Fluorine-containing polyether organosilicone, preparation method thereof and polyurethane foam

Abstract

The invention relates to the technical field of organic silicon surfactants, in particular to fluorine-containing polyether organic silicon, a preparation method of the fluorine-containing polyether organic silicon and polyurethane foam. The side chain of the fluorine-containing polyether organic silicon comprises fluorine-containing allyl polyether formed by ring opening of 3-methyl-3-[(2, 2, 3, 3, 3-pentafluoropropoxy) methyl] oxetane. According to the fluorine-containing polyether organic silicon provided by the embodiment of the invention, the advantage that the surface tension is greatly reduced by the fluoroalkyl is fully utilized, so that uniform and massive generation of bubble nuclei is promoted in the foaming process of polyurethane foam, a firm interface film is formed on a bubble hole wall, the stability of the foam is remarkably improved, the bubble holes are prevented from being combined or collapsed, and the foaming performance of the polyurethane foam is improved. The rigid polyurethane foam formed by foaming presents a fine and uniform foam hole structure, has a high percentage of close area, and can significantly reduce the heat conductivity coefficient and improve the heat insulation efficiency.

Description

TECHNICAL FIELD

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

[0002] Hard polyurethane foam has shown significant advantages in thermal insulation materials due to its excellent thermal insulation performance, and has become the preferred choice in high-end application fields such as building energy saving, industrial pipeline insulation, cold chain and deep cooling equipment, and liquefied gas storage and transportation. Compared with natural insulation materials (such as rock wool) and other synthetic insulation materials (such as expanded polystyrene EPS and extruded polystyrene XPS), hard polyurethane foam has a lower thermal conductivity and can achieve the same or even better thermal insulation effect at a thinner thickness, thereby showing outstanding performance in energy saving efficiency and space utilization.

[0003] The thermal insulation performance of hard polyurethane foam mainly depends on its surface quality and internal cell structure. An ideal thermal insulation foam should have the characteristics of no obvious defects on the surface, fine and uniform internal cells, and high closed cell rate. However, during the preparation of the foam.

[0004] During the growth of the bubbles, the liquid film is thinned and broken due to the capillary force, the liquid migrates from the bubble wall to the edge, the gas in bubbles of different sizes can diffuse from small bubbles to large bubbles, and the bubbles may also merge due to collision, further damaging the uniformity of the cells.

[0005] To suppress the above problems, foam stabilizers are generally used in industry, the main component of which is a comb-like polyether silicone surfactant with siloxane as the main chain and polyether as the side chain. It can emulsify the foaming raw materials, promote uniform mixing, ensure the coordination of foaming and crosslinking reactions, reduce the surface tension of the material, and make it easier for the air mixed in the stirring process to form a large number of bubble nuclei, laying the foundation for fine and uniform cell structure. More importantly, the foam stabilizer plays a key role in the bubble stabilization mechanism. When the liquid film is thinned due to local stretching, the surface active agent concentration decreases, triggering a surface tension gradient, prompting the surface active agent molecules to migrate to the thin area and bringing the underlying liquid backflow, thereby repairing the liquid film. At the same time, the surface active agent can reduce the surface tension of the liquid film, reduce the pressure difference between bubbles of different sizes, inhibit gas diffusion, and alleviate bubble coarsening. In addition, the close arrangement layer formed by the surface active agent on the surface of the liquid film not only blocks gas diffusion, but also significantly enhances the mechanical strength of the liquid film, avoiding the rupture of the bubble during the growth process due to external shear force and reducing surface defects.

[0006] The structural characteristics of the polyether organosilicon surfactant have a significant influence on the thermal insulation performance of the foam. By regulating the length of the siloxane backbone, the grafting structure, the number and the position of the polyether side chain, the spatial configuration and the interfacial behavior of the copolymer can be effectively optimized, thereby improving the thermal insulation performance of the polyurethane foam. However, with the continuous expansion of the application field of the polyurethane foam and the increasingly stringent performance requirements, it is difficult to meet the demand for thermal insulation performance of high-end applications by relying on the conventional adjustment of the structure of the polyether organosilicon copolymer.

[0007] Since the organic fluoropolymer has extremely low surface tension, the introduction of the polyether organosilicon surfactant into the organic fluoropolymer can effectively reduce the surface tension of the material, and promote the entry of air to form more bubble cores during stirring. During the foaming process, the fluorine-containing segment can be adsorbed on the interface of the bubble liquid film, further reducing the surface tension of the liquid film. Based on the surface tension gradient generated by the Marangoni effect, the local weak points caused by liquid film drainage can be repaired, the merging of bubbles and the rupture of liquid film can be inhibited, thereby stabilizing the cell structure, improving the closed cell rate, and enhancing the thermal insulation performance of the polyurethane foam.

[0008] For example, patent CN117024747A discloses a fluorine-containing polyether organosilicon copolymer, which is formed by grafting a polyperfluoropropylene oxide modified allyl polyglyceryl ether and an allyl polyether onto a hydrogen-containing polymethylsiloxane backbone. It can be used as a foam stabilizer to reduce the thermal conductivity of polyurethane foam. However, the synthesis path adopted by this patent has certain limitations: after chlorination of the polyperfluoropropylene oxide monocarboxylic acid, it reacts with the allyl polyglyceryl ether and is grafted. Due to steric hindrance, the fluorine compound groups and the hydroxymethyl groups are spaced apart on the side chain, which weakens the ability of adjacent hydroxymethyl groups to reduce the surface tension of the fluorine compound. In addition, only one polyperfluoropropylene oxide modified segment is grafted onto each siloxane backbone, which further limits its surface activity effect. Therefore, the performance of this copolymer as a foam stabilizer in reducing the thermal conductivity of polyurethane foam is limited.

[0009] In order to break through the bottleneck of the existing molecular structure design and fully utilize the potential of fluorine-containing polyether organosilicon copolymer in foam stabilization and thermal insulation enhancement, it is necessary to develop new fluorine-containing polyether organosilicon surfactants based on the existing architecture to promote a new round of breakthroughs in the thermal insulation performance of polyurethane foam.

[0010] In view of this, the present application is proposed. SUMMARY

[0011] The present application aims to provide a fluorine-containing polyether organosilicon, a preparation method thereof and a polyurethane foam.

[0012] The present application is implemented as follows: In a first aspect, the present application provides a fluorine-containing polyether silicone, which has a side chain comprising a fluorine-containing allyl polyether formed by ring opening of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane.

[0013] In an optional embodiment, the structural formula is as follows: (CH3)3Si-O-[Si(CH3)2O] m -[Si(CH3)R1O] p -[Si(CH3)R2O] q -Si(CH3)3; wherein: m has a value of 30-75, p+q has a value of 4-10, and p / (p+q)=0.2-0.4; R1=-CH2CH2CH2O(CH2CH2O) a (CH2CHCH3O) b (CH2CR3CH3CH2O) c H; R2=-CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y H; R3= -CH2OCH2CF2CF3; a=10-30, b=0-3, c=2-5; x=10-35, y=0-10.

[0014] In a second aspect, the present application provides a preparation method of the fluorine-containing polyether silicone according to the foregoing embodiment, comprising: reacting 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane and an allyl polyether to form a fluorine-containing allyl polyether; mixing the fluorine-containing allyl polyether, the allyl polyether, and a hydrogen-containing polymethylsiloxane to perform a hydrosilylation.

[0015] In an optional embodiment, the step of forming the fluorine-containing allyl polyether comprises: mixing a solvent, an allyl polyether, 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane, and a catalyst to perform a reaction.

[0016] In an optional embodiment, the conditions for forming the fluorine-containing allyl polyether meet at least one of the following requirements: (1) the solvent comprises a polyhalogenated C1-C3 alkane; preferably dichloromethane; (2) the molar ratio of the solvent to the allyl polyether is (3-5):1; (3) the catalyst comprises a boron complex; preferably boron trifluoride-tetrahydrofuran; (4) the molar ratio of the allyl polyether to the catalyst is 1:(1-1.2); (5) the reaction temperature is 30-50℃.

[0017] In an optional embodiment, the allyl polyether is a block copolymer prepared from allyl alcohol, oxirane and propylene oxide.

[0018] In an optional embodiment, the step of hydrosilylation comprises mixing the hydrogen-containing polymethylsiloxane, the fluorine-containing allyl polyether, a solvent, a platinum catalyst and a cocatalyst at 85-95℃, and then adding the allyl polyether and the platinum catalyst to react at 100-120℃.

[0019] In an optional embodiment, the conditions of hydrosilylation meet at least one of the following requirements: (1) the solvent comprises a benzene solvent, preferably toluene; (2) the mass ratio of the solvent to the total mass of the fluorine-containing allyl polyether, the allyl polyether and the hydrogen-containing polymethylsiloxane is (30-80):100; (3) the molar ratio of the sum of the double bonds of the fluorine-containing allyl polyether and the allyl polyether to the silicon-hydrogen bond of the hydrogen-containing polymethylsiloxane is 1.2-1.6:1.

[0020] In a third aspect, the present application provides a polyurethane foam prepared from the fluorine-containing polyether organosilicon according to the foregoing embodiments.

[0021] In an optional embodiment, it further comprises a polyether polyol or a polyester polyol, and the mass content of the fluorine-containing polyether organosilicon is 1-5 parts, preferably 2-3 parts, based on 100 parts by mass of the polyether polyol or the polyester polyol.

[0022] The present application has the following beneficial effects: (1) the present application can select allyl polyethers with different structures and graft different numbers of side chains on the allyl polyether to prepare fluorine-containing allyl polyethers prepared by ring-opening of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane, realizing high flexibility and customizability of fluorine-containing polyether organosilicon in molecular structure design, precise control of the performance of high molecular compounds, and meeting different application scenarios and formula requirements, thereby meeting diversified actual application requirements.

[0023] (2) The fluorine-containing polyether silicone provided by the embodiment of the present application makes full use of the advantage of fluorine alkyl greatly reducing surface tension, not only promotes uniform and large generation of bubble nuclei in the foaming process of polyurethane foam, but also forms a firm interface film on the cell wall, significantly improves the stability of the foam, prevents cell merging or collapse, and the rigid polyurethane foam formed by foaming presents a fine and uniform cell structure and has a high closed cell rate, can significantly reduce the thermal conductivity, and improve the thermal insulation efficiency. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0025] The fluorine-containing polyether silicone provided by the embodiment of the present application has a side chain comprising a fluorine-containing allyl polyether formed by opening a 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane, that is, a fluorine-containing allyl polyether formed by 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane and an allyl polyether.

[0026] The fluorine-containing polyether silicone provided by the embodiment of the present application makes full use of the advantage of fluorine alkyl greatly reducing surface tension, not only promotes uniform and large generation of bubble nuclei in the foaming process of polyurethane foam, but also forms a firm interface film on the cell wall, significantly improves the stability of the foam, prevents cell merging or collapse, and the rigid polyurethane foam formed by foaming presents a fine and uniform cell structure and has a high closed cell rate, can significantly reduce the thermal conductivity, and improve the thermal insulation efficiency.

[0027] The structural formula of the fluorine-containing polyether silicone is as follows: (CH3)3Si-O-[Si(CH3)2O] m -[Si(CH3)R1O] p -[Si(CH3)R2O] q -Si(CH3)3; Wherein: The value of m is 30-75, the value of p+q is 4-10, and p / (p+q)=0.2-0.4; R1=-CH2CH2CH2O(CH2CH2O) a (CH2CHCH3O) b (CH2CR3CH3CH2O) cH; R2= -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y H; R3= -CH2OCH2CF2CF3; a=10-30,b=0-3,c=2-5; x=10-35,y=0-10。

[0028] In a second aspect, the present application also provides a preparation method of the fluorine-containing polyether organosilicon, comprising: S1, forming a fluorine-containing allyl polyether; reacting 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane with an allyl polyether; specifically, mixing a solvent, an allyl polyether, 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane and a catalyst to react.

[0029] Further specifically, the solvent and the allyl polyether are added into a reactor, stirred at 30-50°C for 30-40 min; the catalyst is added and stirred for 50-70 min; then, 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane is slowly added within 60-80 min, the mixture is continuously stirred for 60-80 min, quenched by adding sodium bicarbonate, washed with deionized water twice, and the solvent is removed to obtain the fluorine-containing allyl polyether.

[0030] The solvent includes a polyhalogenated C1-C3 alkane; for example, but not limited to, dichloromethane. The molar ratio of the solvent to the allyl polyether is (3-5):1; for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, or any value between (3-5):1. The molar ratio of the allyl polyether to the catalyst is 1:(1-1.2); for example, 1:1, 1:1.1, 1:1.15, 1:1.2, or any value between 1:(1-1.2). The catalyst includes a boron complex; for example, boron trifluoride-tetrahydrofuran. The allyl polyether is a block copolymer prepared from an allyl alcohol, an oxirane and an epoxide.

[0031] S2, hydrosilylation; The fluorine-containing allyl polyether, the allyl polyether and the hydrogen-containing polymethylsiloxane are mixed to perform hydrosilylation. Specifically, the hydrogen-containing polymethylsiloxane, the fluorine-containing allyl polyether, a solvent, a platinum catalyst and a cocatalyst are mixed to react at 85-95°C, and then the allyl polyether and the platinum catalyst are added to react at 100-120°C.

[0032] Further, hydrogen-containing polymethylsiloxane, fluorine-containing allyl polyether, solvent are added into the reactor, and the reaction is carried out under atmospheric pressure and heating to 90-95℃ for 30-90min in the presence of platinum catalyst and co-catalyst; then, the allyl polyether and platinum catalyst are continuously added, and the reaction is carried out under heating to 100-120℃ for 4.0-10.0h, and the solvent is removed under reduced pressure to obtain the fluorine-containing polyether organosilicon.

[0033] The solvent includes benzene solvents, such as, but not limited to, toluene. The mass ratio of the solvent to the total mass of the fluorine-containing allyl polyether, the allyl polyether and the hydrogen-containing polymethylsiloxane is (30-80):100; for example, 30:100, 40:100, 50:100, 60:100, 70:100, 80:100, or any value between (30-80):100. The molar ratio of the sum of the double bonds of the fluorine-containing allyl polyether and the allyl polyether to the silicon-hydrogen bond of the hydrogen-containing polymethylsiloxane is 1.2-1.6:1; for example, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, or any value between 1.2-1.6:1. The platinum catalyst includes, but is not limited to, chloroplatinic acid catalyst.

[0034] It should be noted that the types and amounts of catalysts and co-catalysts used in the reaction of the hydrogen-containing polymethylsiloxane, the fluorine-containing allyl polyether and the allyl polyether refer to the patents CN 110982080 and CN 103044687.

[0035] In a third aspect, the present application provides a polyurethane foam prepared from the fluorine-containing polyether organosilicon. Specifically, the raw materials for forming the polyurethane foam include the fluorine-containing polyether organosilicon, polyether polyol or polyester polyol, and the mass content of the fluorine-containing polyether organosilicon is 1-5 parts, preferably 2-3 parts, based on 100 parts by mass of the polyether polyol or the polyester polyol.

[0036] The features and properties of the present application are further described in detail below in conjunction with the examples.

[0037] Example 1 The present application provides a preparation method of fluorine-containing polyether organosilicon, which includes: S1, preparing a fluorine-containing allyl polyether; Into a reactor, 35.2 g of dichloromethane and 80.88 g of allyl polyether (Shanghai Aldrin Biochemical Technology Co., Ltd., same below) were added and stirred at 30°C for 30 min; 19.32 g of boron trifluoride-tetrahydrofuran catalyst was added and stirred for 60 min. Then, 64.60 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane monomer was slowly added dropwise into the reactor within 60 min; after the dropwise addition was completed, stirring was continued for 60 min. Sodium bicarbonate was added to quench, and washed twice with deionized water, and the solvent was removed to obtain a fluorine-containing allyl polyether.

[0038] S2, hydrosilylation; Into a reactor, 35.93 g of hydrogen-containing polymethylsiloxane (prepared according to the patent CN 115584028A, same below), 13.45 g of fluorine-containing allyl polyether, 80.00 g of toluene, 4 ppm of chloroplatinic acid catalyst and 70 ppm of triethylamine promoter were added, and heated to 90°C under normal pressure for 1 h. 50.62 g of allyl polyether and 10 ppm of chloroplatinic acid catalyst were continuously added, and heated to 110°C for 8.0 h. The solvent was removed under reduced pressure to obtain a fluorine-containing polyether organosilicon surfactant. The structure characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 50 -[Si(CH3)R1O] 1.5 -[Si(CH3)R2O] 4.5 -Si(CH3)3; Wherein: R1= -CH2CH2CH2O(CH2CH2O) 12 (CH2CR3CH3CH2O)2H R2= -CH2CH2CH2O(CH2CH2O) 13 (CH2CHCH3O)4H; R3= -CH2OCH2CF2CF3.

[0039] Example 2 The present application provides a preparation method of fluorine-containing polyether organosilicon, comprising: S1, preparing a fluorine-containing allyl polyether; Into a reactor, 38.87 g of dichloromethane and 81.57 g of allyl polyether were added, stirred at 35°C for 30 min; 15.36 g of boron trifluoride-tetrahydrofuran catalyst was added, stirred for 60 min; then 64.20 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane monomer was slowly added dropwise into the reactor within 60 min; after the dropwise addition was completed, continue to stir for 60 min. Quench by adding sodium bicarbonate, washed twice with deionized water, and the solvent was removed to obtain a fluorine-containing allyl polyether.

[0040] S2, hydrosilylation; Into a reactor, 34.54 g of hydrogen-containing polymethylsiloxane, 16.75 g of fluorine-containing allyl polyether, 60.00 g of toluene, 3 ppm of chloroplatinic acid catalyst and 65 ppm of triethanolamine cocatalyst were added, heated to 90°C under normal pressure for 1 h. Continue to add 48.71 g of allyl polyether and 10 ppm of chloroplatinic acid catalyst, heat to 100°C for 6.0 h, and remove the solvent under reduced pressure to obtain a fluorine-containing polyether organosilicon surfactant. The structure characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 39 -[Si(CH3)R1O]1-[Si(CH3)R2O]3-Si(CH3)3; Wherein: R1= -CH2CH2CH2O(CH2CH2O) 15 (CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5H; R3= -CH2OCH2CF2CF3.

[0041] Example 3 The embodiment of the present application provides a preparation method of fluorine-containing polyether organosilicon, comprising: S1, preparing a fluorine-containing allyl polyether; Into a reactor, 38.87 g of dichloromethane and 81.57 g of allyl polyether were added, stirred at 35°C for 30 min; 15.36 g of boron trifluoride-tetrahydrofuran catalyst was added, stirred for 60 min; then 64.20 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane monomer was slowly added dropwise into the reactor within 60 min; after the dropwise addition was completed, continue to stir for 60 min. Quench by adding sodium bicarbonate, washed twice with deionized water, and the solvent was removed to obtain a fluorine-containing allyl polyether.

[0042] S2, hydrosilylation; Into a reactor were added 27.45 g of hydrogen-containing polymethylsiloxane, 18.09 g of fluorine-containing allyl polyether, 60.00 g of toluene, 4 ppm of chloroplatinic acid catalyst, and 50 ppm of N, N dimethyl aniline promoter, heated to 90°C under normal pressure for 1 h. 54.46 g of allyl polyether and 15 ppm of chloroplatinic acid catalyst were continuously added, heated to 105°C for 5.0 h, and the solvent was removed under reduced pressure to obtain a fluorine-containing polyether silicone surfactant. The structure thereof is characterized as follows: (CH3)3Si-O-[Si(CH3)2O] 67 -[Si(CH3)R1O] 2.5 -[Si(CH3)R2O] 6.5 -Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)2(CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 20 (CH2CHCH3O)3H; R3= -CH2OCH2CF2CF3.

[0043] Example 4 The embodiment of the present application provides a preparation method of fluorine-containing polyether silicone, comprising: S1, preparing fluorine-containing allyl polyether; Into a reactor were added 35.2 g of dichloromethane and 80.88 g of allyl polyether, stirred at 30°C for 30 min; 19.32 g of boron trifluoride-tetrahydrofuran catalyst was added, and stirred for 60 min; then 64.60 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy) methyl] oxetane monomer was slowly added dropwise into the reactor within 60 min; after the dropwise addition was completed, stirring was continued for 60 min. Sodium bicarbonate was added to quench, and then washed twice with deionized water, and the solvent was removed to obtain fluorine-containing allyl polyether.

[0044] S2, hydrosilylation; Into a reactor were added 34.26 g of hydrogen-containing polymethylsiloxane, 18.37 g of fluorine-containing allyl polyether, 90.00 g of toluene, 5 ppm of chloroplatinic acid catalyst, and 75 ppm of N, N dimethyl aniline catalyst, heated to 95°C under normal pressure for 1 h. 47.36 g of allyl polyether and 16 ppm of chloroplatinic acid catalyst were continuously added, heated to 110°C for 5.0 h. The solvent was removed under reduced pressure to obtain a fluorine-containing polyether silicone surfactant. The structure thereof is characterized as follows: (CH3)3Si-O-[Si(CH3)2O]71 -[Si(CH3)R1O]3-[Si(CH3)R2O]5-Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 12 (CH2CR3CH3CH2O)2H R2= -CH2CH2CH2O(CH2CH2O) 16 (CH2CHCH3O)4H; R3= -CH2OCH2CF2CF3.

[0045] Example 5 The embodiment of the present application provides a preparation method of fluorine-containing polyether silicone, comprising: S1, preparing fluorine-containing allyl polyether; 41.04g of dichloromethane and 76.29g of allyl polyether are added into the reactor, 35 o C stirring for 30min; 14.87g of boron trifluoride-tetrahydrofuran catalyst is added and stirred for 60min; then 67.79g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy) methyl] oxetane monomer is slowly added into the reactor within 60min; after the addition is completed, continue to stir for 60min, quench by adding sodium bicarbonate, and wash twice with deionized water, and then remove the solvent to obtain the fluorine-containing allyl polyether.

[0046] S2, hydrosilylation; 27.71g of hydrogen-containing polymethylsiloxane, 21.73g of fluorine-containing allyl polyether, 65.00g of toluene, 6ppm of chloroplatinic acid catalyst and 80ppm of triethanolamine catalyst are added into the reactor, and heated to 95℃ under normal pressure for 1h. 50.56g of allyl polyether and 15ppm of chloroplatinic acid catalyst are continuously added, and heated to 105℃ for 6.0h. The solvent is removed under reduced pressure to obtain the fluorine-containing polyether silicone surfactant. The structure characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 60 -[Si(CH3)R1O] 2.5 -[Si(CH3)R2O] 5.5 -Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 15 (CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)6H; R3= -CH2OCH2CF2CF3.

[0047] Example 6 The embodiment of the present application provides a preparation method of fluorine-containing polyether silicone, comprising: S1, preparing fluorine-containing allyl polyether; 41.04g of dichloromethane and 76.29g of allyl polyether were added into the reactor, stirred at 35℃ for 30min; 14.87g of boron trifluoride-tetrahydrofuran catalyst was added and stirred for 60min; then 67.79g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy) methyl] oxetane monomer was slowly added into the reactor within 60min; after the addition was completed, continue to stir for 60min, quench by adding sodium bicarbonate, and wash twice with deionized water, and remove the solvent to obtain the fluorine-containing allyl polyether.

[0048] S2, hydrosilylation; 38.35g of hydrogen-containing polymethylsiloxane, 23.56g of fluorine-containing allyl polyether, 70.00g of toluene, 5ppm of chloroplatinic acid catalyst and 55ppm of triethylamine catalyst were added into the reactor, and heated to 90℃ under normal pressure for 1h. Continue to add 38.09g of allyl polyether and 12ppm of chloroplatinic acid catalyst, and heat to 100℃ for 5.0h. Remove the solvent under reduced pressure to obtain the fluorine-containing polyether silicone surfactant. The structure characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 43 -[Si(CH3)R1O] 1.5 -[Si(CH3)R2O] 3.5 -Si(CH3)3; Wherein: R1= -CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)2(CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 11 (CH2CHCH3O)2H; R3= -CH2OCH2CF2CF3.

[0049] Comparative Example 1 The comparative example provides a preparation method of polyether silicone, comprising: Into a reactor were added 36.83 g of hydrogen-containing polymethylsiloxane, 63.17 g of allyl polyether, 80.00 g of toluene, 10 ppm of chloroplatinic acid catalyst, and 70 ppm of triethylamine promoter, and the mixture was heated to 110°C under normal pressure for 8.0 h. The solvent was removed under reduced pressure to obtain a fluorine-containing polyether silicone surfactant. The structure thereof was characterized as follows: (CH3)3Si-O-[Si(CH3)2O] 50 -[Si(CH3)R2O]6-Si(CH3)3; wherein: R2= -CH2CH2CH2O(CH2CH2O) 13 (CH2CHCH3O)4H.

[0050] As can be seen, the only difference between the present comparative example and Example 1 is that the present comparative example does not use a fluorine-containing allyl polyether.

[0051] Comparative Example 2 The present comparative example provides a method for preparing a polyether silicone, comprising: Into a reactor were added 38.21 g of hydrogen-containing polymethylsiloxane, 7.96 g of allyl polyether (I), 53.83 g of allyl polyether (II), 80.00 g of toluene, 10 ppm of chloroplatinic acid catalyst, and 70 ppm of triethylamine promoter, and the mixture was heated to 110°C under normal pressure for 8.0 h. The solvent was removed under reduced pressure to obtain a fluorine-containing polyether silicone surfactant. The structure thereof was characterized as follows: (CH3)3Si-O-[Si(CH3)2O] 50 -[Si(CH3)R1O] 1.5 -[Si(CH3)R2O] 4.5 -Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 12 H R2= -CH2CH2CH2O(CH2CH2O) 13 (CH2CHCH3O)4H; R3= -CH2OCH2CF2CF3; Comparative Example 3 The present comparative example provides a method for preparing a polyether silicone, comprising: S1, synthesizing a fluorine-containing allyl polyether; Into a reactor were added 38.87 g of dichloromethane 81.57 allyl polyether, 35 oC stirring for 30 min; adding 15.36 g of boron trifluoride-tetrahydrofuran catalyst and stirring for 60 min; slowly adding 64.20 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane monomer within 60 min, continuing to stir the mixture for 60 min, quenching by adding sodium bicarbonate, washing twice with deionized water, and stripping off the solvent to obtain the fluorine-containing allyl polyether.

[0052] S2, hydrosilylation; adding 32.54 g of hydrogen-containing polymethylsiloxane, 31.55 g of fluorine-containing allyl polyether, 60.00 g of toluene, 3 ppm of chloroplatinic acid catalyst, and 65 ppm of triethanolamine cocatalyst into a reactor, heating to 90°C under normal pressure for 1 h; continuing to add 35.91 g of allyl polyether and 10 ppm of chloroplatinic acid catalyst, heating to 100°C for 6.0 h, and removing the solvent under reduced pressure to obtain the fluorine-containing polyether organosilicon surfactant. The structural characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 39 -[Si(CH3)R1O]2-[Si(CH3)R2O]2-Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 15 (CH2CR3CH3CH2O)3H R2= -CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)5H; R3= -CH2OCH2CF2CF3.

[0053] Comparative Example 4 This comparative example provides a method for preparing a polyether organosilicon, comprising: S1, synthesizing a fluorine-containing allyl polyether; adding 41.04 g of dichloromethane and 76.29 g of allyl polyether into a reactor, 35 o C stirring for 30 min; adding 14.87 g of boron trifluoride-tetrahydrofuran catalyst and stirring for 60 min; slowly adding 67.79 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane monomer within 60 min, continuing to stir the mixture for 60 min, quenching by adding sodium bicarbonate, washing twice with deionized water, and stripping off the solvent to obtain the fluorine-containing allyl polyether.

[0054] S2, hydrosilylation; Into a reactor were added 25.19 g of hydrogen-containing polymethylsiloxane, 22.10 g of fluorine-containing allyl polyether, 60.00 g of toluene, 4 ppm of chloroplatinic acid catalyst, and 50 ppm of N,N-dimethylaniline promoter, heated to 90°C under normal pressure for 1 h, then 52.71 g of allyl polyether and 15 ppm of chloroplatinic acid catalyst were continuously added, heated to 105°C for 5.0 h, and the solvent was removed under reduced pressure to obtain a fluorine-containing polyether organosilicon surfactant. The structural characterization thereof is as follows: (CH3)3Si-O-[Si(CH3)2O] 80 -[Si(CH3)R1O]4-[Si(CH3)R2O]8-Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)2(CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 20 (CH2CHCH3O)3H; R3= -CH2OCH2CF2CF3.

[0055] Comparative Example 5 The present comparative example provides a preparation method of a polyether organosilicon, comprising: S1, synthesis of a fluorine-containing allyl polyether; Into a reactor were added 41.04 g of dichloromethane and 76.29 g of allyl polyether, 35 o stirred for 30 min, 14.87 g of boron trifluoride-tetrahydrofuran catalyst was added and stirred for 60 min, then 67.79 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl] oxetane monomer was slowly added dropwise into the reactor within 60 min, after the dropwise addition was completed, stirring was continued for 60 min, quenched by adding sodium bicarbonate, washed twice with deionized water, and the solvent was removed to obtain a fluorine-containing allyl polyether.

[0056] S2, hydrosilylation; Into a reactor were added 28.96 g of hydrogen-containing polymethylsiloxane, 9.08 g of fluorine-containing allyl polyether, 65.00 g of toluene, 6 ppm of chloroplatinic acid catalyst, and 80 ppm of triethanolamine catalyst, heated to 95°C under normal pressure for 1 h, then 61.96 g of allyl polyether and 15 ppm of chloroplatinic acid catalyst were continuously added, heated to 105°C for 6.0 h, and the solvent was removed under reduced pressure to obtain a fluorine-containing polyether organosilicon surfactant. The structural characterization thereof is as follows: (CH3)3Si-O-[Si(CH3)2O] 60-[Si(CH3)R1O]1-[Si(CH3)R2O]7-Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 15 (CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 15 (CH2CHCH3O)6H; R3= -CH2OCH2CF2CF3.

[0057] Comparative Example 6 The present comparative example provides a method for preparing a polyether organosilicon, comprising: S1, synthesis of fluorine-containing allyl polyether; 41.04 g of dichloromethane and 76.29 g of allyl polyether were added to the reactor, 35 o C stirring for 30 min; 14.87 g of boron trifluoride-tetrahydrofuran catalyst was added and stirred for 60 min; then 67.79 g of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy) methyl] oxetane monomer was slowly added dropwise into the reactor within 60 min; after the dropwise addition was completed, continue to stir for 60 min, quench by adding sodium bicarbonate, and wash twice with deionized water, and remove the solvent to obtain the fluorine-containing allyl polyether.

[0058] S2, hydrosilylation; 37.86 g of hydrogen-containing polymethylsiloxane, 25.77 g of fluorine-containing allyl polyether, 70.00 g of toluene, 5 ppm of chloroplatinic acid catalyst and 55 ppm of triethylamine catalyst were added to the reactor, and heated to 90°C under normal pressure for 1 h; 36.37 g of allyl polyether and 12 ppm of chloroplatinic acid catalyst were continuously added, and heated to 100°C for 5.0 h, and the solvent was removed under reduced pressure to obtain a fluorine-containing polyether organosilicon surfactant. The structure is characterized as follows: (CH3)3Si-O-[Si(CH3)2O] 25 -[Si(CH3)R1O]1-[Si(CH3)R2O]2-Si(CH3)3; wherein: R1= -CH2CH2CH2O(CH2CH2O) 14 (CH2CHCH3O)2(CH2CR3CH3CH2O)3H R2=-CH2CH2CH2O(CH2CH2O) 11 (CH2CHCH3O)2H; R3= -CH2OCH2CF2CF3.

[0059] Comparative Example 7 The present comparative example provides a method for preparing a polyether organosilicon, comprising: A fluorine-containing polyether organosilicon surfactant was prepared according to the method of patent CN117024747A using the hydrogen-containing polymethylsiloxane and allyl polyether in Example 1. The structure characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 50 -[Si(CH3)R1O]1-[Si(CH3)R2O]5-Si(CH3)3; Wherein: R1=-CH2CH2CH2O(CH2CH(CH2OH)O) 16 (CH2CH(CH2OH)O)2R3 R2= -CH2CH2CH2O(CH2CH2O) 13 (CH2CHCH3O)4H; R3=-COCF(CF3)(OCF2CFCF3)4F.

[0060] Comparative Example 8 The present comparative example provides a method for preparing a polyether organosilicon, comprising: A fluorine-containing polyether organosilicon surfactant was prepared according to the method of patent CN117024747A using the hydrogen-containing polymethylsiloxane and allyl polyether in Example 1. The structure characterization is as follows: (CH3)3Si-O-[Si(CH3)2O] 43 -[Si(CH3)R1O]1-[Si(CH3)R2O]4-Si(CH3)3; Wherein: R1=-CH2CH2CH2O(CH2CH(CH2OH)O) 12 (CH2CH(CH2OR3)O)3R3 R2= -CH2CH2CH2O(CH2CH2O) 11 (CH2CHCH3O)2H; R3=-COCF(CF3)(OCF2CFCF3)2F.

[0061] Application Example The fluorine-containing polyether organosilicons of Examples 1-6 and the polyether organosilicons of Comparative Examples 1-8 were used as polyurethane foam stabilizers to prepare rigid polyurethane foams, wherein the components of the rigid polyurethane foams are shown in Table 1 below.

[0062] Table 1 Components of rigid polyurethane foams

[0063] The rigid polyurethane foam prepared according to the above formula was subjected to performance testing, and the results are shown in Table 2, wherein the thermal conductivity (λ) was determined in accordance with GB / T 10295-2008, and the closed cell content was determined in accordance with GB / T 10799-2008.

[0064] Table 2 Test results of rigid polyurethane foam

[0065] Compared with Example 1, Comparative Example 1 does not add fluorine-containing polyether, but only adds conventional allyl polyether to synthesize polyether organosilicon, and Comparative Example 2 adds polyether but the terminal does not contain fluorine to synthesize organosilicon with conventional allyl polyether; compared with Examples 2 and 5, Comparative Examples 3 and 5 contain fluorine-containing polyether in amounts higher and lower than the range defined in the examples of the present application, respectively; compared with Examples 4 and 6, Comparative Examples 3 and 6 have organosilicon structures higher and lower than the range required in the examples of the present application, respectively; compared with Examples 1 and 6, Comparative Examples 7 and 8 synthesize fluorine-containing polyether organosilicon surfactants according to the method of patent CN117024747A.

[0066] The results in Table 2 show that, compared with the comparative examples, the rigid polyurethane foam prepared by the fluorine-containing polyether organosilicon provided in the examples of the present application has more fine and compact cells, higher closed cell rate, and significantly lower thermal conductivity.

[0067] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Those skilled in the art can make various modifications and changes to the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A fluorine-containing polyether silicone, characterized by, The side chain thereof comprises a fluorine-containing allyl polyether formed by ring-opening of 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane.

2. The fluoro- polyether silicone according to claim 1, wherein The structural formula is as follows: (CH3)3Si-O-[Si(CH3)2O] m -[Si(CH3)R1O] p -[Si(CH3)R2O] q -Si(CH3)3; Wherein: The value of m is 30-75, the value of p+q is 4-10, and p / (p+q)=0.2-0.4; R1= -CH2CH2CH2O(CH2CH2O) a (CH2CHCH3O) b (CH2CR3CH3CH2O) c H; R2= -CH2CH2CH2O(CH2CH2O) x (CH2CHCH3O) y H; R3=-CH2OCH2CF2CF3; a=10-30, b=0-3, c=2-5; x=10-35, y=0-10.

3. A process for the preparation of the fluoropolymethylenesiloxane of claim 1, characterized in that, Comprise: Reacting 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane and allyl polyether to form a fluorine-containing allyl polyether; Mixing the fluorine-containing allyl polyether, allyl polyether and hydrogen-containing polymethylsiloxane to carry out hydrosilylation.

4. The production method according to claim 3, characterized by, The step of forming the fluorine-containing allyl polyether comprises: mixing a solvent, allyl polyether, 3-methyl-3-[(2,2,3,3,3-pentafluoropropoxy)methyl]oxetane and a catalyst to react.

5. The preparation method according to claim 4, characterized in that, The conditions for forming the fluorine-containing allyl polyether meet at least one of the following requirements: (1) The solvent comprises a polyhalogenated C1-C3 alkane; preferably dichloromethane; (2) The molar ratio of the solvent to the allyl polyether is (3-5):1; (3) The catalyst comprises a boron complex; preferably boron trifluoride-tetrahydrofuran; (4) The molar ratio of the allyl polyether to the catalyst is 1:(1-1.2); (5) The reaction temperature is 30-50°C.

6. The production method according to claim 4 or 5, characterized by, The allyl polyether is a block copolymer prepared from allyl alcohol, oxirane and propylene oxide.

7. The preparation method according to claim 3, characterized in that, The step of hydrosilylation comprises: mixing the hydrogen-containing polymethylsiloxane, the fluorine-containing allyl polyether, a solvent, a platinum catalyst and a cocatalyst to react at 85-95°C, and then adding allyl polyether and a platinum catalyst to react at 100-120°C.

8. The preparation method according to claim 7, characterized in that, The conditions for hydrosilylation meet at least one of the following requirements: (1) The solvent comprises a benzene solvent, preferably toluene; (2) The mass ratio of the solvent to the total mass of the fluorine-containing allyl polyether, the allyl polyether and the hydrogen-containing polymethylsiloxane is (30-80):100; (3) The molar ratio of the sum of the double bonds of the fluorine-containing allyl polyether and the allyl polyether to the silicon-hydrogen bond of the hydrogen-containing polymethylsiloxane is 1.2-1.6:

1.

9. A polyurethane foam characterized by, It is prepared from the fluorine-containing polyether organosilicon of claim 1.

10. The polyurethane foam according to claim 9, characterized in that, It further comprises a polyether polyol or a polyester polyol, and the mass content of the fluorine-containing polyether organosilicon is 1-5 parts, preferably 2-3 parts, based on 100 parts by mass of the polyether polyol or the polyester polyol.

Images