CN112679721B - Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol - Google Patents
Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol Download PDFInfo
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Abstract
The invention provides a preparation method of high molecular weight and low viscosity sorbitol-based polyether polyol and the obtained sorbitol-based polyether polyol, wherein the method comprises the following steps: taking solid sorbitol as an initiator and an epoxy compound as a monomer, and polymerizing to obtain a sorbitol-based polyether polyol intermediate product; putting a part of sorbitol-based polyether polyol intermediate product into a reaction container; and mixing the residual sorbitol-based polyether polyol intermediate product with an epoxy compound, and then dripping the mixture into a reaction container for polymerization to obtain the sorbitol-based polyether polyol product. The method reduces the viscosity of the high molecular weight sorbitol polyether polyol, improves the fluidity, improves the condition of uniform mixing of the high molecular weight sorbitol polyether polyol and foaming components, and has narrower molecular weight distribution and lower unsaturation degree under the condition of keeping the functionality unchanged, thereby avoiding poor fluidity caused by overhigh molecular weight in the process of preparing the foam plastic, causing defects of the foaming product and nonuniform foaming due to nonuniform mixing.
Description
Technical Field
The invention relates to preparation of polyether polyol, in particular to preparation of sorbitol-based polyether polyol, and particularly relates to a preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and the obtained polyether polyol.
Background
In the general polyether polyol category, the preparation of polyether by polymerization of ethylene glycol, propylene glycol, glycerin, hexanetriol, pentaerythritol, xylitol and sucrose as initiators with epoxy compounds has been reported, and these polyether products can be used for various applications of soft, semi-soft and rigid foams.
Solid sorbitol is used as a high-functionality initiator, the foam plastic prepared by taking sorbitol polyether as a raw material is superior to products taking glycerol polyether, xylitol polyether and sucrose polyether as bases in the aspects of aging performance, dimensional stability, mechanical performance, softening temperature, oil resistance and the like, and can be used as heat insulation, sound insulation, moisture resistance and structural materials, and particularly, the high-molecular high-functionality sorbitol polyether can effectively improve the fineness of foam pores, improve the dimensional stability of the foam and enhance the openness of the foam.
The current general preparation process of 6-functionality sorbitol polyether is as follows: taking solid sorbitol as an initiator, using a solvent to reduce the viscosity of an initial system, using alkali metal as a catalyst, carrying out polymerization reaction with an epoxy compound at a certain temperature and under a certain pressure to generate crude sorbitol polyether, and then emulsifying, neutralizing, adsorbing and filtering the crude sorbitol polyether polyol to obtain a sorbitol polyether polyol finished product. However, the process cannot prepare high molecular weight sorbitol polyether, and particularly in the later reaction stage, the side reactions are more, so that the molecular weight distribution is wide, the small molecules are more, and the unsaturation degree is high, which all limit the further use of the sorbitol polyether.
At present, in order to obtain sorbitol-based polyether polyol with high molecular weight and high functionality, two-stage reaction is generally required, wherein in the first stage, sorbitol polyether with low molecular weight is prepared by using an alkali metal as a catalyst by using a traditional process, and in the second stage, the sorbitol polyether with low molecular weight is continuously reacted with an epoxy compound by using a bimetallic catalyst to produce the sorbitol-based polyether polyol with high molecular weight and high functionality, but as the molecular weight of polyether is gradually increased, the viscosity of a system is increased in geometric grade, so that the use of the sorbitol-based polyether polyol with high molecular weight and high functionality is not facilitated for downstream customers.
Chinese patent CN102617848A discloses a method for preparing sorbitol-based polyether polyol, wherein a modifier is added during the preparation process to improve the fluidity of sorbitol-based polyether polyol, but the corresponding product functionality is also reduced, which may have a certain influence on the mechanical properties of the foam product.
Chinese patent CN109651609A relates to a preparation method of polyether polyol with high EO content, which adopts a double initiator, adds the initiator by a segmented charging method, and under the action of a catalyst, sequentially and alternately adds propylene oxide and ethylene oxide by a regular interval method to carry out polymerization reaction, thus obtaining the polyether polyol with high EO content. However, this process gives polyether polyols having a broad molecular weight distribution and a functionality of less than 6.
Disclosure of Invention
In order to overcome the problems in the prior art, the traditional second-stage reaction is improved, specifically, a part of sorbitol-based polyether polyol intermediate products obtained in the first-stage reaction are taken and placed in a reaction kettle, the rest of sorbitol-based polyether polyol intermediate products are mixed with an epoxy compound, and the mixture is gradually dripped into the reaction kettle to react at a certain reaction temperature, so that the required sorbitol-based polyether polyol with low viscosity, low unsaturation degree, high molecular weight and high functionality degree can be obtained.
One of the objects of the present invention is to provide a process for preparing a high molecular weight, low viscosity sorbitol based polyether polyol, comprising the steps of:
step 1, taking solid sorbitol as an initiator and an epoxy compound as a monomer, and polymerizing in the presence of an alkali metal catalyst to obtain a sorbitol-based polyether polyol intermediate product;
step 2, taking a part of sorbitol-based polyether polyol intermediate product and placing the intermediate product into a reaction container;
and 3, mixing the residual sorbitol-based polyether polyol intermediate product with an epoxy compound, dripping into the reaction container in the step 2, and polymerizing to obtain the sorbitol-based polyether polyol product.
In the present invention, the solid sorbitol is selected from solid sorbitol and/or crystalline sorbitol.
In a preferred embodiment, the epoxy compound is a compound containing an epoxy group.
Wherein, the epoxy group can be subjected to ring-opening polymerization under certain conditions to obtain the polyether.
In a further preferred embodiment, the epoxide compound is selected from one or more of propylene oxide, ethylene oxide and derivatives thereof, such as propylene oxide and/or ethylene oxide.
The traditional high molecular weight sorbitol-based polyether polyol is prepared by taking solid sorbitol as an initiator and adopting a two-stage polymerization process within a certain pressure and temperature range, and in the second stage process, an epoxy compound is gradually dripped into a reaction kettle containing a sorbitol polyether intermediate product for reaction. However, the high molecular weight polyether produced by the method has higher viscosity and wider molecular weight distribution, and is easy to be mixed with a foaming formula unevenly, so that the foam product has defects. Or, in the traditional process, the micromolecule regulator and the epoxy compound are mixed and then dripped into a reaction kettle containing the sorbitol polyether intermediate product for reaction, although the viscosity of the high molecular weight polyether produced by the method is reduced, the corresponding product functionality is also reduced, and the mechanical property of the foam product is influenced to a certain extent.
Therefore, in order to solve the above problems, the inventors have found through a great deal of experimental studies that, in the second stage of polymerization, if the sorbitol-based polyether polyol intermediate is added to the reaction system in batches, the viscosity of the product can be significantly reduced, the fluidity of the product can be improved, the uniform mixing of the product and the foaming component can be improved, and the molecular weight distribution is narrower and the unsaturation degree is lower under the condition that the functionality is not changed, so that the problems of poor fluidity caused by too high molecular weight in the process of preparing the foam plastic and the defects and uneven foaming of the foaming product caused by uneven mixing can be avoided.
In a preferred embodiment, step 1 is carried out at 70 to 130 ℃, preferably 90 to 110 ℃.
In a preferred embodiment, the molecular weight of the sorbitol polyether polyol intermediate product obtained in the step 1 is 200-1000 g/mol, wherein the moisture content is less than or equal to 0.05%, and the pH value is 5-7.
Wherein, the molecular weight of the intermediate product must be controlled to be about 200-1000 g/mol, and too low and too high can affect the catalytic activity of the bimetallic catalyst in the next step.
In a preferred embodiment, step 1 comprises the following substeps:
step 1-1, in the presence of solid sorbitol, an alkali metal catalyst and an optional solvent, dropwise adding an epoxy compound to a set amount, and removing the solvent after the pressure is not changed any more;
step 1-2, continuously dropwise adding an epoxy compound to a set amount, preferably removing the unreacted epoxy compound after the pressure is not changed any more, and obtaining a crude sorbitol-based polyether polyol intermediate product;
and 1-3, carrying out post-treatment on the crude product of the sorbitol-based polyether polyol intermediate product to obtain the sorbitol-based polyether polyol intermediate product.
In a preferred embodiment, in step 1-1, the alkali metal-based catalyst is selected from one or more of potassium hydroxide, sodium alkoxide, and potassium alkoxide.
In a further preferred embodiment, in step 1-1, the alkali metal-based catalyst is selected from potassium hydroxide and/or sodium hydroxide.
In a preferred embodiment, the alkali metal catalyst used in step 1-1 is used in an amount of 0.2 to 1.0wt%, preferably 0.2 to 0.5wt%, based on 100wt% of the total weight of the solid sorbitol and the epoxy compound used in step 1.
In a preferred embodiment, in step 1, the alkali metal-based catalyst is added in portions, preferably in two portions.
In a further preferred embodiment, a portion of the alkali metal-based catalyst is added in step 1-1, and the remainder of the alkali metal-based catalyst is added in step 1-2.
In a further preferred embodiment, the weight ratio of the part of the alkali metal catalyst added in step 1-1 to the rest of the alkali metal catalyst added in step 1-2 is 1 (5-10), preferably 1 (6-8).
The alkali metal catalyst is added into the reaction system in batches, and a little alkali metal catalyst is added in the initial polymerization process, so that the quantity of alkoxide generated in the initial reaction system is small, the viscosity of the system is much lower than that of the alkali metal catalyst which is added completely, the contact area between the initial reaction system and the epoxy compound in the first-stage polymerization is increased, the reaction speed is improved, and meanwhile, the solvent is prevented from being added in the initial reaction stage. After the epoxy compound in the first polymerization is polymerized, the viscosity of the whole polymerization system is greatly reduced due to the addition of the epoxy compound, and at the moment, the residual alkali metal catalyst is added, so that the viscosity of the system is increased, but the influence on the reaction rate of the subsequent epoxy compound is not great.
In a preferred embodiment, in step 1-1, the solvent is selected from the group consisting of dimethylformamide, carbon tetrachloride, dimethyl sulfoxide and 1, 3-dimethylimidazole
One or more of the quinolinones.
In a further preferred embodiment, in step 1-1, the solvent is selected from dimethylformamide and/or 1, 3-dimethylimidazole
(ii) a quinolinone.
In a further preferred embodiment, the solvent used in step 1-1 is used in an amount of 0 to 8wt%, preferably 2 to 8wt%, based on 100wt% of the total weight of the solid sorbitol and epoxy compound used in step 1.
Wherein a small amount of solvent is added in step 1-1 in order to reduce the viscosity of the system at the initial stage of the reaction. However, in the first polymerization stage, if the alkali metal-based catalyst is added in portions, the solvent may not be added at the initial stage of the polymerization, i.e., the content thereof may be 0 wt%.
In a preferred embodiment, the epoxy compound added dropwise in step 1-1 is used in an amount of 2 to 7wt%, preferably 3 to 5wt%, based on 100wt% of the total weight of the solid sorbitol and the epoxy compound used in step 1.
In which the epoxide is gradually dropped and the viscosity is gradually lowered, and if too much epoxide is added, water reacts with it because water is generally present in the solvent.
In a preferred embodiment, the ratio of the epoxy compound added in step 1-2 to the epoxy compound added in step 1-1 is (10-40): 1, preferably (10-25): 1.
In step 1-1, the solvent needs to be removed in advance, otherwise the subsequent reaction may be affected.
In the step 1, the intermediate product of the sorbitol-based polyether polyol with low molecular weight is controlled by controlling the dosage ratio of the epoxy compound to the sorbitol.
In a preferred embodiment, in steps 1-3, the post-treatment comprises sequentially emulsifying, neutralizing, adsorbing, dehydrating, filtering.
In a further preferred embodiment, the post-treatment of steps 1-3 is carried out as follows:
(I) adding water into the crude sorbitol polyether for emulsification;
(II) adding oxalic acid or phosphoric acid, and neutralizing until the pH value is 4.5-6;
and (3) because the adsorbent in the step (III) is alkaline, the pH value after neutralization in the step (II) is slightly lower than the index of a finished product.
(III) adding an adsorbent to perform adsorption, wherein the adsorbent is preferably selected from one or more of magnesium silicate, aluminum silicate and magnesium aluminum silicate;
(IV) dehydrating and filtering to obtain the sorbitol-based polyether polyol product.
In a further preferred embodiment, the adsorbent is used in an amount of (0.1 to 0.4) wt% based on 100wt% of the total weight of the solid sorbitol and epoxy compound used in step 1.
Wherein, the non-limited part of the post-treatment in the steps 1-3 is carried out by adopting the scheme disclosed in the prior art.
In a preferred embodiment, in step 2, a bimetallic catalyst is added to the reaction vessel.
In a further preferred embodiment, the bimetallic catalyst is a bimetallic cyanide complex catalyst, such as Zn [ Co (CN) 6 ] 2 And/or Zn [ Fe (CN) 6 ] 2 。
In a further preferred embodiment, the amount of the double metal cyanide complex catalyst is 0.002 to 0.01wt%, preferably 0.002 to 0.005 wt%, based on 100wt% of the sorbitol-based polyether polyol intermediate and the epoxy compound used in step 2 and step 3.
In a preferred embodiment, the ratio of the amount of the partial sorbitol-based polyether polyol intermediate in step 2 to the amount of the residual sorbitol-based polyether polyol intermediate in step 3 is 1: (0.1-0.6).
In a further preferred embodiment, the ratio of the amount of the partial sorbitol-based polyether polyol intermediate in step 2 to the amount of the residual sorbitol-based polyether polyol intermediate in step 3 is 1: (0.2-0.4).
Wherein, if the proportion of the intermediate sorbitol-based polyether polyol to be added to the reaction vessel to be mixed with the epoxy compound is too low, the effect of narrow low viscosity distribution is not obtained, and if the proportion is too high, the amount of the final epoxy compound is too small, the desired molecular weight may not be obtained after polymerization, and a broad molecular weight distribution may be caused, and the contrary is obtained.
In a preferred embodiment, in step 3, the weight ratio of the residual sorbitol-based polyether polyol intermediate product to the epoxy compound is (1-30): (70-99).
The dosage ratio refers to 70-99 parts of the epoxy compound based on 1-30 parts of the residual sorbitol-based polyether polyol intermediate.
Wherein, the weight ratio of the residual sorbitol-based polyether polyol intermediate product to the epoxy compound in the step 3 can be adjusted according to the required molecular weight of the product.
In a preferred embodiment, step 2 is carried out at 100 to 150 ℃, preferably at 110 to 130 ℃.
In a preferred embodiment, the sorbitol-based polyether polyol product obtained in step 3 has an average functionality of 6, a number average molecular weight of 3000-16000g/mol, a moisture content of 0.08% or less, and a pH of 5 to 7.
The viscosity of the sorbitol polyether polyol product obtained by the method is lower than that of the same polyether polyol synthesized by the same process by 100-2000mPa.s, preferably lower than that of the sorbitol polyether polyol product obtained by the same process by 200-1000 mPa.s.
A second object of the present invention is to provide a sorbitol-based polyether polyol, preferably prepared by the process described in the first object of the present invention.
In a preferred embodiment, the sorbitol-based polyether polyol has an average functionality of 6, a number average molecular weight of 3000-16000g/mol, a moisture content of 0.08% or less, and a pH of 5-7.
In a preferred embodiment, the sorbitol-based polyether polyol has a viscosity of 500 to 4000mPa.s, for example 1500 to 2500 mPa.s.
The method reduces the viscosity of the high molecular weight sorbitol polyether polyol, improves the fluidity, improves the uniform mixing condition of the high molecular weight sorbitol polyether polyol and the foaming component, and has narrower molecular weight distribution and lower unsaturation degree under the condition of keeping the functionality unchanged, thereby avoiding poor fluidity caused by overhigh molecular weight in the process of preparing the foam plastic, causing defects of the foaming product and nonuniform foaming caused by nonuniform mixing.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method is simple, safe, environment-friendly and easy to realize;
(2) the method reduces the viscosity of the high molecular weight sorbitol polyether polyol, improves the fluidity, improves the uniform mixing condition of the high molecular weight sorbitol polyether polyol and the foaming component, and has narrower molecular weight distribution and lower unsaturation degree under the condition that the functionality degree is kept unchanged, thereby avoiding poor fluidity caused by overhigh molecular weight in the process of preparing the foam plastic, thereby avoiding defects of the foaming product and nonuniform foaming caused by nonuniform mixing;
(3) the sorbitol polyether polyol obtained by the method has low viscosity, low unsaturation degree, high molecular weight and high functionality, and can be well applied to the field of high-quality foams.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The DMC catalysts used in the examples and comparative examples are referred to in CN101302287A, example 1.
In the examples and comparative examples, the average functionality was calculated from the formulation of the charge, the average functionality being 6 when all the initiators added were sorbitol; the number average molecular weight and the molecular weight distribution index are obtained by GPC detection, the unsaturation degree is titrated by mercuric acetate and sodium hydroxide standard solution, and the viscosity is measured by a rotational viscometer.
[ example 1 ]
600g of solid sorbitol and 50g of 1, 3-dimethylimidazole were added to a 2L stainless steel reactor
Stirring the mixture evenly, adding 4.1g of potassium hydroxide, performing nitrogen replacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve the mixture, starting to add 60g of propylene oxide to react after the temperature is up to 80 ℃, removing the solvent 1, 3-dimethyl imidazole in a vacuum state after dropping until the pressure is stable
And (3) continuously and gradually adding 1200g of propylene oxide, after dripping until the pressure is stable, removing unreacted monomers in vacuum, cooling, discharging, emulsifying, neutralizing, adsorbing, dehydrating and filtering to obtain the sorbitol polyether intermediate product A.
Adding 100g of sorbitol polyether intermediate product A and 0.06g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and mixing uniformly, dehydrating for more than 1 hour in a vacuum state, mixing 30g of sorbitol polyether intermediate product A and 1700g of propylene oxide uniformly during the period, gradually adding the mixture into the reaction kettle at a reaction temperature of 125 ℃ through a dropping pump, pulling vacuum to remove unreacted monomers after the dropping is finished until the pressure is stable, and cooling and discharging to obtain a sorbitol polyether finished product 1. Specific test data are shown in table 1.
[ example 2 ]
550g of solid sorbitol and 35g of 1, 3-dimethylimidazole were added to a 2L stainless steel reactor
Uniformly stirring the quinolinone and 25g of N, N-dimethylformamide, adding 4.5g of potassium hydroxide, performing nitrogen replacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, starting to add 70g of propylene oxide for reaction after the temperature is 80 ℃, removing the solvent 1, 3-dimethylimidazole in a vacuum state after the internal pressure is dropped until the pressure is stable
And (3) adding the pyrrolidone and the N, N-dimethylformamide, then continuously and gradually adding 1200g of propylene oxide, after dropping, pulling vacuum to remove unreacted monomers after the internal pressure is stabilized, cooling, discharging, and refining to obtain the sorbitol polyether intermediate product B.
Adding 90g of sorbitol polyether intermediate product B and 0.07g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and mixing uniformly, dehydrating for more than 1 hour in a vacuum state, mixing 20g of sorbitol polyether intermediate product B, 1500g of propylene oxide and 230g of ethylene oxide uniformly during the period, gradually adding the mixture into the reaction kettle by a dropping pump at a reaction temperature of 125 ℃, removing unreacted monomers by vacuum after the dropping is finished and the pressure is stabilized, cooling and discharging to obtain a sorbitol polyether finished product 2. Specific test data are shown in table 1.
[ example 3 ]
Adding 600g of solid sorbitol into a 2L stainless steel reaction kettle, stirring uniformly, adding 0.7g of potassium hydroxide, performing nitrogen displacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, starting to add 65g of propylene oxide to react after 80 ℃, adding 4.5g of potassium hydroxide after finishing dropping until the pressure is stable, performing nitrogen displacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, continuing to gradually add 1200g of propylene oxide after 80 ℃, after finishing dropping until the pressure is stable, removing unreacted monomers in vacuum, cooling to discharge, emulsifying, neutralizing, adsorbing, dehydrating and filtering to obtain a sorbitol polyether intermediate product.
Adding 100g of sorbitol polyether intermediate product and 0.06g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and mixing uniformly, dehydrating for more than 1 hour in a vacuum state, mixing 30g of sorbitol polyether intermediate product and 1700g of propylene oxide uniformly during the period, gradually adding the mixture into the reaction kettle at a reaction temperature of 125 ℃ through a dropping pump, pulling vacuum to remove unreacted monomers after the dropping is finished until the pressure is stable, cooling and discharging to obtain a sorbitol polyether finished product 3. Specific test data are shown in table 1.
[ example 4 ]
600g of solid sorbitol and 70g of 1, 3-dimethylimidazole were added to a 2L stainless steel reactor
Stirring the quinolinone evenly, adding 5.58g of potassium hydroxide, carrying out nitrogen replacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, starting to add 70g of propylene oxide for reaction after the temperature reaches 90 ℃, removing the solvent 1, 3-dimethyl imidazole in a vacuum state after dropping till the pressure is stable
And (3) continuously and gradually adding 1200g of propylene oxide, after dripping until the pressure is stable, removing unreacted monomers in vacuum, cooling, discharging, emulsifying, neutralizing, adsorbing, dehydrating and filtering to obtain the sorbitol polyether intermediate product.
Adding 100g of sorbitol polyether intermediate product and 0.037g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and uniformly mixing, dehydrating for more than 1 hour in a vacuum state, uniformly mixing 40g of sorbitol polyether intermediate product and 1700g of propylene oxide during the period, gradually adding the mixture into the reaction kettle at the reaction temperature of 130 ℃ through a dropping pump, after the dropping is finished until the pressure is stable, removing unreacted monomers by vacuum pumping, cooling and discharging, and thus obtaining a sorbitol polyether finished product 4. Specific test data are shown in table 1.
Similar to examples 1-3, the obtained product has the advantages of narrow molecular weight distribution, low viscosity and the like.
[ example 5 ]
600g of solid sorbitol and 65g of 1, 3-dimethylimidazole were added to a 2L stainless steel reactor
Stirring the linezolid evenly, adding 8.95g of potassium hydroxide, carrying out nitrogen replacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, starting to add 85g of propylene oxide for reaction after the temperature reaches 110 ℃, removing the solvent 1, 3-dimethyl imidazole in a vacuum state after dripping till the pressure is stable, and then removing the solvent
And (3) continuously and gradually adding 1200g of propylene oxide, after dripping until the pressure is stable, removing unreacted monomers in vacuum, cooling, discharging, emulsifying, neutralizing, adsorbing, dehydrating and filtering to obtain the sorbitol polyether intermediate product.
Adding 85g of sorbitol polyether intermediate product and 0.091g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and uniformly mixing, dehydrating for more than 1 hour in a vacuum state, uniformly mixing 43g of sorbitol polyether intermediate product and 1700g of propylene oxide during the period, gradually adding the mixture into the reaction kettle at the reaction temperature of 150 ℃ through a dropping pump, after the dropping is finished until the pressure is stable, removing unreacted monomers by pulling vacuum, cooling and discharging, thus obtaining the sorbitol polyether finished product 5. Specific test data are shown in table 1.
Similar to examples 1-3, the obtained product has the advantages of narrow molecular weight distribution, low viscosity and the like.
[ example 6 ] A method for producing a polycarbonate
Adding 600g of solid sorbitol into a 2L stainless steel reaction kettle, stirring uniformly, adding 0.8g of potassium hydroxide, performing nitrogen displacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, starting to add 90g of propylene oxide to react after 80 ℃, adding 5.3g of potassium hydroxide after finishing dropping until the pressure is stable, performing nitrogen displacement, measuring the oxygen content in the kettle to be less than 150ppm, heating to dissolve, continuing to gradually add 1200g of propylene oxide after 70 ℃, removing unreacted monomers in vacuum after finishing dropping until the pressure is stable, cooling to discharge, emulsifying, neutralizing, adsorbing, dehydrating and filtering to obtain the sorbitol polyether intermediate product.
Adding 105g of sorbitol polyether intermediate product and 0.05g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and mixing uniformly, dehydrating for more than 1 hour in a vacuum state, uniformly mixing 16g of sorbitol polyether intermediate product and 1089g of propylene oxide during the period, gradually adding the mixture into the reaction kettle through a dropping pump at the reaction temperature of 110 ℃, after dropping is finished until the pressure is stable, removing unreacted monomers by vacuum pumping, cooling and discharging to obtain a sorbitol polyether finished product 6. Specific test data are shown in table 1.
Similar to examples 1-3, the obtained product has the advantages of narrow molecular weight distribution, low viscosity and the like.
Comparative example 1
Adding 130g of the sorbitol polyether intermediate product obtained in the embodiment 1 and 0.06g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and mixing uniformly, dehydrating for more than 1 hour in a vacuum state, gradually adding 1700g of propylene oxide into the reaction kettle through a dropping pump at the reaction temperature of 125 ℃, pulling vacuum to remove unreacted monomers after the internal pressure is dropped until the pressure is stable, cooling and discharging to obtain the sorbitol polyether finished product. Specific test data are shown in table 1.
Comparative example 2
Adding 110g of the sorbitol polyether intermediate product obtained in the example 2 and 0.07g of DMC catalyst into a 2L stainless steel reaction kettle, stirring and mixing uniformly, dehydrating for more than 1 hour in a vacuum state, mixing 1500g of propylene oxide and 230g of ethylene oxide uniformly during the period, gradually adding the mixture into the reaction kettle by a dropping pump at a reaction temperature of 125 ℃, removing unreacted monomers by pulling vacuum after the dropping is finished and the pressure is stable, cooling and discharging to obtain a sorbitol polyether finished product. Specific test data are shown in table 1.
Table 1: test data
Claims (13)
1. A preparation method of sorbitol polyether polyol comprises the following steps:
step 1, polymerizing solid sorbitol serving as an initiator and an epoxy compound serving as a monomer to obtain a sorbitol-based polyether polyol intermediate product; step 1 is carried out in the presence of an alkali metal-based catalyst and optionally a solvent, and when no solvent is used, the alkali metal-based catalyst is added in portions;
step 2, taking a part of sorbitol-based polyether polyol intermediate product and placing the intermediate product into a reaction container;
step 3, mixing the residual sorbitol-based polyether polyol intermediate product with an epoxy compound, and then dripping the mixture into the reaction container in the step 2 to polymerize to obtain the sorbitol-based polyether polyol product;
the number average molecular weight of the sorbitol polyether polyol intermediate product obtained in the step 1 is 200-1000 g/mol;
in the step 2, a bimetallic catalyst is added into the reaction container, and the bimetallic catalyst is a bimetallic cyanide complex catalyst; the dosage of the bimetallic cyanide complex catalyst is 0.002-0.01 wt%, wherein the dosage is calculated by 100wt% of the total weight of the sorbitol polyether polyol intermediate and the epoxy compound adopted in the steps 2 and 3;
the dosage ratio of the part of sorbitol-based polyether polyol intermediate product in the step 2 to the residual sorbitol-based polyether polyol intermediate product in the step 3 is 1: (0.1-0.6).
2. The production method according to claim 1, wherein the epoxy compound is a compound containing an epoxy group.
3. The method according to claim 2, wherein the epoxy compound is one or more selected from the group consisting of propylene oxide, ethylene oxide and derivatives thereof.
4. The production method according to claim 1,
the dosage ratio of the part of sorbitol-based polyether polyol intermediate product in the step 2 to the residual sorbitol-based polyether polyol intermediate product in the step 3 is 1: (0.2-0.4); and/or
In the step 3, the weight using amount ratio of the residual sorbitol-based polyether polyol intermediate product to the epoxy compound is (1-30): (70-99).
5. The production method according to claim 1,
step 1 is carried out at 70-130 ℃; and/or
Step 2 is carried out at 100-150 ℃.
6. The production method according to claim 5,
step 1 is carried out at 90-110 ℃; and/or
And step 2 is carried out at 110-130 ℃.
7. The method according to any one of claims 1 to 6, wherein the step 1 comprises the substeps of:
step 1-1, in the presence of solid sorbitol, an alkali metal catalyst and an optional solvent, dropwise adding an epoxy compound to a set amount, and removing the solvent after the pressure is not changed any more;
step 1-2, continuously dropwise adding the epoxy compound to a set amount, and removing the unreacted epoxy compound after the pressure is not changed any more to obtain a crude sorbitol-based polyether polyol intermediate product;
and 1-3, carrying out post-treatment on the crude product of the sorbitol-based polyether polyol intermediate product to obtain the sorbitol-based polyether polyol intermediate product.
8. The production method according to claim 7,
in step 1-1, the alkali metal-based catalyst is selected from one or more of potassium hydroxide, sodium alkoxide, and potassium alkoxide; and/or
In step 1-1, the solvent is selected from one or more of dimethylformamide, carbon tetrachloride, dimethyl sulfoxide and 1, 3-dimethylimidazolidinone.
9. The method according to claim 8, wherein in step 1-1, the alkali metal catalyst is selected from potassium hydroxide and/or sodium hydroxide.
10. The method of claim 8,
the dosage of the alkali metal catalyst in the step 1-1 is 0.2-1.0wt%, wherein the dosage is calculated by 100wt% of the total weight of the solid sorbitol and the epoxy compound adopted in the step 1; and/or
The solvent used in step 1-1 is 0-8wt%, wherein the amount is 100wt% of the total weight of the solid sorbitol and the epoxy compound used in step 1.
11. The method of claim 10,
the dosage of the alkali metal catalyst in the step 1-1 is 0.2-0.5 wt%, wherein the dosage is calculated by 100wt% of the total weight of the solid sorbitol and the epoxy compound adopted in the step 1; and/or
The dosage of the solvent in the step 1-1 is 2-8 wt%, wherein the dosage is calculated by 100wt% of the total weight of the solid sorbitol and the epoxy compound adopted in the step 1.
12. The production method according to claim 7,
the dosage of the epoxy compound dripped in the step 1-1 is 2-7 wt%, wherein the dosage is calculated by 100wt% of the total weight of the solid sorbitol and the epoxy compound adopted in the step 1; and/or
The dosage ratio of the epoxy compound continuously dripped in the step 1-2 to the epoxy compound dripped in the step 1-1 is (10-40): 1.
13. The production method according to claim 12,
the dosage of the epoxy compound dripped in the step 1-1 is 3-5%, wherein the dosage is calculated by 100wt% of the total weight of the solid sorbitol and the epoxy compound adopted in the step 1; and/or
The dosage ratio of the epoxy compound continuously dripped in the step 1-2 to the epoxy compound dripped in the step 1-1 is (10-25): 1.
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