CN1757661A - Novel end hydroxy polyether contg. cyclohexane, and its synthesis art - Google Patents
Novel end hydroxy polyether contg. cyclohexane, and its synthesis art Download PDFInfo
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- CN1757661A CN1757661A CN 200510031848 CN200510031848A CN1757661A CN 1757661 A CN1757661 A CN 1757661A CN 200510031848 CN200510031848 CN 200510031848 CN 200510031848 A CN200510031848 A CN 200510031848A CN 1757661 A CN1757661 A CN 1757661A
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- tetrahydrofuran
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Abstract
A hydroxy terminated polyether used to improve the strength, hardness, transparency and high-temp tolerance of polyurethane material features that its molecular main chain contains rigid hexacyclic structure. Its preparing process includes such steps as reaction between boron tri-fluoride ether, ethanediol, epoxy cyclohexane, tetrahydrofuran, epoxy chloropropane epoxy ethane and epoxy propane in dichlormetane at-10-10 deg.C for 4-5 hr, adding water to terminate the reaction, laying aside for layering, taking organic phase, and vacuum distilling to remove unreacted monomers and solvent.
Description
Technical field
Patent of the present invention relates to a class novel end hydroxy polyether and a synthesis technique thereof.
Background technology
Polyether glycol is a kind of important fine chemical product, is mainly used in goods such as producing polyurethane coating, elastomerics, spandex, binding agent.At present, the whole world year consumption polyether glycol is more than 4,000,000 tons, yearly capacity has U.S. DOW (Tao Shi) chemical company in the transnational company more than 100,000 tons, Arco (A Ke) chemical company and Shell (shell) chemical company, Bayer company etc., other renowned companies also have BASF (BASF) company, Olin (Olympic) company, Mobay (not shellfish) company, UCC (connection carbon) company, R-P (Luo Na-Planck) company, Eni Chem (ENI chemistry) company, Japan AGC-Olin Corp, Mitsui east pressure company, Sanyo changes into company's military field drug company, Korea S polyvalent alcohol company etc.In recent years, the polyethers manufacture of China has also obtained significant progress.Along with the development of polyurethane industrial and the demand in fine chemical product market, in recent years, the polyethers new variety of major company of external a few family constantly have report, mainly contain polyether polyol with high activity, high solid content polymer polyol, nitrogenous polyvalent alcohol etc.Domestic urethane then based on the propylene oxide polyethers, has only a small amount of oxyethane and propylene oxide block polyethers, tetrahydrofuran (THF) polyethers etc. with the polyether glycol kind, and kind is limited, and polyether glycol in Chinese domestic production amount well below market demand.Produce the competitive power in market at home and abroad in order to improve homemade polyether glycol, polyethers producer will reduce cost on the one hand, carry out products propaganda, encourage polyurethane production factory to use homemade polyether glycol, the polyether glycol of strengthening research, developing new product variety on the other hand is also imperative.
Summary of the invention
The object of the present invention is to provide a kind of novel polyether and synthesis technique thereof.More definite says, has following structural formula in the novel polyether molecular backbone chain of the present invention:
About the existing report of the copolymerization between the cyclic monomers such as tetrahydrofuran (THF), oxyethane and propylene oxide [Beijing Institute of Technology's journal, 1992,12 (SI): 30～38] [elastomerics, 1998,8 (4): 27～30] [USP4139567,1979] are because this class copolyether molecular backbone chain is linear, be flexible chain, be mainly used in the synthesis of polyurethane elastomerics.This patent utilizes epoxy cyclohexane and tetrahydrofuran (THF) (or epoxy chloropropane, or the mixture of tetrahydrofuran (THF) and epoxy chloropropane) carries out cationoid polymerisation, synthesized a class novel polyether, its molecular backbone chain contains the rigidity six-membered ring structure, can improve intensity, hardness, transparency and the thermotolerance etc. of polyether(poly)urethane material.
The synthesis technique of novel epoxy hexanaphthene-tetrahydrofuran (THF) copolyether is: make catalyzer with boron trifluoride diethyl etherate 1.41～5.23, ethylene glycol 0.31-0.93 is an initiator, epoxy cyclohexane 98～196, tetrahydrofuran (THF) 0～142, epoxy chloropropane 0～185, oxyethane 0～88, propylene oxide 0～116, make solvent with methylene dichloride 200, temperature of reaction-10～10 ℃ is reacted and is added suitable quantity of water termination reaction, standing demix separatory after 4～6 hours, get the organic phase decompression and steam unreacted monomer and solvent, obtain the thick product of water white transparency.
Embodiment
Embodiment 1
Press mass ratio and in reactor, add methylene chloride 200, ethylene glycol 0.62 and boron trifluoride diethyl etherate 1.41, stir 30min down at 0 ℃; Slowly add epoxy cyclohexane 196, controlled temperature is no more than 5 ℃, polyreaction 5 hours; Adding water 400 stops polyreaction and stirs washing in 5 minutes; With mixture standing demix separatory, again the organic phase underpressure distillation is removed unreacted intact epoxy cyclohexane, methylene chloride and small amount of moisture, get the equal polyethers of water white transparency thick liquid epoxy cyclohexane, yield 91.4%.
Embodiment 2
Get tetrahydrofuran (THF) 144, boron trifluoride diethyl etherate 2.82, ethylene glycol 0.62 adding reactor by mass ratio, open stirring system, insulation is at-5 ℃ of reaction 40min; Slowly add epoxy cyclohexane 98, in 1h, add, keep interior-5 ℃ of still, react 2.5h again; Add entry 400 washing termination reactions, the standing demix separatory; Get the organic phase decompression and steam unreacted monomer and solvent, obtain the thick product of water white transparency, yield 94.0%.
Embodiment 3
Get tetrahydrofuran (THF) 72, boron trifluoride diethyl etherate 1.41, ethylene glycol 0.31 adding reactor by mass ratio, open stirring system, insulation is at-5 ℃ of reaction 30min; Slowly add epoxy cyclohexane 196, in 1h, add, keep interior-5 ℃ of still, react 3h again; Add entry 400 washing termination reactions, the standing demix separatory; Get the organic phase decompression and steam unreacted monomer and solvent, obtain the thick product of water white transparency, yield 95.5%.
Embodiment 4
Get epoxy chloropropane 185, boron trifluoride diethyl etherate 1.41, ethylene glycol 0.31 adding reactor by mass ratio, open stirring system, insulation is at-5 ℃ of reaction 30min; Slowly add epoxy cyclohexane 98, in 1h, add, keep interior-5 ℃ of still, react 3h again; Add entry 400 washing termination reactions, the standing demix separatory; Get the organic phase decompression and steam unreacted monomer and solvent, obtain the thick product of water white transparency, yield 98.0%.
Embodiment 5
Press mass ratio and in reactor, add methylene chloride 200, ethylene glycol 0.62 and boron trifluoride diethyl etherate 1.41, stir 30min down at 0 ℃; Slowly add epoxy cyclohexane 98 and epoxy chloropropane 185 mixed solutions, add in 1h, controlled temperature is no more than 5 ℃, polyreaction 5 hours; Adding water 400 stops polyreaction and stirs washing in 5 minutes; With mixture standing demix separatory, again the organic phase underpressure distillation is removed unreacted intact epoxy cyclohexane, methylene chloride and small amount of moisture, get the equal polyethers of water white transparency thick liquid epoxy cyclohexane, yield 91.4%.
Embodiment 6
Get tetrahydrofuran (THF) 72, boron trifluoride diethyl etherate 1.41, ethylene glycol 0.31 adding reactor by mass ratio, open stirring system, insulation is at-5 ℃ of reaction 30min; Slowly add epoxy cyclohexane 98 and epoxy chloropropane 185 mixed solutions, in 1h, add, keep interior-5 ℃ of still, react 3h again; Add entry 400 washing termination reactions, the standing demix separatory; Get the organic phase decompression and steam unreacted monomer and solvent, obtain the thick product of water white transparency, yield 93.5%.
Embodiment 7
With embodiment 2 synthetic polyethers and TDI is the feedstock production polyurethane coating film, and its performance is as follows: pencil hardness HB; Shock strength 50kgcm; Glossiness 93.5%.
Embodiment 8
With embodiment 3 synthetic polyethers and TDI is the feedstock production polyurethane coating film, and its performance is as follows: pencil hardness 2B; Shock strength 40kgcm; Glossiness 84.8%.
Claims (3)
1. a class novel end hydroxy polyether has following structural formula in its molecular backbone chain:
2. as claim 1 described novel end hydroxy polyether, its main raw material is one or more in epoxy cyclohexane and tetrahydrofuran (THF), epoxy chloropropane, oxyethane, the propylene oxide.
3. as the synthesis technique of claim 1 described novel end hydroxy polyether, it is characterized in that: make catalyzer with boron trifluoride diethyl etherate 1.41～5.23, ethylene glycol 0.31-0.93 is an initiator, epoxy cyclohexane 98～196, tetrahydrofuran (THF) 0～142, epoxy chloropropane 0～185, oxyethane 0～88, propylene oxide 0～116 is made solvent with methylene dichloride 200, temperature of reaction-10～10 ℃, react and add the suitable quantity of water termination reaction after 4～6 hours, the standing demix separatory is got the organic phase decompression and is steamed unreacted monomer and solvent, obtains the thick product of water white transparency.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510031848 CN1757661A (en) | 2005-07-11 | 2005-07-11 | Novel end hydroxy polyether contg. cyclohexane, and its synthesis art |
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| CN 200510031848 CN1757661A (en) | 2005-07-11 | 2005-07-11 | Novel end hydroxy polyether contg. cyclohexane, and its synthesis art |
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| CN1757661A true CN1757661A (en) | 2006-04-12 |
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| CN 200510031848 Pending CN1757661A (en) | 2005-07-11 | 2005-07-11 | Novel end hydroxy polyether contg. cyclohexane, and its synthesis art |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897169A (en) * | 2012-12-25 | 2014-07-02 | 辽宁奥克化学股份有限公司 | Alkenyl-terminated unsaturated polyether, preparation method and application thereof |
| CN104744682A (en) * | 2013-12-27 | 2015-07-01 | 辽宁奥克化学股份有限公司 | Polyoxyalkyl ether, preparing method and applications thereof and polycarboxylate water reducing agent prepared from the polyoxyalkyl ether |
| CN108440736A (en) * | 2018-03-27 | 2018-08-24 | 郑州博物馆 | A kind of transparent polyurethane for paper relics protection reinforces liquid |
| CN108586238A (en) * | 2018-04-28 | 2018-09-28 | 湘潭大学 | It is poly-（1,2- cyclohexanediols）Single endcapping acrylate and preparation method thereof |
| CN111072946A (en) * | 2019-11-29 | 2020-04-28 | 黎明化工研究设计院有限责任公司 | Method for preparing hydroxyl-terminated cyclohexene oxide-ethylene oxide-tetrahydrofuran terpolymer ether by using bulk method |
-
2005
- 2005-07-11 CN CN 200510031848 patent/CN1757661A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897169A (en) * | 2012-12-25 | 2014-07-02 | 辽宁奥克化学股份有限公司 | Alkenyl-terminated unsaturated polyether, preparation method and application thereof |
| CN103897169B (en) * | 2012-12-25 | 2016-04-27 | 辽宁奥克化学股份有限公司 | A kind of end thiazolinyl unsaturated polyether and its preparation method and application |
| CN104744682A (en) * | 2013-12-27 | 2015-07-01 | 辽宁奥克化学股份有限公司 | Polyoxyalkyl ether, preparing method and applications thereof and polycarboxylate water reducing agent prepared from the polyoxyalkyl ether |
| CN108440736A (en) * | 2018-03-27 | 2018-08-24 | 郑州博物馆 | A kind of transparent polyurethane for paper relics protection reinforces liquid |
| CN108440736B (en) * | 2018-03-27 | 2020-09-25 | 郑州博物馆 | Transparent polyurethane reinforced liquid for protecting paper cultural relics |
| CN108586238A (en) * | 2018-04-28 | 2018-09-28 | 湘潭大学 | It is poly-（1,2- cyclohexanediols）Single endcapping acrylate and preparation method thereof |
| CN111072946A (en) * | 2019-11-29 | 2020-04-28 | 黎明化工研究设计院有限责任公司 | Method for preparing hydroxyl-terminated cyclohexene oxide-ethylene oxide-tetrahydrofuran terpolymer ether by using bulk method |
| CN111072946B (en) * | 2019-11-29 | 2023-04-14 | 黎明化工研究设计院有限责任公司 | Method for preparing hydroxyl-terminated cyclohexene oxide-ethylene oxide-tetrahydrofuran terpolymer ether by using bulk method |
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