CN111518268A - Preparation method of polyether polyol - Google Patents
Preparation method of polyether polyol Download PDFInfo
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- CN111518268A CN111518268A CN202010466780.4A CN202010466780A CN111518268A CN 111518268 A CN111518268 A CN 111518268A CN 202010466780 A CN202010466780 A CN 202010466780A CN 111518268 A CN111518268 A CN 111518268A
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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
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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
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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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
- C08G65/2696—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 process or apparatus used
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Abstract
The invention relates to a method for preparing high molecular weight polyether polyol, wherein the method comprises the following steps: 1) adding a first part of epoxy compound into the mixture of the treated inorganic acid, the bimetallic catalyst and the first part of low molecular weight polyether for induced polymerization to prepare a polyether polyol intermediate containing an active catalyst; 2) adding a second part of epoxy compound into the polyether polyol intermediate, and mixing for later use; 3) treating a second part of low molecular weight polyether, and then adding the mixture prepared in the step 2) to perform polymerization reaction; 4) continuing to add a third portion of epoxy compound according to the amount of epoxy compound required for preparing the theoretical molecular weight of the polyether polyol to carry out polymerization; 5) aging and removing the monomer to obtain the polyether polyol. The polyether polyol with low viscosity and narrow distribution can be obtained by the method.
Description
Technical Field
The invention relates to the field of polyether polyol synthesis, in particular to a method for preparing polyether polyol.
Background
The DMC catalyst is adopted to prepare polyether polyol, which is a process route recognized in the industry and has higher economic value, and the prepared product has obvious advantages in the aspects of molecular weight distribution and unsaturation degree, and is widely used for producing Case polyether at present. However, the DMC catalyst inevitably has the phenomenon of ultrahigh molecular weight tailing, and is particularly obvious when high molecular weight polyether is prepared, so that the product viscosity is obviously increased, the molecular weight distribution is widened, and the application of the DMC catalyst in the downstream field is severely limited.
Patent CN103635506B provides a process for preparing polyether polyols having an equivalent molecular weight of 8000-20000mg/mol, preferably 9000-20000mg/mol, particularly preferably 10000-16000mg/mol, which process is characterized in that alkylene oxide is metered into the reactor over a period of 15-23 h. The reaction is prolonged by adjusting the feed rate of the alkylene oxide, which is favorable for reducing the viscosity of the product, but the influence of the high molecular components generated in the induction stage on the product cannot be avoided.
Patent CN107200837A provides a method for preparing polyether polyol by using DMC catalyst circulation, which realizes the preparation of intermediate target polyether polyol by using DMC catalyst circulation and the preparation of target polyol by using the intermediate target polyether polyol. The method requires the addition of a small amount of unactivated catalyst and the addition of all the catalyst to the initiator at once results in a higher initial concentration and a tendency to produce high molecular weight components.
Patent CN1138810C provides a method for producing polyether polyol, all the required initiator and catalyst are added into the reactor, and the induction time is shortened by continuously adding a small amount of alkylene oxide during the induction to ensure the constant pressure of the reactor. If the reaction kettle and raw materials are properly prepared, only a short time is needed from the initiation of the catalyst induction to the completion of the catalyst induction, and the pressure stabilization in the induction period by continuously adding the olefinide is difficult to realize.
Patent CN1145655C provides a process for producing polyether polyols having a narrow distribution and a low viscosity by suspending a bimetallic catalyst in an inert suspending agent and activating it with 1-30% of alkylene oxide relative to the total amount of suspending agent and alkylene oxide, and then passing a starter/alkylene oxide mixture. The method for preparing polyether polyol needs to add and remove inert solvent, and increases production cost.
Patent CN108070082A provides a method for preparing polyether polyol with low viscosity and high molecular weight, which comprises, after the successful catalytic induction of the bimetal mixed in the oligomer, adding epoxide and small molecular initiator into the system simultaneously, aging and degassing to obtain polyether polyol. The addition of epoxy compounds with small molecule alcohols is advantageous for the preparation of low viscosity products, but the patent still suffers from the presence of very high molecular weight tails due to the induction process and high initial catalyst concentrations.
In order to solve the above-mentioned technical disadvantages, it is necessary to find a novel preparation process for providing a high molecular weight polyether polyol having a low viscosity and a narrow distribution.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a process for the preparation of a polyether polyol, preferably a polymeric polyether polyol. The method adopts a pre-activation catalyst mode to carry out induction activation on the catalyst, and adds the epoxy compound into the polyether polyol intermediate, thereby effectively reducing the catalyst concentration of the system in the reaction process, and in addition, the polyether polyol intermediate continuously participates in the reaction, and the polyether polyol with low viscosity and narrow distribution can be ensured to be obtained.
In order to achieve the above object, the present invention provides a method for preparing polyether polyol, comprising the steps of:
1) carrying out nitrogen replacement, gas stripping and dehydration on a mixture of inorganic acid, a bimetallic catalyst and a first part of low molecular weight polyether, then adding a first part of epoxy compound (a) into the mixture for induction so as to activate the catalyst, and further adding a first part of epoxy compound (b) into the mixture for polymerization so as to prepare a polyether polyol intermediate containing an active catalyst;
2) adding a second part of epoxy compound into the polyether polyol intermediate, and mixing for later use;
3) feeding a second part of low molecular weight polyether into the mixture prepared in the step 2) to perform polymerization reaction;
4) continuing to add a third portion of epoxy compound according to the amount of epoxy compound required for preparing the theoretical molecular weight of the polyether polyol to carry out polymerization;
5) aging and removing the monomer to obtain the polyether polyol.
In this context, it will be understood by those skilled in the art that in said step 4), the "amount of epoxy compound required for the theoretical molecular weight of said polyether polyol" refers to the amount of epoxy compound that needs to be consumed for the reaction of the epoxy compound with an amount of low molecular weight polyether or polyether polyol intermediate to form said polyether polyol, in case the charged epoxy compound has completely reacted with the low molecular weight polyether or the formed polyether polyol intermediate.
In this context, the aging step can be adjusted accordingly by the person skilled in the art, as the case may be, by aging with residual consumption of epoxide; preferably, the aging can be carried out by a step of continuously maintaining the original reaction temperature after the addition of the epoxy compound, and the stirring speed for 15min to 1h, preferably 30 min.
In this context, by removing monomers to remove fully reacted monomers from the product, the skilled person can adapt the removal step accordingly to the actual situation; preferably, the demonomerization can be carried out by turning on a vacuum pump after the aging is finished, controlling the pressure to be < -0.085MPa, and maintaining the pressure for 0.5-1 h.
In one embodiment, the low molecular weight polyether has a number average molecular weight of no more than 4000, for example 400-; for example, the low molecular weight polyether may be a homopolymer, a random polymer, or a block polymer prepared by mixing one or more of propylene oxide, ethylene oxide, propylene oxide, and butylene oxide, starting with a mixture of one or more of ethylene glycol, propylene glycol, glycerol, TMP, pentaerythritol, and sorbitol.
In one embodiment, in step 1), the inorganic acid is one of phosphoric acid and sulfuric acid, or a mixture of phosphoric acid and sulfuric acid mixed in any ratio. In the present invention, the amount of mineral acid used depends mainly on the amount of low molecular weight polyether of the first fraction. The inorganic acid is in the range of from 30 to 300ppm, preferably from 50 to 150ppm, such as 65ppm, 80ppm or 100ppm, based on the weight of the first portion of low molecular weight polyether.
In the present invention, the bimetallic catalyst is not particularly limited as long as it is a bimetallic catalyst commonly used in the art for catalyzing ring opening of epoxy compounds to prepare polyethers.
In one embodiment, in step 1), the bimetallic catalyst is selected from one or more of the group consisting of zinc hexacyanocobaltate type, and cobalt hexacyanocobaltate type bimetallic catalysts, such as zinc hexacyanocobaltate type. The bimetallic catalyst is 200-2000ppm, preferably 400-1500ppm, such as 540ppm, 1100ppm, based on the total weight of the first portion of the low molecular weight polyether and the first portion of the epoxy compound.
In one embodiment, the oxirane compound is propylene oxide or a mixture of ethylene oxide and propylene oxide, where the mass fraction of ethylene oxide is < 90%. The epoxy compounds charged in the steps 1) to 5) may be the same or different, for example, the same.
In this context, X ppm of a substance is to be understood as X parts per million of the substance based on the mass of the total solution; for example, 30-300ppm of mineral acid based on the weight of the first portion of low molecular weight polyether means that the mass of mineral acid is from thirty to three hundred parts per million based on the weight of the first portion of low molecular weight polyether; the bimetallic catalyst is 200-2000ppm based on the total weight of the first portion of the low molecular weight polyether and the first portion of the epoxy compound, meaning that the mass of the bimetallic catalyst comprises two hundred to two thousand parts per million based on the total weight of the first portion of the low molecular weight polyether and the first portion of the epoxy compound.
In one embodiment, preferably, the preparation method of the polyether polyol intermediate in the step 1) is:
(a) stirring the mixture of the first part of low molecular weight polyether and the inorganic acid at 800rpm of 500-;
(b) controlling the vacuum degree of the system obtained in the step (a) to be less than 15kpa, preferably less than 5kpa, continuously vacuumizing for 5-15min, preferably 10-15min, introducing nitrogen to the pressure of 150-300kpa, preferably 250-300kpa, and repeating the operation for 2-5 times, preferably 3-4 times;
(c) heating the system treated in the step (b) to 110-150 ℃, preferably 125-145 ℃, introducing nitrogen and simultaneously vacuumizing, controlling the system pressure to be less than 10kpa, keeping for 1-3h, preferably 1.5-2h, and then introducing nitrogen into the system to normal pressure;
(d) maintaining the system temperature after the treatment in the step c at 145 ℃ of 125-;
wherein the sum of the first part epoxy compound (a) and the first part epoxy compound (b) is the first part epoxy compound.
In one embodiment, the first portion of epoxy compounds is used in an amount that is capable of providing the polyether polyol intermediate with a molecular weight that is greater than 1 times and not more than 5 times, preferably 1.5 to 3 times, that of the low molecular weight polyether. Preferably, the first part of the epoxy compound (a) is used in an amount of 2 to 20 wt. -%, preferably 5 to 10 wt. -%, based on the mass of the first part of the low molecular weight polyether. In the present invention, the main purpose of step (1) is to obtain an active catalyst-containing polyether polyol intermediate, which is advantageous in that the finally obtained polyether polyol has a narrow molecular weight distribution. The proportion of the amount of the first portion of low molecular weight polyether to the total amount of low molecular weight polyether (i.e. the sum of the first portion and the second portion of low molecular weight polyether) may be suitably adjusted to the actual situation, e.g. the amount of the first portion of low molecular weight polyether is 30-80%, preferably 45-75%, e.g. 48%, 54% or 62% by weight of the total low molecular weight polyether.
Preferably, in the preparation method described herein, the reaction liquid or reactant obtained in each step is homogeneous.
In one embodiment, the second portion of epoxy compound in step 2) is used in an amount of 60 to 95 weight percent, preferably 75 to 90 weight percent, based on the total weight of epoxy compound (typically, the total weight of the second portion of epoxy compound and the third portion of epoxy compound) required to increase the second portion of low molecular weight polyether and the polyether intermediate obtained in step 1) to a target molecular weight.
It will be understood by those skilled in the art that, in the present invention, the low molecular weight polyether in step 3) is the same as or different from, for example, the low molecular weight polyether in step 1), and both the displacement and stripping dehydration operations can be performed in accordance with steps (b) and (c).
In one embodiment, in step 3), the polymerization temperature is 125-145 ℃, preferably 130-140 ℃. And in the step 3), slowly feeding the mixture prepared in the step 2) into the low molecular weight polyether after displacement and stripping dehydration, wherein the feeding time of the mixture prepared in the step 2) is 5-18h, preferably 8-15 h.
In one embodiment, the feeding time of the third part of the epoxy compound in the step 4) is 2 to 8 hours, preferably 4 to 6 hours, and the reaction temperature is the same as the reaction temperature in the step 1).
In one embodiment, the polyether polyol has a number average molecular weight of 8000-. It will be appreciated by those skilled in the art that the polyether polyol may be synthesized in a continuous process or in a batch process, such as in a batch process.
According to the invention, the catalyst is induced to activate by pre-reaction during preparation of the polyether polyol intermediate with lower molecular weight, so that the induction step during preparation of the polyether polyol with higher molecular weight is avoided, and the influence on polymerization is reduced. Meanwhile, a large amount of epoxy compounds are added into the polyether polyol intermediate, so that the concentration of the system catalyst in the reaction process can be effectively reduced, and in addition, the polyether polyol intermediate continuously participates in the reaction, so that the polyether polyol with low viscosity and narrow distribution can be obtained by adopting an intermittent process, and the number average molecular weight can reach 8000-. The polyether polyol prepared by the invention can be used as basic polyether for preparing silane-terminated polyether and can be used in the field of adhesives and sealants.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The raw material sources are as follows:
the low molecular weight polyether and the propylene oxide are from Wanhua chemical group, Inc., and the phosphoric acid, the sulfuric acid and the ethylene oxide are from national medicine group, chemical reagent, Inc.;
the bimetallic catalyst is synthesized by the following method:
at the rotation speed of 1500rpm, 25g of zinc chloride is added into 200ml of aqueous solution containing 8g of potassium cobalt cyanate to obtain suspension, and then 100g of tert-butyl alcohol and 100g of water are rapidly added, and stirring is carried out for 30 min. Adding a mixture of 2g of polypropylene glycol with number average molecular weight of 2000, 10g of tert-butyl alcohol and 100g of water into the suspension, stirring for 10min, filtering to obtain a solid, and washing the solid with an aqueous isopropanol solution to K+<50ppm, drying and grinding to obtainObtaining the powdery zinc-cobalt bimetallic catalyst.
The method is the same as the above catalyst synthesis method, except that the potassium cobalt cyanate is replaced by potassium ferricyanate to obtain the zinc-iron type bimetallic catalyst.
In the following examples and comparative examples, the catalysts used in example 2 and comparative example 2 were zinc-iron type bimetallic catalysts, and the rest were zinc-cobalt type bimetallic catalysts. In the following examples and comparative examples, reagents used were analytical grade unless otherwise specified.
The test method comprises the following steps:
the hydroxyl value is measured according to GB/T12008.3-2009; the viscosity is measured according to GB/T12008.7-2010; the molecular weight distribution was obtained by GPC testing: PS is used as a marked line, two pieces of PolyPore are used in series, the sample injection volume is 20ul, and the running time is 45 min.
Example 1
600g of propylene glycol polyoxypropylene ether having a number average molecular weight of 400 was mixed with 0.03g of phosphoric acid at 500rpm for 3min, 0.68g of a bimetallic catalyst was added thereto, mixed and stirred at 1000rpm for 5min, and then the whole was added to the reaction vessel. Controlling the vacuum degree of the system to be 15kpa, continuously vacuumizing for 5min, then introducing nitrogen into the system until the pressure is 150kpa, and repeating the steps for 3 times to complete the replacement; heating to 110 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 1h, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; raising the temperature to 125 ℃, adding 30g of propylene oxide, finishing induction after the pressure is reduced and the temperature is raised, maintaining the temperature at 125 ℃, continuously introducing 1170g of propylene oxide within 2 hours to obtain polyether homogeneous liquid which contains 375ppm of active catalyst and in which the number average molecular weight of the polyether polyol intermediate is 1200, cooling to 25 ℃, and adding 9135g of propylene oxide for later use.
Adding 150g of propylene glycol polyoxypropylene ether with the number average molecular weight of 400 into another reaction kettle, heating to 125 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 18 hours; 3915g of propylene oxide were then added, taking 8 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 8000. The hydroxyl number tested was 14.38mgKOH/g, the viscosity was 2200cp @25 ℃ and the molecular weight distribution was 1.10.
Example 2
350g of propylene glycol polyoxypropylene ether with the number average molecular weight of 1500 and 0.02g of sulfuric acid are mixed for 5min at 600rpm, 0.46g of bimetallic catalyst is added, mixed and stirred at 1200rpm for 7min, and then the whole material is added into a reaction kettle. Controlling the vacuum degree of the system to be 10kpa, continuously vacuumizing for 8min, and then introducing nitrogen into the system until the pressure is 200kpa, and repeating the steps for 3 times to complete replacement; heating to 120 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 1h, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; heating to 125 deg.C, adding 21g propylene oxide, inducing when the pressure is reduced and the temperature is increased, maintaining at 130 deg.C, continuously introducing 224g propylene oxide within 1h to obtain polyether homogeneous liquid containing 773ppm active catalyst and polyether polyol intermediate with number average molecular weight of 2550, cooling to 25 deg.C, and adding 5854g propylene oxide for use.
Adding 800g of propylene glycol polyoxypropylene ether with the number average molecular weight of 1500 into another reaction kettle, heating to 130 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 7.5 hours; 1951g of propylene oxide were subsequently added, taking 2.5 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 12000. The hydroxyl value tested was 10.12mgKOH/g, the viscosity was 5800cp @25 ℃ and the molecular weight distribution was 1.11.
Example 3
500g of propylene glycol polyoxypropylene ether having a number average molecular weight of 4000 and 0.033g of phosphoric acid were mixed at 800rpm for 5min, 0.83g of a bimetallic catalyst was added thereto, and the mixture was mixed and stirred at 2000rpm for 10min, and then the whole was charged into a reaction vessel. Controlling the vacuum degree of the system to be 10kpa, continuously vacuumizing for 10min, and then introducing nitrogen into the system until the pressure is 300kpa, and repeating the steps for 3 times to complete replacement; heating to 120 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 2 hours, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; heating to 135 deg.C, adding 50g propylene oxide, inducing when the pressure is reduced and the temperature is increased, maintaining at 135 deg.C, continuously introducing 200g propylene oxide within 1h to obtain polyether homogeneous liquid containing 1100ppm active catalyst and polyether polyol intermediate with number average molecular weight of 6000, cooling to 25 deg.C, and adding 2905g propylene oxide for use.
Adding 600g of propylene glycol polyoxypropylene ether with the number average molecular weight of 4000 into another reaction kettle, heating to 145 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 5 hours; 1245g of propylene oxide were subsequently added, over 2 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 20000. The hydroxyl number tested was 5.68mgKOH/g, the viscosity was 12600cp @25 ℃ and the molecular weight distribution was 1.21.
Example 4
500g of glycerol polyoxypropylene polyoxyethylene ether with the number average molecular weight of 3000 and 0.051g of phosphoric acid are mixed for 5min at 800rpm, 0.41g of bimetallic catalyst is added, mixed and stirred at 2000rpm for 8min, and then all materials are added into a reaction kettle. Controlling the vacuum degree of the system to be 10kpa, continuously vacuumizing for 10min, and then introducing nitrogen into the system until the pressure is 300kpa, and repeating the steps for 5 times to complete replacement; heating to 120 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 2 hours, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; heating to 130 ℃, adding 40g of propylene oxide, finishing induction after the pressure is reduced and the temperature is increased, maintaining the temperature at 130 ℃, continuously introducing 460g of propylene oxide within 1 hour to obtain polyether homogeneous liquid containing 411ppm of active catalyst and the polyether polyol intermediate with the number average molecular weight of 6000, cooling to 25 ℃, and adding 3413.3g of propylene oxide for later use.
Adding 600g of glycerol polyoxypropylene polyoxyethylene ether with the number average molecular weight of 3000 into another reaction kettle, heating to 135 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 12 hours; 853.3g of propylene oxide were subsequently added, taking 3 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain the polyether polyol with the molecular weight of 16000. The hydroxyl value tested was 10.34mgKOH/g, the viscosity was 7200cp @25 ℃ and the molecular weight distribution was 1.13.
Example 5
450g sorbitol polyoxypropylene ether with number average molecular weight of 750 and 0.068g phosphoric acid are mixed for 3min at 800rpm, 1.71g bimetallic catalyst is added, mixed and stirred for 10min at 1500rpm, and then the whole material is added into a reaction kettle. Controlling the vacuum degree of the system to be less than 5kpa, continuously vacuumizing for 8min, and then introducing nitrogen into the system until the pressure is 300kpa, and repeating the steps for 3 times to complete replacement; heating to 135 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 3 hours, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; heating to 145 ℃, adding 31.5g of propylene oxide, finishing induction after the pressure is reduced and the temperature is increased, maintaining the temperature at 145 ℃, continuously introducing 733.5g of propylene oxide within 2h to obtain polyether homogeneous liquid which contains 1407ppm of active catalyst and in which the number average molecular weight of polyether polyol intermediate is 2025, cooling to 30 ℃, and adding 16868g of propylene oxide for later use.
Adding 500g sorbitol polyoxypropylene ether with the number average molecular weight of 750 into another reaction kettle, heating to 145 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 16 hours; 4217g of propylene oxide were subsequently added, over a period of 8 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 18000. The hydroxyl number tested was 19.24mgKOH/g, the viscosity was 4600cp @25 ℃ and the molecular weight distribution was 1.15.
Example 6
450g of propylene glycol polyoxypropylene ether with the number average molecular weight of 2000 and 0.036g of phosphoric acid are mixed for 5min at 700rpm, 0.53g of bimetallic catalyst is added, mixed and stirred at 1800rpm for 10min, and then the whole material is added into a reaction kettle. Controlling the vacuum degree of the system to be less than 5kpa, continuously vacuumizing for 10min, and then introducing nitrogen into the system until the pressure is 300kpa, and repeating the steps for 5 times to complete replacement; raising the temperature to 140 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 2.5 hours, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; raising the temperature to 135 ℃, adding 45g of propylene oxide and ethylene oxide mixture, wherein the mass ratio of ethylene oxide in the mixture is 75%, finishing the induction after the pressure is reduced and the temperature is raised, maintaining the temperature at 135 ℃, continuously introducing 720g of epoxy compound within 2h to obtain the polyether homogeneous liquid which contains 431ppm of active catalyst and in which the number average molecular weight of the polyether polyol intermediate is 5400, reducing the temperature to 25 ℃, and adding 3168g of epoxy compound for later use.
Adding 480g of propylene glycol polyoxypropylene ether with the number average molecular weight of 2000 into another reaction kettle, heating to 140 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 6.2 hours; 2112g of epoxy compound are subsequently added, taking 3.5 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 15000. The hydroxyl value tested was 7.62mgKOH/g, the viscosity was 7600cp @25 ℃ and the molecular weight distribution was 1.16.
The comparative example is the same as the corresponding examples in terms of low molecular weight polyether, epoxy compound, reaction temperature, catalyst and acid concentration, and amount of induced PO, and the epoxy compound feed time in the comparative example is the same as the feed time of the polyether homogeneous liquid containing the active catalyst in the corresponding example.
Comparative example 1
500g of propylene glycol polyoxypropylene ether having a number average molecular weight of 400 was mixed with 0.025g of phosphoric acid at 500rpm for 3min, 0.36g of a bimetallic catalyst was added thereto at 1000rpm, and the mixture was stirred for 5min, and then the whole was charged into a reaction vessel. Controlling the vacuum degree of the system to be 15kpa, continuously vacuumizing for 5min, and then introducing nitrogen into the system until the pressure is 150kpa, and repeating the steps for 3 times to complete replacement; heating to 110 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 1h, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; heating to 125 deg.C, adding 25g propylene oxide, inducing when the pressure is reduced and the temperature is increased, maintaining 125 deg.C, continuously introducing 9475g propylene oxide for 18h, maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 8000. The hydroxyl value tested was 15.21mgKOH/g, the viscosity was 3640cp @25 ℃ and the molecular weight distribution was 1.20.
Comparative examples 2, 3, 4, 5, 6 were completed according to the method in comparative example 1 and the corresponding example process, wherein the starting materials and amounts of comparative examples 2, 3, 4, 5, 6 are given in table 1 below:
comparative example 7
500g of propylene glycol polyoxypropylene ether having a number average molecular weight of 400 was mixed with 0.025g of phosphoric acid at 500rpm for 3min, 0.81g of a bimetallic catalyst was added thereto at 1000rpm, and the mixture was stirred for 5min and then the whole was added to the reaction vessel. Controlling the vacuum degree of the system to be 15kpa, continuously vacuumizing for 5min, then introducing nitrogen into the system until the pressure is 150kpa, and repeating the steps for 3 times to complete the replacement; heating to 110 ℃, introducing nitrogen, starting a vacuum pump to control the system pressure to be less than 10kpa, continuing for 1h, finishing gas stripping dehydration, and introducing nitrogen into the system to normal pressure; heating to 125 ℃, adding 25g of propylene oxide, finishing induction after the pressure is reduced and the temperature is increased, maintaining the temperature at 125 ℃, continuously introducing 3475g of propylene oxide within 7.5h to obtain polyether homogeneous liquid which contains 202ppm of active catalyst and in which the number average molecular weight of the polyether polyol intermediate is 3200, cooling to 25 ℃, and adding 9520g of propylene oxide for later use.
Adding 400g of propylene glycol polyoxypropylene ether with the number average molecular weight of 400 into another reaction kettle, heating to 125 ℃ after replacement, gas stripping and dehydration, and continuously adding the polyether homogeneous phase liquid containing the active catalyst into the reaction kettle for 18 hours; 4080g of propylene oxide without active catalyst were subsequently added over a period of 7 h. Maintaining the reaction temperature, aging for 30min, and removing unreacted propylene oxide to obtain polyether polyol with molecular weight of 8000. The hydroxyl value tested was 14.96mgKOH/g, the viscosity was 3800cp @25 ℃ and the molecular weight distribution was 1.28.
The product indices for each example and each comparative example are given in table 2 below:
TABLE 2 indexes of products of examples and comparative examples
In comparative example 7, the molecular weight of the polyether polyol intermediate was increased 8 times that of the low molecular weight polyether, and the product obtained had an increased viscosity and a broadened molecular weight distribution (PDI) as compared with the product obtained in example 1. It is also clear from comparative examples 2 to 6 that the high molecular weight polyethers obtained by the present invention have significant advantages in terms of viscosity and molecular weight distribution over the comparative examples compared to polyethers obtained by conventional routes.
In conclusion, the preparation of the high molecular weight polyether polyol by adopting the method has obvious advantages in the aspects of hydroxyl value, viscosity, molecular weight distribution and the like, and the method can be realized by a batch process.
Claims (10)
1. A method of preparing a polyether polyol comprising the steps of:
1) adding a first part of epoxy compound into a mixture of inorganic acid, a bimetallic catalyst and a first part of low molecular weight polyether for induction and polymerization to prepare a polyether polyol intermediate containing an active catalyst;
2) adding a second part of epoxy compound into the polyether polyol intermediate, and mixing for later use;
3) feeding a second part of low molecular weight polyether into the mixture prepared in the step 2) to perform polymerization reaction;
4) continuing to add a third portion of epoxy compound according to the amount of epoxy compound required for preparing the theoretical molecular weight of the polyether polyol to carry out polymerization;
5) aging and removing the monomer to obtain the polyether polyol.
2. Process for the preparation of polyether polyols according to claim 1, wherein the amount of the first portion of epoxy compounds is such that the molecular weight of the polyether polyol intermediate is more than 1 times and not more than 5 times, preferably 1.5 to 3 times, that of the first portion of low molecular weight polyether.
3. Process for the preparation of polyether polyols according to claim 1 or 2, characterized in that the amount of the second part of epoxy compounds in step 2) is 60-95 wt. -%, preferably 75-90 wt. -%, based on the total weight of the second part of epoxy compounds and the third part of epoxy compounds.
4. The process for the preparation of polyether polyols according to any one of claims 1 to 3, wherein the number average molecular weight of the low molecular weight polyether of the first and second portions is 400-4000, preferably 400-3000;
preferably, in step 1), the first part of low molecular weight polyether is subjected to nitrogen displacement and stripping dehydration before reaction, and in step 3), the second part of low molecular weight polyether is subjected to nitrogen displacement and stripping dehydration before addition;
preferably, the first portion of low molecular weight polyether is used in an amount of 30 to 80%, preferably 45 to 75% by weight of the total low molecular weight polyether.
5. The method for producing polyether polyol according to any one of claims 1 to 4, wherein the inorganic acid is one of phosphoric acid and sulfuric acid, or a mixture of phosphoric acid and sulfuric acid mixed in any ratio; preferably, the inorganic acid is from 30 to 300ppm, preferably from 50 to 150ppm, based on the weight of the first portion of the low molecular weight polyether;
the bimetallic catalyst is selected from one or more of zinc hexacyanocobaltate type, zinc hexacyanocobaltate type and cobalt hexacyanocobaltate type bimetallic catalysts, preferably zinc hexacyanocobaltate type; preferably, the bimetallic catalyst is 200-2000ppm, preferably 400-1500ppm, based on the total weight of the first portion of the low molecular weight polyether and the first portion of the epoxy compound.
6. Process for the preparation of polyether polyols according to any one of claims 1 to 5, characterized in that the first, second or third epoxide compound is propylene oxide or a mixture of ethylene oxide and propylene oxide, wherein the mass fraction of ethylene oxide is < 90% in the case of a mixture of ethylene oxide and propylene oxide.
7. The process for the preparation of a polyether polyol as claimed in any one of claims 1 to 6, wherein in step 3), the polymerization temperature is 125-145 ℃, preferably 130-140 ℃;
the feeding time of the mixture prepared in the step 2) is 5-18h, preferably 8-15 h;
the feeding time of the third part of the epoxy compound in the step 4) is 2 to 8 hours, preferably 4 to 6 hours, and the reaction temperature is consistent with the polymerization reaction temperature in the step 1).
8. The preparation method according to any one of claims 1 to 7, characterized in that the polyether polyol has a number average molecular weight of 8000-.
9. Process for the preparation of polyether polyols according to any of the preceding claims, characterized in that the process for the preparation of the polyether polyol intermediate in step 1) is:
(a) stirring the mixture of the first part of low molecular weight polyether and the inorganic acid at 800rpm of 500-;
(b) controlling the vacuum degree of the system obtained in the step (a) to be less than 15kpa, preferably less than 5kpa, continuously vacuumizing for 5-15min, preferably 10-15min, introducing nitrogen to the pressure of 150-300kpa, preferably 250-300kpa, and repeating the operation for 2-5 times, preferably 3-4 times;
(c) heating the system treated in the step (b) to 110-150 ℃, preferably 125-145 ℃, introducing nitrogen and simultaneously vacuumizing, controlling the system pressure to be less than 10kpa, keeping for 1-3h, preferably 1.5-2h, and then introducing nitrogen into the system to normal pressure;
(d) maintaining the system temperature after the treatment in the step (c) at 125-145 ℃, preferably at 130-140 ℃, adding a first part of epoxy compound (a) into the reaction system to induce and activate the bimetallic catalyst, finishing the induction after the system pressure drops and the temperature rises, continuously introducing a first part of epoxy compound (b) to carry out polymerization reaction to obtain a polyether polyol intermediate containing the active catalyst, and cooling to 20-40 ℃, preferably at 25-30 ℃ for later use;
wherein the sum of the first part epoxy compound (a) and the first part epoxy compound (b) is the first part epoxy compound.
10. The process according to claim 9, wherein the first fraction of epoxy compound (a) is used in an amount of 2 to 20 wt. -%, preferably 5 to 10 wt. -%, based on the mass of the first fraction of low molecular weight polyether.
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