CN100588673C - Process of preparing alkyl dead-end polyether by polyether with parahydroxyl at molecular chain end - Google Patents

Process of preparing alkyl dead-end polyether by polyether with parahydroxyl at molecular chain end Download PDF

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CN100588673C
CN100588673C CN200610154875A CN200610154875A CN100588673C CN 100588673 C CN100588673 C CN 100588673C CN 200610154875 A CN200610154875 A CN 200610154875A CN 200610154875 A CN200610154875 A CN 200610154875A CN 100588673 C CN100588673 C CN 100588673C
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polyethers
polyether
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alkali
alkyl
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CN100999580A (en
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王伟松
王新荣
孟照平
万庆梅
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Zhejiang Huangma Technology Co Ltd
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王伟松
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Abstract

The process of preparing polyether with end capping alkyl group belongs to the field of polyether synthesis technology. The process includes the reaction of polyether with sec hydroxyl group in the end of molecular chain and strong nucleophilic reagent alkali, the further reaction with alkyl halide, neutralizing with alkali, water washing and filtering to obtain polyether with end capping alkyl group. The strong nucleophilic reagent alkali is alcohol solution of sodium methoxide, alcohol solution of potassium methoxide, solid sodium methoxide, solid potassium methoxide or their mixture; and the alkyl halide is C1-C4 alkyl chloride or alkyl bromide. The present invention has very high reaction activity and effectively raised end capping rate.

Description

Molecule chain end is the method that the polyethers of secondary hydroxyl prepares alkyl capped polyether
Technical field
The polyethers that the present invention relates to a kind of molecule chain end and be secondary hydroxyl prepares the method for alkyl capped polyether, belongs to the synthesis technical field of end capped polyether.
Background technology
Alkyl capped polyether not only keeps many superperformances of original monoalkyl polyethers, and owing to the reactive hydrogen on original monoalkyl polyether compound terminal hydroxyl is replaced by hydrophobic alkyl, improve the chemical stability of whole molecule, thereby shown unique function.Alkyl capped polyether is mainly used in the following aspects: (1) utilizes it to alkaline stability, can be used in the low-sudsing detergent; Foam stabilizer when (2) the end capped polyether modified organic silicon can be used as polyurethane foam material production; (3) as the preparation medium monomer of excellent property; (4) as the component of ucon oil.
Because alkyl capped polyether has purposes widely, and alkyl capped polyether preparation method's research is received much concern.The preparation of existing alkyl capped polyether is reacted with the end-capping reagent that contains corresponding alkyl by polyethers and to be made normally in the presence of solid alkali metal oxyhydroxide or its solution.The polyethers of having introduced hydroxyl as U.S. Pat 5811594 and US6028229 generates alkyl capped polyether with the haloalkane reaction in the presence of solid potassium hydroxide or sodium hydroxide.In the end capping of polyethers, it is the key step that end capping is carried out that alkali and polyether reactant generate alkoxide.Because the reactive behavior of secondary hydroxyl is lower than the reactive behavior of primary hydroxyl, when the pfpe molecule chain end is primary hydroxyl usually, just can make polyethers generation alkoxide with the conventional solid alkali metal oxyhydroxide that end blocking method adopted such as sodium hydroxide or potassium hydroxide.And be the polyethers of secondary hydroxyl for molecule chain end, be difficult to make polyethers to generate corresponding alkoxide with conventional solid alkali metal oxyhydroxide or its solution, thereby cause the end-blocking rate very low.
Summary of the invention
The polyethers that to the purpose of this invention is to provide a kind of molecule chain end that can effectively improve the end-blocking rate be secondary hydroxyl prepares the method for alkyl capped polyether.
The present invention is the method that the polyethers of secondary hydroxyl prepares alkyl capped polyether for molecule chain end, and described molecule chain end is that the polyethers of secondary hydroxyl has following general formula (I):
Figure C20061015487500041
Wherein: A is C 1-C 20The carbochain group, R 1Be-H, methyl or ethyl, R 2Be methyl or ethyl, m+n=3-300, polyether segment are homopolymerization or block copolymerization;
The alkyl capped polyether of preparation gained has following general formula (II):
Figure C20061015487500042
R wherein 3Be C 1-C 4
It is characterized in that adding strong nucleophilic reagent alkali earlier in the polyethers of above-mentioned general formula (I) reacts, reaction end back adds haloalkane and continues reaction in reaction system, neutralize and washing with alkali at last, filters and obtains alkyl capped polyether; The alcoholic solution that described strong nucleophilic reagent alkali is sodium methylate, the alcoholic solution of potassium methylate, solid sodium methylate, the mixture of any one or more of solid methanol potassium; Described haloalkane is C 1-C 4Alkyl chloride or bromoalkane.
The polyethers of described general formula (I) can be 1: 1.5 with the mol ratio of strong nucleophilic reagent alkali~and 3.0.
The temperature of reaction that the strong nucleophilic reagent alkali of described adding reacts can be 70~120 ℃, and the reaction times is 0.5~1.5 hour, and reaction pressure is-0.085~-0.098Mpa.
The polyethers of described general formula (I) and the mol ratio of haloalkane can be 1: 1.5~and 3.0.
The temperature of reaction that described adding haloalkane continues reaction can be 30~60 ℃, and the reaction times is 4~8 hours.
Essence of the present invention is in the presence of strong nucleophilic reagent sodium methylate or potassium methylate, under vacuum condition, take out the methyl alcohol that dereaction generates, making the low molecule chain end of reactive behavior is that the polyethers of secondary hydroxyl fully reacts and generates corresponding alkoxide, and then react with the haloalkane end-capping reagent, reactive activity is very high, when having solved alkali metal hydroxide with routine and being used for terminal end capping for the secondary hydroxyl polyethers, the problem that the end-blocking rate is lower, can make molecule chain end is that the end-blocking rate of the polyethers of secondary hydroxyl reaches more than 90%, thereby for molecule chain end is carried out alkyl-blocked a kind of efficient ways that provides for the polyethers of secondary hydroxyl.
Embodiment
Embodiments of the invention are strong nucleophilic reagent with the methanol solution of sodium methylate, and n-butyl bromide is an end-capping reagent, and reaction equation is as follows:
RONa+C 4H 9Br→ROC 4H 9+NaBr (2)
Wherein:
Figure C20061015487500052
A is C 1-C 20The carbochain group, R 1Be-H, methyl or ethyl, R 2Be methyl or ethyl, m+n=3-300, polyether segment are homopolymerization or block copolymerization.
Because such alkaloid substance is the strong nucleophilic reagent with alkoxyl group, its alkalescence is greater than alkali metal hydroxide, has high reaction activity and high, at suitable condition of negative pressure, take out the methyl alcohol that dereaction is produced, above-mentioned reaction equation (1) is carried out to the right, thereby make polyethers generate corresponding alkoxide, and then the adding haloalkane, make end-blocking rate high product.
The end-blocking rate is defined as among the embodiment of the present invention:
Figure C20061015487500053
Embodiment 1:
Take into account in the round-bottomed flask of 1000ml of dropping funnel and add vinyl carbinol polyethenoxy ether (hydroxyl value 73) 400g having electronics constant speed stirrer, reflux condensing tube, temperature, the alcoholic solution 188g of sodium methylate, under vacuum tightness-0.085~-0.098 condition, 90~95 ℃ were reacted 1 hour, be cooled to 45~50 ℃, drip the 164g n-butyl bromide, dripped off in about 3 hours, dropwise the back and continue 45~50 ℃ of reactions 4 hours.Add 200g water, stirred 0.5 hour at 40~45 ℃, standing demix is removed water then, and being neutralized to PH with alkali is 6~8, and vacuum hydro-extraction obtains the alkyl capped polyether product after the adding super-cell filters.
Prior art Comparative Examples 1:
Take into account in the round-bottomed flask of 1000ml of dropping funnel and add vinyl carbinol polyethenoxy ether (hydroxyl value 73) 400g having electronics constant speed stirrer, reflux condensing tube, temperature, solid potassium hydroxide 59g, 90~95 ℃ were reacted 1 hour, be cooled to 45~50 ℃, drip the 164g n-butyl bromide, dripped off in about 3 hours, and dropwised the back and continue 45~50 ℃ of reactions 4 hours.Add 200g water, stirred 0.5 hour at 40~45 ℃, standing demix is removed water then, and being neutralized to PH with alkali is 6~8, and vacuum hydro-extraction obtains the alkyl capped polyether product after the adding super-cell filters.
Embodiment 2:
Take into account in the round-bottomed flask of 1000ml of dropping funnel and add allyl alcohol polyether (EO/PO=55/45 having electronics constant speed stirrer, reflux condensing tube, temperature, block, end is the PO segment, and hydroxyl value is 36) 600g, the alcoholic solution 176g of sodium methylate, under vacuum tightness-0.085~-0.098 condition, 90~95 ℃ were reacted 1 hour, were cooled to 40~45 ℃, dripped the 148g n-butyl bromide, dripped off in about 3 hours, and dropwised the back and continue 40~45 ℃ of reactions 4 hours.Add 300g water, stirred 0.5 hour at 40~45 ℃, standing demix is removed water then, and being neutralized to PH with alkali is 6~8, and vacuum hydro-extraction obtains the alkyl capped polyether product after the adding super-cell filters.
Prior art Comparative Examples 2:
Take into account in the round-bottomed flask of 1000ml of dropping funnel and add allyl alcohol polyether (EO/PO=55/45 having electronics constant speed stirrer, reflux condensing tube, temperature, block, end is the PO segment, hydroxyl value is 36) 600g, solid potassium hydroxide 54.8g, 90~95 ℃ were reacted 1 hour, be cooled to 40~45 ℃, drip the 148g n-butyl bromide, dripped off in about 3 hours, dropwise the back and continue 40~45 ℃ of reactions 4 hours.Add 300g water, stirred 0.5 hour at 40~45 ℃, standing demix is removed water then, and being neutralized to PH with alkali is 6~8, and vacuum hydro-extraction obtains the alkyl capped polyether product after the adding super-cell filters.
Processing parameter and reaction result are listed in the table below in the foregoing description and the prior art Comparative Examples:
End-capping reagent Strong nucleophilic reagent alkali Polyethers/alkali/end-capping reagent The end-blocking rate
Embodiment 1 N-butyl bromide The methanol solution of sodium methylate 1∶2.0∶2.3 93%
Prior art Comparative Examples 1 N-butyl bromide Potassium hydroxide 1∶2.0∶2.3 30%
Embodiment 2 N-butyl bromide The methanol solution of sodium methylate 1∶2.5∶2.8 90%
Prior art Comparative Examples 2 N-butyl bromide Potassium hydroxide 1∶2.5∶2.8 35%

Claims (4)

1, a kind of molecule chain end is the method that the polyethers of secondary hydroxyl prepares alkyl capped polyether, and described molecule chain end is that the polyethers of secondary hydroxyl has following general formula (I):
Figure C2006101548750002C1
Wherein: A is C 1-C 20The carbochain group, R 1Be-H, methyl or ethyl, R 2Be methyl or ethyl, m+n=3-300, polyether segment are homopolymerization or block copolymerization;
The alkyl capped polyether of preparation gained has following general formula (II):
Figure C2006101548750002C2
R wherein 3Be C 1-C 4
It is characterized in that adding strong nucleophilic reagent alkali earlier in the polyethers of above-mentioned general formula (I) reacts, reaction end back adds haloalkane and continues reaction in reaction system, neutralize and washing with alkali at last, filters and obtains alkyl capped polyether; The alcoholic solution that described strong nucleophilic reagent alkali is sodium methylate, the alcoholic solution of potassium methylate, solid sodium methylate, the mixture of any one or more of solid methanol potassium; Described haloalkane is C 1-C 4Alkyl chloride or bromoalkane; The temperature of reaction that the strong nucleophilic reagent alkali of described adding reacts is 70~120 ℃, and the reaction times is 0.5~1.5 hour, reaction pressure is-0.085~-0.098Mpa.
2, be the method that the polyethers of secondary hydroxyl prepares alkyl capped polyether by the described molecule chain end of claim 1, the polyethers that it is characterized in that described general formula (I) is 1: 1.5~3.0 with the mol ratio of strong nucleophilic reagent alkali.
3, be the method that the polyethers of secondary hydroxyl prepares alkyl capped polyether by the described molecule chain end of claim 1, it is characterized in that the polyethers of described general formula (I) and the mol ratio of haloalkane are 1: 1.5~3.0.
4, be the method that the polyethers of secondary hydroxyl prepares alkyl capped polyether by the described molecule chain end of claim 1, it is characterized in that the temperature of reaction that described adding haloalkane continues reaction is 30~60 ℃, the reaction times is 4~8 hours.
CN200610154875A 2006-11-28 2006-11-28 Process of preparing alkyl dead-end polyether by polyether with parahydroxyl at molecular chain end Active CN100588673C (en)

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CN101235144B (en) * 2007-12-21 2011-04-13 浙江皇马科技股份有限公司 Method for preparing low hydroxyl value alkyl capped polyether
CN102382290A (en) * 2011-11-02 2012-03-21 浙江合诚化学有限公司 Method for synthesizing triallyl polyether
CN103626990A (en) * 2013-11-27 2014-03-12 浙江皇马科技股份有限公司 Method for synthesizing trimethyl allyl polyoxypropylene ether
CN104788296B (en) * 2014-09-22 2017-01-11 山东诚创医药技术开发有限公司 Preparation method of methyldecane as impurity of colesevelam hydrochloride
CN106188483A (en) * 2016-07-18 2016-12-07 中科院广州化学有限公司南雄材料生产基地 A kind of via material environment-friendly type block polyether emulsifying agent and preparation method thereof
CN110330640B (en) * 2019-07-15 2022-02-18 万华化学集团股份有限公司 Refining method of high molecular weight alkyl terminated polyether
CN112679723B (en) * 2020-12-28 2023-04-07 上海东大化学有限公司 Two-end alkyl-terminated PAG polyether and preparation method thereof

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