN101550093A (en) * | 2009-05-15 | 2009-10-07 | 北京化工大学 | Method for preparing dyadic vinyl ethers monomer |
-
2011
- 2011-08-03 CN CN2011102211732A patent/CN102584634B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4775732A (en) * | 1988-01-11 | 1988-10-04 | Allied-Signal Inc. | Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes |
| US5159098A (en) * | 1990-09-10 | 1992-10-27 | Isp Investments Inc. | Alk-1-enyloxy carbamates |
| EP0924234A1 (en) * | 1997-12-16 | 1999-06-23 | Morton International, Inc. | Solid vinyl ether terminated urethane curing agent |
| CN101550093A (en) * | 2009-05-15 | 2009-10-07 | 北京化工大学 | Method for preparing dyadic vinyl ethers monomer |
Non-Patent Citations (4)
| Title |
|---|
| 《Progress in Organic Coatings》 20040131 N. Kayaman等 "Synthesis and characterization of UV-curable vinyl ether functionalized urethane oligomers" 第2.3部分, 图1 1-9 第49卷, * |
| 《高等学校化学学报》 20041130 庞来兴等 "二苯基碘鎓盐引发氨酯型乙烯基醚热聚合" 第1.2部分 1-9 第25卷, 第11期 * |
| N. KAYAMAN等: ""Synthesis and characterization of UV-curable vinyl ether functionalized urethane oligomers"", 《PROGRESS IN ORGANIC COATINGS》 * |
| 庞来兴等: ""二苯基碘鎓盐引发氨酯型乙烯基醚热聚合"", 《高等学校化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558491A (en) * | 2011-10-20 | 2012-07-11 | 湖北固润科技股份有限公司 | Polyurethane oligomer taking vinyl ether as end group and synthesis method |
| CN112646546A (en) * | 2020-12-22 | 2021-04-13 | 张学明 | Bridge deck waterproof material and preparation method thereof |
| CN115386334A (en) * | 2022-09-03 | 2022-11-25 | 烟台德邦科技股份有限公司 | UV (ultraviolet) moisture dual-curing organopolysiloxane composition and preparation method thereof |
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| CN102584634B (en) | 2013-11-20 |
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Inventor after: Zou Yingquan Inventor after: Feng Ping Inventor after: He Changhua Inventor before: Zou Yingquan Inventor before: Feng Ping Inventor before: He Changhua |
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Denomination of invention: Polyurethane with vinyl ether as end group and synthesis method thereof Effective date of registration: 20211210 Granted publication date: 20131120 Pledgee: China Construction Bank Jingmen jinlongquan sub branch Pledgor: HUBEI GURUN TECHNOLOGY Co.,Ltd. Registration number: Y2021420000138 |