CN112011042B - Preparation method of high molecular weight low viscosity polyether polyol - Google Patents
Preparation method of high molecular weight low viscosity polyether polyol Download PDFInfo
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- CN112011042B CN112011042B CN202010804075.0A CN202010804075A CN112011042B CN 112011042 B CN112011042 B CN 112011042B CN 202010804075 A CN202010804075 A CN 202010804075A CN 112011042 B CN112011042 B CN 112011042B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
Abstract
The preparation method of the high molecular weight low viscosity polyether polyol provided by the invention comprises the following steps: mixing an initiator, DMC and protonic acid, introducing an initiating amount of epoxy compound under inert atmosphere to initiate reaction, then continuously introducing the rest epoxy compound to control the temperature of a reaction system to be 140-155 ℃, keeping the pressure floating of the reaction system to be less than 0.2MPa, aging after the introduction is finished, and degassing to obtain high-molecular-weight low-viscosity polyether polyol; wherein the equivalent molecular weight of the initiator is greater than 100g/mol less than the equivalent molecular weight of the high molecular weight low viscosity polyether polyol. The temperature of the reaction system is controlled between 140 and 155 ℃, and the pressure floating in the system is kept to be less than 0.2MPa, so that the prepared polyether polyol has the characteristics of high molecular weight, low viscosity, uniform molecular weight distribution and narrow pressure difference range at higher reaction temperature.
Description
Technical Field
The invention relates to the technical field of polyether polyol, in particular to a preparation method of high molecular weight low viscosity polyether polyol.
Background
Polyether polyol synthesized by DMC catalysis mostly has the advantages of low unsaturation degree, narrow molecular weight distribution and the like. Therefore, polyether polyol synthesized by DMC catalysis is widely used in the field of polyurethane elastomer material synthesis, the viscosity of the polyether polyol is required to be high in the use process, the polyether polyol is easier to operate in the use process due to the relatively low viscosity, and the polyether polyol and isocyanate react uniformly due to uniform molecular weight distribution. It is therefore desirable to reduce the viscosity of the polyether polyols as much as possible while ensuring a narrow molecular weight.
However, as the molecular weight of the polyether polyol produced increases, for example, 4000 or more in equivalent molecular weight, the high molecular weight tailing phenomenon becomes more serious, so that the viscosity of the polyether polyol tends to rapidly increase; thereby limiting the later use of polyether polyols.
Based on the above problems, chinese patent document CN108070082a discloses a process for preparing a relatively low viscosity high molecular weight polyether polyol, comprising the steps of:
1) Adding an initial initiator (polyoxypropylene propylene glycol ether and/or polyoxypropylene glycerol ether), an unactivated multimetal cyanide complex catalyst and protonic acid into a reaction kettle, heating, and then introducing inert gas for bubbling and degassing;
2) Continuously introducing inert gas into the reaction kettle to ensure that the pressure in the reaction kettle is positive;
3) Epoxide is added to initiate the multimetal cyanide complex catalyst;
4) Epoxide and a small molecule initiator (ethylene glycol, propylene glycol and the like) are added to carry out polymerization reaction;
5) Aging, and vacuum degassing to obtain the polyether polyol.
By adding the small molecular initiator at the same time when the epoxide is added, the viscosity of the prepared polyether polyol is obviously reduced compared with the polyether polyol with the same molecular weight prepared without adding the small molecular initiator. However, the addition of small molecule initiators places higher demands on the reaction equipment: the small molecular initiator must be added by a matched pipeline and feeding equipment; and the small molecular initiator can be inevitably taken as an initiator to participate in the reaction, so that the molecular weight of the mixed initiator is reduced, the amount of the epoxy compound which is subsequently introduced is increased, the amplifying capacity of the reaction kettle is exceeded, and the large-scale industrial production is not facilitated.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the equipment requirement is high and the large-scale industrial production is not favored when the polyether polyol with high molecular weight and low viscosity is synthesized in the prior art, thereby providing the preparation method of the polyether polyol with high molecular weight and low viscosity.
Therefore, the invention provides the following technical scheme:
a process for preparing a high molecular weight low viscosity polyether polyol comprising the steps of:
mixing an initiator, DMC and protonic acid, introducing an initiating amount of epoxy compound under inert atmosphere to initiate reaction, then continuously introducing the rest epoxy compound to control the temperature of a reaction system to be 140-155 ℃, keeping the pressure floating in the reaction system to be less than 0.2MPa, and aging and degassing after the introduction to prepare the high molecular weight low viscosity polyether polyol;
wherein the equivalent molecular weight of the initiator is greater than 100g/mol less than the equivalent molecular weight of the high molecular weight low viscosity polyether polyol.
Wherein: equivalent molecular weight=56100/hydroxyl number, the unit of hydroxyl number being mgKOH/g;
the DMC is a double metal cyanide complex catalyst.
Further, the pressure of the reaction system is 0.4MPa or less. That is, the pressure difference (i.e., pressure floating) is controlled to be less than or equal to 0.2MPa in the polymerization reaction process, so long as the operation pressure allowed by the equipment is less than or equal to 0.4 MPa.
Further, in the process of introducing the residual epoxy compound, the pressure in the system is kept to be floating less than 0.15MPa.
Further, the pressure in the system is kept floating by less than 0.1MPa during the introduction of the remaining epoxy compound.
Further, the initiator is a polyether polyol having a functionality of 1 to 8.
The implementation of the scheme of the present invention can be satisfied as long as the equivalent molecular weight is more than 100g/mol and less than that of the objective product (equivalent molecular weight of the finally produced high molecular weight low viscosity polyether polyol). For example, the initiator polyether polyol may alternatively be D204 (difunctional polyether polyol, equivalent molecular weight 200G/mol), G305 (trifunctional polyether polyol, equivalent molecular weight 167G/mol), or the like.
Further, the protonic acid is one or a mixture of nitric acid, phosphoric acid and sulfuric acid.
Further, the epoxy compound is one or more of propylene oxide, ethylene oxide and butylene oxide;
the inert atmosphere is one or more of nitrogen, carbon dioxide, helium and argon.
Further, after mixing the starter, DMC and protonic acid, heating to 60-155 ℃, then introducing inert gas to carry out vacuum bubbling degassing, wherein the degassing pressure is below-0.085 MPa, and the degassing time is 30-120min.
Further, DMC is 30-100 ppm of the mass of the epoxy compound, and protonic acid is 40-200 ppm of the mass of the initiator.
Further, aging is carried out until the system pressure is kept unchanged for 25-35 min, and then degassing is carried out for 30-120min at 80-155 ℃ and below-0.085 MPa.
The invention also provides the polyether polyol prepared by the preparation method of the high molecular weight low viscosity polyether polyol.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the high molecular weight low viscosity polyether polyol, provided by the invention, in the process of continuously introducing the residual epoxy compound, the temperature of a reaction system is controlled to be 140-155 ℃, and the pressure floating in the system is kept to be less than 0.2MPa, so that the prepared high molecular weight polyether polyol has the characteristics of low viscosity, low unsaturation degree, uniform molecular weight distribution and narrow pressure difference in a relatively high reaction temperature and relatively narrow pressure difference range; meanwhile, as the reaction temperature and pressure conditions are mild, the requirements on equipment in the preparation process are reduced, and common reaction equipment can meet the implementation of the scheme, thereby being beneficial to large-scale industrial production.
2. The preparation method of the high molecular weight low viscosity polyether polyol provided by the invention can obviously reduce the viscosity and the polydispersity of the prepared high molecular weight polyether polyol by further limiting the pressure floating in a system to be less than 0.15MPa or 0.1MPa.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Existing double metal cyanide complex catalysts can meet the embodiments of the scheme in the invention; however, for convenience of comparison, zinc hexacyanocobaltate was used as the double metal cyanide complex catalyst (DMC) in each of the following examples and comparative examples.
The aim of the degassing process of introducing nitrogen in the following embodiment of the invention is to remove trace water and air, so that the degassing time of the whole reaction system is generally 30-120min under the nitrogen atmosphere according to the requirements of the volume of a reaction kettle, the addition amount of raw materials and the like on the premise of meeting the requirements.
Example 1
This example provides a method for preparing propylene glycol polyoxypropylene ether
50g of initiator (D204 is adopted in the embodiment) and 0.087g of zinc hexacyanocobaltate are put into a 2L stainless steel reaction kettle at room temperature, phosphoric acid is added to make the mass of the phosphoric acid 80ppm of the initiator, then the reaction kettle is sealed, the pressure is maintained, leakage replacement is tried out, vacuum pumping is carried out, nitrogen is introduced after the temperature is raised to 140 ℃, the pressure is maintained at-0.095 MPa, and the whole reaction kettle is degassed under the nitrogen atmosphere;
then 30g of propylene oxide is introduced under the pressure of minus 0.1MPa, zinc hexacyanocobaltate is initiated to react (at the moment, the pressure of the reaction kettle is obviously reduced, the temperature is obviously increased), 1420g of propylene oxide is continuously introduced into the reaction kettle, the reaction temperature is controlled between 140 and 145 ℃, the pressure of a reaction system is controlled between minus 0.1 and 0.05MPa, so that the pressure floating in the reaction system is kept to be less than 0.15MPa, after the propylene oxide is introduced, the reaction kettle is aged until the pressure is kept for 30min without reducing, then the reaction kettle is degassed for 30min under the pressure of minus 130 to 140 ℃ and minus 0.095MPa, redundant water and unreacted propylene oxide are removed, and the reaction kettle is cooled to 80 to 90 ℃ and discharged, thus obtaining the propylene glycol polyoxypropylene ether.
Example 2
This example provides a method for preparing propylene glycol polyoxypropylene ether
50.03g of initiator (D204 is adopted in the embodiment) and 0.087g of zinc hexacyanocobaltate are put into a 2L stainless steel reaction kettle at room temperature, phosphoric acid is added to make the mass of the phosphoric acid 80ppm of the initiator, then the reaction kettle is sealed, the pressure is maintained, leakage is replaced, vacuum pumping is carried out, nitrogen is introduced after the temperature is raised to 140 ℃, the pressure is maintained at-0.095 MPa, and the whole reaction kettle is degassed under nitrogen atmosphere;
then 30g of propylene oxide is introduced under the pressure of minus 0.1MPa to trigger zinc hexacyanocobaltate to react (the pressure of the reaction kettle is obviously reduced and the temperature is obviously increased); continuously introducing 1420g of propylene oxide into a reaction kettle, controlling the reaction temperature to 140-145 ℃, controlling the pressure of a reaction system to be minus 0.1-0 Mpa so as to keep the pressure floating in the reaction system to be less than 0.1Mpa, aging until the pressure in the reaction kettle is kept unchanged for 30min after the propylene oxide is introduced, then degassing for 30min at 130-140 ℃ and minus 0.095Mpa to remove redundant water and unreacted propylene oxide, cooling to 80-90 ℃ and discharging to obtain the propylene glycol polyoxypropylene ether.
Example 3
This example provides a method for preparing glycerol polyoxypropylene ether
At room temperature, 37.5G of initiator (G305 is adopted in the embodiment) and 0.088G of zinc hexacyanocobaltate are put into a 2L stainless steel reaction kettle, phosphoric acid is added to make the mass of the phosphoric acid 80ppm of the initiator, then the reaction kettle is sealed, the pressure is maintained, leakage is replaced, vacuum pumping is carried out, nitrogen is introduced after the temperature is raised to 140 ℃, the pressure is maintained at-0.095 MPa, and the whole reaction kettle is degassed under nitrogen atmosphere;
then 23g of propylene oxide is introduced under the pressure of minus 0.1MPa to trigger zinc hexacyanocobaltate to react (the pressure of the reaction kettle is obviously reduced and the temperature is obviously increased); continuously introducing 1432.5g of propylene oxide into the reaction kettle, controlling the reaction temperature to 140-145 ℃, controlling the pressure of a reaction system to be minus 0.1-0.05 Mpa so as to keep the pressure floating in the reaction system to be less than 0.15Mpa, aging until the pressure in the reaction kettle is kept unchanged for 30min after the propylene oxide is introduced, then degassing for 60min at 130-140 ℃ and minus 0.095Mpa to remove redundant water and unreacted propylene oxide, cooling to 80-90 ℃ and discharging to obtain the glycerol polyoxypropylene ether.
Comparative example 1
This comparative example provides a process for preparing propylene glycol polyoxypropylene ether
50g of initiator (D204 is adopted in the embodiment) and 0.087g of zinc hexacyanocobaltate are put into a 2L stainless steel reaction kettle at room temperature, phosphoric acid is added to make the mass of the phosphoric acid 80ppm of the initiator, then the reaction kettle is sealed, the pressure is maintained, leakage replacement is tried out, vacuum pumping is carried out, nitrogen is introduced after the temperature is raised to 140 ℃, the pressure is maintained at-0.095 MPa, and the whole reaction kettle is degassed under the nitrogen atmosphere;
then introducing 30g of propylene oxide under-0.1 MPa, and observing obvious pressure drop and temperature rise to show that zinc hexacyanocobaltate is initiated; continuously introducing 1420g of propylene oxide into a reaction kettle, controlling the reaction temperature to be 140-145 ℃, controlling the pressure of a reaction system to be minus 0.1-0.15 Mpa so as to keep the pressure floating in the reaction system to be less than 0.25Mpa, aging until the pressure in the reaction kettle is kept unchanged for 30min after the propylene oxide is introduced, then degassing for 30min at 130-140 ℃ and minus 0.095Mpa to remove redundant water and unreacted propylene oxide, cooling to 80-90 ℃ and discharging to obtain the propylene glycol polyoxypropylene ether.
Comparative example 2
This comparative example provides a process for preparing propylene glycol polyoxypropylene ether
50g of zinc hexacyanocobaltate (D204 is adopted in the embodiment) and 0.087g of phosphoric acid are put into a 2L stainless steel reaction kettle at room temperature, phosphoric acid is added to make the mass of the phosphoric acid 80ppm of that of an initiator, then the reaction kettle is sealed, pressure maintaining and leakage test are carried out for replacement, vacuum pumping is carried out, nitrogen is introduced after the temperature is raised to 140 ℃, the pressure is kept at-0.095 MPa, and degassing is carried out to make the whole reaction kettle under the nitrogen atmosphere;
then introducing 30g of propylene oxide under-0.1 MPa, and observing obvious pressure drop and temperature rise to show that zinc hexacyanocobaltate is initiated; continuously introducing 1420g of propylene oxide into a reaction kettle, controlling the reaction temperature to be 130-135 ℃, controlling the pressure of a reaction system to be minus 0.1-0.05 Mpa so as to keep the pressure floating in the reaction system to be less than 0.15Mpa, aging until the pressure in the reaction kettle is kept unchanged for 30min after the propylene oxide is introduced, then degassing for 30min at 130-135 ℃ and minus 0.095Mpa to remove redundant water and unreacted propylene oxide, cooling to 80-90 ℃ and discharging to obtain the propylene glycol polyoxypropylene ether.
Experimental example
The polyether polyols prepared in each of the examples and comparative examples were each tested for hydroxyl number, water content, viscosity and polydispersity, and the specific test results are shown in the following table.
The calculation method of the equivalent molecular weight is 56100/hydroxyl value, and the unit of the hydroxyl value is mgKOH/g;
the method for testing the hydroxyl value is the method A to the method of phthalic anhydride in GB/T12008.3;
the water content test method is according to the method B (automatic titration) instrument test method in GB/T22313;
viscosity test method according to method B-rotational viscosity method in GB/T12008.7;
the polydispersity was measured by gel permeation chromatography with tetrahydrofuran as eluent and a flow rate of 1.0mL/min with a chromatographic column
HR 0.5THF, polystyrene standard, and differential reflectance detector.
Table 1 test results
As can be seen from the data in the above table, the technical scheme of the invention is that the high molecular weight polyether polyol prepared by simultaneously controlling the polymerization reaction pressure difference of the reaction system to be less than 0.2MPa and the reaction temperature to be 140-155 ℃ has low viscosity and narrow polydispersity.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (8)
1. A process for preparing a high molecular weight, low viscosity polyether polyol comprising the steps of:
mixing an initiator, DMC and protonic acid, introducing an initiating amount of epoxy compound under an inert atmosphere to initiate a reaction, then continuously introducing the rest epoxy compound to control the temperature of a reaction system to 140-155 ℃, keeping the pressure floating in the reaction system to be less than 0.15MPa, and aging and degassing after the introduction to prepare the high molecular weight low viscosity polyether polyol;
wherein the equivalent molecular weight of the initiator is greater than 100g/mol less than the equivalent molecular weight of the high molecular weight low viscosity polyether polyol;
the initiator is a polyether polyol having a functionality of 2.
2. The method for producing a high molecular weight low viscosity polyether polyol according to claim 1, wherein the pressure in the system is kept floating by less than 0.1MPa during the introduction of the remaining epoxy compound.
3. The method for producing a high molecular weight low viscosity polyether polyol according to claim 1, wherein the protonic acid is one or more of nitric acid, phosphoric acid and sulfuric acid.
4. The method for producing a high molecular weight low viscosity polyether polyol according to claim 1, wherein the epoxy compound is a mixture of one or more of propylene oxide, ethylene oxide and butylene oxide;
the inert atmosphere is one or more of nitrogen, carbon dioxide, helium and argon.
5. The method for preparing a high molecular weight low viscosity polyether polyol according to any one of claims 1 to 4, wherein the temperature is raised to 60 to 155 ℃ after mixing the starter, DMC and protonic acid, and then inert gas is introduced for vacuum bubbling and degassing, the degassing pressure is below-0.085 MPa, and the degassing time is 30 to 120min.
6. The method for preparing a high molecular weight low viscosity polyether polyol according to claim 1, wherein DMC is 30 to 100ppm by mass of an epoxy compound and protonic acid is 40 to 200ppm by mass of an initiator.
7. The method for preparing the high molecular weight low viscosity polyether polyol according to claim 1, wherein the aging is carried out for 30-120min at 80-155 ℃ and minus 0.085MPa after the system pressure is kept constant for 25-35 min.
8. A polyether polyol produced by the process for producing a high molecular weight low viscosity polyether polyol according to any one of claims 1 to 7.
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