CN102584634B - 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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- CN102584634B CN102584634B CN2011102211732A CN201110221173A CN102584634B CN 102584634 B CN102584634 B CN 102584634B CN 2011102211732 A CN2011102211732 A CN 2011102211732A CN 201110221173 A CN201110221173 A CN 201110221173A CN 102584634 B CN102584634 B CN 102584634B
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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
Since West Germany Beyer Co., Ltd delivered luminous energy was applied to the cured coating film technology nineteen sixty-eight, the research and development of ultraviolet light polymerization (solidifying hereinafter to be referred as UV) tackiness agent was also developed rapidly.China began one's study and develops the UV curing technology from early 1970s.UV is coating material solidified has advantages of that many traditional coatings are incomparable: capacity usage ratio is high, applicable heat-sensitive substrate material, and pollution-free, film forming speed is fast, and film quality is high, is therefore the new generation of green Chemicals.Wherein the cation photocuring technology is a kind of in UV-curing technology, it has the impact that is not subjected to oxygen, volumetric shrinkage is little, the advantages such as adhesive power is strong, therein ethylene base ether is one of active maximum monomer of cationoid polymerisation, and to have a polymerization velocity fast due to vinyl ethers compound, and polymerization is not subjected to oxygen interference, low toxicity, the advantage such as tasteless, so vinyl ethers compound has very practical using value in the fields such as coating, tackiness agent, printing sensitization sheet material.The present invention, in view of these advantages, has innovated a series of compounds that contain the urethane of vinyl ehter bond, and the product that the 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
Purpose of the present invention is exactly in the fields such as coating, tackiness agent, printing sensitization sheet material, the advantage of very practical using value to be arranged 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 formula, R2, R3 are aliphatic hydrocarbon or aromatic hydrocarbon.
Synthetic method comprises: under the anhydrous inert atmosphere, in vulcabond, drip polyvalent alcohol and stir, temperature is controlled at 0～50 ℃, reaction 2～4h, wherein the two-NCO reactive behavior in vulcabond is not simultaneously, optimal reaction temperature is 0 ℃, and optimum reacting time is 2.5h, after having reacted, adds catalyzer and is warming up to 60～80 ℃, drip the hydroxyalkyl vinyl ether with solvent cut, after dropwising, continue stirring reaction 3～4h, finally obtain product.
The catalyzer that uses is 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.As isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), hexahydrotoluene dicyanate (HTDI), tetramethylxylylene diisocyanate (TMXDI) etc.
Polyvalent alcohol is aliphatic dihydroxy alcohol or dibasic alcohol polyether compound.As ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, polypropylene glycol 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 is 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, to guarantee isocyanate groups, reacts completely.
The solvent that uses is tetrahydrofuran (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 starts temperature and is controlled at 0 ℃, be warming up to afterwards 60 ℃, when reactant is tolylene diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, reaction starts temperature and is controlled at 50 ℃, is warming up to afterwards 80 ℃.
Reaction needed is carried out under the condition of anhydrous and oxygen-free inflated with nitrogen protection, before the solvent of use and raw material reaction, must purify and dewater.The glassware that uses need to be before reaction re-uses in 100～110 ℃ of oven dry half hours.
Via above step, obtained following a series of monomeric compounds, concrete structure is as follows:
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, under UV-light, cationoid polymerisation occurs.Have that rate of polymerization is fast, polymerization is not subjected to that oxygen disturbs, synthesis technique is simple, low toxicity, the advantage such as tasteless, therefore in photo-curing material, has good actual application value.
Embodiment
Below with reference to embodiment, describe the present invention in detail.
[embodiment 1]
The synthetic method of monomer P-1:
In the four-hole bottle agitator, thermometer, dropping funnel, reflux condensing tube are installed, add IPDI (isophorone diisocyanate) 11.1115g (0.05mol), in bottle, fill N
2Protection, add PPG400 (polypropylene glycol 400) 10.0000g (0.025mol) in dropping funnel.Slowly drip, after dropwising, ice-water bath reaction 2.5h.Add DBTDL (dibutyl tin laurate) 0.2ml, react at normal temperatures 10min, then temperature is increased to 60 ℃, slowly drips HBVE (4-hydroxy butyl vinyl ether) 6.0424g (0.052mol) that diluted with solvents tetrahydrofurane, after dropwising, continue reaction 4h.After having reacted, revolve to steam and remove THF (tetrahydrofuran (THF)), this product that finally obtains, this product are viscous liquid.
[embodiment 2]
The synthetic method of monomer P-2:
Spent glycol substitutes the polypropylene glycol in [embodiment 1], and all the other reagent and consumption are identical with [embodiment 1].
[embodiment 3]
The synthetic method of monomer P-6:
With the hydroxyethyl vinyl ether, substitute the 4-hydroxy butyl vinyl ether in [embodiment 1], all the other reagent and consumption are identical with [embodiment 1].
[embodiment 4]
The synthetic method of monomer P-12:
With the hydroxyl cyclohexyl vinyl ether, substitute the 4-hydroxy butyl vinyl ether in [embodiment 1], all the other reagent and consumption
Identical with [embodiment 1].
[embodiment 5]
The synthetic method of monomer P-17:
In the four-hole bottle agitator, thermometer, dropping funnel, reflux condensing tube are installed, add TDI (tolylene diisocyanate) 8.708g (0.05mol), in bottle, fill N
2Protection, add propylene glycol 1.9023g (0.025mol) in dropping funnel.Temperature is controlled to 60～65 ℃ of reaction 3h left and right.After having reacted, add DBTDL (dibutyl tin laurate) 0.2ml, then temperature is increased to 80 ℃, slowly drips HBVE (4-hydroxy butyl vinyl ether) 6.0424g (0.052mol) that diluted with solvents tetrahydrofurane, after dropwising, continue reaction 4h.After having reacted, revolve to steam and remove THF and get final product.
[embodiment 6]
The synthetic method of monomer P-16:
With polypropylene glycol, substitute the propylene glycol in [embodiment 5], all the other reagent and consumption are identical with [embodiment 5].
[embodiment 7]
The synthetic method of monomer P-23:
Use respectively polypropylene glycol, vinyl ethyl ether base ether substitutes propylene glycol, the 4-hydroxy butyl vinyl ether in [embodiment 5], and all the other reagent and consumption are identical with [embodiment 5].
[embodiment 8]
The synthetic method of monomer P-34:
In the four-hole bottle agitator, thermometer, dropping funnel, reflux condensing tube are installed, add HMDI (hexamethylene diisocyanate) 8.41g (0.05mol), in bottle, fill N
2Protection, add PPG400 (polypropylene glycol 400) 10.0000g (0.025mol) in dropping funnel.Slowly drip, after dropwising, reaction 3h.Then add DBTDL (dibutyl tin laurate) 0.2ml, temperature is controlled at 50 ℃ of left and right always, slowly drip again HBVE (4-hydroxy butyl vinyl ether) 6.0424g (0.052mol) that diluted with solvents tetrahydrofurane, dropwise afterreaction 4h.After having reacted, revolve to steam and remove THF and can obtain product.
[embodiment 9]
The synthetic method of monomer P-36:
With butyleneglycol, substitute the polypropylene glycol in [embodiment 8], all the other reagent and consumption are identical with [embodiment 7].
[embodiment 10]
The synthetic method of monomer P-37:
With vinyl ethyl ether base ether, substitute the 4-hydroxy butyl vinyl ether in [embodiment 8], all the other reagent and consumption are identical with [embodiment 8].
[embodiment 11]
The synthetic method of monomer P-44:
With the hydroxyl cyclohexyl vinyl ether, substitute the 4-hydroxy butyl vinyl ether in [embodiment 8], all the other reagent and consumption are identical with [embodiment 8].
Claims (1)
1. urethane synthetic method that end group is vinyl ether, this end group is that the structural formula of the urethane of vinyl ether is:
It is characterized in that: in the four-hole bottle agitator, thermometer, dropping funnel, reflux condensing tube are installed, add isophorone diisocyanate 0.05 mol, in bottle, fill N
2Protection; in dropping funnel, add 0.025mol polypropylene glycol 400, slowly drip, after dropwising; ice-water bath reaction 2.5h; add dibutyl tin laurate 0.2 ml, react at normal temperatures 10min, then temperature is increased to 60 ℃; slowly drip 4-hydroxy butyl vinyl ether 0.052 mol that diluted with solvents tetrahydrofurane; after dropwising, continue reaction 4 h, after having reacted, revolve to steam and remove tetrahydrofuran (THF), finally obtain this product.
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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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| CN102584634B true CN102584634B (en) | 2013-11-20 |
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Families Citing this family (3)
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| 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 |
| CN112646546B (en) * | 2020-12-22 | 2022-10-18 | 珠海市澜诺新材料科技有限公司 | 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 |
|---|
| "Synthesis and characterization of UV-curable vinyl ether functionalized urethane oligomers";N. Kayaman等;《Progress in Organic Coatings》;20040131;第49卷;第2.3部分, 图1 * |
| "二苯基碘鎓盐引发氨酯型乙烯基醚热聚合";庞来兴等;《高等学校化学学报》;20041130;第25卷(第11期);第1.2部分 * |
| N. Kayaman等."Synthesis and characterization of UV-curable vinyl ether functionalized urethane oligomers".《Progress in Organic Coatings》.2004,第49卷第2.3部分, 图1. |
| 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》.2004,第25卷(第11期),第1.2部分. |
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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 |
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