A solid superbase catalyst and a method for preparing isomeric alcohol polyethers using the same

Abstract

The application belongs to the technical field of polyether preparation, and discloses a solid superbase catalyst and a method for preparing isomeric alcohol polyether by using the same. The solid superbase catalyst comprises a catalyst carrier and a strong base loaded on the catalyst carrier; the strong base is at least one selected from CH3OK, CH3ONa, KOH and NaOH; and the catalyst carrier comprises one of MgO, ZrO2 and Al2O3. The solid superbase catalyst provided by the application is composed of a catalyst carrier and a strong base loaded on the catalyst carrier, and has high catalytic activity and high reaction efficiency. When the solid superbase catalyst is used as a catalyst, isomeric alcohol polyether with low odor, narrow molecular weight distribution and few by-products can be prepared.

Description

Technical Field

[0001] This invention belongs to the field of polyether preparation technology, specifically relating to a solid superbase catalyst and a method for preparing isomeric alcohol polyethers using the same. Background Technology

[0002] Isomeric alcohol polyethers are polymers of isomeric alcohols and epoxides, possessing excellent wetting, emulsifying, detergency, dispersing, and lubricating properties. They are widely used in industries such as daily chemicals, detergents, textiles, leather, electroplating, papermaking, and synthetic fibers. However, a range of isomeric alcohol polyethers currently produced exhibit unstable properties, leading to quality issues in practical applications such as strong odor, unstable cleaning power, and poor repeatability. Research indicates that the width of the isomeric alcohol polyether's structural distribution and the amount of byproducts directly affect the product's application performance. Products with a narrow distribution and low byproducts have a mild odor, low dynamic surface tension, strong penetration, good foaming properties, and good compatibility with other components, making them widely used in agriculture, emulsion polymerization, petroleum, personal care, mining, and detergents.

[0003] Currently, the main process for preparing isomeric alcohol polyethers uses sodium hydroxide and potassium hydroxide as catalysts to react with epoxides to generate isomeric alcohol polyethers. This process produces isomeric alcohol polyethers with a strong odor, wide distribution, low catalyst activity, and requires a large amount of catalyst. The neutralized product is also opaque. Some studies have proposed a two-step method to synthesize isomeric alcohol polyethers with narrow distribution, first using Lewis acid catalysis followed by traditional base catalysis. Although Lewis acid catalysis can yield isomeric alcohol polyethers of higher quality, the two-step method is cumbersome and produces many byproducts, which can affect the product's application performance.

[0004] Therefore, there is an urgent need to provide a method for preparing isomeric alcohol polyethers that can produce products with low odor, narrow molecular weight distribution, and few byproducts. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a solid superbase catalyst and a method for preparing isomeric alcohol polyethers using the same. The solid superbase catalyst provided by the present invention can produce isomeric alcohol polyethers with low odor, narrow molecular weight distribution, and few byproducts.

[0006] This invention provides a solid superbase catalyst.

[0007] Specifically, a solid superbase catalyst includes a catalyst support and a strong base supported on the catalyst support; the strong base is selected from at least one of CH3OK, CH3ONa, KOH, and NaOH; the catalyst support includes one of MgO, ZrO2, and Al2O3.

[0008] In some embodiments of the present invention, the loading of the strong base is 5% to 60%, that is, the mass ratio of the strong base to the catalyst support is (0.05 to 0.6):1. Preferably, the mass ratio of the strong base to the catalyst support is (0.1 to 0.5):1, such as 0.2:1, 0.3:1, 0.5:1, etc.

[0009] This invention provides a method for preparing the above-mentioned solid superbase catalyst.

[0010] Specifically, the preparation method of the above-mentioned solid superbase catalyst includes the following steps:

[0011] The solid superbase catalyst is prepared by mixing a strong base, a catalyst support, and water, grinding, and drying.

[0012] In some embodiments of the present invention, the catalyst support is pretreated by washing, filtering, drying and calcining in sequence before being mixed with the strong alkali.

[0013] More specifically, the preparation method of the above-mentioned solid superbase catalyst includes the following steps: weighing the catalyst support and strong base, placing them in a mortar, and mixing them to obtain a mixture; adding deionized water according to the mass ratio of the mixture to water of 1:(0.8~1.2), and grinding thoroughly; drying, and then grinding evenly again; finally placing the obtained sample in an oven and drying it at 100~120℃ to constant weight.

[0014] The present invention also provides a method for preparing isomeric alcohol polyethers.

[0015] Specifically, a method for preparing an isomeric alcohol polyether includes the following steps:

[0016] Using isomeric alcohols and epoxides as raw materials, a polymerization reaction is carried out under the above-mentioned solid superbase catalyst to obtain isomeric alcohol polyethers.

[0017] More specifically, a method for preparing an isomeric alcohol polyether includes the following steps:

[0018] The isomeric alcohol was mixed with the above-mentioned solid superbase catalyst, heated after being placed in nitrogen, and then an epoxy compound was added to react. After the reaction pressure did not drop, the mixture was cooled and degassed to obtain the isomeric alcohol polyether.

[0019] In some embodiments of the present invention, the molar ratio of the isomeric alcohol to the epoxide is 1:4 to 60.

[0020] In some embodiments of the present invention, the amount of the solid superbase catalyst added is 0.02% to 0.04% of the total mass of the isomeric alcohol polyether.

[0021] In some embodiments of the present invention, the epoxy compound includes ethylene oxide and / or propylene oxide. That is, the epoxy compound includes ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide in any proportion. By controlling the type of epoxide and the method of addition, isomeric alcohol polyethers with monoblock, diblock, triblock, or random structures can be formed. Furthermore, the structural arrangement of the EO and PO chains in the isomeric alcohol polyether does not affect the stability of the product.

[0022] In some embodiments of the present invention, the temperature of nitrogen application is 20-50°C, and the number of nitrogen applications is 1-4.

[0023] In some embodiments of the present invention, the heating process involves heating to 90–150°C.

[0024] In some embodiments of the present invention, the feeding rate of the epoxy compound is 1-15 g / min, and the pressure is controlled not to exceed 0.5 MPa during the addition of the epoxy compound, such as 0.4 MPa.

[0025] In some embodiments of the present invention, the reaction temperature is 90°C to 95°C.

[0026] In some embodiments of the present invention, the cooling process involves cooling to 60–120°C. Degassing begins when the temperature drops to 60–120°C. The degassing time is 5–30 minutes.

[0027] The present invention also provides an isomeric alcohol polyether.

[0028] Specifically, an isomeric alcohol polyether is prepared by the above method, and the general molecular structure of the isomeric alcohol polyether is shown in formula (1):

[0029]

[0030] In formula (1): b is the number of propylene oxide molecules in the molecule, b = 0 to 20; a and c are the number of ethylene oxide molecules in the molecule, a = 0 to 20 and c = 0 to 20; ROH is an isomer of C8 to C18.

[0031] In some embodiments of the present invention, the C8-C18 isomeric alcohols refer to primary alcohols with branched chains having 8 to 18 carbon atoms. For example, a C8 isomeric alcohol can be 2-ethyl-1-hexanol (CAS: 104-76-7), 6-methyl-1-heptanol (CAS: 26952-21-6), or a mixture of isomeric alcohols with C8 as the main component; a C10 isomeric alcohol can be 2-propyl-1-heptanol (CAS: 25339-17-7), or a mixture of isomeric alcohols with C10 as the main component; a C13 isomeric alcohol can be 2-methyl-1-dodecyl alcohol (CAS: 68526-86-3), or a mixture of isomeric alcohols with C13 as the main component, and so on. The C8-C18 isomeric alcohols also include mixtures of any two or more compounds of C8 to C18 isomeric alcohols in any proportion.

[0032] The solid superbase catalyst provided by this invention comprises a catalyst support and a strong base supported on the catalyst support. In the solid superbase catalyst, the strong base (CH3OK, CH3ONa, KOH, NaOH) modifies the surface of catalyst supports such as MgO, ZrO2, and Al2O3 to form superbases. Specifically, the generation of superbase sites is closely related to the paramagnetic centers formed by the capture of electrons released by alkali metals by anion holes on the surfaces of MgO, ZrO2, and Al2O3, and the accompanying electron-inductive effect. Alkali metal ions adsorbed on the microcrystalline surfaces of the catalyst support... 2- This led to O 2- The increase in the net negative charge of the clusters improved O 2- Its electron-donating ability produces a super-alkaline state. Therefore, using it to prepare isomeric alcohol polyethers can result in products with narrow molecular weight distribution and low by-product content.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] (1) The solid superbase catalyst provided by the present invention is composed of a catalyst support and a strong base supported on the catalyst support. It has high catalytic activity and high reaction efficiency. Using it as a catalyst, isomeric alcohol polyethers with low odor, narrow molecular weight distribution and few by-products can be prepared.

[0035] (2) The preparation method of the isomeric alcohol polyether provided by the present invention is stable, and the prepared product has excellent properties and stable quality. The increase in molecular weight of the isomeric alcohol block polyether, the structural mode of the EO chain and PO chain in the isomeric alcohol polyether, and the increase in the number of carbon atoms of the initiator in the isomeric alcohol polyether do not affect the stability of the product.

[0036] (3) The isomeric alcohol polyether provided by the present invention has low odor, narrow molecular weight distribution, transparent color, few by-products, and wide range of applications; and the production process is simple, the catalyst can be reused, and the production cost is low. Detailed Implementation

[0037] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0038] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0039] Example 1

[0040] A method for preparing a solid superbase catalyst specifically includes the following steps:

[0041] 1g of CH3OK and 10g of MgO were mixed evenly in a mortar, 11g of deionized water was added, and then the mixture was ground thoroughly. After drying, the mixture was ground evenly again, and the resulting sample was placed in an oven and dried overnight at 100℃. A 10% CH3OK / MgO solid superbase catalyst was thus prepared.

[0042] The solid superbase catalyst prepared above is applied to the preparation of isomeric alcohol polyethers, specifically including the following steps:

[0043] First, 260g of 6-methyl-1-heptanol and 0.13g of 10% CH3OK / MgO catalyst were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 90℃, and 176g of ethylene oxide was added dropwise at 10g / min. The reaction temperature was controlled at 90℃~95℃ and the reaction pressure at 0~0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. Then, 232g of propylene oxide was added dropwise at 1g / min. The reaction temperature was controlled at 90℃~95℃ and the reaction pressure at 0~0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 10min. After degassed, the reactor was cooled to 60℃ and filtered through a silk cloth to obtain isomeric alcohol block polyether 334.

[0044] Comparative Example 1

[0045] This comparative example uses the same methods as Example 1 for preparing isomeric alcohol block polyether 334, except that 10% CH3OK / MgO is replaced with CH3OK. Since CH3OK has low catalytic activity, the amount of CH3OK added is 0.39 g (3 times the normal amount). After degassing, the temperature is lowered to 60°C, and glacial acetic acid is added for neutralization. The amount of glacial acetic acid added is 0.39 g.

[0046] Comparative Example 2

[0047] This comparative example uses the same methods as Example 1 for preparing isomeric alcohol block polyether 334, except that 10% CH3OK / MgO is replaced with MgO. Since MgO has low catalytic activity, the amount of MgO added is 0.39 g. After degassing, the temperature is lowered to 60°C, and glacial acetic acid is added for neutralization. The amount of glacial acetic acid added is also 0.39 g.

[0048] Comparative Example 3

[0049] First, add 260g of 6-methyl-1-heptanol and 0.13g of BF3·(CH3CH2)2O to a 2.5L high-pressure reactor. Seal the reactor, start stirring and evacuate. Then, replace the gas in the reactor with nitrogen three times. Raise the temperature to 90℃ and add 176g of ethylene oxide dropwise at 10g / min. Control the reaction temperature at 90℃~95℃ and the reaction pressure at 0~0.5MPa. After the addition is complete, let it mature until the pressure does not drop. Then degas for 10min, cool it to below 40℃, and purge it with nitrogen to atmospheric pressure.

[0050] Add 0.39g KOH to the reactor, seal the reactor, start stirring and evacuate, then replace the gas in the reactor with nitrogen three times, raise the temperature to 90℃, add 232g propylene oxide dropwise at 1g / min, control the reaction temperature at 90℃~95℃, and the reaction pressure at 0~0.5MPa. After the addition is complete, mature until the pressure does not drop, degas (pressure less than -0.098MPa) for 10min, neutralize with 0.39g glacial acetic acid, cool to 60℃ after neutralization, filter through silk cloth and discharge to obtain isomeric alcohol block polyether 334.

[0051] Example 2

[0052] A method for preparing a solid superbase specifically includes the following steps:

[0053] 5g of CH3OK and 10g of MgO were mixed evenly in a mortar, 15g of deionized water was added, and then the mixture was ground thoroughly. After drying, the mixture was ground evenly again, and the resulting sample was placed in an oven and dried overnight at 100℃. A 50% CH3OK / MgO solid superbase catalyst was thus prepared.

[0054] The catalyst prepared above was used in the preparation of isomeric alcohol polyethers, and the specific steps were the same as in Example 1.

[0055] Example 3

[0056] A method for preparing a solid superbase specifically includes the following steps:

[0057] Mix 5g KOH and 10g MgO in a mortar until homogeneous, add 15g deionized water, and then grind thoroughly. Dry, grind again until homogeneous, and place the resulting sample in an oven at 100℃ overnight. A 50% KOH / MgO solid superbase catalyst is thus prepared.

[0058] The catalyst prepared above was used in the preparation of isomeric alcohol polyethers, and the specific steps were the same as in Example 1.

[0059] Example 4

[0060] A method for preparing a solid superbase specifically includes the following steps:

[0061] 3g KOH and 10g ZrO2 were mixed evenly in a mortar, 15g deionized water was added, and then the mixture was ground thoroughly. After drying, the mixture was ground evenly again, and the resulting sample was placed in an oven and dried overnight at 110℃. A 30% KOH / ZrO2 solid superbase catalyst was thus prepared.

[0062] The catalyst prepared above was used in the preparation of isomeric alcohol polyethers, and the specific steps were the same as in Example 1.

[0063] Example 5

[0064] A method for preparing a solid superbase specifically includes the following steps:

[0065] Mix 5g KOH, 5g MgO, and 5g Al2O3 in a mortar until homogeneous, add 15g deionized water, and then grind thoroughly. Dry, grind again until homogeneous, and place the resulting sample in an oven at 120℃ overnight. A 50% KOH / MgO-Al2O3 solid superbase catalyst is thus prepared.

[0066] The catalyst prepared above was used in the preparation of isomeric alcohol polyethers, and the specific steps were the same as in Example 1.

[0067] Example 6

[0068] First, 260g of 6-methyl-1-heptanol and 0.43g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 100°C, and 352g of ethylene oxide was added dropwise at 13g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. Then, 464g of propylene oxide was added dropwise at 2g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 15min. After degassed, the reactor was cooled to 65°C and filtered through a silk cloth to obtain isomeric alcohol block polyether 538.

[0069] Example 7

[0070] First, 260g of 6-methyl-1-heptanol and 0.76g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 140°C, and 704g of ethylene oxide was added dropwise at 15g / min. The reaction temperature was controlled at 140°C to 150°C, and the reaction pressure was 0 to 0.5MPa. After the addition was complete, the reactor was allowed to mature until the pressure did not drop. Then, 928g of propylene oxide was added dropwise at 5g / min. The reaction temperature was controlled at 140°C to 150°C, and the reaction pressure was 0 to 0.5MPa. After the addition was complete, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 20 minutes. After degassed, the reactor was cooled to 65°C and filtered through a silk cloth to obtain isomeric alcohol block polyether 946.

[0071] Example 8

[0072] First, 130g of 6-methyl-1-heptanol and 0.87g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 140°C, and 880g of ethylene oxide was added dropwise at 15g / min. The reaction temperature was controlled at 140°C to 150°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. Then, 1160g of propylene oxide was added dropwise at 10g / min. The reaction temperature was controlled at 140°C to 150°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 20min. After degassed, the reactor was cooled to 65°C and filtered through a silk cloth to obtain isomeric alcohol block polyether 2170.

[0073] Example 9

[0074] First, 130g of 6-methyl-1-heptanol and 0.4g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirring was turned on and a vacuum was drawn. Then, the gas in the reactor was replaced with nitrogen three times. The temperature was raised to 140℃, and 880g of ethylene oxide was added dropwise at 15g / min. The reaction temperature was controlled at 140℃~150℃ and the reaction pressure was 0~0.5MPa. After the addition was completed, the mixture was allowed to mature until the pressure did not drop. The mixture was degassed (pressure less than -0.098MPa) for 20min. After degassed, the temperature was lowered to 65℃ and the mixture was filtered through a silk cloth to obtain isomeric alcohol polyoxyethylene ether 1010.

[0075] Example 10

[0076] First, 130g of 6-methyl-1-heptanol and 0.4g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirring was turned on and a vacuum was drawn. Then, the gas in the reactor was replaced with nitrogen three times. The temperature was raised to 140℃, and 880g of propylene oxide was added dropwise at 10g / min. The reaction temperature was controlled at 140℃~150℃ and the reaction pressure was 0~0.5MPa. After the addition was completed, the mixture was allowed to mature until the pressure did not drop. The mixture was degassed (pressure less than -0.098MPa) for 20min. After degassed, the temperature was lowered to 65℃ and the mixture was filtered through a silk cloth to obtain isomeric alcohol polyoxypropylene ether 1010.

[0077] Example 11

[0078] First, 130g of 6-methyl-1-heptanol and 0.4g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirring was turned on and a vacuum was drawn. Then, the gas in the reactor was replaced with nitrogen three times. The temperature was raised to 140°C, and 880g of a mixture of propylene oxide and propylene oxide was added dropwise at a rate of 10g / min. The reaction temperature was controlled at 140°C to 150°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the mixture was allowed to mature until the pressure did not drop. The mixture was then degassed (pressure less than -0.098MPa) for 20min. After degassed, the temperature was lowered to 65°C and the mixture was filtered through a silk cloth to obtain isomeric alcohol random polyether 1010.

[0079] Example 12

[0080] First, 130g of 6-methyl-1-heptanol and 0.4g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, stirred, and evacuated. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 140°C, and 176g of ethylene oxide was added dropwise at 15g / min. The reaction temperature was controlled at 140°C to 150°C, and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure no longer dropped. Then, 550g of propylene oxide was added dropwise at 10g / min. The reaction temperature was controlled at 140℃~150℃ and the reaction pressure at 0~0.5MPa. After the addition was completed, the mixture was allowed to mature until the pressure no longer dropped. Then, 154g of ethylene oxide was added dropwise at 15g / min. The reaction temperature was controlled at 140℃~150℃ and the reaction pressure at 0~0.5MPa. After the addition was completed, the mixture was allowed to mature until the pressure no longer dropped. The mixture was then degassed (pressure less than -0.098MPa) for 20min. After degassed, the mixture was cooled to 65℃ and filtered through a silk cloth to obtain isomeric alcohol block polyether 1010.

[0081] Example 13

[0082] First, 316g of 2-propyl-1-heptanol and 0.43g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 100°C, and 298g of ethylene oxide was added dropwise at 13g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. Then, 464g of propylene oxide was added dropwise at 2g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 15min. After degassed, the reactor was cooled to 65°C and filtered through a silk cloth to obtain isomeric alcohol block polyether 538.

[0083] Example 14

[0084] First, 400g of isotretinoin and 0.43g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 100°C, and 298g of ethylene oxide was added dropwise at 13g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. Then, 380g of propylene oxide was added dropwise at 2g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 15min. After degassed, the reactor was cooled to 65°C and discharged through a silk cloth filter to obtain isomeric alcohol block polyether 538.

[0085] Example 15

[0086] First, 542g of isooctadecyl alcohol and 0.43g of the 50% KOH / MgO-Al2O3 catalyst prepared in Example 5 were added to a 2.5L high-pressure reactor. The reactor was sealed, the stirrer was turned on and a vacuum was drawn. Then, the gas inside the reactor was replaced with nitrogen three times. The temperature was raised to 100°C, and 228g of ethylene oxide was added dropwise at 13g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. Then, 309g of propylene oxide was added dropwise at 2g / min. The reaction temperature was controlled at 100°C to 105°C and the reaction pressure was 0 to 0.5MPa. After the addition was completed, the reactor was allowed to mature until the pressure did not drop. The reactor was degassed (pressure less than -0.098MPa) for 15min. After degassed, the reactor was cooled to 65°C and discharged through a silk cloth filter to obtain isomeric alcohol block polyether 538.

[0087] Example 16

[0088] The catalyst filtered in Example 15 (if less than 0.43g, new catalyst was added to bring the total to 0.43g) was used in the preparation of isomeric alcohol polyethers, and the specific steps were the same as in Example 15.

[0089] Example 17

[0090] The catalyst filtered in Example 16 (if less than 0.43g, new catalyst was added to bring the total to 0.43g) was used in the preparation of isomeric alcohol polyethers, following the same steps as in Example 15.

[0091] Example 18

[0092] The catalyst filtered in Example 17 (if less than 0.43g, new catalyst was added to bring the total to 0.43g) was used in the preparation of isomeric alcohol polyethers, following the same steps as in Example 15.

[0093] Example 19

[0094] The catalyst filtered in Example 18 (if less than 0.43g, new catalyst was added to bring the total to 0.43g) was used in the preparation of isomeric alcohol polyethers, following the same steps as in Example 15.

[0095] Product effectiveness test

[0096] 1. The appearance, hydroxyl value, and molecular weight distribution of the products obtained in Example 1 and Comparative Examples 1-3 were compared, and the free dioxane, ethylene oxide, and propylene oxide were determined. A comparison of the catalyst types in Example 1 and Comparative Examples 1-3 is shown in Table 1, and the product performance comparison results are shown in Table 2.

[0097] (1) The contents of free dioxane, ethylene oxide and propylene oxide were determined by gas chromatography.

[0098] (2) The hydroxyl value was determined according to the method of GB / T 7383-2020 "Determination of hydroxyl value of nonionic surfactants".

[0099] (3) The molecular weight distribution coefficient was determined by gel chromatography.

[0100] Table 1. Catalyst types used in Example 1 and Comparative Examples 1-3

[0101] project Catalyst types Example 1 <![CDATA[10%CH3OK / MgO]]> Comparative Example 1 <![CDATA[CH3OK]]> Comparative Example 2 MgO Comparative Example 3 <![CDATA[First step: BF3·(CH3CH2)2O, second step: KOH]]>

[0102] Table 2 Comparison of product performance between Example 1 and Comparative Examples 1-3

[0103]

[0104] As shown in Table 2, the product prepared in Example 1 has a narrow molecular weight distribution, the lowest content of free EO, PO, and dioxane (all below the instrument detection limit), a transparent appearance, and a hydroxyl value consistent with the molecular weight corresponding to the feed. The products prepared in Comparative Examples 1 and 2 have a wider molecular weight distribution than those in Example 1, their hydroxyl values ​​differ significantly from the molecular weights corresponding to the feed, and they are opaque. While the product prepared in Comparative Example 3 has a narrow molecular weight distribution, it has a high dioxane content and is also opaque.

[0105] 2. The products obtained in Examples 1-5 were compared in appearance, and their hydroxyl values ​​and molecular weight distributions were determined, as well as the levels of free dioxane, ethylene oxide, and propylene oxide. A comparison of the catalyst types used in Examples 1-5 is shown in Table 3, and the results of the product performance comparison are shown in Table 4.

[0106] Table 3. Catalysts used in Examples 1-5

[0107]

[0108]

[0109] Table 4 Comparison of product performance results obtained in Examples 1-5

[0110]

[0111] As can be seen from Table 4, the products prepared in Examples 1 to 5 have a narrow molecular weight distribution, low content of free EO, PO and dioxane, transparent appearance, and hydroxyl values ​​that match the molecular weights of the feed materials.

[0112] 3. The products obtained in Examples 1 and 6-8 were compared in appearance, and their hydroxyl values ​​and molecular weight distributions were determined, as well as the levels of free dioxane, ethylene oxide, and propylene oxide. A comparison of the catalyst types used in Examples 6-8 is shown in Table 5, and the results of the product performance comparison are shown in Table 6.

[0113] Table 5. Process parameters for Examples 1 and 6-8

[0114]

[0115] Table 6. Comparison of product performance results obtained in Examples 1, 6-8

[0116]

[0117] As shown in Table 6, the products prepared in Examples 1 and 6-8 have narrow molecular weight distributions, low contents of free EO, PO, and dioxane, are transparent, and their hydroxyl values ​​match the molecular weights of the feed materials. This indicates that the quality of the products prepared using the method of this invention remains stable as the molecular weight of the isomeric alcohol block polyether increases.

[0118] 4. The products obtained in Examples 1 and 9-12 were compared in appearance, and their hydroxyl values ​​and molecular weight distributions, as well as the free dioxane, ethylene oxide, and propylene oxide were determined. A comparison of the catalyst types used in Examples 9-12 is shown in Table 7, and the results of the product performance comparison are shown in Table 8.

[0119] Table 7 Process parameters for Examples 1 and 9-12

[0120]

[0121] Table 8 Comparison of product performance results obtained in Examples 1 and 9-12

[0122]

[0123] As shown in Table 8, the products prepared in Examples 1 and 9-12 have narrow molecular weight distributions, low contents of free EO, PO, and dioxane, are transparent, and have hydroxyl values ​​consistent with the molecular weights corresponding to the feed ingredients. The data indicate that the structural configurations of the EO and PO chains in the isomeric alcohol polyether do not affect the stability of the preparation method of this invention.

[0124] 5. The products obtained in Examples 1 and 13-15 were compared in appearance, and their hydroxyl values ​​and molecular weight distributions, as well as the free dioxane, ethylene oxide, and propylene oxide were determined. A comparison of the catalyst types used in Examples 13-15 is shown in Table 9, and the results of the product performance comparison are shown in Table 10.

[0125] Table 9. Types of isomeric alcohols used in Examples 1 and 13-15

[0126] project Types of isomer alcohols Example 1 6-Methyl-1-heptanol Example 13 2-Propyl-1-heptanol Example 14 Isomerized tridecyl alcohol Example 15 Isomeroctadecanol

[0127] Table 10 Comparison of product performance results obtained in Examples 1 and 13-15

[0128]

[0129]

[0130] The data in Table 10 show that increasing the number of carbon atoms in the initiator of the isomeric alcohol polyether does not affect the stability of the preparation method of the present invention.

[0131] 6. The products obtained in Examples 1 and 15-19 were compared in appearance, and their hydroxyl values, molecular weight distributions, free dioxane, ethylene oxide, and propylene oxide were determined. The performance comparison results of the products prepared in Examples 15-19 are shown in Table 11.

[0132] Table 11 Comparison of product performance results obtained in Examples 15-19

[0133]

[0134] As shown in Table 11, the solid superbase catalyst prepared by this invention maintains excellent catalytic activity even after being reused four times, and the quality of the prepared product remains stable. However, upon the fifth reuse, the catalytic activity decreases, the hydroxyl value increases, and the distribution becomes wider. Therefore, this indicates that the solid superbase catalyst prepared by this invention can be reused at least four times.

[0135] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A process for the preparation of a polyether of isomeric alcohols, characterized in that, The method comprises the following steps: The isomeric alcohol polyether is prepared by polymerization of isomeric alcohol and epoxide under the catalysis of the solid super-strong base catalyst; The solid super-strong base catalyst comprises a catalyst carrier and a strong base loaded on the catalyst carrier; the strong base is at least one selected from CH3OK, CH3ONa, KOH and NaOH; and the catalyst carrier comprises one of MgO, ZrO2 and Al2O3; The mass ratio of the strong base to the catalyst carrier is (0.05-0.6):1; The addition amount of the solid super-strong base catalyst is 0.02%-0.04% of the total mass of the isomeric alcohol polyether.

2. The process for the preparation of isomeric polyethers according to claim 1, characterized in that, The preparation method of the solid super-strong base catalyst comprises the following steps: The strong base, the catalyst carrier and water are mixed, ground, and dried to obtain the solid super-strong base catalyst.

3. The method for preparing a polyether of isomeric alcohols according to claim 1, characterized in that, The method comprises the following steps: The isomeric alcohol is mixed with the solid super-strong base catalyst, heated after nitrogen is filled, and then the epoxide is added for reaction; after the reaction pressure does not decrease, the isomeric alcohol polyether is prepared by cooling and degassing treatment.

4. The method for producing isomeric alcohol polyether according to claim 1 or 3, characterized by, The molar ratio of the isomeric alcohol to the epoxide is 1:4-60.

5. The method for producing isomeric alcohol polyether according to claim 1 or 3, characterized by, The epoxide comprises oxirane and / or oxetane.

6. The production method according to claim 5, wherein The feeding speed of the epoxide is 1-15 g / min, and the pressure is controlled to be not higher than 0.5 MPa during the addition of the epoxide.

7. A polyether of isomeric alcohols, characterized in that, The isomeric alcohol polyether is prepared by the preparation method of any one of claims 1-6, and the molecular structure general formula of the isomeric alcohol polyether is shown in formula (1): Formula (1); In formula (1), b is the number of oxetane in the molecule, b=0-20, a and c are the number of oxirane in the molecule, a=0-20, and c=0-20; and ROH is C8-C18 isomeric alcohol.

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