High-molecular-weight low-viscosity polyether polyol as well as preparation method and application thereof

Abstract

The invention provides high-molecular-weight low-viscosity polyether polyol and a preparation method and application thereof.The preparation method includes the step that mixed dihydric alcohol serves as an initiator and reacts with an epoxy compound under the action of a double-metal cyanide complex catalyst and an auxiliary acid, and the mixed dihydric alcohol contains propylene glycol and bifunctional polyether polyol. By adopting the technical scheme provided by the invention, the ultra-high molecular weight and low viscosity polyether polyol for the MS adhesive can be prepared.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical technology, specifically relating to a high molecular weight, low viscosity polyether polyol, its preparation method, and its application. Background Technology

[0002] With the accelerated structural adjustment and technological upgrading of my country's polyurethane industry, the polyether industry has revealed numerous problems, including severe homogenization of low-end products, a shortage of high-end products with weak competitiveness, insufficient sustainable development capabilities, and room for improvement in greening, intelligentization, and standardization. Developing high-performance polyether polyols has always been a development direction for the polyurethane industry. Among these, high-performance MS (silane-modified polyether) sealants have become a research hotspot. These are ultra-high molecular weight polyether polyols with a molecular weight of approximately 8000–12000, characterized by low unsaturation, high molar mass, and narrow distribution. They are the main raw material for synthesizing silane-modified polyether sealants (MS sealants). Compared with commonly used sealants, the synthesized MS sealants have significant advantages in environmental friendliness, coatability, wide material adhesion, and weather resistance, and can be used for sealing interior and exterior walls of buildings, doors and windows of transportation vehicles, etc. However, a common problem is that during the preparation of ultra-high molecular weight polyether polyols, as the target molecular weight increases and the molecular chain lengthens, side reactions increase, leading to a wider molecular weight distribution and increased viscosity of the polyether, which significantly affects the downstream application performance of the polyether product.

[0003] To address the aforementioned problems, extensive research has been conducted. Chinese patent CN 111072947A discloses a method for preparing high molecular weight, low viscosity polyether polyols. By adding an appropriate proportion of alicyclic hydrocarbons to an epoxy compound, the prepared high molecular weight polyether polyol exhibits advantages such as low unsaturation, narrow molecular weight distribution, and low viscosity, which is beneficial for the subsequent applications of polyether polyols. However, this method involves cumbersome processes and suffers from poor stability. Summary of the Invention

[0004] To address the aforementioned problems in the prior art, this invention proposes a method for preparing high molecular weight, low viscosity polyether polyols for MS adhesives. The resulting high molecular weight polyether polyol product for MS adhesives has a hydroxyl value of 9-15 mgKOH / g, exhibits low viscosity and a narrow molecular weight distribution, and demonstrates good applicability.

[0005] One objective of this invention is to provide a method for preparing high molecular weight, low viscosity polyether polyols, comprising the step of reacting a mixed diol as an initiator (Ⅰ) with an epoxy compound under the action of a bimetallic cyanide complexing catalyst (Ⅰ) and an auxiliary acid (Ⅰ), wherein the mixed diol contains propylene glycol (Ⅰ) and a difunctional polyether polyol, wherein the difunctional polyether polyol comprises difunctional polyether polyol A with a number average molecular weight of 200-800 and difunctional polyether polyol B with a number average molecular weight of 1500-2500, preferably, the difunctional polyether polyol comprises difunctional polyether polyol A with a number average molecular weight of 300-500 and difunctional polyether polyol B with a number average molecular weight of 1800-2200.

[0006] According to the present invention, the preparation method of the difunctional polyether polyol is as follows: using propylene glycol (II) and a diol containing cyclic groups as initiators (II), the mixture of propylene oxide and cyclohexane oxide is reacted (II) under the action of a bimetallic cyanide complexing catalyst (II) and an auxiliary acid (II) to obtain the difunctional polyether polyol.

[0007] According to the present invention, in the preparation method of the difunctional polyether polyol:

[0008] The cyclic diol is selected from at least one of furanyl diethanol, cyclopentanediol, and cyclohexanediol;

[0009] The mass ratio of propylene glycol (II) to the diol containing cyclic groups is 45:55 to 99:1, preferably 50:50 to 90:10.

[0010] The mass ratio of propylene oxide to cyclohexane oxide is 50:50 to 99:1, preferably 60:40 to 95:5;

[0011] The bimetallic cyanide complex catalyst (II) is selected from at least one of Zn(II)Fe(III) bimetallic cyanide complex catalyst and Zn(II)Co(III) bimetallic cyanide complex catalyst;

[0012] The auxiliary acid (II) is selected from at least one of phosphoric acid and sulfuric acid;

[0013] The amount of the bimetallic cyanide complexing catalyst (II) is 5 to 150 ppm of the total amount of the difunctional polyether polyol product, preferably 15 to 120 ppm.

[0014] The amount of the auxiliary agent acid (II) is 10 to 200 ppm of the total amount of the difunctional polyether polyol product, preferably 20 to 170 ppm;

[0015] The conditions for reaction (II) are: reaction temperature 100-180℃, preferably 100-150℃; reaction pressure 0.005-0.8MPa, preferably 0.01-0.4MPa.

[0016] In the preparation process of the difunctional polyether polyol, the amount of initiator (II), propylene oxide and cyclohexane oxide is not particularly limited, and can be adjusted according to the molecular weight of the desired difunctional polyether polyol. For example, the total mass ratio of the initiator (II) and the epoxy compound (propylene oxide and cyclohexane oxide) is 1:(1-30), preferably 1:(1-25).

[0017] According to the present invention, the preparation method of the high molecular weight low viscosity polyether polyol includes the following specific steps:

[0018] Step (1) Use a mixed diol as an initiator (Ⅰ) and mix it evenly with a bimetallic cyanide complexing catalyst (Ⅰ) and an auxiliary acid (Ⅰ);

[0019] Step (2) After vacuum dehydration under nitrogen bubbling, a portion of epoxy compound is added to initiate reaction (I);

[0020] Step (3) Add the remaining epoxy compound to continue the reaction (Ⅰ'), and after the reaction, age and degas to obtain the high molecular weight low viscosity polyether polyol.

[0021] According to the present invention, in step (1) of the method for preparing the high molecular weight low viscosity polyether polyol:

[0022] Based on a total weight of 100 wt% of the mixed diols, the content of propylene glycol (I) is 10-80 wt%, the content of difunctional polyether polyol A is 15-60 wt%, and the content of difunctional polyether polyol B is 1-50 wt%; preferably, based on a total weight of 100 wt% of the mixed diols, the content of propylene glycol (I) is 20-60 wt%, the content of difunctional polyether polyol A is 25-55 wt%, and the content of difunctional polyether polyol B is 1-40 wt%.

[0023] The bimetallic cyanide complex catalyst (Ⅰ) is selected from at least one of Zn(Ⅱ)Fe(Ⅲ) bimetallic cyanide complex catalyst and Zn(Ⅱ)Co(Ⅲ) bimetallic cyanide complex catalyst;

[0024] The auxiliary acid (Ⅰ) is selected from at least one of phosphoric acid and sulfuric acid;

[0025] The amount of the bimetallic cyanide complexing catalyst (Ⅰ) is 10 to 150 ppm of the total amount of the obtained polyether polyol, preferably 15 to 120 ppm;

[0026] The amount of the auxiliary acid (Ⅰ) is 10 to 200 ppm of the total amount of the initiator (Ⅰ), preferably 20 to 170 ppm.

[0027] According to the present invention, in the preparation method of the high molecular weight low viscosity polyether polyol:

[0028] The epoxy compound is selected from at least one of epoxide alkanes, preferably a mixture of propylene oxide, ethylene oxide, butane oxide, and cyclohexane oxide; further, based on a total amount of the epoxy compound of 100 wt%, the amount of propylene oxide is 50-97 wt%, the amount of ethylene oxide is 1-25 wt%, the amount of butane oxide is 1-30 wt%, and the amount of cyclohexane oxide is 1-30 wt%; preferably, based on a total amount of the epoxy compound of 100 wt%, the amount of propylene oxide is 55-95 wt%, the amount of ethylene oxide is 1-20 wt%, the amount of butane oxide is 1-25 wt%, and the amount of cyclohexane oxide is 1-25 wt%.

[0029] In the preparation of the high molecular weight low viscosity polyether polyol, the amount of initiator (I) and epoxy compound is not particularly limited, and can be adjusted according to the molecular weight of the desired high molecular weight low viscosity polyether polyol. For example, the mass ratio of the initiator (I) to the total mass of the epoxy compound is 1:(5-75), preferably 1:(8-50).

[0030] In step (2), the amount of epoxy compound added is 1 to 30 wt% of the total amount of epoxy compound, preferably 3 to 25 wt%.

[0031] According to the present invention, in the preparation method of the high molecular weight low viscosity polyether polyol:

[0032] In step (2), the vacuum dehydration conditions are: pressure of -0.05 to -0.1 MPa and time of 2 to 5 hours;

[0033] In step (2), the conditions for reaction (I) are as follows: the reaction is carried out under a protective gas atmosphere, the reaction temperature is 110-120℃, the reaction pressure is 0.01-0.15MPa, and the reaction time is 0.1-1.5 hours.

[0034] In step (3), the reaction (Ⅰ') conditions are as follows: the reaction is carried out under a protective gas atmosphere, the reaction temperature is 125-155℃, the reaction pressure is 0.01-0.35MPa, and the reaction time is 1-5 hours.

[0035] In step (3), the aging conditions are: temperature of 125-135℃ and time of 1-3 hours.

[0036] The second objective of this invention is to provide a high molecular weight, low viscosity polyether polyol obtained by the above preparation method, wherein the high molecular weight, low viscosity polyether polyol has a hydroxyl value of 9-15 mgKOH / g, a viscosity of 2000-4000 mPa·s / 25℃, and a molecular weight distribution index of 1.03-1.12.

[0037] The fourth objective of this invention is to provide an application of the above-mentioned high molecular weight, low viscosity polyether polyol in the synthesis of silane-modified polyether sealant (MS sealant).

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] 1. Based on the reaction characteristics of bimetallic cyanide complex catalysts, this invention introduces cyclic groups into the polyether molecular structure, which to a certain extent increases the steric hindrance between groups, controls the reaction rate, and reduces the generation of ultra-high molecular weight molecules; and by using initiators of different molecular weights, the chain growth rate is controlled, side reactions are reduced, and the product performance is better.

[0040] 2. The polyether polyol product for MS adhesive obtained by this invention has a hydroxyl value of 9-15 mgKOH / g, low product viscosity and narrow molecular weight distribution, and good applicability; the viscosity is 2000-4000 mPa·s / 25℃, and the molecular weight distribution index is 1.03-1.12. Detailed Implementation

[0041] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0042] The testing instruments and conditions used in this embodiment are as follows:

[0043] Viscosity testing was conducted according to the rotational viscosity method in GB / T 12008.7-2010. A rotational viscometer was used, and the measurement was performed directly at 25℃. This method is suitable for measuring the viscosity of polyether polyols with a viscosity range of 10-100000 mPa·s.

[0044] The hydroxyl value was determined according to the phthalic anhydride method in GB / T 12008.3-2009. An accurately weighed sample was added to an Erlenmeyer flask, and the hydroxyl groups reacted with the phthalic anhydride dissolved in pyridine under reflux at 98±2℃. Excess phthalic anhydride was titrated with sodium hydroxide solution.

[0045] The molecular weight distribution was obtained by gel permeation chromatography (GPC).

[0046] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0047] The reactors used in Examples 1-5 of this invention are 5L stainless steel pressure-resistant reactors.

[0048] The bimetallic catalysts (Zn(II)Fe(III) bimetallic cyanide complex catalysts and Zn(II)Co(III) bimetallic cyanide complex catalysts) are bimetallic cyanide complex catalysts from Huai'an Bad.

[0049] Example 1

[0050] Preparation of difunctional polyether polyols with a number average molecular weight of 300:

[0051] 170g of propylene glycol, 170g of furanyl dimethyl alcohol, 0.015g of Zn(II)Fe(III) bimetallic cyanide complex catalyst, and 0.02g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 396g of propylene oxide and 264g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 100℃ and the reaction pressure was 0.4MPa, yielding a difunctional polyether polyol with a number average molecular weight of 300.

[0052] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 50:50; the mass ratio of propylene oxide to cyclohexane oxide is 60:40; the amount of Zn(II)Fe(III) bimetallic cyanide complex catalyst is 15 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 20 ppm of the total amount of difunctional polyether polyol products.)

[0053] Preparation of difunctional polyether polyols with a number average molecular weight of 2000:

[0054] 32g of propylene glycol, 13.8g of furanyl dimethyl alcohol, 0.08g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.1g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 763g of propylene oxide and 191.2g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 130℃ and the reaction pressure was 0.1MPa, yielding a difunctional polyether polyol with a number average molecular weight of 2000.

[0055] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 70:30; the mass ratio of propylene oxide to cyclohexane oxide is 80:20; the amount of Zn(II)Co(III) bimetallic cyanide complex catalyst is 80 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 100 ppm of the total amount of difunctional polyether polyol products.)

[0056] Preparation of high molecular weight, low viscosity polyether polyols:

[0057] 64.5g of propylene glycol, 107.5g of difunctional polyether polyol with a molecular weight of 300, and 43g of difunctional polyether polyol with a molecular weight of 2000 were mixed evenly. 0.09g of Zn(II)Co(III) bimetallic cyanide complexing catalyst and 0.3g of sulfuric acid were added and mixed evenly. The mixture was then vacuum dehydrated under nitrogen bubbling for 5 hours. Subsequently, 139g of epoxide was added under a nitrogen atmosphere. The reaction system temperature was controlled at 125℃, the reaction system pressure at 0.07MPa, the reaction temperature at 110℃, the reaction pressure at 0.01MPa, and the reaction time at 0.1 hours. Then, the remaining 2646g of epoxy compound was continuously introduced, which was a mixture of 1671g of propylene oxide, 27.9g of ethylene oxide, 557g of butane oxide, and 529.1g of cyclohexane oxide. The temperature of the reaction system was controlled at 125℃, the pressure in the reaction system was 0.07MPa, and the reaction time was 5 hours. After that, it was aged at 125℃ for 3 hours and degassed to obtain ultra-high molecular weight, low viscosity MS adhesive polyether polyol A with a number average molecular weight of 8014.

[0058] In this mixture, by mass percentage, propylene glycol accounts for 30% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 300 accounts for 50%, and difunctional polyether polyol with a number average molecular weight of 2000 accounts for 20%. The amount of bimetallic cyanide complexing catalyst is 30 ppm of the obtained polyether polyol. The amount of acid is 100 ppm of the obtained polyether polyol. The amount of propylene oxide is 60% of the total mass of the epoxides, ethylene oxide is 1%, butane oxide is 20%, and cyclohexane oxide is 19%. The mass of pre-added epoxides is 5% of the total mass of the epoxides.

[0059] Example 2

[0060] Preparation of difunctional polyether polyols with a number average molecular weight of 500:

[0061] 146g of propylene glycol, 16.5g of furanyl dimethyl alcohol, 0.12g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.17g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 795.6g of propylene oxide and 41.9g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 150℃ and the reaction pressure was 0.3MPa, yielding a difunctional polyether polyol with a number average molecular weight of 500.

[0062] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 90:10; the mass ratio of propylene oxide to cyclohexane oxide is 95:5; the amount of Zn(II)Co(III) bimetallic cyanide complex catalyst is 120 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 170 ppm of the total amount of difunctional polyether polyol products.)

[0063] Preparation of difunctional polyether polyols with a number average molecular weight of 1800:

[0064] 38.4 g of propylene glycol, 9.6 g of furanyl dimethyl alcohol, 0.1 g of Zn(II)Fe(III) bimetallic cyanide complex catalyst, and 0.15 g of phosphoric acid were mixed evenly. Then, 856.8 g of propylene oxide and 95.2 g of cyclohexane oxide were continuously added under a nitrogen atmosphere. The reaction temperature was 140 °C and the reaction pressure was 0.3 MPa to obtain a difunctional polyether polyol with a number average molecular weight of 1800.

[0065] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 80:20; the mass ratio of propylene oxide to cyclohexane oxide is 90:10; the amount of Zn(II)Fe(III) bimetallic cyanide complex catalyst is 100 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 150 ppm of the total amount of difunctional polyether polyol products.)

[0066] Preparation of high molecular weight, low viscosity polyether polyols:

[0067] 76.2 g of propylene glycol, 41.6 g of a difunctional polyether polyol with a molecular weight of 500, and 20.7 g of a difunctional polyether polyol with a molecular weight of 1800 were mixed evenly. 0.3 g of a Zn(II)Co(III) bimetallic cyanide complexing catalyst and 0.09 g of sulfuric acid were added and mixed evenly. The mixture was vacuum dehydrated for 3 hours under nitrogen bubbling. Then, 572.3 g of epoxide was pre-added under a nitrogen atmosphere. The reaction temperature was 120℃, the reaction pressure was 0.15 MPa, and the reaction time was 1.5 hours. Subsequently, the remaining 2289.2 g of epoxide was continuously introduced, consisting of a mixture of 2718.5 g of propylene oxide, 85.8 g of ethylene oxide, 28.6 g of butane oxide, and 28.6 g of cyclohexane oxide. The reaction temperature was controlled at 135℃, the reaction pressure at 0.15 MPa, and the reaction time was 1 hour. After aging at 135℃ for 1 hour and degassing, ultra-high molecular weight, low viscosity MS adhesive polyether polyol B with a number average molecular weight of 10017 was obtained.

[0068] In this mixture, by mass percentage, propylene glycol accounts for 55% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 500 accounts for 30% of the total initiator mass, and difunctional polyether polyol with a number average molecular weight of 1800 accounts for 15% of the total initiator mass. The amount of bimetallic cyanide complexing catalyst is 100 ppm of the obtained polyether polyol B. The amount of sulfuric acid is 30 ppm of the obtained polyether polyol B. In the epoxy compound, propylene oxide accounts for 95% of the total epoxy compound mass, ethylene oxide accounts for 3% of the total epoxy compound mass, butane oxide accounts for 1% of the total epoxy compound mass, and cyclohexane oxide accounts for 1% of the total epoxy compound mass. The mass of pre-added epoxy compound is 20% of the total epoxy compound mass.

[0069] Example 3

[0070] Preparation of difunctional polyether polyols with a number average molecular weight of 400:

[0071] 145.2 g of propylene glycol, 96.8 g of furanyl dimethyl alcohol, 0.03 g of Zn(II)Fe(III) bimetallic cyanide complex catalyst, and 0.03 g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 530.6 g of propylene oxide and 227.4 g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 110 °C and the reaction pressure was 0.05 MPa, yielding a difunctional polyether polyol with a number average molecular weight of 400.

[0072] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 60:40; the mass ratio of propylene oxide to cyclohexane oxide is 70:30; the amount of Zn(II)Fe(III) bimetallic cyanide complex catalyst is 30 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 30 ppm of the total amount of difunctional polyether polyol products.)

[0073] Preparation of difunctional polyether polyols with a number average molecular weight of 1900:

[0074] 28.8 g of propylene glycol, 23.5 g of furanyl dimethyl alcohol, 0.09 g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.13 g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 616 g of propylene oxide and 331.7 g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 120 °C and the reaction pressure was 0.2 MPa, yielding a difunctional polyether polyol with a number average molecular weight of 1900.

[0075] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 55:45; the mass ratio of propylene oxide to cyclohexane oxide is 65:35; the amount of Zn(II)Co(III) bimetallic cyanide complexing catalyst is 90 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 130 ppm of the total amount of difunctional polyether polyol products.)

[0076] Preparation of high molecular weight, low viscosity polyether polyols:

[0077] 39.2 g of propylene glycol, 35.2 g of difunctional polyether polyol with a number average molecular weight of 400, and 3.9 g of difunctional polyether polyol with a number average molecular weight of 1900 were mixed evenly. 0.18 g of Zn(II)Co(III) bimetallic cyanide complex catalyst and 0.45 g of phosphoric acid were added and mixed evenly. The mixture was vacuum dehydrated under nitrogen bubbling for 2 hours. Then, 584.3 g of epoxide compound was pre-added under a nitrogen atmosphere. The reaction temperature was 115℃, the reaction pressure was 0.1 MPa, and the reaction time was 1 hour. Subsequently, the remaining 2337.4 g of epoxide compound, consisting of a mixture of 1870 g of propylene oxide, 438.2 g of ethylene oxide, 29.2 g of butane oxide, and 584.3 g of cyclohexane oxide, was continuously introduced. The reaction system temperature was controlled at 135℃, the reaction pressure at 0.01 MPa, and the reaction time was 2 hours. After aging at 130℃ for 2 hours and degassing, ultra-high molecular weight, low viscosity MS adhesive polyether polyol C with a number average molecular weight of 12064 was obtained.

[0078] In this mixture, by mass percentage, propylene glycol accounts for 50% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 400 accounts for 45% of the total initiator mass, and difunctional polyether polyol with a number average molecular weight of 1900 accounts for 5% of the total initiator mass. The amount of bimetallic cyanide complexing catalyst is 60 ppm of the obtained polyether polyol C. The amount of acid is 150 ppm of the obtained polyether polyol C. In the epoxy compounds, propylene oxide accounts for 64% of the total epoxy compound mass, ethylene oxide accounts for 15% of the total epoxy compound mass, butane oxide accounts for 1% of the total epoxy compound mass, and cyclohexane oxide accounts for 20% of the total epoxy compound mass. The mass of pre-added epoxy compounds is 20% of the total epoxy compound mass.

[0079] Example 4

[0080] Preparation of difunctional polyether polyols with a number average molecular weight of 2200:

[0081] 24.6 g of propylene glycol, 20.1 g of furanyl dimethyl alcohol, 0.06 g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.07 g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 621 g of propylene oxide and 334.3 g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 120 °C and the reaction pressure was 0.2 MPa, yielding a difunctional polyether polyol with a number average molecular weight of 2200.

[0082] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 55:45; the mass ratio of propylene oxide to cyclohexane oxide is 65:35; the amount of Zn(II)Co(III) bimetallic cyanide complex catalyst is 60 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 70 ppm of the total amount of difunctional polyether polyol products.)

[0083] Preparation of high molecular weight, low viscosity polyether polyols:

[0084] 79g of propylene glycol, 126.4g of a difunctional polyether polyol with a number-average molecular weight of 400 (same as in Example 3), and 110.6g of a difunctional polyether polyol with a number-average molecular weight of 2200 were mixed evenly. 0.15g of a Zn(II)Fe(III) bimetallic cyanide complex catalyst and 0.15g of phosphoric acid were added and mixed evenly. The mixture was vacuum dehydrated under nitrogen bubbling for 4 hours. Then, 403g of epoxide was pre-introduced under a nitrogen atmosphere. The reaction temperature was 112°C, the reaction pressure was 0.12 MPa, and the reaction time was 0.2 hours. Subsequently, the remaining 2281g of epoxide was continuously introduced. This epoxide consisted of a mixture of 2147.2g of propylene oxide, 134.2g of ethylene oxide, 134.2g of butane oxide, and 268.4g of cyclohexane oxide. The reaction temperature was controlled at 130°C, the reaction pressure at 0.30 MPa, and the reaction time was 3 hours. After aging at 130℃ for 2.5 hours and degassing, ultra-high molecular weight, low viscosity MS colloid polyether polyol D with a number average molecular weight of 8976 was obtained.

[0085] In this mixture, by mass percentage, propylene glycol accounts for 25% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 400 accounts for 40% of the total initiator mass, and difunctional polyether polyol with a number average molecular weight of 2200 accounts for 35% of the total initiator mass. The amount of bimetallic cyanide complexing catalyst is 50 ppm of the obtained polyether polyol D. The amount of acid is 50 ppm of the obtained polyether polyol D. In the epoxy compounds, propylene oxide accounts for 80% of the total epoxy compound mass, ethylene oxide accounts for 5% of the total epoxy compound mass, butane oxide accounts for 5% of the total epoxy compound mass, and cyclohexane oxide accounts for 10% of the total epoxy compound mass. The mass of pre-added epoxy compounds is 15% of the total epoxy compound mass.

[0086] Example 5

[0087] Preparation of difunctional polyether polyols with a number average molecular weight of 2100:

[0088] 29.1 g of propylene glycol, 15.7 g of furanyl dimethyl alcohol, 0.07 g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.12 g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 716.4 g of propylene oxide and 238.8 g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 125 °C and the reaction pressure was 0.35 MPa, yielding a difunctional polyether polyol with a number average molecular weight of 2100.

[0089] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 65:35; the mass ratio of propylene oxide to cyclohexane oxide is 75:25; the amount of Zn(II)Co(III) bimetallic cyanide complexing catalyst is 70 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 120 ppm of the total amount of difunctional polyether polyol products.)

[0090] Preparation of high molecular weight, low viscosity polyether polyols:

[0091] 82.9 g of propylene glycol, 34.6 g of difunctional polyether polyol with a number average molecular weight of 400 (same as in Example 3), and 20.8 g of difunctional polyether polyol with a number average molecular weight of 2100 were mixed evenly. 0.045 g of Zn(II)Fe(III) bimetallic cyanide complex catalyst and 0.51 g of phosphoric acid were added and mixed evenly. The mixture was then vacuum dehydrated under nitrogen bubbling for 2.5 hours. Subsequently, 286.2 g of epoxide compound was pre-added under a nitrogen atmosphere. The reaction temperature was 113°C, the reaction pressure was 0.05 MPa, and the reaction time was 0.5 hours. Then, the remaining 2575.6g of epoxy compound was continuously introduced. This epoxy compound consisted of a mixture of 2575.6g propylene oxide, 57.2g ethylene oxide, 28.6g butane oxide, and 200.3g cyclohexane oxide. The reaction system was maintained at 150℃ and 0.35MPa for 4 hours. Afterward, it was aged at 125℃ for 1.5 hours and degassed to obtain ultra-high molecular weight, low viscosity MS adhesive polyether polyol E with a number average molecular weight of 9672.

[0092] In this mixture, by mass percentage, propylene glycol accounts for 60% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 400 accounts for 25% of the total initiator mass, and difunctional polyether polyol with a number average molecular weight of 2100 accounts for 15% of the total initiator mass. The amount of bimetallic cyanide complexing catalyst is 15 ppm of the obtained polyether polyol E. The amount of acid is 170 ppm of the obtained polyether polyol E. In the epoxy compounds, propylene oxide accounts for 90% of the total epoxy compound mass, ethylene oxide accounts for 2% of the total epoxy compound mass, butane oxide accounts for 1% of the total epoxy compound mass, and cyclohexane oxide accounts for 7% of the total epoxy compound mass. The mass of pre-added epoxy compounds is 10% of the total epoxy compound mass.

[0093] Example 6

[0094] Preparation of difunctional polyether polyols with a number average molecular weight of 450:

[0095] 148.5 g of propylene glycol, 49.5 g of furanyl dimethyl alcohol, 0.05 g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.11 g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 681.7 g of propylene oxide and 120.3 g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 115 °C and the reaction pressure was 0.25 MPa, yielding a difunctional polyether polyol with a number average molecular weight of 450.

[0096] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 75:25; the mass ratio of propylene oxide to cyclohexane oxide is 85:15; the amount of Zn(II)Fe(III) bimetallic cyanide complex catalyst is 50 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 110 ppm of the total amount of difunctional polyether polyol products.)

[0097] Preparation of difunctional polyether polyols with a number average molecular weight of 1850:

[0098] 38g of propylene glycol, 6.8g of furanyl dimethyl alcohol, 0.04g of Zn(II)Fe(III) bimetallic cyanide complex catalyst, and 0.05g of phosphoric acid were mixed evenly. Then, under a nitrogen atmosphere, 577.2g of propylene oxide and 339g of cyclohexane oxide were continuously added. The reaction temperature was 105℃ and the reaction pressure was 0.15MPa, yielding a difunctional polyether polyol with a number average molecular weight of 1850.

[0099] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 85:15; the mass ratio of propylene oxide to cyclohexane oxide is 63:37; the amount of Zn(II)Fe(III) bimetallic cyanide complex catalyst is 40 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 50 ppm of the total amount of difunctional polyether polyol products.)

[0100] Preparation of high molecular weight, low viscosity polyether polyols:

[0101] 51.2 g of propylene glycol, 140.8 g of difunctional polyether polyol with a number average molecular weight of 450, and 64 g of difunctional polyether polyol with a number average molecular weight of 1850 were mixed evenly. 0.36 g of Zn(II)Fe(III) bimetallic cyanide complex catalyst and 0.06 g of sulfuric acid were added and mixed evenly. The mixture was then vacuum dehydrated under nitrogen bubbling for 3.5 hours. Subsequently, 686 g of epoxide was pre-added under a nitrogen atmosphere. The reaction temperature was 116℃, the reaction pressure was 0.03 MPa, and the reaction time was 1.2 hours. Then, the remaining 2058g of epoxy compound was continuously introduced, which was a mixture of 1509.2g of propylene oxide, 548.8g of ethylene oxide, 631.1g of butane oxide, and 54.9g of cyclohexane oxide. The temperature of the reaction system was controlled at 155℃, the pressure in the reaction system was 0.25MPa, and the reaction time was 4.5 hours. After that, it was aged at 130℃ for 2.3 hours and degassed to obtain ultra-high molecular weight, low viscosity MS adhesive polyether polyol F with a number average molecular weight of 8373.

[0102] In the mixed initiator, by mass percentage, propylene glycol accounts for 20% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 450 accounts for 55% of the total initiator mass, and difunctional polyether polyol with a number average molecular weight of 1850 accounts for 25% of the total initiator mass. The amount of bimetallic cyanide complexing catalyst is 120 ppm of the obtained polyether polyol. The amount of acid is 20 ppm of the initiator mass. In the epoxy compound, propylene oxide accounts for 55% of the total epoxy compound mass, ethylene oxide accounts for 20% of the total epoxy compound mass, butane oxide accounts for 23% of the total epoxy compound mass, and cyclohexane oxide accounts for 2% of the total epoxy compound mass. The mass of the pre-added epoxy compound is 25% of the total epoxy compound mass.

[0103] Example 7

[0104] Preparation of difunctional polyether polyols with a number average molecular weight of 350:

[0105] 151.6 g of propylene glycol, 134.4 g of furanyl dimethyl alcohol, 0.02 g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.06 g of phosphoric acid were mixed evenly. Then, an epoxy compound, consisting of 656.9 g of propylene oxide and 57.1 g of cyclohexane oxide, was continuously added under a nitrogen atmosphere. The reaction temperature was 120 °C and the reaction pressure was 0.2 MPa, yielding a difunctional polyether polyol with a number average molecular weight of 350.

[0106] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 53:47; the mass ratio of propylene oxide to cyclohexane oxide is 82:8; the amount of Zn(II)Co(III) bimetallic cyanide complex catalyst is 20 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 60 ppm of the total amount of difunctional polyether polyol products.)

[0107] Preparation of difunctional polyether polyols with a number average molecular weight of 1950:

[0108] 25g of propylene glycol, 7.1g of furanyl dimethyl alcohol, 0.11g of Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.08g of phosphoric acid were mixed evenly. Then, under a nitrogen atmosphere, 809.2g of propylene oxide and 165.8g of cyclohexane oxide were continuously added. The reaction temperature was 110℃ and the reaction pressure was 0.3MPa, yielding a difunctional polyether polyol with a number average molecular weight of 1950.

[0109] (The mass ratio of propylene glycol to furanyl dimethyl alcohol is 78:22; the mass ratio of propylene oxide to cyclohexane oxide is 83:17; the amount of Zn(II)Co(III) bimetallic cyanide complex catalyst is 110 ppm of the total amount of difunctional polyether polyol products; the amount of phosphoric acid is 80 ppm of the total amount of difunctional polyether polyol products.)

[0110] Preparation of high molecular weight, low viscosity polyether polyols:

[0111] 60.1g of propylene glycol, 84.1g of difunctional polyether polyol with a number average molecular weight of 350, and 96.2g of difunctional polyether polyol with a number average molecular weight of 1950 were mixed evenly. 0.27g of Zn(II)Fe(III) bimetallic cyanide complexing catalyst and 0.39g of sulfuric acid were added and mixed evenly. The mixture was then vacuum dehydrated under nitrogen bubbling for 4.5 hours. Subsequently, 82.8g of epoxide compound was pre-added under a nitrogen atmosphere. The reaction temperature was 117℃, the reaction pressure was 0.07MPa, and the reaction time was 0.7 hours. Then, the remaining 2676.8g of epoxy compound was continuously introduced, which was a mixture of 1655.8g of propylene oxide, 276g of ethylene oxide, 690g of butane oxide, and 137.8g of cyclohexane oxide. The temperature of the reaction system was controlled at 155℃, the pressure in the reaction system was 0.25MPa, and the reaction time was 3.5 hours. After that, it was aged at 135℃ for 1.3 hours and degassed to obtain ultra-high molecular weight, low viscosity MS adhesive polyether polyol G with a molecular weight of 11000.

[0112] In the mixed initiator, by mass percentage, propylene glycol accounts for 25% of the total initiator mass, difunctional polyether polyol with a number average molecular weight of 350 accounts for 35% of the total initiator mass, and difunctional polyether polyol with a number average molecular weight of 1950 accounts for 40% of the total initiator mass. The amount of bimetallic cyanide complexing catalyst is 90 ppm of the obtained polyether polyol. The amount of acid is 130 ppm of the initiator mass. In the epoxy compound, propylene oxide accounts for 60% of the total epoxy compound mass, ethylene oxide accounts for 10% of the total epoxy compound mass, butane oxide accounts for 25% of the total epoxy compound mass, and cyclohexane oxide accounts for 5% of the total epoxy compound mass. The mass of pre-added epoxy compound is 3% of the total epoxy compound mass.

[0113] Comparative Example 1

[0114] 187.5 g of a difunctional polyether polyol with a number average molecular weight of 500 (same as in Example 2), 0.09 g of a Zn(II)Fe(III) bimetallic cyanide complex catalyst, and 0.3 g of sulfuric acid were mixed evenly and dehydrated under vacuum for 5 hours under nitrogen bubbling. Then, 140 g of propylene oxide was added under a nitrogen atmosphere at a reaction temperature of 115°C, a reaction pressure of 0.1 MPa, and a reaction time of 1 hour. The remaining 2672.5 g of propylene oxide was then continuously introduced, and the reaction system temperature was controlled at 125°C, the reaction pressure at 0.07 MPa, and the reaction time was 2 hours. After aging at 130°C for 2 hours and degassing, comparative product M with a molecular weight of 8130 was obtained.

[0115] Comparative Example 2

[0116] 153.8 g of a difunctional polyether polyol with a number average molecular weight of 500 (same as in Example 2), 0.15 g of a Zn(II)Co(III) bimetallic cyanide complex catalyst, and 0.15 g of phosphoric acid were mixed evenly and vacuum dehydrated under nitrogen bubbling for 3 hours. Then, 284.6 g of epoxide was pre-added under a nitrogen atmosphere. The reaction temperature was 110°C, the reaction pressure was 0.12 MPa, and the reaction time was 2 hours. Subsequently, the remaining 2561.6 g of epoxide was continuously introduced. The epoxide consisted of 1821.6 g of propylene oxide, 426.9 g of ethylene oxide, 28.5 g of butane oxide, and 569.2 g of cyclohexane oxide. The reaction system temperature was controlled at 155°C, the reaction pressure at 0.25 MPa, and the reaction time was 3 hours. After aging at 135°C for 3 hours and degassing, comparative product N with a number average molecular weight of 9756 was obtained.

[0117] The properties of the MS gel polyether polyols obtained in Examples 1-7 of this invention are shown in Table 1, and the properties of the products obtained in the comparative examples are also shown in Table 1.

[0118] Table 1 Performance Analysis Results

[0119] Hydroxyl value (mgKOH / g) Viscosity (mPa.s / 25℃) Molecular weight distribution Example 1 14 2000 1.03 Example 2 11.2 3000 1.05 Example 3 9.3 3800 1.12 Example 4 12.5 2100 1.10 Example 5 11.6 3300 1.06 Example 6 13.4 2500 1.06 Example 7 10.2 3500 1.07 Comparative Example 1 13.8 5600 1.17 Comparative Example 2 11.5 4300 1.15

[0120] As can be seen from Table 1, the polyether polyol product for high molecular weight MS adhesive of the present invention has a hydroxyl value of 9-15 mgKOH / g, and has a low product viscosity and a narrow molecular weight distribution.

[0121] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0122] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a high molecular weight, low viscosity polyether polyol, comprising the steps of reacting a mixed diol as an initiator (Ⅰ) with an epoxide compound under the action of a bimetallic cyanide complexing catalyst (Ⅰ) and an auxiliary acid (Ⅰ), wherein, The mixed diol contains propylene glycol (I) and difunctional polyether polyol.

2. The preparation method according to claim 1, characterized in that, The preparation method of the difunctional polyether polyol is as follows: using propylene glycol (II) and a diol containing cyclic groups as initiators (II), the mixture of propylene oxide and cyclohexane oxide is reacted (II) under the action of a bimetallic cyanide complexing catalyst (II) and an auxiliary acid (II) to obtain the difunctional polyether polyol.

3. The preparation method according to claim 2, characterized in that, The cyclic diol is selected from at least one of furanyl diethanol, cyclopentanediol, and cyclohexanediol; and / or, The mass ratio of propylene glycol (II) to the diol containing cyclic groups is 45:55 to 99:1, preferably 50:50 to 90:10; and / or, The mass ratio of propylene oxide to cyclohexane oxide is 50:50 to 99:1, preferably 60:40 to 95:5; and / or, The bimetallic cyanide complex catalyst (II) is selected from at least one of Zn(II)Fe(III) bimetallic cyanide complex catalyst and Zn(II)Co(III) bimetallic 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 bimetallic cyanide complexing catalyst (II) is 5–150 ppm of the total amount of the difunctional polyether polyol product, preferably 15–120 ppm; and / or, The amount of the auxiliary agent acid (II) is 10-200 ppm of the total amount of the difunctional polyether polyol product, preferably 20-170 ppm; and / or, The conditions for reaction (II) are: reaction temperature 100-180℃, preferably 100-150℃; and / or reaction pressure 0.005-0.8MPa, preferably 0.01-0.4MPa.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The preparation method of the high molecular weight, low viscosity polyether polyol includes the following specific steps: Step (1) Use a mixed diol as an initiator (Ⅰ) and mix it evenly with a bimetallic cyanide complexing catalyst (Ⅰ) and an auxiliary acid (Ⅰ); Step (2) After vacuum dehydration under nitrogen bubbling, a portion of epoxy compound is added to initiate reaction (I); Step (3) Add the remaining epoxy compound to continue the reaction (Ⅰ'), and after the reaction, age and degas to obtain the high molecular weight low viscosity polyether polyol.

5. The preparation method according to claim 4, characterized in that, In step (1): The difunctional polyether polyols include difunctional polyether polyol A with a number average molecular weight of 200-800 and difunctional polyether polyol B with a number average molecular weight of 1500-2500; preferably, based on the total weight of the mixed diols being 100 wt%, the content of propylene glycol (I) is 10-80 wt%, the content of difunctional polyether polyol A is 15-60 wt%, and the content of difunctional polyether polyol B is 1-50 wt%; more preferably, based on the total weight of the mixed diols being 100 wt%, the content of propylene glycol (I) is 20-60 wt%, the content of difunctional polyether polyol A is 25-55 wt%, and the content of difunctional polyether polyol B is 1-40 wt%; and / or, The bimetallic cyanide complex catalyst (Ⅰ) is selected from at least one of Zn(Ⅱ)Fe(Ⅲ) bimetallic cyanide complex catalyst and Zn(Ⅱ)Co(Ⅲ) bimetallic 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 bimetallic cyanide complexing catalyst (Ⅰ) is 10–150 ppm, preferably 15–120 ppm, of the total amount of the obtained polyether polyol; and / or, The amount of the auxiliary acid (Ⅰ) is 10 to 200 ppm of the total amount of the initiator (Ⅰ), preferably 20 to 170 ppm.

6. The preparation method according to claim 4, characterized in that, In step (2): The epoxy compound is selected from at least one of epoxide alkanes, preferably a mixture of propylene oxide, ethylene oxide, butane oxide, and cyclohexane oxide; and / or, In step (2), the amount of epoxy compound added is 1-30 wt% of the total epoxy compound, preferably 3-25 wt%; and / or, The conditions for vacuum dehydration are: pressure -0.05 to -0.1 MPa, time 2 to 5 hours; and / or, The conditions for reaction (I) are as follows: the reaction is carried out under a protective gas atmosphere, the reaction temperature is 110-120℃, the reaction pressure is 0.01-0.15MPa, and the reaction time is 0.1-1.5 hours.

7. The preparation method according to claim 6, characterized in that, Based on a total epoxide content of 100 wt%, the amount of propylene oxide is 50-97 wt%, the amount of ethylene oxide is 1-25 wt%, the amount of butane oxide is 1-30 wt%, and the amount of cyclohexane oxide is 1-30 wt%; preferably, based on a total epoxide content of 100 wt%, the amount of propylene oxide is 55-95 wt%, the amount of ethylene oxide is 1-20 wt%, the amount of butane oxide is 1-25 wt%, and the amount of cyclohexane oxide is 1-25 wt%.

8. The preparation method according to claim 4, characterized in that, In step (3): The conditions for reaction (Ⅰ') are as follows: the reaction is carried out under a protective gas atmosphere, the reaction temperature is 125–155 °C, the reaction pressure is 0.01–0.35 MPa, and the reaction time is 1–5 hours; and / or, The aging conditions are: temperature 125-135℃, time 1-3 hours.

9. A high molecular weight, low viscosity polyether polyol obtained by the preparation method according to any one of claims 1 to 8, characterized in that, The high molecular weight, low viscosity polyether polyol has a hydroxyl value of 9–15 mgKOH / g, a viscosity of 2000–4000 mPa·s / 25℃, and a molecular weight distribution index of 1.03–1.

12.

10. The application of the high molecular weight, low viscosity polyether polyol of claim 9 in the synthesis of silane-modified polyether sealant.