CN113292716A - Preparation method of self-emulsifying ester based on meta-phenyl ester - Google Patents
Preparation method of self-emulsifying ester based on meta-phenyl ester Download PDFInfo
- Publication number
- CN113292716A CN113292716A CN202110564762.4A CN202110564762A CN113292716A CN 113292716 A CN113292716 A CN 113292716A CN 202110564762 A CN202110564762 A CN 202110564762A CN 113292716 A CN113292716 A CN 113292716A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- self
- ester
- emulsifying
- 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.)
- Pending
Links
Classifications
-
- 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
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of self-emulsifying ester based on trimellitic ester, which comprises the steps of mixing trimellitic anhydride and polyethylene glycol for the first esterification reaction, and further adding monohydric alcohol and a catalyst for the second esterification reaction, wherein the obtained self-emulsifying ester product has excellent anti-foaming property. Furthermore, the acid value of the product is adjusted to be neutral after the second esterification reaction is finished, so that the acid value is not required to be adjusted in subsequent application, and the using steps are simplified.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of self-emulsifying ester based on meta-phenyl ester.
Background
Self-emulsifying esters currently include two main types: one kind of non-ionic self-emulsifying ester has molecular structure containing polyoxyethylene ether block and thus has no foam resistance. One is self-emulsifying ester containing ester group and carboxyl group, and the product needs to be neutralized by adding a certain amount of alkaline substances when in use. It is therefore desirable to provide a self-emulsifying ester product having excellent foam resistance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of self-emulsifying ester based on partial benzene ester.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of self-emulsifying ester based on meta-phenyl ester, which comprises the following steps:
(1) mixing trimellitic anhydride and polyethylene glycol to perform esterification reaction;
preferably, the molar ratio of the trimellitic anhydride to the polyethylene glycol is 1 (0.5-1.5), preferably 1:1.
Preferably, the polyethylene glycol has a molecular weight of 200-1000, preferably 600.
Preferably, the reaction temperature is 130-150 ℃, preferably 140 ℃; the reaction time is 0.5-2h, preferably 1 h; the reaction is carried out under an inert atmosphere, preferably nitrogen.
(2) Adding monohydric alcohol and a catalyst into the reaction system in the step (1) to continue the esterification reaction;
preferably, the molar ratio of the monohydric alcohol to the trimellitic anhydride is 1 (0.5-1.5), preferably 1:1.
Preferably, the monohydric alcohol is selected from one or more of C6-C18 straight chain alcohol or branched chain alcohol.
Preferably, the catalyst is selected from one or more of titanate catalyst, solid acid catalyst or ionic liquid catalyst, specifically selected from p-monobutyl tin oxide, titanate, p-toluenesulfonic acid, sulfamic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, hypophosphorous acid, sodium bisulfate, and ionic liquid catalyst. The addition amount of the catalyst is one thousandth to five thousandth of the total mass of reactants, namely the mass sum of the trimellitic anhydride, the polyethylene glycol and the monohydric alcohol.
Preferably, the reaction temperature is 180-220 ℃, preferably 200 ℃; the reaction time is 4 to 10 hours, preferably 6 to 7 hours.
(3) And (3) after the esterification reaction in the step (2) is finished, removing water generated in the reaction, and adjusting the acid value of the product to be neutral to obtain the self-emulsifying ester based on the meta-phenyl ester.
Preferably, the water produced in the removal reaction is introduced into the reaction system with an inert gas, preferably nitrogen, at the reaction temperature of step (2).
Preferably, the acid value of the product is adjusted with sodium hydroxide or sodium carbonate.
The invention has the beneficial effects that:
the invention provides a preparation method of self-emulsifying ester based on trimellitic ester, which comprises the steps of mixing trimellitic anhydride and polyethylene glycol for the first esterification reaction, and further adding monohydric alcohol and a catalyst for the second esterification reaction, wherein the obtained self-emulsifying ester product has excellent anti-foaming property.
Furthermore, the acid value of the product is adjusted to be neutral after the second esterification reaction is finished, so that the acid value is not required to be adjusted in subsequent application, and the using steps are simplified.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The invention relates to a preparation method of self-emulsifying ester based on meta-phenyl ester, which comprises the following steps:
(1) mixing trimellitic anhydride and polyethylene glycol to perform esterification reaction;
in one embodiment of the present invention, the molar ratio of trimellitic anhydride to polyethylene glycol is 1 (0.5-1.5), preferably 1:1. The reaction does not need to add a solvent, and the polyethylene glycol can be used as alcohol and the solvent to participate in the reaction.
In one embodiment of the present invention, the molecular weight of the polyethylene glycol is 200-1000, i.e. PEG 200-1000 is selected, and PEG 600 is preferably used. If the molecular weight of polyethylene glycol is too high, the fluidity at low temperature is deteriorated, and the pour point of the product is increased, so that the product is likely to precipitate in the emulsion. Pour point is the lowest temperature at which the cooled sample can flow under the specified test conditions, expressed in degrees celsius.
In one embodiment of the invention, the reaction temperature is 130 ℃ and 150 ℃, preferably 140 ℃; the reaction time is 0.5-2h, preferably 1 h; the reaction is carried out under an inert atmosphere, preferably nitrogen.
(2) Adding monohydric alcohol and a catalyst into the reaction system in the step (1) to continue the esterification reaction;
in one embodiment of the present invention, the molar ratio of the monohydric alcohol to the trimellitic anhydride is 1 (0.5-1.5), preferably 1:1.
In one embodiment of the invention, the monohydric alcohol is selected from one or more of C6-C18 linear or branched alcohols, such as 1-hexanol, 2-hexanol, 1-heptanol, 2-heptanol, 1-octanol, isooctanol, n-nonanol, n-decanol, n-dodecanol.
In one embodiment of the present invention, the catalyst is selected from one or more of titanate-based catalyst, solid acid-based catalyst or ionic liquid-based catalyst, specifically selected from p-monobutyl tin oxide, titanate, p-toluenesulfonic acid, sulfamic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, hypophosphorous acid, sodium bisulfate, and ionic liquid catalyst. The addition amount of the catalyst is one thousandth to five thousandth of the total mass of reactants, namely the mass sum of the trimellitic anhydride, the polyethylene glycol and the monohydric alcohol.
In one embodiment of the invention, the reaction temperature is 180-220 ℃, preferably 200 ℃; the reaction time is 4 to 10 hours, preferably 6 to 7 hours.
(3) And (3) after the esterification reaction in the step (2) is finished, removing water generated in the reaction, and adjusting the acid value of the product to be neutral to obtain the self-emulsifying ester based on the meta-phenyl ester.
In one embodiment of the present invention, the water produced in the reaction is removed by introducing an inert gas, preferably nitrogen, into the reaction system at the reaction temperature of step (2). The inert gas carries the water formed out of the reaction system when it escapes.
In one embodiment of the invention, the acid number of the product is adjusted with sodium hydroxide or sodium carbonate.
The above reaction equation is shown below:
example 1
A preparation method of self-emulsifying ester based on partial benzene ester comprises the following steps:
(1) trimellitic anhydride and PEG 600 were mixed in a molar ratio of 1:1 and reacted at 140 ℃ under a nitrogen atmosphere for 1 h.
(2) Adding 1-hexanol and catalyst titanate into the reaction system in the step (1), and heating to 200 ℃ to continue reacting for 6 h. Wherein the molar ratio of the 1-hexanol to the trimellitic anhydride is 1:1, and the addition amount of the catalyst is one thousandth of the total mass of the reactants.
(3) And (3) after the esterification reaction in the step (2) is finished, introducing nitrogen into the reaction system at the reaction temperature for bubbling, and removing water generated in the reaction. And sodium hydroxide was added to adjust the acid value of the product to 7.0 to obtain a self-emulsifying ester based on a meta-phenyl ester.
Example 2
A preparation method of self-emulsifying ester based on partial benzene ester comprises the following steps:
(1) trimellitic anhydride and PEG 600 were mixed in a molar ratio of 1:1 and reacted at 140 ℃ under a nitrogen atmosphere for 1 h.
(2) Adding 1-octanol and a catalyst methanesulfonic acid into the reaction system in the step (1), and heating to 200 ℃ to continue reacting for 6 hours. Wherein the molar ratio of the 1-hexanol to the trimellitic anhydride is 1:1, and the addition amount of the catalyst is five thousandths of the total mass of the reactants.
(3) And (3) after the esterification reaction in the step (2) is finished, introducing nitrogen into the reaction system at the reaction temperature for bubbling, and removing water generated in the reaction. And sodium carbonate was added to adjust the acid value of the product to 7.0 to obtain a self-emulsifying ester based on the meta-phenyl ester.
Example 3
A preparation method of self-emulsifying ester based on partial benzene ester comprises the following steps:
(1) trimellitic anhydride and PEG 600 were mixed in a molar ratio of 1:1.5 and reacted at 140 ℃ under a nitrogen atmosphere for 1 h.
(2) Adding n-dodecanol and a catalyst sodium bisulfate into the reaction system in the step (1), and heating to 200 ℃ to continue reacting for 6 hours. Wherein the molar ratio of the 1-hexanol to the trimellitic anhydride is 1:1.5, and the addition amount of the catalyst is one thousandth of the total mass of the reactants.
(3) And (3) after the esterification reaction in the step (2) is finished, introducing nitrogen into the reaction system at the reaction temperature for bubbling, and removing water generated in the reaction. And sodium carbonate was added to adjust the acid value of the product to 7.0 to obtain a self-emulsifying ester based on the meta-phenyl ester.
Example 4
A preparation method of self-emulsifying ester based on partial benzene ester comprises the following steps:
(1) trimellitic anhydride and PEG 600 were mixed in a molar ratio of 1:0.5 and reacted at 140 ℃ under a nitrogen atmosphere for 1 h.
(2) Adding n-nonanol and a catalyst of hypophosphorous acid into the reaction system in the step (1), and heating to 200 ℃ to continue the reaction for 6 hours. Wherein the molar ratio of the 1-hexanol to the trimellitic anhydride is 1:0.5, and the addition amount of the catalyst is three thousandths of the total mass of the reactants.
(3) And (3) after the esterification reaction in the step (2) is finished, introducing nitrogen into the reaction system at the reaction temperature for bubbling, and removing water generated in the reaction. And sodium carbonate was added to adjust the acid value of the product to 7.0 to obtain a self-emulsifying ester based on the meta-phenyl ester.
Foam suppressing and defoaming capability test
And (3) adopting a Roche foam instrument to test the foam inhibiting and defoaming capability of the self-emulsifying ester prepared by the method, wherein:
1) and (3) defoaming time test: 200mL of a sodium dodecyl sulfate solution with the mass fraction of 2% is added into a measuring cylinder with the volume of 1000mL at room temperature to serve as foaming liquid, then a bubbling pipe is inserted into the bottom of the measuring cylinder, nitrogen is introduced at the speed of 5L/min, and bubbling is stopped until the height of the foam reaches 800 mL. 1mL of self-emulsifying ester was immediately added to the tube and the time for the foam to drop to 50mL was recorded using a stopwatch, which was the time for defoaming. The shorter the defoaming time, the better the defoaming performance of the self-emulsifying ester.
2) And (3) testing the foam inhibition time: and after the defoaming performance test is finished, opening a blast pipe switch, introducing nitrogen into the measuring cylinder at the speed of 3L/min, and recording by using a stopwatch, wherein the time when the foam height rises to 800mL is the foam inhibition time. The longer the foam suppressing time, the better the foam suppressing performance of the self-emulsifying ester.
The defoaming time and foam suppressing time of the above examples are shown in Table 1.
TABLE 1
| Examples | Defoaming time(s) | Bubble suppressing time(s) |
| Example 1 | 20 | 85 |
| Example 2 | 22 | 83 |
| Example 3 | 25 | 81 |
| Example 4 | 28 | 79 |
From the experimental results of examples 1 to 4, it is known that the self-emulsifying ester provided by the invention has good defoaming and foam inhibiting performance.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of self-emulsifying ester based on partial benzene ester is characterized by comprising the following steps:
(1) mixing trimellitic anhydride and polyethylene glycol to perform esterification reaction;
(2) adding monohydric alcohol and a catalyst into the reaction system in the step (1) to continue the esterification reaction;
(3) and (3) after the esterification reaction in the step (2) is finished, removing water generated in the reaction, and adjusting the acid value of the product to be neutral to obtain the self-emulsifying ester based on the meta-phenyl ester.
2. The process according to claim 1, wherein in step (1), the molar ratio of the trimellitic anhydride to the polyethylene glycol is 1 (0.5-1.5), preferably 1:1.
3. The method according to claim 1, wherein in step (1), the molecular weight of the polyethylene glycol is 200-1000, preferably 600.
4. The method according to claim 1, wherein in step (1), the reaction temperature is 130-150 ℃, preferably 140 ℃; the reaction time is 0.5-2h, preferably 1 h; the reaction is carried out under an inert atmosphere, preferably nitrogen.
5. The process according to claim 1, wherein in step (2), the molar ratio of the monohydric alcohol to the trimellitic anhydride is 1 (0.5-1.5), preferably 1:1.
6. The method according to claim 1, wherein in the step (2), the monohydric alcohol is selected from one or more of C6-C18 straight chain alcohol or branched chain alcohol.
7. The method according to claim 1, wherein in the step (2), the catalyst is selected from one or more of titanate catalyst, solid acid catalyst or ionic liquid catalyst, and the addition amount of the catalyst is one thousandth to five thousandth of the total mass of the reactants.
8. The method as claimed in claim 1, wherein, in the step (2), the reaction temperature is 180-220 ℃, preferably 200 ℃; the reaction time is 4 to 10 hours, preferably 6 to 7 hours.
9. The method according to claim 1, wherein in the step (3), the water generated in the reaction is removed by introducing an inert gas, preferably nitrogen, into the reaction system at the reaction temperature of the step (2).
10. The method of claim 1, wherein in step (3), the acid value of the product is adjusted with sodium hydroxide or sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110564762.4A CN113292716A (en) | 2021-05-24 | 2021-05-24 | Preparation method of self-emulsifying ester based on meta-phenyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110564762.4A CN113292716A (en) | 2021-05-24 | 2021-05-24 | Preparation method of self-emulsifying ester based on meta-phenyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113292716A true CN113292716A (en) | 2021-08-24 |
Family
ID=77324280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110564762.4A Pending CN113292716A (en) | 2021-05-24 | 2021-05-24 | Preparation method of self-emulsifying ester based on meta-phenyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113292716A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3994951A (en) * | 1975-07-17 | 1976-11-30 | Pennwalt Corporation | Polyoxyalkylene fluoroalkyltrimellitates |
| EP0497404A1 (en) * | 1991-01-25 | 1992-08-05 | Dsm N.V. | Internal emulsifier system based on alkylene oxide units |
| US5686553A (en) * | 1995-11-16 | 1997-11-11 | Kuraray Co., Ltd. | Copolyesters and molded articles comprising the same |
| US20080139691A1 (en) * | 2006-10-21 | 2008-06-12 | Harald Blum | UV-curable polyurethane dispersions |
| US20090269577A1 (en) * | 2008-04-24 | 2009-10-29 | Ppg Industries Ohio, Inc. | Waterborne anti-chip primer coating composition |
| CN101747491A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
| CN102219984A (en) * | 2010-04-16 | 2011-10-19 | 东丽纤维研究所（中国）有限公司 | Antistatic copolyester and production method and application |
| CN102719013A (en) * | 2012-07-01 | 2012-10-10 | 桂林理工大学 | Method for modifying Lignin/PP (Propene Polymer) wood-plastic composite material by flexible-chain-contained reactive solubilizer |
| CN104263456A (en) * | 2014-09-28 | 2015-01-07 | 广州米奇化工有限公司 | Multifunctional self-emulsifying ester and preparation method thereof |
| CN106750255A (en) * | 2016-12-23 | 2017-05-31 | 广东省石油与精细化工研究院 | A kind of preparation method and applications of anionic and nonionic type reactive emulsifier |
| WO2017117346A1 (en) * | 2015-12-30 | 2017-07-06 | Afton Chemical Corporation | Polymeric emulsifier and lubricity additives for aqueous metal removal forming rolling, or other applications |
| CN110591061A (en) * | 2019-08-27 | 2019-12-20 | 威尔（福建）生物有限公司 | Glycerol polyether ester for emulsifier special for pesticide and preparation method thereof |
| CN110832005A (en) * | 2017-07-07 | 2020-02-21 | 科莱恩国际有限公司 | Alkoxylated polycarboxylates |
-
2021
- 2021-05-24 CN CN202110564762.4A patent/CN113292716A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3994951A (en) * | 1975-07-17 | 1976-11-30 | Pennwalt Corporation | Polyoxyalkylene fluoroalkyltrimellitates |
| EP0497404A1 (en) * | 1991-01-25 | 1992-08-05 | Dsm N.V. | Internal emulsifier system based on alkylene oxide units |
| US5686553A (en) * | 1995-11-16 | 1997-11-11 | Kuraray Co., Ltd. | Copolyesters and molded articles comprising the same |
| US20080139691A1 (en) * | 2006-10-21 | 2008-06-12 | Harald Blum | UV-curable polyurethane dispersions |
| US20090269577A1 (en) * | 2008-04-24 | 2009-10-29 | Ppg Industries Ohio, Inc. | Waterborne anti-chip primer coating composition |
| CN101747491A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
| CN102219984A (en) * | 2010-04-16 | 2011-10-19 | 东丽纤维研究所（中国）有限公司 | Antistatic copolyester and production method and application |
| CN102719013A (en) * | 2012-07-01 | 2012-10-10 | 桂林理工大学 | Method for modifying Lignin/PP (Propene Polymer) wood-plastic composite material by flexible-chain-contained reactive solubilizer |
| CN104263456A (en) * | 2014-09-28 | 2015-01-07 | 广州米奇化工有限公司 | Multifunctional self-emulsifying ester and preparation method thereof |
| WO2017117346A1 (en) * | 2015-12-30 | 2017-07-06 | Afton Chemical Corporation | Polymeric emulsifier and lubricity additives for aqueous metal removal forming rolling, or other applications |
| CN106750255A (en) * | 2016-12-23 | 2017-05-31 | 广东省石油与精细化工研究院 | A kind of preparation method and applications of anionic and nonionic type reactive emulsifier |
| CN110832005A (en) * | 2017-07-07 | 2020-02-21 | 科莱恩国际有限公司 | Alkoxylated polycarboxylates |
| CN110591061A (en) * | 2019-08-27 | 2019-12-20 | 威尔（福建）生物有限公司 | Glycerol polyether ester for emulsifier special for pesticide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王俊明: "自乳化酯在乳化型金属加工液中的应用研究进展", 《第四届全国金属加工润滑技术学术研讨会文集》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10184040B2 (en) | Polyarylethersulfone copolymers | |
| US20210403620A1 (en) | Functionalized poly(2,6-dimethyl phenylene oxide) oligomers containing dicyclopentadiene, method of producing the same and use thereof | |
| CN101978020B (en) | Heat transfer apparatus and methods including hydrofluorocarbonates | |
| CN103183822B (en) | A kind of unsaturated ammonia ester polyoxyalkyl ether and preparation method thereof | |
| EP3978468B1 (en) | Compound and composition | |
| US12098099B2 (en) | Polycarboxylic acid water-reducing agent with high adaptability to temperature and method for preparing the same | |
| CN108219127A (en) | A kind of esters monomer polyethers, poly carboxylic acid series water reducer and preparation method thereof | |
| JP2008523178A (en) | Process for the preparation of pure alpha-alkoxy-omega-hydroxy-polyalkylene glycols | |
| CN101700964A (en) | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether | |
| CN113292716A (en) | Preparation method of self-emulsifying ester based on meta-phenyl ester | |
| JP3067541B2 (en) | Glycerin polyalkylene glycol ether derivative and method for producing the same | |
| CN111533852A (en) | Solid polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108570151B (en) | Polymonothiocarbonate-polyester copolymer, preparation method and application | |
| US20160075833A1 (en) | Polyarylethersulfone copolymers | |
| JPS6026493B2 (en) | polyether carbonate | |
| WO2022163360A1 (en) | Method for producing (meth)acyrlic acid ester compound | |
| JP4832009B2 (en) | Sulfocarboxylic acid agent and sulfocarboxylic acid ester agent | |
| JP2017500419A (en) | Improved polytetramethylene ether glycol production process | |
| JP2007211236A (en) | Method for producing phosphoric ester-based polymer | |
| EP3424980A1 (en) | Alkoxylated polycarboxylic acid amides | |
| CN109589650B (en) | Polymer long-acting defoaming agent and preparation method thereof | |
| JP2011132383A (en) | Method for producing cement dispersing agent | |
| US8207367B2 (en) | Method for producing polymerizable phosphate ester | |
| CN109438667A (en) | It is coated with production polyurethane foamed composite material | |
| CN108707074A (en) | A method of preparing low acid value tricarboxymethyl propane oleate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210824 |