Organosilicon foam stabilizer, preparation method thereof and polyurethane foam

Abstract

The invention relates to the technical field of foam stabilizers, in particular to an organosilicon foam stabilizer, a preparation method thereof and polyurethane foam. The silicone foam stabilizer includes a copolymer; in the formula, R is represented by a structural formula of-CH2CH2CH2 (CH2CH2O) x (CH2CH (CH3) O) yCOC6H4OH, and R is represented by a structural formula of-CH2CH2CH2 (CH2CH2O) x (CH2CH (CH3) O) yCOC6H4OH. And in the formula 1 # imgabs, the structural formula of R1 is-CH2CH2CH2 (CH2CH2O) x1 (CH2CH (CH3) O) y1COC6H2 (OH) 3. The organic silicon foam stabilizer not only can realize the balance of trepanning and foam stabilization of slow-rebound polyurethane foam, but also can enable the foam to have the effect of removing acarus and mites without adding other materials for removing acarus and mites.

Description

Technical Field

[0001] The invention relates to the technical field of foam stabilizers, in particular to an organosilicon foam stabilizer and a preparation method thereof and polyurethane foam. Background Art

[0002] Slow-rebound polyurethane foam is commonly known as memory foam, viscoelastic sponge, and aerospace foam. The pore structure of slow-rebound polyurethane foam material is relatively open, with low density, good air permeability, strong elastic recovery ability, and strong sound and vibration absorption ability. It has been widely used in many fields, such as furniture, automobiles, medical treatment, and aerospace.

[0003] Silicone foam stabilizer is an important raw material in the preparation of slow-rebound polyurethane foam. Its dosage is small, but it plays an important role in emulsifying materials, cell nucleation, stabilizing bubbles and cell opening. However, these foam stabilizers can only achieve the effect of foam stabilization. For example, in the prior art, a silicone copolymer with a cross-linked structure is formed by introducing multiple unsaturated double bonds, and the slow-rebound foam is regulated by designing the cross-linking degree and polyether silicone structure. This silicone surfactant is very helpful in improving the open-cell properties of the foam. The polyether silicone structure can be controlled, but the cross-linking degree is difficult to control during the actual synthesis process.

[0004] In addition, the organosilicon foam stabilizer in the prior art cannot achieve the effect of sterilization and mite removal. If the foam is to be sterilized and mite removed, it is necessary to add boric acid glass powder to remove mites or add inorganic sterilizing agents or physically mix amino alcohols to achieve the sterilization of the foam. For example, JP 7202055B discloses that boric acid glass powder is added to the polyurethane foam foaming formula to make the polyurethane foam have a good anti-mite effect. US 4937273 discloses that an inorganic sterilizing agent loaded with metal ions on zeolite powder is added to the polyurethane foam foaming system to make the polyurethane foam have a good sterilization effect. And US20030019813A1 discloses that amino alcohol is physically added to the polyurethane foam system, and after a series of treatments, the polyurethane foam has a good sterilization effect.

[0005] Therefore, there is no record of making polyurethane foam have anti-mite and antibacterial effects without adding any other substances to the polyurethane foam formula, or in other words, the silicone foam stabilizer in the prior art cannot simply achieve the antibacterial and anti-mite effects.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The purpose of the present invention is to provide an organosilicon foam stabilizer and a preparation method thereof and polyurethane foam. The embodiment of the present invention provides an organosilicon foam stabilizer, which can not only achieve a balance between opening and stabilizing the pores of a slow-rebound polyurethane foam, but also enable the foam to have a mite and sterilization effect without adding other sterilization and mite removal materials.

[0008] The present invention is achieved in that:

[0009] In a first aspect, the present invention provides an organosilicon foam stabilizer, which comprises a side chain copolymer as shown in the following formula 1 and a linear copolymer as shown in formula 2;

[0010]

[0011] Among them, the structural formula of R is: -CH 2 CH 2 CH 2 (CH 2 CH 2 O) x (CH 2 CH(CH 3 )O) y CO C 6 H 4 OH; m=60~120, n=3~15, m+n=63~130, x=15~45, y=20~50;

[0012]

[0013] Among them, R 1 The structural formula is: -CH 2 CH 2 CH 2 (CH 2 CH 2 O) x1 (CH 2 CH(CH 3 )O) y1 COC 6 H 2 (OH) 3 ; Wherein m1=10~30, x1=5~25, y1=0~20.

[0014] In an optional embodiment, the mass ratio of the linear copolymer to the side chain copolymer is 1:(1.0-2.0).

[0015] In an optional embodiment, the organosilicon foam stabilizer is a stabilizer for preparing slow-rebound polyurethane foam.

[0016] In a second aspect, the present invention provides a method for preparing the organosilicon foam stabilizer described in the aforementioned embodiment, comprising: mixing the side chain copolymer shown in Formula 1 and the straight chain copolymer shown in Formula 2.

[0017] In an optional embodiment, the mixing conditions include: temperature of 40-60° C. and time of 1-2 h.

[0018] In an optional embodiment, the steps for preparing the side chain copolymer shown in Formula 1 include:

[0019] Allyl polyether and plant phenol are synthesized to form allyl polyether ester containing terminal phenolic hydroxyl group;

[0020] An allyl polyether ester containing a terminal phenolic hydroxyl group is subjected to an addition reaction with a hydrogen-containing polysiloxane.

[0021] In an optional embodiment, the preparation step of the allyl polyether ester containing a terminal phenolic hydroxyl group comprises: mixing the allyl polyether, the plant phenol and a first catalyst to react;

[0022] Preferably, the method comprises: mixing and dissolving the plant phenol and a ketone solvent, and then mixing the mixture with the allyl polyether and the first catalyst to react, and removing the ketone solvent after the reaction is completed;

[0023] Preferably, the mass ratio of the plant phenol to the ketone solvent is 1:(0.5-1.5);

[0024] Preferably, the first catalyst is selected from any one of concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, phosphotungstic acid, molybdic acid and ion exchange resin;

[0025] Preferably, the amount of the first catalyst is 1 to 5% of the total mass of the allyl polyether and the plant phenol;

[0026] Preferably, the molar ratio of the allyl polyether to the plant phenol is 1:(1.2-1.6);

[0027] Preferably, the reaction conditions include: temperature of 40-90° C. and time of 2-6 h.

[0028] In an optional embodiment, the step of the addition reaction comprises: mixing and reacting an allyl polyether ester containing a terminal phenolic hydroxyl group, a hydrogen-containing polysiloxane and a second catalyst;

[0029] Preferably, the second catalyst is selected from a platinum catalyst, more preferably chloroplatinic acid;

[0030] Preferably, the second catalyst is used in an amount of 5-15 ppm;

[0031] Preferably, the molar ratio of the hydrogen-containing polysiloxane to the allyl polyether ester having terminal phenolic hydroxyl groups is 1:(1.1-1.5);

[0032] Preferably, the conditions for the addition reaction include: a temperature of 70-130° C. and a time of 3-7 h.

[0033] In an optional embodiment, the preparation steps of the linear copolymer shown in Formula 2 are similar to those of the side chain copolymer shown in Formula 1, except that the structural formulas of the selected plant phenol and hydrogen-containing polysiloxane are different.

[0034] In a third aspect, the present invention provides a polyurethane foam, the raw materials of which include the organosilicon foam stabilizer described in the aforementioned embodiment;

[0035] Preferably, the polyurethane foam is a slow-rebound polyurethane foam.

[0036] The present invention has the following beneficial effects: the present invention provides an organic silicon foam stabilizer formed by two different copolymers, so that the organic silicon foam stabilizer can balance the opening and stabilization of the slow polyurethane foam, thereby achieving a uniform and delicate foam cell structure with a good hand feel. At the same time, the foam can have a sterilization and mite removal effect without adding other sterilization and mite removal agents, thereby improving the performance of the polyurethane foam. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0038] In a first aspect, the present invention provides an organosilicon foam stabilizer, which comprises a side chain copolymer as shown in the following formula 1 and a linear copolymer as shown in formula 2;

[0039]

[0040] Among them, the structural formula of R is: -CH 2 CH 2 CH 2 (CH 2 CH 2 O) x (CH 2 CH(CH 3 )O) y CO C 6 H 4OH; m=60~120, n=3~15, m+n=63~130, x=15~45, y=20~50;

[0041] For example, m is any value between 60 and 120, such as 60, 70, 80, 90, 100, 110, 120, and 130, or a range value between any two values.

[0042] n is any value between 3 and 15, such as 3, 5, 8, 10, 12 and 15, or a range between any two values.

[0043] m+n is any value between 63 and 130, such as 63, 70, 80, 00, 110, 120 and 130, or a range value between any two values.

[0044] x is any value between 15 and 45, such as 15, 20, 25, 30, 35, and 40, or a range between any two values.

[0045] y is any value between 20 and 50, such as 20, 25, 30, 35, 40, 45 and 50, or a range between any two values.

[0046]

[0047] Among them, R 1 The structural formula is: -CH 2 CH 2 CH 2 (CH 2 CH 2 O) x1 (CH 2 CH(CH 3 )O) y1 COC 6 H 2 (OH) 3 ; Wherein m1=10~30, x1=5~25, y1=0~20.

[0048] m1 is any value between 10 and 30, such as 10, 15, 20, 25 and 30, or a range value between any two values.

[0049] x1 is any value between 5 and 25, such as 5, 10, 15, 20, and 25, or a range between any two values.

[0050] y1 is any value between 0 and 20, such as 0, 5, 10, 15, and 20, or a range between any two values.

[0051] The organosilicon foam stabilizer provided by the embodiment of the present invention only includes the side chain copolymer shown in Formula 1 and the straight chain copolymer shown in Formula 2, and does not include other raw materials with antibacterial and mite removal properties, so that the foam prepared subsequently still has the antibacterial and mite removal effect, and there is no need to add additional raw materials with antibacterial and mite removal properties during the foam preparation process.

[0052] Among them, the mass ratio of the linear copolymer and the side chain copolymer is 1:(1.0-2.0), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 and 1:2, etc., any value between 1:(1.0-2.0) or a range value between any two values.

[0053] In a second aspect, the present invention provides a method for preparing the organosilicon foam stabilizer described in the aforementioned embodiment, comprising: mixing the side chain copolymer shown in Formula 1 and the straight chain copolymer shown in Formula 2.

[0054] The mixing conditions include: a temperature of 40-60°C and a time of 1-2h. For example, the temperature is any value between 40-60°C such as 40, 45, 50, 55 and 60, or a range between any two values. The time is any value between 1-2h such as 1h, 1.5h and 2h, or a range between any two values.

[0055] The steps for preparing the side chain copolymer shown in Formula 1 include:

[0056] Allyl polyether and plant phenol are synthesized to form allyl polyether ester containing phenolic hydroxyl group at the terminal; and the allyl polyether ester containing phenolic hydroxyl group at the terminal is subjected to addition reaction with hydrogen-containing polysiloxane.

[0057] Specifically, the plant phenol and the ketone solvent are mixed and dissolved, and then mixed with the allyl polyether and the first catalyst to react, and the ketone solvent is removed after the reaction is completed.

[0058] The mass ratio of the plant phenol to the ketone solvent is 1:(0.5-1.5), for example, any value between 1:0.5, 1:0.8, 1:1, 1:1.2 and 1:1.5 or a range between any two values. The ketone solvent includes but is not limited to acetone.

[0059] The amount of the first catalyst is 1-5% of the total mass of the allyl polyether and the plant phenol; for example, 1%, 2%, 3%, 4% and 5%, etc., any value between 1% and 5%, or a range between any two values. The first catalyst is selected from any one of concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, phosphotungstic acid, molybdic acid and ion exchange resin.

[0060] The molar ratio of allyl polyether to the plant phenol is 1:(1.2-1.6); for example, any value between 1:(1.2-1.6) or a range between any two values ​​such as 1:1.2, 1:1.3, 1:1.4, 1:1.5 and 1:1.6. Plant phenols include but are not limited to salicylic acid and gallic acid, and may also include caffeic acid, ellagic acid, ferulic acid, and catechins. Allyl polyether can be purchased directly from existing manufacturers.

[0061] The reaction conditions include: a temperature of 40-90°C and a time of 2-6h. For example, the temperature is any value between 40-90°C, such as 40°C, 50°C, 60°C, 70°C, 80°C and 90°C, or a range between any two values. The time is any value between 2-6h, such as 2h, 3h, 4h, 5h and 6h, or a range between any two values. The reaction is carried out using a reflux device equipped with a water separator.

[0062] The step of the addition reaction comprises: mixing the allyl polyether ester containing phenolic hydroxyl groups at the end, hydrogen-containing polysiloxane and the second catalyst, heating them, and keeping the temperature to react.

[0063] Among them, the second catalyst is selected from platinum catalyst, for example, including but not limited to chloroplatinic acid; the dosage of the second catalyst is 5-15ppm, for example, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm and 15ppm, etc., any value between 5-15ppm or a range value between any two values.

[0064] The molar ratio of the hydrogen-containing polysiloxane to the allyl polyether ester having terminal phenolic hydroxyl groups is 1:(1.1-1.5), for example, any value between 1:1.1, 1:1.2, 1:1.3, 1:1.4 and 1:1.5 or a range between any two values.

[0065] The addition reaction conditions include: a temperature of 70-130° C., such as 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., or any range between 70-130° C. The reaction time is 3-7 h, such as 3 h, 4 h, 5 h, 6 h, 7 h, or any range between 3-7 h, such as 3 h, 4 h, 5 h, 6 h, 7 h, or any range between 2 values.

[0066] Hydrogen-containing polysiloxanes include but are not limited to p is any value between 10 and 100, and q is any value between 1 and 15.

[0067] The preparation steps of the linear copolymer shown in Formula 2 are similar to those of the side chain copolymer shown in Formula 1, except that the selected plant phenol and hydrogen-containing polysiloxane have different structural formulas. For example, the plant phenol used in the synthesis of the linear copolymer shown in Formula 2 may include but is not limited to gallic acid, and its hydrogen-containing polysiloxane may include but is not limited to n is any value between 2 and 40. Other conditions are also within the limits of the method for preparing the side chain type copolymer represented by formula 1 above.

[0068] In a third aspect, the present invention provides a polyurethane foam, the raw materials of which include the organosilicon foam stabilizer described in the aforementioned embodiment;

[0069] Preferably, the polyurethane foam is a slow-rebound polyurethane foam.

[0070] The other components or raw materials or the dosage of each component of the polyurethane foam can refer to the component selection and dosage of polyurethane foam in the prior art.

[0071] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0072] Example 1

[0073] An embodiment of the present invention provides an organosilicon foam stabilizer, which includes an organosilicon copolymer C and an organosilicon copolymer D shown in the following structural formula, wherein the mass ratio of the organosilicon copolymer D to the organosilicon copolymer C is 100:120.

[0074] The structural formula of the silicone copolymer C is

[0075]

[0076] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 18 (CH 2 CH(CH3 )O) 22 COC 6 H 4 OH;

[0077] The structural formula of organosilicon copolymer D is

[0078]

[0079] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 COC 6 H 2 (OH) 3 .

[0080] The present invention provides a method for preparing the above-mentioned organosilicon foam stabilizer, comprising:

[0081] S1. Synthesizing allyl polyether esters with different structures and containing terminal phenolic hydroxyl groups;

[0082] 17.7 g of salicylic acid was dissolved in 15.7 g of acetone, and then put into a three-necked flask equipped with a water separator with 206.8 g of terminal allyl polyether with a molecular weight of 2126 (37.3% ethylene oxide, 62.7% propylene oxide, weight ratio) (purchased from Nanjing Zhongshan Chemical Co., Ltd., the same below) and 5.2 g of ion exchange resin (purchased from Tianjin Yunkai Resin Technology Co., Ltd.), stirred and heated to 50°C, kept warm for 4 hours, removed the solvent and filtered to obtain allyl polyether ester A.

[0083] 45.6 g of gallic acid was dissolved in 38.7 g of acetone, and then put into a three-necked flask equipped with a water separator with 203.8 g of terminal allyl polyether with a molecular weight of 1008 (65.5% ethylene oxide, 34.5% propylene oxide, weight ratio) and 3.5 g of concentrated sulfuric acid. The mixture was stirred and heated to 60°C. The mixture was kept warm for 3 h. 13.5 g of sodium bicarbonate was added for neutralization for 2 h. The solvent was removed and filtered to obtain allyl polyether ester B.

[0084] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0085] The 65.2g structure is (abbreviated as MD 80 D' 6M, homemade, the same below) hydrogen-containing polysiloxane and 178.7g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 65°C, 10ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 105°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0086]

[0087] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 18 (CH 2 CH(CH 3 )O) 22 COC 6 H 4 OH.

[0088] The 96.8g structure is (abbreviated as HMD 20 MH, the same below) (self-made, the same below) hydrogenated polysiloxane and 183.8g allyl polyether ester B were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 8ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After keeping the temperature for 5h, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0089]

[0090] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 COC 6 H 2 (OH) 3 .

[0091] S3, mixed;

[0092] Weigh 100 g of organosilicon copolymer D and 120 g of organosilicon copolymer C and stir at 50° C. for 1 hour.

[0093] Example 2

[0094] An embodiment of the present invention provides an organosilicon foam stabilizer, which includes an organosilicon copolymer C and an organosilicon copolymer D shown in the following structural formula, wherein the mass ratio of the organosilicon copolymer D to the organosilicon copolymer C is 150:150.

[0095] The structural formula of the silicone copolymer C is

[0096]

[0097] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 28 COC 6 H 4 OH.

[0098] The structural formula of organosilicon copolymer D is

[0099]

[0100] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 18 (CH 2 CH(CH 3 )O) 8 COC 6 H 2 (OH) 3 .

[0101] The present invention provides a method for preparing the above-mentioned organosilicon foam stabilizer, comprising:

[0102] S1. Synthesizing allyl polyether esters with different structures and containing terminal phenolic hydroxyl groups;

[0103] 19.5 g of salicylic acid was dissolved in 18.7 g of acetone and then put into a three-necked flask equipped with a water separator with 268.6 g of terminal allyl polyether with a molecular weight of 2562 (34.3% ethylene oxide, 65.7% propylene oxide, weight ratio) and 6.3 g of p-toluenesulfonic acid. The temperature was raised to 60°C and kept warm for 4 hours. The solvent was removed and filtered to obtain allyl polyether ester A.

[0104] 28.4 g of gallic acid was dissolved in 30.7 g of acetone and then put into a three-necked flask equipped with a water separator with 150.5 g of terminal allyl polyether with a molecular weight of 1314 (60.3% ethylene oxide, 39.7% propylene oxide, weight ratio) and 2.3 g of potassium hydroxide. The temperature was raised to 70°C and the reaction was kept warm for 3 hours. 25.8 g of dilute hydrochloric acid was added for neutralization for 2 hours. The solvent was removed and filtered to obtain allyl polyether ester B.

[0105] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0106] Convert 52.8g structure to MD 65 D' 5 M hydrogen-containing polysiloxane and 173.2g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 70°C, 9ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 100°C. After the reaction was kept at this temperature for 5h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0107]

[0108] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 28 COC 6 H 4 OH.

[0109] 47.6g structure as HMD 18 MH hydrogen-containing polysiloxane and 120.9 g of allyl polyether ester D prepared in step 2 were put into a four-necked flask, stirred, and when the temperature was raised to 70°C, 7 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 90°C. After the reaction was kept at this temperature for 6 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0110]

[0111] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 18 (CH 2 CH(CH 3 )O) 8 COC 6 H 2 (OH) 3 .

[0112] S3, mixed;

[0113] Weigh 150 g of organosilicon copolymer C and 150 g of organosilicon copolymer D and stir at 45° C. for 2 h.

[0114] Example 3

[0115] An embodiment of the present invention provides an organosilicon foam stabilizer, which includes an organosilicon copolymer C and an organosilicon copolymer D shown in the following structural formula, wherein the mass ratio of the organosilicon copolymer D to the organosilicon copolymer C is 120:160.

[0116] The structural formula of the silicone copolymer C is

[0117]

[0118] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 16 (CH 2 CH(CH 3 )O) 30 COC 6 H 4 OH;

[0119] The structural formula of organosilicon copolymer D is

[0120]

[0121] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 9 COC 6 H 2 (OH) 3 .

[0122] The present invention provides a method for preparing the above-mentioned organosilicon foam stabilizer, comprising:

[0123] S1. Synthesizing allyl polyether esters with different structures and containing terminal phenolic hydroxyl groups;

[0124] 19.4 g of salicylic acid was dissolved in 17.3 g of acetone and then put into a three-necked flask equipped with a water separator with 260.5 g of terminal allyl polyether with a molecular weight of 2502 (28.1% ethylene oxide, 71.9% propylene oxide, weight ratio) and 5.6 g of p-toluenesulfonic acid. The temperature was raised to 60°C and kept for reaction for 4 hours. The solvent was removed and filtered to obtain allyl polyether ester A.

[0125] 30.9 g of gallic acid was dissolved in 29.7 g of acetone and then put into a three-necked flask equipped with a water separator with 204.6 g of terminal allyl polyether with a molecular weight of 1460 (60.3% ethylene oxide, 39.7% propylene oxide, weight ratio) and 6.4 g of phosphoric acid. The temperature was raised to 45°C and kept warm for 5 hours. 23.6 g of sodium bicarbonate was added for neutralization for 2 hours. The solvent was removed and filtered to obtain allyl polyether ester B.

[0126] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0127] Convert 74.2g structure to MD 92 D' 7 M hydrogen-containing polysiloxane and 238.3g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 12ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 100°C. After the reaction was kept at this temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0128]

[0129] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 16 (CH 2 CH(CH 3 )O) 30 COC 6 H 4 OH.

[0130] 55.6g structure as HMD 15 MH hydrogen-containing polysiloxane and 190.3 g of allyl polyether ester B prepared in step 2 were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 6 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0131]

[0132] Where R 1 -CH 2 CH 2 CH2 (CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 9 COC 6 H 2 (OH) 3 .

[0133] S3, mixed;

[0134] Weigh 120 g of organosilicon copolymer D and 160 g of organosilicon copolymer C and stir at 60° C. for 1 hour.

[0135] Example 4

[0136] An embodiment of the present invention provides an organosilicon foam stabilizer, which includes an organosilicon copolymer C and an organosilicon copolymer D shown in the following structural formula, wherein the mass ratio of the organosilicon copolymer D to the organosilicon copolymer C is 100:150.

[0137] The structural formula of the silicone copolymer C is

[0138]

[0139] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 28 (CH 2 CH(CH 3 )O) 40 COC 6 H 4 OH;

[0140] The structural formula of organosilicon copolymer D is

[0141]

[0142] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 12 (CH 2 CH(CH 3 )O) 6 COC 6 H 2 (OH) 3 .

[0143] The present invention provides a method for preparing the above-mentioned organosilicon foam stabilizer, comprising:

[0144] S1. Synthesizing allyl polyether esters with different structures and containing terminal phenolic hydroxyl groups;

[0145] 16.2 g of salicylic acid was dissolved in 16.9 g of acetone and then put into a three-necked flask equipped with a water separator with 287.6 g of terminal allyl polyether with a molecular weight of 3610 (34.1% ethylene oxide, 65.9% propylene oxide, weight ratio) and 6.4 g of molybdic acid. The temperature was raised to 60°C and the reaction was kept warm for 4 hours. The solvent was removed and filtered to obtain allyl polyether ester A.

[0146] 40.9 g of gallic acid was dissolved in 38.5 g of acetone and then put into a three-necked flask equipped with a water separator with 186.8 g of terminal allyl polyether with a molecular weight of 934 (56.5% ethylene oxide, 43.5% propylene oxide, weight ratio) and 3.4 g of sodium hydroxide. The temperature was raised to 80°C and kept warm for 3 hours. 30.6 g of dilute hydrochloric acid was added for neutralization for 2 hours. The solvent was removed and filtered to obtain allyl polyether ester B.

[0147] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0148] Convert 65.2g structure to MD 75 D' 5 M hydrogen-containing polysiloxane and 267.5g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 68°C, 10ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 105°C. After the reaction was kept at this temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0149]

[0150] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 28 (CH 2 CH(CH 3 )O) 40 COC 6 H 4 OH.

[0151] Convert 68.4g into HMD 22 MH hydrogen-containing polysiloxane and 111.6g allyl polyether ester B were put into a four-necked flask, stirred, and when the temperature was raised to 66°C, 8ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5h, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0152]

[0153] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 12 (CH 2 CH(CH 3 )O) 6 COC 6 H 2 (OH) 3 .

[0154] S3, mixed;

[0155] Weigh 100 g of organosilicon copolymer D and 150 g of organosilicon copolymer C and stir at 55° C. for 1 hour.

[0156] Example 5

[0157] An embodiment of the present invention provides an organosilicon foam stabilizer, which includes an organosilicon copolymer C and an organosilicon copolymer D shown in the following structural formula, wherein the mass ratio of the organosilicon copolymer D to the organosilicon copolymer C is 80:140.

[0158] The structural formula of the silicone copolymer C is

[0159]

[0160] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 25 (CH 2 CH(CH 3 )O) 35 COC 6 H 4 OH.

[0161] The structural formula of organosilicon copolymer D is

[0162]

[0163] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 10 (CH 2 CH(CH 3)O) 3 COC 6 H 2 (OH) 3 .

[0164] The present invention provides a method for preparing the above-mentioned organosilicon foam stabilizer, comprising:

[0165] S1. Synthesizing allyl polyether esters with different structures and containing terminal phenolic hydroxyl groups;

[0166] 17.6 g of salicylic acid was dissolved in 20.6 g of acetone and then put into a three-necked flask equipped with a water separator with 305.8 g of terminal allyl polyether with a molecular weight of 3188 (34.5% ethylene oxide, 65.5% propylene oxide, weight ratio) and 8.4 g of phosphotungstic acid. The temperature was raised to 60°C and the reaction was kept warm for 3 hours. The solvent was removed and filtered to obtain allyl polyether ester A.

[0167] 73.5 g of gallic acid was dissolved in 75.2 g of acetone and then put into a three-necked flask equipped with a water separator with 226.6 g of terminal allyl polyether with a molecular weight of 672 (65.5% ethylene oxide, 34.5% propylene oxide, weight ratio) and 7.5 g of molybdic acid. The temperature was raised to 50°C and the reaction was kept warm for 5 hours. The solvent was removed and filtered to obtain allyl polyether ester B.

[0168] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0169] Convert 52.8g structure to MD 110 D' 9 M hydrogen-containing polysiloxane and 232.4g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 69°C, 13ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 110°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0170]

[0171] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 25 (CH 2 CH(CH 3 )O) 35 COC 6 H 4 OH.

[0172] 67.6g structure as HMD 17MH hydrogen-containing polysiloxane and 122.9 g of allyl polyether ester B prepared in step 2 were put into a four-necked flask, stirred, and when the temperature was raised to 65°C, 7 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0173]

[0174] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 10 (CH 2 CH(CH 3 )O) 3 COC 6 H 2 (OH) 3 .

[0175] S3, mixed;

[0176] Weigh 80 g of organosilicon copolymer D and 140 g of organosilicon copolymer C and stir at 60° C. for 1 hour.

[0177] Example 6

[0178] An embodiment of the present invention provides an organosilicon foam stabilizer, which includes an organosilicon copolymer C and an organosilicon copolymer D shown in the following structural formula, wherein the mass ratio of the organosilicon copolymer D to the organosilicon copolymer C is 80:150.

[0179] The structural formula of the silicone copolymer C is

[0180]

[0181] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 30 (CH 2 CH(CH 3 )O) 45 COC 6 H 4 OH;

[0182] The structural formula of organosilicon copolymer D is

[0183]

[0184] Where R 1 -CH2 CH 2 CH 2 (CH 2 CH 2 O) 22 (CH 2 CH(CH 3 )O) 10 COC 6 H 2 (OH) 3 .

[0185] The present invention provides a method for preparing the above-mentioned organosilicon foam stabilizer, comprising:

[0186] S1. Synthesizing allyl polyether esters with different structures and containing terminal phenolic hydroxyl groups;

[0187] 17.3 g of salicylic acid was dissolved in 20.5 g of acetone and then put into a three-necked flask equipped with a water separator with 319.2 g of terminal allyl polyether with a molecular weight of 3988 (33.1% ethylene oxide, 66.9% propylene oxide, weight ratio) and 9.3 g of p-toluenesulfonic acid. The temperature was raised to 60°C and the reaction was kept warm for 4 hours. The solvent was removed and filtered to obtain allyl polyether ester A.

[0188] 35.6 g of gallic acid was dissolved in 36.8 g of acetone and then put into a three-necked flask equipped with a water separator with 240.9 g of terminal allyl polyether with a molecular weight of 1606 (60.3% ethylene oxide, 39.7% propylene oxide, weight ratio) and 5.5 g of phosphotungstic acid. The temperature was raised to 60°C and the reaction was kept warm for 5 hours. After adding a solvent removal agent and filtering, allyl polyether ester B was obtained.

[0189] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0190] Convert 43.8g structure to MD 86 D' 7 M hydrogen-containing polysiloxane and 226.7g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 70°C, 12ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 100°C. After the reaction was kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0191]

[0192] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 30 (CH 2 CH(CH 3 )O)45 COC 6 H 4 OH.

[0193] 75.7g structure as HMD 24 MH hydrogen-containing polysiloxane and 183.5g allyl polyether ester B were put into a four-necked flask, stirred, and when the temperature was raised to 70°C, 8ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 90°C. After the reaction was kept at this temperature for 6 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0194]

[0195] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 22 (CH 2 CH(CH 3 )O) 10 COC 6 H 2 (OH) 3 .

[0196] S3, mixed;

[0197] Weigh 80 g of organosilicon copolymer D and 150 g of organosilicon copolymer C and stir at 40° C. for 2 h.

[0198] Comparative Example 1

[0199] This comparative example provides a method for preparing a silicone foam stabilizer, comprising:

[0200] S1, terminal allyl polyethers of different molecular weights;

[0201] A terminal allyl polyether with a molecular weight of 3610 (34.1% ethylene oxide, 65.9% propylene oxide, weight ratio) and a terminal allyl polyether with a molecular weight of 934 (56.5% ethylene oxide, 43.5% propylene oxide, weight ratio) were capped with methyl to obtain allyl polyethers A and B (the specific capping method is described in patent CN111732723B).

[0202] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0203] Convert 65.5g structure to MD 75 D' 5M hydrogen-containing polysiloxane and 256.7g allyl polyether A were put into a four-necked flask, stirred, and when the temperature was raised to 68°C, 10ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 105°C. After the reaction was kept at this temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0204]

[0205] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 28 (CH 2 CH(CH 3 )O) 40 CH 3 .

[0206] The 69.5g structure is HMD 22 MH hydrogen-containing polysiloxane and 98.3g allyl polyether B were put into a four-necked flask, stirred, and when the temperature was raised to 66°C, 8ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5h, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0207]

[0208] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 12 (CH 2 CH(CH 3 )O) 6 CH 3 .

[0209] S3, mixed;

[0210] Weigh 100 g of organosilicon copolymer D and 150 g of organosilicon copolymer C and stir at 55° C. for 1 hour.

[0211] Comparative Example 2

[0212] S1, terminal allyl polyethers of different molecular weights;

[0213] Allyl polyether A and B were obtained by capping the terminal allyl polyether with a molecular weight of 2502 (28.1% ethylene oxide, 71.9% propylene oxide, weight ratio) and the terminal allyl polyether with a molecular weight of 1460 (60.3% ethylene oxide, 39.7% propylene oxide, weight ratio) with methyl groups.

[0214] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0215] Convert 75.2g structure to MD 92 D' 7 M hydrogen-containing polysiloxane and 232.9g allyl polyether A were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 12ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 100°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0216]

[0217] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 16 (CH 2 CH(CH 3 )O) 30 CH 3 .

[0218] Transform 58.5g into HMD 15 MH hydrogenated polysiloxane and 180.0g allyl polyether B were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 6ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5h, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0219]

[0220] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 9 CH 3 .

[0221] S3, mixed;

[0222] Weigh 120 g of organosilicon copolymer D and 160 g of organosilicon copolymer C and stir at 60° C. for 1 hour.

[0223] Comparative Example 3

[0224] S1, terminal allyl polyethers of different molecular weights;

[0225] A terminal allyl polyether with a molecular weight of 3610 (34.1% ethylene oxide, 65.9% propylene oxide, weight ratio) and a terminal allyl polyether with a molecular weight of 934 (56.5% ethylene oxide, 43.5% propylene oxide, weight ratio) were capped with acetoxy to obtain allyl polyethers A and B (the specific capping method is described in patent CN109851771B).

[0226] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0227] Convert 65.5g structure to MD 75 D' 5 M hydrogen-containing polysiloxane and 258.7g allyl polyether A were put into a four-necked flask, stirred, and when the temperature was raised to 68°C, 10ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 105°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0228]

[0229] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 28 (CH 2 CH(CH 3 )O) 40 COCH 3 ;

[0230] The 69.5g structure is HMD 22 MH hydrogen-containing polysiloxane and 100.2g allyl polyether B were put into a four-necked flask, stirred, and when the temperature was raised to 66°C, 8ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5h, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0231]

[0232] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 12 (CH 2 CH(CH 3 )O) 6 COCH 3 .

[0233] S3, mixed;

[0234] Weigh 100 g of organosilicon copolymer D and 150 g of organosilicon copolymer C and stir at 55° C. for 1 hour.

[0235] Comparative Example 4

[0236] S1, terminal allyl polyethers of different molecular weights;

[0237] Allyl polyether A and B were obtained by capping a terminal allyl polyether with a molecular weight of 2502 (28.1% ethylene oxide, 71.9% propylene oxide, weight ratio) and a terminal allyl polyether with a molecular weight of 1460 (60.3% ethylene oxide, 39.7% propylene oxide, weight ratio) with acetoxy groups.

[0238] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0239] Convert 75.2g structure to MD 92 D' 7 M hydrogen-containing polysiloxane and 235.7g allyl polyether A were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 12ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 100°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0240]

[0241] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 16 (CH 2 CH(CH 3 )O) 30 COCH 3 ;

[0242] Transform 58.5g into HMD 15 MH hydrogenated polysiloxane and 183.7 g of allyl polyether B were placed in a four-necked flask, stirred, and heated to 60°C. 6 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0243]

[0244] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 20 (CH 2 CH(CH3 )O) 9 COCH 3 .

[0245] S3, mixed;

[0246] Weigh 120 g of organosilicon copolymer D and 160 g of organosilicon copolymer C and stir at 60° C. for 1 hour.

[0247] Comparative Example 5

[0248] S1, terminal allyl polyether esters with different structural formulas;

[0249] 23.2 g of gallic acid was dissolved in 24.7 g of acetone, and then put into a three-necked flask equipped with a water separator with 206.8 g of terminal allyl polyether with a molecular weight of 2126 (37.3% ethylene oxide, 62.7% propylene oxide, weight ratio) and 5.5 g of ion exchange resin. The mixture was stirred and heated to 50°C. The mixture was kept warm for 4 hours, and the solvent was removed and filtered to obtain allyl polyether ester A.

[0250] 40.8 g of salicylic acid was dissolved in 38.7 g of acetone, and then put into a three-necked flask equipped with a water separator with 203.8 g of terminal allyl polyether with a molecular weight of 1008 (65.5% ethylene oxide, 34.5% propylene oxide, weight ratio) and 3.5 g of concentrated sulfuric acid. The mixture was stirred and heated to 60°C. The reaction was kept warm for 3 h, 13.5 g of sodium bicarbonate was added for neutralization for 2 h, the solvent was removed and filtered to obtain allyl polyether ester B.

[0251] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0252] Convert 65.2g structure to MD 80 D' 6 M hydrogen-containing polysiloxane and 182.3g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 65°C, 10ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 105°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0253]

[0254] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 18 (CH 2 CH(CH 3 )O) 22 COC 6 H 2 (OH) 3 ;

[0255] 96.8g structure as HMD 20 MH hydrogenated polysiloxane and 178.7 g of allyl polyether ester B were put into a four-necked flask, stirred, and when the temperature was raised to 60°C, 8 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After keeping the temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0256]

[0257] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 COC 6 H 4 OH.

[0258] S3, mixed;

[0259] Weigh 100 g of organosilicon copolymer D and 120 g of organosilicon copolymer C and stir at 50° C. for 1 hour.

[0260] Comparative Example 6

[0261] S1, terminal allyl polyether esters with different structural formulas;

[0262] 23.3g of gallic acid was dissolved in 33.6g of acetone and then put into a three-necked flask equipped with a water separator with 305.8g of terminal allyl polyether (34.5% ethylene oxide, 65.5% propylene oxide, weight ratio) and 8.4g of phosphotungstic acid, and the mixture was heated to 60°C, kept warm for 3h, and the solvent was removed and filtered to obtain allyl polyether ester A;

[0263] 62.8 g of salicylic acid was dissolved in 55.2 g of acetone and then put into a three-necked flask equipped with a water separator with 226.6 g of terminal allyl polyether with a molecular weight of 672 (65.5% ethylene oxide, 34.5% propylene oxide, weight ratio) and 7.5 g of molybdic acid. The temperature was raised to 50°C and the reaction was kept warm for 5 hours. The solvent was removed and filtered to obtain allyl polyether ester B.

[0264] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0265] Convert 52.8g structure to MD 110 D' 9M hydrogen-containing polysiloxane and 235.6g allyl polyether ester A were put into a four-necked flask, stirred, and when the temperature was raised to 69°C, 13ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 110°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0266]

[0267] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 25 (CH 2 CH(CH 3 )O) 35 COC 6 H 2 (OH) 3 ;

[0268] 67.6g structure as HMD 17 MH hydrogen-containing polysiloxane and 114.8 g of allyl polyether ester B prepared in step 2 were put into a four-necked flask, stirred, and when the temperature was raised to 65°C, 7 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0269]

[0270] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 10 (CH 2 CH(CH 3 )O) 3 COC 6 H 4 OH.

[0271] S3, mixed;

[0272] Weigh 80 g of organosilicon copolymer D and 140 g of organosilicon copolymer C and stir at 60° C. for 1 hour.

[0273] Comparative Example 7

[0274] S1, terminal allyl polyethers of different molecular weights;

[0275] 206.8g of terminal allyl polyether with a molecular weight of 2126 (37.3% ethylene oxide, 62.7% propylene oxide, weight ratio) was terminated with methyl to obtain allyl polyether A, and the terminal allyl polyether with a molecular weight of 1008 (65.5% ethylene oxide, 34.5% propylene oxide, weight ratio) was terminated with acetoxy to obtain allyl polyether B.

[0276] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0277] Convert 66.2g structure to MD 80 D' 6 M hydrogen-containing polysiloxane and 170.8g allyl polyether A were put into a four-necked flask, stirred, and when the temperature was raised to 65°C, 10ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 105°C. After keeping the temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0278]

[0279] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 18 (CH 2 CH(CH 3 )O) 22 CH 3 ;

[0280] 95.8g structure as HMD 20 MH hydrogenated polysiloxane and 165.7 g of allyl polyether B were placed in a four-necked flask, stirred, and heated to 60°C. 8 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After being kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0281]

[0282] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 COCH 3 .

[0283] S3, mixed;

[0284] Weigh 100 g of organosilicon copolymer D and 120 g of organosilicon copolymer C and stir at 50° C. for 1 hour.

[0285] Comparative Example 8

[0286] S1, terminal allyl polyethers of different molecular weights;

[0287] The terminal allyl polyether with a molecular weight of 3188 (34.5% ethylene oxide, 65.5% propylene oxide, weight ratio) was terminated with acetoxy to obtain allyl polyether A; the terminal allyl polyether with a molecular weight of 672 (65.5% ethylene oxide, 34.5% propylene oxide, weight ratio) was terminated with methyl to obtain allyl polyether B.

[0288] S2, synthesizing silicone copolymer C and silicone copolymer D;

[0289] Convert 52.6g structure to MD 110 D' 9 M hydrogen-containing polysiloxane and 225.8g allyl polyether A were put into a four-necked flask, stirred, and when the temperature was raised to 69°C, 13ppm chloroplatinic acid catalyst was added, and the temperature was continued to rise to 110°C. After the reaction was kept at this temperature for 4h, the temperature was lowered to obtain an organosilicon copolymer C, whose structural formula is

[0290]

[0291] Where R is -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 25 (CH 2 CH(CH 3 )O) 35 COCH 3 ;

[0292] 87.7g structure as HMD 17 MH hydrogen-containing polysiloxane and 112.3 g of allyl polyether B were put into a four-necked flask, stirred, and when the temperature was raised to 65°C, 7 ppm of chloroplatinic acid catalyst was added, and the temperature was continued to rise to 95°C. After the reaction was kept at this temperature for 5 hours, the temperature was lowered to obtain an organosilicon copolymer D, whose structural formula is

[0293]

[0294] Where R 1 -CH 2 CH 2 CH 2 (CH 2 CH 2 O) 10 (CH 2CH(CH 3 )O) 3 CH 3 .

[0295] S3, mixed;

[0296] Weigh 80 g of organosilicon copolymer D and 140 g of organosilicon copolymer C and stir at 60° C. for 1 hour.

[0297] Experimental example

[0298] The polyurethane foam stabilizers of Examples 1-6 and Comparative Examples 1-8 were used to prepare polyurethane foams, respectively. The operation and process conditions for preparing the polyurethane foams were the same except for the polyurethane foam stabilizers, and all of them were the existing methods for preparing polyurethane foams. The specific formula for preparing the polyurethane foam of the present invention is shown in Table 1.

[0299] Table 1 Formulation of polyurethane foam

[0300] Material composition Mass share Polyether polyol 3010 35 Polyether polyol 2070 65 water 1.6 Triethylenediamine 0.2 Stannous Octoate 0.1 Bis(dimethylaminoethyl) ether 0.1 Toluene diisocyanate TDI80 70 Cell opener 1 Foam stabilizer 1

[0301] The prepared polyurethane foam was tested, wherein the density of the polyurethane foam was tested according to the national standard "GB / T6343-2009", the air permeability of the polyurethane foam was tested according to the standard "DINISO4638-1993 Flexible Foam Polymer Materials. Determination of Air Permeability", and the inhibition rate of the slow-rebound foam on bacteria and mites was tested according to the test methods of the national standard antibacterial performance evaluation "GB / T 20944.3-2008" and the national standard anti-mite performance evaluation "GB / T 24253-2009". The results are shown in Tables 2 and 3.

[0302] Table 2 Polyurethane foam properties

[0303]

[0304]

[0305] Note: The pore structure is characterized by 4 levels from coarse to fine: + represents coarse, ++ represents relatively coarse, +++ represents fine, and ++++ represents very fine.

[0306] The foam feel is characterized by 4 levels from hard to soft: 1 represents hard, 2 represents relatively hard, 3 represents soft, and 4 represents very soft.

[0307] Table 3 Inhibition rate of slow rebound foam on different bacteria and mites after 48h of culture

[0308]

[0309]

[0310] According to the above table, compared with the organosilicon copolymers synthesized by using methyl and acetoxy end-capping for polyether ends and gallic acid end-capping for polyether with relatively large molecular weight and salicylic acid end-capping for polyether with relatively small molecular weight in the comparative example, the organosilicon copolymers synthesized by using salicylic acid end-capping for polyether with relatively large molecular weight and gallic acid end-capping for polyether with relatively small molecular weight in the present invention as stabilizers for polyurethane foams to form slow-rebound polyurethane foams, which not only have more uniform and delicate pore structure, better air permeability and better hand feel, but also, in particular, the foams also have certain anti-mite and antibacterial effects.

[0311] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A silicone foam stabilizer, characterized in that: It includes a side chain copolymer shown in the following formula 1 and a straight chain copolymer shown in formula 2; Among them, the structural formula of R is: -CH2CH2CH2(CH2CH2O) x (CH2CH(CH3)O) y CO C6H4OH; m=60~120, n=3~15, m+n=63~130, x=15~45, y=20~50; Among them, the structural formula of R1 is: -CH2CH2CH2(CH2CH2O) x1 (CH2CH(CH3)O) y1 COC6H2(OH)3; wherein m1=10~30, x1=5~25, y1=0~20.

2. The organosilicon foam stabilizer according to claim 1, characterized in that: The mass ratio of the linear copolymer to the side chain copolymer is 1:(1.0-2.0).

3. The organosilicon foam stabilizer according to claim 1, characterized in that: The organosilicon foam stabilizer is a stabilizer for preparing slow-rebound polyurethane foam.

4. A method for preparing the organosilicon foam stabilizer according to claim 1, characterized in that: include: The side chain type copolymer represented by Formula 1 and the straight chain type copolymer represented by Formula 2 are mixed.

5. The preparation method according to claim 4, characterized in that: The mixing conditions include: temperature of 40-60°C and time of 1-2h.

6. The preparation method according to claim 4, characterized in that: The steps for preparing the side chain copolymer shown in Formula 1 include: Allyl polyether and plant phenol are synthesized to form allyl polyether ester containing terminal phenolic hydroxyl group; An allyl polyether ester containing a terminal phenolic hydroxyl group is subjected to an addition reaction with a hydrogen-containing polysiloxane.

7. The preparation method according to claim 6, characterized in that: The preparation steps of the allyl polyether ester containing a phenolic hydroxyl group at the end include: mixing the allyl polyether, the plant phenol and a first catalyst to react; Preferably, the method comprises: mixing and dissolving the plant phenol and a ketone solvent, and then mixing the mixture with the allyl polyether and the first catalyst to react, and removing the ketone solvent after the reaction is completed; Preferably, the mass ratio of the plant phenol to the ketone solvent is 1:(0.5-1.5); Preferably, the first catalyst is selected from any one of concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, phosphotungstic acid, molybdic acid and ion exchange resin; Preferably, the amount of the first catalyst is 1 to 5% of the total mass of the allyl polyether and the plant phenol; Preferably, the molar ratio of the allyl polyether to the plant phenol is 1:(1.2-1.6); Preferably, the reaction conditions include: temperature of 40-90° C. and time of 2-6 h.

8. The preparation method according to claim 6, characterized in that: The addition reaction step comprises: mixing and reacting an allyl polyether ester containing a phenolic hydroxyl group at the end, a hydrogen-containing polysiloxane and a second catalyst; Preferably, the second catalyst is selected from a platinum catalyst, more preferably chloroplatinic acid; Preferably, the second catalyst is used in an amount of 5-15 ppm; Preferably, the molar ratio of the hydrogen-containing polysiloxane to the allyl polyether ester having terminal phenolic hydroxyl groups is 1:(1.1-1.5); Preferably, the conditions for the addition reaction include: a temperature of 70-130° C. and a time of 3-7 h.

9. The preparation method according to claim 6, characterized in that: The preparation steps of the linear copolymer shown in Formula 2 are similar to those of the side chain copolymer shown in Formula 1, except that the structural formulas of the selected plant phenol and hydrogen-containing polysiloxane are different.

10. A polyurethane foam, characterized in that: The raw materials include the organosilicon foam stabilizer according to claim 1; Preferably, the polyurethane foam is a slow-rebound polyurethane foam.

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