巴西专利BR112014015138B1 composition of polysiloxane oligomer containing epoxy, process for producing it, composition compris

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专利摘要:
POLYSILOXAN OLIGOMER COMPOSITIONS CONTAINING EPOXY, PROCESSES FOR PRODUCTION AND USES OF THE SAME The present invention relates to polysiloxane oligomer compositions containing stable, zero or low VOC epoxy that provide a high degree of chemical resistance to compositions containing organic resins, while which, at the same time, maintain or improve the flexibility of these compositions containing organic resins, processes for preparing epoxy-containing polysiloxane oligomers compositions, and for use in coatings, sealants, adhesives, and composites containing them.
公开号:BR112014015138B1
申请号:R112014015138-5
申请日:2012-12-18
公开日:2021-03-16
发明作者:Naryana Padmanabha Iyer；Lesley Hwang；Vikram Kumar；Christian Geismann；Constantine Kondos；Shiu-Chin Su
申请人:Momentive Performance Materials Inc；
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FIELD OF THE INVENTION
[001] The present invention relates to polysiloxane oligomer compositions containing epoxy, preparation process, and use thereof. BACKGROUND OF THE INVENTION
[002] The use of monomeric epoxy-functional silanes in coatings, adhesives, sealants, and composites applications is known. Recently, oligomeric epoxy-functional silanes have been described as an important component of water-based coatings. For example, U.S. Patent Nos. 7,732,552 and 7,893,183 describe waterborne coating compositions containing oligomeric epoxy functional silanes and one or more optional ingredients such as surfactants, pH adjusting agent, cosolvents, monomeric silanes, binders, crosslinkers and dispersions of pigment paste. These oligomeric epoxy-functional silanes are prepared from glycidoxy silane and / or cycloaliphatic epoxy silane having 2 or 3 alkoxy groups and less than 1.5 equivalent of water in the presence of a catalyst, in which water is fed continuously during the reaction .
[003] Oligomeric epoxy-functional silanes can likewise be prepared by other methods.
[004] For example, US Patent Application Publication No. 2010/0191001 describes oligomeric epoxy-functional silanes prepared using 0.001 less than 5 moles of water per mole of the silane alkoxy function and not using any either additional hydrolysis or condensation catalyst apart from boric acid as a hydrolysis catalyst and condensation component.
[005] Unfortunately, although the use of oligomeric epoxy-functional silanes in the coating compositions can improve the chemical resistance of the coatings, the flexibility of the coatings can be compromised due to a higher degree of crosslinking associated with the use of epoxy-functional silanes high molecular weight oligomers. In addition, emissions of volatile organic compound (VOCs) in the form of coatings alcohols containing the low molecular weight epoxy silane oligomers described in the prior art may be high due to the partial hydrolysis of monomeric epoxy functional alkoxysilane.
Consequently, there is a continuing need in the coatings industry for a stable, zero or low VOC containing epoxy-containing polysiloxane oligomer composition that improves the chemical resistance of coatings while at the same time maintaining or improving the flexibility of the coating containing this epoxy-containing polysiloxane oligomer composition. The present invention provides an answer to that need. SUMMARY OF THE INVENTION
[007] In one aspect, the present invention is directed to an epoxy-containing polysiloxane oligomer composition comprising: (i) 5 to 65 mole percent of a Formula (I) polysiloxane:
(ii) from 10 to 55 mole percent of a polysiloxane of Formula (II):
(iii) 5 to 45 mole percent of a polysiloxane of Formula (III):
(iv) from 1 to 20 mole percent of a Formula (IV) polysiloxane:
(v) 0.1 to 20 mole percent of a polysiloxane of Formula (V):
where each occurrence of R1 is -CH2CH2CH2- and the molar percentage of components (i), (ii), (iii), (iv) and (v) is based on the sum of the molar quantities of components (i), (ii), (iii), (iv) and (v).
[008] In another embodiment, the epoxy-containing composition of the present invention also comprises a stabilizing agent.
[009] The epoxy-containing polysiloxane oligomer composition of the invention can be prepared by a process comprising: (a) hydrolyzing a silane of general formula (VI)
where: R1 is -CH2CH2CH2-; R2 is a monovalent alkyl group of 1 to 3 carbon atoms; and R3 is a monovalent alkyl group of 1 to 3 carbon atoms; in the presence of 2 to 15 moles of water per mole of silane and, optionally, a hydrolysis catalyst, at a temperature between 10 ° to 100 ° C to provide an intermediate containing a silanol and an alcohol; (b) removing alcohol by distillation; (c) removing the water to condense the silanol to provide an epoxy-containing polysiloxane oligomer composition comprising from 5 to 65 mole percent of the polysiloxane of formula (I), from 10 to 55 mole percent of polysiloxane of formula (II), from 5 to 45 mole percent of the polysiloxane of Formula (III), from 1 to 20 mole percent of the polysiloxane of formula (IV), and from 0.1 to 20 mole percent of polysiloxane of formula (V), in which Formulas (I), (II), (III), (IV) and (V) are as defined above, in which the molar percentages of components (i), (ii) , (iii), (iv) and (v) are based on the sum of the molar quantities of components (i), (ii), (iii), (iv) and (v); and optionally (d) adding a stabilizing agent,
[010] In another aspect, the present invention relates to a composition comprising: (i) the polysiloxane oligomer composition containing epoxy as described above; (ii) an organic resin containing at least one functional group selected from the group consisting of epoxy, carboxylic acid, carboxylate anion, amino, ureido, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanate; and (iii) at least one additional component selected from the group consisting of a solvent, surfactant, particulate metal, pigment, biocide, filler, thixotropic, catalyst, curing agent, pH adjusting agent and leveling agent.
[011] These and other aspects will become evident when you read the following description of the invention. BRIEF DESCRIPTION OF THE DRAWINGS
[012] Fig. 1 illustrates the effect of using a stabilizing agent to improve the stability of the epoxy-containing polysiloxane oligomer composition.
[013] Fig. 2 illustrates the degree 60 gloss as a function of double scrubbing with MEK after a three-day post-cure at room temperature for Example 6 and Comparative Example D.
[014] Fig. 3 illustrates the degree 60 brightness as a function of double scrubbing with MEK after a ten day post-cure at room temperature for Example 6 and Comparative Examples D and E. DETAILED DESCRIPTION OF THE INVENTION
[015] It has surprisingly been found that the epoxy-containing polysiloxane oligomer composition of the invention provides a high degree of chemical resistance for coatings, while at the same time maintaining or improving the flexibility of the coatings. In addition, the epoxy-containing polysiloxane oligomer compositions of the invention impart very low or zero VOCs in the form of alcohols to the coating formulations.
[016] Advantageously, in one embodiment, the epoxy-containing polysiloxane oligomer composition of the invention comprises: (i) 5 to 65 mole percent, more specifically 9 to 30 mole percent, and even more specifically from 10 to 20 mole percent of a polysiloxane of Formula (I):
(ii) from 10 to 55 mole percent, more specifically from 30 to 50 mole percent, and even more specifically from 35 to 48 mole percent of a Formula (II) polysiloxane:
(iii) 5 to 45 mole percent, more specifically from 20 to 40 mole percent, and even more specifically from 25 to 35 mole percent of a Formula (III) polysiloxane:
(iv) from 1 to 20 mole percent, more specifically from 5 to 18 mole percent and even more specifically from 7 to 15 mole percent of a Formula (IV) polysiloxane:
(v) 0.1 to 20 mole percent, more specifically from 2 to 8 mole percent, and even more specifically from 3 to 6 mole percent of umpolisiloxanode Formula (V): -
where R1 is -CH2CH2CH2- and the molar percentage of components (i), (ii), (iii), (iv) and (v) is based on the sum of the molar quantities of components (i), (ii), (iii ), (iv) and (v).
[017] In another embodiment, the composition of the polysiloxane oligomer composition containing epoxy comprises 5 to 65 percent of the peak area, more specifically 9 to 30 percent of the peak area, and even more specifically 10 to 20 percent of the peak area of component (i); from 10 to 55 percent of the peak area, more specifically from 30 to 50 percent of the peak area, and even more specifically from 35 to 48 percent of the peak area of the component (ii); from 5 to 45 percent of the peak area, more specifically from 20 to 40 percent of the peak area, and even more specifically from 25 to 35 percent of the peak area of the component (iii); from 1 to 20 percent of the peak area, more specifically from 5 to 18 percent of the peak area and even more specifically from 7 to 15 percent of the peak area of the component (iv); and from 0.1 to 20 percent of the peak area, more specifically from 2 to 8 percent of the peak area, and even more specifically from 3 to 6 percent of the peak area of component (v), in that the percentage of the peak area of the components (i), (ii), (iii), (iv) and (v) is based on the sum of the peak areas as determined by the liquid chromatographic mass spectrometric method ( LC-MS) of components (i), (ii), (iii), (iv) and (v), as described here.
[018] In yet another embodiment, the epoxy-containing composition has a viscosity of 50 centistokes to 250 centistokes and more specifically 100 centistokes to 200 centistokes at 20 ° C using a bubble viscometer and performed according to the ASTM method D-1545.
[019] In another embodiment, the epoxy content is 5.2 milliequivalents per gram to 5.7 milliequivalents per gram, and more specifically, 5.3 milliequivalents per gram to 5.6 milliequivalents per gram, as determined by a titration method involving the reaction of the polysiloxane oligomer composition containing epoxy with hexadecyltrimethylammonium bromide in acetic acid and titrating the acetate anion with perchloric acid.
[020] In yet another embodiment, the amount of releasable alcohol generated from the reaction of the polysiloxane oligomer compositions containing epoxy with water is less than 1 weight percent, more specifically less than 0.5 weight percent, and even more specifically, less than 0.2 weight percent, based on the sum of the weights of components (i), (ii), (iii), (iv) and (v). In one embodiment, the percent by weight of the releasable alcohol is calculated using a 13-C NMR method in which the relative molar amount of the alkoxysilyl SiOC carbon is used to calculate the weight of the alcohol by multiplying the relative molar amount of the carbon of alkoxysilyl SiOC by the molecular weight of the alcohol, and the molar amount of the methylsilyl SiCH3 carbon is used to calculate the sum of the weights of the components (i), (ii), (iii), (iv) and (v) by multiplying the relative molar quantities of the methyl silyl SiCH3 carbon are 162 by 162, and the percentage by weight of the releasable alcohol is calculated by dividing the weight of the alcohol by the weight of the components (i), (ii), (iii), (iv) and (v) and multiplying the quotient by 100%.
[021] In yet another modality, the epoxy-containing composition of the invention comprises less than 10 percent by mole, more specifically, less than 5 percent by mole, and even more specifically, less than 3 percent by mole. soft, epoxy-containing polysiloxane oligomer components having 6 or more silicon atoms, based on the sum of the molar quantities of components (i), (ii), (iii), (iv) and (v). In yet another embodiment, the average molecular weight of the epoxy-containing polysiloxane oligomer composition is between 500 grams per mole and 700 grams per mole, as determined by a GPC method using polystyrene standards, as described here .
[022] The epoxy-containing polysiloxane oligomer composition of the invention can be prepared by a process including the step of hydrolyzing a silane of Formula (VI):
to form a silanol, by removing the by-product alcohols, and condensing the silanol by removing water, where: R1 is -CH2CH2CH2-; R2 is a monovalent alkyl group of 1 to 3 carbon atoms; and R3 is a monovalent alkyl group of 1 to 3 carbon atoms;
[023] Advantageously, R2 and R3 are independently a methyl or ethyl group.
[024] Specifically, the process of the invention comprises the steps of: (a) hydrolyzing a silane of the General Formula (VI) in the presence of 2 to 15 moles of water per mole of the silane and, optionally, a hydrolysis catalyst, in a temperature from 10 ° to 100 ° C to provide an intermediate containing a silanol and an alcohol; (b) removing the alcohol by distillation; (c) removing the water to condense the silanol to the desired polysiloxane oligomer composition comprising from 5 to 65 mole percent, more specifically from 9 to 30 mole percent, and even more specifically from 10 to 20 mole percentage of the polysiloxane of Formula (I), from 10 to 55 mole percent, more specifically from 30 to 50 mole percent, and even more specifically from 35 to 48 mole percentage of the polysiloxane of Formula (II), from 5 to 45 mole percent, more specifically from 20 to 40 mole percent, and even more specifically from 25 to 35 mole percent of the polysiloxane of Formula (III), from 1 to 20 mole percent, more specifically from 5 to 18 mole percentage and even more specifically from 7 to 15 mole percentage of the polysiloxane of Formula (IV), and from 0.1 to 20 mole percent, more specifically from 2 to 8 mole percent, and even more specifically from 3 to 6 mole percent of the polysiloxane of Formula (V), where Formulas (I), (II), (III), (IV) and (V) are as defined above, where the mole percentage of components (i), (ii), (iii), (iv) and (v) is based on the sum of the molar quantities of components (i), (ii), ( iii), (iv) and (v); and optionally (d) adding a stabilizing agent, thereby making the polysiloxane oligomer composition of the invention.
[025] In the mixing step (a), the silane of Formula (VI) is hydrolyzed in the presence of 2 to 15 moles of water per mole of the silane, specifically 4 to 10 moles of water per mole of the silane, more specifically 5 to 7 moles of water per mole of silane, and optionally in the presence of a catalyst.
[026] The catalyst can be metal salts, alkyl ammonium salts, ion exchange resins, carboxylic acids, mineral acids or metal chelates. Preferably, the catalysts are poor nucleophiles that do not react easily with the glycidoxyl group of the silane and are poor catalysts for the condensation of the silanol intermediate of step (a). These preferred catalysts include carboxylic acids having a pKa value of 2 to 5, and more preferably 3.5 to 4.8. Representative and non-limiting examples of catalysts include formic acid, acetic acid, propanoic acid, 1-butanoic acid and tartaric acid. The acid catalyst can be used in amounts ranging from 1 part per million (ppm) to 1 weight percent based on the weight of the Formula VI silane, more specifically from 5 ppm to 1,000 ppm and even more specifically from 50 ppm to 500 ppm.
[027] The hydrolysis temperature of step (a) is from 10 ° C to 100 ° C, more specifically, from 15 ° C to 50 ° C, and even more specifically from 20 ° C to 35 ° C. The hydrolysis of step (a) can be carried out under sub-atmospheric, atmospheric or super-atmospheric pressure. The hydrolysis pressure of step (a) is from 0.01 kilopascals to 200 kilopascals, and more specifically from 80 kilopascals to 110 kilopascals. The hydrolysis time can vary from 1 minute to 200 hours, more specifically from 1 hour to 100 hours and even more specifically from 16 hours to 96 hours.
[028] Alcohol by-products can be removed by distillation. In one embodiment, the removal of alcohol from step (b) is carried out by distillation at a pressure of 0.01 kilopascals to 200 kilopascals, more specifically from 0.1 kilopascals to 110 kilopascals, and even more specifically from 2 kilopascals to 105 kilopascals. kilo-pascal. The temperature for distillation can vary from 10 ° C to 100 ° C, more specifically from 20 ° C to 80 ° C, and even more specifically, from 25 ° C to 60 ° C.
[029] The removal of water and condensation of silanol from step (c) can be performed by distillation. In one embodiment, the removal of water and condensation of silanol from step (c) are carried out by distillation at a pressure of 0.01 kilopascals to 200 kilopascals, more specifically from 0.1 kilopascals to 110 kilopascals, and even more specifically from 2 kilopascals to 105 kilopascals. The temperature for distillation can vary from 10 ° C to 100 ° C, more specifically from 20 ° C to 80 ° C, and even more specifically, from 40 ° C to 75 ° C. The time to reach condensation may vary, depending on the temperature and pressure used. Typically, the removal of water and condensation of silanol from step (c) requires from 1 hour to 200 hours, more specifically from 2 hours to 24 hours and even more specifically from 3 hours to 16 hours. The removal of water and condensation of the silanols can be assisted by spraying the reaction mixture from step (c) with an inert gas, such as nitrogen.
[030] In one mode, the amount of water to be removed in step (c) can be calculated from the equation: Wwd = 18.02Msa [Mwa - Mwr - 0.235x] where: Wwd = amount of water removed in step (c) in grams; Mwa = number in moles of water added in step (a) per mole of silane; Msa = number in moles of silane added in step (a); Mwr = number in moles of reacted water per mole of silanes; x = 1 if the alcohol by-product is ethanol, and x = 0 if the alcohol by-product is methanol, propanol or isopropanol.
[031] The value of Mwr is 1.25 mole of water per mole of silane to 1.45 mole of water per mole of silane.
[032] When the alcohol removed in step (b) forms an azeotrope with water, as in the case of ethanol, then for each mole of silane initially added in step (a), 0.235 mole of water is removed in step (c) due to the water azeotrope: ethanol. The water azeotrope: ethanol is 4.4 percent by weight of water and 95.6 percent by weight of ethanol, or 0.117 mole of water per mole of ethanol. If the alcohol does not form an azeotrope with water, then the value of 0.235 (x) is zero.
[033] In one embodiment, the process is carried out in which in step (a) the silane is 3-glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropylmethyldiethoxysilane and the amount of water is 5 to 7 moles per mole of silane; hydrolysis is carried out at a temperature of 20 ° C to 30 ° C, a pressure of 80 to 105 kilopascals, and a time ranging from 10 to 100 hours; removing alcohol from step (b) at a temperature of 25 ° C to 60 ° C, pressure from 2 to 105 kilopascals for 1 to 10 hours; removal of water and condensation of silanol from step (c) at a temperature of 40 ° C to 75 ° C, pressure from 1 kilopascal to 15 kilopascal for a time of 2 to 16 hours and in which the amount of water removed per mole of silane is 62.1 grams of water per mole of silane to 104.5 grams of water per mole of silane.
[034] Optionally, a stabilizing agent can be added in one step (d) to the polysiloxane oligomer composition containing epoxy after the water is removed. Suitable stabilizing agents are represented by Formula (VII): R4 (OR5) p (VII) where: R4 is a boron atom, an HP group (= O) (-) 2, a group P (= O ) (-) 3, an R6C (= O) (-) group, a polyvalent hydrocarbon group containing from 3 to 20 carbon atoms or a polyvalent heterocarbon group containing from 3 to 20 carbon atoms; each R5 is independently a hydrogen, a group R6C (= O) (-), or a hydrocarbon containing from 1 to 6 carbon atoms; each R6 is independently a monovalent hydrocarbon containing 1 to 5 carbon atoms; and p is an integer from 1 to 6.
[035] Specifically, R4 is a boron atom or a diva-lens hydrocarbon group selected from the group consisting of alkylene, cycloalkylene, alkylene, arylene and aralkylene containing from 4 to 12 carbon atoms. More specifically, R4 is boron, group P (= O) (-) 3, group CH3C (= O) (-), group 2-methylpropylene, 1-methoxy-2,3-propylene, 1,2-hexylene , or 2,3-dimethyl-2,3-butylene; R5 is hydrogen, CH3C (= O (-), methyl or ethyl; and p is 1,2 or 3.
[036] Representative non-limiting examples of the stabilizing agent are boric acid, phosphoric acid, phosphorous acid, acetic acid, acetic acid anhydride, glycerol, 2-methyl-1,3-propanediol, 1-methoxy-2,3 -propanediol, 1,2-hexanediol, and 2,3-dimethyl-2,3-butanediol.
[037] The stabilizing agent can be used in amounts ranging from 100 parts per million to 25 weight percent, based on the sum of the weights of components (i), (ii), (iii), (iv), and (v). Specifically, the stabilizing agent can be used in 100 parts per million to 2 weight percent, based on the sum of the weights of the components (i), (ii), (iii), (iv), and (v), when R4 is boron atom, HP (= O) (-) 2, P (= O) (-) 3, or (CH3) C (= O) (-), or from 1 to 25 weight percent, based on the sum of the weights of the components (i), (ii), (iii), (iv), and (v), when R4 is a polyvalent hydrocarbon containing from 3 to 20 carbon atoms.
[038] In one embodiment, the weight percentages of components (i), (ii), (iii), (iv) and (v) are determined using a liquid-spectrometric mass chromatographic method (LC-MS) that has been adapted from the ESI Ionization Method described in the reference, "Quantitative mass spectrometry of technical polymers: a comparison of several ionization methods", W. Yan, et al., Eur. Mass Spectrom. 4, 467-474 (1998). The method involves dissolving the sample of the polysiloxane containing epoxy in acetonitrile at a concentration of 0.1 weight percent before analysis. The analysis is performed with a Waters LCT Premier XE LC / MS instrument. An Atlantis dC18 column (2.1x30mm, 3um) and the following gradient are used:

[039] The flow rate is 0.3 ml / min, and the injection volume is 1.00 ml. The mass spectrometer is operated with the following settings:

[040] The peak area for each component (i) to (v) is divided by the sum of the peak areas for components (i), (ii), (iii), (iv) and (v) and the quotients are multiplied by 100%. The mole percentage of the components can be calculated from the percentage of the peak area, as determined by the liquid-spectrometric mass chromatographic method (LC-MS) described above and fixing the response factor, which is the mole percentage by percentage of the peak area for each of the components (i), (ii), (iii), (iv) and (v) equal to 1.
[041] In yet another embodiment, the average numerical molecular weight of the epoxy-containing polysiloxane oligomer composition is determined by a gel permeation chromatographic method (GPC). GPC methods involve using a Waters 2690 Chromatograph equipped with Waters 2460 Variable Wavelength UV and Waters 2420 ELS and Millenium System data collection. This detector is typically used for concentration operating at 45 ° C using N2 as a nebulizer gas. The columns are a 100 x 4.6 mm guard column and two 300x7.6 mm linear mixed bed columns with a reported molecular weight range of 100-20,000,000 (polystyrene). All columns are packed with 5-micron particle size styrene-divinylbenzene beads, and have 0.2 micron input chips and 0.5 micron output chips and manufactured by Phenomenex Spherogel Linear (2). The operating conditions are: Solvent: chloroform. Flow rate: 1.0 mL / min. Injection volumes: 10 microliters. Sample concentrations: 1.0-1.5% by weight.
[042] All samples are filtered through 0.45 micron disposable filters to remove undissolved particulate matter. The gauges are based on narrow molecular weight polystyrene patterns that ranged from 264 grams per mole to 2,800,000 grams per mole. To correct small changes in flow rate, a drop of toluene is added to each sample and the retention time measured by UV absorption. A retention time correction is performed for each analysis based on the toluene retention times.
[043] The epoxy-containing polysiloxane oligomer composition of the invention has many applications. Consequently, in one embodiment, the present invention is directed to a composition comprising (i) a polysiloxane oligomer composition containing the invention's epoxy; (ii) an organic resin containing at least one functional group selected from the group consisting of epoxy, carboxylic acid, carboxylate anion, amine, ureide, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanate; and (iii) at least one additional component selected from the group consisting of a solvent, surfactant, particulate metal, pigment, biocide, filler, thixotropic, catalyst, curing agent, buffering agent and leveling agent.
[044] Specifically, the organic resin (ii) can be an epoxy resin, an isocyanate-terminated polymer, an alkoxysilyl-terminated polyurethane, an alkoxysilyl-terminated polyether, a polyamide, a polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyamines , copolymers of an alkene and (meth) acrylic, copolymers of (meth) acrylate and (meth) acrylic acid, terpolymers of an alkene, (meth) acrylate ester and (meth) acrylic acid, an extended phenolic resin of urea and a phenolic resin. More specifically, organic resin (ii) is an epoxy resin selected from the group consisting of bis-phenol diglycidyl ether, bis-phenol diglycidyl ether, phenolic novolac epoxy resin, bisphenol glycidyl ether , aliphatic polyol glycidyl ether, glycidyl amide, glycidyl amine, thio-glycidyl resin, glycidyl ester of dicarboxylic acids, tetra phenol ethane tetraglycidyl ether, cresol epoxy, novolac and combinations thereof. Commercial epoxy resins that are suitable for use in these inventions are listed in: Handbook of Epoxi Resins, Henry Lee and Kris Neville, McGraw-Hill Book Company, New York (1967), Appendix 4-2, the entire contents incorporated here by reference.
[045] The organic resin (ii) can be in the form of an emulsion or a dispersion, in which the resin is emulsified with water using surfactants or spread over water. The solids content of the emulsion or dispersion can be from 0.1 to 70 weight percent, more specifically from 5 to 60 weight percent and even more specifically from 30 to 55 weight percent, based on weight total emulsion or dispersion.
[046] The curing agent is not particularly limited and can be dicarboxylic acids, carboxylic acid anhydrides, aziridines, fatty acid polyamides, dicyandiamiamide, acrylamides, imidazoles, hydrazidines, ethylene imines, thioureas, sulfonamides, acrylamides, guanamines, melamine, urea, polyamines, imidazoline-polyamines, or polyamine-amides. Representative and non-limiting examples include m-phenylenediamine, 4,4'methylenediamine, diaminodiphenylsulfone, benzildimethylamine, benzyl dimethylamine, dimethylethanolamine, diethylethanolamine, 2-picoline, 4-picoline, 2,6-lutidine and mixtures thereof.
[047] Suitable solvents include water, alcohols, ketones, esters, amides, ether-alcohols, hydrocarbons, and mixtures thereof. Representative and non-limiting solvents include water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, mono -2-ethylexyl ethylene glycol ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol ether monobutyl, butyl carbitol, dipropylene glycol ether dimethyl, butyl glycol, butyl diglycol, ethylene glycol monomethyl acetate, ethylene glycol monobutyl acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, methoxypropyl acetate, butyl cellosolved acetate, butylcarbitol acetate, propylene glycol n-butyl acetate, t-butyl acetate, propylene glycol, 2-butoxyethanol, methyl ethyl ketone, dimethyl ketone, ethyl acetate, ethyl propanoate, dimethylformamide, toluene, xylene, mineral alcohols, naphtha, and mixtures thereof. The solvent is present in an amount ranging from 0.1 to 99 weight percent, more specifically from 5 to 90 weight percent and even more specifically from 15 to 80 weight percent, based on the total weight of the composition a which the solvent should be added.
[048] The surfactant can be a cationic surfactant, anionic surfactant or a nonionic surfactant or any combination thereof. The surfactant has a hydrophilic-lipophilic balance (HLB) ranging from 5 to 13. The amount of surfactant can be in the range of 0.1 to 6 weight percent, more specifically 1 to 5 weight percent, based on total weight of the composition to which the solvent is to be added. Representative and non-limiting examples of surfactants include alkyl phenol ethoxylate surfactant, polyether siloxane surfactant, quaternary ammonium halide surfactant, ammonium alkyl phosphate salts, alkali or alkaline earth metal ions, esters organic phosphates, diether sulfosuccinates, or mixtures thereof.
[049] The particulate metal can be a corrosion protection charge or a pigment. Particulate metal is any finely divided aluminum, manganese, cadmium, nickel, stainless steel, tin, magnesium, zinc, alloys thereof or iron alloy, or organic metal or metal phosphate salts or inhibitors. More specifically, the particulate metal is zinc powder, zinc flake, aluminum powder, or aluminum in a dispersion form of powder or paste. The particulate metal can be a mixture of any of the foregoing, as well as alloys and intermetallic mixtures thereof. The flake can be mixed with powdery metal powder, however, typically only with secondary amounts of powder. Metal powders typically have a particle size such that all particles pass 100 mesh and a major amount passes 325 mesh ("mesh" when used herein is the U.S. Standard Sieve Series). The powders are generally spherical instead of the flake's foliage characteristics. Where the metal particulate is a combination of zinc and aluminum, aluminum can be present in the same amounts, ranging from 2 to 50 weight percent of the particulate metal. Particulate metal includes metal oxides, such as cerium oxide, aluminum oxide, iron oxide, silicon oxide and the like. Some particulate metal particles can be dispersed in an aqueous solvent, such as colloidal cerium oxide or colloidal silica. The metal content of the particulate will typically not exceed more than 70 weight percent of the total weight of the composition, based on the total weight of the composition to which the particulate metal is to be added, but is preferably used in amounts of 1.5 to 35 percent by weight. Another particulate metal also includes metal salts where representative and non-limiting examples are zinc chromates, zinc po-tassium chromates, zinc phosphates, aluminotriphosphates, aluminum zinc phosphates, molybdates, wolframates, zirconates and vanadates, salts of 5-nitrophthalic acid zinc or iron phosphide.
[050] The thickener is a polymeric compound that contributes to the viscosity of the composition. A thickener can be water-soluble cellulose ether, xanthum gum, associative urethane thickeners, associated nonionic free urethane thickeners, which are typically opaque, high-boiling liquids or modified clays. The thickener, when present, can contribute an amount between 0.01 and 2 weight percent, based on the total weight of the composition to which the thickener must be added. Representative and non-limiting thickeners include hydroxyethyl cellulose ether, methyl cellulose, methyl ethyl cellulose, highly processed hectorite clay, organically modified and activated smectite clay or mixtures thereof. When the thickener is used, it is usually the last ingredient added to the composition.
[051] Loads may include those for modifying density, physical property, improvements such as mechanical properties or sound absorption, fire retardancy or other benefits including those that may involve improved savings. For example, calcium carbonate or other fillers can reduce the cost of the manufactured composition; aluminum trihydrate or other fire retardant fillers can improve fire retardancy; barium sulfate or other high density fillers can be used for sound absorption; microspheres of materials such as glass or polymers can improve physical properties. High aspect ratio fillers that are used to modify mechanical properties such as hardness or flexural modulus include artificial fibers such as ground glass fiber or graphite fiber, natural mineral fibers such as wollastonite, natural animal fibers such as wool or fiber plants such as cotton, artificial plaque fillers such as broken glass and natural mineral plaque fillings such as mica. When used, the cargo can be used in an amount ranging from 0.1 to 80 percent by weight, and more specifically from 5 to 50 percent by weight, based on the total weight of the composite to which the cargo is to be placed. added.
[052] The composition may include surfactants to reduce foam, aiding deaeration, or modifying a surface, such as increased damage resistance, reduced friction coefficient, flattening or leveling effects, and improved abrasion resistance. The surfactant material may include silicone based materials, such as polyether silicone copolymers and silicone oils, and hydrophobized silica particles. These surfactants are typically used in the range from 0.01 weight percent to 5 weight percent, based on the total weight of the composition, to which the surfactant must be added. Representative and non-limiting surfactants include CoatOSil * 100E deformator, CoatOSil * 1211 wetting agent, CoatOSil * 1220 surfactant, CoatOSil * 1221 surfactant, CoatOSil * 3500 agent, CoatOSil * 3501, CoatOSil * 3505 or CoatOSil * 3573 used to reduce the coefficient of friction, the CoatOSil * 3509 agent used to improve damage resistance and the CoatOSil * 700IE agent, used to level and flow, all sold commercially by Momentive Performance Materials Inc.
[053] A biocide is a chemical or micro-organism that can deter, render harmless or exert a controlling effect on any harmful organism by chemical or biological means. A biocide can be a pesticide or an antimicrobial agent. Many biocides are synthetic, but a class of natural biocides is derived from bacteria and plants. Biocides are used in amounts ranging from 0.01 weight percent to 2 weight percent, based on the total weight of the composition to which the surfactant is to be added. Representative and non-limiting examples of chemical biocides include acrolein, alfachloralo se, aluminum fofida, bifentrina, boric acid, boric oxide, brodifacoum, bromadiline, chlorofacinone, cotianidine, cumatetralil, dazomete, dicloofluanide, difenacoum, difetacetam, difetacetam, difetaconm disodium octaborate, and mixtures thereof. Representative and non-limiting examples of biocides based on microorganisms include bacteria brassica oleracea, brassica oleracea gemmifera and Clostridium botulinum.
[054] The epoxy-containing polysiloxane oligomer compositions of the present invention can be used as a component in mineral-charged coatings, sealants, adhesives or composites. In use, these coatings, seals, adhesives or mineral-loaded composites can be applied to a desired substrate by conventional techniques. The substrate illustrative includes plastic, metal, wood, concrete and glass surfaces. Consequently, in one embodiment, the present invention is directed to a substrate that has a composition applied to it, wherein the composition contains (i) an epoxy-containing polysiloxane oligomer composition of the invention; (ii) an organic resin containing at least one functional group selected from the group consisting of epoxy, carboxylic acid, carboxylate anion, amino, ureido, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanate; and (iii) at least one additional component selected from the group consisting of a solvent, surfactant, particulate metal, pigment, biocide, filler, thixotropic, catalyst, curing agent and leveling agent. The composition can be cured to provide desired properties for the substrate.
[055] Advantageously, polysiloxane oligomer compositions containing epoxy of the present invention are useful as a coating additive to improve chemical resistance, while maintaining the flexibility of the cured coating and not contributing to VOCs in the environment during use. Coatings containing the epoxy-containing polysiloxane oligomer composition of the present invention may include powder coatings, conversion coatings, passivation coatings, primers, high solids coatings, water based coatings, base coatings solvent, e-coatings, hard coatings and the like. These coatings can be used to decorate a surface, protect from abrasion, damage or chemical cauterization, inhibit corrosion of metal surfaces, attach different coating together or to the surface, inhibit the encrustation of surfaces by biological organisms, or improve resistance when sliding from the surface.
[056] It is understood that the following examples are to illustrate, but in no way limit the scope of the present invention. All parts and percentages are by weight and all temperatures are in degrees Celsius, unless explicitly stated otherwise. EXAMPLES Example 1
[057] Preparation of Composition Polysiloxane Oligomer containing Epoxy 1
[058] Two round-bottomed reaction flasks of 5 liters equipped with a mechanical stirrer, condenser and temperature probe were loaded with silane, water and catalysts. In the first flask, 3-glycidoxypropylmethyldiethoxysilane (3262.0 grams, 13.1 moles of Silquest * A-2287, available from Momentive Per-formance Materials Inc.) and acetic acid catalyst containing water (1427.6 grams of solution , 79.3 moles of water and 2.4 X 10-4 moles of acetic acid) were loaded. In the second bottle, 3-glycidoxypropylmethyldiethoxysilane (3252.9 grams, 13.1 moles of Silquest * A-2287, available from Momentive Performance Materi-als Inc.) and acetic acid catalyst containing water (1414.3 grams, 78.6 moles of water and 2.4 X 10-4 moles of acetic acid) were loaded. The mixtures were stirred for a period of 96 hours at room temperature to carry out the hydrolysis of the silane. The flasks were then equipped with a distillation head. Water and ethanol were removed from the distillation unit as an azeotrope at an initial temperature of 23-24 ° C and a pressure of 16.0 kilopascals to 17.3 kilopascals (120-130 mmHg) and slowly raised in temperature to remove the remaining azeotrope. The temperature was also raised to a final temperature of 60 ° C and the pressure decreased to a terminal pressure ranging from 0.013 kilopascals to 1.2 kilopascals (0.1 to 9 mmHg) to remove water and condense silanol. The contents of the two reaction vessels were then combined in a reaction vessel, and any remaining volatiles were removed at a temperature of 60 ° C and a pressure of 0.26 kilopascals (2 mmHg). The reaction vessel was then sprayed with nitrogen for 11 hours at 70-80 ° C in 13.3 kilopascals (100 mmHg). After spraying, boric acid (1.2 grams, available from Sigma-Aldrich) was loaded into the reaction vessel to provide the polysiloxane oligomer composition containing epoxy 1. The composition was analyzed to have the following properties:
[059] Epoxy content: 5.32 meq / gram through titration
[060] Oligomer distribution as determined by the LC-MS method, described here: component (i) 16.3 mole percent; component (ii) 40.7 mole percentage; component (iii) 31.6 percent by mole; component (iv) 11.2 percent by mole; component (v) 0.2 mole percent.
[061] Other components included a hexamer at 2 mole percent, and a heptamer at less than <0.5 mole percent.
[062] Viscosity: 177 centistokes, per bubble viscometer at 20 ° C,
[063] Ethanol or Ethanol: 0 mole percent (undetected) by the 13C NMR method, described here. Example 2
[064] Preparation of the Polysiloxane Oligomer Composition containing Epoxy 2
[065] 3-Glycidoxypropylmethyldiethoxysilane (248 grams, 1 mole) was loaded into a round necked 3-neck flask equipped with a mechanical stirrer. Aqueous boric acid solution (108 grams of solution, 6 moles of water and 0.054 grams of boric acid, 8.75 X 10-4 moles of boric acid) was added to the flask and stirred at an ambient temperature of approximately 25 ° C and pressure atmospheric pressure over a period of 16 hours. The reaction flask was then equipped with a distillation head and a vacuum pump. The mixture was heated to a temperature of 78-80 ° C to remove the azeotrope of ethanol and water and then a volatile by-product of water was removed with the application of vacuum for a period of 3 hours. The polysiloxane oligomer composition containing epoxy 2 was cooled at room temperature and stored under nitrogen. The product analyzes were:
[066] Epoxy content: 5.49 meq / gram through titration
[067] Oligomer distribution as determined by the LC-MS method, described here: component (i) 15.3 mole percent; component (ii) 42.8 percent by mole; component (iii) 30.5 percent by mole; component (iv) 11.2 percent by mole; component (v) 0.2 mole percent.
[068] Other components included a hexamer at 2 mole percent, and a heptamer at less than <0.5 mole percent.
[069] Viscosity: 125 centistokes, through a bubble viscometer at 20 ° C,
[070] Ethanol or Ethanol content: 0.5 mole percent by the 13-C NMR method, described here. Example 3
[071] Preparation of the Polysiloxane Oligomer Composition containing Epoxy 3
[072] 3-Glycidoxypropylmethyldiethoxysilane (1464.56 grams, 5.89 moles, available from Momentive Performance Materials Inc.) and aqueous acetic acid solution (655.25 grams of solution, 36.4 moles of water, 1.0 X 10-4 mole of acetic acid) were loaded into a round-bottomed flask equipped with a mechanical stirrer, condenser, and temperature probe. The mixture was stirred for a period of 24 hours at room temperature to hydrolyze the silane. After equipping the flask with a distillation head, the mixture was heated to a temperature of 23 ° C at a pressure of 12.1 kilopascals (91 mmHg), which was slowly increased to a temperature of 30 ° C at a pressure of 0 , 7 kilopascals (5 mmHg) to remove ethanol and water. The reaction vessel was then sprayed with nitrogen for 4.5 hours at a temperature of 90 ° C and a pressure of 10.8 kilopascals (81 mmHg). 2-Methyl-1,3-propanediol (20.46 grams) was mixed with the polysiloxane oligomer composition containing epoxy (173.57 grams).
[073] Oligomer distribution as determined by the LC-MS method, described here: component (i) 24.0 mole percent; component (ii) 46.2 mole percent component (iii) 18.6 mole percent; component (iv) 3.7 percent by mole; component (v) 7.5 percent by mole.
[074] Other components included a 0.4 percent mole hexamer. Comparative Example A
[075] Preparation of the Composition of Epoxy-Functional Silane Oligomer Comparative A
[076] 3-Glycidoxypropylmethyldiethoxysilane (36.04 grams, 0.145 mole), water (3.92 grams, 0.22 mole), and Dry Ion Exchange Resin Purolite CT-275 were loaded into a rounded base flask equipped with a mechanical stirrer, condenser, and temperature probe. The reaction vessel was heated to 74 ° C for 3 hours, and subsequently extracted under vacuum at a temperature of 75 ° C and 0.11 kilopascals (0.85 mmHg) to provide the comparative epoxy-functional silane hydrolyzate composition A The composition was analyzed using a gas chromatographic method using an Agilent 6850 Series GC System, HP 5 capillary column, helium gas vehicle, thermal conductivity detector and a temperature profile of 80 ° C for 2 minutes and then an increase of 10 ° C / minute until a temperature of 250 ° C is reached, followed by a control period of 10 minutes. The composition contained 13.3 weight percent 3-glycidoxypropylmethyldiethoxysilane.
[077] The epoxy-functional silane hydrolyzate composition A contained 13.3 weight percent 3-glycidoxypropylmethyldiethoxysilane because only 1.52 mole of water was added per mole of silane in step (a). Composition A contained residual ethoxysilyl groups that, in use, generated ethanol, a volatile organic compound that contributes to emissions into the environment. The epoxy-containing polysiloxane oligomer compositions of the present invention do not contain significant amounts of ethoxysilyl groups and therefore do not contribute to the emission of volatile organic compound during use. Example 4 Stability Tests
[078] The oligomer distribution of the products of Example 1, Example 2 and Example 3 has been monitored over time. Figure 1 is a graph of the average number of the heavy peak area of silicon atoms per sum of the peak area of all components of the composition, as determined using the liquid chromatography-mass spectrometry method over time. Illustrates the effect of using a stabilizing agent (d) to improve the stability of the epoxy-containing polysiloxane oligomer composition.
[079] As shown in Figure 1, the product of Example 1 gained 0.0063 units of Si per day (0.19 units of Si per month). The product of Example 2 gained 0.0148 units of Si per day (0.444 units of Si per month). The product of Example 3 gained 0.0017 units of Si per day (0.0521 per month). The addition of boric acid in step (d) produced a polysiloxane oligomer composition containing epoxy relatively more stable than when boric acid was added in step (a). 2-Methyl-1,3-propanediol was likewise an effective stabilizing agent when used at 11.8 weight percent. Example 5
[080] Coating Formulations Containing Polysiloxane Containing Epoxy Oligomer Composition from Example 1
[081] Part A: Preparation of the Coating Formulation Containing the Polysiloxane Oligomer containing Epoxy from Example 1.
[082] A coating formulation comprising the epoxy-containing polysiloxane oligomer of Example 1, which has a releasable 0 mole percent ethoxy / ethanol content was prepared. The epoxy-containing polysiloxane oligomer of Example 1 (22.72 grams) was added to a 250mL wide-mouthed glass jar under stirring. Deionized water (38.91 grams) was added followed by cellosolved butyl (22.99 grams). Finally, trimethylolpropane triacrylate (1.41 grams of SR 351, available from Sartomer) was added to the mixture. The mixture was vigorously stirred by hand for approximately one minute to form Part A.
[083] Part B: Preparation of the Amine Catalyst Blend
[084] In a 250mL wide-mouthed glass jug, a non-ionic aqueous dispersion, 53% solids, of a modified polyamine adduct curing agent with an amine value of 235 to 265 milligrams / gram (155.16 grams of EpiKuer 6870-W-53, available from Momentive Specialty Chemicals Inc.) was added. Deionized water (9.00 grams, 0.5 mole) was added with stirring and then tris (dimethyl amino-methyl) phenol (3253, 4.50 grams of EpiKure, available from Mo-mentive Specialty Chemicals Inc.) was added to the glass jar. The material mixture was vigorously stirred by hand for approximately one minute. The material was then stored, for example, for use as the curative mixture of amine 5 and Comparative Examples B and C.
[085] Part B of curative amine B (62.51 grams) was added to Part A (86.03 grams). The mixture was vigorously stirred for one minute before spraying. Comparative Example B
[086] Coating Formulation Containing CoatOSil * MP200 Epoxy Resin
[087] A coating formulation containing a 3-glycidoxylpropyl polysilsesquioxane (CoatOSil * MP200 that has a releasable methanol, a dangerous air pollutant (HAP) content of -20 weight percent and a VOC release of ~ 200g / L, available from Momentive Performance Materials Inc.) has been prepared. CoatOSil * MP200 (24.33 grams) was added to the jug with stirring. Deionized water (38.70 grams) was added followed by butyl cellosolvede (23.10 grams). Finally, trimethylolpropane tri-acrylate (1.41 grams of SR 351, available from Sartomer) was added to the mixture to form Part A. The amine dressing prepared in Example 5 (59.54 grams of Part B) was added to Part A (86.13 grams). The mixture was vigorously stirred for one minute before spraying. Comparative Example C
[088] Absent Polysiloxane Oligomer Coating Formulation Containing Epoxy of the Present Invention
[089] A coating formulation was prepared by adding deionized water (38.90 grams), butyl cellosolvede (22.98 grams), trimethylol propane triacrylate (1.41 grams of SR351, available from Sartomer) and finally, a non-ionic aqueous dispersion of 53 weight percent solids, of an EPONTM Resin 1001 epoxy solid type Bis A (68.40 grams Epirez 6520-WH-53, available from Modern Specialty Chemicals Inc.) into a 250 mL glass jar. The mixture was then vigorously stirred manually for approximately one minute to produce Part A. To this mixture, the amine dressing prepared above in Example 5 (38.28 grams of Part B) was added to Part A (131.69 grams ) and vigorously stirred for one minute before spraying. Example 6 and Comparative Examples D and E
[090] Test Of Coating Formulations of Example 5 and Comparative Examples B and C
[091] The substrate that was used to test the coating compositions was Cold Roll Steel APR10184 substrate available from ACT Test Panels.
[092] The solution for cleaning the Cold Roll Steel consisted of 0.06 weight percent Triton X-100, 0.52 weight percent anhydrous sodium metasilicate, 0.49 weight percent sodium carbonate anhydrous, 0.35 weight percent sodium phosphate, basic anhydrous, all available from Aldrich, and 98.57 weight percent deionized water.
[093] The Cold Roll Steels panels have been cleaned. The cleaning solution was heated to a temperature between 65 ° C to 70 ° C. The Cold Roll Steels panels were immersed in the stirred cleaning solution, heated for 2 to 3 minutes to remove any oil contaminants. The panels were removed from the solution and immediately rinsed with deionized water. Kimwipe Kimtech Delicate task Wi-pers, available from Kimberly Clark, were then used to scrub the dry paperboard. The panels were then lightly sprayed with water to de-terminate the water leak from the cleaned panels, according to ASTM F-22, "Standard Method of Test for Hydrophobic Surface Films by the Water Break Test. If the panels show the bills of water, then the cleaning process will be repeated. If the water has formed a continuous shine, then the panels will be dried with a Kimwipe cloth and stored for use.
[094] The coating formulations of Example 5 and Comparative Examples B and C were then sprayed onto the exposed Cold Roll Steels panels. The spray application was conducted with a starting spray gun from gravity powered gravity powered StartingLine HVLP, available from DeVilbiss. The coatings were sprayed at a wall pressure of 241.3 kilopascals (35 lb / in2). The spray application technique which was a side-by-side scan of the spray on the panel at a rate of approximately 2,540 centimeter / minute (1,000 inches / minute), indexing the panel up and down by approximately 5.0 centimeters ( 2 inches) by scanning up to approximately 25.4 microns (1.0 mil) of coating thickness was applied to the panel.
[095] The panels were then cured under ambient temperature conditions for 24 hours, and then tested for resistance to clearance using Double Rubs of methyl ethyl ketone (MEK) according to AATCC 8 using the Crockmeter device and 4 layers cotton fabric, for gloss according to ASTM D523, for pencil hardness according to ASTM D3363, and for Gardner Direct & Reverse Impact Strength according to ASTM D2794 using a weight of 4 pounds. Test results were measured at 1, 3, and 10 days unless otherwise specified.
[096] The test results are shown in Tables 1-3 and Figures 2 and 3.
[097] Table 1. MEK Double Scrub Results are shown. Double scrubbing with MEK is reported as the number of double scrubbing until the metal is exposed or until the 999+ scrubbing is completed.

[098] Table 2. Results of the Pencil Hardness Test of re-dressing compositions

[099] Table 3. Results of the test of the resistance test of the coating compositions.

[0100] The test results indicate that the coating composition of Example 5 had double rubs with MEK of more than 999, indicating chemical resistance, and reverse impact of 160, indicating flexibility. The coating of Comparative Example B had double rubs with MEK of more than 999, but the reverse impact was less than 20 after 10 days, indicating poorer flexibility than the coating of Example 5. Likewise, the coating of Comparative Example C had friction MEK of only 21 after 1 day, which slowly increased to 800 double rubs after 40 days indicating poorer chemical resistance than the coating of Example 5, although its flexibility, as indicated by the reverse impact, is comparable. Only the coating composition containing the epoxy-containing polysiloxane oligomer composition of the present invention had good chemical resistance without sacrificing flexibility. Comparative Example F
[0101] Coating Formulations Containing 3-Glycidoxypropylmethyldiethoxysilane
[0102] A two-part coating formula was prepared using 3 - glycidoxypropylmethyldiethoxysilane, the precursor silane used to prepare the polysiloxane oligomer composition containing epoxy.
[0103] Part A: Preparation of the Coating Formulation Containing 3-Glycidoxypropylmethyldiethoxysilane.
[0104] A coating formulation containing 3-glycidoxypropylmethyldiethoxysilane was prepared. A medium viscosity hydrogenated the hydrogenated epoxy-4,4'-isopropylidenodiphenol resin (28.5 grams of Epoxy resin 1510, available from Momentive Specialty Chemicals Inc.), micronized rutile titanium dioxide (25 grams of Bayertitan R -KB-4, available from Bayer AG), a functional methoxy methylphenyl polysiloxane (14.6 grams of TSR-165, available from Momentive Performance Materials Inc.) and 3-glycidoxypropylmethyldiethoxysilane (9.5 grams of Silquest * A-2287, available from Momentive Performance Materials Inc.) were added to a 250mL wide-mouthed glass jar under agitation. The mixture was vigorously stirred by hand for approximately one minute to form Part A.
[0105] Part B: Preparation of Curative Amine Mixture
[0106] A medium viscosity reactive polyamide curing agent based on dimerized fatty acid and polyamines with an amine content of 330 to 360 milligrams / gram (3125) was loaded into a 250ml wide-mouthed glass jar. , 9.2 grams of Epikure curing agent, available from Momentive Performance Chemical Inc.), 3-aminopropyltriethoxysilane (11.2 grams of Silquest * A-1100 silane, available from Momentive Performance Materials Inc.) and dibutyl dilaurate tin (2 grams of tin catalyst from Fomrez SUL-4, available from Momentive Perforce-mance Materials Inc.). The mixture of materials was vigorously stirred by hand for approximately one minute.
[0107] Part A and Part B were mixed and vigorously stirred for one minute before spraying. Example 7
[0108] Coating Formulation Containing Polysiloxane Oligomer containing Epoxy in Example 2.
[0109] Part A: Preparation of Coating Formulation Containing the Polysiloxane Oligomer containing Epoxy in Example 2.
[0110] A formulation coating containing the polysiloxane oligomer containing the epoxy of Example 2 was prepared. A medium viscosity hydrogenated the 4,4 'epoxy resin - isopropylidenodiphenol (27.8 grams of Eponex 1510 resin, available from Momentive Specialty Chemicals Inc.), micronized rutile titanium dioxide (25 grams of Bayertitan R-KB- 4, available from Bayer AG), a functional methoxy methylphenyl polysiloxane (14.6 grams of TSR-165, available from Momentive Performance Materials Inc.) and an epoxy-containing polysiloxane oligomer composition prepared in Example 2 (9.3 grams) added to a 250mL wide-mouthed glass jug with stirring. The mixture was vigorously stirred by hand for approximately one minute to form Part A.
[0111] Part B: Preparation of Curative Amine Mixture
[0112] A medium viscosity reactive polyamide curing agent based on dimerized fatty acid and polyamines with an amine content of 330 to 360 milligram / gram (3125) were loaded into a 250mL wide-mouth glass jar. , 9.6 grams of Epikure curing agent, available from Momentive Specialty Chemicals Inc.), 3-aminopropyltriethoxysilane (11.17 grams of Silquest * A-1100 silane, available from Momentive Performance Materials Inc.) and dibutyltin dilaurate (2 grams of tin catalyst from Fomrez SUL-4, available from Momentive Perforce-mance Materials Inc.). The mixture of materials was vigorously stirred by hand for approximately one minute.
[0113] Part A and Part B were mixed and vigorously stirred for one minute before spraying. Example 8 and Comparative Example G
[0114] Testing of the Coating Formulations of Example 7 and Comparative Example F
[0115] The substrate that was used to test the coating compositions was Cold Roll Steel substrate APR10184 available from ACT Test Panels.
[0116] The solution for cleaning Cold Roll Steel consisted of 0.06 weight percent Triton X-100, 0.52 weight percent anhydrous sodium metasilicate, 0.49 weight percent sodium carbonate anhydrous, 0.35 weight percent sodium phosphate, dibasic anhydrous, all available from Aldrich, and 98.57 weight percent deionized water.
[0117] Cold Roll Steels panels have been cleaned. The cleaning solution was heated to a temperature between 65 ° C to 70 ° C. Cold Roll Steels panels were immersed in the agitated cleaning, heated for 2 to 3 minutes to remove any oil contaminants. The panels were removed from the solution and immediately rinsed with deionized water. Kimwipe Kimtech Task Wipers, available from Kimberly Clark, was then used to scrub dry panels. The panels were then lightly sprayed with water to determine the water leakage from the cleaned panels. If the panels show the water bills, then the cleaning process will be repeated. If the water has formed a continuous glow, then the panels will be dried with a Kimwipe cloth and stored for use.
[0118] The coating formulations of Example 7 and Comparative Examples F were then sprayed onto the exposed Cold Roll Steels panels to form the test panels for Example 8 and Comparative Example G, respectively. The spray application was conducted with a starting spray gun from gravity powered gravity powered StartingLine HVLP, available from DeVilbiss. The coatings were sprayed at a wall pressure of 241.3 kilopascals (35 lb / in2). The spray application technique which was a side-by-side scan of the spray on the panel at a rate of approximately 2.540 centimeters / minute (1,000 inches / minute), indexing the panel above and below at approximately 5.0 centimeters (2 inches) by scanning up to approximately 25.4 microns (1.0 mil) of coating thickness was applied to the panel.
[0119] The panels were then cured under ambient temperature conditions for 24 hours, and then tested for resistance to clearance using double rubs of methyl ethyl ketone (MEK) according to AATCC 8 using the Crockmeter device and 4 layers of cotton fabric, and for the shine according to ASTM D523. Gloss retention was measured before and after 200 MEK double smears. The test results are reported in Table 4.
[0120] Table 4. Gloss retentions for coating formulations, test results for

[0121] The coating composition containing the epoxy-containing polysiloxane oligomer composition of Example 2 had a better initial gloss and gloss retention than the similar coating composition containing the monomeric silane, 3-glycidoxypropylmethyldiethoxysilane. The 96% gloss retention for the coating of Example 7 indicates better chemical resistance than that seen for Comparative Example G which had only 79% gloss retention.
[0122] The foregoing description of the specific modalities will thus fully reveal the general nature of the invention that others can, by applying knowledge within the experience of the technique, easily modify and / or adapt such specific modalities to various requests, without undue experimentation , without departing from the general concept of the present invention. Therefore, such adaptations and modifications are intended to be within the meaning and range of equivalents of the modalities described, based on the teaching and guidance presented here, and the invention is intended to cover all such adaptations and modifications that are included in the spirit and broad scope of the appended claims. It should also be understood that the phraseology or terminology is here for the purpose of description and not as a limitation, such that the terminology or phraseology of the present specification will be interpreted by the skilled technician taking into account the teachings and guidance.

权利要求:
Claims (26)
[0001]
1.-Composition of polysiloxane oligomer containing epoxy CHARACTERIZED by the fact that it comprises: (i) (0 from 5 to 65 mole percent of a polysiloxane of Formula (I):
[0002]
2. Composition of epoxy-containing polysiloxane oligomer according to claim 1, CHARACTERIZED by the fact that component (i) is 9 to 30 mole percent, component (ii) is 30 to 50 mole percent soft; component (iii) is 20 to 40 mole percent; component (iv) is 5 to 18 mole percent; component (v) is 2 to 8 mole percent, where the molar percentage of components (i), (ii), (iii), (iv) and (v) is based on the sum of the molar quantities of the components (i), (ii), (iii), (iv) and (v).
[0003]
3. Composition of epoxy-containing polysiloxane oligomer, according to claim 2, CHARACTERIZED by the fact that component (i) is 10 to 20 mole percent, component (ii) is 35 to 48 percent mole soft; component (iii) is 25 to 35 mole percent; component (iv) is 7 to 15 mole percent; and component (v) is 3 to 6 mole percent, where the molar percentage of components (i), (ii), (iii), (iv) and (v) is based on the sum of the molar quantities of components (i), (ii), (iii), (iv) and (v).
[0004]
4. Polysiloxane oligomer composition containing epoxy according to claim 1, CHARACTERIZED by the fact that the polysiloxane oligomer composition has a viscosity of 50 centistokes to 250 centistokes at 20 ° C in accordance with the ASTM D-1545 method .
[0005]
5. Polysiloxane oligomer composition containing epoxy according to claim 1, CHARACTERIZED by the fact that the polysiloxane oligomer composition has an average molecular weight number of 500 grams per mole to 700 grams per mole.
[0006]
6. Polysiloxane oligomer composition containing epoxy according to claim 1, CHARACTERIZED by the fact that the polysiloxane oligomer composition has less than 1 percent by weight of releasable alcohol, based on the sum of the component weights ( i), (ii), (iii), (iv) and (v).
[0007]
7. Composition of polysiloxane oligomer containing epoxy, according to claim 1, CHARACTERIZED by the fact that it further comprises a stabilizing agent with Formula (VII): R4 (OR5) p (VII) in which: R4is an atom of boron, an HP (= O) (-) 2 group, a P (= O) (-) 3 group, an R6C group (= O) (-), a polyvalent hydrocarbon group containing from 3 to 20 carbon atoms or a polyvalent heterocarbon group containing from 3 to 20 carbon atoms; each R5 is independently a hydrogen, an R6C (= O) (-) group, or a hydrocarbon containing from 1 to 6 carbon atoms; each R6 is independently a monovalent hydrocarbon from 1 to 5 carbon atoms; ep is an integer from 1 to 6.
[0008]
8. Composition of polysiloxane oligomer containing epoxy according to claim 7, CHARACTERIZED by the fact that the stabilizing agent is selected from the group consisting of boric acid, phosphoric acid, phosphoric acid, acetic acid, acid anhydride acetic, glycerol, 2-methyl-1,3-propanediol, 1-methoxy-2,3-propanediol, 1,2-hexanediol, and 2,3-dimethyl-2,3-butanediol.
[0009]
9. Process for the production of the polysiloxane oligomer composition, as defined in claim 1, CHARACTERIZED by the fact that it comprises: (to hydrolyze a silane of general formula (VI)
[0010]
10. Process according to claim 9, CHARACTERIZED by the fact that step (b) is carried out under a pressure of 0.1 kilopascals to 200 kilopascals.
[0011]
11. Process according to claim 9, CHARACTERIZED by the fact that step (c) is carried out under a pressure of 0.1 kilopascals to 200 kilopascals.
[0012]
12. Process according to claim 9, CHARACTERIZED by the fact that the stabilizing agent has the formula (VII): R4 (OR5) p (VII) where: R4is a boron atom, an HP group (= O ) (-) 2, a P (= O) (-) 3 group, an R6C (= O) (-) group, a polyvalent hydrocarbon group containing from 3 to 20 carbon atoms or a polyvalent heterocarbon group containing from 3 at 20 carbon atoms, each R5 is independently a hydrogen, an R6C (= O) (-) group, or a hydrocarbon containing from 1 to 6 carbon atoms; each R6 is independently a monovalent hydrocarbon containing from 1 to 5 carbon atoms; ep is an integer from 1 to 6.
[0013]
13. Process according to claim 12, CHARACTERIZED by the fact that the stabilizing agent is selected from the group consisting of boric acid, phosphoric acid, phosphorous acid, acetic acid, acetic acid anhydride, glycerol, 2-methyl-1,3-propanediol, 1-methoxy-2,3-propanediol, 1,2-hexanediol, and 2,3-dimethyl-2,3-butanediol.
[0014]
14. Process, according to claim 9, CHARACTERIZED by the fact that it also comprises performing the reaction of step (a) in the presence of a catalyst.
[0015]
15. Process according to claim 14, CHARACTERIZED by the fact that the catalyst is selected from the group consisting of metal salts, carboxylic acids, mineral acids or metal chelates.
[0016]
16. Composition CHARACTERIZED by the fact that it comprises: (i) the composition of epoxy-containing polysiloxane oligomer, as defined in claim 1; (ii) an organic resin containing at least one functional group selected from the group consisting of epoxy, acid carboxylic, carboxylate anion, amino, ureido, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanate; and (iii) at least one additional component selected from the group consisting of a solvent, surfactant, particulate metal, pigment, biocide, filler, thixotropic agent, catalyst, curing agent, and a leveling agent.
[0017]
17. Composition according to claim 16, CHARACTERIZED by the fact that the organic resin (ii) is an epoxy resin, an isocyanate-terminated polymer, an alkoxysilyl-terminated polyurethane, an alkoxysilyl-terminated polyether, a polyamide, a polyvinyl acetate, a polyvinyl alcohol, a polycarbonate, a polyamine, a copolymer of an alkene and (meth) acrylic, a copolymer of (meth) acrylate and (meth) acrylic acid, a terpolymer of an alkene, ester (meth) ) acrylate and (meth) acrylic acid, a phenolic resin extended with urea, a phenolic resin, or combinations thereof.
[0018]
18. Composition according to claim 16, CHARACTERIZED by the fact that the organic resin (ii) is an emulsion or a dispersion.
[0019]
19. Composition, according to claim 16, CHARACTERIZED by the fact that the organic resin (ii) is an epoxy resin selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, residues in epoxy phenolic novolac, bisphenol glycidyl ether, aliphatic polyol glycidyl ether, glycidyl amide, glycidyl amine, thioglycidyl resins, acid-dicarboxylic glycidyl ester, tetra phenol ethanol, tetraaglycidyl ethanol, novacol and glycol of these.
[0020]
20. Composition according to claim 16, CHARACTERIZED by the fact that the curing agent is selected from the group consisting of dicarboxylic acids, carboxylic acid anhydrides, aziridines, fatty acid polyamides, dicyandiamide, acrylamides, imidazoles, hydrazidines, ethylene imines, thioureas, sulfonamides, acrylamides, guanamines, melamine, urea, polyamines, imidazoline-polyamines and polyamines-amides.
[0021]
21. Composition according to claim 16, CHARACTERIZED by the fact that the solvent is selected from the group consisting of water, alcohols, ketones, esters, amides, ether-alcohols, and mixtures thereof.
[0022]
22. Composition according to claim 16, CHARACTERIZED by the fact that the composition is a coating, sealant, adhesive or composite.
[0023]
23. Composition according to claim 22, CHARACTERIZED by the fact that the coating is selected from the group consisting of powder coatings, conversion coatings, passivation coatings, primers, high-content coatings solids, water-based coatings, solvent-based coatings, e-coatings and hard coatings.
[0024]
24. Composition according to claim 23, CHARACTERIZED by the fact that the coating is selected from the group consisting of conversion coatings and passivation coatings.
[0025]
25. Substrate CHARACTERIZED by the fact that it has the composition as defined in claim 16, applied to it.
[0026]
26. Substrate, according to claim 25, CHARACTERIZED by the fact that the composition is cured.

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同族专利:

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CN104080870A|2014-10-01|

KR101869689B1|2018-07-19|

JP2015510521A|2015-04-09|

US20130158159A1|2013-06-20|

US9243152B2|2016-01-26|

EP2794788B1|2015-07-22|

US8728345B2|2014-05-20|

BR112014015138A2|2017-06-13|

US20140221531A1|2014-08-07|

CN104080870B|2016-12-07|

KR20140116848A|2014-10-06|

JP6166734B2|2017-07-19|

TW201331298A|2013-08-01|

WO2013096272A1|2013-06-27|

EP2794788A1|2014-10-29|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2021-01-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-03-16| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US13/329,430|2011-12-19|

US13/329,430|US8728345B2|2011-12-19|2011-12-19|Epoxy-containing polysiloxane oligomer compositions, process for making same and uses thereof|

PCT/US2012/070277|WO2013096272A1|2011-12-19|2012-12-18|Epoxy-containing polysiloxane oligomer compositions, process for making same and uses thereof|

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