CN109942803B - Esterified capped allyl polyether and preparation method thereof - Google Patents
Esterified capped allyl polyether and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of ester-terminated polyether synthesis, in particular to esterified terminated allyl polyether and a preparation method thereof, wherein the esterified terminated allyl polyether is prepared by taking allyl polyether as a raw material and acetic anhydride as an esterification reagent, wherein the molar ratio of polyether to acetic anhydride is 1.0: 1.1-4.0, carrying out esterification reaction at the temperature of 120-140 ℃; after removing most of acid by high vacuum deacidification and vacuum pumping nitrogen bubbling deacidification in sequence, pumping the acid into a circulating spraying device through external circulation to remove the residual acetic acid and acetic anhydride under the high vacuum condition; finally, residual trace acetic anhydride is converted into acetic acid through a water treatment process, so that the acetic anhydride is prevented from influencing the activity of a catalyst chloroplatinic acid used for hydrosilylation. The invention provides a preparation method of esterified terminated allyl polyether, which has the advantages of high deacidification efficiency, low process cost, low requirement on equipment and the like, and can obtain esterified terminated polyether with high terminating rate, so that the product performance is more excellent and stable, and particularly, the prepared product has the advantages of low hydroxyl value, low acid value, low moisture, stable performance and the like.
Description
Technical Field
The invention relates to the field of synthesis of ester-terminated polyether, in particular to esterified terminated allyl polyether and a preparation method thereof.
Background
Allyl polyether is the main synthetic raw material of polyether modified organic silicon foam stabilizer, and is widely used for polyurethane foaming, oil field demulsifier, coating leveling agent, emulsifier, defoamer and the like.
The esterification terminated allyl alcohol polyether is polyether with terminal hydroxyl hydrogen substituted by ester group and has the features of low foam, high lipophilicity, low flow point, low viscosity, high oxidation stability, high heat resistance, high coking resistance, etc. When the non-terminated polyether is subjected to hydrosilylation with hydrogen-containing silicone oil, a silicon-hydrogen bond and hydroxyl are also easy to generate a cross-linking reaction under the catalysis of chloroplatinic acid, so that the viscosity of a product is greatly increased, and the application of the product is not facilitated.
Chinese patent CN101117379A discloses a method for synthesizing acetyl terminated allyl alcohol polyether, which comprises the steps of carrying out condensation reflux reaction on allyl alcohol polyether and acetic anhydride as raw materials, removing most of acid by nitrogen bubbling under a vacuum condition after condensation reflux reaction, and removing residual acetic acid and acetic anhydride by a falling film evaporator under a high vacuum condition. The method has high requirements on equipment and high early investment cost.
Chinese patents CN101497689A, CN102911352B and CN106633030A disclose an acetyl terminated polyether process, which uses allyl alcohol polyether and acetic anhydride as raw materials, removes most of acid by nitrogen bubbling deacidification under vacuum condition, adds water to hydrolyze the residual acetic anhydride into acetic acid, and then removes acetic acid and water by nitrogen bubbling or falling film evaporator to obtain the acetyl terminated polyether.
In the three patents, under the condition that a certain amount of acid exists, water is added to convert acetic anhydride into acetic acid, and then the acetic acid is reduced, but after the water is added, the generated acetyl terminated polyether is hydrolyzed under the acidic condition, so that the hydroxyl value is increased, the terminating rate is reduced, and the product requirement with higher terminating rate requirement is difficult to meet.
Disclosure of Invention
The invention aims to provide esterified terminated allyl polyether and a preparation method thereof, and aims to solve the problem of low terminating rate in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
an esterification end capping allyl polyether has the following structural formula,
CH2＝CHCH2O(CH2CH2O)X[CH2CH(CH3)O]YCOCH3(ii) a Wherein X is 2-80 and Y is 2-80.
The preparation method of the esterified capped allyl polyether is characterized by comprising the following steps:
1) an esterification stage: taking allyl polyether as a raw material and acetic anhydride as an esterification reagent, placing the raw material and the acetic anhydride in a reaction kettle, replacing the raw material with nitrogen, heating to 120-140 ℃, and reacting for 2.0-5.0 hours;
2) and (3) deacidifying:
2.1) vacuumizing and deacidifying: vacuumizing the step 1) to-0.095 to-0.1 Mpa, and deacidifying at the temperature of 120-130 ℃ for 0.5-2.0 hours;
2.2) deacidification by nitrogen bubbling: bubbling nitrogen from the bottom of the reaction kettle in the step 2.1) at a vacuum degree of-0.070 to-0.085 Mpa for deacidification at 110-130 ℃ for 0.5-2.0 hours;
2.3) circulating spray deacidification: pumping the mixture obtained in the step 2.2) into a circulating spray deacidification device through external circulation to perform high vacuum deacidification, wherein the vacuum degree is-0.095 to-0.1 Mpa, and the circulating spray deacidification is performed for 1.0 to 5.0 hours;
3) a water treatment stage:
3.1) water treatment process: cooling the temperature in the step 2.3) to 60-70 ℃, adding deionized water with the mass fraction of 2-10%, and stirring for 0.5-2.0 hours at the temperature of 60-70 ℃;
3.2) dehydration: heating the step 3.1) to 100-120 ℃, dehydrating for 0.5-2.0 hours under the vacuum degree of-0.09-0.1 Mpa, and cooling and discharging.
The preparation method of the esterified capped allyl polyether is characterized by comprising the following steps: the chain segment structure of the allyl alcohol polyether adopts one of random, block, homopolymerization or copolymerization; the purity of the nitrogen used for nitrogen replacement is 99.9-99.99 percent, and the nitrogen is bottled nitrogen or pipeline nitrogen.
The preparation method of the esterified capped allyl polyether is characterized by comprising the following steps: the mol ratio of allyl polyether to acetic anhydride in the step 1) is 1.0: 1.1 to 4.0.
The preparation method of the esterified capped allyl polyether is characterized by comprising the following steps: the nitrogen adopted in the step 2.2) is 99.9-99.99 percent and is bottled nitrogen or pipeline nitrogen.
The preparation method of the esterified capped allyl polyether is characterized by comprising the following steps: the Sott mean diameter (SMD, Sauter mean diameter) of the liquid drops in the circulating spray deacidification device in the step 2.3) is 100 and 1000 mu m.
The preparation method of the esterified capped allyl polyether is characterized by comprising the following steps: after the deacidification in the step 2.3) is finished, the acid value of the sample is less than or equal to 0.1 mgKOH/g.
The invention discloses a preparation method of any esterified terminated allyl polyether, which is characterized by comprising the following steps: the prepared esterification terminated allyl alcohol polyether has a termination rate of more than or equal to 99.5 percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method provided by the invention has the advantages of high deacidification efficiency, low process cost, low requirement on equipment and the like, and can obtain the esterified capped polyether with high capping rate, so that the product performance is more excellent and stable, and particularly the prepared esterified capped allyl polyether has the advantages of low hydroxyl value, low acid value, low moisture, stable performance and the like.
(2) The esterification terminated allyl alcohol polyether can efficiently remove acetic acid and acetic anhydride by combining a nitrogen bubbling and circulating spray deacidification method. Compared with deacidification of a falling film evaporator, the method has lower requirement on equipment and higher economical efficiency.
(3) According to the invention, the acid value is reduced to be below 0.1mgKOH/g, and deionized water is added to treat a sample, so that the influence of residual trace acetic anhydride on the activity of a chloroplatinic acid catalyst in a hydrosilylation process can be avoided, the phenomenon of ester group hydrolysis of acetyl terminated polyether generated under the condition of high acid value can be avoided, and the preparation of esterified terminated allyl polyether with high activity, stable structure and high termination rate is facilitated.
Drawings
FIG. 1 is a schematic diagram of a synthesis apparatus in the preparation method of esterified capped allyl polyether of the present invention.
1-a vacuum pump; 2-a stirrer; 3-a nozzle; 4-a valve; 5-a circulating pump; 6-heat exchanger.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The end-capping efficiency of the invention is calculated according to the following calculation formula:
the hydroxyl numbers of the polyethers and of the capped polyethers in the examples and comparative examples are in accordance with the International part 3 of the plastics polyether polyol: determination of hydroxyl value (GB/T12008.3-2009).
The synthesis apparatus used in the examples is shown in FIG. 1.
Example 1
1200 parts of allyl alcohol random polyether (Mn ═ 2000g/mol) and 120 parts of acetic anhydride are sequentially added into a reaction kettle, the reaction kettle is sealed after vacuum pumping and nitrogen replacement, the temperature is raised to 120-130 ℃, and the stirring reaction is carried out for 4 hours. And (3) connecting a reduced pressure distillation device, and keeping the temperature at 120-130 ℃ and the vacuum degree at-0.095 to-0.1 Mpa for 1 hour. Then blowing nitrogen and adjusting the flow rate of the nitrogen to ensure that the vacuum degree is-0.080 to-0.085 Mpa, and keeping the temperature at 120-130 ℃ for 1 hour. Stopping blowing nitrogen, starting a circulating spraying device, continuously and circularly spraying and deacidifying for 2 hours at the temperature of 120-130 ℃ under the vacuum degree of-0.095-0.1 Mpa, and measuring the acid value of the sample to be 0.07 mgKOH/g. Cooling to 65-70 ℃, adding deionized water with the mass fraction of 3%, stirring at constant temperature for 30 minutes, heating to 105-110 ℃, keeping the vacuum degree at-0.095 MPa, dehydrating for 2 hours, cooling to 50 ℃, and discharging. The capping rate of the prepared esterified capped allyl random polyether was 99.7%.
Example 2
1200 parts of allyl alcohol random polyether (Mn ═ 5200g/mol) and 70 parts of acetic anhydride are sequentially added into a reaction kettle, vacuum pumping is carried out for nitrogen replacement, then the reaction kettle is sealed, the temperature is increased to 130-140 ℃, and stirring reaction is carried out for 3 hours. And (3) connecting a reduced pressure distillation device, cooling to 125-130 ℃, and removing the temperature for 1 hour under the vacuum degree of-0.095 to-0.1 Mpa. Then blowing nitrogen and adjusting the flow rate of the nitrogen to ensure that the vacuum degree is-0.080 to-0.085 Mpa, and keeping the temperature at 125-130 ℃ for 2 hours. Stopping blowing nitrogen, starting a circulating spraying device, continuously and circularly spraying and deacidifying for 1.5 hours at the temperature of 125-130 ℃ under the vacuum degree of-0.095-0.1 Mpa, and measuring the acid value of the sample to be 0.03 mgKOH/g. Cooling to 65-70 ℃, adding 5% deionized water, stirring at constant temperature for 60 minutes, heating to 105-110 ℃, keeping the vacuum degree at-0.095 to-0.1 Mpa, dehydrating for 2 hours, cooling to 50 ℃, and discharging. The capping rate of the prepared esterified capped allyl random polyether is 99.5%.
In order to highlight the beneficial effects of the present invention, the following comparative example experiment was also performed.
Comparative example 1
1200 parts of allyl alcohol random polyether (Mn ═ 2000g/mol) and 120 parts of acetic anhydride are sequentially added into a reaction kettle, the reaction kettle is sealed after vacuum pumping and nitrogen replacement, the temperature is raised to 120-130 ℃, and the stirring reaction is carried out for 4 hours. And (3) connecting a reduced pressure distillation device, and keeping the temperature at 120-130 ℃ and the vacuum degree at-0.095 to-0.1 Mpa for 1 hour. Then blowing nitrogen gas and adjusting the flow rate of the nitrogen gas to ensure that the vacuum degree is-0.080 to-0.085 Mpa, reducing the temperature at 120-130 ℃ for 1 hour, and determining the acid value of the sample to be 3 mgKOH/g. Cooling to 65-70 ℃, adding deionized water with the mass fraction of 3%, stirring at constant temperature for 30 minutes, heating to 105-110 ℃, keeping the vacuum degree at-0.095 MPa, dehydrating for 2 hours, cooling to 50 ℃, and discharging. The capping rate of the prepared esterified capped allyl random polyether was 95.2%.
Comparative example 2
1200 parts of allyl alcohol random polyether (Mn ═ 5200g/mol) and 70 parts of acetic anhydride are sequentially added into a reaction kettle, vacuum pumping is carried out for nitrogen replacement, then the reaction kettle is sealed, the temperature is increased to 130-140 ℃, and stirring reaction is carried out for 3 hours. And (3) connecting a reduced pressure distillation device, cooling to 125-130 ℃, and removing the temperature for 1 hour under the vacuum degree of-0.095 to-0.1 Mpa. Then blowing nitrogen gas and adjusting the flow rate of the nitrogen gas to ensure that the vacuum degree is-0.080 to-0.085 Mpa, reducing the temperature at 125-130 ℃ for 2 hours, and determining the acid value of the sample to be 2.5 mgKOH/g. Cooling to 65-70 ℃, adding deionized water with the mass fraction of 5%, stirring at constant temperature for 60 minutes, heating to 105-110 ℃, keeping the vacuum degree at-0.095-0.1 Mpa, dehydrating for 2 hours, cooling to 50 ℃, and discharging. The capping rate of the prepared esterified capped allyl random polyether was 96.5%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of esterification terminated allyl polyether is characterized in that the esterification terminated allyl polyether has the following structural formula,
CH2＝CHCH2O(CH2CH2O)X[CH2CH(CH3)O]YCOCH3(ii) a Wherein X is 2-80, and Y is 2-80;
the method specifically comprises the following steps:
1) an esterification stage: taking allyl polyether as a raw material and acetic anhydride as an esterification reagent, placing the raw material and the acetic anhydride in a reaction kettle, replacing the raw material with nitrogen, heating to 120-140 ℃, and reacting for 2.0-5.0 hours;
2) and (3) deacidifying:
2.1) vacuumizing and deacidifying: vacuumizing the step 1) to-0.095 to-0.1 Mpa, and deacidifying at the temperature of 120-130 ℃ for 0.5-2.0 hours;
2.2) deacidification by nitrogen bubbling: bubbling nitrogen from the bottom of the reaction kettle in the step 2.1) at a vacuum degree of-0.070 to-0.085 Mpa for deacidification at 110-130 ℃ for 0.5-2.0 hours;
2.3) circulating spray deacidification: pumping the mixture obtained in the step 2.2) into a circulating spray deacidification device through external circulation to perform high vacuum deacidification, wherein the vacuum degree is-0.095 to-0.1 Mpa, and the circulating spray deacidification is performed for 1.0 to 5.0 hours;
3) a water treatment stage:
3.1) water treatment process: cooling the temperature in the step 2.3) to 60-70 ℃, adding deionized water with the mass fraction of 2-10%, and stirring for 0.5-2.0 hours at the temperature of 60-70 ℃;
3.2) dehydration: heating the step 3.1) to 100-120 ℃, dehydrating for 0.5-2.0 hours under the vacuum degree of-0.09-0.1 Mpa, and cooling and discharging.
2. The method of preparing an esterified capped allyl polyether of claim 1, comprising: the chain segment structure of the allyl alcohol polyether adopts one of random, block, homopolymerization or copolymerization; the purity of the nitrogen used for nitrogen replacement is 99.9-99.99 percent, and the nitrogen is bottled nitrogen or pipeline nitrogen.
3. The method of preparing an esterified capped allyl polyether of claim 1, comprising: the mol ratio of allyl polyether to acetic anhydride in the step 1) is 1.0: 1.1 to 4.0.
4. The method of preparing an esterified capped allyl polyether of claim 1, comprising: the purity of the nitrogen in the step 2.2) is 99.9-99.99 percent, and the nitrogen is bottled nitrogen or pipeline nitrogen.
5. The method of preparing an esterified capped allyl polyether of claim 1, comprising: the Suateur average diameter of the liquid drops in the circulating spray deacidification device in the step 2.3) is 100-1000 mu m.
6. The method of preparing an esterified capped allyl polyether of claim 1, comprising: after the deacidification in the step 2.3) is finished, the acid value of the sample is less than or equal to 0.1 mgKOH/g.
7. The process for preparing an esterified capped allyl polyether of any one of claims 1 to 6, characterized in that: the prepared esterification terminated allyl alcohol polyether has a termination rate of more than or equal to 99.5 percent.
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| CN109942803B (en) * | 2017-12-21 | 2021-04-06 | 江苏美思德化学股份有限公司 | Esterified capped allyl polyether and preparation method thereof |
| CN109851771B (en) * | 2018-12-12 | 2021-08-17 | 南京美思德新材料有限公司 | High molecular weight esterification terminated allyl polyether and synthesis method thereof |
| CN112831040A (en) * | 2020-12-31 | 2021-05-25 | 烟台市顺达聚氨酯有限责任公司 | Method for synthesizing polyester ether polyol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB709482A (en) * | 1950-06-06 | 1954-05-26 | Ciba Ltd | Polyethylene glycol derivatives and method of making same |
| CN102911352A (en) * | 2012-10-25 | 2013-02-06 | 浙江皇马科技股份有限公司 | Preparation method of low-molecular-weight acetyl-terminated allyl alcohol polyether |
| CN106633030A (en) * | 2016-12-20 | 2017-05-10 | 江苏钟山化工有限公司 | Esterified base terminated allyl alcohol polyether with high molecular weight and narrow distribution and preparation method of esterified base terminated allyl alcohol polyether |
| CN109942803A (en) * | 2017-12-21 | 2019-06-28 | 江苏美思德化学股份有限公司 | A kind of esterification end-capping allyl polyethers and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB709482A (en) * | 1950-06-06 | 1954-05-26 | Ciba Ltd | Polyethylene glycol derivatives and method of making same |
| CN102911352A (en) * | 2012-10-25 | 2013-02-06 | 浙江皇马科技股份有限公司 | Preparation method of low-molecular-weight acetyl-terminated allyl alcohol polyether |
| CN106633030A (en) * | 2016-12-20 | 2017-05-10 | 江苏钟山化工有限公司 | Esterified base terminated allyl alcohol polyether with high molecular weight and narrow distribution and preparation method of esterified base terminated allyl alcohol polyether |
| CN109942803A (en) * | 2017-12-21 | 2019-06-28 | 江苏美思德化学股份有限公司 | A kind of esterification end-capping allyl polyethers and preparation method thereof |
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