CN112661944A - Polyester plasticizer and preparation method thereof - Google Patents
Polyester plasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN112661944A CN112661944A CN202011598362.7A CN202011598362A CN112661944A CN 112661944 A CN112661944 A CN 112661944A CN 202011598362 A CN202011598362 A CN 202011598362A CN 112661944 A CN112661944 A CN 112661944A
- Authority
- CN
- China
- Prior art keywords
- temperature
- acid
- parts
- polyester plasticizer
- reducing
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a polyester plasticizer and a preparation method thereof, wherein the polyester plasticizer comprises the following raw materials in parts by mass: 12-20 parts of dibasic acid, 15-25 parts of dihydric alcohol, 4-7 parts of monohydric alcohol, 2-4 parts of catalyst and 3-5 parts of stabilizer. 1) Separately preheating the dibasic acid and the dihydric alcohol; 2) firstly, adding monohydric alcohol into a reaction kettle, then uniformly pouring preheated dibasic acid and dihydric alcohol into the reaction kettle, and adding a catalyst and a stabilizer; 3) adding monohydric alcohol into a reaction kettle; 4) measuring the acid value, measuring the acid once every 3-5 minutes, distilling under reduced pressure and reducing the temperature for keeping, reducing the pressure to 0.4-0.5Mpa, reducing the temperature to 180-200 ℃, preserving the temperature for 10 minutes, testing the acidity, and reducing the temperature to room temperature if the acid value is less than 5mg/g, thus completing the preparation of the product. According to the polyester plasticizer and the preparation method thereof provided by the invention, the traditional dibasic acid and the dihydric alcohol are used for preheating, so that the reaction can be better carried out and is more thorough.
Description
Technical Field
The invention relates to the field of preparation of polyester plasticizers, in particular to a polyester plasticizer and a preparation method thereof.
Background
The polyester plasticizer as an important series of products of the plasticizer has the characteristics of excellent extraction resistance, migration resistance and volatility resistance, and super-performance of oil resistance and high temperature resistance, and is called as a permanent plasticizer. At present, polyester plasticizers are developing towards high molecular weight, and can be used in a large number of polymer products such as acrylic rubber products, epichlorohydrin rubber products, nitrile rubber products, butadiene rubber and PVC combined use. However, the existing polyester plasticizer is relatively complex in preparation process, and the prepared product has fewer effective components, so that the product is not good in quality.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a polyester plasticizer and a preparation method thereof, wherein the preparation method is simple, the content of active substances in the prepared product is high, the detection can be carried out, and the outflow of inferior-quality products is prevented.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a polyester plasticizer comprises the following raw materials in parts by mass: 12-20 parts of dibasic acid, 15-25 parts of dihydric alcohol, 4-7 parts of monohydric alcohol, 2-4 parts of catalyst and 3-5 parts of stabilizer.
A preparation method of a polyester plasticizer comprises the following specific steps:
1) preheating the dibasic acid and the dihydric alcohol separately, heating the dibasic acid to 75-80 ℃ at a heating speed of 3-5 ℃, and heating the dihydric alcohol to 55-65 ℃ at a heating speed of 3-5 ℃;
2) firstly, adding monohydric alcohol into a reaction kettle, then uniformly pouring preheated dibasic acid and dihydric alcohol into the reaction kettle, adding a catalyst and a stabilizer, heating to 220-240 ℃ at the speed of 5-8 ℃, keeping the pressure of the reaction kettle at 0.7-0.9MPa, and keeping the temperature for 5-10 minutes after the temperature is raised;
3) adding monohydric alcohol into a reaction kettle, continuously heating to 260 ℃, and keeping the temperature to react for 15-20 ℃;
4) measuring the acid value, measuring the acid once every 3-5 minutes, distilling under reduced pressure and reducing the temperature for keeping, reducing the pressure to 0.4-0.5Mpa, reducing the temperature to 180-200 ℃, preserving the temperature for 10 minutes, testing the acidity, and reducing the temperature to room temperature if the acid value is less than 5mg/g, thus completing the preparation of the product;
5) measuring the saponification value of the product, putting 1-1.5g of the prepared plasticizer in a conical flask or a beaker, adding 30ml of potassium hydroxide ethanol solution, installing a condenser tube, refluxing for 1.5-2 hours in a boiling water bath, leaching the inner wall of the condenser tube by using ethanol solution with the concentration of more than 75%, dripping 2-3ml of phenol red indicator after 10-15 minutes, dripping 0.6mol/L of hydrochloric acid standard solution until the color of the solution disappears, and observing the volume of the used hydrochloric acid standard solution.
In a refinement, the dibasic acid is at least one of adipic acid, sebacic acid, or azelaic acid.
As an improvement, the dihydric alcohol is 1, 2-propylene glycol, 1, 3-butanediol or ethylene glycol.
As an improvement, the monohydric alcohol is C6-C8The alcohol of (1).
As an improvement, the catalyst is an organic tin salt substance.
As a modification, the concentration of the potassium hydroxide ethanol solution in the step 5) is 0.5 mol/L.
The invention has the beneficial effects that:
the preparation method is simple in preparation process, the traditional dibasic acid and the traditional dihydric alcohol are used for preheating, the reaction can be better carried out, the reaction is more thorough, more effective amount of the product can be obtained, the content of effective substances of the prepared product is high, the detection can be carried out, and the defective products are prevented from flowing out.
Detailed Description
The invention is illustrated below by means of specific examples, without being restricted thereto.
Example one
A polyester plasticizer comprises the following raw materials in parts by mass: 12 parts of dibasic acid, 15 parts of dihydric alcohol, 4 parts of monohydric alcohol, 2 parts of catalyst and 3 parts of stabilizer.
The preparation method of the polyester plasticizer is characterized by comprising the following specific steps of:
1) preheating the dibasic acid and the dihydric alcohol separately, wherein the temperature of the dibasic acid is increased to 75 ℃ at the temperature increasing speed of 3 ℃, and the temperature of the dihydric alcohol is increased to 55-65 ℃ at the temperature increasing speed of 3 ℃;
2) firstly, adding monohydric alcohol into a reaction kettle, then uniformly pouring preheated dibasic acid and dihydric alcohol into the reaction kettle, adding a catalyst and a stabilizer, heating to 220 ℃ at the speed of 5 ℃, keeping the pressure of the reaction kettle at 0.7Mpa, and keeping the temperature for 5 minutes after heating;
3) adding monohydric alcohol into a reaction kettle, continuously heating to 260 ℃, and keeping the temperature for reaction for 15 ℃;
4) measuring the acid value, measuring the acid once every 3 minutes, distilling under reduced pressure and reducing the temperature for keeping, reducing the pressure to 0.4Mpa, reducing the temperature to 180 ℃, preserving the temperature for 10 minutes, testing the acidity, and reducing the temperature to room temperature if the acid value is less than 5mg/g, thus completing the preparation of the product;
5) measuring the saponification value of the product, putting 1g of the prepared plasticizer in a conical flask or a beaker, adding 30ml of potassium hydroxide ethanol solution, installing a condenser tube, refluxing for 1.5 hours in a boiling water bath, leaching the inner wall of the condenser tube by using ethanol solution with the concentration of more than 75%, dripping 2-3ml of phenol red indicator after 10 minutes, dripping 0.6mol/L of hydrochloric acid standard solution until the color of the solution disappears, and observing the volume of the used hydrochloric acid standard solution.
The dibasic acid is at least one of adipic acid, sebacic acid or azelaic acid.
The dihydric alcohol is 1, 2-propylene glycol, 1, 3-butanediol or ethylene glycol.
The monohydric alcohol is C6-C8The alcohol of (1).
The catalyst is organic tin salt substance.
The concentration of the potassium hydroxide ethanol solution in the step 5) is 0.5 mol/L.
Example two
A polyester plasticizer comprises the following raw materials in parts by mass: 20 parts of dibasic acid, 25 parts of dihydric alcohol, 7 parts of monohydric alcohol, 4 parts of catalyst and 5 parts of stabilizer.
A preparation method of a polyester plasticizer comprises the following specific steps:
1) preheating the dibasic acid and the dihydric alcohol separately, wherein the temperature of the dibasic acid is increased to 80 ℃ at the temperature increasing speed of 5 ℃, and the temperature of the dihydric alcohol is increased to 65 ℃ at the temperature increasing speed of 5 ℃;
2) firstly, adding monohydric alcohol into a reaction kettle, then uniformly pouring preheated dibasic acid and dihydric alcohol into the reaction kettle, adding a catalyst and a stabilizer, heating to 240 ℃ at the speed of 8 ℃, keeping the pressure of the reaction kettle at 0.9Mpa, and keeping the temperature for 10 minutes after heating;
3) adding monohydric alcohol into a reaction kettle, continuously heating to 260 ℃, and keeping the temperature for reaction for 20 ℃;
4) measuring the acid value, measuring the acid once every 5 minutes, distilling under reduced pressure and reducing the temperature for keeping, reducing the pressure to 0.5Mpa, reducing the temperature to 200 ℃, preserving the temperature for 10 minutes, testing the acidity, and reducing the temperature to room temperature if the acid value is less than 5mg/g, thus completing the preparation of the product;
5) measuring the saponification value of the product, putting 1.5g of the prepared plasticizer in a conical flask or a beaker, adding 30ml of potassium hydroxide ethanol solution, installing a condenser tube, refluxing for 2 hours in a boiling water bath, leaching the inner wall of the condenser tube by using ethanol solution with the concentration of more than 75%, dropwise adding 3ml of phenol red indicator after 15 minutes, dropping 0.6mol/L of hydrochloric acid standard solution until the color of the solution disappears, and observing the volume of the used hydrochloric acid standard solution.
The dibasic acid is at least one of adipic acid, sebacic acid or azelaic acid.
The dihydric alcohol is 1, 2-propylene glycol, 1, 3-butanediol or ethylene glycol.
The monohydric alcohol is C6-C8The alcohol of (1).
The catalyst is organic tin salt substance.
The concentration of the potassium hydroxide ethanol solution in the step 5) is 0.5 mol/L.
EXAMPLE III
A polyester plasticizer comprises the following raw materials in parts by mass: 16 parts of dibasic acid, 20 parts of dihydric alcohol, 5 parts of monohydric alcohol, 3 parts of catalyst and 4 parts of stabilizer.
A preparation method of a polyester plasticizer comprises the following specific steps:
1) preheating the dibasic acid and the dihydric alcohol separately, wherein the temperature of the dibasic acid is raised to 77 ℃ at the temperature raising speed of 4 ℃, and the temperature of the dihydric alcohol is raised to 60 ℃ at the temperature raising speed of 4 ℃;
2) firstly, adding monohydric alcohol into a reaction kettle, then uniformly pouring preheated dibasic acid and dihydric alcohol into the reaction kettle, adding a catalyst and a stabilizer, heating to 230 ℃ at the speed of 7 ℃, keeping the pressure of the reaction kettle at 0.8Mpa, and keeping the temperature for 7 minutes after heating;
3) adding monohydric alcohol into a reaction kettle, continuously heating to 260 ℃, and keeping the temperature for reaction at 18 ℃;
4) measuring the acid value, measuring the acid once every 4 minutes, distilling under reduced pressure and reducing the temperature for keeping, reducing the pressure to 0.45Mpa, reducing the temperature to 190 ℃, preserving the temperature for 10 minutes, testing the acidity, and reducing the temperature to room temperature if the acid value is less than 5mg/g, thus completing the preparation of the product;
5) measuring the saponification value of the product, putting 1.2g of the prepared plasticizer in a conical flask or a beaker, adding 30ml of potassium hydroxide ethanol solution, installing a condenser tube, refluxing for 1.8 hours in a boiling water bath, leaching the inner wall of the condenser tube by using ethanol solution with the concentration of more than 75%, dripping 2.5ml of phenol red indicator after 13 minutes, dripping 0.6mol/L of hydrochloric acid standard solution until the color of the solution disappears, and observing the volume of the used hydrochloric acid standard solution.
The dibasic acid is at least one of adipic acid, sebacic acid or azelaic acid.
The dihydric alcohol is 1, 2-propylene glycol, 1, 3-butanediol or ethylene glycol.
The monohydric alcohol is C6-C8The alcohol of (1).
The catalyst is organic tin salt substance.
The concentration of the potassium hydroxide ethanol solution in the step 5) is 0.5 mol/L.
Table 1 shows the comparison table of the index test between the products of the examples and two products manufactured by the conventional general process on the market:
it can be seen from table 1 that the plasticizer produced by the process of the present invention has a higher lipid content, on average, close to 99.9%, a lower acid value, a higher average molecular mass, a higher effective amount, a lower volatility, a high plasticizing efficiency, and better performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The polyester plasticizer is characterized by comprising the following raw materials in parts by mass: 12-20 parts of dibasic acid, 15-25 parts of dihydric alcohol, 4-7 parts of monohydric alcohol, 2-4 parts of catalyst and 3-5 parts of stabilizer.
2. The polyester plasticizer according to claim 1, wherein said dibasic acid is at least one of adipic acid, sebacic acid, or azelaic acid.
3. The polyester plasticizer according to claim 1, wherein the diol is 1, 2-propanediol, 1, 3-butanediol, or ethylene glycol.
4. The polyester plasticizer according to claim 1, wherein the monohydric alcohol is C6-C8The alcohol of (1).
5. The polyester plasticizer according to claim 1, wherein the catalyst is an organotin salt.
6. The preparation method of the polyester plasticizer is characterized by comprising the following specific steps of:
1) preheating the dibasic acid and the dihydric alcohol separately, heating the dibasic acid to 75-80 ℃ at a heating speed of 3-5 ℃, and heating the dihydric alcohol to 55-65 ℃ at a heating speed of 3-5 ℃;
2) firstly, adding monohydric alcohol into a reaction kettle, then uniformly pouring preheated dibasic acid and dihydric alcohol into the reaction kettle, adding a catalyst and a stabilizer, heating to 220-240 ℃ at the speed of 5-8 ℃, keeping the pressure of the reaction kettle at 0.7-0.9MPa, and keeping the temperature for 5-10 minutes after the temperature is raised;
3) adding monohydric alcohol into a reaction kettle, continuously heating to 260 ℃, and keeping the temperature to react for 15-20 ℃;
4) measuring the acid value, measuring the acid once every 3-5 minutes, distilling under reduced pressure and reducing the temperature for keeping, reducing the pressure to 0.4-0.5Mpa, reducing the temperature to 180-200 ℃, preserving the temperature for 10 minutes, testing the acidity, and reducing the temperature to room temperature if the acid value is less than 5mg/g, thus completing the preparation of the product;
5) measuring the saponification value of the product, putting 1-1.5g of the prepared plasticizer in a conical flask or a beaker, adding 30ml of potassium hydroxide ethanol solution, installing a condenser tube, refluxing for 1.5-2 hours in a boiling water bath, leaching the inner wall of the condenser tube by using ethanol solution with the concentration of more than 75%, dripping 2-3ml of phenol red indicator after 10-15 minutes, dripping 0.6mol/L of hydrochloric acid standard solution until the color of the solution disappears, and observing the volume of the used hydrochloric acid standard solution.
7. The method for preparing a polyester plasticizer according to claim 2, wherein the concentration of the ethanolic potassium hydroxide solution in the step 5) is 0.5 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011598362.7A CN112661944A (en) | 2020-12-30 | 2020-12-30 | Polyester plasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011598362.7A CN112661944A (en) | 2020-12-30 | 2020-12-30 | Polyester plasticizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112661944A true CN112661944A (en) | 2021-04-16 |
Family
ID=75410353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011598362.7A Pending CN112661944A (en) | 2020-12-30 | 2020-12-30 | Polyester plasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112661944A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4122057A (en) * | 1974-09-03 | 1978-10-24 | Emery Industries, Inc. | Mixed-terminated polyester plasticizers |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
| CN104926648A (en) * | 2015-06-06 | 2015-09-23 | 山东岩海建设资源有限公司 | Polyester plasticizer as well as preparation method and application thereof |
| CN110078902A (en) * | 2019-05-24 | 2019-08-02 | 镇江巨杰新材料技术研发中心(有限合伙) | A kind of synthetic method of polyglycol ester plasticizer |
-
2020
- 2020-12-30 CN CN202011598362.7A patent/CN112661944A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4122057A (en) * | 1974-09-03 | 1978-10-24 | Emery Industries, Inc. | Mixed-terminated polyester plasticizers |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
| CN104926648A (en) * | 2015-06-06 | 2015-09-23 | 山东岩海建设资源有限公司 | Polyester plasticizer as well as preparation method and application thereof |
| CN110078902A (en) * | 2019-05-24 | 2019-08-02 | 镇江巨杰新材料技术研发中心(有限合伙) | A kind of synthetic method of polyglycol ester plasticizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103450794B (en) | Scratch resistance PU luminous floor paint and preparation method thereof | |
| CN104395386A (en) | Method for producing ester-based plasticizer and ester-based plasticizer produced thereby | |
| CN112661944A (en) | Polyester plasticizer and preparation method thereof | |
| CN115044024A (en) | Biodegradable copolymer for plasticizing and toughening polyvinyl chloride and preparation method thereof | |
| CN1948199A (en) | Coloured transparent glass paint and its preparation method and application | |
| CN104404819A (en) | Multifunctional paint used for outer package of wine box and preparation method thereof | |
| CN108531540B (en) | Novel mercury-free environment-friendly hematoxylin dye solution and preparation method thereof | |
| CN105504238A (en) | Preparation method of monobutyl ether alcohol terminated polyester plasticizer | |
| CN110144242A (en) | A kind of Modified Chlorinated Paraffin and preparation method thereof, application | |
| CN107603431B (en) | A kind of amino-stoving varnish multi-functional promotor and preparation method thereof | |
| US20190185605A1 (en) | Method For Preparing Core-Shell Copolymer, Core-Shell Copolymer And Resin Composition Including The Same | |
| CN102391482B (en) | Non-toxic environmentally friendly nadic anhydride polyester plasticizer and preparation method thereof | |
| JPS61126127A (en) | Lubricant polyester | |
| CN104193973A (en) | Hydroxyl-terminated water-based polyester resin and preparation method thereof | |
| CN102018668A (en) | Preparation method of aceglutamide | |
| CN107674529A (en) | A kind of automobile varnish and its production technology of efficiently quick service | |
| CN108641097A (en) | A kind of preparation method of phase inversion waterborne organic silicon lotion | |
| CN107573998A (en) | A kind of DOT6 borate type braking fluids | |
| CN105348544B (en) | A kind of preparation method of small grain size rosin ester emulsion | |
| CN114213918A (en) | Water-based wood clear primer and preparation method thereof | |
| CN109293907A (en) | It is a kind of based on biomass be monomer high molecular weight polyesters, Preparation method and use | |
| CN113754536A (en) | Preparation method of triethylene glycol di-n-caprylate | |
| CN106188588A (en) | The preparation method of chitosan-based antioxidation composite membrane based on tea polyphenols | |
| CN104490799B (en) | A kind of Phloroglucinol for injection lyophilised compositions and its preparation method | |
| CN109651093B (en) | Preparation method of bis-hydroxyethyl bisphenol fluorene ether |
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 |
Application publication date: 20210416 |
|
| RJ01 | Rejection of invention patent application after publication |