Organosilicon surfactant for polyurethane foam, and preparation method and application thereof

Abstract

The invention discloses an organic silicon surfactant for polyurethane foam as well as a preparation method and application of the organic silicon surfactant, and relates to the technical field of surfactants. A terpene compound with a specific structure is introduced into an organic silicon main chain through chemical modification, bio-based modification of a surfactant is realized on the premise of maintaining foam opening performance and other stable mechanical properties, and the foam is endowed with good antibacterial performance; bio-based polyol and part of petrochemical-based polyol are compounded as a dilution system, so that the environmental load and the production cost are reduced, the application potential of the material is expanded, and the environment-friendly and low-carbon development direction is met. The high-resilience polyurethane foam prepared by using the organosilicon surfactant provided by the invention has good comprehensive properties (such as compression strength, resilience and dimensional stability), and also shows good antibacterial property.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of surfactants, in particular to a silicone surfactant for polyurethane foam, a preparation method and application thereof. BACKGROUND

[0002] High resilience polyurethane foam (HR) is widely used in the fields of automobile seats, household bedding and medical cushioning materials due to its excellent mechanical properties, resilience and outstanding durability. In the preparation process of HR foam, surfactants, as key additives, not only play a role in regulating the cell structure, but also directly affect the mechanical properties of the foam and the use quality of the final product. At present, under the background of promoting sustainable development and green chemical industry worldwide, reducing dependence on fossil raw materials has become an urgent need for the transformation and upgrading of the polyurethane industry. However, the traditional silicone surfactant used is still mainly derived from petrochemical resources, which has obvious shortcomings in sustainability and carbon footprint.

[0003] At present, there are limited reports on the development of bio-based silicone surfactants for high resilience polyurethane foam. In the face of the continued tightening of environmental protection policies and the urgent need for green transformation of the industry, developing bio-based silicone surfactants suitable for high-performance HR foam has become a key breakthrough in promoting sustainable development of the industry.

[0004] In view of this, the present application is proposed. SUMMARY

[0005] The purpose of the present application is to provide a silicone surfactant for polyurethane foam, a preparation method and application thereof, aiming to provide a bio-based silicone surfactant suitable for high-performance HR foam.

[0006] The present application is realized as follows: In a first aspect, the present application provides a silicone surfactant for polyurethane foam, comprising components A, B and C in the following proportions by mass percentage: 1-45% of component A, 45-90% of component B and 5-60% of component C. The structural formula of component A is: ; In the formula, the value range of x, y and z satisfies: 1≤x≤15, 0 The structure of R1 group is: -CH2CH2CH2O(CH2CH2O) a (CH2CH(CH3)O) b R3, wherein the value range of a is 1 to 10, the value range of b is 1 to 10, and the value range of a+b is 2 to 15; R3 is an alkyl group containing 1 to 4 carbon atoms. R2 is a terpene compound of the general formula (C5H8) n ; Component B is a copolymer with terminal hydroxyl groups derived from a polyol; Component C is a bio-based polyol.

[0007] In an optional embodiment, the three components include, in mass percentage, 5%-25% of component A, 50%-70% of component B, and 20%-40% of component C, and the sum of the mass percentages of the three components is 100%.

[0008] In an optional embodiment, the terpene compound is selected from at least one of a monoterpene, a sesquiterpene, a diterpene, a triterpene, a tetraterpene, or a polyterpene with n>8; Preferably, the terpene compound is selected from any one or several of the following: , , , , and .

[0009] In an optional embodiment, the polyol used to prepare component B is a low-molecular-weight polyol selected from at least one of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and diethylene glycol; Preferably, component B is a low-molecular-weight polyether polyol with a number average molecular weight of 500 to 2000.

[0010] In an optional embodiment, the bio-based polyol is selected from at least one of a plant oil-based polyol, a natural polysaccharide and derivative thereof-based polyol, a rosin ester-based polyol, and a lignocellulose-based polyol; Preferably, the plant oil-based polyol includes castor oil-based polyol, soybean oil-based polyol, palm oil-based polyol, tung oil-based polyol, flaxseed oil-based polyol, and sunflower seed oil-based polyol; Preferably, the natural polysaccharide and derivative thereof-based polyol includes starch-based polyol, sucrose polyether polyol, and cellulose and derivatives thereof; Preferably, the rosin ester-based polyol includes esterified rosin-based polyol, maleated rosin adduct polyol, and turpentine oil-based polyol.

[0011] In a second aspect, the present application provides a method for preparing the silicone surfactant for the polyurethane foam of any one of the preceding embodiments, which uses a hydrogen-containing polysiloxane and a terpene compound to prepare component A; Mixing component A, component B, and component C.

[0012] In an alternative embodiment, the preparation of component A comprises: mixing the hydrogen-containing polysiloxane, the solvent, the Karstedt catalyst and the cocatalyst, heating to 80-100°C, adding the terpene compound dropwise, controlling the dropwise addition time to be 0.5-1.0 h, and reacting for 0.5-2.0 h after the dropwise addition is completed; then adding the allyl polyether and the Karstedt catalyst to the system, and continuing to react at 100-120°C for 2-7 h, and removing the solvent after the reaction is completed. Preferably, the amount of Karstedt catalyst used is 3-20 ppm of the total mass of the raw materials. Preferably, the cocatalyst is at least one selected from diethanolamine, triethanolamine, acetamide, triethylamine and N-butyl ethanolamine; and the amount of cocatalyst used is 50-500 ppm of the total mass of the raw materials. Preferably, the solvent is at least one selected from toluene and isopropanol.

[0013] In an alternative embodiment, the preparation of the hydrogen-containing polysiloxane comprises: using octamethylcyclotetrasiloxane, high-hydrogen-containing polysiloxane with a hydrogen content of 1.0-2.0%, and hexamethyldisiloxane as raw materials, and reacting at 30-80°C for 3-10 h in the presence of an acidic catalyst. Preferably, the acidic catalyst is at least one selected from acid clay, concentrated sulfuric acid, acid resin and triflic acid, and more preferably is concentrated sulfuric acid or acid resin; and the amount of acidic catalyst used is 0.5-6% of the total mass of the reactants. Preferably, when concentrated sulfuric acid is used as the catalyst, sodium bicarbonate is used for neutralization treatment after the reaction is completed.

[0014] In a third aspect, the present application provides the use of the silicone surfactant for polyurethane foam in any one of the preceding embodiments or prepared by the preparation method in any one of the preceding embodiments in the preparation of polyurethane foam.

[0015] In a fourth aspect, the present application provides a polyurethane foam, the preparation process of which uses the silicone surfactant for polyurethane foam in any one of the preceding embodiments or prepared by the preparation method in any one of the preceding embodiments.

[0016] The present application has the following beneficial effects: the present application introduces specific structure terpenes into the silicone main chain through chemical modification, realizes the biological modification of surfactants under the premise of maintaining the stability of foam open hole performance and other mechanical properties, and gives the foam good antibacterial performance; using biological polyols and part of petrochemical polyols as a dilution system not only reduces environmental load and production cost, but also expands the application potential of the material, which meets the green and low-carbon development direction. The high resilience polyurethane foam prepared by using the silicone surfactant provided by the present application has good comprehensive performance (such as compression strength, resilience and dimensional stability), and also shows good antibacterial performance. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0018] The embodiments of the present application provide a silicone surfactant for polyurethane foam, which comprises component A 1%-45%, component B 45%-90% and component C 5%-60% according to mass percentage.

[0019] The structural formula of component A is: ; In the formula, the value range of x, y and z satisfies: 1≤x≤15, x can be 1, 3, 5, 8, 10, 13, 15, etc.; 0

[0020] The structure of R1 group is: -CH2CH2CH2O(CH2CH2O) a (CH2CH(CH3)O) b R3, wherein the value range of a is 1 to 10 (such as 1, 3, 5, 8, 10, etc.), the value range of b is 1 to 10 (such as 1, 3, 5, 8, 10, etc.), and the value range of a+b is 2 to 15 (such as 2, 5, 8, 10, 13, 15, etc.); R3 is an alkyl group containing 1 to 4 carbon atoms.

[0021] R2 is a terpene compound with the general formula (C5H8) n The specific type of terpene compound is not limited.

[0022] Component B is a copolymer with terminal hydroxyl groups derived from a polyhydroxyl compound, and component C is a bio-based polyol.

[0023] It should be noted that in component A, the present application introduces a natural terpene compound with a specific structure into the silicone surfactant through a hydrosilylation reaction, achieving an innovation in the molecular structure of bio-based modified silicone surfactants. By optimizing the ratio of siloxane segments to grafted polyether, and combining bio-based alternatives to petrochemical-based diluents, the environmental load of the product is significantly reduced while maintaining or even improving the overall performance of the foam (such as compression strength, resilience, and dimensional stability). In addition, the introduction of terpene-based bio-based groups also endows the foam material with certain antibacterial properties, expanding its application potential.

[0024] Specifically, the mass fraction of component A can be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.; the mass fraction of component B can be 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc.; and the mass fraction of component C can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 59%, etc.

[0025] In preferred embodiments, the sum of the mass percentages of the three components is 100%, including 5%-25% of component A, 50%-70% of component B, and 20%-40% of component C, according to mass percentage. By optimizing the amount of the three components, the overall performance of the surfactant foam and its antibacterial properties are further improved.

[0026] In some embodiments, the terpene compound is selected from at least one of monoterpene (n=2), sesquiterpene (n=3), diterpene (n=4), dipterpene (n=5), triterpene (n=6), tetraterpene (n=8), and polyterpene (n>8), and the terpene compound can be any one or several of the above.

[0027] In preferred embodiments, the terpene compound is selected from any one or several of the following: (limeene), (limeene), (beta-pinene), (camphene), (dihydromyrcene), and (limeene). When the terpene compound is any one or several of the above, the overall performance of the surfactant foam is improved to a higher degree.

[0028] In an optional embodiment, the polyol used to prepare component B is a low molecular weight polyol selected from at least one of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and diethylene glycol, which can be any one or more of the above. The low molecular weight polyol is a starter for component B, which is polymerized to obtain component B with a desired molecular weight.

[0029] In a preferred embodiment, component B is a low molecular weight polyether polyol with a number average molecular weight of 500 to 2000, and the specific type is not limited, which can be 500, 600, 700, 800, 900, 1000, 1300, 1500, 1800, 2000, etc. In some embodiments, the bio-based polyol of component C is selected from at least one of a plant oil-based polyol, a natural polysaccharide and derivative-based polyol, a rosin ester-based polyol, and a lignocellulose-based polyol, which can be any one or more of the above. Among them, the plant oil-based polyol includes castor oil-based polyol, soybean oil-based polyol, palm oil-based polyol, tung oil-based polyol, flaxseed oil-based polyol, sunflower seed oil-based polyol, etc. The natural polysaccharide and derivative-based polyol includes starch-based polyol, sucrose polyether polyol, cellulose and its derivatives, etc. The rosin ester-based polyol includes esterified rosin-based polyol, maleated rosin adduct polyol, and turpentine-based polyol, etc.

[0030] The embodiment of the present application provides a preparation method of a silicone surfactant for polyurethane foam, and the steps are as follows: S1, preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane is obtained by using octamethylcyclotetrasiloxane, high hydrogen-containing polysiloxane (1.5%), and hexamethyldisiloxane as raw materials, reacting at 30-80°C for 3-10h in the presence of an acidic catalyst.

[0031] Specifically, the reaction temperature can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc.; the reaction time can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.

[0032] In some embodiments, the acidic catalyst is selected from at least one of acidic clay, concentrated sulfuric acid, acidic resin, and triflic acid, which can be any one or more of the above. The acidic catalyst is preferably concentrated sulfuric acid or acidic resin. When using concentrated sulfuric acid as the catalyst, sodium bicarbonate is used for neutralization treatment after the reaction is completed.

[0033] Further, the amount of the acid catalyst is 0.5%-6% of the total mass of the reaction materials, such as 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, etc. Specifically, the "total mass of the reaction materials" refers to the total mass of the methylcyclotetrasiloxane, the high-hydrogen polysiloxane, and the hexamethyldisiloxane.

[0034] S2, Preparation of Component A Component A is prepared by reacting the high-hydrogen polysiloxane and the terpenoid compound. The general formula of Component A is: .

[0035] The meanings of x, y, and z in Component A are as described above.

[0036] In some embodiments, the preparation of Component A comprises: mixing the high-hydrogen polysiloxane, the solvent, the Karstedt catalyst, and the cocatalyst, under the protection of an inert gas such as nitrogen, heating to 80-100°C (such as 80°C, 85°C, 90°C, 95°C, 100°C, etc.), adding the terpenoid compound in a dropwise manner, controlling the dropwise addition time to be 0.5-1.0 h (such as 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1.0 h, etc.), and reacting for 0.5-2.0 h (such as 0.5 h, 0.8 h, 1.0 h, 1.3 h, 1.5 h, 1.8 h, 2.0 h, etc.) after the dropwise addition is completed; then adding the allyl polyether and the Karstedt catalyst to the system, and continuing to react at 100-120°C (such as 100°C, 105°C, 110°C, 115°C, 120°C, etc.) for 2-7 h (such as 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, etc.), and removing the solvent after the reaction is completed to obtain the modified organosilicon copolymer, i.e., Component A.

[0037] Further, the amount of the Karstedt catalyst is 3-20 ppm of the total mass of the raw materials, such as 3 ppm, 5 ppm, 8 ppm, 10 ppm, 13 ppm, 15 ppm, 18 ppm, 20 ppm, etc. The "total mass of the raw materials" refers to the total mass of the high-hydrogen polysiloxane, the terpenoid compound, and the allyl polyether. Specifically, the Karstedt catalyst can be a commercially available material, which can be purchased from Aldrich.

[0038] Further, the co-catalyst is selected from at least one of diethanolamine, triethanolamine, acetamide, triethylamine and N-butyl ethanolamine, and the co-catalyst can be any one or several of the above. The amount of the co-catalyst is 50 ppm to 500 ppm of the total mass of the raw materials, such as 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, etc. The "total mass of the raw materials" refers to the total mass of the hydrogen-containing polysiloxane, the terpene compound and the allyl polyether.

[0039] In some embodiments, the solvent is selected from at least one of toluene and isopropanol, and the solvent can be any one or several of the above.

[0040] S3, Preparation of the silicone surfactant The silicone surfactant for polyurethane foam is prepared by mixing components A, B and C in a certain mass ratio. The mass percentage of component A is 1-45%, the mass percentage of component B is 40-90%, and the mass percentage of component C is 5-59%, wherein the sum of the mass percentages of components A, B and C is 100%.

[0041] The preparation process provided by the embodiments of the present application is simple, mild and easy to scale up, and is suitable for industrial production, thereby providing a new technical path for developing high-performance bio-based silicone surfactants in the field.

[0042] The silicone surfactant for polyurethane foam provided by the embodiments of the present application can be applied in the preparation of polyurethane foam, and the prepared polyurethane foam has excellent comprehensive performance (such as compressive strength, resilience and dimensional stability) and good antibacterial performance.

[0043] The present application provides a kind of polyurethane foam, its preparation process utilizes the silicone surfactant for polyurethane foam provided by the embodiments of the present application, and the foam has good comprehensive performance (such as compressive strength, resilience and dimensional stability), simultaneously shows good antibacterial property.

[0044] The features and performance of the present application are further described in detail below in conjunction with embodiments.

[0045] Embodiment 1 The present embodiment provides a preparation method of a silicone surfactant for polyurethane foam, and the steps are as follows: (1) Preparation of hydrogen-containing polysiloxane Into a reactor were added 80.30 g octamethylcyclotetrasiloxane, 47.62 g high hydrogen-containing polysiloxane (hydrogen content 1.5%, same below, purchased from Dow Corning, model MHX-1107, same below) and 52.08 g hexamethyldisiloxane, 3.6 g concentrated sulfuric acid (mass fraction 98%, same below) was added as catalyst, and the mixture was reacted at 35°C for 3 h. After the reaction was completed, the mixture was neutralized with sodium bicarbonate, filtered, and the high hydrogen-containing polysiloxane was obtained.

[0046] (2) Preparation of Component A Into a reactor were added 52 g high hydrogen-containing polysiloxane and 15 g isopropyl alcohol, and Karstedt catalyst (10 ppm) and diethanolamine (100 ppm) were added as cocatalysts under nitrogen protection. The temperature was raised to 90°C, and 11.75 g limonene was slowly added dropwise over 0.5 h. After the dropwise addition was completed, the mixture was reacted for another 1 h. Then 78.67 g allyl polyether and Karstedt catalyst (8 ppm) were added to the system, the temperature was raised to 100°C, and the mixture was reacted for another 4 h. After the reaction was completed, the solvent and other low-boiling substances were removed, and Component A was obtained. The molecular formula of Component A is as follows: Si(CH3)3-O-[Si(CH3)2-O] 3.2 -[Si(CH3)R1-O] 1.5 -[Si(CH3)R2-O] 0.7 -Si(CH3)3 wherein R1 = -CH2CH2CH2O(CH2CH2O)4(CH2CH(CH3)O)2CH3; R2= .

[0047] (3) Preparation of Silicone Surfactant The obtained Component A was mixed with Component B (polyether polyol with a molecular weight of 600, purchased from Zhejiang Royalstar Technology Co., Ltd., same below) and Component C (soybean oil polyol with a molecular weight of 1000) at a mass ratio of A:B:C = 1:6:3, and stirred at 40°C for 1 h to obtain a silicone surfactant for high resilience polyurethane foam.

[0048] Example 2 The present example provides a method for preparing a silicone surfactant for polyurethane foam, and the steps are as follows: (1) Preparation of High Hydrogen-Containing Polysiloxane Into a reactor were added 92.07 g octamethylcyclotetrasiloxane, 45.88 g high hydrogen content polysiloxane (hydrogen content 1.5%) and 42.04 g hexamethyldisiloxane, 3.6 g acidic resin (purchased from DuPont Chemical, model: Amberlyst@-35, same below) was added as catalyst, and the reaction was stirred at 65 °C for 4 h. After the reaction was completed, filtration was performed to obtain the hydrogen-containing polysiloxane.

[0049] (2) Preparation of Component A Into a reactor were added 55 g of the hydrogen-containing polysiloxane obtained in step (1) and 15 g of toluene, and nitrogen protection was performed, and Karstedt catalyst (10 ppm) and triethanolamine (100 ppm) were added as co-catalysts. The temperature was raised to 100 °C, and 11.97 g of β-pinene was slowly added dropwise within 0.5 h, and after the dropwise addition was completed, the reaction was continued at 100 °C for 1.5 h. Subsequently, 89.4 g of allyl polyether and Karstedt catalyst (6 ppm) were added to the reaction system, the temperature was raised to 115 °C, and the reaction was continued for 3 h. After the reaction was completed, the solvent and other low-boiling substances were removed to obtain Component A, and the molecular structure thereof is as follows: Si(CH3)3-O-[Si(CH3)2-O] 4.5 -[Si(CH3)R1-O] 1.6 -[Si(CH3)R2-O] 1.0 -Si(CH3)3, wherein R1 = -CH2CH2CH2O (CH2CH2O)1(CH2CH(CH3)O)5CH3; R2= .

[0050] (3) Preparation of a silicone surfactant for high resilience polyurethane foam The obtained Component A was mixed with Component B (polyether polyol with a molecular weight of 800 and ethylene glycol as a starter) and Component C (cashew phenol polyol with a molecular weight of 1500) at a mass ratio of A:B:C = 1:5:4, and stirring was performed at 50 °C for 1 h, and the silicone surfactant for high resilience polyurethane foam was prepared after the mixture was uniformly mixed.

[0051] Example 3 The present example provides a method for preparing a silicone surfactant for polyurethane foam, and the steps are as follows: (1) Preparation of hydrogen-containing polysiloxane Into a reactor were introduced 107.31 g of octamethylcyclotetrasiloxane, 45.69 g of high hydrogen-containing polysiloxane (hydrogen content: 1.5%) and 27.00 g of hexamethyldisiloxane, 9 g of concentrated sulfuric acid was added as a catalyst, and the reaction was carried out at 40°C for 2 h. After the reaction was completed, the reaction solution was neutralized with sodium bicarbonate, and filtered to obtain a hydrogen-containing polysiloxane.

[0052] (2) Preparation of Component A Into a reactor were introduced 54 g of the hydrogen-containing polysiloxane obtained in step (1) and 10.8 g of isopropyl alcohol, and Karstedt catalyst (15 ppm) and diethanolamine (100 ppm) were added as cocatalysts under nitrogen protection. The temperature was raised to 90°C, and 11.7 g of limonene was slowly added dropwise over 0.5 h. After the dropwise addition was completed, the reaction was continued at 90°C for 2 h. Subsequently, 78.39 g of allyl polyether and Karstedt catalyst (5 ppm) were added to the reaction system, the temperature was raised to 100°C, and the reaction was continued for 4.5 h. After the reaction was completed, the solvent and other low-boiling substances were removed to obtain Component A, the molecular structure of which is as follows: Si(CH3)3-O-[Si(CH3)2-O] 7.9 -[Si(CH3)R1-O] 2.3 -[Si(CH3)R2-O] 1.6 -Si(CH3)3, wherein R1 = -CH2CH2CH2O(CH2CH2O)4(CH2CH(CH3)O)2CH3, R2= .

[0053] (3) Preparation of a silicone surfactant for high resilience polyurethane foam The obtained Component A was mixed with Component B (polyether polyol with a molecular weight of 1000 as a starter) and Component C (soybean oil polyol with a molecular weight of 1200) at a mass ratio of A:B:C = 1:6:3, and stirred at 50°C for 1 h to obtain a silicone surfactant for high resilience polyurethane foam.

[0054] Example 4 The present example provides a method for preparing a silicone surfactant for polyurethane foam, the steps of which are as follows: (1) Preparation of hydrogen-containing polysiloxane Into a reactor were introduced 110.90 g of octamethylcyclotetrasiloxane, 46.32 g of high hydrogen-containing polysiloxane (hydrogen content: 1.5%) and 22.78 g of hexamethyldisiloxane, and 7.2 g of an acidic resin was added as a catalyst, and the reaction was carried out at 60°C for 4 h with stirring. After the reaction was completed, the reaction solution was filtered to obtain a hydrogen-containing polysiloxane.

[0055] (2) Preparation of components A and B Into a reactor, 55 g of the hydrogen-containing polysiloxane obtained in step (1) and 13.75 g of toluene were added, and Karstedt catalyst (10 ppm) and acetamide (200 ppm) as a cocatalyst were added under nitrogen protection. The temperature was raised to 90°C, and 10.42 g of β-pinene was slowly added dropwise within 0.5 h. After the dropwise addition was completed, the reaction was continued at 90°C for 1.5 h. Subsequently, 50.31 g of allyl polyether and Karstedt catalyst (6 ppm) were added to the reaction system, the temperature was raised to 115°C, and the reaction was continued for 4 h. After the reaction was completed, the solvent and other low-boiling substances were removed, and component A was obtained, which had the following molecular formula: Si(CH3)3-O-[Si(CH3)2-O] 9.5 -[Si(CH3)R1-O] 2.8 -[Si(CH3)R2-O] 1.8 -Si(CH3)3 wherein R1 = -CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3, R2= .

[0056] (3) Preparation of a silicone surfactant for high-resilience polyurethane foam The obtained component A was mixed with component B (polyether polyol with a molecular weight of 800, using diethylene glycol as a starter) and component C (cashew phenol polyol, with a molecular weight of 1000) at a mass ratio of A:B:C = 1:5:4, and stirred at 50°C for 1 h. After being uniformly mixed, a silicone surfactant for high-resilience polyurethane foam was prepared.

[0057] Example 5 This example provides a method for preparing a silicone surfactant for polyurethane foam, which comprises the following steps: (1) Preparation of hydrogen-containing polysiloxane Into a reactor, 122.94 g of octamethylcyclotetrasiloxane, 39.95 g of high-hydrogen-containing polysiloxane (hydrogen content of 1.5%), and 17.11 g of hexamethyldisiloxane were added, and 3.6 g of concentrated sulfuric acid was added as a catalyst. The reaction was carried out at 40°C for 3 h. After the reaction was completed, the reaction solution was neutralized with sodium bicarbonate, and filtered to obtain hydrogen-containing polysiloxane.

[0058] (2) Preparation of components A and B Into a reactor was added 55 g of the hydrogen-containing polysiloxane obtained in step (1) and 16.5 g of isopropyl alcohol under nitrogen protection, and Karstedt catalyst (8 ppm) and diethanolamine (100 ppm) were added as cocatalysts. The temperature was raised to 85°C, and 10.42 g of myrcene was slowly added dropwise over 0.5 h. After the dropwise addition was completed, the reaction was continued at 85°C for 1.5 h. Subsequently, 50.31 g of allyl polyether and Karstedt catalyst (8 ppm) were added to the reaction system, and the reaction was continued at 100°C for 4 h. After the reaction was completed, the solvent and other low-boiling substances were removed, and component A was obtained. The molecular formula of component A is as follows: Si(CH3)3-O-[Si(CH3)2-O] 13.8 -[Si(CH3)R1-O] 3.1 -[Si(CH3)R2-O] 2.1 -Si(CH3)3, wherein R1 = -CH2CH2CH2O (CH2CH2O)3(CH2CH(CH3)O)1CH3, R2= .

[0059] (3) Preparation of a silicone surfactant for high-resilience polyurethane foam The obtained component A, component B (polyether polyol with a molecular weight of 600 as a starter), and component C (rosin-based polyol with a molecular weight of 1200) were mixed at a mass ratio of A:B:C = 2:5:3, and stirred at 50°C for 1 h to obtain a silicone surfactant for high-resilience polyurethane foam.

[0060] Example 6 This example provides a method for preparing a silicone surfactant for polyurethane foam, and the steps are as follows: (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane was prepared by the method described in step (1) of Example 3.

[0061] (2) Preparation of components A and B Into a reactor was added 60 g of the hydrogen-containing polysiloxane obtained in step (1) and 12 g of toluene under nitrogen protection, and Karstedt catalyst (15 ppm) and diethanolamine (200 ppm) were added as cocatalysts. The temperature was raised to 100°C, and 13.20 g of dihydromyrcene was slowly added dropwise over 0.5 h. After the dropwise addition was completed, the reaction was continued at 100°C for 2 h. Subsequently, 62.76 g of allyl polyether and Karstedt catalyst (8 ppm) were added to the reaction system, and the temperature was raised to 110°C, and the reaction was continued for 5 h. After the reaction was completed, the solvent and other low-boiling substances were removed, and component A was obtained. The molecular formula of component A is as follows: Si(CH3)3-O-[Si(CH3)2-O] 7.9 -[Si(CH3)R1-O] 2.3 -[Si(CH3)R2-O] 1.6 -Si(CH3)3, wherein R1 = -CH2CH2CH2O (CH2CH2O)4(CH2CH(CH3)O)2CH3, R2= .

[0062] (3) Preparation of silicone surfactant for high resilience polyurethane foam The obtained component A is mixed with component B (polyether polyol with molecular weight of 1000 and n-butanol as starter agent) and component C (soybean oil polyol with molecular weight of 1200) at a mass ratio of A:B:C = 1:6:3, stirred at 50°C for 1 h, and then uniformly mixed to obtain the silicone surfactant for high resilience polyurethane foam.

[0063] Example 7 The present example provides a preparation method of a silicone surfactant for polyurethane foam, and the steps are as follows: (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane is prepared by the method described in step (1) of Example 2.

[0064] (2) Preparation of component A Component A is prepared by the method described in step (2) of Example 2.

[0065] (3) Preparation of silicone surfactant for high resilience polyurethane foam The obtained component A is mixed with component B (polyether polyol with molecular weight of 800 and ethylene glycol as starter agent) and component C (cardanol polyol with molecular weight of 1500) at a mass ratio of A:B:C = 2:4:4, stirred at 50°C for 1 h, and then uniformly mixed to obtain the silicone surfactant for high resilience polyurethane foam.

[0066] That is, the difference between Example 7 and Example 2 is only that the proportions of component A, component B and component C are changed.

[0067] Example 8 The present example provides a preparation method of a silicone surfactant for polyurethane foam, and the steps are as follows: (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane is prepared by the method described in step (1) of Example 3.

[0068] (2) Preparation of component A Component A was prepared by the method described in step (2) of Example 3.

[0069] (3) Preparation of silicone surfactant for high resilience polyurethane foam The obtained component A was mixed with component B (polyether polyol with a molecular weight of 1000) and component C (soybean oil polyol with a molecular weight of 1200) in a mass ratio of A:B:C = 3:6:1, and stirred at 50°C for 1 h to obtain a silicone surfactant for high resilience polyurethane foam.

[0070] That is, the difference between Example 8 and Example 3 is only that the proportions of component A, component B and component C are changed.

[0071] Comparative Example 1 (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane was prepared by the method described in step (1) of Example 1.

[0072] (2) Preparation of component A The obtained hydrogen-containing polysiloxane of step (1) was added to a reactor together with 108.02 g of allyl polyether under nitrogen protection, Karstedt catalyst (10 ppm) and triethanolamine (100 ppm) were added as cocatalysts, and the temperature was raised to 120°C for 5 h to obtain component A, whose molecular formula is as follows: Si(CH3)3-O-[Si(CH3)2-O] 3.2 -[Si(CH3)R1-O] 2.2 -Si(CH3)3, wherein R1 = -CH2CH2CH2O(CH2CH2O)4(CH2CH(CH3)O)2CH3.

[0073] (3) Preparation of silicone surfactant for high resilience polyurethane foam The obtained component A was mixed with corresponding components B and C by the method and proportion described in step (3) of Example 1 to obtain a silicone surfactant for high resilience polyurethane foam.

[0074] That is, the difference between Comparative Example 1 and Example 1 is only that limonene is replaced by an equal amount of allyl polyether in step (2).

[0075] Comparative Example 2 (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane was prepared by the method described in step (1) of Example 2.

[0076] (2) Preparation of component A Into a reactor was added 50 g of the hydrogen-containing polysiloxane obtained in step (1) and 113.79 g of allyl polyether, under nitrogen protection, Karstedt catalyst (15 ppm) and diethanolamine (100 ppm) were added as co-catalysts, and the mixture was reacted at 110 °C for 5 h to obtain component A, which has the following molecular formula: Si(CH3)3-O-[Si(CH3)2-O] 4.5 -[Si(CH3)R1-O] 2.6 -Si(CH3)3, wherein R1 = -CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3.

[0077] (3) Preparation of a silicone surfactant for high resilience polyurethane foam The obtained component A was mixed with corresponding components B and C by the method and ratio described in step (3) of Example 2 to prepare a silicone surfactant for high resilience polyurethane foam.

[0078] That is, the difference between Comparative Example 2 and Example 2 is that β-pinene is replaced with an equal amount of allyl polyether in step (2).

[0079] Comparative Example 3 (1) Preparation of a hydrogen-containing polysiloxane The hydrogen-containing polysiloxane was prepared by the method described in step (1) of Example 4.

[0080] (2) Preparation of component A Into a reactor was added 52 g of the hydrogen-containing polysiloxane obtained in step (1) and 119.47 g of allyl polyether, under nitrogen protection, Karstedt catalyst (15 ppm) and diethanolamine (100 ppm) were added as co-catalysts, and the mixture was reacted at 120 °C for 6 h to obtain component A, which has the following molecular formula: Si(CH3)3-O-[Si(CH3)2-O] 9.5 -[Si(CH3)R1-O] 4.6 -Si(CH3)3, wherein R1 = -CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3, (3) Preparation of a silicone surfactant for high resilience polyurethane foam The obtained component A was mixed with corresponding components B and C by the method and ratio described in step (3) of Example 4 to prepare a silicone surfactant for high resilience polyurethane foam.

[0081] That is, the difference between Comparative Example 3 and Example 4 is that β-pinene is replaced by an equal amount of allyl polyether in step (2).

[0082] Comparative Example 4 (1) Preparation of hydrogen-containing polysiloxane A reactor was charged with 127.03 g of octamethylcyclotetrasiloxane, 39.44 g of high-hydrogen-containing polysiloxane (hydrogen content 1.5%), and 13.53 g of hexamethyldisiloxane, and 3.6 g of an acidic resin was added as a catalyst, and the reaction was stirred at 80°C for 4 h. After the reaction was completed, filtration was performed to obtain a hydrogen-containing polysiloxane.

[0083] (2) Preparation of components A and B A reactor was charged with 65 g of the hydrogen-containing polysiloxane obtained in step (1) and 19.5 g of isopropyl alcohol, and Karstedt catalyst (10 ppm based on the total mass of the material) and triethanolamine (100 ppm based on the total mass of the material) were added as cocatalysts under nitrogen protection. The temperature was raised to 90°C, and 12.16 g of limonene was slowly added dropwise within 0.5 h. After the dropwise addition was completed, the reaction was continued at 90°C for 1.5 h. Subsequently, 58.69 g of allyl polyether and Karstedt catalyst (6 ppm based on the total mass of the material) were added to the reaction system, and the temperature was raised to 110°C, and the reaction was continued for 3 h. After the reaction was completed, the solvent and other low-boiling substances were removed to obtain component A, which had the following molecular formula: Si(CH3)3-O-[Si(CH3)2-O] 17.5 -[Si(CH3)R1-O] 3.8 -[Si(CH3)R2-O] 2.5 -Si(CH3)3, wherein R1 = -CH2CH2CH2O (CH2CH2O)3(CH2CH(CH3)O)1CH3, R2= .

[0084] (3) Preparation of a silicone surfactant for high-resilience polyurethane foam The obtained component A was mixed with component B (polyether polyol with a molecular weight of 800 as a starter) and component C (rosin-based polyol with a molecular weight of 1500) at a mass ratio of A:B:C = 1:8:1, and stirred at 50°C for 1 h to obtain a silicone surfactant for high-resilience polyurethane foam.

[0085] Comparative Example 5 (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane was prepared by the method described in step (1) of Example 3.

[0086] (2) Preparation of Component A Component A was prepared according to the method described in step (2) of Example 3.

[0087] (3) Preparation of silicone surfactant for high resilience polyurethane foam The obtained Component A was mixed with Component B (polyether polyol with a molecular weight of 1000 and n-butanol as starter) and Component C (soybean oil polyol with a molecular weight of 1200) at a mass ratio of A:B:C = 6:3:1, and stirred at 50 °C for 1 h to obtain a silicone surfactant for high resilience polyurethane foam.

[0088] Comparative Example 6 (1) Preparation of hydrogen-containing polysiloxane The hydrogen-containing polysiloxane was prepared according to the method described in step (1) of Example 4.

[0089] (2) Preparation of Component A Component A was prepared according to the method described in step (2) of Example 4.

[0090] (3) Preparation of silicone surfactant for high resilience polyurethane foam The obtained Component A was mixed with Component B (polyether polyol with a molecular weight of 800 and diethylene glycol as starter) at a mass ratio of A:B = 1:9, and stirred at 50 °C for 1 h to obtain a silicone surfactant for high resilience polyurethane foam.

[0091] The silicone surfactants prepared in Examples 1-8 and Comparative Examples 1-6 above were used to prepare high resilience polyurethane foams. The high resilience polyurethane foams were prepared by reacting X component and Y component, and the specific preparation method was as follows: Preparation of X component: According to the formula shown in Table 1, the polyols, catalyst, blowing agent and surfactant were accurately weighed by mass fraction at room temperature, mixed and stirred for 20 s to obtain X component.

[0092] Table 1 Evaluation formula

[0093] Y component was TM20, which was a mixture of toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), wherein the mass fraction of TDI was 80% and the mass fraction of MDI was 20%.

[0094] In use, the X component and the Y component are mixed at an isocyanate index of 96%, stirred at a speed of 2000 r / min for 5 s, then the mixture is injected into a standard mold (mold temperature 25 ℃) before free foaming, and after the foam is initiated, grown and cured, a high resilience polyurethane foam is prepared. The relevant data test is carried out on the FOAMAT 285 instrument. Among them, the standard square mold exhaust force test refers to GB / T 10807-2006 "Determination of the hardness of soft polymeric foam (indentation method)"; other physical property tests refer to QB / T 2080-2010 "High resilience soft polyurethane foam"; the antibacterial performance test refers to QB / T 2591-2003 "Antibacterial performance test method and antibacterial effect of antibacterial plastics".

[0095] Table 2 Foam standard square mold exhaust force data corresponding to examples and comparative examples

[0096] As shown in Table 2, by introducing different structures of terpene compounds into the existing polyether modified silicone structure, the open hole performance of the foam remains stable (see comparative examples 1, 2 and 3), and the exhaust force, resilience and air permeability after extrusion of the foam are all improved to varying degrees (refer to the standard square mold exhaust force data). In addition, the partial introduction of plant-based polyols (comparative example 6) has stable corresponding foam performance, and the resilience, air permeability and other properties are slightly improved, further optimizing the cost and environmental friendliness. It is worth noting that the hydrogen-containing polysiloxane main chain structure (comparative example 4) beyond the protection scope of the present application will adversely affect the open hole performance and air permeability of the foam. In addition, when the content of component A is too high (comparative example 5), the exhaust force of the foam increases significantly, shrinkage occurs, and the resilience performance decreases, so this ratio scheme is not desirable.

[0097] Table 3 Foam FOAMAT data corresponding to examples and comparative examples

[0098] From the above data, it can be seen that the introduction of different structures of terpene compounds can still maintain a high level of corresponding foam FOAMAT performance (see Table 3) on the basis of improving the open hole performance of the foam (see Table 2), which is specifically manifested as a higher maximum rising height of the foam and a lower shrinkage rate.

[0099] In addition, the evaluation results of comparative examples 4 and 5 show that the hydrogen-containing polysiloxane structure beyond the protection scope of the present application and the too high content of component A will both cause the shrinkage rate of the foam to increase, adversely affecting the performance of the foam. The introduction of plant-based polyols (comparative example 6) in the formula helps to improve the maximum foaming height of the foam and reduce the shrinkage rate, while further optimizing the cost and environmental friendliness.

[0100] Table 4 Inhibition rate (%) of antibacterial polyurethane foam on different bacteria at 24h

[0101] As shown in Table 4, the inhibition rates of the sample (Example 1 8) on Staphylococcus aureus and Escherichia coli are stable at 79%-85%, indicating that it has a wide, efficient and stable antibacterial effect. In contrast, Comparative Example 1 3, which does not introduce terpene compounds, has an inhibition rate of only 23%-27%, which is significantly lower than the examples of the present application, indicating that the introduction of terpene structure is a key factor to endow the material with antibacterial function. It is worth noting that Comparative Examples 4 and 5 have certain antibacterial properties, but in combination with the aforementioned foam physical performance data, it can be known that its comprehensive performance is not balanced, and there are problems such as foam shrinkage and decreased resilience. Comparative Example 6 does not use C component (bio-based polyol), but also has certain antibacterial properties, which further indicates that the introduction of terpene compounds is the key to realize antibacterial function, and the synergistic effect of bio-based components has a positive significance for performance improvement.

[0102] In summary, the bio-based modified silicone surfactant provided by the present application not only performs excellently in foam mechanical properties and open cell structure, but also shows good effect in antibacterial function, providing a new idea for developing high-performance, multi-functional, green and sustainable silicone surfactant for high-resilience polyurethane foam.

[0103] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A silicone surfactant for polyurethane foam, characterized by, According to the mass percentage, it comprises component A 5%-25%, component B 50%-70% and component C 20%-40%, and the sum of the mass percentages of the three components is 100%. The structural formula of component A is: ； In the formula, the value range of x, y and z satisfies: 1≤x≤15, 0 R1is -CH2CH2CH2O(CH2CH2O) a (CH2CH(CH3)O) b R3, wherein a has a value ranging from 1 to 10, b has a value ranging from 1 to 10, and a + b has a value ranging from 2 to 15; R3is an alkyl group containing 1 to 4 carbon atoms; R2is a terpene compound of the general formula (C5H8) n ​ The component B is a copolymer with terminal hydroxyl groups derived from a polyhydroxyl compound; The component C is a bio-based polyol.

2. The silicone surfactant for polyurethane foam according to claim 1, characterized by, According to the mass percentage, it comprises component A 5%-25%, component B 50%-70% and component C 20%-40%, and the sum of the mass percentages of the three components is 100%.

3. The silicone surfactant for polyurethane foam according to claim 1 or 2, characterized by, The terpene compound is selected from at least one of monoterpenes, sesquiterpenes, diterpenes, triterpenes, tetraterpenes or n>8 polyterpenes; Preferably, the terpene compound is selected from any one or several of the following: 、 、 、 、 and .

4. The silicone surfactant for polyurethane foam according to claim 1 or 2, characterized by, The polyhydroxyl compound used to prepare the component B is a low molecular weight polyol selected from at least one of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol; Preferably, the component B is a low molecular weight polyether polyol with a number average molecular weight of 500-2000.

5. The silicone surfactant for polyurethane foam according to claim 1 or 2, characterized by, The bio-based polyol is selected from at least one of plant oil-based polyols, natural polysaccharide and derivative-based polyols, rosin ester-based polyols and lignocellulose-based polyols; Preferably, the plant oil-based polyol includes castor oil-based polyol, soybean oil-based polyol, palm oil-based polyol, tung oil-based polyol, flaxseed oil-based polyol and sunflower oil-based polyol; Preferably, the natural polysaccharide and derivative-based polyol includes starch-based polyol, sucrose polyether polyol and cellulose and its derivatives; Preferably, the rosin ester-based polyol includes esterified rosin-based polyol, maleated rosin adduct polyol and turpentine-based polyol.

6. A method for preparing the silicone surfactant for the polyurethane foam according to any one of claims 1-5, characterized in that, The component A is prepared by reacting a hydrogen-containing polysiloxane and a terpene compound; The component A, the component B and the component C are mixed.

7. The production method according to claim 6, wherein The preparation process of the component A includes: mixing the hydrogen-containing polysiloxane, a solvent, Karstedt catalyst and a cocatalyst, heating to 80-100°C, adding the terpene compound in a dropwise manner, controlling the dropwise adding time to be 0.5-1.0h, and reacting for 0.5-2.0h after the dropwise adding is completed; then adding an allyl polyether and Karstedt catalyst to the system, and continuing to react at 100-120°C for 2-7h, and removing the solvent after the reaction is completed; Preferably, the amount of the Karstedt catalyst accounts for 3-20ppm of the total mass of raw materials; Preferably, the cocatalyst is selected from at least one of diethanolamine, triethanolamine, acetamide, triethylamine and N-butyl ethanolamine; and the amount of the cocatalyst accounts for 50-500ppm of the total mass of raw materials; Preferably, the solvent is selected from at least one of toluene and isopropyl alcohol.

8. The preparation method according to claim 6, characterized in that, The preparation process of the hydrogen-containing polysiloxane comprises: using octamethylcyclotetrasiloxane, high hydrogen-containing polysiloxane with hydrogen content of 1.0-2.0% and hexamethyldisiloxane as raw materials, reacting at 30-80°C in the presence of an acid catalyst for 3-10h; Preferably, the acid catalyst is selected from at least one of acid clay, concentrated sulfuric acid, acid resin and triflic acid, more preferably concentrated sulfuric acid or acid resin; the amount of the acid catalyst is 0.5-6% of the total mass of the reaction materials; Preferably, when using concentrated sulfuric acid as the catalyst, sodium bicarbonate is used for neutralization treatment after the reaction is completed.

9. Use of the silicone surfactant for polyurethane foam according to any one of claims 1-5 or prepared by the preparation method according to any one of claims 6-8 in the preparation of polyurethane foam.

10. A polyurethane foam characterized by, The polyurethane foam is prepared by using the silicone surfactant for polyurethane foam according to any one of claims 1-5 or prepared by the preparation method according to any one of claims 6-8.

Images