CN104086765B - The preparation method of aliphatics coating polyether glycol - Google Patents
The preparation method of aliphatics coating polyether glycol Download PDFInfo
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- CN104086765B CN104086765B CN201410320901.9A CN201410320901A CN104086765B CN 104086765 B CN104086765 B CN 104086765B CN 201410320901 A CN201410320901 A CN 201410320901A CN 104086765 B CN104086765 B CN 104086765B
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Abstract
The present invention relates to a kind of preparation method of aliphatics coating polyether glycol, belong to polyether glycol synthesis technical field.The present invention, only using tetramethylolmethane as initiator, adopts two sections of polymerization techniques of solution polymerization and polycoordination, reacts preparation 4 functionality polyether glycol with epoxy alkane.Polyether glycol prepared by the present invention possesses the feature of high molecular, low-unsaturation-degree, narrow molecular weight distributions; It can replace the preparation that 2 functionality traditional on market and 3 functionality polyether glycols are applied to polyurethane coating, the hardness of film of polyurethane coating, base material sticking power, weathering resistance and mechanical property can be improved, meet the application requiring of high performance polyurethane coating.
Description
Technical field
The present invention relates to a kind of preparation method of aliphatics coating polyether glycol, belong to polyether glycol synthesis technical field.
Background technology
Polyurethane coating is that be equipped with the response type flexible polyurethane material that various auxiliary agent is made, therefore the structure of polyether glycol and quality directly determine Application Areas and the mechanical performance index of polyurethane coating with isocyanic ester, polyether glycol for main raw material.Conventional polyether polyols mostly is 2 functionality or 3 functionality polyethers of synthesizing for initiator with propylene glycol or glycerol under basic metal catalytic condition, because disproportionation reaction in polymerization process brings more unsaturated monohydroxy-alcohol, cause the polyurethane material mechanical property of preparation relatively poor; The low-unsaturation-degree prepared by bimetallic catalyst system in recent years, high molecular weight polyether are also the polyoxypropylene of 2 functionality or 3 functionality Grazing condition segments substantially, although increase on mechanical strength, there is no too large breakthrough in structure and use properties and in expanding the fields.
Tetramethylolmethane is the linking agent that in coating industry, purposes is wider, can significantly improve the hardness of film, sticking power, glossiness, weather resistance and flame retardant resistance, is therefore incorporated in polyether structure by tetramethylolmethane, will give the use properties of polyether glycol excellence.It is incorporated in initiator by existing patent report on a small quantity prepares rigid-foam polyether polyol, can effectively reduce polyethers viscosity, improve mobility, improves the fine and smooth degree of abscess.But under tetramethylolmethane normal temperature be solid powdery, fusing point is up to 262 DEG C, and the case preparing polyethers as initiator separately does not but have report and related products, and adopts conventional polyether synthesis technique also cannot realize polymerization.
Therefore, develop suitable polyethers synthesis technique, to prepare pure tetramethylolmethane based polyether polyol and to be applied to polyurethane coating industry, there is society and economic worth greatly.
Summary of the invention
The object of this invention is to provide a kind of preparation method of aliphatics coating polyether glycol, prepare the aliphatics coating polyether glycol of high molecular, low-unsaturation-degree, narrow molecular weight distribution, give the mechanical property that polyurethane material is higher.
The preparation method of aliphatics coating polyether glycol of the present invention, is characterized in that: using tetramethylolmethane as initiator, adopts two sections of polymerization techniques of solution polymerization and polycoordination, prepares polyether glycol with propylene oxide reaction.
The preparation method of described aliphatics coating polyether glycol, the synthesis technique of its two sections polymerizations is as follows:
(1) tetramethylolmethane and solvent is added, base metal catalysts is added after stirring, then add propylene oxide monomer to be polymerized, stirring reaction, vacuum deviates from organic solvent, continues to drip propylene oxide and is polymerized, use in phosphoric acid after completion of the reaction and pH to 5-6.8, add Magnesium Silicate q-agent to adsorb, then dry, filtration, obtains polyether glycol 1;
(2) add bimetallic catalyst in the polyether glycol 1 obtained in step (1), then add propylene oxide reaction, obtain target polyether glycol.
Different from rigid-foam polyether, in soft bubble or elastomerics class polyethers, the consumption of initiator can design the size of molecular weight along with polyethers and larger change occur.
The basic catalyst that described reaction is used is one or both in potassium hydroxide or sodium hydroxide, consumption is tetramethylolmethane and first paragraph solution polymerization process propylene oxide weight used sum 0.2% ~ 0.6%.
Described reaction Bimetallic catalyst system used is one or both (the Huaian The Budd Co. in solid powdery double metal cyanide catalyst or emulsion form double metal cyanide catalyst, commercially available prod), 0.002% ~ 0.01% of the polyether glycol that consumption is prepared for first paragraph solution polymerization and second segment polycoordination propylene oxide weight used sum.
Described solvent is 1,3-dimethyl-imidazolinone, methylene dichloride, trichloromethane, acetonitrile, tetrahydrofuran (THF), 2, one or more in 5-dimethyl furan, N, dinethylformamide or dimethyl sulfoxide (DMSO), its consumption is tetramethylolmethane and first paragraph solution polymerization process propylene oxide weight used sum 2% ~ 5%.
In step (1), by controlling the consumption of access ring Ethylene Oxide, by polyether glycol 1 molecular weight control that obtains 400 ~ 1000, pH value controls 5 ~ 6.8, moisture content≤0.05%.
The concrete steps of step (1) are as follows:
First in reactor, tetramethylolmethane and solvent is added, base metal catalysts is added after stirring, be warming up to 70 DEG C ~ 100 DEG C, then add account for tetramethylolmethane and first paragraph solution polymerization process propylene oxide weight used sum 2% ~ 5% propylene oxide monomer be polymerized, stirring reaction 1 ~ 2h, when question response pressure no longer changes, vacuum deviates from solvent, and the ratio being 264 ~ 864:136 according to propylene oxide and tetramethylolmethane mass ratio at 100 DEG C ~ 110 DEG C drips propylene oxide monomer and is polymerized.
The present invention adopts two kinds of catalyst system and two-stage polymerization process, and the first step adopts solution polymerization, solve tetramethylolmethane because of fusing point is too high cannot a difficult problem separately as initiator synthesizing polyether under basic metal catalyst system; Second step adopts polycoordination to achieve the synthesis of high molecular, low-unsaturation-degree, narrow molecular weight distributions polyether glycol.
The present invention has following beneficial effect:
(1) the polyether polyols alcohol functionalities for preparing of the present invention is up to 4, possesses the feature of high molecular (2000-6000), low-unsaturation-degree (≤0.01mol/kg), narrow molecular weight distributions (molecular weight distributing index is about 1.10) simultaneously;
(2) polyether glycol that prepared by the present invention can replace the preparation that 2 functionality traditional on market and 3 functionality polyether glycols are applied to polyurethane coating, the hardness of film of polyurethane coating, base material sticking power, weathering resistance and mechanical property can be improved, meet the application requiring of high performance polyurethane coating.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but it does not limit enforcement of the present invention.
Embodiment 1
(1) in 2L autoclave, 408g tetramethylolmethane and 60g dimethyl sulfoxide (DMSO) is added under room temperature, stir, add 3.6gKOH again, carry out nitrogen replacement, after in survey still, oxygen level is less than 100ppm, be warming up to 100 DEG C, stirring reaction 1h, then add 60g propylene oxide to be polymerized, after stirring reaction 2h, under-0.09MPa, vacuum deviates from solvent dimethyl sulfoxide (DMSO), continue charging propylene oxide 732g, control polymeric reaction temperature 105 DEG C, pressure 0.15MPa, after completion of the reaction, be cooled to 80 DEG C, add 7.7g phosphoric acid and 36g distilled water, stirring reaction 40min, then 1.2g Magnesium Silicate q-agent is added, stir 40min, vacuum hydro-extraction 2 hours under-0.09MPa, filtration obtains polyether glycol 1, stand-by.
(2) in 5L autoclave, 600g polyether glycol 1 and 0.24g pressed powder dmc catalyst is added under room temperature, vacuum hydro-extraction 40min under-0.09MPa, then charging propylene oxide 2400g, maintains reacting kettle inner pressure 0.15MPa, temperature of reaction 130 DEG C.After completion of the reaction, vacuum outgas 40min under-0.09MPa, is cooled to 70 DEG C of dischargings, obtains target polyether glycol A.Dependence test index is in table 1.
Embodiment 2:
(1) in 2L autoclave, 272g tetramethylolmethane and 70g acetonitrile is added under room temperature, stir, add 4.2gKOH again, carry out nitrogen replacement, after in survey still, oxygen level is less than 100ppm, be warming up to 80 DEG C, stirring reaction 1.5h, then add 56g propylene oxide to be polymerized, after stirring reaction 1h, under-0.09MPa, vacuum deviates from solvent acetonitrile, continue charging propylene oxide 1072g, control temperature of reaction 100 DEG C, pressure 0.2MPa, after completion of the reaction, be cooled to 80 DEG C, add 9.00g phosphoric acid and 42g distilled water, stirring reaction 40min, then 1.4g Magnesium Silicate q-agent is added, stir 40min, vacuum hydro-extraction 2 hours under-0.09MPa, filtration obtains polyether glycol 1, stand-by.
(2) in 5L autoclave, add 560g polyether glycol 1 and 0.192g emulsion dmc catalyst under room temperature, vacuum hydro-extraction 40min under-0.09MPa, then charging propylene oxide 2640g, maintain reacting kettle inner pressure 0.15MPa, temperature of reaction 130 DEG C.After completion of the reaction, vacuum outgas 40min under-0.09MPa, is cooled to 70 DEG C of dischargings, obtains target polyether glycol B.Dependence test index is in table 1.
Embodiment 3:
(1) in 2L autoclave, 204g tetramethylolmethane and 45g1 is added under room temperature, 3-dimethyl-imidazolinone, stir, add 9gKOH again, carry out nitrogen replacement, after in survey still, oxygen level is less than 100ppm, be warming up to 70 DEG C, stirring reaction 1h, then add 45g propylene oxide to be polymerized, after stirring reaction 1.5h, under-0.09MPa, vacuum deviates from solvent 1, 3-dimethyl-imidazolinone, continue charging propylene oxide 1251g, control temperature of reaction 110 DEG C, pressure 0.1MPa, after completion of the reaction, be cooled to 80 DEG C, add 19.27g phosphoric acid and 45g distilled water, stirring reaction 40min, then 1.5g Magnesium Silicate q-agent is added, stir 40min, vacuum hydro-extraction 2 hours under-0.09MPa, filtration obtains polyether glycol 1, stand-by.
(2) in 5L autoclave, 500g polyether glycol 1 and 0.075g pressed powder dmc catalyst is added under room temperature, vacuum hydro-extraction 40min under-0.09MPa, then charging propylene oxide 2500g, maintains reacting kettle inner pressure 0.15MPa, temperature of reaction 126 DEG C.After completion of the reaction, vacuum outgas 40min under-0.09MPa, is cooled to 70 DEG C of dischargings, obtains target polyether glycol C.Dependence test index is in table 1.
The dependence test index of polyethers prepared by table 1 embodiment
Polyether glycol the present invention obtained respectively and commercially available traditional 3 functionality polyether glycols are prepared polyurethane coating and carry out performance comparison, in table 2.
The polyethers that table 2 the present invention obtains and commercially available traditional 3 functionality polyethers prepare the performance comparison of polyurethane coating
Note: commercially available 330 is molecular weight 3000, and functionality is the polyether glycol of 3.
Claims (6)
1. a preparation method for aliphatics coating polyether glycol, is characterized in that: using tetramethylolmethane as initiator, adopts two sections of polymerization techniques of solution polymerization and polycoordination, prepares polyether glycol with propylene oxide reaction;
The synthesis technique of two sections of polymerizations is as follows:
(1) add tetramethylolmethane and solvent, after stirring, add base metal catalysts, stirring reaction, then add propylene oxide monomer and carry out polyreaction, vacuum deviates from solvent, continues to drip propylene oxide and is polymerized, carry out aftertreatment after completion of the reaction, obtain polyether glycol 1;
(2) add bimetallic catalyst in the polyether glycol 1 obtained in step (1), then add propylene oxide reaction, obtain target polyether glycol;
Solvent is one or more in 1,3-dimethyl-imidazolinone, methylene dichloride, trichloromethane, acetonitrile, tetrahydrofuran (THF), 2,5-dimethyl furans, N, dinethylformamide or dimethyl sulfoxide (DMSO).
2. the preparation method of aliphatics coating polyether glycol according to claim 1, it is characterized in that: the base metal catalysts reacting used is one or both in potassium hydroxide or sodium hydroxide, consumption is tetramethylolmethane and first paragraph solution polymerization process propylene oxide weight used sum 0.2% ~ 0.6%.
3. the preparation method of aliphatics coating polyether glycol according to claim 1, it is characterized in that: the bimetallic catalyst reacting used is one or both in solid powdery double metal cyanide catalyst or emulsion form double metal cyanide catalyst, 0.002% ~ 0.01% of the polyether glycol that consumption is prepared for first paragraph solution polymerization and second segment polycoordination propylene oxide weight used sum.
4. the preparation method of aliphatics coating polyether glycol according to claim 1, is characterized in that: solvent load is tetramethylolmethane and first paragraph solution polymerization process propylene oxide weight used sum 2% ~ 5%.
5. the preparation method of aliphatics coating polyether glycol according to claim 1, is characterized in that: the middle aftertreatment of step (1) is neutralization, absorption, dry, filtration; Polyether glycol 1 molecular weight control obtained is 400 ~ 1000, and pH value controls 5 ~ 6.8, moisture content≤0.05%.
6. according to the preparation method of the arbitrary described aliphatics coating polyether glycol of claim 2-5, it is characterized in that the concrete steps of step (1) are as follows: first in reactor, add tetramethylolmethane and solvent, base metal catalysts is added after stirring, be warming up to 70 DEG C ~ 100 DEG C, then add account for tetramethylolmethane and first paragraph solution polymerization process propylene oxide weight used sum 2% ~ 5% propylene oxide monomer carry out polyreaction, stirring reaction 1 ~ 2h, when question response pressure no longer changes, vacuum deviates from solvent, the ratio being 264 ~ 864:136 according to propylene oxide and tetramethylolmethane mass ratio at 100 DEG C ~ 110 DEG C drips propylene oxide monomer and is polymerized.
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| US3865806A (en) * | 1970-12-28 | 1975-02-11 | Dow Chemical Co | Low viscosity, low equivalent weight polyether polyols and a method for their preparation |
| US4332936A (en) * | 1978-10-16 | 1982-06-01 | Mobay Chemical Corporation | Method of making polyether polyols from solid hydroxyl containing initiators |
| US5652279A (en) * | 1995-07-26 | 1997-07-29 | Arco Chemical Technology, L.P. | Polyether polyols suitable for flexible polyurethane foam prepared by co-initiation of aqueous solutions of solid polyhydroxyl initiators |
| CN1659210A (en) * | 2002-06-13 | 2005-08-24 | 巴斯福股份公司 | Method for producing polyether alcohols |
| CN101921391A (en) * | 2010-09-21 | 2010-12-22 | 山东蓝星东大化工有限责任公司 | Synthesis method of polyether polyalcohol with low unsaturation degree and high molecular weight |
| CN103709392A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol for automobile sealant |
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- 2014-07-04 CN CN201410320901.9A patent/CN104086765B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3085085A (en) * | 1960-05-03 | 1963-04-09 | Pittsburgh Plate Glass Co | Method of preparing polyethers of mono and disaccharides |
| US3865806A (en) * | 1970-12-28 | 1975-02-11 | Dow Chemical Co | Low viscosity, low equivalent weight polyether polyols and a method for their preparation |
| US4332936A (en) * | 1978-10-16 | 1982-06-01 | Mobay Chemical Corporation | Method of making polyether polyols from solid hydroxyl containing initiators |
| US5652279A (en) * | 1995-07-26 | 1997-07-29 | Arco Chemical Technology, L.P. | Polyether polyols suitable for flexible polyurethane foam prepared by co-initiation of aqueous solutions of solid polyhydroxyl initiators |
| CN1659210A (en) * | 2002-06-13 | 2005-08-24 | 巴斯福股份公司 | Method for producing polyether alcohols |
| CN101921391A (en) * | 2010-09-21 | 2010-12-22 | 山东蓝星东大化工有限责任公司 | Synthesis method of polyether polyalcohol with low unsaturation degree and high molecular weight |
| CN103709392A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol for automobile sealant |
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Inventor after: Liu Jun Inventor after: Sun Zhaoren Inventor after: Ning Xiaolong Inventor after: Ma Haijing Inventor after: Liu Yanliang Inventor before: Liu Jun Inventor before: Sun Zhaoren Inventor before: Ning Xiaolong Inventor before: Ma Haijing Inventor before: Liu Yanliang |
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