CN1117793C - Prepn of alkyl capped polyether - Google Patents
Prepn of alkyl capped polyether Download PDFInfo
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- CN1117793C CN1117793C CN 00135178 CN00135178A CN1117793C CN 1117793 C CN1117793 C CN 1117793C CN 00135178 CN00135178 CN 00135178 CN 00135178 A CN00135178 A CN 00135178A CN 1117793 C CN1117793 C CN 1117793C
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- capped polyether
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Abstract
The present invention relates to a method for preparing end capping polyether by the reaction of polyether whose molecule chain contains hydroxy and alkyl sulfate. Prepared end capping polyether has a general formula A, wherein A represents a carbon chain base group containing 1 to 20 carbon atoms; R1 represents H, methyl or ethyl; R2 represents methyl or ethyl. First, polyether and solid alkali react to generate corresponding alkoxide; second, the corresponding alkoxide and alkyl sulfate react under the condition of evacuation to prepare the end capping polyether. A vacuum degree is controlled between 200 and 600 mmHg. Compared with the prior art, the method still can cause the end capping efficiency of the end capping polyether to reach more than 90% under the condition that the use amount of an end capping raw material is lowered to a great extent.
Description
The present invention relates to method by polyethers that contains hydroxyl in the molecular chain and alkyl sulfuric ester prepared in reaction end capped polyether.
The polyethers that contains hydroxyl in the alkyl capped polyether that hydroxyl is all replaced by alkyl in the molecular chain and the molecular chain is compared, and has higher chemical stability.Utilize the good thermotolerance of alkyl capped polyether, the nonionogenic tenside that can be used as excellent property is used for the finish of chemical fibre high speed spinning, also can be used as additive and is used for resistant to elevated temperatures lubricating oil or thermal oil.Utilize it to alkaline stability, can be used in the alkaline detergent formulation.In addition, most of alkyl capped polyethers also have the bubble of pressing down and low foaming characteristic, so be often used as the monomer of defoamer or low-sudsing detergent.Because alkyl capped polyether has purposes widely, alkyl capped polyether preparation method's research is paid close attention to very much.Alkyl capped polyether is normally in the presence of alkali, carrying out prepared in reaction by polyethers that contains hydroxyl in the molecular chain and alkyl sulfuric ester obtains, as patent US 5,847,229 propose, and adopt two-step approach, promptly earlier solid sodium hydroxide or potassium hydroxide and the polyethers that contains hydroxyl are fully reacted the corresponding alkoxide of generation, alkoxide and methyl-sulfate react then, and comparable method in the past improves the yield of end capped polyether greatly.But because the existence of side reaction comprises patent US 5,847,229 in interior existing method, being used for end capped raw material (as methyl-sulfate) usage quantity is more than 200% of theoretical amount, and closed-end efficiency just can reach more than 90%.
The purpose of this invention is to provide a kind of new method by polyethers that contains hydroxyl in the molecular chain and alkyl sulfuric ester prepared in reaction end capped polyether, compared with the prior art, under the condition that reduces end-blocking raw material consumption by a relatively large margin, the closed-end efficiency of end capped polyether is reached more than 90%, overcome the defective that prior art exists effectively.
No matter be in the presence of alkali, directly carry out the prepared in reaction alkyl capped polyether by polyethers that contains hydroxyl in the molecular chain and alkyl sulfuric ester, still adopt two-step approach, promptly earlier solid sodium hydroxide or potassium hydroxide and the polyethers that contains hydroxyl are fully reacted the corresponding alkoxide of generation, alkoxide and alkyl sulfuric ester carry out the prepared in reaction alkyl capped polyether then.When dropping into alkyl sulfuric ester, always there is unreacted alkali in the reaction system, the therefore side reaction below the existence when alkoxide and alkyl sulfuric ester react:
The alcohol that reaction generates further reacts with alkyl sulfuric ester:
Wherein, M is an alkalimetal ion, and R is corresponding alkyl.
The contriver finds after a large amount of experiments, when adopting two-step approach, when alkoxide and alkyl sulfuric ester react, reaction system is under the suitable condition of negative pressure, take out the alcohol roh that dereaction generates, can suppress the side reaction of above-mentioned formula (2) effectively, thereby reduce the consumption of alkyl sulfuric ester in side reaction.The present invention realizes according to above principle.
The invention provides a kind of method by polyethers that contains hydroxyl in the molecular chain and double alkyl acid ester prepared in reaction end capped polyether, the polyethers that contains hydroxyl in the described molecular chain has following general formula (I):
Wherein: A is the carbochain group that contains 1～20 carbon atom;
R1 is H, methyl or ethyl;
The natural number of x=2～250, the natural number of y=1～10;
Polyether segment is homopolymerization, random copolymerization or block copolymerization;
The end capped polyether of preparation gained has following general formula (II):
Wherein: R2 is methyl or ethyl,
This method may further comprise the steps: 1) reaction of the polyethers of above-mentioned formula I and solid alkali metal oxyhydroxide generates corresponding alkoxide; 2) alkoxide of above-mentioned reaction generation and double alkyl acid ester reaction make the end capped polyether of above-mentioned formula II, be reflected under the condition that vacuumizes and carry out, take out the alcohol that dereaction generates, absolute pressure is controlled at 26～78KPa, and the equivalence ratio that raw material polyethers and double alkyl acid ester feed intake is 1: (1.75～1.95); 3) purified product.
The temperature of reaction of above-mentioned step 1) is 80～120 ℃, and the equivalence ratio that polyethers and solid alkali metal oxyhydroxide feed intake is 1: (1.75～1.95); Above-mentioned step 2) temperature of reaction is 40～100 ℃, and the equivalence ratio that raw material polyethers and double alkyl acid ester feed intake is preferably 1: (1.80～1.95), absolute pressure preferably are controlled at 32.5～65KPa.
Step 1) and step 2) reaction also can in organic solvent, carry out, organic solvent can be taken from a kind of in dimethylbenzene, trimethylbenzene or the phenyl ether or two or more mixtures.Use solvent will more help the carrying out that reacts in the reaction system.
The solid alkali metal oxyhydroxide that above-mentioned step 1) is used can be sodium hydrate solid or potassium hydroxide solid, or both mixtures; Step 2) double alkyl acid ester that uses can be C
1Or C
2Double alkyl acid ester.
The described product purification of step 3) can adopt the existing method that those of ordinary skill is known in this technical field, washes as adopting, filters in the presence of flocculating aids etc.
Compared with the prior art, the invention has the advantages that under the condition that reduces end-blocking raw material consumption greatly, the closed-end efficiency of end capped polyether is reached more than 90%.
To come below that the invention will be further described by embodiment, in an embodiment, closed-end efficiency is defined as:
Embodiment 1:
In the 500ml four-hole boiling flask, add butylol polyether (EO/PO=50/50, random, hydroxyl value 36) 200 grams, solid potassium hydroxide 13.0 grams, sodium sulphite anhydrous 99.3 4.0 grams, nitrogen replacement is 4 times under vigorous stirring, dehydration 1 hour under 90～100 ℃ and 20～25mmHg then, under the condition of 200mmHg and 40～45 ℃, drip 14.6 gram methyl-sulfates, dropwise the back and continue, 60 ℃ of 1 hour, 90 ℃ of reactions reactions 1 hour down down 40～45 ℃ of reactions 2 hours.Recover normal pressure, add 100ml water, stirred 1 hour in 90 ℃, keep 80～90 ℃ of standing demix, remove water, add 10 gram diatomite, in 60～70 ℃ of following vacuum hydro-extractions, filter the end capped polyether product.
Embodiment 2
Charging capacity is butylol polyether 200 grams, potassium hydroxide 14.0 grams, S-WAT 4.0 grams, methyl-sulfate 15.8 grams, and all the other are with embodiment 1.Embodiment 3
In the 500ml four-hole boiling flask, add polyoxyethylene glycol (hydroxyl value 78) 200 grams, solid potassium hydroxide 30.4 grams, sodium sulphite anhydrous 99.3 4.0 grams; dimethylbenzene 80ml; drum nitrogen 10 minutes; azeotropic water removing is 2 hours under nitrogen protection; be cooled to 40～45 ℃ of speed and drip 34.2 gram methyl-sulfates with 4～5 droplets/minute; dropwise the back and continue 40～45 ℃ of reactions 3 hours, 60 ℃ of following 1 hour and 90 ℃ are following 1 hour.Recover normal pressure, add 100ml water, 90 ℃ were stirred 1 hour, added diatomite 10 grams, and azeotropic water removing filters, and removes dimethylbenzene under reduced pressure and gets the end capped polyether product.
Embodiment 4
In the 500ml four-hole boiling flask, add glycerin polyether (EO/PO=30/70, random, hydroxyl value 37) 200 grams, solid potassium hydroxide 14.4 grams, sodium sulphite anhydrous 99.3 4.0 grams, nitrogen replacement is 4 times under vigorous stirring, dehydration 1 hour under 90～100 ℃ and 20～25mmHg then, drip 16.2 gram methyl-sulfates under the condition of 300mmHg and 40～45 ℃, dropwise the back and continue 40～45 ℃ of reactions 2 hours, 60 ℃ of following 1 hour and 80 ℃ are following 1 hour.Recover normal pressure, add 100ml water, 90 ℃ were stirred 1 hour, kept 80～90 ℃ of standing demix, removed water, added 10 gram diatomite, 60～70 ℃ of vacuum hydro-extractions, filter the end capped polyether product.
Embodiment 5
In the 500ml four-hole boiling flask, add tetramethylolmethane polyethers (block, end is the EO segment, EO/PO=30/70, hydroxyl value 49) 200 grams, solid potassium hydroxide 19.1 grams, sodium sulphite anhydrous 99.3 4.0 grams, nitrogen replacement is 4 times under vigorous stirring, and dehydration 1 hour under 90～100 ℃ and 20～25mmHg then drips 21.5 gram methyl-sulfates under the condition of 300mmHg and 40～45 ℃, dropwise the back and continue, 60 ℃ of 1 hour and 80 ℃ 1 hour 40～45 ℃ of reactions 2 hours.Recover normal pressure, add 100ml water, 90 ℃ were stirred 1 hour, kept 80～90 ℃ of standing demix, removed water, added 10 gram diatomite, 60～70 ℃ of vacuum hydro-extractions, filter end capped polyether.
Embodiment 6
Charging capacity is sorbyl alcohol polyethers (block, end is the PO segment, EO/PO=30/70, hydroxyl value 53) 200 grams, solid potassium hydroxide 20.6 grams, sodium sulphite anhydrous 99.3 4.0 grams 23.2 gram methyl-sulfates.All the other are with embodiment 5.Comparative example 1
Begin to adopt normal pressure to the process of 90 ℃ of reaction end from dripping methyl-sulfate, all the other are with embodiment 1.Comparative example 2
Begin to adopt normal pressure to the process of 90 ℃ of reaction end from dripping methyl-sulfate, other condition is identical with embodiment 2.
The reaction result of the foregoing description and comparative example sees Table 1.Table 1.
| Polyethers: potassium hydroxide: methyl-sulfate (equivalence ratio) | Solvent | Step 2) pressure (mmHg) | Closed-end efficiency (%) | |
| Embodiment 1 | 1∶1.80∶1.80 | Do not have | 200 | 91 |
| Embodiment 2 | 1∶1.95∶1.95 | Do not have | 200 | 93 |
| Embodiment 3 | 1∶1.95∶1.95 | Dimethylbenzene | 500 | 93 |
| Embodiment 4 | 1∶1.95∶1.95 | Do not have | 300 | 95 |
| Embodiment 5 | 1∶1.95∶1.95 | Do not have | 300 | 97 |
| Embodiment 6 | 1∶1.95∶1.95 | Do not have | 300 | 92 |
| Comparative example 1 | 1∶1.80∶1.80 | Do not have | Normal pressure | 65 |
| Comparative example 2 | 1∶1.95∶1.95 | Do not have | Normal pressure | 68 |
Claims (10)
1, a kind of method by polyethers that contains hydroxyl in the molecular chain and double alkyl acid ester prepared in reaction end capped polyether, the polyethers that contains hydroxyl in the described molecular chain has following general formula (I):
Wherein:
A is the carbochain group that contains 1～20 carbon atom;
R1 is H, methyl or ethyl;
The natural number of x=2～250, the natural number of y=1～10;
The ether segment is homopolymerization, random copolymerization or block copolymerization;
The end capped polyether of preparation gained has following general formula (II):
Wherein: R2 is methyl or ethyl,
This method may further comprise the steps: 1) reaction of the polyethers of above-mentioned formula (I) and solid alkali metal oxyhydroxide generates corresponding alkoxide; 2) alkoxide of above-mentioned reaction generation and double alkyl acid ester reaction make the end capped polyether of above-mentioned formula (II), be reflected under the condition that vacuumizes and carry out, take out the alcohol that dereaction generates, absolute pressure is controlled at 26～78KPa, and the equivalence ratio that raw material polyethers and double alkyl acid ester feed intake is 1: (1.75～1.95); 3) purified product.
2, the method for preparing end capped polyether according to claim 1, the temperature of reaction that it is characterized in that described step 1) is 80～120 ℃.
3, the method for preparing end capped polyether according to claim 1 is characterized in that the equivalence ratio that described step 1) polyethers and solid alkali metal oxyhydroxide feed intake is 1: (1.75～1.95).
4, the method for preparing end capped polyether according to claim 1 is characterized in that described step 2) temperature of reaction be 40～100 ℃.
5, the method for preparing end capped polyether according to claim 1, it is characterized in that described step 1) and step 2) be reflected in the organic solvent and carry out, organic solvent can be taken from a kind of in dimethylbenzene, trimethylbenzene or the phenyl ether or two or more mixtures.
6, the method for preparing end capped polyether according to claim 1 is characterized in that the solid alkali metal oxyhydroxide that described step 1) is used is sodium hydrate solid or potassium hydroxide solid, or both mixtures.
7, the method for preparing end capped polyether according to claim 1 is characterized in that described step 2) double alkyl acid ester that uses is C
1Or C
2Double alkyl acid ester.
8, the method for preparing end capped polyether according to claim 1 is characterized in that described step 2) absolute pressure be controlled at 32.5～65KPa.
9, the method for preparing end capped polyether according to claim 1 is characterized in that step 2) equivalence ratio that feeds intake of raw material polyethers and double alkyl acid ester is 1: (1.80～1.95).
10, the method for preparing end capped polyether according to claim 1 is characterized in that described step 3) adopts methods such as washing, add the flocculating aids filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00135178 CN1117793C (en) | 2000-12-26 | 2000-12-26 | Prepn of alkyl capped polyether |
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|---|---|---|---|
| CN 00135178 CN1117793C (en) | 2000-12-26 | 2000-12-26 | Prepn of alkyl capped polyether |
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| CN1361192A CN1361192A (en) | 2002-07-31 |
| CN1117793C true CN1117793C (en) | 2003-08-13 |
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| CN 00135178 Expired - Fee Related CN1117793C (en) | 2000-12-26 | 2000-12-26 | Prepn of alkyl capped polyether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
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Granted publication date: 20030813 Termination date: 20101226 |