Alkoxy-functionalized silsesquioxane resins, and processes for their preparation and use.

Abstract

Alkoxy-functionalized silsesquioxane resins and hydrosilylation reaction processes for their preparation are provided. Alkoxy-functionalized silsesquioxane resins are liquid under ambient conditions and are useful in solvent-based and solvent-free moisture-curable compositions such as coating compositions.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application asserts the interests of U.S. Provisional Patent Application No. 63 / 453,261, filed on March 20, 2023, pursuant to Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 453,261 is incorporated herein by reference.

[0002] (Field of invention) Alkoxy-functionalized silsesquioxane resins and processes for their preparation are provided. Alkoxy-functionalized silsesquioxane resins are useful in moisture-curable compositions suitable for forming coatings. [Background technology]

[0003] The coatings industry faces pressure to reduce the use of volatile organic compounds (VOCs) for more environmentally friendly solutions. Therefore, solvent-free liquid products are desirable to leverage the advantages of silicone resins in high-performance applications. For example, heat-resistant coatings derived from solvent-free, moisture-curable compositions are desirable to replace less desirable solvent-based options. Furthermore, moisture curing is desirable because room-temperature curable compositions are preferred for certain applications.

[0004] Solvent-free liquid silicone resins typically require the use of glass transition resins that operate at inherently lower temperatures, resulting in slower curing times compared to solvent-based coating compositions, which is undesirable for achieving the desired hard coating performance.

[0005] Therefore, there is an industry need to improve the curing speed of moisture-curable compositions containing siloxane resins. [Overview of the Initiative]

[0006] An alkoxy-functional silsesquioxane resin and a method for its preparation are provided. The alkoxy-functional silsesquioxane resin can be incorporated into moisture-curable compositions such as coating compositions.

Mode for Carrying Out the Invention

[0007] The alkoxy-functional silsesquioxane resin has the unit formula: (R 2 3SiO 1 / 2 ) c (R 2 2SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) e (ZO 1 / 2 ) f (HO 1 / 2 ) g and includes, where in the formula, each R 2 is independently selected from the group consisting of an alkyl group and a group of formula (I)

[0008]

Chemical formula

[0009] In the above unit formula, the subscripts c, d, and e represent the molar fractions of each unit in the alkoxy-functional silsesquioxane resin. The amount (c + d + e) = 1. The subscripts c, d, and e have values such that 0 ≤ c ≤ 0.25, 0 ≤ d ≤ 0.20, and 0.55 < e ≤ 1. The subscript c may be 0, or may be greater than ০, or at least 0.100, or at least 0.101, or at least 0.102, or at least 0.110, or at least 0.120, or at least 0.130, while at the same time, the subscript c may be at most 0.300, or at most 0.250, or at most 0.240, or at most 0.200, or at most 0.150, or at most 0.110. The subscript c may be from 0 to 0.300, or from 0 to 0.250, or from 0.100 to 0.240, or from 0.102 to 0.240.

[0010] The subscript d may be 0, or greater than 0, or at least 0.001, or at least 0.002, or at least 0.003, or at least 0.004, or at least 0.005, or at least 0.006, while at the same time, the subscript d may be up to 0.020, or up to 0.015, or up to 0.010, or up to 0.009, or up to 0.008, or up to 0.007, or up to 0.006. Alternatively, the subscript d may be between 0 and 0.020, or greater than 0 and up to 0.015, or between 0.006 and 0.010.

[0011] The subscript e is greater than 0.55 and up to 1. Alternatively, the subscript e may be at least 0.550, or at least 0.600, or at least 0.650, or at least 0.700, or at least 0.750, or at least 0.800, while at the same time, the subscript e may be at most 1, or at most 0.995, or at most 0.991, or at most 0.95, or at most 0.925, or at most 0.920, or at most 0.915, or at most 0.910, or at most 0.905, or at most 0.0900. Alternatively, the subscript e may be between 0.905 and 1, or between 0.910 and 1, or between 0.915 and 1, or between 0.990 and 1, or between 0.991 and 1, or between 0.995 and 1, or the subscript e may be 1.

[0012] In the above unit formula, each Z is an independently selected alkyl group. Suitable alkyl groups may be cyclic or acyclic, branched or unbranched, or a combination thereof. Examples of alkyl groups, though not limited to them, include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, tert-pentyl, and / or cyclopentyl), hexyl (e.g., cyclohexyl or n-hexyl), heptyl, octyl, nonyl, and decyl, as well as branched alkyl groups with six or more carbon atoms. Alternatively, each Z may be an alkyl group with one to four carbon atoms, or one to two carbon atoms. Each Z may be methyl or ethyl, or it may be methyl.

[0013] Unit (HO 1 / 2 ) and (ZO 1 / 2 ) represent a hydroxyl group and an alkoxy group bonded to a silicon atom in the resin, respectively (for example, the hydroxyl group and the alkoxy group are graft-bonded R in formula (I) 2 (The part of the molecule other than the group, bonded to the silicon atom in the resin portion of the alkoxy-functionalized silsesquioxane resin). Although we do not wish to be bound by theory, the hydroxyl group and / or alkoxy group in the formula (R) of the alkoxy-functionalized silsesquioxane resin. 2 3SiO 1 / 2 ) Monofunctional unit, formula (R 2 2SiO 2 / 2 The two functional units of ) and formula (R 2 SiO 3 / 2 It can bond to one or more silicon atoms in the three functional units of ).

[0014] In the above unit formula, each alkyl group R 2 R is independently selected and may be one of the alkyl groups mentioned above for Z. Alternatively, 2 Each alkyl group may be methyl. However, at least some groups R 2It has formula (I) (for example, the result of a hydrosilylation reaction in the method described below). In the unit formula, all R 2 5 mol% to 25 mol% of the group may have formula (I), while all R 2 The residue up to 100% of the group is alkyl. Or, all R 2 At least 5 mol%, or at least 6 mol%, or at least 8 mol%, or at least 9 mol%, or at least 10 mol%, or at least 13 mol%, or at least 14 mol%, or at least 15 mol%, of the group has formula (I), and at the same time, all R 2 Up to 25 mol%, or up to 23 mol%, or up to 20 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, of the group has formula (I). Or, R having formula (I) 2 The amount of the group may be 5 mol% to 25 mol%, 5 mol% to 23 mol%, or 6 mol% to 15 mol%.

[0015] In the above unit formula, the subscript f represents the molar amount of alkoxy groups in the resin, and the subscript g represents the molar amount of hydroxyl groups in the resin. The subscripts f and g have values ​​such that 0.01 ≤ f ≤ 0.70, 0 ≤ g ≤ 0.05, and 0.02 ≤ (f + g) ≤ 0.75. Alternatively, the subscript f may have a value of at least 0.01, or at least 0.10, or at least 0.20, or at least 0.30, while at the same time having a value of up to 0.70, or up to 0.60, or up to 0.56, or up to 0.52. Alternatively, the subscript f may have a value such that 0.10 ≤ f ≤ 0.60, or 0.30 ≤ f ≤ 0.60, or 0.37 ≤ f ≤ 0.56, or 0.37 ≤ f ≤ 0.44. Alternatively, the subscript g may have a value of at least 0.005, or at least 0.008, or at least 0.01, while at the same time having a value of at most 0.05, or at most 0.049, or at most 0.045, or at most 0.040, or at most 0.035. Alternatively, the subscript g may have a value such that 0.005 ≤ g ≤ 0.05, or 0.006 ≤ g ≤ 0.049, or 0.006 ≤ g ≤ 0.035, or 0.008 ≤ g ≤ 0.05. Alternatively, the quantity (f+g) may be at least 0.02, or at least 0.20, or at least 0.30, or at least 0.40, or at least 0.41, or at least 0.43, or at least 0.45, while at the same time, the quantity (f+g) may be at most 0.57, or at most 0.52, or at most 0.49, or at most 0.47, or at most 0.45. Alternatively, the quantity (f+g) may have a value such that 0.02≦(f+g)≦0.57, or 0.20≦(f+g)≦0.57, or 0.30≦(f+g)≦0.57, or 0.40≦(f+g)≦0.57, or 0.43≦(f+g)≦0.52, or 0.40≦(f+g)≦0.49.

[0016] In the basis of equation (I) above, the subscripts a, b, and x each represent an integer. Subscript a is 1 or 2, or subscript a may be 1. Subscript b is 0 or 1, or subscript b may be 0, or subscript b may be 1. Subscript x is 0 or 1, or subscript x may be 0.

[0017] In the base of formula (I) above, each alkyl group R 1 These are independently selected and may be the alkyl groups described above for Z. Alternatively, each R 1 It may also be methyl.

[0018] Under equation (I) above, each D 1 D is an independently selected alkylene group. 1 This is empirical formula -C h H 2h - may have, and the subscript h is at least 2, or 2-12, or 2-10, or 2-8, or 2-6, or 2-4, or 2-3. Or each D 1 This may be ethylene, propylene, butylene, or hexylene. Alternatively, each D 1 This could be -C2H4-, for example, ethylene.

[0019] Alkoxy-functionalized silsesquioxane resins are based on the formula (SiO 4 / 2The alkoxy-functional silsesquioxane resin may or may not contain the tetrafunctional siloxane units. The alkoxy-functional silsesquioxane resin is in a liquid state at RT and ambient pressure (e.g., 101.325 kPa) (e.g., by visual inspection). Alternatively, the alkoxy-functional silsesquioxane resin may have Mn in the range of 1,300 g / mol to 4,000 g / mol, or 1,400 g / mol to 3,500 g / mol, or 2,000 g / mol to 2,500 g / mol. Alternatively, the alkoxy-functionalized silsesquioxane resin may have an Mw of 1,000 g / mol to 50,000 g / mol, or 2,000 g / mol to 50,000 g / mol, or 2,500 g / mol to 40,000 g / mol, or 4,000 to 10,000 g / mol, or 1,000 g / mol to 15,000 g / mol, and a PDI of 2 to 4, or 2.3 to 3.9.

[0020] Method for preparing resin The alkoxy-functional silsesquioxane resin described above may be prepared by a hydrosilylation reaction process. This process involves 1) combining starting materials, A) an alkoxy-functional organosilicon compound and B) a silsesquioxane resin, under conditions for hydrosilylation, in the presence of C) a hydrosilylation catalyst. A solvent D) may be optionally used to facilitate the mixing and / or transfer of one or more of the starting materials. For example, C) the hydrosilylation catalyst may be dissolved or dispersed in solvent D) before being combined with starting materials A) and B). Starting material A) the alkoxy-functional organosilicon compound may contain silicon-bonded hydrogen atoms if B) the silsesquioxane resin contains silicon-bonded aliphatic unsaturated groups. Alternatively, A) the alkoxy-functional organosilicon compound may contain aliphatic unsaturated groups if B) the silsesquioxane resin contains silicon-bonded hydrogen atoms.

[0021] The starting material C) is a hydrosilylation catalyst. The hydrosilylation catalyst contains a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation catalyst may be a platinum group metal or a compound or complex of a platinum group metal. For example, the hydrosilylation catalyst may be a rhodium diphosphine chelate such as chloride tris(triphenylphosphane)rhodium(I) (Wilkinson catalyst), [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an alkenyl-functional organopolysiloxane, such as a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum (Karstedt catalyst), or a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby catalyst). Alternatively, the compound or complex may be microencapsulated in a matrix or core-shell structure. Hydrosilylation catalysts are known in the art, for example, as described in International Publication No. 2021 / 081822 to Guo, et al. and the references cited therein. Hydrosilylation catalysts are commercially available, for example, SYL-OFF® 4000 Catalyst and SYL-OFF® 2700 are available from Dow. C) The amount of hydrosilylation catalyst depends on various factors, including the type and amount of starting materials A) and B), and the respective content of silicon-bonded hydrogen atoms and aliphatic unsaturated groups, but C) the amount of hydrosilylation catalyst is sufficient to catalyze the hydrosilylation reaction, for example, to provide at least 1 ppm of platinum group metal based on the combined weight of starting materials A), B), and C), while at the same time, the amount may be sufficient to provide up to 6,000 ppm of platinum group metal on the same basis.Alternatively, the amount of starting material C) may be sufficient to provide platinum group metals in the same range, such as 1 ppm to 1,000 ppm, 1 ppm to 100 ppm, 1 ppm to 50 ppm, 1 ppm to 25 ppm, or 1 ppm to 15 ppm.

[0022] Starting material D) is an optional solvent that can be used to transport one or more of the starting materials. The solvent may be added to facilitate the introduction of certain starting materials, such as C) a hydrosilylation catalyst. The solvents that can be used herein are those that help to fluidize the starting materials but do not react with them in nature. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility means that the solvent is sufficient to dissolve and / or disperse the starting materials. Volatility means the vapor pressure of the solvent.

[0023] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as polydimethylsiloxane, for example, DOWSIL® 200 Fluids and DOWSIL® OS Fluids (commercially available from Dow) with a vapor pressure of 0.5 to 1.5 cSt.

[0024] Alternatively, the solvent may include an organic solvent. The organic solvent may be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; or a combination thereof.

[0025] D) The amount of solvent varies depending on various factors, including the type of solvent selected, as well as the amount and type of other starting materials selected for the composition. However, the amount of solvent may range from 1% to 99% by weight, or from 2% to 90% by weight, based on the combined weight of starting materials A), B), and C).

[0026] The hydrosilylation reaction process can be carried out by any convenient means, such as combining starting materials A), B), and C), and D) if present. Typically, starting materials A) and B) are combined in a reactor. When the reaction is carried out at high or low temperatures, as described below, the reactor may be heated or cooled in any preferred manner, for example, via a jacket, mantle, exchanger, bath, or coil. Starting materials A), B), and C), and optionally D), may be supplied together or separately in a vessel, or arranged in the vessel in any order of addition and in any combination. For example, starting materials A) and C), and optionally D), may be added to the reactor, and starting material B), may be added to it in one aliquot, or starting material B), may be metered into the reactor continuously or intermittently in two or more aliquots. Alternatively, starting materials B) and C), and optionally D), may be added to the reactor, and starting material A) may be added to it in one aliquot, or starting material A) may be metered into the reactor continuously or intermittently in two or more aliquots. The order of addition may vary depending on various factors, including which starting materials have silicon-bonded hydrogen atoms.

[0027] Alternatively, the starting materials A), B), and optionally D) may first be combined before addition, or added sequentially to the container, after which starting material C) may be added to the container containing starting materials A), B), and optionally D). Generally, the term "reaction mixture" as used herein generally refers to a mixture containing starting materials A), B), and C), and optionally D) (for example, one obtained by combining the starting materials as described above).

[0028] The amounts of starting materials A) and B) are not limited and may be any amount sufficient to provide the content of the group of formula (I) in the alkoxy-functionalized silsesquioxane resin described above.

[0029] Step 1 of the process may further include stirring the reaction mixture. Stirring can enhance the mixing and contact of the starting materials A), B), and C), and D), if present, when combined in the reaction mixture. Such contact can also be carried out independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), using other conditions. Other conditions may be adjusted to enhance the contact of starting materials A) and B) for the formation of a reaction product containing an organosilicon compound, and thus enhance the reaction (i.e., isomerization and hydrosilylation).

[0030] Step 1 of the process may further include heating the reaction mixture. The temperature may be between 50°C and 150°C, or between 60°C and 100°C, although this depends on various factors including the vapor pressures of the starting materials A) and B), and D) if present.

[0031] The processes described herein may optionally further include one or more additional steps. For example, the process may further include step 2) purifying the hydrosilylation reaction product to remove and / or recover, for example, unreacted starting materials. Purification may be carried out by any convenient means such as stripping and / or distillation and / or azeotrope with a solvent, filtration, and combinations thereof, while heating and optionally under reduced pressure. Distillation conditions typically include: (i) high temperature; (ii) reduced pressure; or (iii) both high temperature and reduced pressure. High or reduced is in relation to room temperature and atmospheric pressure. Distillation may be continuous or batch and may involve the use of a solvent (e.g., hexane, toluene, or other solvents described herein as starting material D) so that the distillation may be azeotropic distillation.

[0032] As used herein, purification of a hydrosilylation reaction product is typically defined as increasing the relative concentration of the alkoxy-functionalized silsesquioxane resin compared to other compounds combined with it (e.g., in the hydrosilylation reaction product or in its purified form). As understood in the art, purification may include removing other compounds from such combinations (i.e., reducing the amount of impurities and / or unreacted starting materials combined with the alkoxy-functionalized silsesquioxane resin in the hydrosilylation reaction product) and / or removing the alkoxy-functionalized silsesquioxane resin itself from the combination. Any suitable technique and / or protocol for purification may be used. Examples of suitable purification techniques include distillation, stripping / evaporating, extraction, filtration, washing, partitioning, phase separation, adsorption, and chromatography. As understood by those skilled in the art, any of these techniques may be used in combination (e.g., sequentially) with any other technique to purify the hydrosilylation reaction product. Regardless of the specific technique selected, the purification of the hydrosilylation reaction product may be carried out sequentially (i.e., in a line) with the hydrosilylation reaction itself, and therefore may be automated. Alternatively, the purification may be an independent procedure applied to the hydrosilylation reaction product containing the organosilicon compound.

[0033] For example, if A) an alkoxy-functional organosilicon compound has a silicon-bonded hydrogen atom, and B) the silsesquioxane resin has an aliphatic unsaturated group, the process for preparing the above-mentioned alkoxy-functional silsesquioxane resin is: 1) Under the conditions necessary for carrying out the hydrosilylation reaction, A1) Formula:

[0034] [ka] Alkoxy-functional organohydrogensiloxane oligomers (wherein R in the formula) 1 , D 1(, a, and x are as described above), and B1) Unit formula (R 3 3SiO 1 / 2 ) c (R 3 2SiO 2 / 2 ) d (R 3 SiO 3 / 2 ) e (ZO 1 / 2 ) f (HO 1 / 2 )g alkenyl-functionalized silsesquioxane resin (wherein Z, c, d, e, f, and g are as described above, Each R 3 However, independently selected from the group consisting of alkyl groups and alkenyl groups, However, at least one R per molecule 3 However, the starting material contains an alkenyl group. In the presence of the hydrosilylation reaction catalyst C) mentioned above, This may optionally include combining the solvents in the presence of solvent D) as described above. Optional additional steps are as described above.

[0035] Starting material A1) is given by formula: A1)

[0036] [ka] The alkoxy-functional organohydrogensiloxane oligomer is an alkoxy-functional organohydrogensiloxane oligomer, in which R 1 , D 1 A, a, and x are as described above. Alternatively, the alkoxy-functional organohydrogensiloxane oligomer may have subscripts a=1 and x=0. Alternatively, in the formula of A1) alkoxy-functional organohydrogensiloxane oligomer, each R 1 =methyl, each D 1It may have the empirical formula -C2H4-. Alternatively, the alkoxy-functional organohydrogensiloxane oligomer may be trimethoxysilylethyl-1,1,3,3,5,5-hexamethyltrisiloxane, trimethoxysilylethyl-1,1,3,3-tetramethyldisiloxane, or a combination thereof. The alkoxy-functional organohydrogensiloxane oligomers of the above formulas are known in the art and can be prepared by known methods, such as those described in U.S. Patent No. 10,968,317 for Gohndrone, et al., No. 11,098,163 for Gohndrone, et al., No. 11,161,939 for Zhou, et al., No. 11,168,181 for Zhou, et al., and No. 11,492,448 for Gohndrone, et al., and Japanese Patent Application Publication No. 2007077136 for Uehara, et al.

[0037] Starting material B1) has the unit formula (R 3 3SiO 1 / 2 ) c (R 3 2SiO 2 / 2 ) d (R 3 SiO 3 / 2 ) e (ZO 1 / 2 ) f The silsesquioxane resin is an alkenyl-functionalized silsesquioxane resin, where Z, c, d, e, and f are as described above, and each R 3 However, the group consisting of alkyl groups and alkenyl groups capable of undergoing hydrosilylation reactions is independently selected, provided that at least one R is present per molecule. 3 However, it is an alkenyl group. Suitable examples of alkenyl groups may have 2 to 12, 2 to 10, 2 to 8, or 2 to 6 carbon atoms. The alkenyl group can undergo hydrosilylation reactions with silicon-bonded hydrogen atoms. 3 Suitable alkenyl groups include vinyl, allyl, and hexenyl, or vinyl and hexenyl, or vinyl.

[0038] The starting material B1) can be prepared by known methods, for example, by co-hydrolyzing an organosilane having three hydrolyzable moieties (e.g., halogen or alkoxy) per molecule bonded to a silicon atom. For example, starting material B1) can be prepared by the process described in U.S. Patent No. 11,248,119, by varying the starting materials and their amounts. Starting material B1) can be obtained, for example, by co-hydrolyzing methyltrimethoxysilane and vinyltrimethoxysilane, optionally together with additional silanes such as octyltriethoxysilane and octyltrimethoxysilane. Alkoxysilanes having two alkoxy groups per molecule or one alkoxy group per molecule, such as dimethyldimethoxysilane or trimethylmethoxysilane, may be included to add bifunctional and / or monofunctional siloxane units to the silsesquioxane resin, respectively. An acid catalyst such as trifluorophosphoric acid, water, and / or alcohol can be used to promote the co-hydrolysis.

[0039] Alternatively, when A) the alkoxy-functional organic silicon compound has an aliphatic unsaturated group and B) the silsesquioxane resin has a silicon-bonded hydrogen atom, the process for preparing the above-mentioned alkoxy-functional silsesquioxane resin is 1) under the conditions for carrying out the hydrosilylation reaction, A2) an alkoxy-functional organic silicon compound of the formula R 1 x R 5 Si(OR 1 ) 3-x (wherein R 1 and x are as defined above, and R 5 is an alkenyl group capable of undergoing a hydrosilylation reaction) and B2) the unit formula (R 4 3SiO 1 / 2 ) c (R 4 2SiO 2 / 2 ) d (R 4 SiO3 / 2 ) e (ZO 1 / 2 ) f hydridofunctional silsesquioxane resin of wherein Z, c, d, e, and f are as described above, and each R 4 is independently selected from the group consisting of an alkyl group and H, provided that at least one R 4 per molecule is H), and a starting material containing the same is combined in the presence of the above-mentioned C) hydrosilylation reaction catalyst optionally in the presence of the above-mentioned D) solvent.

[0040] Starting material A2) is an alkoxy-functional organic silicon compound and has at least one alkenyl group per molecule. The alkoxy-functional organic silicon compound may be an alkoxysilane of the formula R 1 x R 5 Si(OR 1 ) 3-x wherein R 1 and x are as described above, and R 5 is an alkenyl group capable of undergoing a hydrosilylation reaction. Examples of suitable alkenyl groups may have 2 to 12, or 2 to 10, or 2 to 8, or 2 to 6 carbon atoms. It may have. The alkenyl group can undergo a hydrosilylation reaction with a silicon-bonded hydrogen atom. R 5Suitable alkenyl groups are exemplified by vinyl, allyl, and hexenyl, or by vinyl and hexenyl, or by vinyl. Suitable alkoxy-functional silanes for starting material A2) are known in the art and commercially available. For example, alkenyl-functional trialkoxysilanes such as allyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and vinyltris(methoxyethoxy)silane; alkenyl-functional dialkoxysilanes such as vinylphenyldiethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; and alkenyl-functional monoalkoxysilanes such as trivinylmethoxysilane are all available from Gelest, Inc. in Morrisville, Pennsylvania, USA.

[0041] Starting material B2) has the unit formula (R 4 3SiO 1 / 2 ) c (R 4 2SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (ZO 1 / 2 ) f The hydride-functionalized silsesquioxane resin, in which Z, c, d, e, and f are as described above, and each R 4 However, the R is independently selected from the group consisting of alkyl groups and H, provided that there is at least one R per molecule. 4 However, it is H. Starting material B2) can be prepared by known methods such as those described above for starting material B1) by substituting an alkenyl-functionalized alkoxysilane with a suitable starting material such as a hydride-functionalized alkoxysilane. For example, starting material B2) can be prepared by changing the starting material and its amount by the process described in U.S. Patent No. 11,248,119.

[0042] The products of these processes are the alkoxy-functionalized silsesquioxane resins described above. These alkoxy-functionalized silsesquioxane resins are useful in curable compositions, such as coating compositions, including conformal coating compositions.

[0043] Moisture-curing composition The alkoxy-functionalized silsesquioxane resins prepared as described above can be used in moisture-curable compositions such as coating compositions. For example, the alkoxy-functionalized silsesquioxane resins described herein can be used in moisture-curable (polyorganosiloxane) compositions for electrical / electronic devices, such as those described in U.S. Patent Application Publication No. 2021 / 0238444, where the alkoxy-functionalized silsesquioxane resins described herein are used in addition to or instead of the resin described in U.S. Patent Application Publication No. 2021 / 0238444.

[0044] The moisture-curable composition may include I) the alkoxy-functionalized silsesquioxane resin described above, and II) a condensation reaction catalyst.

[0045] The starting material II) is a condensation catalyst. Examples of II) condensation catalysts include, but are not limited to, tin compounds such as dimethyltin dineodecanoate and tin octanoate; and titanium compounds such as tetra(isopropoxy)titanium; organotitanium chelates such as tetra(n-butoxy)titanium and tetra(t-butoxy)titanium; and di(isopropoxy)bis(ethylacetate)titanium; di(isopropoxy)bis(methylacetate)titanium; di(isopropoxy)bis(acetylacetonate)titanium; and bis(ethylacetate-O1',O3")bis(propane-2-olate)titanium. Condensation catalysts are known and commercially available in the art. For example, organotitanates and zirconates are commercially available from Dorf Ketal under the trade name TYZOR®.

[0046] The content of starting material II) is not limited as long as it is an amount that can impart sufficient curability to the moisture-curable composition. For example, the content of starting material II) may be 0.01 to 20 parts by weight, or 0.01 to 15 parts by weight, or 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight, or 0.01 to 1 part by weight, or 0.05 to 10 parts by weight, or 0.05 to 5 parts by weight, based on 100 parts by weight of the combined content of starting materials I) and II). Although we do not wish to be bound by theory, it is thought that if the content of condensation reaction catalyst II) is above the lower limit of the above range, the resulting composition will cure sufficiently with moisture in the air, and if the content is below the upper limit of the above range, the surface curing rate of the resulting composition may be improved.

[0047] The moisture-curable composition may optionally further comprise one or more additional starting materials (i.e., in addition to I) an alkoxy-functionalized silsesquioxane resin and II) the condensation reaction catalyst described above). For example, the composition may further comprise III) a solvent, IV) an alkoxysilane, V) a fluorescent whitening agent and / or a UV indicator, VI) a rust inhibitor, VII) a chelating agent, VIII) an adhesion promoter, and IX) at least one of two or more combinations of III) to VIII).

[0048] Starting material III) is a solvent, which may be the solvent described above for starting material D). Alternatively, suitable solvents for use in moisture-curable compositions include, but are not limited to, aliphatic hydrocarbon solvents such as heptane, octane, nonane, decane, and undecane; and siloxane solvents such as linear dimethylsiloxane oligomers (described above), cyclic dimethylsiloxane oligomers, and tetrakis(trimethylsiloxy)silane.

[0049] III) The solvent content is not limited as long as it is an amount that improves the coating performance of the resulting moisture-curable composition. If present, the solvent content III) may be 0.1 to 50 parts by weight, or 0.1 to 30 parts by weight, or 0.1 to 20 parts by weight, or 0.1 to 15 parts by weight, or 0.1 to 10 parts by weight, relative to 100 parts by weight, based on 100 parts by weight of the combined content of starting materials I) and II). Alternatively, the moisture-curable composition may be substantially free of organic solvents. As used herein, “substantially free of organic solvents” means that organic solvents are not intentionally added to the moisture-curable composition, but this does not exclude residual solvents present in one or more of the other starting materials used in the moisture-curable composition. For example, the moisture-curable composition may not contain organic solvents. Alternatively, the moisture-curable composition may contain an amount of organic solvent that is undetectable by gas chromatography. Alternatively, the moisture-curable composition may contain up to 100 ppm of organic solvents remaining in the starting materials used to prepare the moisture-curable composition.

[0050] Starting material IV) is given by the general formula: R 6 i Si(OR 7 ) (4-i) It is an alkoxysilane which may be represented by the formula, where R 6 It is a monovalent hydrocarbon group, R 7 R is an alkyl group, and the subscript i is an integer. In the formula for alkoxysilanes, R 6 This is a monovalent hydrocarbon group. Examples of such groups include, but are not limited to, alkyl groups such as those mentioned above for Z; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and octadecenyl; and aryl groups such as phenyl, tolyl, xylyl, naphthyl, benzyl, phenethyl, and phenylpropyl. Alternatively, each R 6 R can be independently selected from alkyl or alkenyl groups. Alternatively, each R 6R can be independently selected from methyl or vinyl. 7 This is an independently selected alkyl group. Examples of such groups include alkyl groups such as those mentioned above for Z. Alternatively, each R 7 The element may be independently selected from methyl or ethyl. The subscript i is an integer with a value between 0 and 2, or 1 or 2.

[0051] IV) Examples of alkoxysilanes include, but are not limited to, dimethyldimethoxysilane, methyltrimethoxysilane, methylphenyldimethoxysilane, and dimethyldiethoxysilane. Starting material IV) may be one or more of these alkoxysilanes in combination. Alternatively, starting material IV) may contain, or be composed of, dimethyldimethoxysilane and / or methyltrimethoxysilane. Such alkoxysilanes are known in the art and are commercially available as described above with respect to starting materials B1) and B2). Alternatively, alkoxysilanes and condensation catalysts may be commercially available as moisture-curing packages, such as under the trade name TYZOR® from Dorf Ketal.

[0052] IV) The content of alkoxysilane is not limited as long as it is an amount that can impart a sufficient shelf life to the resulting composition. Alternatively, the content of IV) alkoxysilane may be 0.5 to 20 parts by weight, or 1 to 20 parts by weight, or 1 to 15 parts by weight, or 0.5 to 10 parts by weight, based on 100 parts by weight of the combined content of starting materials I) and II). Although we do not wish to be bound by theory, if the content of IV) alkoxysilane is above the lower limit of the above range, the resulting moisture-curable composition will cure rapidly with moisture in the air, and if the content is below the upper limit of the above range, the curability of the resulting moisture-curable composition will be sufficient, and the shelf life of the composition under moisture barrier conditions will be improved.

[0053] Starting material V) is a fluorescent whitening agent and / or UV indicator, which may be a molecule that fluoresces under light irradiation at 365 nm and / or 405 nm. Examples of fluorescent whitening agents include, but are not limited to, benzoxazole derivatives such as 2,5-bis(benzo[d]oxazole-2-yl)thiophene derivatives, for example, 2,5-bis(5-(tert-butyl)benzo[d]oxazole-2-yl)thiophene, marketed under the trade name TINOPAL OB by BASF; diaminostilbenn-disulfonates such as the disodium salt of 4,4'-bis-(2-morpholino-4anilino-s-triazine-6-ylamino)stilbenndisulfonate, marketed under the trade name Tinopal DMS by Ciba-Geigy AG; and bisphenyl-distyrill derivatives such as the disodium salt of 2,2'-bis-(phenyl-styryl)disulfonate, marketed under the trade name Tinopal CBS by Ciba-Geigy AG, as well as diarylpyrazoline derivatives. An exemplary 2,5-bis(benzo[d]oxazole-2-yl)thiophene derivative has the general formula:

[0054] [ka] It may have, in the formula, each R 8 It is independently selected from the group consisting of H and alkyl groups with 1 to 30 carbon atoms.

[0055] The content of starting material V) in the moisture-curable composition is not limited, as long as the amount is such that the visibility of the coating prepared with the moisture-curable composition is improved under UV light exposure compared to a coating made with the same moisture-curable composition except that starting material V) is omitted. For example, the content of starting material V) may be 0.001 to 0.1 parts by weight, or 0.005 to 0.1 parts by weight, or 0.005 to 0.05 parts by weight, or 0.005 to 0.05 parts by weight, based on 100 parts by weight of the combined content of starting materials I) and II).

[0056] Starting material VI) is a rust inhibitor. Examples of rust inhibitors include, but are not limited to, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, benzotriazole, tolyltriazole, carboxybenzotriazole, 1H-benzotriazole-5-methylcarboxylate, 3 -amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, chlorobenzotriazole, nitrobenzotriazole, aminobenzotriazole, cyclohexano[1,2-d]triazole, 4,5,6,7-tetrahydroxytolyltriazole, 1-hydroxybenzotriazole, ethylbenzotriazole, naphthotriazole, 1-N,N-bis(2-ethylhexyl)-[(1,2,4-triazole-1-yl) [methylamine]amine, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]tolyltriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]carboxybenzotriazole, 1-[N,N-bis(2-hydroxyethyl)-aminomethyl]benzotriazole, 1-[N,N-bis(2-hydroxyethyl)-aminomethyl]tolyltriazole, 1-[N,N-bis(2-hydroxyethyl)-aminomethyl]carboxybenzotriazole 1-[N,N-bis(2-hydroxypropyl)aminomethyl]carboxybenzotriazole, 1-[N,N-bis(1-butyl)aminomethyl]carboxybenzotriazole, 1-[N,N-bis(1-octyl)aminomethyl]carboxybenzotriazole, 1-(2',3'-di-hydroxypropyl)benzotriazole, 1-(2',3'-di-carboxyethyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',Examples include 5'-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 1-hydroxybenzotriazole-6-carboxylic acid, 1-oleoylbenzotriazole, 1,2,4-triazole-3-ol, 5-amino-3-mercapto-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 1,2,4-triazole-3-carboxamide, 4-aminourazole, and 1,2,4-triazole-5-one.

[0057] The amount of rust inhibitor is not limited as long as it is sufficient to suppress corrosion of the substrate covered with the cured product of the resulting moisture-curable composition. The amount of rust inhibitor may be 0.01 ppm to about 3% by weight of the composition.

[0058] Starting material VII) is a chelating agent. Examples of chelating agents include, but are not limited to, α-substituted acetoacetates such as methyl acetoacetate and ethyl acetoacetate. The content of the chelating agent is not limited as long as it is sufficient to impart sufficient stability to the resulting moisture-curable composition. For example, the content of the chelating agent may be 0.01 to 20 parts by mass, or 0.01 to 15 parts by mass, per 100 parts by weight of the total amount of starting materials I) and II).

[0059] Starting material VIII) is an adhesion promoter. Examples of adhesion promoters include, but are not limited to, epoxy group-containing alkoxysilanes such as 3-glycidoxytrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 4-oxysilanylbutyltrimethoxysilane; acrylic group-containing alkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; amino group-containing alkoxysilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; and reaction mixtures of the above epoxy group-containing alkoxysilanes and the above amino group-containing alkoxysilanes. Alternatively, the adhesion promoter includes, or is selected from, a reaction mixture of the epoxy group-containing alkoxysilane and the amino group-containing alkoxysilane described above. Adhesion promoters are known in the art and are commercially available, such as DOWSIL® Z-6011 Silane, DOWSIL® Z-6121 Silane, DOWSIL® Z-6137 Silane, XIAMETER® OFS-6011 Silane, and XIAMETER® OFS-6610 Silane, all of which are available from Dow.

[0060] The content of the adhesion promoter in the moisture-curable composition is not limited as long as it is an amount that can impart sufficient adhesion to the various substrates that the composition comes into contact with during curing. For example, the content of the adhesion promoter may be 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight, based on 100 parts by weight of the combined content of starting materials I) and II).

[0061] A moisture-curable composition may be prepared by any convenient means, such as mixing, in the above amounts, a starting material comprising I) an alkoxy-functionalized silsesquioxane resin and II) a condensation reaction catalyst, along with any optional additional starting materials, at RT. The starting materials may be combined and mixed in any order. In a one-component composition, the starting materials may be mixed under anhydrous conditions. Alternatively, the moisture-curable composition may be prepared as a multi-component kit, such as a two-component kit. For example, a two-component kit may include a base portion and a curing agent portion, and optionally, instructions for mixing the base portion and curing agent portion before use. The base portion may comprise I) an alkoxy-functionalized silsesquioxane resin and one or more of the additional starting materials. The curing agent portion may comprise II) a condensation reaction catalyst and one or more of the additional starting materials, such as IV) an alkoxysilane. The base portion and the curing agent portion may each be prepared by any convenient means under anhydrous or ambient conditions. The base and hardener components can be combined immediately before use by any convenient means, such as mixing. The base and hardener components can be combined in a relative ratio of base:hardener ranging from 1:1 to 10:1.

[0062] The apparatus used for mixing the starting materials for a moisture-curable composition is not particularly limited. Examples of suitable mixing apparatus may be selected depending on the type and amount of each starting material chosen. For example, a stirring batch kettle may be used for relatively low-viscosity compositions. Alternatively, a continuous kneading apparatus, such as an extruder including a twin-screw extruder, may be used for more viscous compositions. Exemplary methods that may be used to prepare the moisture-curable compositions described herein are disclosed in U.S. Patent Applications Publication Nos. 2009 / 0291238 and 2008 / 0300358.

[0063] A method for preparing a moisture-curable film is provided. The method for preparing the film includes applying a moisture-curable composition to a substrate. The method further includes forming a film on the substrate.

[0064] There may be various methods for applying moisture-curing properties to a substrate. For example, the step of applying the moisture-curing composition to the substrate may be performed using a wet coating method. Specific examples of wet coating methods suitable for this method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, inkjet printing, and combinations thereof.

[0065] The substrate is not limited and may be any material, may be continuous or discontinuous, and may have any size, shape, dimensions, and surface roughness. In certain embodiments, the substrate includes plastic, which may be thermosetting and / or thermoplastic. However, the substrate may also be glass, metal, paper, wood, silicone, or other materials, or a combination thereof. Alternatively, the substrate may be all or part of an electrical / electronic device.

[0066] Typically, the process involves applying a moisture-curable composition to a substrate to create a wet film on the substrate, and forming a wet film on the substrate involves drying the wet film on the substrate to form a film. For example, drying the wet film may optionally include (i) evaporating the solvent from the wet film (if a solvent is present), optionally (ii) exposing the wet film to a high temperature to expel the solvent (if a solvent is present), and (iii) curing the wet film. Curing of the wet film may occur via exposure to atmospheric moisture. While we do not wish to be bound by theory, it is conceivable that alkoxy groups from alkoxy-functionalized silsesquioxane resins may react (e.g., cure) such that the film is a reaction product of the alkoxy-functionalized silsesquioxane resin and optionally one or more additional starting materials in the moisture-curable composition.

[0067] The film may be separable from the substrate (e.g., peelable) or may be chemically and / or physically bonded to the substrate. The substrate may be subjected to a single-piece hot plate or a single-piece or separate furnace for drying / curing the deposit. The substrate may optionally have a continuous or discontinuous shape, size, dimensions, surface roughness, and other properties. Alternatively, the substrate may have a high softening point temperature. However, moisture-curable compositions and methods are not limited in this way.

[0068] Typically, film formation involves exposing a wet film to a high temperature for a certain period of time. The high temperature is typically 50°C to 250°C, or 100°C to 200°C, or 110°C to 190°C, or 120°C to 180°C, or 130°C to 170°C, or 140°C to 160°C, or 145°C to 155°C. This time is typically sufficient to allow the alkoxy-functionalized silsesquioxane resin to dry and / or cure, or at least cure (e.g., crosslink). This time may be greater than 0 hours and up to 10 hours, or greater than 0 hours and up to 5 hours, or greater than 0 hours and up to 2 hours. This time may be divided into drying / curing cycles (e.g., first curing and post-curing), where the first curing is, for example, 1 hour, and the post-curing is, for example, 1 hour. The high temperature may be independently selected in such cycles, or may be the same in each cycle. Alternatively, the film may be formed by simply exposing the wet film to ambient conditions, that is, by drying it at RT in the presence of atmospheric moisture and without any high temperatures.

[0069] The film may also be formed by a repeating process, depending on the film thickness and other dimensions. For example, a first deposit may be formed and optionally exposed to a first high temperature for a first time to obtain a partially dried and / or hardened deposit. Then, a second deposit may be placed on top of the first deposit, or the deposit may be partially dried and / or hardened and optionally exposed to a second high temperature for a second time to obtain a second partially dried and / or hardened deposit. This process may be repeated, for example, 1 to 50 times to construct the film as desired. Each high temperature and time may be selected independently, may be the same as or different from each other. The repeating process may be wet-on-wet. Alternatively, the repeating process may be wet-on-dry, depending on the drying / hardening state of the partially dried and / or hardened deposits.

[0070] The film may have a variety of thicknesses depending on its end application. Typically, the film may have a thickness greater than 0 μm and up to 4,000 μm, or greater than 0 μm and up to 3,000 μm, or greater than 0 μm and up to 2,000 μm, or greater than 0 μm and up to 1,000 μm, or greater than 0 μm and up to 500 μm, or greater than 0 μm and up to 250 μm, or greater than 0 μm and up to 100 μm, or 1 to 50 μm, or 20 to 30 μm. However, other thicknesses, such as 0.1 to 200 μm, are also expected. For example, the film thickness may be any one of the following: 0.2-175 μm; 0.5-150 μm; 0.75-100 μm; 1-75 μm; 2-60 μm; 3-50 μm; 4-40 μm; or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 150, 175, and 200 μm.

[0071] Regardless of the method by which the film is formed, once the film is formed on a substrate from an emulsion and / or composition, the film may undergo further post-treatment such as heating, humidification, catalytic post-treatment, light irradiation, or electron beam irradiation.

[0072] If desired, the film may be subjected to further processing depending on its end use. For example, the film may be subjected to oxide deposition (e.g., SiO2 deposition), resist deposition and patterning, etching, chemical stripping or plasma stripping, metal coating, or metal deposition. Such further processing techniques are generally known. Such deposition may be chemical vapor deposition (low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and plasma-assisted chemical vapor deposition, etc.), physical vapor deposition, or other vacuum vapor deposition techniques. Many such further processing techniques involve high temperatures, especially vacuum vapor deposition, and given the excellent thermal stability, the film is well suited to these. However, depending on the end use of the film, it may be used without such further processing.

[0073] Alternatively, the substrate may include an electrical / electronic device. A coated electrical / electronic device may be obtained by using the moisture-curing composition described above. The electrical / electronic device is not particularly limited, but is exemplified by an electrical / electronic device comprising an electrical circuit and / or electrodes. Such a coated electrical / electronic device is considered to have good or excellent reliability due to good or excellent adhesion to the substrate in contact with it during the curing of the moisture-curing composition, and / or good or excellent thermal shock stability. [Examples]

[0074] The following examples are provided to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are shown in Table 1 below.

[0075] [Table 1]

[0076] In this Reference Example 1, a sample of vinyl-functionalized silsesquioxane resin was prepared as follows: A 1000 mL three-necked flask was fitted with a magnetic stirring rod, a water-cooled condenser, a thermocouple, and a nitrogen blanket. The following starting materials were placed in the flask: 1) Methoxysilane in the amounts shown in Table 2 below, followed by triflic acid in the amounts shown in Table 2 below. The amount of DI water shown in Table 2 below was slowly added to the flask, starting with a rotary evaporator (RT). Exothermic reaction up to 64°C was observed. The contents of the flask were then heated at 65°C for 2 hours. A certain amount of methanol was removed by distillation using a Dean-Stark apparatus. The contents of the flask were cooled to 50°C, and triflic acid was neutralized by adding CaCO3. The contents of the flask were mixed overnight in a rotary evaporator. The resulting product was stripped under reduced pressure of 4 mmHg using a rotary evaporator heated in an oil bath at 80°C. Next, the flask contents were cooled to RT and pressure filtered through a 47 mm diameter Magna nylon-supported plain 0.45 μm filter. Vinyl-functionalized silsesquioxane resin was produced.

[0077] In this Reference Example 2, samples of vinyl-functionalized MDT resin were prepared as described above in Reference Example 1, except that octyltriethoxysilane and tetramethyldisiloxane were added. Samples CE2 and CE4 were prepared by this method. These samples are summarized in Table 3 below.

[0078] In this Reference Example 3, a sample of hydride-functionalized silsesquioxane resin was prepared as follows. A thermocouple, a Teflon stirring paddle attached to a glass stirring rod, a Dean Stark apparatus attached to a water-cooled condenser, and a nitrogen blanket were attached to a 1 L three-necked flask. The following starting materials were placed in the flask. Methoxysilane in the amounts shown in Table 2 was added, followed by triflic acid in the amounts shown in Table 2. The amount of DI water shown in Table 2 was slowly added to the flask, starting at RT. Exothermic reaction was observed up to 58°C. The contents of the flask were then heated at 65°C for 30 minutes. A certain amount of methanol was removed using the Dean Stark apparatus. Tetramethyldisiloxane was added to the flask, followed by DI water in the amounts shown in Table 4. The contents of the flask were heated at 55°C for 3 hours. The temperature inside the flask was then raised to 70°C and methanol was removed by distillation. The amount removed was 77 g. Triflic acid was neutralized by adding CaCO3. The flask contents were mixed overnight in RT. The resulting product was stripped under reduced pressure of 3 mmHg using a rotary evaporator heated in an oil bath at 80°C. The flask contents were then cooled to RT and pressure filtered through a 47 mm diameter Magna nylon-supported plain 0.45 μm filter. Vinyl-functionalized silsesquioxane resins were prepared. CE5 and CE6 were prepared using this process. CE6 used different ratios of starting materials than CE5. These samples are summarized in Table 4 below.

[0079] In this Reference Example 4, a sample of octyl-functionalized DT resin was prepared as follows. The same apparatus as in Reference Example 1 was used. Methyltrimethoxysilane (355 g), octyltriethoxysilane (41 g), and D4 cyclic compound (18 g) were added to the flask. Triflic acid (0.21 g) was then added, followed by the slow addition of DI water (71 g), starting at room temperature. Exothermic reaction was observed up to 64°C, after which the flask contents were heated at 65°C for 2 hours. Some alcohol (methanol and ethanol) was removed using a Dean-Stark apparatus. The amount removed was 213 g. Next, n-heptane (144 g) was added, followed by calcium carbonate (0.83 g) to neutralize the triflic acid. The flask contents were mixed for 1 hour while cooling. The volatile matter was removed by distillation to a vapor temperature of 98°C. The amount removed was 91 g. The obtained product was filtered through a 47 mm diameter Magna nylon-supported plain 0.45 μm filter. The resulting resin was stripped at 1–2 mmHg using a rotary evaporator heated in an oil bath at 80°C. CE8 and CE9 were prepared using this process. These samples are summarized in Table 4 below.

[0080] [Table 2]

[0081] [Table 3]

[0082] [Table 4]

[0083] In this reference example 5, the ETM-converted DT resin was prepared as follows. The 250 mL flask was equipped with a thermocouple, a magnetic stirring rod, and a water-cooled condenser. Unit formula D from Comparative Example 3 Me2 0.009 T Me 0.843T Vi 0.148 A vinyl functionalized resin (50 g), an ETM converter (26 g), and toluene (76 g) were placed in a flask. A nitrogen blanket was applied. The contents of the flask were heated to 70°C, and Karstedt catalyst (an amount sufficient to provide 10 ppm of Pt based on the combined weight of the resin and ETM) was added. The contents of the flask were heated at 100°C for 21 hours. The SiH content as an indicator of the reaction product was monitored using FTIR. The resulting product was stripped using a rotary evaporator heated in an oil bath at 80°C until dry at 0.5–1 mmHg. Samples IE2, IE3, and IE5 were prepared by this procedure by varying the amount of starting material. These samples are summarized in Table 5 below. In Table 5 below, quantities are in grams unless otherwise specified.

[0084] In this Reference Example 6, the ETM-converted DT resin was prepared according to the method of Reference Example 5, except that the CE2 resin was used as the vinyl-functionalized resin starting material for sample IE4, and the CE4 resin was used as the vinyl-functionalized resin starting material for sample IE6. These samples are summarized in Table 6 below. In Table 6 below, quantities are in grams unless otherwise specified.

[0085] In this reference example 7, samples IE7 and IE8 were prepared as follows: A thermocouple, magnetic stirring rod, and water-cooled condenser were attached to a 500 mL three-necked flask. Formula M was then added to this flask. H 0.102 T Me 0.892 Resin (sample CE5) or M H 0.102 T Me 0.892The resin (sample CE6) and heptane were added. A nitrogen blanket was applied. The contents of the flask were heated to 80°C. Karstedt's Pt catalyst was added in an amount equal to 5 ppm Pt based on the resin. Vinyltrimethoxysilane was slowly added using a dropping funnel. The temperature rose to 94°C. The contents of the flask were heated to approximately 100°C for 3 hours. FTIR was used to confirm that the reaction was complete. The product was stripped to dry at 1-2 mmHg using a rotary evaporator heated in an oil bath at 80°C. These samples are summarized in Table 7 below. In Table 7 below, quantities are in grams unless otherwise specified.

[0086] In this reference example 8, sample IE9 was prepared as follows: A thermocouple, magnetic stirring rod, and water-cooled condenser were attached to a 500 mL three-necked flask. The flask was then filled with T prepared as described above. Me 0.853 T Vi 0.147 Resin (150g), sample CE7, and heptane (81g) were placed in the flask. A nitrogen blanket was applied. The flask contents were heated to 50°C, and then Karstedt's Pt catalyst was added in an amount that yielded 5 ppm of Pt based on the resin + MeHSi(OMe)2. MeHSi(OMe)2 (30g) was slowly added to the flask using a dropping funnel. The flask contents were heated at 60°C for a total of 23 hours. At 5 hours, enough additional Karstedt's Pt catalyst was added to increase the Pt concentration to 10 ppm, and then at 22 hours, enough additional Karstedt's Pt catalyst was added to increase the Pt concentration to 15 ppm. The progress of the reaction was monitored by FTIR. The resulting product was stripped to dry at 1-2 mmHg using a rotary evaporator heated in an oil bath at 80°C. This sample is summarized in Table 8 below.

[0087] [Table 5]

[0088] [Table 6]

[0089] [Table 7]

[0090] Note: IE7 was prepared using CE5 resin, and IE8 was prepared using CE6 resin.

[0091] [Table 8]

[0092] [Table 9]

[0093] [Table 10]

[0094] [Table 11]

[0095] [Table 12]

[0096] In this Reference Example 9, the curability of several resins prepared as described above was tested by combining 99 parts by weight of the resins. 1 part by weight of Moisture Cure Package (TYZOR® PITA-SM) was mixed using a dental mixer at 2000 rpm for 30 seconds. The resulting coating composition was a homogeneous, transparent liquid. The composition was stabilized for 24 hours and then applied to a substrate.

[0097] Each composition was coated onto A-36 aluminum Q-panel at 25 mm / second in a 10 mil draw-down square (5 cm wide) using a Zehntner automatic coater (ZAA2300) equipped with a vacuum board. After applying each composition, the surface of each resulting coating was tested for tackiness every 60 seconds until the tack-free time was achieved. The tack-free time was recorded when a finger was gently pressed against the coating surface and immediately released, and no wet coating adhered to the nitrile glove.

[0098] Tables 10 and 11 below show that a tack-free time of less than 30 minutes could be achieved only in the case of resins containing alkoxy functional groups later grafted onto the resin via vinyl or SiH moieties present on the resin. This provides for the first time a path toward rapidly curing alkoxy-functionalized siloxane resins in which the alkoxy groups on the resin are not merely leftover from synthesis, but are also intentionally introduced away from the resin core at desired concentrations.

[0099] [Table 13]

[0100] Note: In Table 10, the sample labeled CE was DOWSIL® 2405 Resin, a commercially available product from Dow.

[0101] [Table 14]

[0102] Definitions and Use of Terms All quantities, ratios, and percentages are by weight unless otherwise indicated by the context of the specification. The articles “a,” “an,” and “the” each refer to one or more unless otherwise indicated by the context of the specification. The singular form includes the plural form unless otherwise indicated by the context of the specification. The “Summary of the Invention” and “Abstract” are incorporated herein by reference. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in the “Manual of Patent Examining Procedure Ninth Edition,” Revision 08.2017, Last Revised January 2018 at section §2111.03 I, II, and III. Any feature or aspect of the Invention may be used in combination with any other feature or aspect listed herein. Abbreviations used herein have their definitions in Table 12.

[0103] [Table 15]

[0104] Test method An example of a test method for determining the hydrolyzable group content of silsesquioxane resin is as follows: The hydrolyzable group content is determined in deuterated benzene, 29 Si and 13 It is analyzed by 13C NMR. The total hydrolyzable content is: 29 It is measured by Si NMR analysis and reported as a mole fraction based on Si units. The amount of this hydrolyzable group, which is methoxy, is 13 This is determined by 13C NMR analysis (using 1,4-dioxane as an internal standard). The difference between the total hydrolyzable group content and the amount of methoxy was the amount of OH groups present.

[0105] GPC samples were prepared at a 1% (weight / weight) concentration in certified THF, filtered through a 0.45 μm PTFE syringe filter, and analyzed by comparison with polystyrene standards. The relative calibration curve (tertiary fit) used for molecular weight determination was based on 12 polystyrene standards with a molecular weight range of 580–1,735,000 Daltons. The chromatography apparatus consisted of a vacuum degasser, a Viscotek VE3580 RI detector, and a Viscotek GPCmax VE2001 Solvent / Sample Module fitted with two (300 mm × 7.5 mm) Polymer Laboratories Mixed C columns (molecular weight separation range 200–3,000,000), with a guard column mounted in front of them. Separation was performed using certified grade THF programmed to flow at 1.0 mL / min, with the injection volume set to 100 μL, and the columns and detector heated to 35°C. Data collection took 30 minutes, and processing was performed using OmniSEC software.

Claims

1. Unit formula: (R ２ ３ SiO １／２ ) ｃ (R ２ ２ SiO ２／２ ) ｄ (R ２ SiO ３／２ ) ｅ (ZO １／２ ) ｆ (HO １／２ ) ｇ is an alkoxy-functional silsesquioxane resin containing, wherein, Each R ２ However, alkyl groups and the base of formula (I) 【Chemistry 1】 Independently selected from the group consisting of, In equation (I), Each R １ However, it is an alkyl group that is selected independently. Each D １ However, it is an alkylene group that is selected independently. The subscripts a, b, and x are, The subscript 'a' is 1 or 2, The subscript b is 0 or 1, An integer whose subscript x is either 0 or 1, However, R is present in an average of 5 mol% to 25 mol% per molecule. ２ However, it has formula (I), The subscripts c, d, and e represent the mole fractions of each unit in the alkoxy-functionalized silsesquioxane resin, and the subscripts c, d, and e are, 0 ≤ c ≤ 0.25, 0 ≤ d ≤ 0.20, 0.55 < e ≤ 1, and The quantity (c + d + e) ​​has a value such that it equals 1. Each Z is an independently selected alkyl group. The subscript f represents the molar amount of alkoxy groups in the resin, and the subscript g represents the molar amount of hydroxyl groups in the resin. The subscripts f and g are, 0.01 ≤ f ≤ 0.70, 0 ≤ g ≤ 0.05, and The value has such that 0.02 ≤ (f + g) ≤ 0.75, The alkoxy-functionalized silsesquioxane resin is in a liquid state at 23°C ± 3°C and 101.325 kPa.

2. The subscript a = 1, The subscript b = 1, Each D １ However, experimental formula C ２ H ４ - has, Each R １ However, it is methyl, Each R that is not a base of equation (I) ２ However, it is methyl, The silsesquioxane resin according to claim 1, wherein each Z is independently selected from the group consisting of methyl and ethyl.

3. The subscript b = 0, Each D １ However, experimental formula C ２ H ４ - has, Each R １ However, it is methyl, Each R that is not a base of equation (I) ２ However, it is methyl, The alkoxy-functionalized silsesquioxane resin according to claim 1, wherein each Z is independently selected from the group consisting of methyl and ethyl.

4. R ２ However, per molecule, unit (R ２ SiO ３／２ The alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 3, having formula (I) in at least one case of ).

5. The alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 4, wherein the alkoxy-functionalized silsesquioxane resin has a weight-average molecular weight of 1,000 g / mol to 15,000 g / mol as measured by gel permeation chromatography.

6. A method for preparing an alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 5, 1) Under the conditions necessary for carrying out the hydrosilylation reaction, A) Alkyl-functional organosilicon compounds, and B) Silsesquioxane resin, However, a starting material comprising A) an alkoxy-functional organosilicon compound and B) a silsesquioxane resin, wherein one of A) the alkoxy-functional organosilicon compound and B) the silsesquioxane resin has a silicon-bonded hydrogen atom, and the other of A) the alkoxy-functional organosilicon compound and B) the silsesquioxane resin has an aliphatic unsaturated group capable of undergoing a hydrosilylation reaction, C) In the presence of a hydrosilylation reaction catalyst, Optionally combine in the presence of solvent D. This results in the formation of a hydrosilylation reaction product containing the alkoxy-functionalized silsesquioxane resin, A method comprising optionally 2) purifying the hydrosilylation reaction product.

7. A method for preparing an alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 6, 1) Under the conditions necessary for carrying out the hydrosilylation reaction, A) Alkyl-functional organosilicon compounds and B) Starting material containing silsesquioxane resin, C) In the presence of a hydrosilylation reaction catalyst, This includes optionally combining them in the presence of solvent D), The method wherein one of A) the alkoxy-functional organosilicon compound and B) the silsesquioxane resin has a silicon-bonded hydrogen atom, and the other of B) the silsesquioxane resin and A) the alkoxy-functional organosilicon compound contains an aliphatic unsaturated group.

8. A method for preparing an alkoxy-functionalized silsesquioxane resin according to claim 1 or 2, 1) Under the conditions necessary for carrying out the hydrosilylation reaction, A) Formula: 【Chemistry 2】 Alkoxy-functional organohydrogensiloxane oligomers (wherein R in the formula) １ , D １ , a, and x are as described above), and B) Unit formulas (R ３ ３ SiO １／２ ) ｃ (R ３ ２ SiO ２／２ ) ｄ (R ３ SiO ３／２ ) ｅ (ZO １／２ ) ｆ (HO １／２ ) ｇ It comprises an alkenyl-functionalized silsesquioxane resin, wherein Z, c, d, e, f, and g are as described above. Each R ３ However, independently selected from the group consisting of alkyl groups and alkenyl groups, However, at least one R per molecule ３ However, the starting material has an alkenyl group, C) In the presence of a hydrosilylation reaction catalyst, A method comprising optionally combining in the presence of solvent D).

9. A method for preparing an alkoxy-functionalized silsesquioxane resin according to claim 1 or 3, 1) Under the conditions necessary for carrying out the hydrosilylation reaction, A) Formula R １ ｘ R ５ Si ( OR １ ) ３－ｘ an alkoxy-functional organosilicon compound (wherein R is the formula) １ And x is as described above, R ５ (However, it is an alkenyl group) and B) Unit formulas (R ４ ３ SiO １／２ ) ｃ (R ４ ２ SiO ２／２ ) ｄ (R ４ SiO ３／２ ) ｅ (ZO １／２ ) ｆ (HO １／２ ) ｇ It comprises a hydride-functionalized silsesquioxane resin, where Z, c, d, e, f, and g are as described above. Each R ４ However, independently selected from the group consisting of alkyl groups and H, However, at least one R per molecule ４ However, the starting material is H, C) In the presence of a hydrosilylation reaction catalyst, A method comprising optionally combining in the presence of solvent D).

10. A moisture-curing composition, I) An alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 6, II) A moisture-curable composition comprising a condensation reaction catalyst.

11. The composition according to claim 10, further comprising III) a solvent, IV) an alkoxysilane, V) a fluorescent whitening agent, a UV indicator, or both, VI) a rust inhibitor, VII) a chelating agent, VIII) an adhesion promoter, and IX) an additional starting material selected from the group consisting of two or more combinations thereof.

12. The composition according to claim 10 or 11, wherein the composition substantially contains no organic solvent.

13. A method for preparing a film, wherein the method is 1) Applying the moisture-curing composition according to any one of claims 10 to 12 onto a substrate, 2) A method comprising forming the film on the substrate from the moisture-curing composition.

14. Forming the film on the substrate is Forming a wet film on the aforementioned substrate, The process includes drying the wet film on the substrate to form the film, and drying the wet film is (i) If a solvent is optionally present, evaporate the solvent from the wetted film. If (ii) solvent is optionally present, expose the wetted film to a high temperature to expel the solvent from it. (iii) curing the wet film, or The method according to claim 13, comprising any combination of (iv)(i) to (iii).

15. A membrane prepared by the method of claim 13 or 14.

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