CN106633030B - Preparation method of high molecular weight narrow distribution esterification terminated allyl alcohol polyether - Google Patents
Preparation method of high molecular weight narrow distribution esterification terminated allyl alcohol polyether Download PDFInfo
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- CN106633030B CN106633030B CN201611186603.0A CN201611186603A CN106633030B CN 106633030 B CN106633030 B CN 106633030B CN 201611186603 A CN201611186603 A CN 201611186603A CN 106633030 B CN106633030 B CN 106633030B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
Abstract
The invention discloses a high molecular weight narrow distribution acetyl terminated allyl alcohol polyether and a preparation method thereof. The preparation method comprises the following steps: allyl alcohol and epoxide are used as raw materials, high molecular weight allyl alcohol polyether with narrow distribution is synthesized by a segmentation method under the catalysis of alkali, and the polyether is refined and then directly reacts with acetic anhydride to complete the esterification and end capping process. Most of acetic anhydride and acetic acid produced by reaction are removed by vacuumizing under nitrogen bubbling, then a small amount of water is added in batches to decompose the anhydride into the acetic acid, the deacidification process is completed in a short time, and the damage of long-time high temperature to the unsaturation degree of polyether is avoided. The allyl alcohol polyether obtained by the invention has narrow molecular weight distribution, stable process and good repeatability, and the obtained product has higher reaction activity.
Description
Technical Field
The invention belongs to an acetyl terminated polyether synthesis process, and particularly relates to a high molecular weight narrow distribution allyl alcohol polyether termination method.
Background
Allyl alcohol polyether is a main raw material for synthesizing polyether modified polysiloxane, and is widely used as a polyurethane foam stabilizer, a textile auxiliary, an oil field demulsifier, a coating leveling agent, a defoaming agent, an emulsifier and the like. The end-capped polyether is polyether with terminal hydroxyl substituted by other functional groups, and compared with hydroxyl polyether, the polyether has the properties of high chemical stability, low foaming performance, low viscosity and the like. When the hydroxyl polyether is subjected to hydrosilylation, a silicon-hydrogen bond and a hydroxyl group are easy to generate a crosslinking reaction under the catalysis of chloroplatinic acid, so that the viscosity of a product is increased, and the quality of the product is influenced. In polyurethane soft foam levelling agents, the presence of hydroxyl groups results in closed cells of the foam, and therefore the synthesis of the soft foam levelling agent requires a high molecular weight allyl alcohol terminated polyether in order to ensure the open cell properties of the foam.
The traditional base catalytic polymerization reaction belongs to an anionic reaction, chain initiation and growth are based on the rapid transfer of protons, and the speed of transferring the protons to a polymer chain is slowed down after the reaction is carried out, because the speed is influenced by factors such as the relative concentration of active groups is lowered and the viscosity of a system is increased, so that the conversion rate of epoxide is reduced and the side reaction rate is increased, and therefore, the synthesis of monofunctional high molecular weight polyether is difficult. A plurality of patents report methods for synthesizing high molecular weight polyether by using bimetal as a catalyst, but the bimetal catalyst has the advantages that no EO or polyether with lower EO content is polymerized, high molecular allyl alcohol polyether used for a soft foam stabilizer generally contains 30-50% of EO, the molecular weight distribution is wider when the bimetal polymerization is adopted, and a certain amount of polymerization byproducts can influence the application performance of the product.
After the esterification of the polyether with acetic anhydride, the residual acetic anhydride poisons the catalytic action of platinum in the hydrosilylation process, so that the excess acetic anhydride must be removed completely. Patent CN101735444 reports a method for azeotropic removal of acetic anhydride by using toluene as a dehydrating agent, and the method has the problems that a large amount of toluene is needed, which not only affects the environment, but also a small amount of toluene remains after the reaction is completed, which affects the downstream application. Patent CN101497689 reports that acetyl terminated allyl alcohol polyether is obtained by adding water to decompose acetic anhydride during deacidification, removing acetic acid by falling film evaporator, adding refining agent to adsorb and filter.
Disclosure of Invention
The invention aims to provide acetyl terminated allyl alcohol polyether with narrow distribution of high molecular weight and a preparation method thereof.
The technical scheme of the invention is as follows:
an acetyl terminated allyl alcohol polyether of high molecular weight and narrow distribution, having the formula:
wherein n is 20-70, and m is 20-70.
A process for preparing the above acetyl terminated allyl alcohol polyether having a narrow distribution of high molecular weight, which comprises the steps of:
1. synthesis of high molecular weight narrow distribution allyl alcohol polyether
a. Adding 193 g of allyl alcohol and 1-3 g of catalyst alkali into a 2000ml stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 450-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 3-4 hours, then removing unreacted epoxide through decompression, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol A, wherein the number-average molecular weight of the polyether Polyol A is 200-300, and the molecular weight distribution coefficient D is 1.01;
b. adding 300 g of polyether Polyol A and 1-3 g of catalyst alkali into the reaction kettle, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 600-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 3-4 hours, then removing unreacted epoxide by decompression, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol B, wherein the number average molecular weight of the polyether Polyol B is 900-1000, and the molecular weight distribution coefficient D is 1.02;
c. adding 400 g of polyether Polyol B and 1-3 g of catalyst alkali into the reaction kettle, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 600-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 3-4 hours, then removing unreacted epoxide by pressure reduction, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol C, wherein the number average molecular weight is 2250-3000, and the molecular weight distribution coefficient D is 1.05;
d. adding 500 g of polyether Polyol C and 1-3 g of catalyst alkali into the reaction kettle, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 500-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 4-6 hours, then decompressing to remove unreacted epoxide, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol D, wherein the number average molecular weight of the polyether Polyol D is 4500-7000, and the molecular weight distribution coefficient D is 1.08.
2. Esterification of polyethers
Adding 600 g of polyether Polyol D and 20-30 g of acetic anhydride into 1000ml of a stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, replacing with nitrogen, heating to 100-160 ℃, and carrying out heat preservation reaction for 2.0-10.0; starting vacuum, vacuumizing to remove redundant acid, blowing nitrogen from the bottom of the reaction kettle in the process, stopping vacuumizing after 2.0-4.0 hours, sucking 5-10 g of deionized water under negative pressure, stirring for 0.5-1.0 hours, starting vacuum deacidification again, blowing nitrogen from the bottom of the reaction kettle, sampling after 1.0-3.0 hours to detect the acetic anhydride residue, repeating the operations of adding water, stirring and vacuumizing when the acetic anhydride residue is more than 20ppm, stopping vacuum when the acetic anhydride residue is less than 20ppm, directly cooling and discharging to obtain the acetyl terminated allyl alcohol polyether with high molecular weight and narrow distribution, wherein the terminating rate is more than or equal to 95%.
In the above method, the epoxide comprises one or more of ethylene oxide, propylene oxide and butylene oxide.
In the above method, the alkali catalyst comprises metallic sodium, metallic potassium, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium hydride or potassium hydride.
In the method, the number average molecular weight of the product is 3000-7000, preferably 4000-6000.
The method is a segmented synthesis process, taking 5000 molecular weight polyether as an example, the molecular weight synthesized in the first segment is 300, the molecular weight synthesized in the second segment is 1000, the molecular weight synthesized in the third segment is 2500, the molecular weight synthesized in the fourth segment is 5000, and the magnification times of the molecular weights are gradually reduced.
According to the method, no catalyst is needed to be added in the esterification reaction of the polyether, the molar ratio of the allyl alcohol polyether to the acetic anhydride is 1: 1.1-2.5, the reaction time is 2.0-10.0 hours, the reaction temperature is 100-160 ℃, the nitrogen bubbling vacuumizing deacidification temperature is 120-170 ℃, the vacuum degree is 0.065-0.085 MPa, and the vacuumizing deacidification time is 2.0-4.0 hours.
The esterification end capping method does not need to be cooled, water is directly added in batches under negative pressure to decompose acetic anhydride into acetic acid, the water addition amount is 0.5-5.0% of the weight of polyether each time, the vacuum deacidification is continued after the water is added and stirred for 0.5-1.0 h, the acetic anhydride residue is sampled and detected after 1.0-2.0 h, the vacuum is stopped when the acetic anhydride residue is less than 20ppm, and the operation is continued when the acetic anhydride residue exceeds 20 ppm.
The acetyl terminated allyl alcohol polyether prepared by the segmented base catalysis method not only solves the problem that monofunctional high molecular weight polyether is difficult to obtain by base catalysis, but also avoids the problem of epoxide depolymerization caused by bimetallic catalysis, has good repeatability, and the obtained product has narrow molecular weight distribution and better hydrosilylation reaction activity. The method of adding water in batches is adopted to decompose the residual acetic anhydride into acetic acid with lower boiling point, and the acetic acid can be completely removed only by adopting a nitrogen bubbling vacuumizing mode, so that the damage of long-time high-temperature vacuum to the product unsaturation degree is greatly reduced. In addition, the invention avoids vacuum equipment such as a falling film evaporator and the like, the product does not need to be refined, the process is simple, and the method is suitable for large-scale industrial production.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention.
Example 1
1. Synthesis of high molecular weight narrow distribution allyl alcohol polyether
a. 193 g of allyl alcohol and 2 g of potassium hydroxide are added into a 1000ml stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, nitrogen is replaced twice, then the temperature is raised to 110 ℃, 807 g of a mixture (mass ratio is 1:1) of propylene oxide and ethylene oxide is started to be slowly introduced, the pressure is kept at 0.3MPa in the reaction process, and the reaction time is 3-4 hours. Removing unreacted epoxide by decompression, then cooling the reaction substance to room temperature, discharging to obtain polyether Polyol A, wherein the number average molecular weight is 300, and the molecular weight distribution coefficient D is 1.01;
b. adding 300 g of polyether Polyol A and 2 g of potassium hydroxide into the reaction kettle, replacing nitrogen for two times, heating to 110 ℃, starting to slowly introduce 700 g of a mixture (mass ratio is 1:1) of propylene oxide and ethylene oxide, keeping the pressure at 0.3MPa in the reaction process, and reacting for 3-4 hours. Removing unreacted epoxide by decompression, then cooling the reaction substance to room temperature, discharging to obtain polyether Polyol B, wherein the number average molecular weight is 1000, and the molecular weight distribution coefficient D is 1.02;
c. adding 400 g of polyether Polyol B and 2 g of potassium hydroxide into the reaction kettle, replacing with nitrogen twice, heating to 110 ℃, starting to slowly introduce 600 g of a mixture (mass ratio is 1:1) of propylene oxide and ethylene oxide, keeping the pressure at 0.3MPa in the reaction process, and reacting for 3-4 hours. Removing unreacted epoxide by decompression, then cooling the reaction substance to room temperature, discharging to obtain polyether Polyol C, wherein the number average molecular weight is 2500, and the molecular weight distribution coefficient D is 1.05;
d. adding 500 g of polyether Polyol C and 2 g of potassium hydroxide into the reaction kettle, replacing nitrogen for two times, heating to 110 ℃, starting to slowly introduce 500 g of a mixture (mass ratio is 1:1) of propylene oxide and ethylene oxide, keeping the pressure at 0.3MPa in the reaction process, and reacting for 4-6 hours. Removing unreacted epoxide by decompression, then cooling the reaction mass to room temperature, and discharging to obtain polyether Polyol D, wherein the number average molecular weight is 5000, and the molecular weight distribution coefficient D is 1.08.
2. Esterification of polyethers
Adding 600 g of polyether D (M is 5000) and 25 g of acetic anhydride into a 1000ml stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, replacing with nitrogen, heating to 120-130 ℃, and carrying out heat preservation reaction for 4 hours; starting vacuum, vacuumizing to remove redundant acid, blowing nitrogen from the bottom of the reaction kettle in the process, stopping vacuumizing after 2.0 hours, sucking 5 g of deionized water under negative pressure, stirring for 0.5 hours, starting vacuum deacidification again, blowing nitrogen from the bottom of the reaction kettle, sampling and detecting the residual amount of acetic anhydride after 1.0 hour, repeating the operations of adding water, stirring and vacuumizing when the residual amount of acetic anhydride is more than 20ppm, stopping vacuum when the residual amount of acetic anhydride is less than 20ppm, directly cooling and discharging to obtain the acetyl terminated allyl alcohol polyether with high molecular weight and narrow distribution, wherein the terminating rate is 98.2%.
Example 2
1. Synthesis of high molecular weight narrow distribution allyl alcohol polyether
a. b, c are carried out as in example 1;
d. adding 500 g of polyether Polyol C and 2 g of potassium hydroxide into the reaction kettle, replacing with nitrogen twice, heating to 110 ℃, starting to slowly introduce 800 g of a mixture (mass ratio is 1:1) of propylene oxide and ethylene oxide, keeping the pressure at 0.3MPa in the reaction process, and reacting for 4-6 hours. Removing unreacted epoxide under reduced pressure, cooling the reaction mass to room temperature, and discharging to obtain polyether Polyol D, wherein the number average molecular weight is 6500, and the molecular weight distribution coefficient D is 1.12.
2. Esterification of polyethers
Adding 600 g of polyether D (M is 6500) and 20 g of acetic anhydride into a 1000ml stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, replacing with nitrogen, heating to 120-130 ℃, and carrying out heat preservation reaction for 4 hours; starting vacuum, vacuumizing to remove redundant acid, blowing nitrogen from the bottom of the reaction kettle in the process, stopping vacuumizing after 2.0 hours, sucking 5 g of deionized water under negative pressure, stirring for 0.5 hours, starting vacuum deacidification again, blowing nitrogen from the bottom of the reaction kettle, sampling and detecting the residual amount of acetic anhydride after 1.0 hour, repeating the operations of adding water, stirring and vacuumizing when the residual amount of acetic anhydride is more than 20ppm, stopping vacuum when the residual amount of acetic anhydride is less than 20ppm, directly cooling and discharging to obtain the acetyl terminated allyl alcohol polyether with high molecular weight and narrow distribution, wherein the terminating rate is 97.5%.
Claims (4)
1. A process for preparing a high molecular weight narrowly distributed acetyl terminated allyl alcohol polyether characterized in that said high molecular weight narrowly distributed acetyl terminated allyl alcohol polyether has the following formula:
wherein n is 20-70, and m is 20-70;
the polyether synthesis method is characterized by comprising the following steps:
(1) synthesis of high molecular weight narrow distribution allyl alcohol polyether
a. Adding 193 g of allyl alcohol and 1-3 g of catalyst alkali into a 2000ml stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 450-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 3-4 hours, then removing unreacted epoxide through decompression, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol A, wherein the number-average molecular weight of the polyether Polyol A is 200-300, and the molecular weight distribution coefficient D is 1.01;
b. adding 300 g of polyether Polyol A and 1-3 g of catalyst alkali into the reaction kettle, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 600-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 3-4 hours, then removing unreacted epoxide by decompression, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol B, wherein the number average molecular weight of the polyether Polyol B is 900-1000, and the molecular weight distribution coefficient D is 1.02;
c. adding 400 g of polyether Polyol B and 1-3 g of catalyst alkali into the reaction kettle, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 600-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 3-4 hours, then removing unreacted epoxide by pressure reduction, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol C, wherein the number average molecular weight is 2250-3000, and the molecular weight distribution coefficient D is 1.05;
d. adding 500 g of polyether Polyol C and 1-3 g of catalyst alkali into the reaction kettle, heating to 110-120 ℃ after nitrogen replacement, starting to slowly introduce 500-800 g of epoxide, keeping the pressure at 0.1-0.3 MPa in the reaction process, reacting for 4-6 hours, then removing unreacted epoxide under reduced pressure, cooling the reaction substance to room temperature, and discharging to obtain polyether Polyol D, wherein the number average molecular weight of the polyether Polyol D is 4500-6000, and the molecular weight distribution coefficient D is 1.08;
(2) esterification of polyethers
Adding 600 g of polyether Polyol D and 20-30 g of acetic anhydride into 1000ml of a stainless steel autoclave provided with a thermometer, a pressure gauge, a stirrer and an epoxide inlet pipe, replacing with nitrogen, heating to 100-160 ℃, and carrying out heat preservation reaction for 2.0-10.0 hours; starting vacuum, vacuumizing to remove redundant acid, blowing nitrogen from the bottom of the reaction kettle in the process, stopping vacuumizing after 2.0-4.0 hours, sucking 12 g of deionized water under negative pressure, stirring for 0.5-1.0 hours, starting vacuum deacidification again, blowing nitrogen from the bottom of the reaction kettle, sampling after 1.0-3.0 hours to detect the acetic anhydride residual quantity, repeating the operations of adding water, stirring and vacuumizing when the acetic anhydride residual quantity is more than 20ppm, stopping vacuum when the acetic anhydride residual quantity is less than 20ppm, directly cooling and discharging to obtain the acetyl terminated allyl alcohol polyether with high molecular weight and narrow distribution.
2. The method of claim 1, further comprising: the epoxide is a mixture of ethylene oxide and propylene oxide.
3. The method of claim 1, further comprising: the alkali catalyst comprises metallic sodium, metallic potassium, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium hydride or potassium hydride.
4. The method of claim 1, further comprising: the method is a synthesis process by a segmentation method, the number average molecular weight synthesized in the first section (a) is 300, the number average molecular weight synthesized in the second section (b) is 1000, the number average molecular weight synthesized in the third section (c) is 2500, the number average molecular weight synthesized in the fourth section (d) is 5000, and the magnification times of the molecular weights are gradually reduced.
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| 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 |
| CN114276548A (en) * | 2021-11-24 | 2022-04-05 | 天津工业大学 | Polyether modified organic silicon coating leveling agent and preparation method thereof |
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| CN101117379A (en) * | 2007-07-24 | 2008-02-06 | 王伟松 | Method for synthesizing acetyl blocked allyl alcohol polyether |
| CN103709391A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Method for synthesis of low-unsaturation degree, high-molecular weight and high-activity polyether polyol |
| CN105061750A (en) * | 2015-08-05 | 2015-11-18 | 扬州晨化新材料股份有限公司 | High-double bond content allyl polyether production method |
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| CN102911352B (en) * | 2012-10-25 | 2014-11-05 | 浙江皇马科技股份有限公司 | Preparation method of low-molecular-weight acetyl-terminated allyl alcohol polyether |
| CN106084197A (en) * | 2016-06-22 | 2016-11-09 | 青神鑫统领建材有限公司 | A kind of preparation method of narrow ditribution polyethers |
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| CN101117379A (en) * | 2007-07-24 | 2008-02-06 | 王伟松 | Method for synthesizing acetyl blocked allyl alcohol polyether |
| CN103709391A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Method for synthesis of low-unsaturation degree, high-molecular weight and high-activity polyether polyol |
| CN105061750A (en) * | 2015-08-05 | 2015-11-18 | 扬州晨化新材料股份有限公司 | High-double bond content allyl polyether production method |
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