CN101343358B - End capping polyether prepared with end hydroxyl radical polyether and preparation thereof - Google Patents
End capping polyether prepared with end hydroxyl radical polyether and preparation thereof Download PDFInfo
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- CN101343358B CN101343358B CN2008100219530A CN200810021953A CN101343358B CN 101343358 B CN101343358 B CN 101343358B CN 2008100219530 A CN2008100219530 A CN 2008100219530A CN 200810021953 A CN200810021953 A CN 200810021953A CN 101343358 B CN101343358 B CN 101343358B
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Abstract
The invention discloses end capping polyether which is prepared by hydroxyl-terminated polyether and the preparation method thereof. The reaction condition is mild, and the end capping rate can achieve higher than 95 percent. The end capping polyether prepared by the hydroxyl-terminated polyether is provided with the structure that R is C1-C20 carbon chain group, R1 is-H, -CH3 or -CH2CH3, R2 is -H, -CH3 or -CH2CH3, m and n are respectively the number of the chain segment of OCH2-CHR1 and OCH2-CHR2 in the chain segment of the polyether, m is 0 to 45, m plus n is 1 to 210, and the chain segments of n and m are respectively homopolymerized, segmented or randomly copolymerized.
Description
Technical field
The present invention relates to a kind of end capped polyether and preparation method thereof, more specifically to a kind of end capped polyether by end hydroxy polyether preparation and preparation method thereof.
Background technology
End capped polyether is meant that its terminal hydroxy group is by 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.Because the chain end hydroxyl is replaced by other groups, end capped polyether has higher chemical stability.The special construction of end capped polyether has caused its special physics and chemical property, is widely used in modified polyether fields such as organic silicon modified by polyether, cleaning, textile printing and dyeings.
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 potassium hydroxide are fully reacted the corresponding alkoxide of generation with polyethers, alkoxide and end-capping reagent halohydrocarbons reaction make end capped polyether then.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, aspect such as organic-silicon-modified.
The end capped polyether of method for preparing is alkyl capped polyethers such as methyl or ethyl, but there is the unstable and not high problem of end-blocking rate of end-blocking rate in it.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that exists in the above-mentioned present technology, a kind of end capped polyether by the end hydroxy polyether preparation is provided.
The present invention simultaneously also provides the preparation method of this end capped polyether.
Technical scheme of the present invention is as follows:
End capped polyether by the end hydroxy polyether preparation of the present invention, it has following structure:
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=0～45, m+n=1～210, the segment of n and m is homopolymerization, block or random copolymerization.
The preparation method of end capped polyether of the present invention may further comprise the steps: end hydroxy polyether and bases compound react, and obtain corresponding alkoxide; The alkoxide that obtains and end-capping reagent trimethylchlorosilane continue reaction, reacting coarse product is carried out refinement treatment after, obtain end capped polyether, wherein said end hydroxy polyether has following structure:
R(OCH
2—CHR
1)
m——(OCH
2—CHR
2)
n—OH
In this structure: R is C
1-C
20The carbochain group, R
1For-H ,-CH
3Or-CH
2CH
3, R
1For-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=0～45, m+n=1～210, the segment of n and m is homopolymerization, block or random copolymerization.
Among the preparation method of end capped polyether of the present invention, its described bases compound is one or more the mixture in sodium hydroxide, potassium hydroxide, the sodium methylate, the mol ratio of end hydroxy polyether and bases compound is 1:1.0～1:2.0, temperature of reaction is 60～120 ℃, reaction times is 1.0～3.0 hours, reaction pressure is-0.08～-0.10Mpa.
Among the preparation method of end capped polyether of the present invention, the mol ratio of its described alkoxide and end-capping reagent trimethylchlorosilane is 1:1～1:2.5, and temperature of reaction is 35～80 ℃, and the reaction times is 1.5～4.0 hours.
Compared with prior art the invention has the beneficial effects as follows:
Most critical part of the present invention is to adopt in the end capped polyether trimethylchlorosilane as end-capping reagent, utilize the strong basicity of the sodium alkoxide that polyethers and alkali forms and the strongly-acid of trimethylchlorosilane to carry out end capping, this reaction conditions gentleness, and sufficient reacting, the end-blocking rate can reach more than 95%.
In addition, can utilize the present invention that the not high polyethers of alkyl capped polyether end-blocking rate is assisted end-blocking, thereby obtain the end capped polyether that has two kinds of different capping groups of high end-blocking rate.
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 dropping funnel are housed
2=CH-CH
2-(OCH
2CH
2)
10-(OCH
2CHCH
3)
4OH) 350g adds sodium hydroxide 45g, and adds solubility promoter methyl alcohol 100ml;-0.08～-0.10Mpa under, 85 ℃ of reactions 2.5 hours down; Be cooled to 60 ℃, drip trimethylchlorosilane 83g, dropwised in about 1 hour, dropwise the back and continue reaction 1.5 hours; With acid the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether.
The end capped polyether of this examples preparation, its end-blocking rate is analyzed end-blocking rate such as table 1 through infrared test.
Embodiment 2
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 1000ml that agitator, reflux condensing tube, thermometer and dropping funnel are housed
2=CH-CH
2-(OCH
2CH
2)
16-(OCH
2CHCH
3)
7OH) 500g adds sodium hydroxide 25g, and adds solubility promoter methyl alcohol 50ml ,-0.08～-0.10Mpa under, 80 ℃ of reactions 3.0 hours down; Be cooled to 60 ℃, drip trimethylchlorosilane 60g, dropwised in about 40 minutes, dropwise the back and continue reaction 1.0 hours; With acid the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether.
The end capped polyether of this examples preparation, its end-blocking rate is analyzed end-blocking rate such as table 1 through infrared test.
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 dropping funnel are housed
2=CH-CH
2-(OCH
2CH
2)
10-(OCH
2CHCH
3)
4OH) 350g adds sodium methylate 40g, and adds solubility promoter methyl alcohol 100ml ,-0.08～-0.10Mpa under, 120 ℃ of reactions 2.5 hours down; Be cooled to 60 ℃, drip trimethylchlorosilane 80g, dropwised in about 1 hour, dropwise the back and continue reaction 1.5 hours; With acid the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether.
The end capped polyether of this examples preparation, its end-blocking rate is analyzed end-blocking rate such as table 1 through infrared test.
Embodiment 4
(its structure is CH to add allyl alcohol polyether in the round-bottomed flask of the 1000ml that agitator, reflux condensing tube, thermometer and dropping funnel are housed
2=CH-CH
2-(OCH
2CH
2)
16-(OCH
2CHCH
3)
7OH) 500g adds sodium methylate 22g, and adds solubility promoter methyl alcohol 50ml ,-0.08～-0.10Mpa under, 80～90 ℃ of reactions 3.0 hours down; Be cooled to 60 ℃, drip trimethylchlorosilane 55g, dropwised in about 40 minutes, dropwise the back and continue reaction 1.0 hours; With acid the pH value of reaction product is adjusted to 5～6, adds diatomite and polyethers finishing agent and handled 2 hours, can obtain end capped polyether.
The end capped polyether of this examples preparation, its end-blocking rate is analyzed end-blocking rate such as table 1 through infrared test.
The end capped polyether end-blocking rate of table 1 examples preparation of the present invention
| Example | The end-blocking rate |
| Embodiment 1 | 96.2 |
| Embodiment 2 | 95.9 |
| Embodiment 3 | 98.2 |
| Embodiment 4 | 97.5 |
Claims (3)
1. end capped polyether by end hydroxy polyether preparation is characterized in that having following structure:
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=0～45, m+n=1～210, the segment of n and m is homopolymerization, block or random copolymerization.
2. the preparation method of an end capped polyether as claimed in claim 1, it is characterized in that may further comprise the steps: end hydroxy polyether and bases compound react, and obtain corresponding alkoxide; The alkoxide that obtains and end-capping reagent trimethylchlorosilane continue reaction, reacting coarse product is carried out refinement treatment after, obtain end capped polyether; The mol ratio of wherein said alkoxide and end-capping reagent trimethylchlorosilane is 1: 1～1: 2.5, and temperature of reaction is 35～80 ℃, and the reaction times is 1.5～4.0 hours.
3. the preparation method of end capped polyether according to claim 2, it is characterized in that described bases compound is one or more the mixture in sodium hydroxide, potassium hydroxide, the sodium methylate, the mol ratio of end hydroxy polyether and bases compound is 1: 1.0～1: 2.0, temperature of reaction is 60～120 ℃, reaction times is 1.0～2.0 hours, reaction pressure is-0.08～-0.10Mpa.
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|---|---|---|---|
| CN2008100219530A CN101343358B (en) | 2008-08-20 | 2008-08-20 | End capping polyether prepared with end hydroxyl radical polyether and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101343358A CN101343358A (en) | 2009-01-14 |
| CN101343358B true CN101343358B (en) | 2010-08-25 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492130B (en) * | 2011-12-07 | 2014-01-01 | 江苏美思德化学股份有限公司 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
| CN108164692B (en) * | 2016-12-07 | 2020-02-07 | 上海东大化学有限公司 | Silicon modified polyether and preparation method and application thereof |
| CN108165381B (en) * | 2016-12-07 | 2020-04-28 | 上海东大化学有限公司 | Cleaning agent for spraying and preparation method thereof |
| 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 |
| CN108166257B (en) * | 2016-12-07 | 2019-12-31 | 上海东大化学有限公司 | Mercerizing penetrating agent and preparation method thereof |
| CN108166250B (en) * | 2016-12-07 | 2020-02-07 | 上海东大化学有限公司 | Scouring agent and preparation method and application thereof |
| CN108329478A (en) * | 2018-02-02 | 2018-07-27 | 无锡龙驰氟硅新材料有限公司 | A kind of Silante terminated MS resins and preparation method thereof |
| CN108671850B (en) * | 2018-05-11 | 2019-12-10 | 中国石油天然气股份有限公司 | Fluorine-silicon surfactant containing single perfluorooctyl and oil-based foam oil displacement agent |
| CN110483761A (en) * | 2019-09-20 | 2019-11-22 | 广东普赛达密封粘胶有限公司 | A kind of method of two steps synthesis end silicone based polyether |
| CN112480391B (en) * | 2020-11-26 | 2022-12-09 | 淄博正大聚氨酯有限公司 | Silicon-containing polyether polyol and preparation method thereof |
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Owner name: JIANGSU MAYSTA CHEMICAL CO., LTD. Free format text: FORMER NAME: NANJING DYMATIC SHICHUANG CHEMICAL CO., LTD. |
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Address after: 210046 No. 18, Nanjing economic and Technological Development Zone, Jiangsu, Nanjing Patentee after: Jiangsu Maysta Chemical Co., Ltd. Address before: 210046 No. 18, Nanjing economic and Technological Development Zone, Jiangsu, Nanjing Patentee before: Nanjing Dymatic Shichuang Chemical Co., Ltd. |