CN110540640A - Preparation method of special dispersing agent for shoe materials - Google Patents
Preparation method of special dispersing agent for shoe materials Download PDFInfo
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- CN110540640A CN110540640A CN201910885702.5A CN201910885702A CN110540640A CN 110540640 A CN110540640 A CN 110540640A CN 201910885702 A CN201910885702 A CN 201910885702A CN 110540640 A CN110540640 A CN 110540640A
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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
- C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride groups
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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
- C08G65/3328—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof heterocyclic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a preparation method of a special dispersing agent for shoe materials, wherein the dispersing agent adopts high-activity raw materials and multifunctional basic polyether, and specifically comprises the steps of dehydration, esterification reaction, oxygen content measurement, catalyst addition, oxygen content measurement, end capping reaction and the like, so that the special dispersing agent for shoe materials is developed, the reaction activity, the dispersibility and the hardness of products can be improved, the continuously improved downstream customer requirements can be met, and the special dispersing agent is suitable for the whole polyurethane shoe material industry.
Description
Technical Field
The invention relates to a preparation method of a dispersing agent, in particular to a special dispersing agent for shoe materials.
Background
The shoe industry in China is different from military projects, the shoe industry presents a strong development situation in more than ten years of shortness, China is the largest shoe manufacturing production area in the world, and a very complete industrial chain and industrial development platform are provided at present. The shoe industry in China already shows an industry cluster type development state.
Therefore, the special dispersing agent for shoe materials has very considerable market prospect, and accounts for about 5 percent of the total amount of polyether. In recent years, the market of polyurethane stock solution in China is influenced by the price of raw materials, the growth speed is slowed down, and the proportion of the existing polyurethane shoe materials is less than 6 percent, so the market space of the existing polyurethane shoe materials is still large. In addition, because the industrial entry threshold of polyether is low, the production capacity of polyether is rapidly expanded, and therefore, the polyether market has a serious problem of over-supply.
At present, the technology of the special dispersing agent for shoe materials in the market is not mature enough, equipment is old, the device is backward, products are frequently switched, and the product quality is unstable. Starting from the raw materials, the quality of the product is improved, and the product is more competitive in the market.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a special dispersing agent for shoe materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
A preparation method of a special dispersing agent for shoe materials, wherein the dispersing agent adopts high-activity raw materials and multifunctional basic polyether, and specifically comprises the following steps:
Step one, dehydration: and (3) putting 88-95 parts by weight of high-activity polyether into an intermittent kettle, heating for dehydration at the temperature of 100 ℃ and 120 ℃, under the pressure of less than or equal to-0.093 MPa, and testing the moisture once every 2 hours, wherein the moisture content is less than or equal to 0.05 percent, and the product is qualified.
Step two, esterification reaction: cooling the material to 40-60 ℃, adding 0.5-5 parts by weight of maleic anhydride, bubbling nitrogen for half an hour at the pressure of 0.02-0.2MPa and at the temperature of 40-60 ℃.
Step three, measuring the oxygen content: less than or equal to 100 PPm.
Step four, adding a catalyst: the temperature is controlled at 125-135 ℃, the pressure is released at the beginning of timing, the pressure release time is 2 hours, the pressure is released to the normal pressure, and 0.01 to 0.05 weight part of catalyst is poured into the reactor through a feeding opening.
Step five, measuring the oxygen content: less than or equal to 100 PPm.
Step six, end-capping reaction: firstly, pressure is relieved to 0.02-0.04 Mpa; then adding 3-9 parts by weight of ethylene oxide, wherein the pressure is less than or equal to 0.4Mpa, and the temperature is as follows: 120 ℃ and 135 ℃; internal pressure 10 hours, temperature: at the temperature of 120 ℃ and 135 ℃, the pressure is less than or equal to 0.43 MPa; the prepared product is light yellow-amber, and the acid value and the viscosity of the finished product are measured.
preferably, the high activity polyether of step one is selected from those having a functionality of 4 to 8.
Preferably, the catalyst in the fourth step is one of a divalent metal oxide, a divalent metal naphthenate and a quaternary ammonia base.
As can be seen from the above description, the present invention has advantages compared with the prior art:
1. The high-activity multifunctional polyether is selected, the hardness of the product is effectively improved, the basic polyether reacts with ethylene oxide, and the prepared dispersing agent containing the induced unsaturated double bond can improve the performance of the dispersing agent, reduce the viscosity of the product and reduce the cost of customers;
2. the polyether and the ethylene oxide with high activity can effectively improve the reaction activity of the product, improve the conversion rate of the product, have low residual monomer and reduce the pressure of environmental protection.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 special dispersing agent for the shoe material comprises the following raw material components in parts by weight:
high-activity polyether: 88-95 parts, maleic anhydride: 0.5-5 parts of catalyst: 0.01-0.05 part, ethylene oxide: 3-9 parts.
The high-activity polyether in the step one has a functionality of 4-8.
And the catalyst in the fourth step is one of divalent metal oxide, divalent metal naphthenate and quaternary ammonia base.
example 1
A preparation method of a special dispersing agent for shoe materials, wherein the dispersing agent adopts high-activity raw materials and multifunctional basic polyether, and specifically comprises the following steps:
Step one, dehydration: 88 weight portions of high activity polyether is put into an intermittent kettle to be heated and dehydrated, the temperature is 100 ℃, the pressure is less than or equal to-0.093 MPa, the moisture is measured every 2 hours, and the moisture is less than or equal to 0.05 percent and is qualified.
Step two, esterification reaction: cooling the material to 40 ℃, adding 0.5 weight part of maleic anhydride, bubbling nitrogen for half an hour at the pressure of 0.02MPa and the temperature of 40 ℃.
Step three, measuring the oxygen content: less than or equal to 100 PPm.
step four, adding a catalyst: timing and releasing pressure when the temperature is increased to 125 ℃, releasing pressure for 2 hours to normal pressure, and pouring 0.01 weight part of catalyst into the reactor through a charging hole.
Step five, measuring the oxygen content: less than or equal to 100 PPm.
Step six, end-capping reaction: firstly, the pressure is relieved to 0.02 Mpa; then adding 3 parts by weight of ethylene oxide, wherein the pressure is less than or equal to 0.4Mpa, and the temperature is as follows: 120 ℃; internal pressure 10 hours, temperature: 120 ℃ and the pressure is less than or equal to 0.43 Mpa; the prepared product is light yellow-amber, and the acid value and the viscosity of the finished product are measured.
example 2
A preparation method of a special dispersing agent for shoe materials, wherein the dispersing agent adopts high-activity raw materials and multifunctional basic polyether, and specifically comprises the following steps:
step one, dehydration: 95 parts by weight of high-activity polyether is put into an intermittent kettle to be heated and dehydrated, the temperature is 120 ℃, the pressure is less than or equal to-0.093 MPa, the moisture is measured every 2 hours, and the moisture is less than or equal to 0.05 percent and is qualified.
Step two, esterification reaction: cooling the material to 60 ℃, adding 5 parts by weight of maleic anhydride, bubbling nitrogen for half an hour at the pressure of 0.2MPa and the temperature of 60 ℃.
Step three, measuring the oxygen content: less than or equal to 100 PPm.
Step four, adding a catalyst: timing and releasing pressure at 135 ℃, releasing pressure for 2 hours to normal pressure, and pouring 0.05 weight part of catalyst into the reactor through a charging hole.
Step five, measuring the oxygen content: less than or equal to 100 PPm.
Step six, end-capping reaction: firstly, pressure is relieved to 0.04 Mpa; then adding 9 parts by weight of ethylene oxide, wherein the pressure is less than or equal to 0.4Mpa, and the temperature is as follows: 135 deg.C; internal pressure 10 hours, temperature: 135 deg.C, and pressure not more than 0.43 MPa; the prepared product is light yellow-amber, and the acid value and the viscosity of the finished product are measured.
Example 3
Step one, dehydration: 90 parts by weight of high-activity polyether is put into an intermittent kettle to be heated and dehydrated, the temperature is 110 ℃, the pressure is less than or equal to-0.093 MPa, the moisture is measured every 2 hours, and the moisture is less than or equal to 0.05 percent and is qualified.
step two, esterification reaction: the material is cooled to 50 ℃, 2.97 parts by weight of maleic anhydride is added, nitrogen is bubbled for half an hour, the pressure is 0.12MPa, and the temperature is 50 ℃.
Step three, measuring the oxygen content: less than or equal to 100 PPm.
step four, adding a catalyst: timing and releasing pressure at 130 ℃ when the temperature is raised, releasing pressure for 2 hours to normal pressure, and pouring 0.03 weight part of catalyst into the reactor through a charging hole.
step five, measuring the oxygen content: less than or equal to 100 PPm.
Step six, end-capping reaction: firstly, pressure is relieved to 0.02-0.04 Mpa; then adding 7 parts by weight of ethylene oxide, wherein the pressure is less than or equal to 0.4Mpa, and the temperature is as follows: 120 ℃ and 135 ℃; internal pressure 10 hours, temperature: at the temperature of 120 ℃ and 135 ℃, the pressure is less than or equal to 0.43 MPa; the prepared product is light yellow-amber, and the acid value and the viscosity of the finished product are measured.
The invention has the following innovation points:
1) High-activity multifunctional polyether is selected to improve the hardness of downstream products;
2) The basic polyether reacts with ethylene oxide, and the prepared dispersing agent containing the induced unsaturated double bond can improve the performance of the dispersing agent, reduce the viscosity of downstream products and reduce the cost of customers;
3) The raw materials with high activity, namely polyether and ethylene oxide, can improve the reaction activity of downstream products, improve the conversion rate of the products, have low residual monomer and reduce the pressure of environmental protection.
table 1 shows the main technical indexes of the dispersant prepared by the invention
| The dispersant prepared by the invention | |
| Moisture (%) | ＜0.1 |
| Acid value (mgKOH/g) | ＜50 |
| Viscosity (mPa.s/25 ℃ C.) | 3000-5000 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a special dispersing agent for shoe materials is characterized in that the dispersing agent adopts high-activity raw materials and multifunctional basic polyether, and specifically comprises the following steps:
Step one, dehydration: and (3) putting 88-95 parts by weight of high-activity polyether into an intermittent kettle, heating for dehydration at the temperature of 100 ℃ and 120 ℃, under the pressure of less than or equal to-0.093 MPa, and testing the moisture once every 2 hours, wherein the moisture content is less than or equal to 0.05 percent, and the product is qualified.
Step two, esterification reaction: cooling the material to 40-60 ℃, adding 0.5-5 parts by weight of maleic anhydride, bubbling nitrogen for half an hour at the pressure of 0.02-0.2MPa and at the temperature of 40-60 ℃.
Step three, measuring the oxygen content: less than or equal to 100 PPm.
Step four, adding a catalyst: the temperature is controlled at 125-135 ℃, the pressure is released at the beginning of timing, the pressure release time is 2 hours, the pressure is released to the normal pressure, and 0.01 to 0.05 weight part of catalyst is poured into the reactor through a feeding opening.
Step five, measuring the oxygen content: less than or equal to 100 PPm.
Step six, end-capping reaction: firstly, pressure is relieved to 0.02-0.04 Mpa; then adding 3-9 parts by weight of ethylene oxide, wherein the pressure is less than or equal to 0.4Mpa, and the temperature is as follows: 120 ℃ and 135 ℃; internal pressure 10 hours, temperature: at the temperature of 120 ℃ and 135 ℃, the pressure is less than or equal to 0.43 MPa; the prepared product is light yellow-amber, and the acid value and the viscosity of the finished product are measured.
2. The preparation method of the special dispersing agent for shoe materials according to claim 1, characterized by comprising the following steps: the high-activity polyether in the step one has a functionality of 4-8.
3. The preparation method of the special dispersing agent for shoe materials according to claim 1, characterized by comprising the following steps: and the catalyst in the fourth step is one of divalent metal oxide, divalent metal naphthenate and quaternary ammonia base.
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| CN201910885702.5A CN110540640A (en) | 2019-09-19 | 2019-09-19 | Preparation method of special dispersing agent for shoe materials |
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| CN201910885702.5A CN110540640A (en) | 2019-09-19 | 2019-09-19 | Preparation method of special dispersing agent for shoe materials |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1218174A (en) * | 1982-04-01 | 1987-02-17 | Gerhard G. Ramlow | Process for the preparation of white graft polymer dispersions and flame retardant polyurethane foams |
| US4690956A (en) * | 1982-04-01 | 1987-09-01 | Basf Corporation | Process for the preparation of graft polymer dispersions and flame-retardant polyurethane foams |
| CN101311203A (en) * | 2006-12-15 | 2008-11-26 | 韩国锦湖石油化学株式会社 | Method for preparing polymer polyol stabilizer from maleic anhydride and the polymer polyol stabilizer therefore |
| CN102471478A (en) * | 2009-07-03 | 2012-05-23 | 拜尔材料科学股份公司 | Process for preparing polyether polyols containing terminal primary hydroxyl groups |
-
2019
- 2019-09-19 CN CN201910885702.5A patent/CN110540640A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1218174A (en) * | 1982-04-01 | 1987-02-17 | Gerhard G. Ramlow | Process for the preparation of white graft polymer dispersions and flame retardant polyurethane foams |
| US4690956A (en) * | 1982-04-01 | 1987-09-01 | Basf Corporation | Process for the preparation of graft polymer dispersions and flame-retardant polyurethane foams |
| CN101311203A (en) * | 2006-12-15 | 2008-11-26 | 韩国锦湖石油化学株式会社 | Method for preparing polymer polyol stabilizer from maleic anhydride and the polymer polyol stabilizer therefore |
| CN102471478A (en) * | 2009-07-03 | 2012-05-23 | 拜尔材料科学股份公司 | Process for preparing polyether polyols containing terminal primary hydroxyl groups |
Non-Patent Citations (1)
| Title |
|---|
| 李茂元: "聚合物多元醇的生产技术", 《深圳聚氨酯国际会议论文集》 * |
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Application publication date: 20191206 |