Fluorocarbon chain-terminated polyether modified organosilicon leveling agent and preparation method thereof

Abstract

The invention provides a polyether modified organic silicon leveling agent, which belongs to the field of leveling agents, and has the following structural formula: # imgabs0 #, wherein m, n, p and q are integers, m is equal to 2-10, n is equal to 5-50, p is equal to 5-50, and q is equal to 0-10; r1 is selected from one of OOCC2H2COO, OOCC2H4COO, # imgabs 1 #, # imgabs 2 # and # imgabs 3 #, and R2 is selected from one of OOCC2H2COO, OOCC2H4COO, # imgabs 1 #, # imgabs 2 # and R2 is selected from fluorine-containing alkyl, and when m is equal to 2, the number of carbon atoms of R2 is 6-8; and when m is greater than or equal to 3, the carbon atom number of R2 is 4-8. According to the invention, fluorocarbon chain modification is carried out at the tail end of polyether, so that the modified organic silicon leveling agent with stronger shrinkage-proof tension is obtained.

Description

Technical Field

[0001] The invention belongs to the field of leveling agents, and specifically relates to a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent and a preparation method thereof. Background Art

[0002] Leveling agent is a kind of additive widely used in coating, ink and other industries. Its main function is to improve the fluidity of the coating film, thereby improving the surface quality and appearance of the coating. Leveling agent is composed of polar segments and non-polar segments. The polar segments improve the compatibility with the system, while the non-polar segments are incompatible with the system and migrate to the surface of the system, reducing the surface tension of the system, avoiding surface defects such as shrinkage cavities and orange peel, and making the coating obtain a smooth and flat surface.

[0003] Organic silicon leveling agent refers to polydimethylsiloxane and its modified products, but its wetting ability and anti-cratering ability are still insufficient. Organic fluorine has very low surface tension and excellent anti-cratering ability, but pure fluorocarbon has poor compatibility with coating and ink systems. Some existing technologies use perfluoroethylene and hydrogenated silicone oil for silylation, and the yield of this reaction is very low; there are also reports on the synthesis of fluorinated silicone polymers, which react polymethylhydrogensiloxane and perfluoro-1-decene at 65°C for 5 days. The process is cumbersome and the reaction time is too long.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a fluorocarbon chain-terminated polyether modified silicone leveling agent and a preparation method thereof, and obtains a modified silicone leveling agent with stronger anti-shrinkage tension by modifying the polyether end with a fluorocarbon chain.

[0006] According to the first aspect of the present invention, a fluorocarbon chain-terminated polyether-modified silicone leveling agent is provided, which has the following structural formula: ; Wherein, m, n, p, q are all integers, m = 2 ~ 10, n = 5 ~ 50, p = 5 ~ 50, q = 0 ~ 10; R1 is selected from OOCC2H2COO, OOCC2H4COO, , or One of; R2 is selected from a fluorinated alkyl group. When m=2, the number of carbon atoms of R2 is 6 to 8; when m≥3, the number of carbon atoms of R2 is 4 to 8. Preferably, n≥15, p≥18.

[0007] Preferably, q≥2.

[0008] More preferably, the fluorinated alkyl group is a straight-chain fluorinated alkyl group.

[0009] Preferably, the acid value of the fluorocarbon chain-terminated polyether-modified silicone leveling agent is less than 3 mgKOH / g.

[0010] It should be noted that the polyether-modified silicone leveling agent described in the present invention is not necessarily a block copolymer, and m, n, p, and q merely represent the number of corresponding groups. The connection sequence of each group may be random or block, and the present invention does not impose any limitation on this.

[0011] According to the second aspect of the present invention, a method for preparing the fluorocarbon chain-terminated polyether-modified silicone leveling agent as described in the first aspect of the present invention is provided, characterized in that it comprises the following steps: S1: Hexamethyldisiloxane (MM), octamethylcyclotetrasiloxane (D4), tetramethylcyclotetrasiloxane (D4H) and the first catalyst are mixed and then heated to react to obtain hydrogen-containing silicone oil; S2: mixing the hydrogen-containing silicone oil, allyl polyether and the second catalyst and heating them to react to obtain polyether-modified silicone oil; The structure of the allyl polyether is as follows: , where R' is or ; S3: mixing the polyether-modified silicone oil, the fluorine-containing carbon chain carboxylic acid and the third catalyst, and then heating the mixture to react, so as to obtain a fluorine-carbon chain-terminated polyether-modified organic silicone leveling agent.

[0012] The reaction formula of step S1 is as follows: ; Preferably, in step S1, the first catalyst is acidic clay.

[0013] The reaction formula of step S2 is as follows: ; Preferably, in step S2, R' is The present invention prefers epoxy-terminated allyl polyether, which is conducive to the subsequent reaction with fluorine-containing carbon chain carboxylic acid. Compared with allyl polyethers terminated by other groups (such as hydroxyl), the reaction is more complete and the yield is higher.

[0014] Preferably, in step S2, the second catalyst is a Custer catalyst.

[0015] The reaction formula of step S3 may be as follows: ; In the above reaction formula, R'' is a fluorine-containing segment.

[0016] Preferably, in step S3, the fluorine-containing carbon chain carboxylic acid is prepared by the following method: mixing an acid anhydride and a fluorine-containing alcohol having 4 to 8 carbon atoms in a molar ratio of 1:1, and heating to react, to obtain; The acid anhydride is selected from one of maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

[0017] Preferably, the fluorine-containing alcohol may be one of hexafluorobutanol, octafluoropentanol, nonafluorohexanol, nonafluorooctanol, dodecafluoroheptanol, tridecafluorooctanol or pentafluorooctanol.

[0018] For example, when the fluorine-containing alcohol is hexafluorobutanol and the acid anhydride is selected from maleic anhydride, the reaction formula for preparing the above-mentioned fluorine-containing carbon chain carboxylic acid is as follows: ; It should be noted that, in order to implement environmental protection requirements, the present invention only selects some common fluorine-containing alcohols for testing, but it is understandable that fluorine-containing alcohols with higher fluorine content can also be used for modification of polyether ends, thereby obtaining a modified silicone leveling agent with strong anti-shrinkage tension.

[0019] More preferably, the fluorine content of the fluorine-containing alcohol is greater than 60%.

[0020] Preferably, in step S1, the molar ratio of the raw materials is MM:D4:D4H=4:n:m; and / or, in step S2, the molar ratio of the hydrogen-containing silicone oil to the allyl polyether is 1:m; and / or, in step S3, the molar ratio of the polyether-modified silicone oil to the fluorine-containing carbon chain carboxylic acid is 1:m.

[0021] Preferably, in step S3, the third catalyst is triphenylphosphine.

[0022] Preferably, in step S1, the temperature of the temperature-raising reaction is raised to 30-60°C, and the insulation time is 8-12 hours; and / or, in step S2, the temperature of the temperature-raising reaction is raised to 70-100°C, and the insulation time is 3-6 hours; and / or, in step S3, the temperature of the temperature-raising reaction is raised to 80-120°C, and the insulation time is 4-10 hours.

[0023] According to the third aspect of the present invention, the use of the fluorocarbon chain-terminated polyether-modified silicone leveling agent as described in the first aspect of the present invention in coatings is proposed.

[0024] Preferably, the coating is selected from polyurethane coating or amino baking varnish coating.

[0025] Preferably, the amount of the fluorocarbon chain-terminated polyether-modified silicone leveling agent is 0.1 wt% to 0.2 wt% of the coating.

[0026] According to one embodiment of the present invention, there are at least the following beneficial effects: The present invention combines the characteristics of organosilicon and organofluorine additives by designing and synthesizing the molecular structure to obtain a novel fluorine-modified organosilicon leveling agent. The organosilicon leveling agent has a polyether side chain terminated by a fluorocarbon chain, and while maintaining good compatibility with the coating ink system, further reduces the surface tension, and the formed paint film has a strong anti-cratering ability, and the distinctness of image is not significantly reduced. DETAILED DESCRIPTION

[0027] The concept and technical effects of the present invention will be clearly and completely described below in conjunction with embodiments to fully understand the purpose, features and effects of the present invention.

[0028] Unless otherwise specified, the raw materials, reagents or devices used in the following examples and comparative examples can be obtained from conventional commercial sources or by existing known methods.

[0029] Among them, hexamethyldisiloxane, octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane were all purchased from Hesheng Silicon Industry Co., Ltd.; acidic clay, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and triphenylphosphine were all purchased from Dongguan Yongzheng Chemical Co., Ltd.; HY series epoxy-terminated allyl polyethers were purchased from Jiangsu Zhongshan Chemical Co., Ltd.; trifluoroethanol, pentafluoropropanol, hexafluorobutanol, octafluoropentanol, nonafluorohexanol, nonafluorooctanol, dodecafluoroheptanol, tridecafluorooctanol and pentafluorooctanol were all purchased from Harbin Xuejia Chemical Co., Ltd.; BYK066N was purchased from BYK Chemical; Setalux 1753 SS-70 acrylic resin was purchased from Allnex Resins; Desmodur N3390 was purchased from Covestro; xylene, butyl acetate and propylene glycol methyl ether acetate were all purchased from Yida Company.

[0030] The preparation of the fluorinated carbon chain carboxylic acid intermediate is as follows: add anhydride and fluoroalcohol into a four-necked flask under nitrogen atmosphere, stir, heat to 100°C and keep warm for 4 hours to obtain. The anhydride and fluoroalcohol used are shown in Table 1 below, and the acid value of the fluorinated carbon chain carboxylic acid intermediate is tested. When the corresponding acid value is reached, it can be considered that the raw materials are basically reacted completely.

[0031] Table 1 Preparation of fluorinated carbon chain intermediates

[0032] Example 1 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 370 g D4 and 120 g D4H into a four-necked flask, add 50 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0033] (2) Add 163 g of hydrogenated silicone oil, 150 g of allyl polyether HY300 (p=4, q=0) with a molecular weight of 300, and 0.15 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0034] (3) Add 99 g of fluorine-containing carbon chain intermediate 1, 1 g of triphenylphosphine and 313 g of epoxy polyether modified silicone oil A1 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0035] Example 2 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 740 g D4 and 120 g D4H into a four-necked flask, add 50 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=2, n=10) with a molecular weight of 1022.

[0036] (2) Add 102.2 g of hydrogenated silicone oil, 140 g of allyl polyether HY700 (p=15, q=0) with a molecular weight of 700, and 0.15 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A2 with a molecular weight of 2422.

[0037] (3) Add 49.6 g of fluorine-containing carbon chain intermediate 2, 1 g of triphenylphosphine and 242.2 g of epoxy polyether modified silicone oil A2 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0038] Example 3 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 1110 g D4 and 120 g D4H into a four-necked flask, add 50 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=2, n=15) with a molecular weight of 1392.

[0039] (2) Add 139.2 g of hydrogenated silicone oil, 180 g of allyl polyether HY900 (p=18, q=0) with a molecular weight of 900, and 0.3 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A3 with a molecular weight of 3192.

[0040] (3) Add 56 g of fluorine-containing carbon chain intermediate 3, 1 g of triphenylphosphine and 319.2 g of epoxy polyether modified silicone oil A3 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0041] Example 4 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 370 g D4 and 120 g D4H into a four-necked flask, add 50 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0042] (2) Add 163 g of hydrogenated silicone oil, 150 g of allyl polyether HY300 (p=4, q=0) with a molecular weight of 300, and 0.15 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0043] (3) Add 181 g of fluorine-containing carbon chain intermediate 5, 1 g of triphenylphosphine and 313 g of epoxy polyether modified silicone oil A1 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0044] Example 5 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 370 g D4 and 120 g D4H into a four-necked flask, add 50 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0045] (2) Add 163 g of hydrogenated silicone oil, 150 g of allyl polyether HY300 (p=4, q=0) with a molecular weight of 300, and 0.15 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0046] (3) Add 215 g of fluorine-containing carbon chain intermediate 6, 1.5 g of triphenylphosphine and 313 g of epoxy polyether modified silicone oil A1 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0047] Example 6 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 370 g D4 and 120 g D4H into a four-necked flask, add 50 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0048] (2) Add 163 g of hydrogenated silicone oil, 150 g of allyl polyether HY300 (p=4, q=0) with a molecular weight of 300, and 0.15 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0049] (3) Add 231 g of fluorine-containing carbon chain intermediate 7, 1.5 g of triphenylphosphine and 313 g of epoxy polyether modified silicone oil A1 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0050] Example 7 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, and its structural formula is the same as that of Embodiment 1.

[0051] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps: (1) Add 162 g MM, 1480 g D4 and 180 g D4H into a four-necked flask, add 150 g acid clay and stir evenly, heat to 50 °C, keep warm for 10 h, filter and obtain hydrogenated silicone oil (m=3, n=20) with a molecular weight of 1822.

[0052] (2) Add 182.2 g of hydrogenated silicone oil, 300 g of allyl polyether HY1001 (p=20, q=2) with a molecular weight of 1000, and 0.5 g of Castel catalyst into a four-necked flask and stir evenly. Heat to 80°C and keep warm for 4 h to obtain epoxy polyether modified silicone oil A4 with a molecular weight of 4822.

[0053] (3) Add 5.94 g of fluorine-containing carbon chain intermediate 1, 0.3 g of triphenylphosphine and 48.22 g of epoxy polyether modified silicone oil A4 into a four-necked flask and stir evenly. Heat to 100 °C and keep warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0054] Example 8 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, and its structural formula is the same as that of Embodiment 2.

[0055] The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.3 g of triphenylphosphine and 7.44 g of fluorine-containing carbon chain intermediate 2 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for reaction for 4 h until the acid value of the product is less than 3 mgKOH / g.

[0056] Example 9 This embodiment provides a fluorocarbon chain-terminated polyether-modified silicone leveling agent, whose structural formula is the same as that of Example 3.

[0057] The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.3 g of triphenylphosphine and 8.4 g of fluorine-containing carbon chain intermediate 3 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0058] Example 10 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.4 g of triphenylphosphine and 9.9 g of fluorine-containing carbon chain intermediate 4 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0059] Embodiment 11 This embodiment provides a fluorocarbon chain-terminated polyether-modified silicone leveling agent, whose structural formula is the same as that of Example 4.

[0060] The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.4 g of triphenylphosphine and 10.86 g of fluorine-containing carbon chain intermediate 5 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0061] Example 12 This embodiment provides a fluorocarbon chain-terminated polyether-modified silicone leveling agent, whose structural formula is the same as that of Example 5.

[0062] The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.4 g of triphenylphosphine and 12.9 g of fluorine-containing carbon chain intermediate 6 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0063] Example 13 This embodiment provides a fluorocarbon chain-terminated polyether-modified silicone leveling agent, whose structural formula is the same as that of Example 6.

[0064] The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 13.86 g of fluorine-containing carbon chain intermediate 7 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0065] Embodiment 14 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 13.92 g of fluorine-containing carbon chain intermediate 8 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0066] Embodiment 15 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 15.36 g of fluorine-containing carbon chain intermediate 9 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0067] Example 16 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 15.48 g of fluorine-containing carbon chain intermediate 10 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for reaction for 4 h until the acid value of the product is less than 3 mgKOH / g.

[0068] Embodiment 17 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 15.54 g of fluorine-containing carbon chain intermediate 11 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0069] Embodiment 18 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 11.7 g of fluorine-containing carbon chain intermediate 12 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0070] Embodiment 19 This embodiment provides a fluorocarbon chain-terminated polyether-modified organic silicon leveling agent, the structural formula of which is as follows: ; The preparation process of the fluorocarbon chain-terminated polyether-modified organic silicone leveling agent is different from that of Example 7 in step (3): 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 14.94 g of fluorine-containing carbon chain intermediate 13 are added to a four-necked flask and stirred evenly, and the temperature is raised to 100° C. and then kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0071] Test example The products obtained in Examples 1 to 19 and epoxy polyether modified silicone oils A1 to A4 were used as leveling agents to prepare PU varnishes, wherein the PU varnishes were prepared from component A and component B in a ratio of 100:40 by mass, and the compositions of the components A and B are shown in Table 2. The PU varnishes were sprayed on the bottom plate, the film thickness was controlled to be 30 μm, and dried at 80° C. for 1 h.

[0072] In the above method, the varnish prepared by the formula in Table 2 was used to test the anti-cratering performance. The grease was first removed with butyl acetate on a 20*20 cm tinplate, and then the varnishes of the formula in Table 2 were sprayed. After baking at 80°C, a varnish dry film of 30 μm was obtained, and the surface cratering was observed. The BYK orange peel meter was used to test the distinctness of image by the formula in Table 3, and the results are shown in Table 4 below.

[0073] Table 2 Composition of component A and component B

[0074] Table 3 Another composition of component A and component B

[0075] Table 4 Anti-cratering grade and distinctness of image test results

[0076] Remark: aGrade 0 is the best, indicating 0 shrinkage cavities on the board surface; grade 1 indicates less than 5 shrinkage cavities on the board surface; grade 2 indicates 5-10 shrinkage cavities on the board surface; grade 3 indicates 10-15 shrinkage cavities on the board surface; grade 4 indicates 15-20 shrinkage cavities on the board surface; and grade 5 is the worst, indicating more than 20 shrinkage cavities on the board surface.

[0077] The anti-cratering grades of the leveling agents provided in Examples 1-3 and 7-8 are similar to those of the corresponding epoxy polyether modified silicone oils A1-A4, indicating that when the end-capped fluorocarbon chain in the leveling agent is too short (the number of carbon atoms is less than 4), it is not very helpful for anti-cratering.

[0078] Referring to Examples 1-3, when the number of fluorocarbon chain-terminated side chains is small (m=2), the fluorocarbon chain with a small number of carbon atoms (less than 6) does not help much in preventing shrinkage craters, but as the length of the fluorocarbon chain increases, referring to Examples 4-6, the anti-shrinkage crater level is significantly improved. Referring to Examples 9-10, when the number of fluorocarbon chain-terminated side chains is large (m≥3), the shorter fluorocarbon chain can also significantly improve the anti-shrinkage crater performance.

[0079] Referring to Examples 7 and 18, when the fluorine contents of the end-capped fluorocarbon chains are similar, the longer the fluorocarbon chain, the better the anti-shrinkage performance; referring to Examples 13, 18, and 19, when the length of the end-capped fluorocarbon chain is certain, the higher the fluorine content, the better the anti-shrinkage performance.

[0080] It can be seen that fluorocarbon end-capping modification significantly improves the anti-cratering ability of the silicone leveling agent, but has no significant effect on the distinctness of image of the paint film. For polyether-modified silicone leveling agents that are not fluorocarbon end-capped, the larger the molecular weight of the silicone main chain, the better the anti-cratering performance.

[0081] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A fluorocarbon chain-terminated polyether-modified silicone leveling agent, characterized in that: Has the following structural formula: ； Wherein, m, n, p, q are all integers, m = 2 ~ 10, n = 5 ~ 50, p = 5 ~ 50, q = 0 ~ 10; R1 is selected from OOCC2H2COO, OOCC2H4COO, , or One of; R2 is selected from a fluorinated alkyl group. When m=2, the number of carbon atoms of R2 is 6 to 8; when m≥3, the number of carbon atoms of R2 is 4 to 8.

2. The fluorocarbon chain-terminated polyether-modified silicone leveling agent according to claim 1, characterized in that: n≥15, p≥18.

3. The fluorocarbon chain-terminated polyether-modified silicone leveling agent according to claim 1, characterized in that: The fluorinated alkyl group is a linear fluorinated alkyl group.

4. The fluorocarbon chain-terminated polyether-modified silicone leveling agent according to claim 1, characterized in that: The acid value of the fluorocarbon chain-terminated polyether-modified organic silicon leveling agent is less than 3 mgKOH / g.

5. A method for preparing the fluorocarbon chain-terminated polyether-modified silicone leveling agent according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: mixing hexamethyldisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and a first catalyst and heating the mixture to react to obtain hydrogen-containing silicone oil; S2: mixing the hydrogen-containing silicone oil, allyl polyether and the second catalyst and heating them to react to obtain polyether-modified silicone oil; The structure of the allyl polyether is as follows: , where R' is or ; S3: mixing the polyether-modified silicone oil, the fluorine-containing carbon chain carboxylic acid and the third catalyst, and then heating the mixture to react, so as to obtain a fluorine-carbon chain-terminated polyether-modified organic silicone leveling agent.

6. The preparation method according to claim 5, characterized in that: In step S2, the R' is .

7. The preparation method according to claim 5, characterized in that: In step S3, the fluorine-containing carbon chain carboxylic acid is prepared by the following method: mixing an acid anhydride and a fluorine-containing alcohol having 4 to 8 carbon atoms in a molar ratio of 1:1, and heating the mixture for reaction to obtain the obtained product; The acid anhydride is selected from one of maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

8. The preparation method according to claim 5, characterized in that: In step S1, the molar ratio of the raw materials is hexamethyldisiloxane:octamethylcyclotetrasiloxane:tetramethylcyclotetrasiloxane=4:n:m; and / or, in step S2, the molar ratio of the hydrogenated silicone oil to the allyl polyether is 1:m; and / or, in step S3, the molar ratio of the polyether-modified silicone oil to the fluorinated carbon chain carboxylic acid is 1:m.

9. The preparation method according to claim 5, characterized in that: In step S1, the temperature of the temperature-raising reaction is raised to 30-60°C, and the insulation time is 8-12 hours; and / or, in step S2, the temperature of the temperature-raising reaction is raised to 70-100°C, and the insulation time is 3-6 hours; and / or, in step S3, the temperature of the temperature-raising reaction is raised to 80-120°C, and the insulation time is 4-10 hours.

10. Use of the fluorocarbon chain-terminated polyether-modified organosilicon leveling agent according to any one of claims 1 to 4 in coatings.

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