Phosphate polysiloxane, organic silicon surfactant, preparation method of organic silicon surfactant and high-resilience polyurethane foam

Abstract

The invention relates to the technical field of surfactants, in particular to phosphate polysiloxane, an organic silicon surfactant, a preparation method of the organic silicon surfactant and high-resilience polyurethane foam. The phosphate-based polysiloxane is selected from compounds shown in the following structural formula: # imgabs0, the phosphate-based polysiloxane can be used for preparing an organic silicon surfactant, so that the surfactant has flame retardance, and foam prepared from the surfactant not only has good flame retardance, but also is stable in performance.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, and in particular to phosphate-based polysiloxane, an organosilicon surfactant, a preparation method thereof and a high-resilience polyurethane foam. Background Art

[0002] High-resilience polyurethane foam (HR) is a type of foam plastic with excellent performance. Compared with ordinary soft foam, high-resilience foam has better elasticity, comfort and durability, so it is widely used in car seats, home mattresses and headrests.

[0003] Polyurethane foam products are flammable. Adding flame retardants to the raw materials for producing polyurethane is currently an effective way to improve the flame retardant properties of polyurethane foam materials. The flame retardants used mainly include reactive flame retardant polyether polyols and non-reactive small molecule flame retardants. Reactive flame retardant polyether polyols mainly introduce flame retardant elements (such as phosphorus, halogens and nitrogen, etc.) or flame retardant structures (such as large heterocycles) into the molecular chain structure of polyether polyols by modification or grafting. The polyurethane foam prepared with this polyether polyol has high cost and low bearing capacity. The varieties of non-reactive small molecule flame retardants mainly include liquid or solid compounds such as Sb2O3, phosphites and chlorides. Although this type of added flame retardant can improve the flame retardant properties of polyurethane foam to a certain extent, the dialysis migration of the flame retardant will cause flame retardant failure.

[0004] The role of surfactants in the foaming process of high-resilience polyurethane foam is well known. It plays an indispensable role in the cell structure, mechanical strength and product performance of polyurethane foam plastics. However, there are relatively few studies on silicone surfactants with flame retardant properties. Therefore, it is of great significance to develop surfactants for high-resilience polyurethane foam with flame retardant properties to improve its flame retardant properties on the basis of stable foam opening performance. In view of this, the present invention is specially proposed.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a phosphate-based polysiloxane, an organosilicon surfactant, a preparation method thereof, and a high-resilience polyurethane foam. The embodiment of the present invention provides a new phosphate-based polysiloxane, which can be used to prepare an organosilicon surfactant, so that the surfactant has flame retardant properties.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides a phosphate-based polysiloxane selected from the compounds represented by the following structural formula:

[0009]

[0010] Wherein, x is any value between 1 and 12, y is 0<y≤5, 0<z≤3, and the value of x+y+z is 2-15;

[0011] The structure of R1 is: -CH2CH2CH2O(CH2CH2O) a (CH2CH(CH3)O) b R3, wherein a is any value between 1-8, b is any value between 1-8, and a+b=2-10, and R3 is a C1-C4 alkyl group;

[0012] The structure of R2 is: Among them, m is 0 or 1; i is 1 or 2; n is 0-4, p is 0-1, and q is 0-3.

[0013] In a second aspect, the present invention provides an organosilicon surfactant, which is used for high-resilience polyurethane foam. The composition of the organosilicon surfactant is as follows, in terms of weight percentage: the weight percentage of component A is 5-40%, the weight percentage of component B is 50-90%, and the weight percentage of component C is 5-35%, and the sum of the weight percentages of the three components of component A, component B and component C is 100%;

[0014] The component A is the phosphate-based polysiloxane described in the above embodiment; the component B is a copolymer of terminal hydroxyl groups derived from a polyhydroxy compound; and the component C is a material-based polyol.

[0015] In a third aspect, the present invention provides a method for preparing the organosilicon surfactant described in the aforementioned embodiment, comprising: mixing component A, component B and component C.

[0016] In a fourth aspect, the present invention provides a high-resilience polyurethane foam, the raw materials of which include the organosilicon surfactant described in the aforementioned embodiment.

[0017] The present invention has the following beneficial effects: The embodiment of the present invention provides a new phosphate-based polysiloxane, which can be used to prepare an organosilicon surfactant, so that the surfactant has flame retardant properties. The organosilicon surfactant can be used to prepare high-resilience polyurethane foam, which can improve the flame retardant properties of high-resilience polyurethane foam, and at the same time has better foam open porosity and other mechanical properties. Specifically, the phosphate-based polysiloxane is mixed with a copolymer of terminal hydroxyl groups derived from bio-based polyols and polyhydroxy compounds, which can not only reduce production costs and improve environmental friendliness, but also broaden the functional characteristics and application range of related materials, and help achieve carbon peak and carbon neutrality. At the same time, the preparation method of the surfactant is simple, easy to operate, and suitable for industrial production. In short, the embodiment of the present invention provides a new idea for the development of environmentally friendly high-resilience polyurethane foam surfactants with flame retardant properties. DETAILED DESCRIPTION

[0018] 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.

[0019] In a first aspect, the present invention provides a phosphate-based polysiloxane selected from the compounds represented by the following structural formula:

[0020]

[0021] Wherein, x is any value between 1 and 12, y is 0<y≤5, 0<z≤3, and the value of x+y+z is 2-15;

[0022] The structure of R1 is: -CH2CH2CH2O(CH2CH2O) a (CH2CH(CH3)O) b R3, wherein a is any value between 1-8, b is any value between 1-8, and a+b=2-10, and R3 is a C1-C4 alkyl group;

[0023] The structure of R2 is: Wherein, m is 0 or 1; i is 1 or 2; n is 0-4, p is 0-1, and q is 0-3. For example, when m=0, i=2; when m=1, i=1.

[0024] The selection of R2 can refer to the following examples of the embodiments of the present invention:

[0025]

[0026] In the second aspect, an embodiment of the present invention provides a silicone surfactant, which can be used to prepare high-resilience polyurethane foam. The composition of the silicone surfactant is as follows, in weight percentage: the weight percentage of component A is 5-40%, the weight percentage of component B is 50-90%, and the weight percentage of component C is 5-35%. The sum of the weight percentages of the three components, component A, component B and component C, is 100%.

[0027] For example, component A is 5%, 10%, 15%, 20%, 25%, 30%, 35% and 40%, etc., any value between 5-40%, or a range value between any two values.

[0028] The B component is any value between 50-90%, such as 50%, 60%, 70%, 80% and 90%, or a range value between any two values.

[0029] The C component is any value between 5-35%, such as 5%, 10%, 15%, 20%, 25%, 30% and 35%, or a range value between any two values.

[0030] Component A is the above-mentioned phosphate-based polysiloxane; the embodiment of the present invention introduces phosphates of different structures, which can improve the flame retardant properties of the silicone surfactant, thereby improving the flame retardant properties of the high-resilience polyurethane foam prepared subsequently, and at the same time, the polyurethane foam has better foam opening properties and other mechanical properties.

[0031] Component B is a copolymer of terminal hydroxyl groups derived from a polyhydroxy compound; for example, a low molecular weight polyether polyol; more preferably, the molecular weight of component B is 300 to 1500; for example, including but not limited to any one of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.

[0032] Component C is a bio-based polyol, such as plant oil-based polyol, natural phenolic polyol, rosin ester-based polyol, wood fiber-based polyol, etc. Specifically, plant oil-based polyols include but are not limited to soybean oil-based, palm oil-based, castor oil-based and tung oil-based polyols; the natural phenolic polyols include but are not limited to any one of cardanol polyol, tannin-based polyol and sugar-based polyol; the rosin ester-based polyol includes but is not limited to any one of rosin-based polyol and turpentine-based polyol; the wood fiber-based polyol includes but is not limited to any one of the polyols prepared from wood cellulose sources such as wood, bamboo and straw.

[0033] The embodiment of the present invention uses the above-mentioned raw material bio-based polyols and traditional petrochemical-based polyols as diluents for mixed use, which can not only reduce production costs and improve environmental friendliness, but also broaden the functional properties and application scope of related materials, and help achieve the carbon peak and carbon neutrality goals.

[0034] The present invention provides a method for preparing the above-mentioned organosilicon surfactant, comprising:

[0035] S1. Preparation of hydrogen-containing polysiloxane:

[0036] Octamethylcyclotetrasiloxane, high hydrogen-containing polysiloxane and hexamethyldisiloxane are used as raw materials, and reacted for 2-8 hours at a reaction temperature of 30-80° C. under the action of an acidic catalyst to obtain hydrogen-containing polysiloxanes with different structures; the hydrogen content of the high hydrogen-containing polysiloxane includes but is not limited to 1.5%.

[0037] The acid catalyst is selected from at least one of acid clay, concentrated sulfuric acid, acid resin and trifluoromethanesulfonic acid, and more preferably concentrated sulfuric acid or acid resin; the amount of the acid catalyst is 0.5-6% of the total mass of the raw materials for forming the hydrogen-containing polysiloxane. If concentrated sulfuric acid is used as a catalyst, sodium bicarbonate is used for neutralization after the reaction is completed.

[0038] S2. Preparation of component A:

[0039] The hydrogen-containing polysiloxane, the phosphate compound, the Karstedt catalyst and the co-catalyst are mixed and reacted, and then mixed with the allyl polyether and the Karstedt catalyst and reacted.

[0040] Specifically, the hydrogen-containing polysiloxane and the phosphate compound obtained in S1 are reacted for 0.5-2h by slow dripping (for example, dripping within 0.5-1h) under the action of Karstedt catalyst and co-catalyst, nitrogen protection, 80-100°C, solvent (for example, toluene or isopropanol), and then allyl polyether and Karstedt catalyst are added to the reaction system, and the temperature is kept at 90-120°C for 2-7h, and the solvent is removed to obtain phosphate-based polysiloxane, namely component A.

[0041] S3. Preparation of silicone surfactant:

[0042] The obtained component A and components B and C are mixed in different mass ratios to obtain an organosilicon surfactant.

[0043] In a fourth aspect, an embodiment of the present invention provides a high-resilience polyurethane foam, the raw materials of which include the above-mentioned silicone surfactant.

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

[0045] Example 1

[0046] An embodiment of the present invention provides a method for preparing a phosphate-based polysiloxane, comprising:

[0047] S1. Preparation of hydrogen-containing polysiloxane;

[0048] 102.52 g of octamethylcyclotetrasiloxane, 41.96 g of high hydrogen-containing polysiloxane (hydrogen content 1.5%) and 35.52 g of hexamethyldisiloxane were reacted at 35° C. for 5 h in the presence of 3.6 g of concentrated sulfuric acid, neutralized with sodium bicarbonate and filtered to obtain hydrogen-containing polysiloxane.

[0049] S2. Preparation of phosphate-based polysiloxane;

[0050] 50g of hydrogen-containing polysiloxane and 20g of isopropanol were added to the reactor. Under the conditions of 10ppm Karstedt catalyst and 100ppm diethanolamine as a co-catalyst, 9.94g of phosphate compound was slowly added dropwise into the reactor at 85°C within 0.5h. The temperature was kept for 1h. Then, 6ppm Karstedt catalyst and 74.32g of allyl polyether were added to the reaction system. The temperature was raised to 90°C and kept for 4h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane, whose molecular formula is:

[0051] Si(CH3)3-O-[Si(CH3)2-O] 5.9 -[Si(CH3)R1-O] 2.0 -[Si(CH3)R2-O] 0.8 -Si(CH3)3

[0052] Among them, R1=-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3;

[0053]

[0054] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0055] Component A (the above-mentioned phosphate-based polysiloxane), component B (1,4-butanediol as an initiator, molecular weight 800) and component C (soybean oil polyol, molecular weight 1200) are mixed in a certain ratio (A is 10%, B is 80%, C is 10%), and stirred at 40°C for 1 hour to form an organosilicon surfactant.

[0056] Example 2

[0057] An embodiment of the present invention provides a method for preparing a phosphate-based polysiloxane, comprising:

[0058] S1. Preparation of hydrogen-containing polysiloxane;

[0059] 112.11 g of octamethylcyclotetrasiloxane, 39.17 g of high hydrogen-containing polysiloxane (hydrogen content 1.5%) and 28.72 g of hexamethyldisiloxane were reacted at 60° C. for 5 h in the presence of 5.4 g of acidic resin to obtain hydrogen-containing polysiloxane.

[0060] S2. Preparation of phosphate-based polysiloxane;

[0061] 58g of hydrogen-containing polysiloxane and 20g of toluene were added to the reactor. Under the conditions of 10ppm Karstedt catalyst and 200ppm triethanolamine as a co-catalyst, 10.39g of phosphate compound was slowly added dropwise into the reactor within 0.5h under nitrogen protection. The temperature was kept at 90°C for 1.5h. Then, 99.46g of allyl polyether and 6ppm of Karstedt catalyst were added to the reaction system. The temperature was raised to 115°C and kept for 3h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane, whose molecular formula is:

[0062] Si(CH3)3-O-[Si(CH3)2-O] 7.9 -[Si(CH3)R1-O] 2.2 -[Si(CH3)R2-O] 1.0 -Si(CH3)3, where R1=-CH2CH2CH2O(CH2CH2O)2(CH2 CH(CH3)O)4CH3,

[0063]

[0064] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0065] Component A (the above-mentioned phosphate-based polysiloxane), component B (diethylene glycol as an initiator, molecular weight 800) and component C (cardanol polyol, molecular weight 1000) are mixed in a certain ratio (A is 10%, B is 70%, and C is 20%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0066] Example 3

[0067] An embodiment of the present invention provides a method for preparing phosphate-based polysiloxane, comprising:

[0068] S1. Preparation of hydrogen-containing polysiloxane;

[0069] 112.68 g of octamethylcyclotetrasiloxane, 43.99 g of high hydrogen-containing polysiloxane (hydrogen content 1.5%) and 23.33 g of hexamethyldisiloxane were reacted at 40° C. for 3 h under the action of 9 g of concentrated sulfuric acid, neutralized with sodium bicarbonate and filtered to obtain hydrogen-containing polysiloxane.

[0070] S2. Preparation of phosphate-based polysiloxane;

[0071] 54g of hydrogen-containing polysiloxane and 18.5g of isopropanol were added to the reactor. Under the conditions of 15ppm Karstedt catalyst and 100ppm diethanolamine as a co-catalyst, 7.88g of phosphate compound was slowly added dropwise into the reactor within 0.5h under nitrogen protection. The temperature was kept at 85°C for 2h. Then, 94.25g of allyl polyether and 5ppm of Karstedt catalyst were added to the reaction system. The temperature was raised to 90°C and kept for 4.5h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane with the molecular formula:

[0072] Si(CH3)3-O-[Si(CH3)2-O] 9.5 -[Si(CH3)R1-O]3-[Si(CH3)R2-O] 1.3 -Si(CH3)3,

[0073] Where R1=-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3,

[0074]

[0075] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0076] Component A (the above-mentioned phosphate-based polysiloxane), component B (dipropylene glycol as an initiator, molecular weight 1000) and component C (soybean oil polyol, molecular weight 1200) are mixed in a certain ratio (A is 15%, B is 65%, and C is 20%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0077] Example 4

[0078] An embodiment of the present invention provides a method for preparing a phosphate-based polysiloxane, comprising:

[0079] S1. Preparation of hydrogen-containing polysiloxane;

[0080] 87.63 g of octamethylcyclotetrasiloxane, 47.24 g of high hydrogen-containing polysiloxane (hydrogen content 1.5%) and 45.13 g of hexamethyldisiloxane were reacted at 65° C. for 5 h in the presence of 9 g of acidic resin to obtain hydrogen-containing polysiloxane.

[0081] S2. Preparation of phosphate-based polysiloxane;

[0082] 52g of hydrogen-containing polysiloxane and 18.5g of toluene were added to the reactor. Under the conditions of 8ppm Karstedt catalyst and 100ppm acetamide co-catalyst, 11.23g of phosphate compound was slowly added dropwise into the reactor within 0.5h under nitrogen protection. The temperature was kept at 90℃ for 1.5h. Then, 107.56g of allyl polyether and 6ppm Karstedt catalyst were added to the reaction system. The temperature was raised to 110℃ and kept for 4.5h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane with the molecular formula:

[0083] Si(CH3)3-O-[Si(CH3)2-O]4-[Si(CH3)R1-O]2-[Si(CH3)R2-O] 0.5 -Si(CH3)3

[0084] Wherein R1=-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)4CH3,

[0085]

[0086] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0087] Component A (the above-mentioned phosphate-based polysiloxane), component B (diethylene glycol as an initiator, molecular weight 800) and component C (cardanol polyol, molecular weight 1000) are mixed in a certain ratio (A is 20%, B is 70%, and C is 10%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0088] Example 5

[0089] An embodiment of the present invention provides a method for preparing a phosphate-based polysiloxane, comprising:

[0090] S1. Preparation of hydrogen-containing polysiloxane;

[0091] 79.29 g of octamethylcyclotetrasiloxane, 45.59 g of high hydrogen-containing polysiloxane (hydrogen content 1.5%) and 55.13 g of hexamethyldisiloxane were reacted at 60° C. for 5 h in the presence of 9 g of acidic resin to obtain hydrogen-containing polysiloxane.

[0092] S2. Preparation of phosphate-based polysiloxane;

[0093] 55g of hydrogen-containing polysiloxane and 20g of isopropanol were added to the reactor. Under the conditions of 10ppm Karstedt catalyst and 100ppm diethanolamine as a co-catalyst, 11.87g of phosphate compound was slowly added dropwise into the reactor within 0.5h under nitrogen protection. The temperature was kept at 85℃ for 1.5h. Then, 64.28g of allyl polyether and 6ppm of Karstedt catalyst were added to the reaction system. The temperature was kept at 90℃ for 5h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane with the molecular formula:

[0094] Si(CH3)3-O-[Si(CH3)2-O]3-[Si(CH3)R1-O] 1.4 -[Si(CH3)R2-O] 0.6 -Si(CH3)3

[0095] Wherein R1=-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3,

[0096]

[0097] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0098] Component A (the above-mentioned phosphate-based polysiloxane), component B (1,4-butanediol as an initiator, molecular weight 800) and component C (rosin-based polyol, molecular weight 1500) are mixed in a certain ratio (A is 20%, B is 60%, and C is 20%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0099] Example 6

[0100] An embodiment of the present invention provides a method for preparing a phosphate-based polysiloxane, comprising:

[0101] S1. Preparation of hydrogen-containing polysiloxane;

[0102] 117.33 g of octamethylcyclotetrasiloxane, 34.52 g of high hydrogen-containing polysiloxane (hydrogen content 1.5%) and 28.15 g of hexamethyldisiloxane were reacted in the presence of 5.4 g of concentrated sulfuric acid at 40° C. for 4.5 h, neutralized with sodium bicarbonate and filtered to obtain hydrogen-containing polysiloxane.

[0103] S2. Preparation of phosphate-based polysiloxane;

[0104] 60g of hydrogen-containing polysiloxane and 21g of toluene were added to the reactor. Under the conditions of 10ppm of chloroplatinic acid catalyst and 100ppm of triethanolamine as a co-catalyst, 11.20g of phosphate compound was slowly added dropwise into the reactor within 0.5h under nitrogen protection. The temperature was kept at 90℃ for 2h. Then 60.70g of allyl polyether and 5ppm of chloroplatinic acid catalyst were added to the reaction system. The temperature was raised to 110℃ and kept for 5h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane with the molecular formula:

[0105] Si(CH3)3-O-[Si(CH3)2-O] 8.5 -[Si(CH3)R1-O] 2.0 -[Si(CH3)R2-O] 0.9 -Si(CH3)3

[0106] Wherein R1=-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3,

[0107]

[0108] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0109] Component A (the above-mentioned phosphate-based polysiloxane), component B (1,4-butanol as an initiator, molecular weight 800) and component C (rosin-based polyol, molecular weight 1500) are mixed in a certain ratio (A is 10%, B is 70%, and C is 20%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0110] Example 7

[0111] The embodiment of the present invention provides a method for preparing phosphate-based polysiloxane, see the preparation method of Example 1.

[0112] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0113] Component A (the above-mentioned phosphate-based polysiloxane), component B (1,4-butanediol as an initiator, molecular weight 800) and component C (soybean oil polyol, molecular weight 1200) are mixed in a certain ratio (A is 20%, B is 65%, and C is 15%), and stirred at 40°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0114] Example 8

[0115] The embodiment of the present invention provides a method for preparing phosphate-based polysiloxane, see the preparation method of Example 2.

[0116] This embodiment provides a method for preparing an organosilicon surfactant, comprising:

[0117] Component A (the above-mentioned phosphate-based polysiloxane), component B (diethylene glycol as an initiator, molecular weight 800) and component C (cardanol polyol, molecular weight 1000) are mixed in a certain ratio (A is 30%, B is 60%, and C is 10%), and stirred at 45°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0118] Comparative Example 1

[0119] This comparative example provides a method for preparing polysiloxane, comprising:

[0120] S1. Preparation of hydrogen-containing polysiloxane;

[0121] Refer to the preparation method of Example 1.

[0122] S2, preparation of polysiloxane;

[0123] 50g of hydrogenated polysiloxane, 104.05g of allyl polyether and 30g of toluene were added into the reactor, and reacted for 5h at 110℃ under the conditions of 10ppm Karstedt catalyst and 100ppm diethanolamine as a co-catalyst under nitrogen protection, and the solvent and other low-boiling substances were removed to obtain polysiloxane with the molecular formula:

[0124] Si(CH3)3-O-[Si(CH3)2-O] 5.9 -[Si(CH3)R1-O] 2.8 -Si(CH3)3,

[0125] Wherein R1=-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3.

[0126] This comparative example provides a method for preparing an organosilicon surfactant, comprising:

[0127] Component A (the above polysiloxane), component B (1,4-butanediol as an initiator, molecular weight 800) and component C (soybean oil polyol, molecular weight 1200) were mixed in a certain ratio (A is 10%, B is 80%, C is 10%), and stirred at 40°C for 1 hour to obtain a silicone surfactant for high resilience polyurethane foam.

[0128] Comparative Example 2

[0129] This comparative example provides a method for preparing polysiloxane, comprising:

[0130] S1. Preparation of hydrogen-containing polysiloxane;

[0131] Refer to the preparation method of Example 3.

[0132] S2, preparation of polysiloxane;

[0133] 53g of hydrogen-containing polysiloxane, 132.15g of allyl polyether and 25.0g of isopropanol were added to the reactor, and the mixture was protected by nitrogen and kept warm at 90°C for 4h under the conditions of 15ppm Karstedt catalyst and 100ppm diethanolamine as a co-catalyst. The solvent and other low-boiling substances were removed to obtain polysiloxane with the molecular formula:

[0134] Si(CH3)3-O-[Si(CH3)2-O] 9.5 -[Si(CH3)R1-O] 4.3 -Si(CH3)3,

[0135] Where R1=-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)5CH3.

[0136] This comparative example provides a method for preparing an organosilicon surfactant, comprising:

[0137] Component A (the above-mentioned polysiloxane), component B (diethylene glycol as an initiator, molecular weight 1000) and component C (rapeseed oil polyol, molecular weight 1000) are mixed in a certain ratio (A is 15%, B is 65%, and C is 20%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high resilience polyurethane foam.

[0138] Comparative Example 3

[0139] This comparative example provides a method for preparing polysiloxane, comprising:

[0140] S1. Preparation of hydrogen-containing polysiloxane;

[0141] Refer to the preparation method of Example 5.

[0142] S2, preparation of polysiloxane;

[0143] 65g of hydrogenated polysiloxane, 108.53g of allyl polyether and 18g of toluene were added into the reactor, and the reaction was carried out at 100°C for 5h under the conditions of 10ppm Karstedt catalyst and 300ppm diethanolamine as a co-catalyst under normal pressure and nitrogen protection, and the solvent and other low-boiling substances were removed to obtain polysiloxane with the molecular formula:

[0144] Si(CH3)3-O-[Si(CH3)2-O]3-[Si(CH3)R1-O]2-Si(CH3)3,

[0145] Wherein R1=-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3.

[0146] This comparative example provides a method for preparing an organosilicon surfactant, comprising:

[0147] Component A (the above-mentioned polysiloxane), component B (1,4-butanediol as an initiator, molecular weight 800) and component C (rosin-based polyol, molecular weight 1500) are mixed in a certain ratio (A is 20%, B is 60%, and C is 20%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0148] Comparative Example 4

[0149] This comparative example provides a method for preparing polysiloxane, comprising:

[0150] S1. Preparation of hydrogen-containing polysiloxane;

[0151] 131.06 g of octamethylcyclotetrasiloxane, 33.57 g of high hydrogen-containing polysiloxane and 15.38 g of hexamethyldisiloxane were reacted at 60° C. for 4 h in the presence of 9 g of acidic resin to obtain hydrogen-containing polysiloxane.

[0152] S2. Preparation of phosphate-based polysiloxane;

[0153] 52g of hydrogen-containing polysiloxane and 18g of isopropanol were added to the reactor. Under the conditions of 10ppm Karstedt catalyst and 100ppm triethanolamine as a co-catalyst, 7.86g of phosphate compound was slowly added dropwise into the reactor within 0.5h under nitrogen protection. The temperature was kept at 90℃ for 1.5h. Then, 66.88g of allyl polyether and 8ppm of Karstedt catalyst were added to the reaction system. The temperature was kept at 90℃ for 3h. The solvent and other low-boiling substances were removed to obtain phosphate-based polysiloxane with the molecular formula:

[0154] Si(CH3)3-O-[Si(CH3)2-O] 16.5 -[Si(CH3)R1-O] 3.4 -[Si(CH3)R2-O] 1.5 -Si(CH3)3, where R1=-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)4CH3,

[0155]

[0156] This comparative example provides a method for preparing an organosilicon surfactant, comprising:

[0157] Component A (the above-mentioned polysiloxane with phosphate group), component B (1,4-butanediol as initiator, molecular weight 800) and component C (rosin-based polyol, molecular weight 1500) are mixed in a certain ratio (A is 10%, B is 80%, C is 10%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high resilience polyurethane foam.

[0158] Comparative Example 5

[0159] This comparative example provides a method for preparing polysiloxane, comprising:

[0160] This comparative example provides a method for preparing phosphate-based polysiloxane, referring to the preparation method of Example 2.

[0161] This comparative example provides a method for preparing an organosilicon surfactant, comprising:

[0162] Component A (the above-mentioned phosphate-based polysiloxane), component B (diethylene glycol as an initiator, molecular weight 800) and component C (cardanol polyol, molecular weight 1000) are mixed in a certain ratio (A is 60%, B is 30%, and C is 10%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0163] Comparative Example 6

[0164] This comparative example provides a method for preparing phosphate-based polysiloxane, referring to the preparation method of Example 4.

[0165] This comparative example provides a method for preparing an organosilicon surfactant, comprising:

[0166] Component A (the above-mentioned phosphate-based polysiloxane) and component B (diethylene glycol as an initiator, molecular weight 800) were mixed in a certain ratio (A is 20%, B is 80%), and stirred at 50°C for 1 hour to obtain a silicone surfactant for high-resilience polyurethane foam.

[0167] Application Examples

[0168] The surfactants obtained in the above Examples 1-8 and Comparative Examples 1-6 are used to prepare polyurethane high-resilience polyurethane foam. Specifically, the high-resilience polyurethane foam is prepared by reacting component X and component Y. The preparation method is as follows:

[0169] Preparation of component X: According to the formula in Table 1, the weighed polyol, catalyst, foaming agent and surfactant are mixed and stirred at room temperature for 20 seconds.

[0170] Table 1 Polyurethane foam formula

[0171]

[0172] The Y component material is TM20, which refers to a mixture of TDI (toluene diisocyanate) and MDI (diphenylmethane diisocyanate), wherein TDI accounts for 80% and MDI accounts for 20%.

[0173] When used, add component X and component Y according to 96% of isocyanate number, stir for 5s at 2000r / min, and pour into a standard mold (mold temperature 25°C) without free foaming. The foam is made into high-resilience polyurethane foam through foaming, growth and maturation, and data testing is carried out on the FOAMAT 285 instrument at the same time. Reference for standard square mold exhaust force test method: "GBT10807-2006 Determination of hardness of flexible foam polymer materials (indentation method)"; other test methods refer to: "QBT 2080-2010 High-resilience flexible polyurethane foam plastics". Reference for flame retardant performance test standard: British BS-5852 fire protection standard. The test results are shown in Tables 2 and 3 below.

[0174] Table 2 Test results

[0175]

[0176] According to Table 2, on the basis of the existing polyether-modified silicone structure, the introduction of phosphate compounds with different structures stabilizes the foam opening performance (Comparative Examples 1, 2, and 3), and at the same time, the foam exhaust force, rebound performance, and air permeability after extrusion are all improved to a certain extent (refer to the standard square mold exhaust force data). In addition, the partial introduction of bio-based polyols (Comparative Example 6) results in stable foam performance, and slightly improved rebound, air permeability and other properties. In addition, it is also optimized from the perspective of cost and environmental protection.

[0177] In terms of flame retardant properties, it can be seen from the weight loss data of the polyurethane high resilience foams corresponding to the embodiments and comparative examples in Table 2 after combustion that the introduction of phosphate compounds with different structures has a relatively obvious improvement in the flame retardant effect of the foam. And from the exhaust power data, it can be seen that the resilience, exhaust power and other properties of the polyurethane high resilience foam prepared by the present invention are also relatively excellent. In addition, the hydrogen-containing polysiloxane main chain structure that is not within the protection scope of the embodiments of the present invention will have an adverse effect on the foam opening and air permeability (Comparative Example 4). At the same time, the content of component A is too high (Comparative Example 5). Although the flame retardant effect is improved, the exhaust power data is significantly increased, the foam shrinks, and the rebound performance deteriorates, which is also undesirable.

[0178] Table 3 FOAMAT data of polyurethane foam

[0179]

[0180]

[0181] It can be seen from the above data that the introduction of phosphate compounds with different structures, on the basis of improving the open cell performance (Table 2), can also maintain the performance of the corresponding FOAMAT test foam at a high level (Table 3), the maximum height of the foam rise is relatively high, and the shrinkage rate is relatively small. In addition, it can be seen from the evaluation results of Comparative Examples 1, 4, and 5 that the hydrogen-containing polysiloxane, component A content, and the non-introduction of the phosphate compound structure that are not within the protection scope of the embodiments of the present invention have an adverse effect on the foam shrinkage rate. At the same time, the introduction of plant-based polyols has a certain improvement effect on the foam performance, such as the relative increase in the maximum height of the foam rise, and the reduction in the shrinkage rate (Comparative Example 6), which has also been optimized and improved from the perspective of cost and environmental protection.

[0182] 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 phosphate-based polysiloxane, characterized in that: It is selected from the compounds represented by the following structural formula: Wherein, x is any value between 1 and 12, y is 0<y≤5, 0<z≤3, and the value of x+y+z is 2-15; The structure of R1 is: -CH2CH2CH2O(CH2CH2O) a (CH2CH(CH3)O) b R3, wherein a is any value between 1-8, b is any value between 1-8, and a+b=2-10, and R3 is a C1-C4 alkyl group; The structure of R2 is: Among them, m is 0 or 1; i is 1 or 2; n is 0-4, p is 0-1, and q is 0-3.

2. The phosphate-based polysiloxane according to claim 1, characterized in that When m=0, i=2; when m=1, i=1; Preferably, R2 is selected from any one of the groups shown in the following structural formulas:

3. An organosilicon surfactant, characterized in that: The organosilicon surfactant is used to prepare high-resilience polyurethane foam. The composition of the organosilicon surfactant is as follows, in terms of weight percentage: the weight percentage of component A is 5-40%, the weight percentage of component B is 50-90%, and the weight percentage of component C is 5-35%. The sum of the weight percentages of the three components, namely, component A, component B and component C, is 100%. The component A is the phosphate-based polysiloxane according to claim 1; the component B is a copolymer of terminal hydroxyl groups derived from polyhydroxy compounds; and the component C is a bio-based polyol.

4. The organosilicon surfactant according to claim 3, characterized in that: The component B is a low molecular weight polyether polyol; Preferably, the molecular weight of component B is 300 to 1500; Preferably, the component B is selected from any one of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.

5. The organosilicon surfactant according to claim 3, characterized in that: The component C is selected from any one of plant oil-based polyols, natural phenolic polyols, rosin-based polyols and wood fiber-based polyols; Preferably, the vegetable oil-based polyol is selected from any one of soybean oil-based, palm oil-based, castor oil-based and tung oil-based polyols; The natural phenolic polyol includes any one of cardanol polyol, tannin polyol and sugar-based polyol; The rosin ester-based polyol includes any one of rosin-based polyol and turpentine-based polyol; The lignocellulosic polyol includes any one of polyols prepared from wood, bamboo and straw sources.

6. A method for preparing the organosilicon surfactant according to claim 3, characterized in that: include: Mix components A, B and C.

7. The preparation method according to claim 6, characterized in that: The preparation step of the component A includes: mixing hydrogen-containing polysiloxane, phosphate compound, Karstedt catalyst and co-catalyst for reaction, and then mixing with allyl polyether and Karstedt catalyst for reaction.

8. The preparation method according to claim 7, characterized in that: The preparation step of the component A comprises: slowly adding a solvent to the hydrogen-containing polysiloxane, the phosphate compound, the Karstedt catalyst and the co-catalyst under an inert gas atmosphere at 80-100° C. for a continuous reaction of 0.5-2 hours, and then adding the allyl polyether and the Karstedt catalyst for a reaction at 90-120° C. for 2-7 hours; Preferably, the amount of the Karstedt catalyst used each time is 3-20 ppm of the total amount of all raw materials forming component A; Preferably, the amount of the co-catalyst is 50-500 ppm of the total amount of all raw materials forming component A; Preferably, the co-catalyst is selected from amine substances, more preferably at least one of diethanolamine, triethanolamine, acetamide, triethylamine and N-butylethanolamine.

9. The preparation method according to claim 7, characterized in that: The preparation steps of the hydrogen-containing polysiloxane include: using octamethylcyclotetrasiloxane, high hydrogen-containing polysiloxane and hexamethyldisiloxane as raw materials, reacting under the action of an acidic catalyst; Preferably, the reaction conditions include: temperature of 30-80°C, time of 2-8h; Preferably, the acidic catalyst is selected from at least one of acidic clay, concentrated sulfuric acid, acidic resin and trifluoromethanesulfonic acid, more preferably concentrated sulfuric acid or acidic resin; Preferably, the acid catalyst is used in an amount of 0.5-6% of the total mass of the raw materials for forming the hydrogen-containing polysiloxane.

10. A high resilience polyurethane foam, characterized in that: The raw materials include the organosilicon surfactant described in claim 3.

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