CN102492130B - Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether - Google Patents
Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether Download PDFInfo
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- CN102492130B CN102492130B CN201110403165.XA CN201110403165A CN102492130B CN 102492130 B CN102492130 B CN 102492130B CN 201110403165 A CN201110403165 A CN 201110403165A CN 102492130 B CN102492130 B CN 102492130B
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- polyether
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Abstract
The invention discloses capped polyether prepared by an alkaline catalytic one-step method. The product has the advantages of light color, few side reactions and high capping rate. The capped polyether prepared by the alkaline catalytic one-step method has the following structure: R(OCH2-CHR1)m-(OCH2-CHR2)n-O-R3, wherein R is a C1-C20 carbon chain group; R1 is -H, -CH3 or -CH2CH3; R2 is -H, -CH3 or -CH2CH3; R3 is a C1-C8 carbon chain group or trimethylsilane; and m and n are the number of chain segments of (OCH2-CHR1) and (OCH2-CHR2) in a polyether chain segment respectively, m is 0 to 40, the sum of m and n is 1 to 200, and chain segments of n and m are homopolymerized, blocked or randomly copolymerized.
Description
Technical field
The present invention relates to a kind of end capped polyether and preparation method thereof, end capped polyether prepared more specifically to a kind of base catalysis single stage method and preparation method thereof.
Background technology
End capped polyether, refer to that its terminal hydroxy group is by with various organic micromolecule compounds, carrying out etherificate, esterification or crosslinking reaction, the polyethers that the reactive hydrogen on hydroxyl is obtained by the alkyl of various short chains, aralkyl, ester group or the replacement of other groups.Because the chain end hydroxyl is replaced by other groups, end capped polyether has cloud point decline, emulsifying power enhancing, foaming power reduction, the sexuality of deoiling enhancing, micelle-forming concentration descends and chemical property is more stable, the characteristics such as applicable high and low temperature use for a long time.Therefore end capped polyether has purposes widely in preparing urethane foam stabilizer, defoamer and fabric finishing agent.
The special performance of end capped polyether causes the concern of domestic and international R&D institution and chemical enterprise day by day.The end blocking method of polyethers mainly can be divided into etherified sealed end, esterification end-blocking and crosslinked end-blocking.In existing closed-end technology, the most frequently used and general method is etherified sealed end.Its reaction principle is under alkaline condition, and polyethers and haloalkane reaction are generated to end capped polyether.The Chinese patent that application number is 01102872.6 and U.S. Pat 4548729, to this kind of elaboration that end blocking method technique is detailed, it adopts two-step approach, first solid sodium hydroxide or potassium hydroxide are fully reacted with polyethers, remove the small-molecule substances such as water or alcohol, generate corresponding alkoxide, then alkoxide and end-capping reagent halohydrocarbons reaction make end capped polyether, and the end-blocking route is as follows:
In addition; also disclosing in " preparation of alkyl capped polyether and application " literary composition in the 2nd phase of calendar year 2001 " Shanghai chemical industry " and having adopted haloalkane and sulfuric ester is the method that end-capping reagent prepares alkyl capped polyether, and should be used as elaboration to alkyl capped polyether at preparation medium, low-sudsing detergent, the aspect such as organic-silicon-modified.
End capped polyether prepared by aforesaid method, be the alkyl capped polyethers such as methyl or ethyl, because the alkalescence in reaction system is excessively strong, needs the factors such as high temperature removal water or alcohol, causes the end-blocking rate of end capped polyether low, and product colour is partially dark, and by product is many.
The Chinese patent that the patent No. is 200810021953.0 in addition also discloses a kind of end capped polyether prepared by end hydroxy polyether and preparation method thereof, the method is also to utilize two-step process to prepare end capped polyether, its preparation method also needs further to simplify, and product performance also need to be optimized.Therefore need to develop a kind of new method end capped polyether of light color successfully to prepare, that by product is few and the end-blocking rate is high.
Summary of the invention
The object of the invention is to solve deficiency and the problem existed in above-mentioned present technology, end capped polyether prepared by a kind of base catalysis single stage method, the advantage that product has is of light color, side reaction is few, the end-blocking rate is high.
The present invention simultaneously also provides the preparation method of this end capped polyether.The method adopts under the basic catalyst condition, utilizes one-step technology to prepare end capped polyether, makes alkalescence slowly discharge, and does not adopt the aqueous solution or the alcoholic solution of alkali, has avoided the processing condition of high temperature and highly basic.
Technical scheme of the present invention is as follows:
End capped polyether prepared by base catalysis single stage method of the present invention, it has following structure:
R(OCH
2-CHR
1)
m-(OCH
2-CHR
2)
n-O-R
3
Wherein: R is C
1-C
20the carbochain group, R
1for-H ,-CH
3or-CH
2cH
3, R
2for-H ,-CH
3or-CH
2cH
3, R
3for C
1-C
8carbochain group or trimethyl silane, m and n are respectively (OCH in polyether segment
2-CHR
1) and (OCH
2-CHR
2) the segment number, m=0～40, m+n=1～200, the segment of n and m is homopolymerization, block or random copolymerization.
The method of end capped polyether prepared by base catalysis single stage method of the present invention, it comprises the following steps: at ambient temperature, end hydroxy polyether and basic catalyst are added as entered in reactor; Then end-capping reagent is passed in reactor, control reactor pressure≤0.1Mpa, pass into and finish rear the intensification, make the temperature of reactor at 60-70 ℃, continue reaction more than 5 hours, after finally reacting coarse product being carried out to refinement treatment, obtain end capped polyether; It is complete that best control speed makes end-capping reagent pass into about 1 hour.
The method of end capped polyether prepared by base catalysis single stage method of the present invention, its further technical scheme is that described end hydroxy polyether has following structure:
R(OCH
2-CHR
1)
m-(OCH
2-CHR
2)
n-OH
Wherein: R is C
1-C
20the carbochain group, R
1for-H ,-CH
3or-CH
2cH
3, R
2for-H ,-CH
3or-CH
2cH
3, m and n are respectively (OCH in polyether segment
2-CHR
1) and (OCH
2-CHR
2) the segment number, m=0～40, m+n=1～200, the segment of n and m is homopolymerization, block or random copolymerization.
The method of end capped polyether prepared by base catalysis single stage method of the present invention, its further technical scheme can also be that described basic catalyst is one or more the mixture in sodium hydroxide, sodium carbonate, sodium bicarbonate, tetramethyl-aqua ammonia or alkali metal borate, the 5-10% that the consumption of basic catalyst is the end hydroxy polyether quality.
The method of end capped polyether prepared by base catalysis single stage method of the present invention, its further technical scheme can also be that described end-capping reagent is methyl chloride or n-butyl bromide.
The method of end capped polyether prepared by base catalysis single stage method of the present invention, the mol ratio that its further technical scheme can also be described end-capping reagent and end hydroxy polyether is 1: 1～1: 2.5, temperature of reaction while passing into end-capping reagent is 35～59 ℃, and the reaction times is 3～7 hours.
Method end-blocking principle of the present invention is as follows:
Compared with prior art the invention has the beneficial effects as follows:
Most critical part of the present invention is under the basic catalyst effect, the low-temp reaction condition, reaction pressure is reduced to 0.1Mpa by 0.2-0.4Mpa, without the high temperature removal aqueous solution or alcoholic solution, changed in the two-step process and must first the end hydroxy polyether saponification have been generated to the process of alkaline intermediate product in reaction process, technological process becomes single stage method by two-step approach, simplified production technique, improved reaction efficiency, reduced production cost, the end-blocking rate can reach more than 90%.
Embodiment
Embodiment 1
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 1000ml that agitator, reflux condensing tube, thermometer and gas feeding device are housed
2=CH-CH
2-(OCH
2cH
2)
10-(OCH
2cHCH
3)
4oH)) 730g (1mol), add sodium hydroxide 43.8g (polyethers quality 6%), the vacuum removal air, make reactor pressure-0.08～-0.10Mpa, then 70.7g (1.4mol) end-capping reagent methyl chloride is passed in reactor, and control speed to make methyl chloride pass into about 1 hour complete, control still internal pressure≤0.1Mpa, after dropwising, be warming up to 60 ℃, continue reaction 5 hours; With acid, the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent to process 2 hours, can obtain end capped polyether.
End capped polyether prepared by this example, according to GB " plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine respectively the front hydroxyl of allyl polyether end-blocking, the hydroxyl value of end capped polyether, can calculate its end-blocking rate, as table 1.
Embodiment 2
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 2000ml that agitator, reflux condensing tube, thermometer and gas feeding device are housed
2=CH-CH
2-(OCH
2cH
2)
25-(OCH
2cHCH
3)
8oH) 1622g (1mol), add potassium hydroxide 130g (polyethers quality 8%), the vacuum removal air, make reactor pressure-0.08～-0.10Mpa, then 65.7g (1.3mol) end-capping reagent methyl chloride is passed in reactor, and control speed to make methyl chloride pass into about 1 hour complete, control still internal pressure≤0.1Mpa, after dropwising, be warming up to 60-70 ℃, continue reaction 5 hours; With acid, the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent to process 2 hours, can obtain end capped polyether.
End capped polyether prepared by this example, according to GB " plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine respectively the front hydroxyl of allyl polyether end-blocking, the hydroxyl value of end capped polyether, can calculate its end-blocking rate, as table 1.
Embodiment 3
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 1000ml that agitator, reflux condensing tube, thermometer and gas feeding device are housed
2=CH-CH
2-(OCH
2cH
2)
10-(OCH
2cHCH
3)
4oH)) 730g (1mol), the compound alkali 43.8g (polyethers quality 6%) that adds sodium hydroxide and sodium bicarbonate, the vacuum removal air, make reactor pressure-0.08～-0.10Mpa, then 70.7g (1.4mol) end-capping reagent methyl chloride is passed in reactor, and control speed to make methyl chloride pass into about 1 hour complete, control still internal pressure≤0.1Mpa, after dropwising, be warming up to 60 ℃, continue reaction 5 hours; With acid, the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent to process 2 hours, can obtain end capped polyether.
End capped polyether prepared by this example, according to GB " plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine respectively the front hydroxyl of allyl polyether end-blocking, the hydroxyl value of end capped polyether, can calculate its end-blocking rate, as table 1.
Embodiment 4
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 2000ml that agitator, reflux condensing tube, thermometer and gas feeding device are housed
2=CH-CH
2-(OCH
2cH
2)
25-(OCH
2cHCH
3)
8oH) 1622g (1mol), add the compound alkali 130g of potassium hydroxide and salt of wormwood (polyethers quality 8%), the vacuum removal air, make reactor pressure-0.08～-0.10Mpa, then 65.7g (1.3mol) end-capping reagent methyl chloride is passed in reactor, and control speed to make methyl chloride pass into about 1 hour complete, control still internal pressure≤0.1Mpa, after dropwising, be warming up to 60-70 ℃, continue reaction 7 hours; With acid, the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent to process 2 hours, can obtain end capped polyether.
End capped polyether prepared by this example, according to GB " plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine respectively the front hydroxyl of allyl polyether end-blocking, the hydroxyl value of end capped polyether, can calculate its end-blocking rate, as table 1.
Embodiment 5
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 1000ml that agitator, reflux condensing tube, thermometer and gas feeding device are housed
2=CH-CH
2-(OCH
2cH
2)
10-(OCH
2cHCH
3)
4oH)) 730g (1mol), add sodium hydroxide 43.8g (polyethers quality 6%), the vacuum removal air, make reactor pressure-0.08～-0.10Mpa, then 70.7g (1.4mol) end-capping reagent methyl chloride is passed in reactor, and control speed to make methyl chloride pass into about 1 hour complete, control still internal pressure≤0.1Mpa, after dropwising, be warming up to 60 ℃, continue reaction 4 hours; With acid, the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent to process 2 hours, can obtain end capped polyether.
End capped polyether prepared by this example, according to GB " plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine respectively the front hydroxyl of allyl polyether end-blocking, the hydroxyl value of end capped polyether, can calculate its end-blocking rate, as table 1.
End capped polyether end-blocking rate prepared by table 1 example of the present invention
| Example | The end-blocking rate |
| Embodiment 1 | 92.2％ |
| Embodiment 2 | 90.9％ |
| Embodiment 3 | 94.2％ |
| Embodiment 4 | 93.5％ |
| Embodiment 5 | 76.3％ |
Claims (1)
1. a base catalysis single stage method prepares the method for end capped polyether, it is characterized in that comprising the following steps: at ambient temperature, end hydroxy polyether and basic catalyst are added in reactor; Then end-capping reagent is passed in reactor, control reactor pressure≤0.1MPa, pass into and finish rear the intensification, make the temperature of reactor at 60-70 ℃, continue reaction more than 5 hours, after finally reacting coarse product being carried out to refinement treatment, obtain end capped polyether;
Wherein:
Described end hydroxy polyether has following structure:
R(OCH
2-CHR
1)
m-(OCH
2-CHR
2)
n-OH
Wherein: R is CH2=CHCH2-, R
1for-H ,-CH
3or-CH
2cH
3, R
2for-H ,-CH
3or-CH
2cH
3, m and n are respectively (OCH in polyether segment
2-CHR
1) and (OCH
2-CHR
2) the segment number, m=0～40, m+n=1～200, the segment of n and m is homopolymerization, block or random copolymerization;
Described basic catalyst is one or more the mixture in sodium hydroxide, sodium carbonate, sodium bicarbonate, Tetramethylammonium hydroxide or alkali metal borate, the 5-10% that the consumption of basic catalyst is the end hydroxy polyether quality;
Described end-capping reagent is methyl chloride or n-butyl bromide;
The mol ratio of described end-capping reagent and end hydroxy polyether is 1:1～1:2.5, and the temperature of reaction while passing into end-capping reagent is 35～59 ℃.
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| CN103193973B (en) * | 2013-04-22 | 2015-06-17 | 苏州思德新材料科技有限公司 | End capping method of allyl polyether |
| CN108164693B (en) * | 2016-12-07 | 2019-11-29 | 上海东大化学有限公司 | A kind of silicon-modified polyether and preparation method thereof, application |
| 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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|---|---|---|---|---|
| CN101343358A (en) * | 2008-08-20 | 2009-01-14 | 南京德美世创化工有限公司 | End capping polyether prepared with end hydroxyl radical polyether and preparation thereof |
| CN101885839A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing blocked allyl polyether |
| CN101982481A (en) * | 2010-10-08 | 2011-03-02 | 广东标美硅氟新材料有限公司 | Preparation method of alkyl blocked allyl polyether |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343358A (en) * | 2008-08-20 | 2009-01-14 | 南京德美世创化工有限公司 | End capping polyether prepared with end hydroxyl radical polyether and preparation thereof |
| CN101885839A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing blocked allyl polyether |
| CN101982481A (en) * | 2010-10-08 | 2011-03-02 | 广东标美硅氟新材料有限公司 | Preparation method of alkyl blocked allyl polyether |
Non-Patent Citations (2)
| Title |
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| 孙宇等.聚氨酯泡沫用封端型非离子表面活性剂的研究.《第十二次聚氨酯泡沫塑料科研、生产、技术交流会议文集》.2011,第234-243页. |
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