Emulsifiers and methods for making the same, emulsions containing perfluoroadditives and methods for making the same, and polyurethane foams

Abstract

The present application relates to polyurethane chemical auxiliary technical field, specifically, it relates to emulsifier and its preparation method, emulsion containing perfluoro auxiliary and its preparation method and polyurethane foam. The emulsifier is the bio-based polyether modified polysiloxane shown in the following structural formula: wherein, m = 30-55, n = 4-12;The general formula of R is -(CH2) p (OC2H4) a (OC3H6) b OR1, wherein p = 2-4, a = 5-15, b = 0-10, R1 is biomass radical. The emulsifier is compatible with the components in the emulsion containing perfluoro auxiliary, can improve the stability of the emulsion, and the polyurethane foam prepared by the emulsion has fine cell, low thermal conductivity and excellent surface quality.

Description

Technical Field

[0001] This invention relates to the field of polyurethane chemical additives technology, and more specifically, to emulsifiers and their preparation methods, emulsions containing perfluorinated additives and their preparation methods, and polyurethane foams. Background Technology

[0002] Rigid polyurethane foam is widely used in building insulation, cold chain logistics, and industrial equipment insulation due to its excellent thermal insulation performance, high specific strength, and good formability. Thermal conductivity is a key indicator for evaluating the insulation performance of rigid foam, and reducing thermal conductivity is of great significance for energy conservation and emission reduction. To obtain even lower thermal conductivity, perfluorinated additives are typically added to the polyether composite. Perfluorinated additives have extremely low interfacial tension, which can significantly increase the bubble nucleation density of the system, thereby obtaining a finer cell structure and achieving a lower foam thermal conductivity.

[0003] However, perfluorinated additives have poor compatibility with the polyols in the polyether blend, easily leading to phase separation and poor storage stability, resulting in stratification before use. This not only causes inconvenience in production and transportation but also leads to uneven distribution of additives during the foaming process, severely affecting the performance of the final foam product.

[0004] To address the aforementioned compatibility issues, the industry commonly employs the method of adding emulsifiers or stabilizers. However, while traditional silicone oil-based surfactants can provide some emulsification and stabilization, their compatibility with perfluorinated additives remains insufficient, resulting in limited emulsification effects and a short stability period.

[0005] Therefore, developing a novel emulsifier that can effectively improve the dispersibility and stability of perfluorinated additives in polyether blends, thereby preparing rigid polyurethane foam with fine pores, low thermal conductivity and excellent surface quality, has become a technical problem that urgently needs to be solved in this field.

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

[0007] The purpose of this invention is to provide an emulsifier and its preparation method, an emulsion containing a perfluorinated additive and its preparation method, and a polyurethane foam. Embodiments of this invention provide a novel emulsifier that exhibits good compatibility with other components in the emulsion, thereby improving the stability of the emulsion. The polyurethane foam prepared from this emulsion possesses fine pores, low thermal conductivity, and excellent surface quality.

[0008] This invention is implemented as follows:

[0009] In a first aspect, the present invention provides an emulsifier, which is a bio-based polyether-modified polysiloxane as shown in the following structural formula:

[0010] Where m = 30~55, n = 4~12;

[0011] The general formula for R is -(CH2). p (OC2H4) a (OC3H6) b OR1, where p=2~4, a=5~15, b=0~10, and R1 is a biomass group.

[0012] In an optional embodiment, the biomass group is derived from any one or at least two of cashew phenol, palm oil, castor oil, and glycerides.

[0013] In a second aspect, the present invention provides an emulsion containing a perfluorinated auxiliary agent, comprising the perfluorinated auxiliary agent and the emulsifier described in the foregoing embodiments;

[0014] Preferably, it comprises a perfluorinated auxiliary agent, an emulsifier, a surfactant, a combined catalyst, a solvent, a foaming agent, and a polyether polyol; wherein the mass ratio of the perfluorinated auxiliary agent, the emulsifier, the surfactant, the combined catalyst, the solvent, the foaming agent, and the polyether polyol is (3~10):(1~5):(1~3):(2~4):(1~3):(10~20):100.

[0015] In an optional embodiment, the raw materials forming the emulsion meet at least one of the following requirements:

[0016] (1) The perfluorinated additives include one of PF-5052, PF-5056, PF-5058, Noah 7160, Noah 2100A, and Noah2100B;

[0017] (2) The combined catalyst includes amines;

[0018] (3) The surfactants include nonionic surfactants;

[0019] (4) The foaming agent includes C3-C8 alkane substances;

[0020] (5) The solvent includes water;

[0021] (6) The polyether polyol includes any one or at least two of H4110, H4110M, H81691, H8175, H8245 and H8246.

[0022] In an optional embodiment, the raw materials forming the emulsion meet at least one of the following requirements:

[0023] (1) The perfluorinated additives include any one of PF-5052, PF-5056, PF-5058, Noah 7160, Noah 2100A, and Noah2100B;

[0024] (2) The combined catalyst comprises at least two of pentamethyldiethylenetriamine, tetramethylhexanediamine, bis-dimethylaminoethyl ether, dimethylbenzylamine, dimethylcyclohexane, triethylenediamine, methylimidazolium, quaternary ammonium salt, and tris(dimethylaminopropyl)hexahydrotriazine;

[0025] (3) The surfactant includes any one or at least two of M-8805, M-8815, M-8830, M-8860, M-88310 and M-88315;

[0026] (4) The foaming agent includes any one or at least two of cyclopentane, isopentane, n-pentane, n-butane, isobutane, 1,1,1,3,3-pentafluoropropane, etc.

[0027] (5) The polyether polyol includes any one or at least two of H4110, H4110M, H81691, H8175, H8245 and H8246;

[0028] (6) The solvent includes water.

[0029] Thirdly, the present invention provides a method for preparing the emulsifier described in the foregoing embodiments, comprising: mixing a hydrogen-containing polysiloxane and an allyl polyether with a bio-based terminal to carry out a hydrosilylation reaction.

[0030] In an optional embodiment, the method includes: mixing the hydrogen-containing polysiloxane, the bio-terminated allyl polyether, and a catalyst to perform a hydrosilylation reaction;

[0031] Preferably, the conditions for the hydrosilylation reaction satisfy at least one of the following requirements:

[0032] (1) The mass ratio of the hydrogen-containing polysiloxane to the bio-terminated allyl polyether is (60-80):(40-20);

[0033] (2) The catalyst is a platinum catalyst;

[0034] (3) The amount of the catalyst used is 5-15 ppm;

[0035] (4) The reaction temperature is 85-105℃; the reaction time is 3-6.

[0036] In an optional embodiment, the method for preparing the hydrogen-containing polysiloxane includes:

[0037] Under acidic catalytic conditions, hexamethyldisiloxane, octamethylcyclotetrasiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and reacted.

[0038] Preferably, the method for preparing the bio-based allyl polyether includes: mixing bio-based raw materials, terminal allyl polyether, and esterification catalyst to carry out a reaction;

[0039] The reaction conditions must satisfy at least one of the following requirements:

[0040] (1) The mass ratio of the bio-based raw material to the terminal allyl polyether is (25-35):(75-65);

[0041] (2) The esterification catalyst includes an acidic substance;

[0042] (3) The reaction conditions include: temperature of 120-160℃ and time of 4-8h.

[0043] Fourthly, the present invention provides a method for preparing an emulsion containing a perfluorinated adjuvant as described in the foregoing embodiments, comprising: mixing the raw materials for forming the emulsion.

[0044] Fifthly, the present invention provides a polyurethane foam comprising a polyisocyanate and an emulsion containing perfluorinated additives as described in the foregoing embodiments.

[0045] The present invention has the following beneficial effects: In the embodiments of the present invention, bio-based polyether modified polysiloxane is used as an emulsifier, which has good compatibility with other components in the emulsion containing perfluorinated additives and can improve the stability of the emulsion containing perfluorinated additives. The polyurethane foam prepared from this emulsion has fine pores, low thermal conductivity and excellent surface quality. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0047] In a first aspect, embodiments of the present invention provide an emulsifier, which is a bio-based polyether-modified polysiloxane, wherein the bio-based polyether-modified polysiloxane is a polymer with the following structural formula:

[0048] Where m = 30~55, for example, m can be any value between 30, 35, 40, 45, 50, 55 or 30-55. n = 4~12; for example, n can be any value between 4, 5, 8, 10, 12 or 4-12.

[0049] The general formula for R is -(CH2). p (OC2H4) a (OC3H6) b OR1, where p = 2 to 4, for example, any value between 2, 3, 4 or 2-4; a = 5 to 15, for example, any value between 5, 8, 10, 12, 15 or 5-15; b = 0 to 10, for example, any value between 0, 1, 3, 5, 7, 10 or 0-10; R1 is a biomass group, and the biomass group of R1 is derived from any one or at least two of palmitoleic acid, ricinoleic acid, cashew phenol and glycerides.

[0050] Secondly, the present invention provides a method for preparing the emulsifier described in the foregoing embodiments, comprising:

[0051] S1. Preparation of hydrogen-containing polysiloxanes;

[0052] Under acidic catalytic conditions, hexamethyldisiloxane, octamethylcyclotetrasiloxane, and 1,3,5,7-tetramethylcyclotetrasiloxane are mixed and subjected to ring-opening, polymerization, and equilibrium reactions. By adjusting the feed ratio of each raw material, hydrogen-containing polysiloxanes with different Si-H bond contents and specific average molecular structures can be prepared. Their average structural formula is MD0. x D H y M, where M is (CH3)3SiO-, D is -Si(CH3)2O-, and D... H The formula is -SiH(CH3)O-, where x corresponds to m in the structural formula and y corresponds to n in the structural formula.

[0053] Specifically, 3.5%–5.0% (mass ratio, the same below) of hexamethyldisiloxane, 75.0%–88.0% of octamethylcyclotetrasiloxane, and 8.5%–18.0% of 1,3,5,7-tetramethylcyclotetrasiloxane are added to a reactor equipped with a stirrer, thermometer, and condenser. Then, 0.1%–1% of an acid catalyst (trifluoromethanesulfonic acid, sulfuric acid, acidic clay, etc.) is added. The reaction mixture is heated to 40–65°C and stirred continuously at this temperature for approximately 3–6 hours to ensure complete reaction. After the reaction is complete, a clear and transparent hydrogen-containing polysiloxane is obtained.

[0054] S2. Preparation of allyl polyethers with bio-based ends;

[0055] Bio-based feedstock, terminal allyl polyether, and esterification catalyst are mixed and reacted to graft biomass groups onto the ends of the terminal allyl polyether. The key to this step is the introduction of biomass groups with long-chain alkyl or benzene ring structures to enhance the compatibility of the final product with perfluorinated additives.

[0056] Specifically, 65%–75% of terminal allyl polyether, 25%–35% of bio-based raw materials (such as palmitic acid, ricinoleic acid, cashew nut shell extract, and glyceryl esters), and 0.1%–0.5% of esterification catalyst (such as acidic substances, including but not limited to p-toluenesulfonic acid and concentrated sulfuric acid) are added to a reactor equipped with a stirrer, a water separator, and a thermometer. The reaction mixture is heated to approximately 120°C–160°C for reaction, and water generated during the reaction is removed through the water separator. After approximately 4–8 hours of reaction, post-treatment yields terminally bio-based allyl polyether.

[0057] S3, hydrosilylation reaction;

[0058] The hydrogen-containing polysiloxane, the bio-terminated allyl polyether, and a catalyst are mixed to undergo a hydrosilylation reaction. Specifically, the hydrogen-containing polysiloxane prepared in S1 is mixed with the bio-terminated allyl polyether prepared in S2, and a hydrosilylation reaction is carried out under the catalysis of a platinum catalyst (e.g., including but not limited to chloroplatinic acid ethanol or isopropanol solution, Karstedt catalyst, etc.), so that the Si-H bonds on the polysiloxane chain combine with the allyl double bonds at the end of the polyether, thereby grafting the bio-based poly-modified ether segment onto the polysiloxane backbone.

[0059] The specific steps are as follows:

[0060] 60%–80% of bio-terminated allyl polyether and 20%–40% of hydrogen-containing polysiloxane were added to a reactor and stirred until homogeneous. The mixture was heated to 85–110°C, and then 5–15 ppm of platinum catalyst (such as an isopropanol or ethanol solution of chloroplatinic acid, or a Karstedt catalyst) was added. Under nitrogen protection, the reaction was maintained at 85–105°C for 3–6 hours. After the reaction was completed, amber-colored, transparent bio-based polyether-modified polysiloxane was obtained through post-treatment, which is the emulsifier of this invention.

[0061] Thirdly, the present invention provides an emulsion containing a perfluorinated auxiliary agent, comprising the perfluorinated auxiliary agent and the emulsifier described in the foregoing embodiments.

[0062] Specifically, it includes perfluorinated additives, emulsifiers, surfactants, combined catalysts, solvents, foaming agents, and polyether polyols; wherein the mass ratio of the perfluorinated additives, emulsifiers, surfactants, combined catalysts, solvents, foaming agents, and polyether polyols is (3~10):(1~5):(1~3):(2~4):(1~3):(10~20):100. For example, it can be any value between 3:1:1:2:1:10:100, 5:2:3:4:1:15:100, 10:5:2:3:3:20:100, 7:3:2:3:2:10:100, or (3~10):(1~5):(1~3):(2~4):(1~3):(10~20):100.

[0063] The perfluorinated additive can be selected from existing perfluorinated additives, such as, but not limited to, one of PF-5052, PF-5056, PF-5058, Noah 7160, Noah 2100A, and Noah 2100B.

[0064] The combined catalyst includes amines; for example, including but not limited to at least two of pentamethyldiethylenetriamine, tetramethylhexanediamine, bis-dimethylaminoethyl ether, dimethylbenzylamine, dimethylcyclohexane, triethylenediamine, methylimidazole, quaternary ammonium salts, and tris(dimethylaminopropyl)hexahydrotriazine.

[0065] Surfactants include nonionic surfactants; for example, including but not limited to any one or at least two of M-8805, M-8815, M-8830, M-8860, M-88310 and M-88315.

[0066] The foaming agent includes C3-C8 alkane substances; for example, including but not limited to any one or at least two of cyclopentane, isopentane, n-pentane, n-butane, isobutane, 1,1,1,3,3-pentafluoropropane, etc.

[0067] The polyether polyol includes any one or at least two of H4110, H4110M, H81691, H8175, H8245 and H8246; the solvent includes water.

[0068] Fourthly, embodiments of the present invention provide a method for preparing an emulsion containing perfluorinated additives, comprising: mixing raw materials for forming the emulsion. Specifically, bio-based polyether-modified polysiloxane is used as an emulsifier, mixed with perfluorinated additives and polyether polyols in a certain proportion, and then surfactants, combined catalysts, solvents, foaming agents, etc. are added. Through high-speed shear emulsification or other homogenization methods, an emulsion containing perfluorinated additives with high stability and resistance to stratification can be prepared. This emulsion can be directly used to prepare polyurethane foam.

[0069] Fifthly, the present invention provides a polyurethane foam comprising a polyisocyanate and an emulsion containing a perfluorinated additive as described in the foregoing embodiments. Specifically, by weight, 100 parts are the emulsion containing the perfluorinated additive and 110-160 parts are the polyisocyanate. The polyisocyanate is polymeric MDI, for example, including but not limited to any one or more of PM-200, PM-2010, PM-130, and PM-2025. This polyurethane foam is a rigid polyurethane foam.

[0070] The preparation method of this polyurethane foam is as follows:

[0071] The temperature of the emulsion containing perfluorinated additives should be controlled at 15-25℃;

[0072] An emulsion containing perfluorinated additives is mixed with a polyisocyanate at 4000 rpm for 3-6 seconds, then poured into a fixed, sealed mold. After curing and demolding, the resulting rigid polyurethane foam is obtained. The material temperature is 15-25℃, the mold temperature is 35-55℃, the overfill rate is 15%-25%, and the demolding time is 130-500 seconds.

[0073] The emulsion containing perfluorinated additives provided in this invention embodiment exhibits excellent storage stability. The polyurethane foam prepared from it, due to the uniform dispersion of the perfluorinated additives and the numerous and consistent nucleation points during the foaming process, ultimately displays significant advantages such as a fine and uniform cell structure, low thermal conductivity, and few surface defects.

[0074] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0075] Example 1

[0076] This invention provides a method for preparing an emulsifier, comprising:

[0077] 14.2 g of hexamethyldisiloxane, 259.5 g of octamethylcyclotetrasiloxane, 26.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 0.3 g of trifluorobenzenesulfonic acid were added to a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 60-65 °C for 3 hours. After post-processing, an average structure of MD was obtained. 40 D H 5M hydrogen-containing polysiloxane. Where M is (CH3)3SiO-, D is -Si(CH3)2O-, and D... H It is -SiH(CH3)O- (the same applies below).

[0078] 215.2g of terminal allyl polyether (EO=12, PO=1, where EO corresponds to a in the structural formula and PO corresponds to b in the structural formula, the same below), 84.8g of palmitoleic acid and 0.5g of p-toluenesulfonic acid were added to a 500ml three-necked flask equipped with a mechanical stirrer. The mixture was reacted at 130℃ for 4h. After post-treatment, allyl polyether PE1 with palmitole groups at the end was obtained.

[0079] 192.6g of palm oil-terminated allyl polyether PE1 and 107.4g of hydrogen-containing polysiloxane MD 40 D H Mix 5M solutions, heat the mixture to 85°C and stir for 10 min, then add 10 ppm of Pt (chloroplatinic acid ethanol solution). Maintain the mixture in the flask at 85°C and react for 5 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the emulsifier BE1, and its structural formula is shown below:

[0080] This embodiment also provides an emulsion containing a perfluorinated auxiliary agent, comprising a perfluorinated auxiliary agent, an emulsifier BE1, a surfactant, a combined catalyst, water, a blowing agent, and a polyether polyol, wherein the ratio of perfluorinated auxiliary agent: emulsifier BE1: surfactant: combined catalyst: water: blowing agent: polyether polyol is 5:3:2:2.5:2:13:100 (mass ratio, the same below). The perfluorinated auxiliary agent is Noah2100B; the surfactant is M-88315; the combined catalyst is a catalyst formed by the ratio of bis-dimethylaminoethyl ether: dimethylcyclohexylamine: tris(dimethylaminopropyl)hexahydrotriazine = 1:3.1:1.2 (mass ratio); the blowing agent is cyclopentane; and the polyether polyol is H4110M.

[0081] The above materials are mixed in proportion and stirred in a high-speed mixer to obtain an emulsion containing perfluorinated additives.

[0082] Example 2

[0083] This invention provides a method for preparing an emulsifier, comprising:

[0084] 13.5 g of hexamethyldisiloxane, 246.7 g of octamethylcyclotetrasiloxane, 40.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 0.4 g of trifluorobenzenesulfonic acid were added to a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 60-65 °C for 3 hours. After post-processing, an average structure of MD was obtained. 40 D H 8M hydrogen-containing polysiloxane.

[0085] 210.9g of terminal allyl polyether (EO=11, PO=1), 89.0g of palmitoleic acid and 0.5g of p-toluenesulfonic acid were added to a 500ml three-necked flask equipped with a mechanical stirrer. The mixture was reacted at 130℃ for 4 hours. After post-treatment, allyl polyether PE2 with palmitole groups at the end was obtained.

[0086] 216.6g of palm oil-terminated allyl polyether PE2 and 83.4g of hydrogen-containing polysiloxane MD were added. 40 D H Mix 8M solutions, heat the mixture to 90°C and stir for 10 min, then add 10 ppm of Pt (chloroplatinic acid ethanol solution). Maintain the mixture in the flask at 90°C and react for 4 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the emulsifier BE2, and its structural formula is shown below:

[0087] Preparation of emulsion containing perfluorinated additives: Prepared in the same manner as in Example 1, except that the emulsifier BE1 is replaced with BE2.

[0088] Example 3

[0089] This invention provides a method for preparing an emulsifier, comprising:

[0090] 13.0 g of hexamethyldisiloxane, 237.5 g of octamethylcyclotetrasiloxane, 48.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 0.4 g of trifluorobenzenesulfonic acid were added to a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 60-65 °C for 3 hours. After post-processing, the average structure was obtained as MD. 40 D H 10 M is a hydrogen-containing polysiloxane.

[0091] 210.0g of terminal allyl polyether (EO=12, PO=0), 90.5g of palmitoleic acid and 0.5g of p-toluenesulfonic acid were added to a 500ml three-necked flask equipped with a mechanical stirrer. The mixture was reacted at 130℃ for 4 hours. After post-treatment, allyl polyether PE3 with palmitole groups at the end was obtained.

[0092] 226.5g of palm oil-terminated allyl polyether PE3 and 73.5g of hydrogen-containing polysiloxane MD were mixed. 40 D H 10 Mix M, heat the mixture to 85°C and stir for 10 min, then add 10 ppm of Pt (chloroplatinic acid ethanol solution). Maintain the mixture in the flask at 85°C and react for 5 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the emulsifier BE3, and its structural formula is shown below:

[0093]

[0094] Preparation of emulsion containing perfluorinated additives: Prepared in the same manner as in Example 1, except that emulsifier BE1 is replaced with BE3.

[0095] Example 4

[0096] This invention provides a method for preparing an emulsifier, comprising:

[0097] 14.4 g of hexamethyldisiloxane, 243.4 g of octamethylcyclotetrasiloxane, 42.7 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 1.0 g of trifluorobenzenesulfonic acid were added to a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 40–45 °C for 5 h. After post-processing, an average structure of MD was obtained. 37 D H 8M hydrogen-containing polysiloxane.

[0098] 203.7g of terminal allyl polyether (EO=13, PO=0), 96.0g of ricinoleic acid and 0.9g of p-toluenesulfonic acid were added, and the mixture was reacted at 130℃ for 4h. After post-treatment, allyl polyether PE4 with castor oil groups at the end was obtained.

[0099] 225.0g of allyl polyether PE4 with castor oil-terminated groups and 75.0g of hydrogen-containing polysiloxane MD 37 D H The mixture was stirred at 8 M for 100°C for 10 min, and then 6 ppm of Pt (Karstedt catalyst) was added. The mixture was maintained at 100°C for 4 h. The resulting amber-colored, transparent, viscous liquid was obtained, which is the emulsifier BE4, with the following structural formula:

[0100]

[0101] Preparation of emulsion containing perfluorinated additives: Prepared in the same manner as in Example 1, except that emulsifier BE1 is replaced with BE4.

[0102] Example 5

[0103] This invention provides a method for preparing an emulsifier, comprising:

[0104] 14.5 g of hexamethyldisiloxane, 231.8 g of octamethylcyclotetrasiloxane, 53.7 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 0.8 g of trifluorobenzenesulfonic acid were added to a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 50-55 °C for 4 hours. After post-processing, an average structure of MD was obtained. 35 D H 10 M is a hydrogen-containing polysiloxane.

[0105] 208.0 g of terminal allyl polyether (EO=14, PO=0), 91.8 g of ricinoleic acid and 0.8 g of p-toluenesulfonic acid were added, and the mixture was reacted at 140 °C for 4 h. After post-treatment, allyl polyether PE5 with castor oil groups at the end was obtained.

[0106] 239.7g of allyl polyether PE5 with castor oil-terminated groups and 60.3g of hydrogen-containing polysiloxane MD were mixed. 35 D H 10 Mix M, heat the mixture to 95°C and stir for 10 min, then add 7 ppm of Pt (Karstedt catalyst). Maintain the mixture in the flask at 95°C and react for 4 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the emulsifier BE5, and its structural formula is shown below:

[0107] Preparation of emulsion containing perfluorinated additives: Prepared in the same manner as in Example 1, except that emulsifier BE1 is replaced with BE5.

[0108] Example 6

[0109] This invention provides a method for preparing an emulsifier, comprising:

[0110] 10.9 g of hexamethyldisiloxane, 249.0 g of octamethylcyclotetrasiloxane, 40.4 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 0.6 g of trifluorobenzenesulfonic acid were added to a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 40-45 °C for 6 hours. After post-processing, an average structure of MD was obtained. 50 D H 10 M is a hydrogen-containing polysiloxane.

[0111] 209.3g of terminal allyl polyether (EO=13, PO=1), 90.5g of ricinoleic acid and 0.8g of p-toluenesulfonic acid were added, and the mixture was reacted at 140℃ for 4h. After post-treatment, allyl polyether PE6 with castor oil groups at the end was obtained.

[0112] 225.3g of allyl polyether PE6 with castor oil-terminated groups and 74.7g of hydrogen-containing polysiloxane MD were mixed. 50 D H 10 Mix M, heat the mixture to 95°C and stir for 10 min, then add 8 ppm of Pt (Karstedt catalyst). Maintain the mixture in the flask at 95°C and react for 4 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the emulsifier BE6, and its structural formula is shown below:

[0113] Preparation of emulsion containing perfluorinated additives: Prepared in the same manner as in Example 1, except that emulsifier BE1 is replaced with BE6.

[0114] Comparative Example 1

[0115] This comparative example provides a method for preparing an emulsifier, including:

[0116] 168.9g of allyl polyether PE7 (EO=12, PO=1) and 131.1g of hydrogen-containing polysiloxane MD 40 D H Mix 5M, heat the mixture to 85°C and stir for 10 min, then add 5 ppm of Pt (chloroplatinic acid ethanol solution). Maintain the mixture in the flask at 85°C and react for 5 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the contrast emulsifier DBE1.

[0117] Preparation of emulsions containing perfluorinated additives: All comparative examples differ from Example 1 in that the type of emulsifier in the examples is changed.

[0118] Comparative Example 2

[0119] This comparative example provides a method for preparing an emulsifier, including:

[0120] 196.2g of allyl polyether PE7 and 103.8g of hydrogen-containing polysiloxane MD 60 D H Mix 8M, heat the mixture to 90°C and stir for 10 min, then add 10 ppm of Pt (chloroplatinic acid ethanol solution). Maintain the mixture in the flask at 90°C and react for 4 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the contrast emulsifier DBE2.

[0121] Comparative Example 3

[0122] This comparative example provides a method for preparing an emulsifier, including:

[0123] 250.4g of terminal allyl polyether (EO=12, PO=12), 49.5g of palmitoleic acid and 1.1g of p-toluenesulfonic acid were added to a 500ml three-necked flask equipped with a mechanical stirrer. The mixture was reacted at 140℃ for 5h. After post-treatment, allyl polyether PE8 with palmitole-terminated groups was obtained.

[0124] 255.0g of palm oil-terminated allyl polyether PE8 and 45.0g of hydrogen-containing polysiloxane MD were mixed. 40 D H 10Mix M, heat the mixture to 95°C and stir for 10 min, then add 15 ppm of Pt (chloroplatinic acid ethanol solution). Maintain the mixture in the flask at 95°C and react for 5 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the contrast emulsifier DBE3.

[0125] Comparative Example 4

[0126] This comparative example provides a method for preparing an emulsifier, including:

[0127] 277.7g of terminal allyl polyether (EO=30, PO=30), 22.3g of palmitoleic acid, and 1.8g of p-benzenesulfonic acid were added, and the mixture was reacted at 150℃ for 6 hours. After post-treatment, allyl polyether PE9 with castor oil groups at the end was obtained.

[0128] 274.8g of palm oil-terminated allyl polyether PE9 and 25.2g of hydrogen-containing polysiloxane MD were mixed. 37 D H Mix 8M, heat the mixture to 100°C and stir for 10 min, then add 20 ppm Pt (Karstedt catalyst). Maintain the mixture in the flask at 100°C and react for 4 h. After treatment, a turbid liquid is obtained, which separates into layers after standing.

[0129] Comparative Example 5

[0130] This comparative example provides a method for preparing an emulsifier, including:

[0131] 199.5g of allyl polyether PE5 with castor oil-terminated groups and 100.5g of hydrogen-containing polysiloxane MD 80 D H 10 Mix M, heat the mixture to 95°C and stir for 10 min, then add 15 ppm of Pt (Karstedt catalyst). Maintain the mixture in the flask at 95°C and react for 4 h. After treatment, an amber-colored, transparent, viscous liquid is obtained, which is the contrast emulsifier DBE5.

[0132] Comparative Example 6

[0133] This comparative example provides a method for preparing an emulsifier, including:

[0134] 259.3g of terminal allyl polyether (EO=18, PO=18), 40.5g of castor oil acid, and 1.0g of p-benzenesulfonic acid were added, and the mixture was reacted at 140℃ for 4h. After post-treatment, allyl polyether PE10 with castor oil groups at the end was obtained.

[0135] 261.3g of allyl polyether PE10 with castor oil-terminated groups and 38.7g of hydrogen-containing polysiloxane MD were mixed. 50 D H10 Mix M, heat the mixture to 95°C and stir for 10 min, then add 20 ppm of Pt (Karstedt catalyst). Maintain the mixture in the flask at 95°C and react for 4 h. After treatment, an amber-colored, misty, viscous liquid is obtained.

[0136] Application examples

[0137] The emulsions containing perfluorinated additives formed in the above examples and comparative examples were used to prepare rigid polyurethane foams, and the specific processes are as follows:

[0138] 1) Maintain the temperature of the prepared perfluorinated additive emulsion at 20~21℃;

[0139] 2) The perfluorinated additive emulsion and isocyanate are mixed at a mass ratio of 100:120 and stirred at 4000 r / min for 5 s. The mixture is then poured into a fixed sealed mold and cured and demolded to obtain the rigid polyurethane foam.

[0140] The conditions for preparing the foam are as follows: material temperature 20.5℃, mold temperature 48℃, overfill rate 20%, and demolding time 360s.

[0141] The prepared rigid polyurethane foam was subjected to performance testing, and the test structure is shown below:

[0142]

[0143] Among them, the foam density and thermal conductivity were measured according to national standards:

[0144] The foam core density test shall be conducted in accordance with the standard GB / T 6343-2009;

[0145] The thermal conductivity of foam was tested according to standard GB / T 10295-2008.

[0146] Surface bubble standard: A diameter ≥ 6cm is classified as A. + A is defined as 3cm ≤ diameter < 6cm, 1A + =2A.

[0147] Storage stability: The emulsion containing perfluorinated additives was stored at 25°C, and the number of days after which the emulsion containing perfluorinated additives showed stratification was observed.

[0148] Based on the above test results, it can be seen that the storage stability of the emulsions containing perfluorinated additives prepared in Comparative Examples 1-3 and 5 is significantly worse than that in Examples 1-6. The sample in Comparative Example 4 showed stratification, and the sample in Comparative Example 6 was opaque, indicating that no fluorinated emulsion was prepared.

[0149] Comparative Examples 1 and 2, which did not use bio-based modified allyl polyether, exhibited significantly worse storage stability and severe surface defects. Comparative Example 3 used bio-based modified allyl polyether, but the propylene oxide value (b) of the polyether was outside the range defined in the embodiments of this invention. While its storage stability was slightly better than the other comparative examples, it was still worse than the examples. Comparative Example 5 used the same bio-based modified allyl as Example 5, but its trend range of hydrogen-containing polysiloxanes exceeded the limits defined in this invention. The blank example, which did not use an emulsifier, showed a significant decrease in storage stability.

[0150] The lack of significant difference in thermal conductivity between the examples and comparative examples is due to the beneficial effect of the strong nucleation properties of the fluorinated additives in the emulsion. However, a comparison of surface defects in the foam shows that the surface defects of the rigid polyurethane foam are significantly reduced after using the emulsifier of the present invention.

[0151] In summary, the emulsion containing perfluorinated additives provided in this invention exhibits good storage stability, and the entire preparation method is simple and easy to operate. The resulting rigid polyurethane foam has low thermal conductivity and few surface defects.

[0152] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An emulsifier, characterized by, It is a bio-based polyether modified polysiloxane shown in the following structural formula: wherein, m = 30-55, n = 4-12; R is of the general formula -(CH2) p (OC2H4) a (OC3H6) b OR1, wherein p = 2-4, a = 5-15, b = 0-10, and R1is a biomass radical, which is a palm oil radical or a castor oil radical.

2. An emulsion containing a perfluoroaid, characterized in that, It comprises a perfluoro aid, an emulsifier of claim 1, a surfactant, a combined catalyst, a solvent, a foaming agent and a polyether polyol; wherein the mass ratio of the perfluoro aid, the emulsifier, the surfactant, the combined catalyst, the solvent, the foaming agent and the polyether polyol is (3-10):(1-5):(1-3):(2-4):(1-3):(10-20):

100.

3. The perfluoroadditive-containing emulsion of claim 2, wherein, The raw materials for forming the emulsion meet at least one of the following requirements: (1) the perfluoro aid comprises one of PF-5052, PF-5056, PF-5058, Noah 7160, Noah 2100A, Noah 2100B; (2) the combined catalyst comprises an amine substance; (3) the surfactant comprises a non-ionic surfactant; (4) the foaming agent comprises a C3-C8 alkane substance; (5) the solvent comprises water; (6) the polyether polyol comprises any one or at least two of H4110, H4110M, H8169, H8175, H8245 and H8246.

4. The perfluoroadditive-containing emulsion of claim 2, wherein, The raw materials for forming the emulsion meet at least one of the following requirements: (1) the perfluoro aid comprises any one of PF-5052, PF-5056, PF-5058, Noah 7160, Noah 2100A, Noah 2100B; (2) the combined catalyst comprises at least two of pentamethyl diethylene triamine, tetramethyl hexanediamine, bis-dimethyl amine ethyl ether, dimethyl benzyl amine, dimethyl cyclohexane, triethylene diamine, methyl imidazole, quaternary ammonium salt and tris(dimethyl aminopropyl) hexahydro triazine; (3) the surfactant comprises any one or at least two of M-8805, M-8815, M-8830, M-8860, M-88310 and M-88315; (4) the foaming agent comprises any one or at least two of cyclopentane, isopentane, n-pentane, n-butane, isobutane and 1,1,1,3,3-pentafluoropropane; (5) the polyether polyol comprises any one or at least two of H4110, H4110M, H8169, H8175, H8245 and H8246; (6) the solvent comprises water.

5. A process for the preparation of the emulsifier of claim 1, characterized in that, Comprise: Mixing hydrogen-containing polysiloxane and allyl polyether with bio-based terminal to carry out silicon hydrogen addition reaction.

6. The production method according to claim 5, characterized by, Comprise: Mixing the hydrogen-containing polysiloxane, the allyl polyether with bio-based terminal and a catalyst to carry out silicon hydrogen addition reaction; Wherein, the conditions of silicon hydrogen addition reaction meet at least one of the following requirements: (1) the mass ratio of the hydrogen-containing polysiloxane and the allyl polyether with bio-based terminal is (60-80):(40-20); (2) the catalyst is a platinum catalyst; (3) the amount of the catalyst is 5-15 ppm; (4) the reaction temperature is 85-105℃; the reaction time is 3-6.

7. The production method according to claim 5 or 6, characterized by, The preparation method of the hydrogen-containing polysiloxane comprises; Under the condition of an acidic catalyst, hexamethyldisiloxane, octamethylcyclotetrasiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane are mixed and reacted; The preparation method of the terminal bio-based allyl polyether includes: mixing a bio-based raw material, a terminal allyl polyether and an esterification catalyst and reacting; The bio-based raw material is palmitoleic acid or ricinoleic acid; The reaction conditions meet at least one of the following requirements: (1) the mass ratio of the bio-based raw material to the terminal allyl polyether is (25-35):(75-65); (2) the esterification catalyst comprises an acidic substance; (3) the reaction conditions include: the temperature is 120-160 DEG C; the time is 4-8h.

8. A process for the preparation of the emulsion containing perfluoroadditive according to claim 2, characterized in that, It comprises: Mixing raw materials to form the emulsion.

9. A polyurethane foam characterized by, It comprises a polyisocyanate and the emulsion containing the perfluoro-containing auxiliary of claim 2.

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