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CN-121991334-A - High molecular weight low viscosity polyether polyol and preparation method and application thereof

CN121991334ACN 121991334 ACN121991334 ACN 121991334ACN-121991334-A

Abstract

The invention provides a high molecular weight low viscosity polyether polyol, a preparation method and application thereof, wherein mixed dihydric alcohol is used as an initiator, and reacts with an epoxy compound under the action of a double metal cyanide complex catalyst and an auxiliary acid, wherein the mixed dihydric alcohol contains propylene glycol and difunctional polyether polyol. By adopting the technical scheme of the invention, the polyether polyol for the MS glue with ultrahigh molecular weight and low viscosity can be prepared.

Inventors

  • ZHU SHU
  • HAO JINGYING
  • GUAN SONGYUN
  • ZHAO KEPIN

Assignees

  • 中国石油化工股份有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (10)

  1. 1. A preparation method of high molecular weight low viscosity polyether polyol comprises the step of reacting mixed dihydric alcohol with epoxy compound under the action of double metal cyanide complex catalyst (I) and auxiliary acid (I) as an initiator (I), wherein the mixed dihydric alcohol contains propylene glycol (I) and difunctional polyether polyol.
  2. 2. The preparation method of the difunctional polyether polyol according to claim 1, wherein propylene glycol (II) and diol containing cyclic groups are used as an initiator (II), and the difunctional polyether polyol is obtained by reacting (II) with a mixture of propylene oxide and cyclohexane oxide under the action of a double metal cyanide complex catalyst (II) and an auxiliary acid (II).
  3. 3. The method according to claim 2, wherein, The dihydric alcohol containing cyclic group is selected from at least one of furan dimethanol, cyclopentanediol and cyclohexanediol, and/or, The mass ratio of the propylene glycol (II) to the diol containing the cyclic group is 45:55-99:1, preferably 50:50-90:10, and/or, The mass ratio of the propylene oxide to the cyclohexane oxide is 50:50-99:1, preferably 60:40-95:5, and/or, The double metal cyanide complex catalyst (II) is selected from at least one of Zn (II) Fe (III) double metal cyanide complex catalyst and Zn (II) Co (III) double metal cyanide complex catalyst, and/or, The auxiliary acid (II) is selected from at least one of phosphoric acid and sulfuric acid, and/or, The amount of the double metal cyanide complex catalyst (II) is 5 to 150ppm, preferably 15 to 120ppm, based on the total amount of the difunctional polyether polyol product, and/or, The amount of the auxiliary acid (II) is 10-200 ppm, preferably 20-170 ppm, of the total amount of the difunctional polyether polyol product, and/or, The reaction (II) is carried out at a reaction temperature of 100-180 ℃, preferably 100-150 ℃, and/or at a reaction pressure of 0.005-0.8 MPa, preferably 0.01-0.4 MPa.
  4. 4. The preparation method of any one of claims 1 to 3, wherein the preparation method of the high molecular weight low viscosity polyether polyol comprises the following specific steps: Step (1) mixing the mixed dihydric alcohol serving as an initiator (I), a double metal cyanide complex catalyst (I) and an auxiliary acid (I) uniformly; Step (2), after vacuum dehydration under nitrogen bubbling, adding part of epoxy compound to initiate reaction (I); and (3) adding the residual epoxy compound to continue the reaction (I'), and aging and degassing after the reaction to obtain the high molecular weight low viscosity polyether polyol.
  5. 5. The method according to claim 4, wherein in the step (1): The difunctional polyether polyol comprises difunctional polyether polyol A with the number average molecular weight of 200-800, difunctional polyether polyol B with the number average molecular weight of 1500-2500, preferably, the content of propylene glycol (I) is 10-80 wt%, the content of difunctional polyether polyol A is 15-60 wt%, the content of difunctional polyether polyol B is 1-50 wt%, more preferably, the content of propylene glycol (I) is 20-60 wt%, the content of difunctional polyether polyol A is 25-55 wt%, the content of difunctional polyether polyol B is 1-40 wt% based on the total weight of the mixed glycol, and/or the content of difunctional polyether polyol B is 1-40 wt% based on the total weight of the mixed glycol, The double metal cyanide complex catalyst (I) is selected from at least one of Zn (II) Fe (III) double metal cyanide complex catalyst and Zn (II) Co (III) double metal cyanide complex catalyst, and/or, The auxiliary acid (I) is selected from at least one of phosphoric acid and sulfuric acid, and/or, The amount of the double metal cyanide complex catalyst (I) is 10 to 150ppm, preferably 15 to 120ppm, based on the total amount of the polyether polyol obtained, and/or, The amount of the auxiliary acid (I) is 10-200 ppm, preferably 20-170 ppm, of the total amount of the initiator (I).
  6. 6. The method according to claim 4, wherein in the step (2): The epoxy compound is selected from at least one of alkylene oxides, preferably a mixture of propylene oxide, ethylene oxide, butylene oxide and cyclohexane oxide, and/or, The addition amount of part of the epoxy compound in the step (2) is 1 to 30wt%, preferably 3 to 25wt% of the total amount of the epoxy compound, and/or, The vacuum dehydration is carried out under the conditions that the pressure is-0.05 to-0.1 MPa and the time is 2 to 5 hours, and/or, The reaction (I) is carried out in a protective gas atmosphere at a temperature of 110-120 ℃ and a pressure of 0.01-0.15 MPa for 0.1-1.5 hours.
  7. 7. The method according to claim 6, wherein, The epoxy resin composition comprises, by weight, 50-97wt% of the total amount of the epoxy compounds, 1-25wt% of ethylene oxide, 1-30wt% of butylene oxide and 1-30wt% of cyclohexane oxide, and preferably 55-95wt% of the total amount of the epoxy compounds, 1-20wt% of ethylene oxide, 1-25wt% of butylene oxide and 1-25wt% of cyclohexane oxide.
  8. 8. The method according to claim 4, wherein in the step (3): The reaction (I') is carried out in a protective gas atmosphere at a temperature of 125-155 ℃, a pressure of 0.01-0.35 MPa, a reaction time of 1-5 hours, and/or, The aging condition is that the temperature is 125-135 ℃ and the time is 1-3 hours.
  9. 9. The high molecular weight low viscosity polyether polyol obtained by the production process according to any one of claims 1 to 8, wherein the high molecular weight low viscosity polyether polyol has a hydroxyl value of 9 to 15mgkoh/g, a viscosity of 2000 to 4000 mpa-s/25 ℃ and a molecular weight distribution index of 1.03 to 1.12.
  10. 10. Use of the high molecular weight low viscosity polyether polyol of claim 9 in the synthesis of a silane modified polyether sealant.

Description

High molecular weight low viscosity polyether polyol and preparation method and application thereof Technical Field The invention belongs to the technical field of petrochemical industry, and particularly relates to a high molecular weight low viscosity polyether polyol, a preparation method and application thereof. Background Along with the acceleration of the structural adjustment of polyurethane industry and the upgrading of industrial technology in China, the polyether industry shows that low-end products are serious in homogeneity, high-end products are few and weak in competitiveness, sustainable development capability is insufficient, the green, intelligent and standardization levels are required to be improved, and the like, so that the polyether polyol with excellent development performance is always the development direction of the polyurethane industry. Among them, the high-performance MS glue polyether polyol product becomes one of the research hot spots. The polyether polyol is an ultrahigh molecular weight polyether polyol product with the molecular weight of about 8000-12000, and has the characteristics of low unsaturation degree, high molar mass, narrow distribution and the like. Compared with the existing common sealant products, the synthesized MS sealant product has outstanding advantages in the aspects of environmental protection, paintability, material bonding universality, weather resistance and the like, and can be applied to sealing of inner and outer walls of buildings, doors and windows of vehicles and the like. However, the general problem existing at present is that in the preparation process of the polyether polyol with ultrahigh molecular weight, along with the increase of target molecular weight and the continuous increase of molecular chains, side reactions are increased in the reaction process, so that the molecular weight distribution of polyether is widened, the viscosity is increased, and the downstream application performance of polyether products is greatly influenced. To solve the above problems, a great deal of research has been conducted. Chinese patent CN 111072947a relates to a process for preparing high molecular weight low viscosity polyether polyols. The prepared high molecular weight polyether polyol has the advantages of low unsaturation degree, narrow molecular weight distribution and low viscosity by adding the alicyclic hydrocarbon compound in a proper proportion into the epoxy compound, and is beneficial to the subsequent application of the polyether polyol. However, the method has complicated process operation and poor stability. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a preparation method of polyether polyol for high molecular weight and low viscosity MS glue. The hydroxyl value of the prepared polyether polyol product for the high molecular weight MS glue is 9-15mgKOH/g, and the polyether polyol has lower product viscosity and narrower molecular weight distribution and has better applicability. The invention aims at providing a preparation method of high molecular weight low viscosity polyether polyol, which comprises the step of reacting mixed glycol with epoxy compound under the action of double metal cyanide complex catalyst (I) and auxiliary acid (I) by taking mixed glycol as an initiator (I), wherein the mixed glycol contains propylene glycol (I) and difunctional polyether polyol, the difunctional polyether polyol comprises difunctional polyether polyol A with the number average molecular weight of 200-800 and difunctional polyether polyol B with the number average molecular weight of 1500-2500, and preferably the difunctional polyether polyol comprises difunctional polyether polyol A with the number average molecular weight of 300-500 and difunctional polyether polyol B with the number average molecular weight of 1800-2200. According to the preparation method of the difunctional polyether polyol, propylene glycol (II) and dihydric alcohol containing cyclic groups are used as an initiator (II), and the difunctional polyether polyol is obtained by reacting (II) with a mixture of propylene oxide and cyclohexane oxide under the action of a double metal cyanide complex catalyst (II) and an auxiliary acid (II). According to the present invention, the difunctional polyether polyol is produced by: The dihydric alcohol containing the cyclic group is at least one selected from furan dimethanol, cyclopentanediol and cyclohexanediol; the mass ratio of the propylene glycol (II) to the diol containing the cyclic group is 45:55-99:1, preferably 50:50-90:10; the mass ratio of the propylene oxide to the cyclohexene oxide is 50:50-99:1, preferably 60:40-95:5; The double metal cyanide complex catalyst (II) is selected from at least one of Zn (II) Fe (III) double metal cyanide complex catalyst and Zn (II) Co (III) double metal cyanide complex catalyst; The auxiliary acid (II) is at least one selected from phosph