Bio-based organic silicon surfactant, and preparation method therefor and use thereof

Abstract

Disclosed in the present disclosure are a bio-based organic silicon surfactant, and a preparation method therefor and the use thereof. The surfactant has the following structure: Si(CH3)3-O-[Si(CH3)2-O]a-[Si(CH3)R1-O]b-[Si(CH3)R2-O]c-Si(CH3)3. By using a comb-shaped structure with a hydrophobic siloxane as a main chain and a hydrophilic polyether as a side chain, a bio-based substance is grafted and introduced to the polyether at the side chain thereof by means of an epoxide ring-opening reaction, thereby adjusting the hydrophilicity and lipophilicity of the organic silicon surfactant to a certain extent and improving the surface activity of the organic silicon surfactant. The introduction of the bio-based substance can reduce the heat conductivity coefficient of polyurethane foam, increase the flow index of the polyurethane foam and improve the heat insulation performance and flowing performance of the foam. In addition, the synthesis of the organic silicon surfactant provides a new synthesis route for the development of a bio-based foam stabilizer; and the preparation method is simple, easily operated and suitable for industrial production.

Description

A bio-based organosilicon surfactant, its preparation method and application

[0001] Cross-reference of related applications

[0002] This disclosure claims priority and benefits to Chinese Patent Application No. 2024106848624, filed with the China National Intellectual Property Administration on May 30, 2024, entitled "A Bio-based Organosilicon Surfactant and Its Preparation Method and Application", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of polyurethane preparation technology, and more specifically, to a bio-based organosilicon surfactant, its preparation method, and its application. Background Technology

[0004] Polyurethane foam stabilizers are additives that play a crucial role in the preparation of polyurethane foam. Their main function is to adjust the foam's cell structure, making it more uniform and fine, while also improving its stability and preventing problems such as foam collapse and agglomeration. Foam stabilizers have a significant impact on the cell structure, strength, thermal conductivity, and air permeability of rigid polyurethane foams, playing an irreplaceable role. Organosilicon surfactants, with their unique surface activity and dispersing properties in polyurethane foams, are also frequently used as polyurethane foam stabilizers in production.

[0005] Typically, the raw materials used in polyurethane foam production are mostly derived from fossil-based materials such as petroleum, coal, and natural gas. Fossil-based materials are stable, easy to process, relatively low in cost, and easy to standardize production; however, they are non-renewable resources and are gradually being depleted. Furthermore, the overexploitation and use of fossil resources has led to energy depletion, climate change, and environmental pollution. Bio-based materials, on the other hand, are a new type of material manufactured using renewable biomass, including crops, trees, other plants, and their residues and contents, through biological, chemical, and physical methods. Bio-based materials are usually made from renewable resources, reducing dependence on non-renewable resources and contributing to sustainable development. Secondly, bio-based materials are relatively easy to degrade in the natural environment, making them more environmentally friendly and effectively mitigating the environmental pollution pressure caused by fossil-based materials.

[0006] Fossil-based polyether polyols are a primary raw material for polyurethane foam production. Currently, much research focuses on preparing bio-based polyether polyols to replace fossil-based polyether polyols, while research on bio-based polyurethane foam stabilizers is relatively scarce. Therefore, given the trend of bio-based materials replacing fossil-based materials, it is necessary to accelerate the development of green, environmentally friendly bio-based foam stabilizers to replace existing foam stabilizers, thereby reducing the use of fossil-based materials and carbon emissions. Simultaneously, by introducing the unique structures of bio-based materials, their application performance can be improved, enhancing the quality of polyurethane foam and meeting the diverse application requirements of rigid polyurethane foams.

[0007] In view of this, this disclosure is hereby made.

[0008] Summary of the Invention

[0009] The purpose of this disclosure is to provide a bio-based organosilicon surfactant, its preparation method, and its application, in order to improve the aforementioned technical problems.

[0010] This disclosure is implemented as follows:

[0011] This disclosure provides a bio-based organosilicon surfactant having the following structure:

[0012] Si(CH3)3-O-[Si(CH3)2-O] a -[Si(CH3)R1-O] b -[Si(CH3)R2-O] c -Si(CH3)3 where a takes values ​​of 5 to 75, b takes values ​​of 0 to 5, and c takes values ​​of 1 to 12;

[0013] R1 is: -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y -

[0014] R2 is: -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y -CH2(OH)-CH2-(CH2CH2O) z R3;

[0015] In R1 and R2, x takes values ​​of 5 to 20, y takes values ​​of 1 to 7, and z takes values ​​of 0 to 12; R3 is selected from at least one of the groups formed after the phenolic hydroxyl or carboxyl group corresponding to cashew phenol, oleic acid, rosin, and eugenol loses hydrogen.

[0016] Optionally, R3 is selected from any one of the groups formed after the phenolic hydroxyl or carboxyl group corresponding to cashew phenol, oleic acid, rosin, and eugenol loses hydrogen.

[0017] Optionally, the plant oleic acid includes at least one of tung oil acid, ricinoleic acid, soybean oleic acid, jatropha oleic acid, palmitic acid, kitchen waste oleic acid, and rubber seed oleic acid.

[0018] Optionally, R3 is selected from Where n = 0, 1, 2, 3.

[0019] Optionally, the value of a is 20 to 60; optionally, the value of b is 0.3 to 3; optionally, the value of c is 1 to 5; optionally, b + c = 2 to 5; optionally, the value of x is 10 to 20; optionally, the value of y is 2 to 7; optionally, the value of z is 0 to 3.

[0020] Optionally, the value of a is 20 to 60; and / or, the value of b is 0.3 to 2.4; and / or, the value of c is 1 to 4; and / or, b + c = 2 to 5; and / or, the value of x is 12 to 18; and / or, the value of y is 2 to 7; and / or, the value of z is 0 or 3.

[0021] Optionally, the value of a is 20 to 60, the value of b is 0.3 to 2.4, the value of c is 1 to 4, b + c = 2 to 5, the value of x is 12 to 18, the value of y is 2 to 7, and the value of z is 0 or 3.

[0022] Secondly, this disclosure also provides a method for preparing the above-mentioned bio-based organosilicon surfactant, comprising: reacting a hydrogen-containing polysiloxane with an epoxy-terminated allyl polyether under the action of a first catalyst to generate a polyether organosilicon copolymer with a siloxane as the main chain and an epoxy-terminated polyether as the side chain; and subjecting the polyether organosilicon copolymer to an epoxy ring-opening reaction with a bio-based substance under the action of a second catalyst to obtain a bio-based organosilicon surfactant; wherein the bio-based substance is selected from at least one of cashew nut shell powder, vegetable oleic acid, rosin, eugenol, and derivatives thereof.

[0023] Optionally, the reaction temperature of the hydrogen-containing polysiloxane with the epoxy-terminated allyl polyether is 70℃~130℃, and the reaction time is 2h~6h.

[0024] Optionally, the first catalyst is a platinum-based catalyst, which may be a chloroplatinic acid catalyst.

[0025] Optionally, the amount of the first catalyst is 5 ppm to 30 ppm of the total mass of the hydrogen-containing polysiloxane and the epoxy-terminated allyl polyether, and can be 8 ppm to 15 ppm.

[0026] Optionally, the molar ratio of hydrogen-containing polysiloxane to epoxy-terminated allyl polyether is 1:(1.3 to 1.6), or optionally 1:(1.3 to 1.4).

[0027] Optionally, the temperature for the epoxy ring-opening reaction is 60℃~120℃, and the reaction time is 2h~6h;

[0028] Optionally, the second catalyst is an alkaline catalyst. Optionally, the alkaline catalyst is at least one selected from NaOH, KOH, sodium methoxide, potassium methoxide, triethylamine, 4-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]undec-7-ene. Optionally, the alkaline catalyst is KOH, sodium methoxide, 4-dimethylaminopyridine, or 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0029] Optionally, the amount of the second catalyst is 0.1% to 3.0% of the total mass of the polyether organosilicon copolymer and the bio-based material;

[0030] Optionally, the molar ratio of the polyether silicone copolymer to the bio-based material is 1:(0.3 to 1.2), or optionally 1:(0.3 to 1).

[0031] Optionally, the hydrogen-containing polysiloxane is prepared by the following steps: using octamethylcyclotetrasiloxane, high-hydrogen-content silicone oil and hexamethyldisiloxane as raw materials, the hydrogen-containing polysiloxane is obtained by reaction under the action of an acidic substance, wherein the hydrogen content of the high-hydrogen-content silicone oil is 1.2% to 1.6%.

[0032] Optionally, the reaction temperature for generating the hydrogen-containing polysiloxane is 20℃~90℃, and the reaction time is 2h~8h; optionally, after the reaction is completed, the pH is adjusted and then filtered.

[0033] Optionally, the acidic substance is concentrated sulfuric acid or acidic clay, and the amount of acidic substance used is 0.4% to 7% of the total mass of the raw materials.

[0034] Optionally, the acidic substance is acidic clay, and the amount of acidic substance used is 2% to 5% of the total mass of the raw materials.

[0035] Thirdly, this disclosure also provides an application of the above-mentioned bio-based organosilicon surfactant in the preparation of rigid polyurethane foam.

[0036] This disclosure offers the following advantages: It provides a novel organosilicon surfactant with a comb-like structure, consisting of a hydrophobic siloxane as the main chain and hydrophilic polyether as the side chain. The polyether side chain is grafted with bio-based substances via an epoxy ring-opening reaction, thereby adjusting the hydrophilicity and lipophilicity of the organosilicon surfactant to a certain extent and improving its surface activity. Using this bio-based organosilicon surfactant as a polyurethane foam stabilizer can reduce the thermal conductivity of polyurethane foam, increase its flow index, and improve its thermal insulation performance. Furthermore, the synthesis of this bio-based organosilicon surfactant provides a new synthetic route for the development of bio-based foam stabilizers; the preparation method is simple, easy to operate, and suitable for industrial production. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of this disclosure clearer, the technical solutions in the embodiments of this disclosure will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0038] The following provides a detailed description of a bio-based organosilicon surfactant, its preparation method, and its application.

[0039] Some embodiments of this disclosure provide a bio-based organosilicon surfactant having the following structure:

[0040] Si(CH3)3-O-[Si(CH3)2-O] a -[Si(CH3)R1-O] b -[Si(CH3)R2-O] c -Si(CH3)3

[0041] Where a ranges from 5 to 75, b ranges from 0 to 5, and c ranges from 1 to 12;

[0042] R1 is: -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y -

[0043] R2 is: -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y -CH2(OH)-CH2-(CH2CH2O) z R3;

[0044] In R1 and R2, x takes values ​​of 5 to 20, y takes values ​​of 1 to 7, and z takes values ​​of 0 to 12; R3 is selected from at least one of the groups formed after the phenolic hydroxyl or carboxyl group corresponding to cashew phenol, oleic acid, rosin, and eugenol loses hydrogen.

[0045] By grafting bio-based substances onto the side chains of polysiloxanes via an epoxy ring-opening reaction, the hydrophilicity and lipophilicity of organosilicon surfactants are adjusted to some extent, thereby improving their surface activity. Furthermore, the bio-based organosilicon surfactants with this structure, when used as stabilizers for polyurethane foams, can reduce the thermal conductivity of polyurethane foams, increase their flow index, and improve their thermal insulation and flow properties.

[0046] For reference, the value of 'a' can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75, or any value between any two of these values. For example, the value of 'a' can be between 20 and 60.

[0047] For reference, the value of b can be 0, 0.1, 0.3, 0.5, 0.6, 0.8, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 3, 3.5, 3.6, 4, 4.5, or 5, or any value between any two of the above values. For example, the value of b is 0.3 to 3.

[0048] For reference, the value of c can be 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 3, 3.5, 3.6, 4, 4.5, 5, 5.5, 6, 6.5, or 7, or any value between any two of the above values. For example, the value of c is 1 to 5.

[0049] It should be noted that, generally speaking, the sum of the values ​​of b and c is an integer. For example, b + c = 2 to 5.

[0050] For reference, in R1 and R2, the value of x can be 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, 17, 18, 19, or 20, or any value between any two of these values. For example, the value of x is 10 to 20; the value of y can be 1, 2, 3, 4, 5, 6, or 7. For example, the value of y is 2 to 7; the value of z can be 0, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 12. For example, the value of z is 0 to 3. It should be noted that, generally speaking, x, y, and z are integers.

[0051] In some embodiments, R3 is selected from any one of the groups formed by the loss of hydrogen from the phenolic hydroxyl or carboxyl groups of cashew phenol, oleic acid, rosin, and eugenol. That is, R3 is the group obtained after the hydrogen of the phenolic hydroxyl or carboxyl group of the above bio-based substances is removed by reaction. In some embodiments, the bio-based silicone surfactant may also be a mixture of several substances with the above chemical structures containing different R3 groups.

[0052] In some embodiments, the plant oleic acid includes at least one of tung oil acid, ricinoleic acid, soybean oleic acid, jatropha oleic acid, palmitic acid, kitchen waste oleic acid, and rubber seed oleic acid. That is, the plant oleic acid can be any one of tung oil acid, ricinoleic acid, soybean oleic acid, jatropha oleic acid, palmitic acid, kitchen waste oleic acid, and rubber seed oleic acid, or it can be a mixture of two or more of the above substances.

[0053] Specifically, in some implementations, R3 is selected from... Where n = 0, 1, 2, 3.

[0054] Furthermore, some embodiments of this disclosure also provide a method for preparing the above-mentioned bio-based organosilicon surfactant, which includes: reacting a hydrogen-containing polysiloxane with an epoxy-terminated allyl polyether under the action of a first catalyst to generate a polyether organosilicon copolymer with a siloxane as the main chain and an epoxy-terminated polyether as the side chain; and performing an epoxy ring-opening reaction between the polyether organosilicon copolymer and a bio-based substance under the action of a second catalyst to obtain a bio-based organosilicon surfactant; wherein the bio-based substance is selected from at least one of cashew nut shell powder, vegetable oleic acid, rosin, eugenol, and derivatives thereof.

[0055] This synthetic method provides a new synthetic route for the development of bio-based foam stabilizers by using epoxy-terminated polyethers as hydrophilic groups on the side chains and then introducing bio-based substances through epoxy ring-opening reactions. The synthetic method is simple, easy to operate, and suitable for industrial production.

[0056] Some embodiments of this disclosure also provide a method for preparing the above-mentioned bio-based organosilicon surfactant, specifically including the following steps:

[0057] S1. Preparation of hydrogen-containing polysiloxanes.

[0058] Specifically, in some embodiments, octamethylcyclotetrasiloxane, high-hydrogen silicone oil, and hexamethyldisiloxane are used as raw materials, and the hydrogen-containing polysiloxane is obtained by reaction under the action of an acidic substance. The hydrogen content of the high-hydrogen silicone oil is 1.2% to 1.6%, for example, 1.2%, 1.3%, 1.4%, 1.5%, or 1.6%, or between any two of the above percentages.

[0059] For reference, the reaction temperature for generating hydrogen-containing polysiloxanes is 20℃ to 90℃. Exemplarily, the reaction temperature can be 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, or 90℃, or between any two of the above temperatures. The reaction time is 2h to 8h. Exemplarily, the reaction time can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, or 8h, or between any two of the above times. Within the above temperature and time range, the reaction can proceed well and achieve optimal reaction results.

[0060] In some implementations, the pH is adjusted and the mixture is filtered after the reaction is complete.

[0061] For reference, the acidic substance is concentrated sulfuric acid or acidic clay, and the amount of acidic substance used is 0.4% to 7% of the total mass of the raw materials. For example, the amount of acidic substance used can be 0.4%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, or 7% of the total mass of the raw materials, or between any two of the above percentages. For example, the acidic substance is acidic clay, and the amount of acidic substance used is 2% to 5% of the total mass of the raw materials.

[0062] S2. Hydrogen-containing polysiloxane and epoxy-terminated allyl polyether are reacted under the action of a first catalyst to generate a polyether organosilicon copolymer with siloxane as the main chain and epoxy-terminated polyether as the side chain.

[0063] Specifically, in some embodiments, the reaction temperature of the hydrogen-containing polysiloxane with the epoxy-terminated allyl polyether is 70°C to 130°C, for example, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, or 130°C, or between any two of the above temperatures, and the reaction time is 2h to 6h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, or 6h, or between any two of the above times.

[0064] For reference, the first catalyst is a platinum-based catalyst, and in some embodiments, a chloroplatinic acid catalyst may be selected.

[0065] For reference, the amount of the first catalyst is 5 ppm to 30 ppm of the total mass of the hydrogen-containing polysiloxane and the epoxy-terminated allyl polyether, such as 5 ppm, 8 ppm, 15 ppm, 20 ppm, 25 ppm or 30 ppm, or between any two of the above proportions. For example, 8 ppm to 15 ppm can be selected.

[0066] In some embodiments, in order to obtain a polymer with a desired degree of polymerization and chemical structure, the molar ratio of hydrogen-containing polysiloxane to epoxy-terminated allyl polyether is 1:(1.3 to 1.6), for example, a molar ratio of 1:1.3, 1:1.4, 1:1.5 or 1:1.6, etc., and optionally 1:(1.3 to 1.4).

[0067] By selecting the above reaction parameters, the desired epoxy-terminated polyether organic copolymer can be generated with better reaction results.

[0068] S3. The polyether silicone copolymer and the bio-based substance are subjected to an epoxy ring-opening reaction in the presence of a second catalyst to obtain a bio-based silicone surfactant.

[0069] For reference, the temperature for the epoxy ring-opening reaction is 60℃ to 120℃, such as 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃ or 120℃, or between any two of the above temperatures; the reaction time is 2h to 6h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, or between any two of the above times.

[0070] For reference, the second catalyst is a basic catalyst, and in some embodiments, the basic catalyst may be selected from at least one of NaOH, KOH, sodium methoxide, potassium methoxide, triethylamine, 4-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Exemplarily, the basic catalyst is KOH, sodium methoxide, 4-dimethylaminopyridine, or DBU.

[0071] For reference, the amount of the second catalyst is 0.1% to 3.0% of the total mass of the polyether silicone copolymer and the bio-based material, such as 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5% or 3%, or between any two of the above percentages.

[0072] In some embodiments, the molar ratio of the polyether silicone copolymer to the bio-based material is 1:(0.3 to 1.2), such as 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2, or between any two of the above ratios, and can be selected as 1:(0.3 to 1).

[0073] By selecting the above reaction parameters, a better epoxy ring-opening reaction can be achieved between the polyether silicone copolymer and the bio-based material, thereby introducing the bio-based material into the side chain of the silicone copolymer. It should be noted that, generally, not all epoxy groups on the side chain are ring-opened and bonded to the bio-based material.

[0074] Furthermore, some embodiments of this disclosure also provide the application of the above-mentioned bio-based silicone surfactant in the preparation of rigid polyurethane foam. Specifically, the bio-based silicone surfactant is used as a polyurethane foam stabilizer in the rigid polyurethane foam preparation process.

[0075] The features and performance of this disclosure will be further described in detail below with reference to embodiments.

[0076] Example 1

[0077] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0078] (1) Synthesize hydrogen-containing polysiloxanes.

[0079] 11.9 g of high-hydrogen silicone oil with 1.5% hydrogen content, 128.7 g of tetramethylcyclotetrasiloxane, 9.4 g of hexamethyldisiloxane, and 6.0 g of acid clay were added to a three-necked flask, heated to 65°C, and kept at that temperature for 5 hours. The mixture was then filtered to obtain hydrogen-containing polysiloxane.

[0080] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0081] 60g of the hydrogen-containing polysiloxane prepared above, 102g of epoxy-terminated allyl polyether, and 10ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 4 hours to obtain a polyether organosilicon copolymer.

[0082] (3) Synthesize bio-based organosilicon surfactants.

[0083] 162g of the polyether silicone copolymer obtained from the above reaction and 14.7g of cashew phenol were added to a reaction vessel, and 2.0g of KOH was added as a catalyst. The mixture was heated to 100℃ under normal pressure and reacted for 4 hours to obtain a bio-based silicone surfactant.

[0084] The structure of this bio-based organosilicon surfactant is as follows:

[0085] Si(CH3)3-O-[Si(CH3)2-O] 28 -[Si(CH3)R1-O] 1.5 -[Si(CH3)R2-O] 1.5 -Si(CH3)3

[0086] in:

[0087] R1=CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5-

[0088] R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5-CH2(OH)-CH2-R3;

[0089] Example 2

[0090] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0091] (1) Synthesize hydrogen-containing polysiloxanes.

[0092] 9.1g of high-hydrogen silicone oil with 1.5% hydrogen content, 133.7g of tetramethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, and 10g of acid clay were added to a three-necked flask, heated to 65°C, and kept at that temperature for 6 hours. The mixture was then filtered to obtain hydrogen-containing polysiloxane.

[0093] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0094] 60g of the hydrogen-containing polysiloxane prepared above, 55.3g of epoxy-terminated allyl polyether, and 9ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 5 hours to obtain a polyether organosilicon copolymer.

[0095] (3) Synthesize bio-based organosilicon surfactants.

[0096] 115.3g of the polyether silicone copolymer obtained from the above reaction and 12.9g of cashew phenol polyoxyethylene ether were added to a reaction vessel, and 1.5g of KOH was added as a catalyst. The mixture was heated to 110℃ under normal pressure and reacted for 3 hours to obtain a bio-based silicone surfactant.

[0097] The structure of this bio-based organosilicon surfactant is as follows:

[0098] Si(CH3)3-O-[Si(CH3)2-O] 38 -[Si(CH3)R1-O] 1.8 -[Si(CH3)R2-O] 1.2 -Si(CH3)3

[0099] in:

[0100] R1=CH2CH2CH2O(CH2CH2O) 12 (CH2CHCH3O)2- R2=-CH2CH2CH2O(CH2CH2O) 12 (CH2CHCH3O)2-CH2(OH)-CH2-(CH2CH2O)3R3;

[0101] Example 3

[0102] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0103] (1) Synthesize hydrogen-containing polysiloxanes.

[0104] 13.5g of high-hydrogen silicone oil with 1.5% hydrogen content, 128.8g of tetramethylcyclotetrasiloxane, 7.7g of hexamethyldisiloxane, and 1.4g of 98% concentrated sulfuric acid were added to a three-necked flask, heated to 45°C, and kept at this temperature for 7 hours. The pH was adjusted to about 7 with NaHCO3, and then filtered to obtain hydrogen-containing polysiloxane.

[0105] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0106] 60g of the hydrogen-containing polysiloxane prepared above, 97.9g of epoxy-terminated allyl polyether, and 8ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 120°C under normal pressure for 3.5 hours to obtain a polyether organosilicon copolymer.

[0107] (3) Synthesize bio-based organosilicon surfactants.

[0108] 157.9g of the polyether silicone copolymer obtained from the above reaction and 13.3g of rosin were added to a reaction vessel, and 2.0g of sodium methoxide was added as a catalyst. The mixture was heated to 120°C under normal pressure and reacted for 3 hours to obtain a bio-based silicone surfactant.

[0109] The structure of this bio-based organosilicon surfactant is as follows:

[0110] Si(CH3)3-O-[Si(CH3)2-O] 33 -[Si(CH3)R1-O] 2.4 -[Si(CH3)R2-O] 1.6 -Si(CH3)3

[0111] in:

[0112] R1=CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)3-

[0113] R2=-CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)3-CH2(OH)-CH2-R3;

[0114] Example 4

[0115] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0116] (1) Synthesize hydrogen-containing polysiloxanes.

[0117] 10.5g of high-hydrogen silicone oil with 1.5% hydrogen content, 133.5g of tetramethylcyclotetrasiloxane, 6g of hexamethyldisiloxane, and 1.2g of 98% concentrated sulfuric acid were added to a three-necked flask, heated to 40°C, and kept at this temperature for 7 hours. The pH was adjusted to about 7 with NaHCO3, and then filtered to obtain hydrogen-containing polysiloxane.

[0118] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0119] 60g of the hydrogen-containing polysiloxane prepared above, 96g of epoxy-terminated allyl polyether, and 10ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 4 hours to obtain a polyether organosilicon copolymer.

[0120] (3) Synthesize bio-based organosilicon surfactants.

[0121] 156g of the polyether silicone copolymer obtained from the above reaction and 23.2g of rosin were added to a reaction vessel, and 2.5g of 4-dimethylaminopyridine was added as a catalyst. The mixture was heated to 110°C under normal pressure and reacted for 4 hours to obtain a bio-based silicone surfactant.

[0122] The structure of this bio-based organosilicon surfactant is as follows:

[0123] Si(CH3)3-O-[Si(CH3)2-O] 44 -[Si(CH3)R1-O] 0.3 -[Si(CH3)R2-O] 2.7 -Si(CH3)3

[0124] in:

[0125] R1=CH2CH2CH2O(CH2CH2O) 18 (CH2CHCH3O)4-

[0126] R2=-CH2CH2CH2O(CH2CH2O) 18 (CH2CHCH3O)4-CH2(OH)-CH2-R3;

[0127] Example 5

[0128] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0129] (1) Synthesize hydrogen-containing polysiloxanes.

[0130] 6.7g of high-hydrogen silicone oil with 1.5% hydrogen content, 135.3g of tetramethylcyclotetrasiloxane, 8.1g of hexamethyldisiloxane, and 6g of acid clay were added to a three-necked flask, heated to 85°C, and kept at that temperature for 4 hours. The mixture was then filtered to obtain hydrogen-containing polysiloxane.

[0131] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0132] 60g of the hydrogen-containing polysiloxane prepared above, 48.5g of epoxy-terminated allyl polyether, and 11ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 4 hours to obtain a polyether organosilicon copolymer.

[0133] (3) Synthesize bio-based organosilicon surfactants.

[0134] 108g of the polyether silicone copolymer obtained from the above reaction and 5.3g of eugenol were added to a reaction vessel, and 1.4g of KOH was added as a catalyst. The mixture was heated to 100℃ under normal pressure and reacted for 4 hours to obtain a bio-based silicone surfactant.

[0135] The structure of this bio-based organosilicon surfactant is as follows:

[0136] Si(CH3)3-O-[Si(CH3)2-O] 35 -[Si(CH3)R1-O] 0.8 -[Si(CH3)R2-O] 1.2 -Si(CH3)3

[0137] in:

[0138] R1=CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)3-

[0139] R2=-CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)3-CH2(OH)-CH2-R3;

[0140] Example 6

[0141] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0142] (1) Synthesize hydrogen-containing polysiloxanes.

[0143] 10.9g of high-hydrogen silicone oil with 1.5% hydrogen content, 134.2g of tetramethylcyclotetrasiloxane, 4.9g of hexamethyldisiloxane, and 1g of 98% concentrated sulfuric acid were added to a three-necked flask, heated to 50°C, and kept at this temperature for 6 hours. The pH was adjusted to about 7 with NaHCO3, and then filtered to obtain hydrogen-containing polysiloxane.

[0144] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0145] 60g of the hydrogen-containing polysiloxane prepared above, 107.8g of epoxy-terminated allyl polyether, and 10ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 4 hours to obtain a polyether organosilicon copolymer.

[0146] (3) Synthesize bio-based organosilicon surfactants.

[0147] 167.8g of the polyether silicone copolymer obtained from the above reaction and 11.7g of eugenol were added to a reaction vessel, and 1.9g of DBU was added as a catalyst. The mixture was heated to 120℃ under normal pressure and reacted for 4 hours to obtain a bio-based silicone surfactant.

[0148] The structure of this bio-based organosilicon surfactant is as follows:

[0149] Si(CH3)3-O-[Si(CH3)2-O] 53 -[Si(CH3)R1-O]1-[Si(CH3)R2-O]4-Si(CH3)3

[0150] in:

[0151] R1=CH2CH2CH2O(CH2CH2O) 16 (CH2CHCH3O)7-

[0152] R2=-CH2CH2CH2O(CH2CH2O) 16 (CH2CHCH3O)7-CH2(OH)-CH2-R3;

[0153] Example 7

[0154] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0155] (1) Synthesize hydrogen-containing polysiloxanes.

[0156] 11.1g of high-hydrogen silicone oil with 1.5% hydrogen content, 132.5g of tetramethylcyclotetrasiloxane, 6.4g of hexamethyldisiloxane, and 1.2g of 98% concentrated sulfuric acid were added to a three-necked flask, heated to 40°C, and kept at this temperature for 6 hours. The pH was adjusted to about 7 with NaHCO3, and then filtered to obtain hydrogen-containing polysiloxane.

[0157] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0158] 60g of the hydrogen-containing polysiloxane prepared above, 99.5g of epoxy-terminated allyl polyether, and 15ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 4.5 hours to obtain a polyether organosilicon copolymer.

[0159] (3) Synthesize bio-based organosilicon surfactants.

[0160] 159.5g of the polyether organosilicon copolymer obtained from the above reaction and 10.8g of castor oil acid were added to a reaction vessel, and 1.8g of triethylamine was added as a catalyst. The mixture was heated to 110℃ under normal pressure and reacted for 4.5 hours to obtain a bio-based organosilicon surfactant.

[0161] The structure of this bio-based organosilicon surfactant is as follows:

[0162] Si(CH3)3-O-[Si(CH3)2-O] 41 -[Si(CH3)R1-O] 2.4 -[Si(CH3)R2-O] 1.6 -Si(CH3)3

[0163] in:

[0164] R1=CH2CH2CH2O(CH2CH2O) 16 (CH2CHCH3O)5-

[0165] R2=-CH2CH2CH2O(CH2CH2O) 16 (CH2CHCH3O)5-CH2(OH)-CH2-R3;

[0166] Example 8

[0167] This embodiment provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0168] (1) Synthesize hydrogen-containing polysiloxanes.

[0169] 7.7g of high-hydrogen silicone oil with 1.5% hydrogen content, 136.3g of tetramethylcyclotetrasiloxane, 6g of hexamethyldisiloxane, and 8g of acid clay were added to a three-necked flask, heated to 85°C, and kept at that temperature for 4 hours. The mixture was then filtered to obtain hydrogen-containing polysiloxane.

[0170] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0171] 60g of the hydrogen-containing polysiloxane prepared above, 63.1g of epoxy-terminated allyl polyether, and 12ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 130°C under normal pressure for 3 hours to obtain a polyether organosilicon copolymer.

[0172] (3) Synthesize bio-based organosilicon surfactants.

[0173] 123.1 g of the polyether organosilicon copolymer obtained from the above reaction and 13.0 g of ricinoleic acid were added to a reaction vessel, and 1.5 g of 4-dimethylaminopyridine was added as a catalyst. The mixture was heated to 100 °C under normal pressure and reacted for 2.5 hours to obtain a bio-based organosilicon surfactant.

[0174] The structure of this bio-based organosilicon surfactant is as follows:

[0175] Si(CH3)3-O-[Si(CH3)2-O] 46 -[Si(CH3)R1-O] 0.9 -[Si(CH3)R2-O] 2.1 -Si(CH3)3

[0176] in:

[0177] R1=CH2CH2CH2O(CH2CH2O) 18 (CH2CHCH3O)2-

[0178] R2=-CH2CH2CH2O(CH2CH2O) 18 (CH2CHCH3O)2-CH2(OH)-CH2-R3;

[0179] Comparative Example 1

[0180] This comparative example provides a method for preparing an organosilicon surfactant, which specifically includes the following steps:

[0181] (1) Synthesize hydrogen-containing polysiloxanes.

[0182] Hydrogen-containing polysiloxanes were synthesized using the same method as in Example 1.

[0183] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0184] The same method as in Example 1 was used to synthesize a polyether organosilicon copolymer with epoxy-terminated polyethers as side chains. This polyether organosilicon copolymer is the organosilicon surfactant of this comparative example.

[0185] Its structure is as follows:

[0186] Si(CH3)3-O-[Si(CH3)2-O] 28 -[Si(CH3)R1-O]3-Si(CH3)3

[0187] in:

[0188] R1=CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5-

[0189] Comparative Example 2

[0190] This comparative example provides a method for preparing an organosilicon surfactant, which specifically includes the following steps:

[0191] (1) Synthesize hydrogen-containing polysiloxanes.

[0192] Hydrogen-containing polysiloxanes were synthesized using the same method as in Example 1.

[0193] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0194] The same method as in Example 2 was used to synthesize a polyether organosilicon copolymer with epoxy-terminated polyethers as side chains. This polyether organosilicon copolymer is the organosilicon surfactant of this comparative example.

[0195] Its structure is as follows:

[0196] Si(CH3)3-O-[Si(CH3)2-O] 38 -[Si(CH3)R1-O]3-Si(CH3)3

[0197] in:

[0198] R1=CH2CH2CH2O(CH2CH2O) 12 (CH2CHCH3O)2-

[0199] Comparative Example 3

[0200] This comparative example provides a method for preparing an organosilicon surfactant, which specifically includes the following steps:

[0201] (1) Synthesize hydrogen-containing polysiloxanes.

[0202] Hydrogen-containing polysiloxanes were synthesized using the same method as in Example 2.

[0203] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0204] 60g of the hydrogen-containing polysiloxane prepared above, 97.8g of allyl-terminated polyether, and 10ppm of chloroplatinic acid catalyst were added to a reaction vessel and reacted at atmospheric pressure to 105°C for 3 hours to obtain a polyether-organic silicone copolymer. This polyether-organic silicone copolymer is the silicone surfactant of this comparative example.

[0205] The structure of this organosilicon surfactant is as follows:

[0206] Si(CH3)3-O-[Si(CH3)2-O] 28 -[Si(CH3)R1-O]3-Si(CH3)3

[0207] in:

[0208] R1=CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5-H.

[0209] Comparative Example 4

[0210] This comparative example provides a method for preparing an organosilicon surfactant, which specifically includes the following steps:

[0211] (1) Synthesize hydrogen-containing polysiloxanes.

[0212] Hydrogen-containing polysiloxanes were synthesized using the same method as in Example 2.

[0213] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0214] 60g of the hydrogen-containing polysiloxane prepared above, 52.2g of allyl-terminated polyether, and 15ppm of chloroplatinic acid catalyst were added to a reaction vessel and heated to 115°C under normal pressure for 4 hours to obtain a polyether-organic silicone copolymer. This polyether-organic silicone copolymer is the silicone surfactant of this comparative example.

[0215] The structure of this organosilicon surfactant is as follows:

[0216] Si(CH3)3-O-[Si(CH3)2-O] 38 -[Si(CH3)R1-O]3-Si(CH3)3

[0217] in:

[0218] R1=CH2CH2CH2O(CH2CH2O) 12 (CH2CHCH3O)2-H.

[0219] Comparative Example 5

[0220] This comparative example provides a method for preparing a bio-based organosilicon surfactant, which specifically includes the following steps:

[0221] (1) Synthesize hydrogen-containing polysiloxanes.

[0222] Hydrogen-containing polysiloxanes were synthesized using the same method as in Example 1.

[0223] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0224] The polyether organosilicon copolymer was synthesized using the same method as in Example 1.

[0225] (3) Synthesize bio-based organosilicon surfactants.

[0226] 162g of the polyether silicone copolymer obtained from the above reaction and 5.6g of cashew phenol were added to a reaction vessel, and 2.5g of sodium methoxide was added as a catalyst. The mixture was heated to 100°C under normal pressure and reacted for 4 hours to obtain a bio-based silicone surfactant.

[0227] The structure of this bio-based organosilicon surfactant is as follows:

[0228] Si(CH3)3-O-[Si(CH3)2-O] 28 -[Si(CH3)R1-O] 2.4 -[Si(CH3)R2-O] 0.6 -Si(CH3)3

[0229] in:

[0230] R1=CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5-

[0231] R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5-CH2(OH)-CH2-R3;

[0232] Comparative Example 6

[0233] This comparative example provides a method for preparing a bio-organic silicon surfactant, which specifically includes the following steps:

[0234] (1) Synthesize hydrogen-containing polysiloxanes.

[0235] Hydrogen-containing polysiloxanes were synthesized using the same method as in Example 2.

[0236] (2) Synthesize polyether organosilicon copolymers with epoxy-terminated polyethers as side chains.

[0237] The polyether organosilicon copolymer was synthesized using the same method as in Example 2.

[0238] (3) Synthesize bio-based organosilicon surfactants.

[0239] 115.3g of the polyether silicone copolymer obtained from the above reaction and 6.5g of cashew phenol polyoxyethylene ether were added to a reaction vessel, and 1.7g of triethylamine was added as a catalyst. The mixture was heated to 110°C under normal pressure and reacted for 3 hours to obtain a bio-based silicone surfactant.

[0240] The structure of this bio-based organosilicon surfactant is as follows:

[0241] Si(CH3)3-O-[Si(CH3)2-O] 38 -[Si(CH3)R1-O] 2.4 -[Si(CH3)R2-O] 0.6 -Si(CH3)3

[0242] in:

[0243] R1=CH2CH2CH2O(CH2CH2O) 12 (CH2CHCH3O)2- R2=-CH2CH2CH2O(CH2CH2O) 12 (CH2CHCH3O)2-CH2(OH)-CH2-(CH2CH2O)3R3;

[0244] Experimental Example 1

[0245] The thermal conductivity of the bio-based silicone surfactants of Examples 1-8, the silicone surfactants of Comparative Examples 1 and 2, the conventional silicone surfactants of Comparative Examples 3 and 4, and the bio-based silicone surfactants outside the protection scope of Comparative Examples 5 and 6, when applied to polyurethane foam products, was tested. The formulations are as follows:

[0246] Table 1. Rigid polyurethane foam formulation

[0247] Preparation of rigid polyurethane foam: The formulation is shown in Table 1. During polyurethane foam preparation, the components of the formulation are mixed and stirred at 6000 r / min. Before the foam freely expands, it is poured into a standard mold (mold temperature 25℃) to produce polyurethane foam.

[0248] The performance of the rigid polyurethane or isocyanate foam obtained above was tested, and the results are shown in Table 2. The thermal conductivity (λ) was determined in accordance with GB / T 10295-2008 Determination of steady-state thermal resistance and related properties of thermal insulation materials, and the closed-cell content was determined in accordance with GB / T 10799-2008 Determination of open-cell and closed-cell volume percentage of rigid foam plastics.

[0249] Table 2 Detection Results

[0250] The results in Table 2 show that, during the preparation of rigid polyurethane foam, polyurethane foam prepared with bio-based silicone surfactants, silicone surfactants, and epoxy-containing silicone surfactants outside the protection scope has poor thermal insulation performance and low closed-cell rate. Polyurethane foam prepared with the bio-based silicone surfactant synthesized in this disclosure has better thermal insulation performance and a higher closed-cell rate.

[0251] Experimental Example 2

[0252] The flow properties of Examples 1-8 and Comparative Examples 1-6 were tested when applied to polyurethane foam products, and their formulations are as follows:

[0253] Table 3 Formula

[0254] Table 4 Test Results

[0255] The results in Table 4 show that, during the preparation of rigid polyurethane foam, polyurethane foam prepared with bio-based silicone surfactants, silicone surfactants, and epoxy-containing silicone surfactants outside the protection scope has poor flow properties and low flow index. Polyurethane foam prepared with the bio-based silicone surfactant synthesized in this disclosure has better flow properties and a higher flow index.

[0256] In summary, the present disclosure provides a bio-based organosilicon surfactant and its preparation method. Using epoxy-terminated polyether as the hydrophilic group, and introducing bio-based substances through an epoxy ring-opening reaction, the hydrophilicity and lipophilicity of the organosilicon surfactant are adjusted to a certain extent, thereby improving its surface activity. Introducing this structure can reduce the thermal conductivity of polyurethane foam, increase its flow index, and improve its thermal insulation performance. This provides a new route for the synthesis of bio-based organosilicon surfactants. The surfactant preparation method is simple, easy to operate, and suitable for industrial production.

[0257] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this disclosure, and are not intended to limit them. Although this disclosure has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this disclosure. Industrial applicability

[0258] This disclosure provides a novel organosilicon surfactant with a comb-like structure, consisting of a hydrophobic siloxane as the main chain and hydrophilic polyether as the side chain. The polyether side chains are grafted with bio-based substances via an epoxy ring-opening reaction, thereby modulating the hydrophilicity and lipophilicity of the organosilicon surfactant to a certain extent and improving its surface activity. Using this bio-based organosilicon surfactant as a polyurethane foam stabilizer can reduce the thermal conductivity of polyurethane foam, increase its flow index, and improve its thermal insulation performance. The synthesis method of this bio-based organosilicon surfactant is simple, easy to operate, and suitable for industrial production.

Claims

1. A bio-based organosilicon surfactant, characterized in that, It has the following structure: Si(CH3)3-O-[Si(CH3)2-O] a -[Si(CH3)R1-O] b -[Si(CH3)R2-O] c -Si(CH3)3 Where a ranges from 5 to 75, b ranges from 0 to 5, and c ranges from 1 to 12; R1 is: R2 is: -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y -CH2(OH)-CH2-(CH2CH2O) z R3; In R1 and R2, x takes values ​​of 5 to 20, y takes values ​​of 1 to 7, and z takes values ​​of 0 to 12; R3 is selected from at least one of the groups formed after the phenolic hydroxyl or carboxyl group corresponding to cashew phenol, oleic acid, rosin, and eugenol loses hydrogen.

2. The bio-based organosilicon surfactant according to claim 1, characterized in that, The plant oleic acid includes at least one of tung oil acid, ricinoleic acid, soybean oleic acid, jatropha oleic acid, palmitic acid, kitchen waste oleic acid, and rubber seed oleic acid.

3. The bio-based organosilicon surfactant according to claim 1 or 2, characterized in that, R3 is selected from any one of the groups formed after the phenolic hydroxyl or carboxyl group corresponding to cashew phenol, oleic acid, rosin, and eugenol loses hydrogen.

4. The bio-based organosilicon surfactant according to any one of claims 1 to 3, characterized in that, R3 is selected from Where n = 0, 1, 2, 3.

5. The bio-based organosilicon surfactant according to any one of claims 1 to 4, characterized in that, The value of a ranges from 20 to 60; And / or, the value of b ranges from 0.3 to 3; And / or, the value of c ranges from 1 to 5; And / or, b+c = 2~5; And / or, x takes values ​​from 10 to 20; And / or, the value of y ranges from 2 to 7; And / or, z takes values ​​from 0 to 3.

6. The bio-based organosilicon surfactant according to any one of claims 1 to 5, characterized in that, The value of a ranges from 20 to 60; And / or, the value of b ranges from 0.3 to 2.4; And / or, the value of c ranges from 1 to 4; And / or, b+c = 2~5; And / or, x takes values ​​from 12 to 18; And / or, the value of y ranges from 2 to 7; And / or, z takes the value 0 or 3.

7. The bio-based organosilica surfactant according to any one of claims 1 to 6, characterized in that, The values ​​of a range from 20 to 60, the values ​​of b range from 0.3 to 2.4, the values ​​of c range from 1 to 4, b + c = 2 to 5, the values ​​of x range from 12 to 18, the values ​​of y range from 2 to 7, and the values ​​of z range from 0 to 3.

8. A method for preparing a bio-based organosilicon surfactant as described in any one of claims 1 to 7, characterized in that, It includes: Hydrogen-containing polysiloxanes and epoxy-terminated allyl polyethers are reacted under the action of a first catalyst to generate polyether organosilicon copolymers with siloxanes as the main chain and epoxy-terminated polyethers as the side chains. The polyether silicone copolymer was subjected to an epoxy ring-opening reaction with a bio-based substance under the action of a second catalyst to obtain a bio-based silicone surfactant. The bio-based substance is selected from at least one of cashew phenol, oleic acid, rosin, eugenol, and their corresponding derivatives.

9. The preparation method according to claim 8, characterized in that, The reaction temperature of the hydrogen-containing polysiloxane with the epoxy-terminated allyl polyether is 70℃~130℃, and the reaction time is 2h~6h. And / or, the first catalyst is a platinum-based catalyst; And / or, the amount of the first catalyst is 5 ppm to 30 ppm of the total mass of the hydrogen-containing polysiloxane and the epoxy-terminated allyl polyether; And / or, the molar ratio of the hydrogen-containing polysiloxane to the epoxy-terminated allyl polyether is 1: (1.3～1.6)。 10. The preparation method according to claim 9, characterized in that, The platinum-based catalyst is a chloroplatinic acid catalyst.

11. The preparation method according to claim 9 or 10, characterized in that, The amount of the first catalyst is 8 ppm to 15 ppm of the total mass of the hydrogen-containing polysiloxane and the epoxy-terminated allyl polyether.

12. The preparation method according to any one of claims 9 to 11, characterized in that, The molar ratio of the hydrogen-containing polysiloxane to the epoxy-terminated allyl polyether is 1:(1.3-1.4).

13. The preparation method according to any one of claims 8 to 12, characterized in that, The epoxy ring-opening reaction is carried out at a temperature of 60℃ to 120℃ for a reaction time of 2h to 6h. And / or, the second catalyst is a basic catalyst; And / or, the amount of the second catalyst is 0.1% to 3.0% of the total mass of the polyether silicone copolymer and the bio-based substance; And / or, the molar ratio of the polyether silicone copolymer to the bio-based substance is 1:(0.3 to 1.2).

14. The preparation method according to claim 13, characterized in that, The molar ratio of the polyether organosilicon copolymer to the bio-based substance is 1:(0.3-1).

15. The preparation method according to claim 13, characterized in that, The alkaline catalyst is at least one of NaOH, KOH, sodium methoxide, potassium methoxide, triethylamine, 4-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

16. The preparation method according to claim 13, characterized in that, The alkaline catalyst is KOH, sodium methoxide, 4-dimethylaminopyridine, or 1,8-diazabicyclo[5.4.0]undec-7-ene.

17. The preparation method according to any one of claims 8 to 16, characterized in that, The hydrogen-containing polysiloxane is prepared by the following steps: using octamethylcyclotetrasiloxane, high-hydrogen-content silicone oil and hexamethyldisiloxane as raw materials, the hydrogen-containing polysiloxane is obtained by reaction under the action of acidic substances, wherein the hydrogen content of the high-hydrogen-content silicone oil is 1.2% to 1.6%.

18. The preparation method according to claim 16, characterized in that, The reaction temperature for generating the hydrogen-containing polysiloxane is 20℃~90℃, and the reaction time is 2h~8h; And / or, after the reaction is complete, adjust the pH and then filter; And / or, the acidic substance is concentrated sulfuric acid or acidic clay, and the amount of the acidic substance is 0.4% to 7% of the total mass of the raw materials.

19. The preparation method according to claim 18, characterized in that, The acidic substance is acidic clay, and the amount of the acidic substance used is 2% to 5% of the total mass of the raw materials.

20. The use of the bio-based organosilicon surfactant as described in any one of claims 1 to 7 in the preparation of rigid polyurethane foam.

Images