A fluorocarbon chain-terminated polyether-modified organosilicon leveling agent and its preparation method

Abstract

The present invention provides a polyether-modified organosilicon leveling agent, belonging to the field of leveling agents. The polyether-modified organosilicon leveling agent has the following structural formula: wherein m, n, p, and q are all integers, m=2-10, n=5-50, p=5-50, and q=0-10; R1 is selected from one of OOCC2H2COO, OOCC2H4COO, , or ; and R2 is selected from a fluorinated alkyl group. When m=2, R2 has 6-8 carbon atoms; when m≥3, R2 has 4-8 carbon atoms. The present invention provides a modified organosilicon leveling agent with enhanced anti-cratering tension by modifying the polyether termini with fluorocarbon chains.

Description

Technical Field

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

[0002] Leveling agents are a type of additive widely used in the coatings, inks, and other industries. Their primary function is to improve the fluidity of the coating, thereby enhancing the surface quality and appearance of the coating. Leveling agents are composed of polar and non-polar segments. The polar segments enhance compatibility with the system, while the non-polar segments are incompatible with the system and migrate to the surface, reducing the surface tension and preventing surface defects such as craters and orange peel, resulting in a smooth and even coating surface.

[0003] Silicone leveling agents refer to polydimethylsiloxane and its modified products, but their wetting and anti-cratering abilities remain limited. Organic fluorine has very low surface tension and excellent anti-cratering properties, but pure fluorocarbons lack compatibility with coating and ink systems. Some existing technologies utilize hydrosilylation of perfluoroethylene with hydrogenated silicone oil, a reaction with very low yields. Other reports on the synthesis of fluorosilicone polymers involve reacting polymethylhydrogensiloxane with perfluoro-1-decene at 65°C for five days, a cumbersome process and excessively long reaction times.

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

[0005] The present invention aims to address at least one of the technical problems existing in the aforementioned prior art. To this end, the present invention provides a fluorocarbon-terminated polyether-modified organosilicon leveling agent and a method for preparing the same. By modifying the polyether termini with fluorocarbon chains, a modified organosilicon leveling agent with enhanced anti-cratering tension is obtained.

[0006] According to the first aspect of the present invention, a fluorocarbon chain-terminated polyether-modified silicone leveling agent is proposed, having the following structural formula:

[0007] ;

[0008] Where m, n, p, and q are all integers, m = 2 to 10, n = 5 to 50, p = 5 to 50, and q = 0 to 10;

[0009] R1 is selected from OOCC2H2COO, OOCC2H4COO, 、 or One of the following;

[0010] 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.

[0011] Preferably, n≥15, p≥18.

[0012] Preferably, q≥2.

[0013] More preferably, the fluorinated alkyl group is a linear fluorinated alkyl group.

[0014] Preferably, the acid value of the fluorocarbon chain-terminated polyether-modified silicone leveling agent is less than 3 mgKOH / g.

[0015] It should be noted that the polyether-modified silicone leveling agent described in the present invention is not necessarily a block copolymer. m, n, p, and q only represent the number of corresponding groups. The connection order of each group can be random or block, and the present invention does not impose any restrictions on this.

[0016] According to a second aspect of the present invention, a method for preparing a fluorocarbon chain-terminated polyether-modified silicone leveling agent as described in the first aspect of the present invention is proposed, characterized in that it comprises the following steps:

[0017] S1: Hexamethyldisiloxane (MM), octamethylcyclotetrasiloxane (D4), tetramethylcyclotetrasiloxane (D4H) and the first catalyst are mixed and then heated to react to obtain hydrogen-containing silicone oil;

[0018] S2: mixing the hydrogenated silicone oil, allyl polyether and the second catalyst and heating the mixture to obtain polyether-modified silicone oil;

[0019] The structure of the allyl polyether is as follows:

[0020] , where R' is or ;

[0021] 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 to obtain a fluorine-carbon chain-terminated polyether-modified organic silicone leveling agent.

[0022] The reaction formula of step S1 is as follows:

[0023] ;

[0024] Preferably, in step S1, the first catalyst is acidic clay.

[0025] The reaction formula of step S2 is as follows:

[0026] ;

[0027] Preferably, in step S2, the 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 with other groups (such as hydroxyl), the reaction is more complete and the yield is higher.

[0028] Preferably, in step S2, the second catalyst is a Custer catalyst.

[0029] The reaction formula of step S3 may be as follows:

[0030] ;

[0031] In the above reaction formula, R'' is a fluorine-containing segment.

[0032] Preferably, in step S3, the fluorine-containing carbon chain carboxylic acid is prepared by the following method: mixing anhydride and a fluorine-containing alcohol having 4 to 8 carbon atoms in a molar ratio of 1:1, heating and reacting to obtain the obtained product;

[0033] The acid anhydride is selected from one of maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

[0034] Preferably, the fluorine-containing alcohol may be one of hexafluorobutanol, octafluoropentanol, nonafluorohexanol, nonafluorooctanol, dodecafluoroheptanol, tridecafluorooctanol or pentafluorooctanol.

[0035] 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:

[0036] ;

[0037] 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.

[0038] More preferably, the fluorine content of the fluorine-containing alcohol is greater than 60%.

[0039] 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 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 fluorine-containing carbon chain carboxylic acid is 1:m.

[0040] Preferably, in step S3, the third catalyst is triphenylphosphine.

[0041] 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-raising reaction is raised to 70-100°C, and the insulation time is 3-6 hours; and / or, in step S3, the temperature-raising reaction is raised to 80-120°C, and the insulation time is 4-10 hours.

[0042] According to a third aspect of the present invention, a use of the fluorocarbon chain-terminated polyether-modified silicone leveling agent described in the first aspect of the present invention in a coating is proposed.

[0043] Preferably, the coating is selected from polyurethane coating or amino baking varnish coating.

[0044] Preferably, the amount of the fluorocarbon chain-terminated polyether-modified silicone leveling agent is 0.1 wt% to 0.2 wt% of the coating.

[0045] According to one embodiment of the present invention, there are at least the following beneficial effects:

[0046] By designing and synthesizing a molecular structure, the present invention combines the characteristics of organosilicon and organofluorine additives to produce a novel fluorine-modified organosilicon leveling agent. This organosilicon leveling agent, which has fluorocarbon-terminated polyether side chains, further reduces surface tension while maintaining good compatibility with coating and ink systems. The resulting paint film exhibits strong anti-cratering properties without significantly reducing distinctness of image. DETAILED DESCRIPTION

[0047] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the embodiments so as to fully understand the purpose, characteristics and effects of the present invention.

[0048] Unless otherwise specified, the raw materials, reagents or devices used in the following examples and comparative examples can be obtained from conventional commercial channels or by existing known methods.

[0049] 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.

[0050] The fluorinated carbon chain carboxylic acid intermediate was prepared as follows: an acid anhydride and a fluoroalcohol were added to a four-necked flask under a nitrogen atmosphere, stirred, and heated to 100°C for 4 hours. The acid anhydride and fluoroalcohol used are shown in Table 1 below. The acid value of the fluorinated carbon chain carboxylic acid intermediate was also measured. The reaction of the raw materials was considered complete when the corresponding acid value was reached.

[0051] Table 1 Preparation of fluorinated carbon chain intermediates

[0052]

[0053] Example 1

[0054] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows:

[0055] ;

[0056] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0057] (1) Add 162g MM, 370g D4 and 120g D4H into a four-necked flask, add 50g acidic clay and stir evenly, heat to 50℃, keep warm for 10h, and filter to obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0058] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0059] (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.

[0060] Example 2

[0061] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0062] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0063] (1) Add 162g MM, 740g D4 and 120g D4H into a four-necked flask, add 50g acid clay and stir evenly, heat to 50℃, keep warm for 10h, filter and obtain hydrogenated silicone oil (m=2, n=10) with a molecular weight of 1022.

[0064] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A2 with a molecular weight of 2422.

[0065] (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.

[0066] Example 3

[0067] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0068] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0069] (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, and filter to obtain hydrogenated silicone oil (m = 2, n = 15) with a molecular weight of 1392.

[0070] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A3 with a molecular weight of 3192.

[0071] (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.

[0072] Example 4

[0073] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0074] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0075] (1) Add 162g MM, 370g D4 and 120g D4H into a four-necked flask, add 50g acid clay and stir evenly, heat to 50℃, keep warm for 10h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0076] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0077] (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.

[0078] Example 5

[0079] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows:

[0080] ;

[0081] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0082] (1) Add 162g MM, 370g D4 and 120g D4H into a four-necked flask, add 50g acid clay and stir evenly, heat to 50℃, keep warm for 10h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0083] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0084] (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.

[0085] Example 6

[0086] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0087] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0088] (1) Add 162g MM, 370g D4 and 120g D4H into a four-necked flask, add 50g acid clay and stir evenly, heat to 50℃, keep warm for 10h, filter and obtain hydrogenated silicone oil (m=2, n=5) with a molecular weight of 652.

[0089] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A1 with a molecular weight of 1252.

[0090] (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.

[0091] Example 7

[0092] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is the same as that of Example 1.

[0093] The preparation process of the fluorocarbon chain-terminated polyether-modified silicone leveling agent comprises the following steps:

[0094] (1) Add 162g MM, 1480g D4 and 180g D4H into a four-necked flask, add 150g acidic clay and stir evenly, heat to 50℃, keep warm for 10h, and filter to obtain hydrogenated silicone oil (m=3, n=20) with a molecular weight of 1822.

[0095] (2) 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 were added to a four-necked flask and stirred evenly. The temperature was raised to 80 °C and the mixture was kept warm for 4 h to obtain epoxy polyether modified silicone oil A4 with a molecular weight of 4822.

[0096] (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.

[0097] Example 8

[0098] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is the same as that of Example 2.

[0099] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.3 g of triphenylphosphine and 7.44 g of fluorocarbon chain intermediate 2 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0100] Example 9

[0101] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is the same as that of Example 3.

[0102] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.3 g of triphenylphosphine and 8.4 g of fluorocarbon chain intermediate 3 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0103] Example 10

[0104] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows:

[0105] ;

[0106] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.4 g of triphenylphosphine and 9.9 g of fluorocarbon chain intermediate 4 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0107] Example 11

[0108] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is the same as that of Example 4.

[0109] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.4 g of triphenylphosphine and 10.86 g of fluorocarbon chain intermediate 5 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0110] Example 12

[0111] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is the same as that of Example 5.

[0112] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.4 g of triphenylphosphine and 12.9 g of fluorocarbon chain intermediate 6 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0113] Example 13

[0114] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is the same as that of Example 6.

[0115] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 13.86 g of fluorocarbon chain intermediate 7 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0116] Example 14

[0117] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0118] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 13.92 g of fluorocarbon chain intermediate 8 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0119] Example 15

[0120] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows:

[0121] ;

[0122] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 15.36 g of fluorocarbon chain intermediate 9 are added to a four-necked flask and stirred evenly. The mixture is heated to 100° C. and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0123] Example 16

[0124] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0125] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 15.48 g of fluorocarbon chain intermediate 10 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0126] Example 17

[0127] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0128] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 15.54 g of fluorocarbon chain intermediate 11 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0129] Example 18

[0130] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0131] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 11.7 g of fluorocarbon chain intermediate 12 are added to a four-necked flask and stirred evenly. The mixture is heated to 100° C. and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0132] Example 19

[0133] This embodiment provides a fluorocarbon chain-terminated polyether-modified organosilicon leveling agent, the structural formula of which is as follows: ;

[0134] The preparation process of the above-mentioned fluorocarbon chain-terminated polyether-modified organic silicone leveling agent differs from that of Example 7 in that step (3) is as follows: 48.22 g of epoxy polyether-modified silicone oil A4, 0.45 g of triphenylphosphine and 14.94 g of fluorocarbon chain intermediate 13 are added to a four-necked flask and stirred evenly. The mixture is heated to 100°C and kept warm for 4 h to react until the acid value of the product is less than 3 mgKOH / g.

[0135] Test example

[0136] PU varnishes were prepared using the products obtained in Examples 1-19 and epoxy polyether-modified silicone oils A1-A4 as leveling agents. The PU varnishes were composed of component A and component B in a ratio of 100:40 by mass. The compositions of components A and B are shown in Table 2. The PU varnishes were sprayed onto the substrate to a film thickness of 30 μm and dried at 80°C for 1 h.

[0137] In the above method, varnishes were prepared using the recipes in Table 2 to test their anti-cratering properties. A 20 x 20 cm tinplate was first degreased with butyl acetate, then sprayed with each varnish from Table 2. After baking at 80°C, a 30 μm dry film was obtained and observed for surface cratering. The formulations in Table 3 were used to test distinctness of image using a BYK orange peel meter. The results are shown in Table 4 below.

[0138] Table 2 Composition of component A and component B

[0139]

[0140] Table 3 Another composition of component A and component B

[0141]

[0142] Table 4 Anti-cratering grade and distinctness of image test results

[0143]

[0144] Remark: a Level 0 is the best, indicating that there are no shrinkage cavities on the board surface; level 1 indicates that there are less than 5 shrinkage cavities on the board surface; level 2 indicates that there are 5-10 shrinkage cavities on the board surface; level 3 indicates that there are 10-15 shrinkage cavities on the board surface; level 4 indicates that there are 15-20 shrinkage cavities on the board surface; and level 5 is the worst, indicating that there are more than 20 shrinkage cavities on the board surface.

[0145] 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 (with less than 4 carbon atoms), it does not help much in preventing shrinkage.

[0146] As shown in Examples 1-3, when the number of fluorocarbon chain-terminated side chains is small (m=2), fluorocarbon chains with fewer carbon atoms (less than 6) do not significantly improve shrinkage crater resistance. However, as the length of the fluorocarbon chain increases, as shown in Examples 4-6, the shrinkage crater resistance level is significantly improved. As shown in Examples 9-10, when the number of fluorocarbon chain-terminated side chains is large (m≥3), shorter fluorocarbon chains can also significantly improve shrinkage crater resistance.

[0147] Referring to Examples 7 and 18, when the fluorine content of the end-capped fluorocarbon chain is similar, the longer the fluorocarbon chain, the better the anti-shrinkage crater performance; referring to Examples 13, 18, and 19, when the length of the end-capped fluorocarbon chain is constant, the higher the fluorine content, the better the anti-shrinkage crater performance.

[0148] It can be seen that fluorocarbon endcapping significantly improves the anti-cratering ability of the silicone leveling agent, while having no significant effect on the distinctness of image of the paint film. For polyether-modified silicone leveling agents that are not fluorocarbon endcapped, the higher the molecular weight of the silicone backbone, the better the anti-cratering performance.

[0149] 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 invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A fluorocarbon chain-terminated polyether-modified silicone leveling agent, characterized in that: Has the following structural formula: ； Where m, n, p, and q are all integers, m = 2 to 10, n = 5 to 50, p = 5 to 50, and q = 0 to 10; R1 is selected from OOCC2H2COO, OOCC2H4COO, 、 or One of the following; R2 is selected from a fluorinated alkyl group. When m=2, the number of carbon atoms in R2 is 6 to 8; when m≥3, the number of carbon atoms in R2 is 4 to 8; The fluorinated alkyl group is selected from one of hexafluorobutanol, octafluoropentanol, nonafluorohexanol, nonafluorooctanol, dodecafluoroheptanol, tridecafluorooctanol or pentafluorooctanol; The polyether is selected from epoxy-terminated allyl polyethers.

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: Hexamethyldisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and a first catalyst are mixed and then heated to react to obtain hydrogen-containing silicone oil; S2: mixing the hydrogenated silicone oil, allyl polyether and the second catalyst and heating the mixture to obtain polyether-modified silicone oil; The structure of the allyl polyether is as follows: , where R' is ; 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 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 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, heating and reacting to obtain the obtained product; The acid anhydride is selected from one of maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

7. 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-raising reaction is raised to 70-100°C, and the insulation time is 3-6 hours; and / or, in step S3, the temperature-raising reaction is raised to 80-120°C, and the insulation time is 4-10 hours.

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

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