CN111057194A - Preparation method of low-viscosity acrylonitrile grafted polyether polyol - Google Patents
Preparation method of low-viscosity acrylonitrile grafted polyether polyol Download PDFInfo
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- CN111057194A CN111057194A CN201911306851.8A CN201911306851A CN111057194A CN 111057194 A CN111057194 A CN 111057194A CN 201911306851 A CN201911306851 A CN 201911306851A CN 111057194 A CN111057194 A CN 111057194A
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- polyether polyol
- acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A preparation method of low-viscosity acrylonitrile grafted polyether polyol, which adopts a batch method to prepare the acrylonitrile grafted polyether polyol, comprises the following steps: preparing a POP intermediate: adding part of basic polyether polyol as a bottom material into a polymerization kettle, uniformly mixing acrylonitrile, a free radical initiator and the rest polyether polyol to form a premix, dropwise adding the premix into the polymerization kettle at a certain temperature for polymerization reaction, and synthesizing grafted polyether polyol which takes acrylonitrile as a single vinyl monomer, namely a POP intermediate; b, taking the POP intermediate prepared in the step a as a bottom material, forming a mixed material by using acrylonitrile, a free radical initiator and polyether polyol, dropwise adding the mixed material into the POP intermediate, and carrying out polymerization reaction; after the reaction is finished, removing the monomer to obtain the acrylonitrile graft polyether glycol product. The viscosity of the acrylonitrile grafted polyether polyol prepared by the method is lower than 4000mPa & s.
Description
Technical Field
The invention relates to a preparation method of low-viscosity acrylonitrile graft polyether polyol, belonging to the technical field of chemical preparation.
Background
Polymer polyol refers to a polyethylene-based polymer suspension, commonly referred to as POP, prepared by in situ polymerization of one or more vinyl monomers in a polyoxyalkylene base polyol. It consists of three main components: (1) a base polyether as a continuous phase; (2) polymer fine particles as a dispersed phase; (3) a dispersant for stably dispersing fine polymer particles.
Methods for preparing polymer polyols are well known and include both batch and continuous processes. The batch process is to put a part of basic polyether and/or a part of initiator and macromonomer at the bottom of a kettle, mix the rest materials and then add the mixture into the kettle at a constant speed for polymerization, and then remove the monomer after the reaction is finished to obtain the product. The continuous process generally adopts a single-kettle or double-kettle reactor, controls a certain speed according to the requirement of the retention time, continuously adds the mixed material of other materials such as basic polyether, vinyl monomer, initiator, macromonomer and the like which are mixed in advance into the kettle, continuously discharges materials at the same time, and continuously removes the unreacted monomer to obtain the product. The viscosity of polymer polyols is an important indicator of their processing characteristics and it has been sought by those skilled in the art to produce POP products having a high solids content and a low viscosity.
The most essential difference between polymer polyols prepared by batch and continuous processes is the distinctly different particle size distribution of the dispersed phase particles. Generally, the continuous process produces a product with a broad particle size distribution that is beneficial for reducing the viscosity of the POP product. The product prepared by the batch method has narrow particle size distribution and relatively high viscosity. Although batch processes have the disadvantage of higher product viscosity, batch processes have advantages over continuous processes in some respects, such as: the investment is low; is suitable for the production of small-batch grade polymer polyols; facilitating the switching of different grades of polymer polyols; the vehicle can be started and stopped at any time according to the marketing condition of the market, and the inventory can be effectively reduced.
Polymer polyols with acrylonitrile as the sole vinyl monomer are one type of POP series products, which differ from other types of POPs in that they are synthesized without macromonomers and chain transfer agents. The polymer polyol is mainly used for producing polyurethane foam, so that the polymer polyol accounts for 40 percent, and the prepared polyurethane foam has the best load-bearing performance.
The ideal polymer polyol is a uniformly dispersed system with low viscosity, good dispersibility, viscosity being one of its main quality characteristics. It has been demonstrated that the viscosity influencing factors of POP with acrylonitrile as the sole vinyl monomer mainly include: (1) the type of production process employed; (2) the type of base polyether polyol; (3) solid content of the product. If the traditional batch process is adopted, the nominal molecular weight of the basic polyether polyol is 4000-6000, the polymer polyol taking acrylonitrile as a single vinyl monomer is produced, and when the solid content is 15-22%, the viscosity of the polymer polyol is generally more than 6000mPa & s. The viscosity is high, which is not beneficial to downstream use.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of low-viscosity acrylonitrile graft polyether polyol, and the viscosity of the acrylonitrile graft polyether polyol prepared by the method is lower than 4000 mPa.
The technical problem of the invention is solved by the following technical scheme:
a preparation method of low-viscosity acrylonitrile grafted polyether polyol, which adopts a batch method to prepare the acrylonitrile grafted polyether polyol, and comprises the following steps:
a. preparing a POP intermediate: adding 10-30% of basic polyether polyol serving as a bottom material into a polymerization kettle, uniformly mixing acrylonitrile, a free radical initiator and the rest polyether polyol to form a premix, dropwise adding the premix into the polymerization kettle at a certain temperature for polymerization reaction, and synthesizing grafted polyether polyol taking acrylonitrile as a single vinyl monomer, namely a POP intermediate;
b. b, adding the POP intermediate prepared in the step a as a bottom material into a polymerization kettle, adding acrylonitrile, a free radical initiator and polyether polyol into a mixing kettle to form a mixed material, heating the material in the polymerization kettle to 105-115 ℃, stopping heating, dropping the material in the mixing kettle into the polymerization kettle for polymerization, dropping the mixed material into the POP intermediate for polymerization;
c. after the reaction is finished, removing the monomer to obtain the acrylonitrile graft polyether glycol product.
In the preparation method of the low-viscosity acrylonitrile grafted polyether polyol, in the steps a and b, the polymerization temperature is 105-120 ℃, and the feeding time is 1-4 hours.
According to the preparation method of the low-viscosity acrylonitrile grafted polyether polyol, the solid content of the POP intermediate is 15-22%.
In the step b, the adding amount of the mixed material is 30-100% of the adding amount of the POP intermediate bottom material.
In the step b, the content of acrylonitrile in the mixed material is 15-22%, the content of the free radical initiator is 0.1-0.5%, and the content of the polyether polyol is 77.5-84.9%.
In the preparation method of the low-viscosity acrylonitrile grafted polyether polyol, the free radical initiator is azobisisobutyronitrile or dimethyl azobisisobutyrate.
In the preparation method of the low-viscosity acrylonitrile grafted polyether polyol, the free radical initiator is azobisisobutyronitrile or dimethyl azobisisobutyrate. The two initiators have proper half-life period within the graft polymerization temperature range of the reaction system and high initiation efficiency, and compared with peroxy compounds which are also free radical initiators, the two initiators do not have acidic byproducts in the decomposition process and have no influence on the acid value of the product.
In the step a, the total addition amount of the basic polyether polyol in the total added materials is 77.5-84.9%, the ratio of acrylonitrile is 15-22%, and the ratio of the free radical initiator is 0.1-0.5%.
The method comprises the steps of preparing acrylonitrile grafted polyether polyol by a step-by-step intermittent method, namely preparing the acrylonitrile grafted polyether polyol in two steps, preparing the grafted polyether polyol with the solid content of 15-22% and taking acrylonitrile as a single vinyl monomer from a first phase by a traditional intermittent method, then taking the grafted polyether polyol as a bottom material, further dropwise adding a mixed material consisting of acrylonitrile, an initiator and polyether polyol, and carrying out polymerization reaction to obtain a final product, wherein the viscosity of the product is lower than 4000mPa & s on the premise of ensuring the solid content.
Detailed Description
The present invention will be described in further detail with reference to examples.
Examples 1-2 are the preparation of POP intermediates.
Example 1
And (3) starting a cooling system of the mixing kettle, controlling the temperature below 15 ℃, sequentially pressing 103.2g of acrylonitrile and 1.3g of azodiisobutyronitrile into the mixing kettle, stirring for 30min, then pressing 238g of basic polyether polyol into the mixing kettle, and uniformly stirring for later use. Starting a polymerization kettle for stirring, pressing 139g of basic polyether polyol into the polymerization kettle, starting a polymerization kettle temperature rising system for replacement twice, rising the temperature of materials in the polymerization kettle to 115 ℃, stopping rising the temperature, adding the materials in a mixing kettle into the polymerization kettle at the temperature of 110-120 ℃, and keeping the total feeding time for about 3 hours. After the materials are added, the reaction is carried out for 2 hours at the temperature of 115-125 ℃. And finally, removing the monomers for 2 hours under the vacuum condition, filtering and discharging to obtain a POP intermediate.
Example 2
And (3) starting a cooling system of the mixing kettle, controlling the temperature below 15 ℃, sequentially pressing 103.2g of acrylonitrile and 1.8g of dimethyl azodiisobutyrate into the mixing kettle, stirring for 30min, then pressing 238g of basic polyether polyol into the mixing kettle, and uniformly stirring for later use. Starting a polymerization kettle for stirring, pressing 139g of basic polyether polyol into the polymerization kettle, starting a polymerization kettle temperature rising system for replacement twice, rising the temperature of materials in the polymerization kettle to 110 ℃, stopping rising the temperature, adding the materials in a mixing kettle into the polymerization kettle at the temperature of 105-115 ℃, and keeping the total feeding time for about 4 hours. After the materials are added, the reaction is carried out for 2 hours at the temperature of 115-125 ℃. And finally, removing the monomer for 1 hour under the vacuum condition, filtering and discharging to obtain a POP intermediate.
The results of analysis of the intermediates prepared in examples 1-2 are shown in Table 1.
Table 1: results of analysis of intermediates prepared in examples 1 to 2
As can be seen from table 1, the viscosity of the prepared POP intermediate was relatively high.
Examples 3 to 5 are preparations of finished products.
Example 3
And (3) starting a cooling system of the mixing kettle, controlling the temperature below 15 ℃, sequentially pressing 66g of acrylonitrile and 0.8g of azodiisobutyronitrile into the mixing kettle, stirring for 30min, then pressing 286g of basic polyether polyol into the mixing kettle, and uniformly stirring for later use. Starting a polymerization kettle for stirring, pressing 450g of POP intermediate into the polymerization kettle, starting a polymerization kettle temperature-raising system for replacement twice, raising the temperature of materials in the polymerization kettle to 115 ℃, stopping raising the temperature, adding the materials in the mixing kettle into the polymerization kettle at the temperature of 110-120 ℃, and keeping the total feeding time about 1 hour. After the materials are added, the reaction is carried out for 2 hours at the temperature of 115-125 ℃. And finally, removing the monomers for 2 hours under the vacuum condition, filtering and discharging to obtain a POP finished product.
Example 4
And (3) starting a cooling system of the mixing kettle, controlling the temperature below 15 ℃, sequentially pressing 76g of acrylonitrile and 0.98g of azodiisobutyronitrile into the mixing kettle, stirring for 30min, then pressing 286g of basic polyether polyol into the mixing kettle, and uniformly stirring for later use. Starting a polymerization kettle for stirring, pressing 450g of POP intermediate into the polymerization kettle, starting a polymerization kettle temperature-raising system for replacement twice, raising the temperature of materials in the polymerization kettle to 105 ℃, stopping raising the temperature, adding the materials in the mixing kettle into the polymerization kettle at the temperature of 105-110 ℃, and keeping the total feeding time for about 1 hour. After the materials are added, the reaction is carried out for 2 hours at the temperature of 115-125 ℃. And finally, removing the monomers for 2 hours under the vacuum condition, filtering and discharging to obtain a POP finished product.
Example 5
And (3) starting a cooling system of the mixing kettle, controlling the temperature below 15 ℃, sequentially pressing 76g of acrylonitrile and 0.98g of dimethyl azodiisobutyrate into the mixing kettle, stirring for 30min, then pressing 286g of basic polyether polyol into the mixing kettle, and uniformly stirring for later use. And starting a polymerization kettle for stirring, pressing 450g of POP intermediate into the polymerization kettle, replacing twice, heating the materials in the polymerization kettle to 115 ℃, stopping heating, adding the materials in the mixing kettle into the polymerization kettle at the temperature of 110-120 ℃, and keeping the total feeding time for about 1 hour. After the materials are added, the reaction is carried out for 2 hours at the temperature of 115-125 ℃. And finally, removing the monomers for 2 hours under the vacuum condition, filtering and discharging to obtain a POP finished product.
Comparative example 1
And (3) starting a cooling system of the mixing kettle, controlling the temperature below 15 ℃, sequentially pressing 103.2g of acrylonitrile and 1.3g of azodiisobutyronitrile into the mixing kettle, stirring for 30min, then pressing 238g of basic polyether polyol into the mixing kettle, and uniformly stirring for later use. Starting a polymerization kettle for stirring, pressing 139g of basic polyether polyol into the polymerization kettle, starting a polymerization kettle temperature rising system for replacement twice, rising the temperature of materials in the polymerization kettle to 115 ℃, stopping rising the temperature, adding the materials in a mixing kettle into the polymerization kettle at the temperature of 110-120 ℃, and keeping the total feeding time for about 3 hours. After the materials are added, the reaction is carried out for 2 hours at the temperature of 115-125 ℃. Finally, removing the monomer for 2 hours under the vacuum condition, filtering and discharging.
The results of the analyses of examples 3 to 5 and comparative example 1 are shown in Table 2.
Table 2: analysis results of examples 3 to 5 and comparative example
| Test index | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Hydroxyl value, mgKOH/g | 28.2 | 27.3 | 27.3 | 27.7 |
| Acid value of mgKOH/g | 0.07 | 0.06 | 0.07 | 0.05 |
| Water content% | 0.04 | 0.05 | 0.04 | 0.05 |
| Viscosity, mPa.s, 25 deg.C | 3100 | 3800 | 4000 | 9300 |
| pH value | 6.3 | 6.7 | 6.7 | 6.7 |
| Solids content% | 18.9 | 20.6 | 20.5 | 20.7 |
| Colour(s) | Yellow colour | Yellow colour | Yellow colour | Yellow colour |
As can be seen from table 2, comparative example 1 is a POP product prepared by a conventional batch process, and the viscosity thereof reaches 9300mPa · s, whereas examples 3 to 5, the viscosity of a POP product prepared by a two-step batch process is significantly reduced, and can be as low as 3100mPa · s.
Claims (7)
1. A preparation method of low-viscosity acrylonitrile graft polyether polyol is characterized by comprising the following steps: the preparation method adopts an intermittent method to prepare the acrylonitrile graft polyether polyol, and comprises the following steps:
a. preparing a POP intermediate: adding 10-30% of basic polyether polyol serving as a bottom material into a polymerization kettle, uniformly mixing acrylonitrile, a free radical initiator and the rest polyether polyol to form a premix, dropwise adding the premix into the polymerization kettle at a certain temperature for polymerization reaction, and synthesizing grafted polyether polyol taking acrylonitrile as a single vinyl monomer, namely a POP intermediate;
b. b, adding the POP intermediate prepared in the step a as a bottom material into a polymerization kettle, adding acrylonitrile, a free radical initiator and polyether polyol into a mixing kettle to form a mixed material, heating the material in the polymerization kettle to 105-115 ℃, stopping heating, dropping the material in the mixing kettle into the polymerization kettle for polymerization, dropping the mixed material into the POP intermediate for polymerization;
c. after the reaction is finished, removing the monomer to obtain the acrylonitrile graft polyether glycol product.
2. The process for preparing a low viscosity acrylonitrile graft polyether polyol as claimed in claim 1, wherein: in the steps a and b, the polymerization reaction temperature is 105-120 ℃, and the feeding time is 1-4 hours.
3. The process for preparing a low viscosity acrylonitrile graft polyether polyol as claimed in claim 2, wherein: the solid content of the POP intermediate is 15-22%.
4. The process for preparing a low viscosity acrylonitrile graft polyether polyol as claimed in claim 3, wherein: in the step b, the adding amount of the mixed material is 30-100% of the adding amount of the POP intermediate bottom material.
5. The process for preparing a low viscosity acrylonitrile graft polyether polyol as claimed in claim 4, wherein: in the step b, the content of acrylonitrile in the mixed material is 15-22%, the content of the free radical initiator is 0.1-0.5%, and the content of the polyether polyol is 77.5% -84.9%.
6. The process for preparing a low viscosity acrylonitrile graft polyether polyol as claimed in claim 5, wherein: the free radical initiator is azobisisobutyronitrile or dimethyl azobisisobutyrate.
7. The process for preparing a low viscosity acrylonitrile graft polyether polyol as claimed in claim 6, wherein: in the step a, the total adding amount of the basic polyether polyol in the total material is 77.5-84.9%, the ratio of acrylonitrile is 15-22%, and the ratio of the free radical initiator is 0.1-0.5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950317A (en) * | 1973-10-29 | 1976-04-13 | Basf Wyandotte Corporation | Process for the preparation of graft copolymer dispersions |
| US4148840A (en) * | 1978-03-29 | 1979-04-10 | Union Carbide Corporation | Polymer/polyol compositions made from preformed polymer/polyols, processes for making same and processes for making polyurethane products therefrom |
| US5488085A (en) * | 1994-08-18 | 1996-01-30 | Arco Chemical Technology, L.P. | Semi-batch process for producing polymer polyols |
-
2019
- 2019-12-18 CN CN201911306851.8A patent/CN111057194A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950317A (en) * | 1973-10-29 | 1976-04-13 | Basf Wyandotte Corporation | Process for the preparation of graft copolymer dispersions |
| US4148840A (en) * | 1978-03-29 | 1979-04-10 | Union Carbide Corporation | Polymer/polyol compositions made from preformed polymer/polyols, processes for making same and processes for making polyurethane products therefrom |
| US5488085A (en) * | 1994-08-18 | 1996-01-30 | Arco Chemical Technology, L.P. | Semi-batch process for producing polymer polyols |
Non-Patent Citations (1)
| Title |
|---|
| 中国石油化工总公司生产部: "《中国石油化工总公司石油化工产品大全》", 31 December 1992, 中国石化出版社 * |
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