CN102492130A - 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
- Publication number
- CN102492130A CN102492130A CN201110403165XA CN201110403165A CN102492130A CN 102492130 A CN102492130 A CN 102492130A CN 201110403165X A CN201110403165X A CN 201110403165XA CN 201110403165 A CN201110403165 A CN 201110403165A CN 102492130 A CN102492130 A CN 102492130A
- Authority
- CN
- China
- Prior art keywords
- polyether
- och
- capped polyether
- chr
- end capped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyethers (AREA)
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, more specifically to end capped polyether of a kind of base catalysis single stage method preparation and preparation method thereof.
Background technology
End capped polyether is meant that its terminal hydroxy group is through carrying out etherificate, esterification or crosslinking reaction with various organic micromolecule compounds, the polyethers that the reactive hydrogen on the hydroxyl is obtained by the alkyl of various short chains, aralkyl, ester group or the replacement of other groups.Owing to 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, characteristics such as suitable high and low temperature use for a long time.Therefore end capped polyether has purposes widely in preparation urethane foam stabilizer, skimmer 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 the existing closed-end technology, the most frequently used and method in common is an etherified sealed end.Its reaction principle is under the condition of alkalescence, and polyethers and haloalkane reaction are generated end capped polyether.Application number is 01102872.6 Chinese patent and U.S. Pat 4548729; To the detailed elaboration of this kind end blocking method technology, it adopts two-step approach, earlier solid sodium hydroxide or Pottasium Hydroxide and polyethers is fully reacted; Remove small-molecule substances such as water or alcohol; Generate corresponding alkoxide, alkoxide and end-capping reagent halohydrocarbons reaction make end capped polyether then, and the end-blocking route is following:
In addition; Also disclosing in " preparation of alkyl capped polyether and application " literary composition in the 2nd phase of calendar year 2001 " Shanghai Chemical " 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, aspect such as organic-silicon-modified.
The end capped polyether of method for preparing is alkyl capped polyethers such as methyl or ethyl, because the alkalescence in the reaction system is strong excessively, needs factors such as high temperature removal water or alcohol, causes the end-blocking rate of end capped polyether low, and product colour is dark partially, and by product is many.
The patent No. is that 200810021953.0 Chinese patent also discloses a kind of end capped polyether by the end hydroxy polyether preparation and preparation method thereof in addition; This method also is to utilize two-step process to prepare end capped polyether; Its preparation method also need further simplify, and product performance also need further to optimize.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 objective of the invention is to solve deficiency and the problem that exists in the above-mentioned present technology, the end capped polyether of a kind of base catalysis single stage method preparation, 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.This 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 high temperature and alkaline processing condition.
Technical scheme of the present invention is following:
The end capped polyether of base catalysis single stage method preparation 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
3Be C
1-C
8Carbochain group or trimethyl silane, m and n are respectively (OCH in the 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 the end capped polyether of base catalysis single stage method preparation of the present invention, it may further comprise the steps: at ambient temperature, end hydroxy polyether and basic catalyst are added as going in the reactor drum; Then end-capping reagent is fed in the reactor drum, controlling reactor internal pressure≤0.1Mpa feed to finish the back and heats up, and the temperature that makes reactor drum continues reaction more than 5 hours at 60-70 ℃, at last reacting coarse product is carried out refinement treatment after, obtain end capped polyether; Preferably control speed makes end-capping reagent about 1 hour, feed to finish.
The method of the end capped polyether of base catalysis single stage method preparation 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 the 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 the end capped polyether of base catalysis single stage method preparation of the present invention; Its further technical scheme can also be that described basic catalyst is one or more the mixture in sodium hydroxide, yellow soda ash, sodium hydrogencarbonate, tetramethyl-aqua ammonia or the alkali metal borate, and the consumption of basic catalyst is the 5-10% of end hydroxy polyether quality.
The method of the end capped polyether of base catalysis single stage method preparation of the present invention, its further technical scheme can also be that described end-capping reagent is methyl chloride or NBB.
The method of the end capped polyether of base catalysis single stage method preparation 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 when feeding end-capping reagent is 35～59 ℃, and the reaction times is 3～7 hours.
Method end-blocking principle of the present invention is following:
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, and reaction pressure is reduced to 0.1Mpa by 0.2-0.4Mpa; Need not the high temperature removal aqueous solution or alcoholic solution in the reaction process, changed the process that must earlier the end hydroxy polyether saponification be generated alkaline intermediate product in the two-step 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 in the round-bottomed flask of the 1000ml that whisking appliance, reflux condensing tube, TM and gas feeding device are housed, to add allyl alcohol polyether
2=CH-CH
2-(OCH
2CH
2)
10-(OCH
2CHCH
3)
4OH)) 730g (1mol) adds 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 fed in the reactor drum, and control speed makes methyl chloride about 1 hour, feed to finish; Control still internal pressure≤0.1Mpa; After dropwising, be warming up to 60 ℃, continue reaction 5 hours; Be adjusted to 5～6 with sour pH value, add zeyssatite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether reaction product.
The end capped polyether of this examples preparation; According to National Standard plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine the hydroxyl before the allyl polyether end-blocking respectively, the hydroxyl value of end capped polyether; Can calculate its end-blocking rate, like table 1.
Embodiment 2
(its structure is CH in the round-bottomed flask of the 2000ml that whisking appliance, reflux condensing tube, TM and gas feeding device are housed, to add allyl alcohol polyether
2=CH-CH
2-(OCH
2CH
2)
25-(OCH
2CHCH
3)
8OH) 1622g (1mol) adds Pottasium 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 fed in the reactor drum, and control speed makes methyl chloride about 1 hour, feed to finish; Control still internal pressure≤0.1Mpa; After dropwising, be warming up to 60-70 ℃, continue reaction 5 hours; Be adjusted to 5～6 with sour pH value, add zeyssatite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether reaction product.
The end capped polyether of this examples preparation is according to National Standard plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine the hydroxyl before the allyl polyether end-blocking respectively, the hydroxyl value of end capped polyether can calculate its end-blocking rate, like table 1.
Embodiment 3
(its structure is CH in the round-bottomed flask of the 1000ml that whisking appliance, reflux condensing tube, TM and gas feeding device are housed, to add allyl alcohol polyether
2=CH-CH
2-(OCH
2CH
2)
10-(OCH
2CHCH
3)
4OH)) 730g (1mol) adds the compound alkali 43.8g (polyethers quality 6%) of sodium hydroxide and sodium hydrogencarbonate, vacuum removal air; Make reactor pressure-0.08～-0.10Mpa, then 70.7g (1.4mol) end-capping reagent methyl chloride is fed in the reactor drum, and control speed makes methyl chloride about 1 hour, feed to finish; Control still internal pressure≤0.1Mpa; After dropwising, be warming up to 60 ℃, continue reaction 5 hours; Be adjusted to 5～6 with sour pH value, add zeyssatite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether reaction product.
The end capped polyether of this examples preparation; According to National Standard plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine the hydroxyl before the allyl polyether end-blocking respectively, the hydroxyl value of end capped polyether; Can calculate its end-blocking rate, like table 1.
Embodiment 4
(its structure is CH in the round-bottomed flask of the 2000ml that whisking appliance, reflux condensing tube, TM and gas feeding device are housed, to add allyl alcohol polyether
2=CH-CH
2-(OCH
2CH
2)
25-(OCH
2CHCH
3)
8OH) 1622g (1mol) adds Pottasium Hydroxide and the compound alkali 130g of 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 fed in the reactor drum, and control speed makes methyl chloride about 1 hour, feed to finish; Control still internal pressure≤0.1Mpa; After dropwising, be warming up to 60-70 ℃, continue reaction 7 hours; Be adjusted to 5～6 with sour pH value, add zeyssatite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether reaction product.
The end capped polyether of this examples preparation; According to National Standard plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine the hydroxyl before the allyl polyether end-blocking respectively, the hydroxyl value of end capped polyether; Can calculate its end-blocking rate, like table 1.
Embodiment 5
(its structure is CH in the round-bottomed flask of the 1000ml that whisking appliance, reflux condensing tube, TM and gas feeding device are housed, to add allyl alcohol polyether
2=CH-CH
2-(OCH
2CH
2)
10-(OCH
2CHCH
3)
4OH)) 730g (1mol) adds 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 fed in the reactor drum, and control speed makes methyl chloride about 1 hour, feed to finish; Control still internal pressure≤0.1Mpa; After dropwising, be warming up to 60 ℃, continue reaction 4 hours; Be adjusted to 5～6 with sour pH value, add zeyssatite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether reaction product.
The end capped polyether of this examples preparation; According to National Standard plastics polyether glycol the 3rd part: the mensuration of hydroxyl value " (GB-T12008.3-2009), determine the hydroxyl before the allyl polyether end-blocking respectively, the hydroxyl value of end capped polyether; Can calculate its end-blocking rate, like table 1.
The end capped polyether end-blocking rate of table 1 examples preparation of the present invention
| Instance | 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 (6)
1. the end capped polyether of base catalysis single stage method preparation is characterized in that having 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
3Be C
1-C
8Carbochain group or trimethyl silane, m and n are respectively (OCH in the 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.
2. the method for the end capped polyether of a base catalysis single stage method preparation is characterized in that may further comprise the steps: at ambient temperature, end hydroxy polyether and basic catalyst are added as going in the reactor drum; Then end-capping reagent is fed in the reactor drum, controlling reactor internal pressure≤0.1Mpa feed to finish the back and heats up, and the temperature that makes reactor drum continues reaction more than 5 hours at 60-70 ℃, at last reacting coarse product is carried out refinement treatment after, obtain end capped polyether.
3. the method for the end capped polyether of base catalysis single stage method preparation according to claim 2 is characterized in 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 the 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.
4. the method for the end capped polyether of base catalysis single stage method preparation according to claim 2; It is characterized in that described basic catalyst is one or more the mixture in sodium hydroxide, yellow soda ash, sodium hydrogencarbonate, tetramethyl-aqua ammonia or the alkali metal borate, the consumption of basic catalyst is the 5-10% of end hydroxy polyether quality.
5. the method for the end capped polyether of base catalysis single stage method preparation according to claim 2 is characterized in that described end-capping reagent is methyl chloride or NBB.
6. the method for the end capped polyether of base catalysis single stage method preparation according to claim 2; The mol ratio that it is characterized in that described end-capping reagent and end hydroxy polyether is 1: 1～1: 2.5; Temperature of reaction when feeding end-capping reagent is 35～59 ℃, and the reaction times is 3～7 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110403165.XA CN102492130B (en) | 2011-12-07 | 2011-12-07 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110403165.XA CN102492130B (en) | 2011-12-07 | 2011-12-07 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102492130A true CN102492130A (en) | 2012-06-13 |
| CN102492130B CN102492130B (en) | 2014-01-01 |
Family
ID=46183996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110403165.XA Active CN102492130B (en) | 2011-12-07 | 2011-12-07 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102492130B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193973A (en) * | 2013-04-22 | 2013-07-10 | 苏州思德新材料科技有限公司 | End capping method of allyl polyether |
| CN108164693A (en) * | 2016-12-07 | 2018-06-15 | 上海东大化学有限公司 | A kind of silicon-modified polyether and preparation method thereof, application |
| CN112679723A (en) * | 2020-12-28 | 2021-04-20 | 上海东大化学有限公司 | Two-end alkyl terminated PAG polyether and preparation method thereof |
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 |
-
2011
- 2011-12-07 CN CN201110403165.XA patent/CN102492130B/en active Active
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 (1)
| Title |
|---|
| 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》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193973A (en) * | 2013-04-22 | 2013-07-10 | 苏州思德新材料科技有限公司 | End capping method of allyl polyether |
| 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 |
| CN108164693A (en) * | 2016-12-07 | 2018-06-15 | 上海东大化学有限公司 | A kind of silicon-modified polyether and preparation method thereof, application |
| CN112679723A (en) * | 2020-12-28 | 2021-04-20 | 上海东大化学有限公司 | Two-end alkyl terminated PAG polyether and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102492130B (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101343358B (en) | End capping polyether prepared with end hydroxyl radical polyether and preparation thereof | |
| CN102977377B (en) | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent | |
| JP5081625B2 (en) | Process for the preparation of pure alpha-alkoxy-omega-hydroxy-polyalkylene glycols | |
| CN102492130B (en) | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether | |
| CN102504239A (en) | Catalyst for preparing polycarboxylate water reducing agent macromonomer and preparation method thereof | |
| CN102079754B (en) | Preparation process of methyltriethoxysilane | |
| CN114106315B (en) | Preparation method of narrow-distribution triethanolamine block polyether, block polyether and application of block polyether | |
| CN101445434A (en) | Synthetic method of methyl blocking polyether | |
| CN110980971B (en) | Non-phosphorus scale and corrosion inhibitor for industrial circulating water and preparation method thereof | |
| CN105622400A (en) | Acrylate synthesis method | |
| CN108864418B (en) | Aging crude oil demulsifier and preparation method thereof | |
| CN101914200B (en) | Method for preparing allyl polyoxyethylene ether | |
| CN100549065C (en) | The synthetic method of acetyl blocked allyl alcohol polyether | |
| CN102432861A (en) | Branching polyether macromonomer and preparation method thereof | |
| CN106278923A (en) | A kind of method preparing Methanamide | |
| CN102604069B (en) | Preparation method of diallyl polyether | |
| EP3559083A1 (en) | Processes for purifying polyether polyols | |
| CN101235144B (en) | Method for preparing low hydroxyl value alkyl capped polyether | |
| CN108751437A (en) | A kind of organosilicon core oil recovery treatment agent and preparation method thereof | |
| CN110724039A (en) | Preparation method of ethylene glycol mono-tert-butyl ether | |
| CN104327039A (en) | Preparation method of rosuvastatin intermediate | |
| EP4083107A1 (en) | Method for purifying branched polyethylene glycol | |
| CN114516834B (en) | Preparation and application of polyhydroxy cation high-temperature oxygen-resistant corrosion inhibitor | |
| CN110878020B (en) | Method for directly preparing dimethyl carbonate under low pressure | |
| CN102942956B (en) | Organic silicon resin grafted crude oil demulsification agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 210046 No. 18, Nanjing economic and Technological Development Zone, Jiangsu, Nanjing Applicant after: Jiangsu Maysta Chemical Co., Ltd. Address before: 210046 No. 18, Nanjing economic and Technological Development Zone, Jiangsu, Nanjing Applicant before: Nanjing Dymatic Shichuang Chemical Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: NANJING DYMATIC SHICHUANG CHEMICAL CO., LTD. TO: JIANGSU MAYSTA CHEMICAL CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |