Process for preparing cyclic siloxazanes and their use for the preparation of amino-functional polyorganosiloxanes - Patents.com

Abstract

A process for preparing cyclic polysiloxazanes is disclosed. The cyclic polysiloxazanes can be optionally converted to α-alkoxy-ω-amino functional polysiloxanes. The cyclic polysiloxazanes or α-alkoxy-ω-amino functional polysiloxanes can be used as capping agents for silanol functional polyorganosiloxanes in the process of making amino functional polyorganosiloxanes.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 63 / 189,726, filed May 18, 2021. U.S. Provisional Application No. 63 / 189,726 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION An improved process for preparing cyclic siloxazanes by hydrosilylation reaction of allyl functional amines with SiH-terminated siloxane oligomers is disclosed. The cyclic siloxazanes are useful for capping silanol groups in silanol functional polyorganosiloxanes. The cyclic siloxazanes and / or the α-alkoxy-ω-amino functional polysiloxanes prepared therefrom can be used to prepare amino functional polyorganosiloxanes. [Background technology]

[0003] Webb et al., U.S. Patent No. 5,026,890, discloses the reaction of olefinic amines, such as allylamine, with polydiorganosiloxanes, such as 1,1,3,3-tetramethyldisiloxane, in the presence of a platinum-containing hydrosilylation catalyst. Depending on the conditions of the reaction, the products can be bis(aminoalkyl)polydiorganosiloxanes and alkenylaminodisiloxanes, which spontaneously convert to cyclic disiloxazanes. The cyclic disiloxazanes can then be converted to bis(aminoalkyl)octaorganotetrasiloxanes by hydrolysis. For example, 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane can be made by adding 1,1,3,3-tetramethyldisiloxane to a large excess of allylamine while heating to reflux.

[0004] [ka]

[0005] When tetramethyldisiloxane (TMDSO) was added to allyl amine (AA) in a 1:1 ratio, a runaway reaction occurred. U.S. Pat. No. 5,026,890 does not demonstrate a successful reaction with a TMDSO:AA ratio less than 1:2. The process suffers from low volumetric efficiency, slow production, low yields of cyclic siloxazanes, and significant safety concerns. The process required handling excess allylamine, a toxic substance. Additionally, the process suffers from unmanageable amounts of initial hydrogen evolution and the potential for uncontrolled exothermic reactions, making the U.S. Pat. No. 5,026,890 process impractical for implementation on an industrial scale.

[0006] Aminofunctional polyorganosiloxanes, such as amine-terminated polydiorganosiloxanes, are useful in personal care applications, such as hair care. Amine-terminated polydiorganosiloxanes can be useful, for example, in hair conditioning applications. Amine-terminated polydiorganosiloxanes made by condensation can suffer from instability, as indicated by viscosity change after aging and / or the development of ammonia odor, which is undesirable for personal care applications. Traditionally, primary amine-terminated polyorganosiloxanes are expensive to make by equilibration, as they require expensive starting materials and catalysts and require multiple process steps to complete.

[0007] Another method of making amine-terminated polyorganosiloxanes uses allylamines or derivatives that hydrolyze to allylamines, which are used to perform hydrosilylation chemistry with SiH-terminated polymers to form amine-terminated polyorganosiloxanes; however, this method suffers from the drawback that the amine-terminated polyorganosiloxane product may contain at least trace amounts of either SiH or allylamine, either of which must be removed before the product can be used in any personal care application.

[0008] Another method of making amine-terminated polyorganosiloxanes is by ammonolysis of chloropropyl-terminated siloxanes. This expensive multi-step method can suffer from the drawback of leaving residual salts (i.e., ammonium chloride) in the amine-terminated polyorganosiloxane product that may require extensive washing to remove, which is less cost-effective and less sustainable. Also, any residual ammonium chloride may produce a malodor, which is undesirable for personal care applications. Summary of the Invention

[0009] A process for preparing cyclic siloxazanes comprising the hydrosilylation reaction of an allyl-functional amine with a SiH-terminated siloxane oligomer in the presence of a hydrosilylation catalyst, which can be used as a capping agent for silanol-functional silanes and / or polyorganosiloxanes to make amino-functional silanes and / or polyorganosiloxanes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Part I. Synthesis of Cyclic Siloxazanes 1. A process for preparing a cyclic siloxazane comprising: 1) a) allyl-functional amines, b) a platinum catalyst capable of catalyzing hydrosilylation reactions; Optionally, c) a formula

[0011] [ka] (In the formula,

[0012] [ka] represents a bond selected from the group consisting of a double bond and a triple bond, subscript a is 1 or 2, and subscript b is 0 or 1, with the proviso that

[0013] [ka] is a double bond, then a=2 and b=1;

[0014] [ka] is a triple bond, a=1 and b=0, and each R 1 is independently selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R 2 is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R 3 is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R 4 is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R 5 is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; R 6 is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms), Thereby forming a reaction mixture and thereafter 2) adding to the reaction mixture d) formula

[0015] [ka] (In the formula, each R 8is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and subscript x is 1 or 2, thereby preparing a reaction product comprising a cyclic siloxazane and a by-product comprising hydrogen (H2); Optionally, 3) purging with an inert gas, thereby removing at least a portion of the hydrogen during step 2); and Optionally, 4) heating the reaction mixture at a temperature between 110° C. and 150° C. for 1 to 6 hours; Optionally, 5) performing a reactive distillation of the reaction product, thereby purifying the cyclic siloxazane.

[0016] Starting Materials a) Allyl-Functional Amines The starting material a) in the process for making cyclic siloxazanes is an allyl-functional amine. The allyl-functional amine has the formula:

[0017] [ka] wherein each R 9 are independently selected from the group consisting of hydrogen and alkyl groups of 1 to 15 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. Suitable alkyl groups are exemplified by branched saturated monovalent hydrocarbyl groups of 6 or more carbon atoms including methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as cycloalkyl groups such as cyclopentyl and cyclohexyl. Alternatively, R 9 Each aryl group in may be methyl. Alternatively, each R 9 can be a hydrogen atom. Alternatively, at least one R 9 can be an alkyl group such as methyl. Without being bound by theory, each R9 When is a hydrogen atom, it is believed that the cyclic siloxazanes may be used as capping agents for silanol-functional silanes and polyorganosiloxanes to make primary amine-functional silanes and polyorganosiloxanes.

[0018] Allyl-functional amines are known in the art and are commercially available. For example, allylamine of formula CH2=CH-CH2NH2, N-allyl-methylamine, N-allylcyclopentylamine, 2-methyl-allylamine, and allylcyclohexylamine are commercially available from Millipore Sigma (St. Louis, Missouri, USA). Alternatively, the allyl-functional amine can be allylamine.

[0019] Starting material b) platinum catalyst The starting material b) in the process for making cyclic siloxazanes is a platinum catalyst. Platinum catalysts are known in the art and commercially available. The platinum catalyst can be platinum metal. Alternatively, the platinum catalyst can contain platinum metal. Suitable platinum catalysts include bi) chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, and platinum dichloride, which can be included in platinum metal compounds. Alternatively, the starting material b) can include b-ii) a complex of the compound of bi) with a low molecular weight organopolysiloxane, or b-iii) a platinum compound microencapsulated in a matrix or core-shell structure. Complexes of platinum with low molecular weight organopolysiloxane include platinum complex with 1,3-1,1,3,3-tetramethyl-divinyl-disiloxane (Karstedt's catalyst) and Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby's catalyst). Alternatively, the hydrosilylation catalyst may be a complex as described above microencapsulated in a resin matrix (b-iv). A platinum catalyst may be suitable for catalyzing the hydrosilylation reaction and / or for dehydrogenative coupling of silicon-hydrogen bonds Si-H from starting material d) with nitrogen-hydrogen bonds NH from starting material a) to generate silicon-nitrogen bonds Si-N and dihydrogen H2. Although platinum catalysts are described above, other platinum group metal hydrosilylation catalysts may also be useful. This may involve using a metal selected from rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation catalyst may be a compound of such a metal, for example, a rhodium diphosphine chelate such as chloridetris(triphenylphosphane)rhodium(I) (Wilkinson's catalyst), [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium, or [1,2-bis(diethylphospino)ethane]dichlorodirhodium.

[0020] Alternatively, the starting material b), the hydrosilylation reaction catalyst, may be selected from the group consisting of i) platinum metal, ii) a compound of platinum, iii) a complex of the compound with an organopolysiloxane, iv) a compound microencapsulated in a matrix or a core-shell type structure, v) a complex of the compound microencapsulated in a matrix or a core-shell type structure, and vi) a combination of two or more thereof.

[0021] Exemplary hydrosilylation catalysts are described in U.S. Patent Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,784,879, 5,036,117, and 5,175,325, and in European Patent No. 0347895(B). Microencapsulated hydrosilylation catalysts and methods for their preparation are known in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654. Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFF™ 4000 Catalyst and SYL-OFF™ 2700 are available from Dow Silicones Corporation.

[0022] The amount of catalyst useful herein will depend on a variety of factors, including the type and amount of other starting materials used in the process, but the amount of catalyst can be sufficient to provide from 10 ppm to 500 ppm, alternatively from 20 ppm to 100 ppm, alternatively from 35 ppm to 60 ppm on the same basis, of Pt, based on the combined weight of all starting materials used in the process to prepare the cyclic siloxazane.

[0023] Starting Material c) Hydrosilylation Reaction Accelerator The starting material c) in the process for making the cyclic siloxazane is an optional hydrosilylation reaction promoter. The starting material c) can be a hydrocarbyloxy-functional dihydrocarbylsilane. The hydrocarbyloxy-functional dihydrocarbylsilane has the formula:

[0024] [ka] wherein

[0025] [ka] represents a bond selected from the group consisting of a double bond and a triple bond, subscript a is 1 or 2, and subscript b is 0 or 1, with the proviso that

[0026] [ka] is a double bond, then a=2 and b=1;

[0027] [ka] is a triple bond, a=1 and b=0, and each R 1 is independently selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R 2 is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R 3 is selected from the group consisting of hydrogen, an alkyl group having 1 to 15 carbon atoms, and an aryl group having 6 to 20 carbon atoms; R 4 is selected from the group consisting of hydrogen, an alkyl group having 1 to 15 carbon atoms, and an aryl group having 6 to 20 carbon atoms; R 5 is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; R 6 is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms. Alternatively, R 5 and R 6 At least one of R may be an aryl group. 5 and R 6are both aryl groups.

[0028] In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 The alkyl group of R 9 may be as described above for. Suitable aryl groups are exemplified by cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1-phenylethyl, 2-phenylethyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, alternatively 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, alternatively 12 to 14 carbon atoms. Alternatively, the aryl group may be phenyl. Alternatively, R 1 , R 2 , and R 3 may each be hydrogen. Alternatively, R 4 may be selected from the group consisting of hydrogen and methyl.

[0029] Alternatively,

[0030] [ka] The bond represented by may be a double bond, R 1 , R 2 , R 3 , R 4 may each be hydrogen. Alternatively, R 5 may be selected from the group consisting of alkyl and aryl, R 6 Alternatively, R can be aryl. 5 may be aryl, R 6 Alternatively, R can be aryl. 5 may be selected from the group consisting of methyl, 2,4,6-trimethylphenyl, and 2,4,6-triisopropylphenyl. 6may be selected from the group consisting of 2,4,6-trimethylphenyl and 2,4,6-triisopropylphenyl.

[0031] Alternatively,

[0032] [ka] The bond represented by may be a triple bond, R 1 , R 2 , and R 3 may each be hydrogen. Alternatively, R 4 may be selected from the group consisting of hydrogen and alkyl, e.g., methyl. Alternatively, R 5 may be selected from the group consisting of alkyl and aryl, R 6 Alternatively, R can be aryl. 5 may be aryl, R 6 Alternatively, R can be aryl. 5 may be selected from the group consisting of methyl, 2,4,6-trimethylphenyl, and 2,4,6-triisopropylphenyl. 6 may be selected from the group consisting of 2,4,6-trimethylphenyl and 2,4,6-triisopropylphenyl.

[0033] Alternatively, the starting material c) the promoter is

[0034] [ka] (1,1-dimethyl-2-propenyl)oxydiphenylsilane,

[0035] [ka] (1-methyl-2-propenyl)oxydiphenylsilane,

[0036] [ka] trans-(3-phenyl-2-propenyl)oxy-dimethylsilane,

[0037] [ka] (1-Methyl-2-propenyl)oxy-dimethylsilane)

[0038] [ka] (1,1-dimethyl-2-propenyl)oxy-dimethylsilane),

[0039] [ka] Allyloxy-dimethylsilane,

[0040] [ka] Allyloxy-diphenylsilane,

[0041] [ka] Allyloxy-bis(2,4,6-trimethylphenyl)silane,

[0042] [ka] Allyloxy-methyl-(2,4,6-tri-isopropylphenyl)silane, and

[0043] [ka] Alternatively, the starting material c) may be a hydrocarbyloxy-functional arylsilane, such as (1,1-dimethyl-2-propenyl)oxydiphenylsilane, (1-methyl-2-propenyl)oxydiphenylsilane, allyloxy-diphenylsilane, allyloxy-bis(2,4,6-trimethylphenyl)silane, allyloxy-methyl-(2,4,6,-tri-isopropylphenyl)silane, and / or (1-methyl-2-propyn-1-yl)oxy-diphenylsilane. Alternatively, the starting material c) accelerator may be selected from the group consisting of allyloxy-bis(2,4,6-trimethylphenyl)silane, allyloxy-methyl-(2,4,6-triisopropylphenyl)silane, and (1-methyl-2-propyn-1-yl)oxy-diphenylsilane.

[0044] Some suitable accelerators of the above formula and methods for preparing them are known, for example, in Japanese Patent Publication No. JP 11209384 (A) and Japanese Patent Application Publication No. 2002255975 (A). Alternatively, the accelerator for use in the process herein can be synthesized by a process including, for example, combining starting materials including an allyl-functional alcohol and an allyl-functional amine to form a mixture, and adding the mixture to a SiH-functional halosilane, which can be optionally carried out in the presence of a solvent (such as those described herein as starting material e). The resulting reaction product can be purified, for example, by filtration, stripping, and / or distillation, to recover the accelerator. Alternatively, the accelerator for use in the process herein can be synthesized by, for example, the methods of Reference Examples 1 and 2 described below.

[0045] Alternatively, accelerators such as the hydrocarbyloxy-functional aryl silanes described above can be used, for example: 1) a) an unsaturated alcohol, and b) combining starting materials, including an amine; c) thereby forming a mixture; and 2) c) adding the mixture to d) a SiH-functional halosilane, thereby forming f) a reaction product including g) an accelerator. The process may optionally be carried out in the presence of e) a solvent. Steps 1) and 2) may be carried out at room temperature, alternatively steps 1) and 2) may be carried out at a temperature between -20°C and 40°C, alternatively steps 0°C and 20°C.

[0046] The above method may optionally further comprise step 3) of recovering g) the promoter from f) the reaction mixture. The recovering in step 3) may be carried out by any convenient means, such as filtration, washing with a solvent, stripping, and / or distillation, to recover g) the promoter from unreacted starting materials, by-products if present, and e) the solvent, if used. One or more of the process steps may be carried out under an inert atmosphere, such as nitrogen. For example, steps 1) and 2) above may optionally further comprise flowing an inert gas through the vessel headspace. Without being bound by theory, it is believed that flowing an inert gas through the reactor headspace may help remove low boiling impurities from the system.

[0047] Starting material a) Unsaturated alcohol The unsaturated alcohol used to prepare the promoter has the formula

[0048] [ka] wherein R 1 , R 2 , R 3 , R 4, and subscripts a and b are as above. Suitable unsaturated alcohols are known in the art and commercially available. For example, allyl alcohol and propargyl alcohol are available from Millipore Sigma (St. Louis, Missouri, USA). The alcohol can be used in a 1:1 ratio to the starting material d) SiH functional halosilane, alternatively 1.1 alcohol to 1 halosilane. Without being bound by theory, it is believed to be important to avoid using too much alcohol, especially in the case of propargyl alcohol HC≡C-CH2-OH, since -OH can react with SiH to generate hydrogen, and hydrogen gas generation occurs slowly. It may also be important to minimize residual halosilane, since halide impurities reduce the selectivity of the catalyst. It may also be important to minimize excess alcohol, as the alcohol, as known to those skilled in the art, increases the solubility of ammonium salts in non-polar organic solvents, making removal of ammonium halide salts by filtration less effective.

[0049] Starting material b) amine The starting material b) in this process for preparing the promoter can be a tertiary amine. The tertiary amine can be a trialkylamine. The trialkylamine has the formula NR 21 3 (in the formula, each R 21may have an independently selected alkyl group of 2 to 16 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 8 carbon atoms, alternatively 2 to 4 carbon atoms. Alternatively, the trialkylamine may be triethylamine. Tertiary amines are known in the art and are commercially available, for example, from Millipore Sigma (St. Louis, Missouri, USA). Alternatively, starting material b) may include pyridine and its derivatives. Starting material b) tertiary amine may be used in a 1:1 molar ratio to starting material d) SiH-functional halosilane, alternatively the amount of starting materials b) and d) may be such that the b):d) ratio is 1.5:1, alternatively 1:1 to 1.1:1. Without wishing to be bound by theory, it is believed to be important to have a sufficient amount of starting material b) (e.g., trialkylamine) to maximize consumption of the halide of d) SiH-functional halosilane. Without wishing to be bound by theory, it is also believed to be important to minimize excess amounts of starting material b) (e.g., trialkylamine) in order to increase the solubility of the ammonium salt in the non-polar organic solvent and reduce the effectiveness of removal of the ammonium halide salt by filtration.

[0050] Starting material d) SiH-functional halosilane The starting material d) in this process for preparing the accelerator is a SiH-functional halosilane. The SiH-functional halosilane has the formula

[0051] [ka] wherein R 5 and R 6is as above, and X is a halogen atom selected from the group consisting of F, Cl, Br, and I, alternatively F, Cl, and Br, alternatively Cl and Br, alternatively Cl, alternatively Br. Examples of suitable SiH-functional halosilanes include diphenylchlorosilane (PhHSiCl), phenylmethylchlorosilane (PhMeHSiCl), chloro-methyl-(2,4,6-tri-isopropyl-phenyl)silane, and chloro-di-(2,4,6-trimethylphenyl)silane. Suitable SiH-functional halosilanes are commercially available. For example, diphenylchlorosilane is available from Millipore Sigma (St. Louis, Missouri, USA). Alternatively, SiH-functional halosilanes can be synthesized by known methods such as the Grignard reaction of a hydridohalosilane with an aryl Grignard reagent, such as an arylmagnesium bromide, in the presence of an ether and, optionally, a solvent as described herein for starting material e) (e.g., a compound of formula H d R 22 e Six (4-d-e) wherein X is as defined above and R 22 is an alkyl group of 1 to 18 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively methyl, subscript d is 1 or 2, subscript e is 0 or 1, and the amount (d+e)<4. One of ordinary skill in the art would be able to prepare the above SiH functional halosilanes with a variety of suitable starting materials using processes such as those disclosed in U.S. Pat. Nos. 7,456,308 and 7,351,847 and references cited therein.

[0052] Starting material e) Solvent The starting material e) in this process for preparing the accelerator is a SiH functional halosilane, which is a solvent that can be optionally added during and / or after step 1) and / or step 2) of the process. Suitable solvents include polyalkylsiloxanes, aromatic hydrocarbons, aliphatic hydrocarbons, mineral spirits, naphtha, or combinations thereof. Polyalkylsiloxanes with suitable vapor pressures can be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyalkylsiloxanes such as DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, 0.5-1.5 cSt, available from Dow Silicones Corporation, Midland, Michigan, USA.

[0053] Alternatively, starting material e) may comprise an organic solvent, which may be an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as heptane, hexane or octane, mineral spirits, naphtha; or a combination thereof.

[0054] The amount of solvent depends on various factors, such as the type of solvent selected, as well as the amount and type of other starting materials selected for the process described herein. However, the amount of solvent can be 0% to 95% based on the total weight of starting materials a), b), c), d) and e). Solvent can be added during step 1) and / or step 2), for example, to facilitate mixing and delivery of one or more starting materials. The process can optionally further include removing all or a portion of the solvent after step 2).

[0055] Alternatively, the accelerator may be synthesized, for example, by a process comprising using as a starting material a compound of formula M-0-CH2-CH=CH2, where M is selected from the group consisting of Li, Na, K, Rb, and Cs, in a 1:1 ratio with starting material d) the SiH-functional halosilane. Alternatively, the hydrocarbyloxy-functional arylsilane may be synthesized, for example, by a process comprising using as a starting material a compound of formula M'-(O-CH2-CH=CH2)2, where M'=Mg, Ca, Sr, Ba, which provide the corresponding metal halide salts.

[0056] The promoter is used in an amount sufficient to provide a platinum to promoter ratio of ≧1:3, alternatively ≧1:5, alternatively ≧1:8, or even higher. However, the amount of promoter in the reaction mixture should be less than 5% of the total mass of the reagents, catalyst, solvent, and promoter. Examples of promoters (and promoter acronyms discussed in the examples) are shown in Table 1 below.

[0057] [Table 1]

[0058] Starting material d) SiH-terminated siloxane oligomer The starting material d) in the process for making cyclic siloxazanes is a SiH-terminated siloxane oligomer. The oligomer has the formula

[0059] [ka] wherein each R 8 is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and the subscript x is 1 or 2. 8 R can be an alkyl or aryl group. 8 Suitable alkyl groups for R 9 This is exemplified by the above for R 8Suitable aryl groups for are exemplified by cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1-phenylethyl, 2-phenylethyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, alternatively 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, alternatively 12 to 14 carbon atoms. Alternatively, R 8 The aryl group of each R may be phenyl. 8 may be an alkyl group, alternatively methyl. Alternatively, the SiH-terminated siloxane oligomer may be selected from the group consisting of 1,1,3,3-tetramethyldisiloxane and 1,1,3,3,5,5-hexamethyltrisiloxane, available from Dow Silicones Corporation (Midland, MI, USA) and Gelest, Inc. (Morrisville, PA, USA), respectively. The amount of starting materials a) and d) is such that the allyl functional amine to oligomer ratio may range from 5:1 to 1:2, alternatively from 2:1 to 1:1.2, alternatively from 1.2:1 to 1:1.1.

[0060] Starting material e) Solvent The starting material e) in the process for preparing cyclic siloxazanes is a solvent that can be optionally added during and / or after step 1) of the process. Suitable solvents include polyalkylsiloxanes, aromatic hydrocarbons, aliphatic hydrocarbons, glycol dialkyl ethers, dialkyl ethers, alkyl-polyglycol ethers, cyclic alkyl ethers, tetrahydrofuran, mineral spirits, naphtha, or combinations thereof. Polyalkylsiloxanes with suitable vapor pressures can be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane, and other low molecular weight polyalkylsiloxanes such as DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, 0.5-1.5 cSt, available from Dow Silicones Corporation (Midland, Michigan, USA).

[0061] Alternatively, starting material e) may comprise an organic solvent, which may be an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as heptane, hexane or octane, tetraglyme, or ethylene glycol n-butyl ether, di-n-butyl ether, tetrahydrofuran, mineral spirits, naphtha, or a combination thereof.

[0062] The amount of solvent will depend on a variety of factors, including the type of solvent selected for use in the process for making the cyclic siloxazanes described above, as well as the amount and type of other starting materials selected. However, the amount of solvent can be from 0% to 50% based on the combined weight of starting materials a), b), c), d), and e). Solvents can be added during step 1) and / or step 2), for example, to facilitate mixing and delivery of one or more starting materials.

[0063] Further details on the process steps Step 1) of the process described herein involves combining starting materials including a) an allyl-functional amine, b) a platinum catalyst capable of catalyzing a hydrosilylation reaction, optionally c) a hydrosilylation reaction promoter, and optionally e) a solvent, as described above. The combining in step 1) may be carried out by mixing the starting materials a) and b), and c), if present, to form a reaction mixture, and heating the reaction mixture to a temperature of up to 150°C, alternatively up to 120°C, alternatively up to 110°C, alternatively up to 95°C, alternatively between 50°C and 150°C.

[0064] Alternatively, when starting material c) is used, starting material b) platinum catalyst and starting material c) hydrosilylation reaction accelerator can be combined in step 1) before combining starting material a) allyl-functional amine. For example, starting material b) and starting material c) can be combined by mixing under ambient conditions (room temperature and ambient pressure) for at least 1 day, alternatively at least 1 week, alternatively 2 weeks, alternatively 1 month, alternatively at least 4 hours, alternatively 4 hours to 4 months, optionally in the presence of e) solvent, before combining with starting material a) in step 1). When starting material c) contains carbon-carbon triple bonds, after combining starting material b) platinum catalyst, the resulting mixture is combined with either starting material a) allyl-functional amine or d) SiH-terminated siloxane oligomer. The mixture prepared by combining starting materials b) and c) can be aged at room temperature for at least 1 week, alternatively 2 weeks, alternatively 1 month, before combining with starting material a) or starting material d). Alternatively, if starting materials b) and c) are mixed at elevated temperatures, for example >30° C. to 90° C., the ageing time can be reduced.

[0065] In step 2) of the process for making cyclic siloxazanes, step 2) may be carried out at a temperature between 20°C and 200°C, alternatively between 50°C and 150°C, alternatively between 70°C and 110°C, alternatively between 70°C and <110°C. Without being bound by theory, it is believed that d) adding the SiH-terminated siloxane oligomer intermittently improves the process safety and yield of the cyclic siloxazane products described herein. By controlling the temperature and d) adding the SiH-terminated siloxane oligomer intermittently (rather than continuously), the possibility of an uncontrolled exothermic reaction may be minimized. For example, step 2) may be carried out at a temperature between 20°C and 200°C, alternatively between 50°C and 150°C, alternatively between 70°C and 110°C. Without being bound by theory, it is believed that d) adding the SiH-terminated siloxane oligomer intermittently (rather than continuously) improves the process safety and yield of the cyclic siloxazane products described herein. By controlling the temperature and d) adding the SiH-terminated siloxane oligomer intermittently (rather than continuously), the possibility of an uncontrolled exothermic reaction may be minimized. For example, step 2) may be carried out at a temperature between 20°C and 200°C, alternatively between 20°C and 200°C. i) providing to the reaction mixture a first aliquot of d) a SiH terminated siloxane oligomer sufficient to provide a first SiH concentration of between 100 ppm and 1000 ppm based on the weight of the reaction mixture; ii) ceasing to feed the SiH terminated siloxane oligomer until a second SiH concentration is measured that is less than the first SiH concentration; and iii) delivering a second aliquot of d) SiH terminated siloxane oligomer to the reaction mixture sufficient to provide a third SiH concentration in the reaction mixture that is greater than the second concentration, wherein the third SiH concentration is between 100 ppm and 1000 ppm based on the weight of the reaction mixture; iv) d) steps ii) and iii) are repeated one or more times until addition of the SiH terminated siloxane oligomer is completed, thereby preparing a reaction product comprising a cyclic siloxazane and a by-product comprising hydrogen (H2).

[0066] In the above process, providing the first aliquot in step i) may be performed by measuring the SiH concentration in the reaction mixture, for example by using an in-situ measurement technique such as Raman spectroscopy or FTIR. Alternatively, providing the first aliquot in step i) may be performed for 2 minutes to 30 minutes, alternatively 10 minutes to 20 minutes, depending on the size of the reactor used. Alternatively, the first aliquot may be >0-40% of the total amount of d) SiH-terminated siloxane oligomer added. Step ii) may be performed for 1-20 hours. The exact time depends on various factors including temperature and the desired reduction in the concentration of unreacted SiH. Step iii) may be performed as described above for step i). Steps ii) and iii) may then be repeated until all of the d) SiH-terminated polyorganosiloxane oligomer has been added. Alternatively, in step i) (and / or step iii)), d) the SiH-terminated polyorganosiloxane oligomer can be fed until the SiH concentration in the reaction mixture is measured at 100 ppm to 1000 ppm, alternatively 200 ppm to 500 ppm, alternatively 250 ppm to 350 ppm. Step ii) can include ceasing the feeding of d) the SiH-terminated polyorganosiloxane oligomer until the SiH concentration falls to <100 ppm, alternatively 100 ppm to 150 ppm, provided that the SiH concentration in step ii) is less than the SiH concentration in steps i) and iii).

[0067] The process may optionally further comprise step 3): removing at least a portion of hydrogen (H2) during step 2). Removal of hydrogen may be carried out, for example, by purging the reaction mixture or the headspace of the reactor used in step 2) with an inert gas such as nitrogen. Without being bound by theory, it is believed that by-product hydrogen may accumulate as the reaction proceeds to a concentration that may deactivate the catalyst. Thus, without being bound by theory, it is believed that removing hydrogen, for example by purging with nitrogen, may prevent or minimize catalyst deactivation.

[0068] The process may optionally further comprise 4) heating the reaction mixture after step 2). Heating may be carried out, for example, at a temperature of 110° C. to 150° C. for 1 to 6 hours, alternatively 2 to 4 hours. Without being bound by theory, it is believed that step 4) allows for consumption of all or substantially all unreacted SiH. Step 4) may be carried out during and / or after step 3).

[0069] The process may optionally further include step 5) purifying the cyclic siloxazane after steps 2) and 3), and, if present, step 4). For example, the above process produces a reaction product that includes the cyclic siloxazane, unreacted starting materials, and solvent, if used. Step 5) may be carried out by stripping and / or distillation, optionally under vacuum, by heating, for example, to 120°C.

[0070] Alternatively, step 5) may comprise a reactive distillation that may be carried out in a batch distillation apparatus comprising a distillation column having a top and a bottom, a reboiler connected to the bottom of the column, and a reflux condenser connected to the top of the column. Step 5) comprises i) combining the redistribution catalyst and the reaction product prepared as above in the distillation apparatus. For example, the redistribution catalyst and the reaction product may be combined in the reboiler of the batch distillation apparatus.

[0071] The redistribution catalyst may be a Bronsted acid or a Lewis acid. For example, mineral acids such as hydrochloric acid, acid salts such as ammonium sulfate, ammonium triflate, or ammonium salts such as alkyl ammonium halides, organic acids such as p-toluenesulfonic acid, and Lewis acids such as methylchlorosilane may be used. Alternatively, ammonium sulfate may be used as the redistribution catalyst. The amount of the redistribution catalyst depends on a variety of factors, including the particular catalyst selected, but the amount may be from 100 ppm to 5,000 ppm, alternatively from 400 ppm to 5,000 ppm, based on the weight of the reaction product being distilled.

[0072] The resulting catalytic reaction mixture can then be heated to boil in the reboiler. The column can be placed under total reflux until the overhead is free (or substantially free) of cyclic siloxazanes. The distillation column can have at least 5 theoretical trays, alternatively at least 10 theoretical trays, alternatively at least 15 theoretical trays. The maximum number of trays is not critical and can be selected for practicality, but the number of trays in the column can be up to 100.

[0073] In step ii) of the reactive distillation in step 5), the distillation can be carried out under conventional methods to remove low boilers including unreacted a) allyl functional amine and, if present, d) SiH terminated siloxane oligomers and / or solvent as an overhead fraction. The reflux ratio in this step can be, for example, 5-200, alternatively 20-200, alternatively 10-100, alternatively 15-50. Most of the low boilers can be removed as an overhead fraction in this step ii). For example, when a) is allylamine and b) is 1,1,3,3-tetramethyldisiloxane, the different boiling points of allylamine (about 52°C) and the product 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (about 180°C) are relatively easy to separate, and therefore a low reflux ratio can be utilized in this early stage of the distillation.

[0074] If the cyclic siloxazane begins to condense in the overhead, such as when the vapor temperature is >5° C. below the solvent boiling point, the reflux can be increased to a higher rate (e.g., 20-200, alternatively 30-100, alternatively 30-80) until the overhead is substantially free of solvent, such as when the condensation temperature is 10° C.<product cyclic siloxazane boiling point. At this point, the reboiler temperature may be reduced as rearrangement begins to occur more substantially, depending on the heat input and boiling rate.

[0075] In step iii) of the reactive distillation in step 5), the reflux ratio used is relatively high (it can be higher than that used in step ii)), and the reactive distillation is continued for a period of time to reactively distill off traces of allyl-functional amine. The reflux ratio can be 40-200, alternatively 50-200, alternatively 60-200. Without being bound by theory, it is believed that the bound allyl-functional amine is redistributed to free allyl-functional amine through reaction in the reboiler, and the resulting free allyl-functional amine moves up the column in the absence of catalyst, thereby preventing further rearrangement, and therefore the slow removal with the selected high reflux ratio allows the formation of allyl-functional amine without removing a large amount of the product cyclic siloxazane, so that the free allyl-functional amine is distilled and concentrated in the column overhead. The process is held at this high reflux ratio for a period of time sufficient to remove the allyl-functional amine to a level of <30 ppm, alternatively <10 ppm, alternatively <1 ppm in the cyclic siloxazane. This period can be 1 hour or more, alternatively 2-8 hours, alternatively 3-6 hours, alternatively 4-6 hours. Without wishing to be bound by theory, it is believed that this long period at high reflux ratio in step iii) allows the redistributable allyl-functional amine to be distilled overhead with only minimal loss of cyclic siloxazane.

[0076] Thereafter, step 5) may further comprise iv) collecting the (purified) cyclic siloxazane. This may be carried out by continuing the distillation and collecting the cyclic siloxazane as an overhead fraction. In this step iv), the reflux ratio may be from 1 to 10, alternatively from 1 to 5. Step 5) may provide the benefit of high yield and purity of the desired cyclic siloxazane.

[0077] The process may optionally further include one or more additional steps as follows: a) after the distillation is completed and the cyclic siloxazane product is recovered, the light distillation fraction containing the allyl functional amine and, if present, the solvent may be recycled to the next batch to improve the overall yield; the first allyl functional amine / solvent rich fraction from step ii) of the distillation in step 5) may be recycled in step 1) of the process described herein; furthermore, the light middle fractions from steps ii) and iii) in step 5) contain the cyclic siloxazane product; these light middle fractions may be recycled to the next batch after step 4) and before and / or during step 5) to optimize the recovery of the cyclic siloxazane product.

[0078] Cyclic Siloxazane The above process produces cyclic siloxazanes, which are

[0079] [ka] (for subscript x=0) and

[0080] [ka] (wherein subscript x=1), 8 and R 9 is as stated above.

[0081] For example, if the SiH-terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the allyl-functional amine is allylamine (each R 8 is methyl, and each R 9 is hydrogen), and the cyclic siloxazane has the formula:

[0082] [ka] which can be abbreviated as -SiMe2OSiMe2C3H6NH- (i.e., 1,1,3,3,-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane), where the SiH terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the allyl-functional amine is an allylamine (where each R 8 is methyl, and each R 9 is hydrogen), then the cyclic siloxazane has the formula:

[0083] [ka] which can be abbreviated as -SiMe2OSiMe2OSiMe2C3H6NH- (i.e., 1,1,3,3,5,5-hexamethyl-2,4-di-oxa-9-aza-1,3,5-trisilacyclononane).

[0084] Alternatively, when the SiH terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the allyl functional amine is N-allyl-N,N-dimethylamine, the cyclic siloxazane has the formula:

[0085] [ka] where the SiH terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the allyl functional amine is N-allyl-N,N-dimethylamine, the cyclic siloxazane has the formula

[0086] [ka] has.

[0087] Alternatively, when the SiH terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the allyl functional amine is 2-methyl-allylamine, the cyclic siloxazane has the formula:

[0088] [ka] and where the SiH terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the allyl functional amine is 2-methyl-allylamine, the cyclic polysiloxazane has the formula

[0089] [ka] , i.e., 1,1,3,3,5,5,7-heptamethyl-2,3-dioxa-9-aza-1,3,5-trisilacyclononane. The cyclic siloxazanes prepared by the above process are useful for preparing amino-functional polyorganosiloxanes.

[0090] Without wishing to be bound by theory, it is believed that the processes described herein can produce cyclic siloxazanes that have beneficial purity profiles. For example, the cyclic siloxazanes can have a SiH content <100 ppmm, an unsaturated olefin content <100 ppmm, and / or an allyl functional amine content <50 ppmm, as determined by GC-FID, GC-mass spectrometry, etc., as described in the Examples below. 1 H NMR, 13 C NMR and 29The purity profile was determined by Si NMR (undetectable contaminants with conservative instrument detection limit of 50 ppm). Moreover, this purity profile is believed to be beneficial for forming amino-functional polyorganosiloxanes suitable for use in personal care applications. Allyl-functional amines and SiH-containing ingredients are generally undesirable in personal care compositions, such as hair care compositions. Thus, the above cyclic siloxazanes are useful for capping silanol-functional polyorganosiloxanes, such as silanol-terminated polydimethylsiloxanes, thereby preparing amino-functional polyorganosiloxanes suitable for use in personal care compositions. Furthermore, the present inventors have surprisingly found that during the synthesis of cyclic -SiMe2OSiMe2C3H6NH-, a new intermediate is formed. The intermediate had the formula H2N(C3H6)SiMe2OSiMe2NH-CH2CH=CH2.

[0091] Part II. Preparation of Amino-Functional Polyorganosiloxanes Process for preparing amino-functional polyorganosiloxanes using cyclic siloxazanes 1. A process for preparing an amino-functional organosilicon compound (e.g., an amino-functional silane and / or an amino-functional polyorganosiloxane), comprising: 1) A) the cyclic siloxazane prepared as above, and D) combining starting materials including a silanol-functional organosilicon compound, which may be selected from the group consisting of DI) a silanol-functional silane, D-II) a silanol-functional polyorganosiloxane, or both DI) and D-II, thereby preparing a reaction product including an amino-functional organosilicon compound; and optionally 2) recovering the amino-functional organosilicon compound.

[0092] Starting Materials DI) Silanol-functional Silanes Silanol-functional silanes have the formula HOSiR 21 R 22 R 23wherein R 21 , R 22 , and R 23 is R 8 Each independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, as described and exemplified above for R. Alternatively, R 21 , R 22 , and R 23 may each independently be an alkyl group of 1 to 15 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. 21 , R 22 , and R 23 may each independently be a branched, saturated monovalent hydrocarbyl group of six or more carbon atoms, including 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 and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as cycloalkyl groups such as cyclopentyl and cyclohexyl. Alternatively, R 21 , R 22 and R 23 Each alkyl group may be methyl, ethyl, propyl or butyl, alternatively ethyl or propyl. Silanol-functional silanes are known in the art and are commercially available. For example, triethylsilanol and triisopropylsilanol are commercially available from Millipore Sigma (St. Louis, Missouri, USA).

[0093] Starting Material D-II) Silanol-Functional Polyorganosiloxane The starting material D-II) in the process for preparing amino-functional polyorganosiloxanes comprises silanol-functional polyorganosiloxanes. Silanol-functional polyorganosiloxanes have at least one silicon-bonded hydroxyl (silanol) group per molecule. The silanol-functional polyorganosiloxanes can be linear, branched, partially branched, cyclic, resinous (i.e., have a three-dimensional network), or can comprise a combination of different structures. For example, the silanol-functional polyorganosiloxanes can comprise any combination of M, D, T, and / or Q siloxy units, so long as the silanol-functional polyorganosiloxane comprises at least one silicon-bonded hydroxyl group. These siloxy units can be combined in various ways to form cyclic, linear, branched, and / or resinous (three-dimensional network) structures. Alternatively, the silanol-functional polyorganosiloxane can be a silanol-functional polydiorganosiloxane. The silanol-functional polyorganosiloxane can have silanol groups at terminal positions, pendant positions, or both terminal and pendant positions.

[0094] The silanol groups may be present in any of the M, D, and / or T units present in the silanol-functional polyorganosiloxane and may be bonded to the same silicon atom (in the case of M and / or D siloxy units). The silanol-functional polyorganosiloxane may, for example, have, as the M units, (R 8 3SiO 1 / 2 ), (R 8 2(OH)SiO 1 / 2 ), (R 8 (OH)SiO 1 / 2 ), and / or ((OH)SiO 1 / 2 ), R 8 is as described above. The silanol-functional polyorganosiloxane may, for example, have the following D units: (R 8 2SiO 2 / 2 ), (R 8 (OH)SiO 2 / 2 ), and / or ((OH)SiO 2 / 2 The silanol-functional polyorganosiloxane may, for example, contain the T unit (R8 SiO 3 / 2 ) and / or ((OH)SiO 3 / 2 Such siloxy units can be combined in any manner, optionally with Q units, to provide silanol-functional polyorganosiloxanes having at least one silicon-bonded OH group per molecule.

[0095] The silanol-functional polyorganosiloxane is branched or resinous when D-II) silanol-functional polyorganosiloxane comprises T and / or Q units. When the silanol-functional polyorganosiloxane is branched or resinous, it is typically a copolymer comprising T and / or Q units in combination with M and / or D units. For example, the silanol-functional polyorganosiloxane can be a DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin, or MDQ resin. Alternatively, the silanol-functional polyorganosiloxane can be linear, in which case the silanol-functional polyorganosiloxane is a silanol-functional polydiorganosiloxane comprising D units in combination with M units.

[0096] The silanol-functional polyorganosiloxane for the starting material D-II) may be a silanol-functional polydiorganosiloxane. The silanol-functional polydiorganosiloxane may be a silanol-functional polydiorganosiloxane having the unit formula (D1): (R 8 3SiO 1 / 2 ) e (R 8 2SiO 2 / 2 ) f (R 8 (OH)SiO 2 / 2 ) g (R 8 2(OH)SiO 1 / 2 ) h wherein R 8is as above, where the subscripts have values ​​such that 2≧e≧0, 4000≧f≧0, 4000≧g≧0, and 2≧h≧0, with the proviso that the amount (e+h)=2, the amount (g+h)≧2, and the amount 4≦(e+f+g+h)≦8000. Alternatively, 4≦(e+f+g+h)≦4000. Alternatively, 10≦(e+f+g+h)≦2,000. Alternatively, the subscripts e through h may have values ​​sufficient to provide a silanol-functional polydiorganosiloxane having a viscosity, measured at 25° C., of from 8 mPa·s to 100,000,000 mPa·s, alternatively from 8 mPa·s to 40,000,000 mPa·s, from 70 mPa·s to less than 1,000,000 mPa·s, alternatively from 70 mPa·s to 500,000 mPa·s, alternatively from 10 mPa·s to 150,000 mPa·s, alternatively from 70 mPa·s to 16,000 mPa·s. 8 may be selected from alkyl and aryl. Alternatively, each R 8 may be selected from methyl and phenyl. Alternatively, all R 8 At least 80% of the groups are methyl.

[0097] Alternatively, the silanol functional polydiorganosiloxane can be a silanol terminated polydiorganosiloxane. The silanol terminated polydiorganosiloxane can have the formula (D2):

[0098] [ka] In the formula, R 11 is OH and R 8and the subscript y has a value sufficient to provide a silanol-functional polydiorganosiloxane having a viscosity, measured at 25° C., of 8 mPa·s to 100,000,000 mPa·s, alternatively 8 mPa·s to 40,000,000 mPa·s, 70 mPa·s to less than 1,000,000 mPa·s, alternatively 70 mPa·s to 500,000 mPa·s, alternatively 70 mPa·s to 500,000 mPa·s, alternatively 10 mPa·s to 150,000 mPa·s, alternatively 70 mPa·s to 16,000 mPa·s (alternatively, y can be 2 to 4000, alternatively y can be 2 to 2000). Silanol-terminated polydiorganosiloxanes suitable for use as starting material A) can be prepared by methods known in the art, such as by hydrolysis and condensation of the corresponding organohalosilanes or by equilibration of cyclic polydiorganosiloxanes.

[0099] Alternatively, the silanol-functional polyorganosiloxane may be a silanol-functional polysiloxane resin. The polysiloxane resin may be a silanol-functional polyorganosiloxane resin having the unit formula (D3): (R 20 3SiO 1 / 2 ) A (R 20 2SiO 2 / 2 ) B (R 20 SiO 3 / 2 ) C (SiO 4 / 2 ) D where the subscripts A, B, C, and D are mole fractions having values ​​such that 0≦A≦0.6, 0≦B≦0.5, 0≦C≦1, 0≦D≦1, with the proviso that the amount (C+D)>0. 20 are independently 8 At least one R per molecule is a monovalent hydrocarbon group, as described above for R, or a hydrolyzable group (e.g., a hydroxyl group or an alkoxy group). 20is a hydrolyzable group. Suitable hydrolyzable groups include hydroxyl, alkoxy, such as methoxy and ethoxy, alkyloxy, such as isopropenyloxy, amidoxy, such as acetamidooxy, and aminoxy, such as N,N-dimethylaminooxy.

[0100] Alternatively, the polysiloxane resin can be D4) a polyorganosilicate resin or D5) a silsesquioxane resin. The polyorganosilicate resin has the formula R 20 3SiO 1 / 2 Monofunctional units (M units) of formula SiO 4 / 2 tetrafunctional silicate units (Q units) of the formula: 20 Alternatively, in the polyorganosilicate resin, R 20 The monovalent hydrocarbon group of R 8 Alternatively, R may be independently selected from the group consisting of alkyl, alkenyl, and aryl, such as those described above for R. 20 The monovalent hydrocarbon radicals of R may be selected from alkyl and aryl. 20 The monovalent hydrocarbon radicals of R may be selected from methyl and phenyl. 20 At least 1 / 3, alternatively at least 2 / 3 of the groups are methyl groups. Alternatively, the M units in the polyorganosilicate resin are (MeSiO 1 / 2 ) and (Me2PhSiO 1 / 2 The polyorganosilicate resins are soluble in liquid organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes (such as those listed above for starting material e) or solvents exemplified by liquid hydrocarbons such as benzene, toluene, xylene, and heptane in the process for preparing the cyclic siloxazanes.

[0101] When prepared, the polyorganosilicate resin contains the M and Q units described above, and the polyorganosiloxane further contains units having silicon-bonded hydroxyl groups and has the formula Si(OSiR 20 3)4[wherein, R 20is as above], for example, neopentamer can be tetrakis(trimethylsiloxy)silane. (above) 29 Si NMR spectroscopy can be used to measure the hydroxyl content and molar ratio of M and Q units, expressed as {M(resin)} / {Q(resin)}, where M and Q units are removed from the neopentamer. The M:Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M:Q ratio can be from 0.5:1 to 1.5:1, alternatively from 0.6:1 to 0.9:1.

[0102] The MQ silicone resin has less than 5.0%, alternatively less than 0.7%, alternatively less than 0.3%, of the formula X″SiO 3 / 2 where X″ represents a hydrolyzable group such as hydroxyl, alkoxy such as methoxy and ethoxy, alkenyloxy such as isopropenyloxy, amidoxy such as acetamidooxy, and aminoxy such as N,N-dimethylaminooxy. The concentration of silanol groups present in the silicone resin can be determined by: 1 H NMR and / or 29 It can be determined using Si NMR.

[0103] The Mn for achieving the desired flow properties of the MQ silicone resin is determined, at least in part, by the Mn of the silicone resin and the R present in the starting material. 20 The Mn of the MQ silicone resin is typically greater than 1,000 Da, alternatively between 1,000 Da and 15,000 Da, alternatively between >3,000 Da and 8,000 Da, alternatively between 4,500 and 7,500 Da.

[0104] MQ silicone resins can be prepared by any suitable method. This type of silicone resin has reportedly been prepared by cohydrolysis of the corresponding silanes or by silica hydrosol capping methods known in the art. Briefly, this method involves reacting silica hydrosol with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a combination thereof under acidic conditions, and recovering the product (MQ resin) containing M and Q units. The resulting MQ resin may contain 2 to 5 weight percent silicon-bonded hydroxyl groups.

[0105] The intermediates used to prepare the polyorganosilicate resins can be triorganosilanes and silanes or alkali metal silicates containing four hydrolyzable substituents. The triorganosilanes are represented by the formula R 8 3SiX 1 [In the formula, R 8 is as above, and X 1 represents a hydrolyzable substituent such as those described above for X". A silane having four hydrolyzable substituents can have the formula SiX 2 4 [where each X 2 is halogen, alkoxy, or hydroxyl. Suitable alkali metal silicates include sodium silicate.

[0106] The polyorganosilicate resins prepared as described above typically contain silicon-bonded hydroxyl groups, i.e., the formula HOSi 3 / 2 , (HO)2Si 2 / 2 , (HO)3Si 1 / 2 , and / or HOR 20 2SiO 1 / 2It contains silicon-bonded hydroxyl groups. The polyorganosilicate resin can contain up to 5% silicon-bonded hydroxyl groups as measured by FTIR spectroscopy. For certain applications, the amount of silicon-bonded hydroxyl groups may desirably be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively between 0.3% and 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin can be converted to trihydrocarbon siloxane groups or different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane or disilazane containing appropriate end groups. The silane containing hydrolyzable groups can be added in a molar excess over the amount necessary to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0107] In one embodiment, starting material D) comprises a polyorganosilicate resin containing the unit formula (D6) (R 20 3SiO 1 / 2 ) c (R 20 2SiO 2 / 2 ) d (SiO 4 / 2 ) e where the subscripts c, d, and e are mole fractions having values such that 0 < c < 0.6, 0 ≤ d < 0.5, 0.4 < e < 1, and R 20 is as defined above, provided that at least one R 20 per molecule is a hydrolyzable group in (D6). Alternatively, the hydrolyzable group of R 20 is selected from a hydroxyl group or an alkoxy group, for example, methoxy or ethoxy, and alternatively, the hydrolyzable group is a hydroxyl group.

[0108] A variety of suitable polyorganosilicate resins are commercially available from sources such as Dow Silicones Corporation (Midland, MI, USA), Momentive Performance Materials (Albany, NY, USA) and Bluestar Silicones USA Corp. (East Brunswick, NJ, USA). For example, DOWSIL® MQ-1600 solid resin, DOWSIL® MQ-1601 solid resin, and DOWSIL® 1250 surfactant, Momentive SR-1000, and Wacker TMS-803 (all commercially available from Dow Silicones Corporation (Midland, Michigan, USA)) are suitable for use in the methods described herein. Alternatively, resins containing M, T and Q units, such as DOWSIL® MQ-1640 Flake resin, may be used. Also commercially available from Dow Silicones Corporation. Such resins may be provided in an organic solvent.

[0109] Alternatively, the polysiloxane resin may be (D7) a silsesquioxane resin, i.e., a polysiloxane resin represented by the formula (R 20 SiO 3 / 2 ) wherein R 20 is as above, except that there is at least one R 20is the hydrolyzable group in (D7). Silsesquioxane resins suitable for use herein are known in the art and commercially available. For example, methylmethoxysiloxane methylsilsesquioxane resins are commercially available as DOWSIL™ US-CF2403 resin from Dow Silicones Corporation (Midland, Michigan, USA). Alternatively, the silsesquioxane resin may have phenylsilsesquioxane units, methylsilsesquioxane units, or a combination thereof. Such resins are known in the art and are commercially available as DOWSIL® 200 Flake resin, also from Dow Silicones Corporation. Alternatively, the silsesquioxane resin may have a structure represented by the formula (R 8 2SiO 2 / 2 ) and / or (R 8 X”SiO 2 / 2 ) and the D unit of the formula (R 8 SiO 3 / 2 ) and / or (X″SiO 3 / 2 ) T units [wherein R 8 and X" are as above], i.e., a DT resin. DT resins are known in the art and commercially available, for example, methoxy-functional DT resins include DOWSIL™ 3074 and DOWSIL™ 3037 resins, and silanol-functional resins include DOWSIL™ 800 Series resins, also available from Dow Silicones Corporation. Other suitable resins include DT resins containing methyl and phenyl groups.

[0110] Starting material D) may be one silanol-functional organosilicon compound or may comprise two or more silanol-functional organosilicon compounds differing in at least one of the following characteristics: structure, viscosity, average molecular weight, siloxane unit, and sequence. Alternatively, starting material D) may comprise a mixture of two or more polyorganosilicate resins. Alternatively, starting material D) may comprise a mixture of two or more silanol-functional polyorganosilicon resins, such as bis-hydroxyl terminated polydiorganosilixanes and polyorganosilicate resins. Alternatively, starting material D) may comprise a mixture of silanol-functional silanes and silanol-functional polyorganosilixanes. Alternatively, starting material D) may comprise a mixture of two or more silsesquioxane resins.

[0111] The amount of starting material depends on various factors, including the type of starting material D) selected and its silanol content. For example, when starting material D) contains a linear silanol-functional polydiorganosiloxane, a molar ratio of 1:1 to 1:1.25 of SiOH to cyclic siloxazane can be used. Alternatively, a 2% to 5% molar excess of cyclic siloxazane relative to the silanol content of starting material D) can be used, and alternatively, up to a 20% molar excess of silanol can be used. Addition of cyclic siloxazane substoichiometrically relative to the silanol content of starting material D-II) can provide reaction product mixtures having residual silanol-functional polyorganosiloxanes, terminal amino-functional polyorganosiloxanes, and polyorganosiloxanes having both silanol and organic amino-functional ends. For the resinous starting material D-II), on average 5%-30% of the residual silanols may not be consumed, with up to >99% typically being capped.

[0112] Step 1) in the process for preparing the amino-functional organosilicon polyorganosiloxane described above, combining the starting materials including (A) and (D), can be carried out by any convenient means, for example, by mixing, optionally with heating. The mixing and heating can be carried out using any convenient means, such as charging the starting materials into a vessel such as a stirred jacketed batch reactor or a reactive distillation apparatus with a jacketed reboiler, and the jacket can be heated and cooled by passing steam / water or a heat transfer fluid through the jacket. The process can be carried out at a temperature of at least 50°C, alternatively at least 85°C, alternatively at least 90°C. Alternatively, the heating in step 1) can be carried out at 50°C to 150°C, alternatively at 85°C to 150°C, alternatively at 90°C to 150°C. The process is carried out for a time sufficient to form the amino-functional polyorganosiloxane.

[0113] In step 1), one of the starting materials A) and D) can be added continuously or incrementally to a vessel containing the other of the starting materials A) and D. Such addition can be carried out manually or using a metering device.

[0114] The above process may optionally further include one or more additional steps. The process may optionally further include step 3) of adding one or more additional starting materials to the reaction mixture in step 1). Alternatively, step 3) may be carried out during and / or after step 1) and before step 2). The additional starting materials may be selected from the group consisting of E) acid pre-catalyst, F) aminoalkyl functional alkoxysilane, G) end-capping agent, H) solvent, and combinations of two or more of F), G), and H).

[0115] Starting material E) Acid precatalyst Starting material E) in the process for preparing the amino-terminated polydiorganosiloxane comprises an acid pre-catalyst. The acid pre-catalyst may be a carboxylic acid. Without being bound by theory, it is believed that the carboxylic acid reacts with the amino functionality in the cyclic siloxazane (or, if present, the α-alkoxy-ω-amino functional polysiloxane, as described below) to form a carboxylate catalyst. The carboxylic acid may be selected from a wide range of carboxylic acids. The carboxylic acid may be, for example, an aliphatic carboxylic acid having 1 to 20 carbon atoms, alternatively 2 to 20 carbon atoms. For example, acetic acid, propionic acid, octanoic acid, decanoic acid, or lauric acid are suitable for use herein. Alternatively, an aliphatic carboxylic acid substituted with a hydrophilic group such as hydroxyl, such as lactic acid, may be used. Alternatively, carboxylic acids substituted with electron-withdrawing moieties, such as halogens such as fluorine or chlorine, or hydroxyl groups, can be used, and examples of such acids substituted with electron-withdrawing moieties are lactic acid and fluoroacetic acid or fluoroalkanoic acids such as 4,4,4-trifluorobutanoic acid.Other suitable carboxylic acids include benzoic acid, citric acid, maleic acid, myristic acid, and salicylic acid.Alternatively, any combination of two or more of the above carboxylic acids can be used.

[0116] F) Aminoalkyl-functional alkoxysilanes The process for preparing the amino-functional polyorganosiloxane may optionally further include adding starting material F), an aminoalkyl-functional alkoxysilane. Without being bound by theory, it is believed that adding F), an amino-functional alkoxysilane, provides an amino-functional organosilicon product, which may be an amino-terminated polyorganosiloxane further comprising pendant amino functional groups.

[0117] The starting material F) contains an aminoalkyl group and an alkoxy group bonded to Si. The aminoalkyl group is represented by the formula (F1): R 13 -(NH-A') q-NH-A-, where A and A' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether linkage; the subscript q is 0 to 4; R 13 is hydrogen, an alkyl group, or a hydrocarbon group having 1 to 4 carbon atoms. 13 can be hydrogen, q can be 0 or 1, and A and A' (if present) each contain 2 to 4 carbon atoms. Examples of suitable aminoalkyl groups include -(CH2)3NH2, -(CH2)4NH2, -(CH2)3NH(CH2)2NH2, -CH2CH(CH3)CH2NH(CH2)2NH2, -(CH2)3NHCH2CH2NH(CH2)2NH2, -CH2CH(CH3)CH2NH2, -CH2CH(CH3)CH2NH(CH2)3NH2, -(CH2)3NH(CH2)4NH2, and -(CH2)3O(CH2)2NH2. The alkoxy group attached to Si may contain a non-reactive substituent or a bond such as an ether bond. Aminoalkyl-functional alkoxysilanes have the formula (F2):

[0118] [ka] wherein A, A', R 13 and the subscript q are as defined above, R' is an alkyl or alkoxyalkyl group having 1 to 6 carbon atoms, e.g., methyl, ethyl, butyl, or methoxyethyl, and R 14 and R 15 are each independently a group -OR' or an optionally substituted alkyl or aryl group. Alternatively, for the preparation of linear polydiorganosiloxanes, R 14 The group can be an alkyl group such as methyl, R 15The group may have the formula -OR', such as methoxy or ethoxy. Examples of aminoalkyl-functional alkoxysilanes suitable for starting material F) include F3) 3-aminopropylmethyldimethoxysilane, F4) 3-aminopropylmethyldiethoxysilane, F5) aminoethyl-aminoisobutylmethyldimethoxysilane, F6) aminoethyl-aminoisobutylmethyldiethoxysilane, F7) 3-aminopropyldimethylethoxysilane, F8) 3-aminopropyldimethylmethoxysilane, F9) 3-(2-aminoethylamino)propyl-dimethoxymethylsilane, F10) 3-(2-aminoethylamino)propyl-diethoxymethylsilane, F11) aminopropylmethyldimethoxysilane, F12) aminopropylmethyldiethoxysilane, and F13) a combination of two or more of F3) to F12). In one embodiment, the aminoalkyl functional alkoxysilane comprises a monoalkoxysilane such as F7) 3-aminopropyldimethylethoxysilane or F9) 3-aminopropyldimethylmethoxysilane, and the amino functional polydiorganosiloxane has amino functional groups pendant therefrom.

[0119] Starting Material G) End-capping Agent The process for preparing an amino-functional organosilicon compound, such as an amino-functional polyorganosiloxane (prepared when starting material D-II is used in the above process), may optionally further include adding an endblocking agent to starting material G). Without being bound by theory, it is believed that, for example, when the amino-functional polydiorganosiloxane prepared by the process described herein has some trihydrocarbylsilyl end groups (e.g., trialkylsilyl end groups such as trimethylsilyl end groups) and some amino functional groups, an endblocking agent may be used to block some of the silanol groups on starting material D-II). The endblocking agent can react with the silanol groups to generate endblocked triorganosilyl units whose triorganosilyl functionality does not react with the silanol groups of starting material A). Suitable endblocking agents are exemplified by (G1) monoalkoxysilane, (G2) silazane, or (G3) both (G1) and (G2).

[0120] (G1) Monoalkoxysilane is represented by the formula (G4): R 16 3SiOR 17 wherein each R 16 are independently monovalent organic groups that do not react with silanol functional groups, and each R 5 is a monovalent hydrocarbon radical having 1 to 6 carbon atoms. Alternatively, R 17 may be an alkyl group having 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms; alternatively R 17 can be methyl. 16 may be a monovalent hydrocarbon group selected from alkyl, alkenyl, and aryl groups. Alternatively, each R 16 may be an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group. 16 may be an alkyl group having 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively each R 16can be methyl. Examples of monoalkoxysilane starting materials (G1) include (G5) trimethylmethoxysilane and (G6) trimethylethoxysilane.

[0121] Suitable (G2) silazanes are represented by the formula (G7): 18 R 19 2Si)2NH, where each R 18 are independently a monovalent hydrocarbon group (R 8 as described herein for R 1 ) and monovalent halogenated hydrocarbon groups (R 2 ) in which at least one hydrogen has been replaced with a halogen atom such as Cl or F. 8 Each R 19 are independently 17 Each R is selected from monovalent hydrocarbon groups of 1 to 6 carbon atoms, as described above for 18 R can be an alkyl group, an alkenyl group, or a halogenated alkyl group. 18 Suitable alkyl groups for include methyl, ethyl, propyl, and butyl. Suitable alkenyl groups include vinyl and allyl. Suitable halogenated alkyl groups include trifluoropropyl. Examples of suitable silazanes for the starting material (G2) include (G8) hexamethyldisilazane, (G9) sym-tetramethyldivinyldisilazane, and (G10) [(CF3CH2CH2)(CH3)2Si]2NH.

[0122] The endblocking agent is optional, and the exact amount depends on various factors, including the desired structure and amine content of the amino-functional polyorganosiloxane formed. However, the endblocking agent may be added in an amount of up to 5% by weight, alternatively 0.1% to 5% by weight, based on the total weight of all starting materials used in the process. If present, all or a portion of starting material G) may be added in step 1). Alternatively, a first portion of starting material G) may be added in step 1), and a second portion of starting material G) may be added in an additional step added to the process after step 1) and before step 2).

[0123] Starting material H) Solvent The process for preparing an amino-functional organosilicon compound may optionally further include adding a solvent to the starting material H). The solvent may be as described above for starting material e) in the process for making a cyclic siloxazane. Without being bound by theory, it is believed that a solvent may be used to introduce one or more of the starting materials, such as starting material D-II), when a polysiloxane resin is selected. The process may use 0% to 200% solvent based on the total weight of all starting materials used in the process. Alternatively, 0% to 90% solvent (on the same basis) may be used. Whether a solvent is used depends on various factors, including the selection of starting material D). For example, a solvent may be used when a silanol-functional polyorganosiloxane resin that is solid at room temperature is selected as starting material D). Alternatively, when starting material D) is a silanol-functional silane and / or a silanol-functional polydiorganosiloxane that is liquid at room temperature, the process may be carried out neat.

[0124] The process for preparing aminofunctional polyorganosiloxanes may optionally further include one or more additional steps in addition to those described above. For example, the process may optionally further include 4) removing residual acid before and / or during step 2) and (E) recovering the aminofunctional polyorganosiloxane from the reaction mixture if an acid precatalyst is added). The aminofunctional polyorganosiloxane may optionally be recovered from the reaction mixture by any convenient means, such as stripping and / or distillation under vacuum. One or more of the process steps may be carried out under an inert atmosphere, such as nitrogen.

[0125] The process for preparing the amino-functional polyorganosiloxane may optionally further comprise quenching the unreacted cyclic siloxazane, the unreacted silanol-functional polyorganosiloxane, or both. The quenching comprises quenching the unreacted cyclic siloxazane with I) water, and B) a cyclic siloxane having the formula R 10The method may be carried out by adding a starting material selected from the group consisting of alcohols of formula R 10 is an alkyl group of 1 to 8 carbon atoms. The quenching can be carried out at any point after step 1) or alternatively before step 2) in the process for preparing the amino-functional polyorganosiloxane.

[0126] B. Processes for Making Alkoxy-Functional Capping Agents Alternatively, for example, the cyclic siloxazanes described above may be further reacted to prepare α-alkoxy-ω-amino functional polysiloxanes useful as capping agents prior to combining the capping agent with D) a silanol functional organosilicon compound, such as D-II) a silanol functional polyorganosiloxane described above. A process for preparing α-alkoxy-ω-amino functional polysiloxanes comprising: I) A) the cyclic siloxazane prepared by the process described above, and B) Formula R 10 OH (in the formula, R 10 is an alkyl group having 1 to 8 carbon atoms, Thereby, the formula

[0127] [ka] (In the formula, each R 8 , R 9 , R 10 and subscript x is as defined above), C) preparing a reaction product comprising an α-alkoxy-ω-amino functional polysiloxane;

[0128] Optionally, II) purifying the reaction product to recover C) the α-alkoxy-ω-amino functional polysiloxane.

[0129] Alternatively, in the α-alkoxy-ω-amino functional polysiloxane, each R 8can be an alkyl group such as methyl, and each R 9 can be hydrogen. The alcohol starting material B) in this process can be selected from the group consisting of methanol and ethanol.

[0130] The above process produces an α-alkoxy-ω-primary amino-functional polysiloxane of the formula:

[0131] [ka] In the formula, each R 8 , R 9 , and R 10 and subscript x is as defined above. Alternatively, each R 8 may be an independently selected alkyl group of 1 to 18 carbon atoms, alternatively methyl. Alternatively, each R 9 may be hydrogen. Alternatively, each R 10 can be methyl or ethyl.

[0132] C. Alternative Processes for Making Amino-Functional Polyorganosiloxanes. The above α-alkoxy-ω-amino functional polysiloxanes are useful in another process for preparing amino functional organosilicon compounds, which comprises 1) The reaction product formed in step I) and / or purified in step II) of the above process is

[0133] [ka] and D) combining starting materials including a silanol-functional organosilicon compound (as described above), thereby forming a reaction mixture; Optionally, 2) heating the reaction mixture to 150° C., alternatively to 90° C., alternatively between 90° C. and 150° C.; 3) E) adding an acid pre-catalyst to the reaction mixture. The process may optionally further include 4) F) adding an aminoalkyl-functional alkoxysilane to the reaction mixture. Starting materials D), E), and F) and their amounts are as described above. Without being bound by theory, it is believed that adding starting material E), an acid pre-catalyst, may be optional when the process is carried out at >90° C., and adding a pre-catalyst is carried out when the process is carried out at 90° C. or less.

[0134] In the process for preparing the amino-functional organosilicon compound, mixing and heating can be carried out using any convenient means, such as charging the starting materials into a vessel such as a stirred jacketed batch reactor or a reactive distillation apparatus with a jacketed reboiler, and the jacket can be heated and cooled by passing steam / water or a heat transfer fluid through the jacket. The starting materials and / or reaction mixture can be kept at room temperature or heated to up to 150°C, alternatively heated to up to 90°C, to promote the reaction. This process is carried out for a time sufficient to form the amino-functional organosilicon compound.

[0135] In steps 1) and 2), one of starting materials A) and D) can be added continuously or incrementally to a vessel containing the other of starting materials A) and D. Such addition can be performed manually or using a metering device.

[0136] The above process may optionally further include one or more additional steps. The process may further include step 4) of adding additional starting materials to the reaction mixture in step 1) and / or step 2). The additional starting materials may be selected from the group consisting of F) aminoalkyl-functional alkoxysilane, G) endblocking agent, H) solvent, and combinations of two or more of F), G), and H). Alternatively, step 4) may be performed during and / or after step 1), before and / or after step 2), or before and / or during step 3). The starting materials D), E), F), G), and H) are as described above. The process for preparing an amino-functional organosilicon compound may optionally further include quenching the unreacted α-alkoxy-ω-amino-functional polysiloxane, the unreacted silanol-functional organosilicon compound, or both. The quenching may further include quenching the unreacted α-alkoxy-ω-amino-functional polysiloxane, the unreacted silanol-functional organosilicon compound, or both. The quenching may include quenching the unreacted α-alkoxy-ω-amino-functional polysiloxane, the unreacted silanol-functional organosilicon compound, or both, with I) water, and B) a silanol-functional organosilicon compound of formula R 10 The method may be carried out by adding a starting material selected from the group consisting of alcohols of formula R 10 is an alkyl group of 1 to 8 carbon atoms. The quenching can be performed at any time after step 1), or alternatively before recovering the amino-functional polyorganosiloxane. The amino-functional polyorganosiloxane can be recovered from the reaction mixture by stripping and / or distillation, optionally under vacuum. One or more of the process steps can be performed under an inert atmosphere, such as nitrogen. For example, steps 1) and 2) above can optionally further include flowing an inert gas through the vessel headspace. Without being bound by theory, it is believed that flowing an inert gas through the reactor headspace can help remove odors and low boiling impurities from the system.

[0137] III. Aminofunctional polyorganosiloxanes The above process produces an amino-functional polyorganosiloxane. When a silanol-terminated polydiorganosiloxane is used as the starting material D-II), the amino-functional polyorganosiloxane is an amino-terminated polydiorganosiloxane. Each R 9is hydrogen, the amino-terminated polydiorganosiloxane is a primary amino-terminated polydiorganosiloxane of the formula

[0138] [ka] In the formula, R 12 OH, R 8 , and -CHCH(R 9 )CH2NH2, where subscript n=(x+y+1). Alternatively, R 12 OH, R 8 and -CH2CH2CH2NH2.

[0139] Alternatively, when a silanol-functional polysiloxane resin is used as starting material D), the amino-functional polyorganosiloxane is an amino-functional polyorganosiloxane resin. 9 When is hydrogen, then the amino-functional polyorganosiloxane resin is a primary amino-functional polyorganosiloxane resin. Primary amino-functional polyorganosiloxane resins have the unit formula: [(H2NCH2CH2CH)R 8 2SiO 1 / 2 ] J [(H2NCH2CH2CH)R 8 SiO 2 / 2 ] K [(H2NCH2CH2CH)SiO 3 / 2 ] L (R 20 3SiO 1 / 2 ) G (R 20 2SiO 2 / 2 ) H (R 20 SiO 3 / 2 ) F (SiO 4 / 2 ) D wherein R 8 and R 20is as above, subscript D is as above, subscript G≦A, subscript H≦B, subscript F≦C. Subscript G≧0, subscript H≧0, subscript F≧0, subscript D≧0. The amount (J+K+L)>1. The amount (L+F+D)>1. The amount (J+K+L+G+H+F+D) has a value sufficient to provide the resin with an Mn of 1,000 g / mol to 12,000 g / mol.

[0140] Personal Care Products The above amino-functional polyorganosiloxanes (e.g., amino-functional polydiorganosiloxanes) can be formulated into personal care products. In general, such products can be prepared at room temperature using a simple propeller mixer, a Brookfield counter-rotating mixer, or a homogenizing mixer, if no material that is solid at room temperature is present. No special equipment or processing conditions are typically required. Depending on the type of form to be made, the preparation method varies, but such methods are known in the art.

[0141] Personal care products can be functional with respect to the part of the body to which they are applied, cosmetic, therapeutic, or some combination thereof. Traditional examples of such products include, but are not limited to, antiperspirants and deodorants, skin care creams, skin care lotions, moisturizers, facial treatments (e.g. acne or wrinkle removers), personal cleansers and washes, bath oils, fragrances, colognes, sachets, sunscreens, pre-shave and after-shave lotions, shaving soaps and foams, hair shampoos, hair conditioners (either leave-in or rinse-off), hair dyes, hair relaxants, hair styling aids (such as sprays, fixatives, mousses, and / or gels); permanents, depilatories, and cuticle coats, make-up, color cosmetics, foundations, concealers, blushers, lipsticks, eyeliners, mascaras, oil removers, color cosmetics removers, powders, medicated creams, pastes or sprays including dental hygiene products, antibiotics, healing promoters, and / or nutrients that can be preventative and / or therapeutic. Generally, personal care products may be formulated with a carrier that allows for application in any conventional form, including, but not limited to, liquids, rinses, lotions, creams, pastes, gels, foams, mousses, ointments, sprays, aerosols, soaps, sticks, soft bars, solid gels, and gels. What constitutes a suitable carrier will be readily apparent to one skilled in the art.

[0142] Amino-functional polyorganosiloxanes can be used in a variety of personal, household, and health care applications. In particular, aminofunctional polydiorganosiloxanes are used in personal care compositions as disclosed in U.S. Pat. No. 6,051,216 (Barr et al.), U.S. Pat. No. 5,919,441 (Mendolia et al.), U.S. Pat. No. 5,981,680 (Petroff et al.), U.S. Patent Application Publication No. 2010 / 0098648 (Yu), and WO 2004 / 060101 (Yu), in sunscreen compositions as disclosed in U.S. Pat. No. 6,916,464 (Hansenne et al.), in cosmetic compositions that also contain film-forming resins as disclosed in WO 2003 / 105801 (Yu), in U.S. Pat. Appl. Pub. No. 2003 / 0235553 (Lu), U.S. Patent Application Publication No. 2003 / 0072730 (Tornilhac), U.S. Patent Application Publication ... They may be used in cosmetic compositions described in EP 03 / 0170188 (Ferrari et al.), EP 1,266,647 (Tornilhac), EP 1,266,648 (Ferrari et al.), EP 1,266,653 (Ferrari et al.), WO 2003 / 105789 (Lu), WO 2004 / 000247 (Lu), and WO 2003 / 106614 (Lu), as additional agents disclosed in WO 2004 / 054523 (Tournilhac), in long-wearing cosmetic compositions disclosed in U.S. Patent Application Publication No. 2004 / 0180032, and in transparent or translucent care and / or makeup compositions discussed in WO 2004 / 054524, all of which are incorporated herein by reference.

[0143] Alternatively, the amino-functional polyorganosiloxanes can be used as part of a color or fixative composition and applied as a pre-treatment, during or after the hair dyeing or perming process, for purposes that can range from color retention and color enhancement to reconditioning the dyed hair fiber. Examples include patent publications U.S. Patent Application Publication No. 2003 / 0152534 to Legrand et al., U.S. Patent Application Publication No. 2003 / 0152541 to Legrand et al., U.S. Patent Application Publication No. 2003 / 0147840 to Legrand, U.S. Patent No. 6,953,484 to Devin-Baudoin et al., U.S. Patent No. 6,916,467 to Devin-Baudoin et al., U.S. Patent Application Publication No. 2004 / 0045098 to Devin-Baudoin et al., U.S. Patent Application Publication No. 2003 / 0126692 to Devin-Baudoin et al., International Publication No. WO 2007 / 071684 to Audousset, and U.S. Patent Application Publication No. 2008 / 0282482 to Audousset et al. by L'Oreal and Noxell No. 7,335,236 to McKelvey by Corp., all of which are incorporated herein by reference.

[0144] The personal care products according to the invention can be applied to the human body, e.g., skin or hair, by standard methods such as application with an applicator, brush, application by hand, pouring, and / or, optionally, rubbing or massaging the product onto or into the body. For example, removal methods for color cosmetics are also well-known standard methods including washing, wiping, and peeling. For use on the skin, the personal care products according to the invention can be used in a conventional manner, e.g., to condition the skin. For this purpose, an effective amount of the product is applied to the skin. Such an effective amount is generally within the range of 1 mg / cm2. 2 ~3mg / cm 2The application to the skin typically involves working the composition into the skin. This method for applying to the skin involves contacting the skin with an effective amount of the composition and then rubbing the composition into the skin. These steps can be repeated as many times as desired to achieve the desired benefits.

[0145] The use of the personal care product according to the invention on hair may employ conventional methods for conditioning hair. An effective amount of the product for conditioning the hair is applied to the hair. Such an effective amount generally ranges from 0.5 g to 50 g, alternatively from 1 g to 20 g. Application to the hair typically involves working the composition through the hair so that most or all of the hair is in contact with the product. This method for conditioning the hair includes the steps of applying an effective amount of a hair care product to the hair and then working the composition through the hair. These steps can be repeated as many times as desired to achieve the desired conditioning effect.

[0146] Non-limiting examples of additives that may be formulated into personal care products in addition to the amino-functional polyorganosiloxanes include (i) additional silicones, (ii) anti-acne agents, (iii) anti-caries agents, (iv) anti-dandruff agents, (v) antioxidants, (vi) biocides, (vii) botanical ingredients, (viii) cleansing agents, (ix) color agents, (x) conditioning agents, (xi) deposition agents such as cationic deposition aids, (xii) electrolytes, (xiii) emollients, (xiv) exfoliants, (xv) foam boosters, (xvi) fragrances, (xvii) protective agents, and the like. Wetting agents, (xviii) occlusive agents, (xix) oils, (xx) pediculicides, (xxi) pH control agents, (xxii) pigments, (xxiii) preservatives, (xxiv) rheology modifiers, (xxv) solvents, (xxvi) stabilizers, (xxvii) stabilizing agents, (xxviii) sunscreens, (xxix) surfactants, (xxx) suspending agents, (xxxi) tanning agents, (xxxii) thickening agents, (xxxiii) vitamins, (xxxiv) waxes, (xxxv) wound healing promoters, and (xxxvi) any two or more of (i) to (xxxv). EXAMPLES

[0147] These examples are intended to illustrate the invention to one of ordinary skill in the art and should not be construed as limiting the scope of the invention as set forth in the claims. Table 2 below lists the starting materials used in these examples.

[0148] [Table 2]

[0149] Part I. Synthesis of Cyclic Siloxazanes In this Reference Example 1, the promoter allyloxy-di-(2,4,6-trimethylphenyl)silane was synthesized as follows: 5.1302 g of chloro-di-(2,4,6-trimethylphenyl)silane was added to a 250 mL flask and dissolved in 110 mL of pentane. In a separate flask, 1.0328 g of allyl alcohol, 1.9709 g of triethylamine were combined and mixed. The mixture was then added to the chloro-di-(2,4,6-trimethylphenyl)silane over a period of 1 hour, resulting in the formation of a large amount of white precipitate. The contents of the flask were stirred for 2 hours. The solid material was filtered off and the supernatant liquid was collected. The solid was washed with 10 mL of pentane, which was combined with the supernatant liquid. The low boiling volatile components were stripped under vacuum to give a cloudy liquid which was dissolved in 60 mL of pentane, filtered again, stripped and collected to give 4.7018 g of allyloxy-di-(2,4,6-trimethylphenyl)silane as a liquid. 1 H NMR, 29 It was characterized by Si NMR and GC-mass spectrometry.

[0150] In this Reference Example 2, the promoter allyloxy-methyl-(2,4,6-tri-isopropyl-phenyl)silane was synthesized as follows: 30 mL of toluene was added to a 250 mL half-jacketed flask cooled to approximately -11°C. 4.9554 g (43.1 mmol) of dichloromethylsilane was added. 25 mL of 0.5 M 2,4,6-triisopropylphenylmagnesium bromide was then slowly added to the flask over 45 minutes, resulting in a light yellow solution and a colorless precipitate. The contents of the flask were stirred for 1 hour while cooling, then warmed to ambient temperature and the contents were stirred for an additional hour. 3.2534 g of 1,4-dioxane was then added to the flask. A large amount of white precipitate formed and the flask contents were stirred for 1 hour. The salts were filtered off from the supernatant liquid. The solid was washed with 30 mL of pentane, which was combined with the other liquids. The volatile components were removed under vacuum to give 2.9466 g of a white microcrystalline solid. The product was identified as chloro-methyl-(2,4,6-tri-isopropyl-phenyl)silane. 1 H NMR, 29 It was characterized by Si NMR and GC-mass spectrometry.

[0151] 2.7908 g of chloro-methyl-(2,4,6-tri-isopropyl-phenyl)silane was added to a 250 mL half-jacketed flask, dissolved in 40 mL of pentane, and cooled to approximately 4° C. In a separate flask, 0.6016 g of allyl alcohol, 1.078 g of triethylamine, and 4.7 g of pentane were combined and mixed. The mixture was then added to the chloro-methyl-(2,4,6-tri-isopropyl-phenyl)silane over 25 minutes. During this time, the flask contents warmed to 9.8° C. and a large amount of white precipitate formed. The flask contents were allowed to warm to ambient temperature and stirred for 2 hours. The solid material was filtered off and the supernatant liquid was collected. The solid was washed with 10 mL of pentane, which was combined with the supernatant liquid. The low boiling volatile components were stripped under vacuum to give a cloudy liquid which was filtered again and collected as allyloxy-methyl-(2,4,6-tri-isopropyl-phenyl)silane. 1 H NMR, 29It was characterized by Si NMR and GC-mass spectrometry.

[0152] In Reference Example 3, the promoter (1-methyl-2-propyn-1-yl)oxy-diphenylsilane was synthesized as follows: 9.9272 g of chlorodiphenylsilane was added to a 250 mL half-jacketed flask, dissolved in 100 mL of pentane, and cooled to about 1° C. In a separate flask, 3.222 g of 1-methyl-prop-2-yn-1-ol, 4.6258 g of triethylamine, and 3.0000 g of pentane were combined and mixed to obtain a yellow solution. The mixture was then added to the chlorodiphenylsilane over 30 minutes. During this time, the flask contents were warmed to 8.9° C. and a large amount of white precipitate formed. The flask contents were allowed to warm to room temperature and stirred for 2 hours. The solid material was filtered off and the supernatant liquid was collected. The solid was washed twice with 30 mL of pentane, and the washings were combined with the supernatant liquid. The low boiling volatile components were stripped under vacuum to give a cloudy liquid. The liquid was then combined with 15 mL of pentane, stirred, and then filtered to give a clear liquid. The liquid was stripped under reduced pressure to give 10.2342 g of a pale yellow, clear liquid consisting of (1-methyl-2-propyn-1-yl)oxy-diphenylsilane. The product was 1 H NMR, 29 It was characterized by Si NMR and GC-mass spectrometry.

[0153] In this Reference Example 4, Pt-promoter catalyst solutions were prepared by mixing a stock solution of a soluble platinum source, such as Karstedt's catalyst [Pt2O(SiMeVi)3] or Ashby's catalyst [Pt(SiMeViO)4], with the promoter at room temperature. Reactivity was evident by a rapid color change from either a colorless or pale yellow solution, typically to an orange to dark red solution, and an exotherm. The mixture was ready for use within 1 hour to 3 days, depending on the promoter used. The mixture was 1 H, 29 Si, and 195 Characterized by Pt NMR. The Pt-promoter stock solution combinations evaluated are shown in Table 3 below.

[0154] [Table 3]

[0155] In this Example 5, a cyclic siloxazane of formula -SiMe2OSiMe2C3H6NH- was prepared by the process of the present invention, the molar ratio of allylamine to TMDSO was 2:1 or greater, and TMDSO was added to allylamine. The amounts are shown in the table below. First, the Pt-promoter solution was mixed with allylamine and any solvent at room temperature in a glass reaction flask equipped with a thermocouple, a magnetic stir bar, and a condenser cooled to -5°C to -20°C. The allylamine / catalyst solution was then heated to reflux temperature. Over time, TMDSO was fed into the mixture, producing a large amount of hydrogen immediately after addition, typically within less than 5 seconds. The solution temperature gradually increased as long as heat was added to the system during the addition of TMDSO and also when feeding TMDSO was interrupted. After feeding TMDSO was completed, the mixture was set to a temperature and stirred for 1 hour to 5 hours, then cooled to room temperature. The product cyclic siloxazane, -SiMe2OSiMe2C3H6NH-, was analyzed by GC-FID, GC-MS, and 1 H NMR, and / or 29 Characterized by Si NMR. The cyclic siloxazane, -SiMe2OSiMe2C3H6NH-, was purified by distillation as described in EP 0342518(A2) with isolated yields ranging from 65% to 85%.

[0156] [Table 4]

[0157] In this Example 6, a cyclic siloxazane of formula -SiMe2OSiMe2C3H6NH- was prepared by the process of the present invention, where the molar ratio of allylamine to TMDSO was 1:1 to less than 1:2, and TMDSO was added to allylamine in the amounts shown in the table below. First, the Pt-promoter solution was mixed with allylamine and any solvent at ambient temperature in a glass reaction flask equipped with a thermocouple, magnetic stir bar, and a condenser cooled to -5°C to -20°C. The allylamine / catalyst solution was then heated to reflux temperature. Over time, TMDSO was fed into the mixture, producing large amounts of hydrogen immediately after addition, typically within less than 5 seconds. The solution temperature gradually increased during the addition of TMDSO until a temperature of 70°C to 110°C was reached, but also increased when feeding TMDSO was discontinued as long as heat was added to the system. After feeding TMDSO was completed, the mixture was set to a temperature of 60°C to 120°C, stirred for 30 minutes to 8 hours, and then cooled to room temperature. The product cyclic siloxazane, -SiMe2OSiMe2C3H6NH-, was analyzed by GC-FID, GC-MS, and 1 H NMR, and / or 29 Characterized by Si NMR. The cyclic siloxazane, -SiMe2OSiMe2C3H6NH-, was purified by distillation techniques described in EP 0342518(A2) with isolated yields ranging from 65% to 85%.

[0158] [Table 5]

[0159] [Table 6]

[0160] In this Example 7, an example from EP 0342518(A2) (corresponding to U.S. Pat. No. 5,026,890) failed to complete the 1:1 TMDSO to allylamine process safely or with any reasonable yield. The report stated, "When a 1:1 molar ratio of allylamine and TMDSO was combined with 40 ppm of catalyst in a nitrogen atmosphere, hydrogen evolution was immediately observed. The mixture was heated to reflux and the pot temperature rose from 43° C. to 73° C. over 65 minutes, then an exothermic reaction occurred which caused an immediate rise to 155° C. The mixture was cooled to 45° C. and stripped under vacuum to yield a very small percentage of cyclic disiloxazane. The residue was steam stripped and shown to be a mixture of bis(3-aminopropyl)polydimethylsiloxane." This example showed that the process of EP 0342518(A2) does not provide good yield or purity of cyclic disiloxazane.

[0161] In this Example 8, slow addition of TMDSO to allylamine containing about 100 ppm Pt(SiMeViO)4 catalyst did not give a complete reaction, instead producing little product past 55% conversion even after 6 hours of mixing, and instead a fine black powder began to precipitate. GC-FID confirmed incomplete conversion to the cyclic siloxazane.

[0162] In this Example 9, a cyclic siloxazane of formula -SiMe2OSiMe2C3H6NH- was prepared by the process of the present invention, in which TMDSO, Pt catalyst, and promoter were added to a suitably sized glass reaction flask equipped with a thermocouple, a magnetic stir bar, and a condenser cooled to -5°C to -20°C. The solution was heated to a temperature between 40°C and 75°C. The amounts are shown in the table below. The Pt catalyst and promoter were either mixed together before being added with the TMDSO or added separately to the TMDSO. The combination of reagents caused the solution to turn yellow. Over time, allylamine was fed to the mixture, producing a large amount of hydrogen immediately after addition, typically within less than 5 seconds. There was also an exotherm that was controlled by the rate of allylamine feed and cooling through the walls of the reaction flask. The exotherm was controlled and the temperature of the reaction flask was maintained at a temperature between 50°C and 110°C by adding heat to the system after interrupting the feeding of TMDSO. After the TMDSO feed was completed, the mixture was set to a temperature of 60°C to 120°C, stirred for 30 minutes to 4 hours, and then cooled to room temperature. The product cyclic siloxazane, -SiMe2OSiMe2C3H6NH-, was analyzed by GC-FID, GC-MS, and NMR. 1 H NMR, and / or 29 Characterized by Si NMR. The cyclic siloxazane, -SiMe2OSiMe2C3H6NH-, was purified by distillation as described in EP 0342518(A2) with isolated yields ranging from 65% to 85%.

[0163] [Table 7]

[0164] [Table 8]

[0165] In this Example 10, a cyclic siloxazane of formula -SiMe2OSiMe2C3H6NH- was synthesized by a process similar to that described in U.S. Pat. No. 5,026,890, with some modifications as follows: To a 250 mL flask equipped with a glass thermowell and a refrigerated reflux condenser, 0.0224 g of 0.104 M Pt(SiMeViO)4 (approximately 2% Pt) and 5.8641 g of allyl-amine were added. The mixture was heated to reflux (Δ0=53.4° C.). 6.8820 g of 1,1,3,3-tetramethyldisiloxane (TMDSO) was added in small portions to attempt to minimize the amount of non-hydrosilylated intermediate (NHI) of formula H2C=CHCH2NHSiMe2OSiMe2H. This process step deviated from the example in U.S. Pat. No. 5,026,890, in which TMDSO was added in one aliquot. The reason for this change was that bulk addition of TMDSO to the allyl-amine would generate quantitative amounts of flammable, incompressible hydrogen gas, which is unacceptable in large production reactors due to safety concerns associated with enormous spontaneous pressure build-up and limited venting for safe handling of the toxic allyl-amine. The reflux temperature slowly increased as TMDSO was added. After 3 hours, about 70% of TMDSO had been added and the temperature had risen to 61.5°C. GC analysis of the flask contents indicated that primarily NHI had formed, with only about 4% conversion to the hydrosilylated cyclic -SiMe2OSiMe2C3H6NH-.

[0166] Heating was discontinued overnight and the solution was stirred at ambient temperature overnight. Heating to reflux was resumed the next day. After 1.5 h, the remaining TMDSO was added and heating was continued for an additional 9.5 h, at which point the temperature rose to 73.9° C. Heating was discontinued and the solution was stirred at room temperature overnight.

[0167] The next day, the solution was heated to reflux for 9 hours, reaching 106.1°C. This also deviated from the process described in Patent No. 5,026,890, where the process was carried out during the heating of one block. The heat source was removed for safety reasons leaving unreacted components at high temperatures, and experiments already showed insufficient conversion. The additional time to complete the process demonstrated the unreliability and slowness in the process described in U.S. Pat. No. 5,026,890. Analysis by GC showed that 95+% of the NHI was converted to cyclic siloxazane of formula -SiMe2OSiMe2C3H6NH-. This comparative example showed that the process of U.S. Pat. No. 5,026,890 is unsuitable for commercial scale operation due to safety concerns and the insufficient conversion achieved during the desired reaction time.

[0168] In this Example 11, cyclic-SiMe2OSiMe2CH2CH2CH2NMe- was synthesized using (1-methyl-2-propyn-1-yl)oxy-diphenylsilane (M1PPP) as the hydrosilylation promoter. 4.92 g of N-methyl-allylamine and 0.087 g of Pt / M1PPP promoter catalyst solution from Example 4g ​​(giving about 23 ppm Pt and 70 ppm promoter in the final solution mixture) were added to a 250 mL single-neck flask equipped with a molten glass thermowell and reflux condenser. The solution was heated to 62.5°C. 9.28 g of TMDSO was added over 3 hours, gradually increasing the temperature to 92°C. Gas was evolved during and after the addition. The solution temperature was then increased to 80°C and stirred for 1 hour, then cooled to ambient temperature. The crude product contained cyclic -SiMe2OSiMe2CH2CH2CH2NMe-, which was characterized by GC-FID and GC-MS. In theory, this material could be purified by the reactive distillation process described herein.

[0169] In this Example 12, cyclic -SiMe2OSiMe2OSiMe2CH2CH2CH2NH- was synthesized using allyloxy-diphenylsilane (APP) as the hydrosilylation promoter. 11.58 g of allylamine and 0.3 g of the Pt / APP promoter catalyst solution from Example 4c (giving about 22 ppm Pt and 65 ppm promoter in the final solution mixture) were added to a 250 mL single-neck flask equipped with a molten glass thermowell and reflux condenser. The solution was heated to 52.7°C. 41.07 g of 1,1,3,3,5,5-hexamethyltrisiloxane (HMTSO) was added to the reaction mixture over 7.5 hours and the temperature was gradually increased to 82.4°C. The solution was then heated to about 95° C. for 30 minutes, then cooled to about 67° C. and held there for 1.5 hours. Gas evolved during and after the addition. The solution temperature was then increased to 80° C., stirred for 1 hour, and then cooled to ambient temperature. The crude product contained cyclic-SiMe2OSiMe2OSiMe2CH2CH2CH2NH-, which was characterized by GC, but only low yields (<25%) were obtained, with the majority of the material undergoing hydrosilylation reactions on both SiH moieties on the trisiloxane, HSiMe2OSiMe2OSiMe2H, to convert to the product of the allylamine, yielding H2NCH2CH2CH2SiMe-2OSiMe2SiMe2CH2CH2CH2NH2 as the major product. In theory, the cyclic-SiMe2OSiMe2OSiMe2CH2CH2CH2NH- could be purified by the reactive distillation process described herein.

[0170] In this Example 13, a cyclic siloxazane of formula -SiMe2OSiMe2C3H6NH- was prepared by the process of the present invention, with a molar ratio of allylamine to TMDSO of 2.4:1. EP 0342518(A1) explained that the ratio of allylamine to TMDSO should be at least about 2:1, preferably about 2.2-2.5:1. Without wishing to be bound by theory, it is believed that this is to avoid the strong exotherm observed when run at a 1:1 ratio.

[0171] In a N2-filled glovebox, 2 g of stock Pt (3800 ppm)-APP promoter (11,500 ppm) in toluene solution was mixed with 23.9 g (0.42 mol) allylamine in a 250 mL single-neck reaction flask equipped with a fused glass thermowell, equipped with a thermocouple and magnetic stir bar, and equipped with a high-efficiency condenser set at approximately -15°C. The allylamine / Pt catalyst solution was then heated to reflux at approximately 52°C. A syringe was then used to intermittently feed 23.2 g (0.17 mol) TMDSO over a 4-hour period, where the average pot temperature was approximately 64°C.

[0172] Example 13 (continued): Purification of (1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane) was carried out using a simple Vigreux distillation column as follows. The condenser on the reactor in the above synthesis was replaced with about 15 cm of Vigreux distillation column connected to a distillation head with the condenser connected to a receiver chilled at about -15°C. The distillation apparatus was first heated to about 94°C at atmospheric pressure to remove most of the excess allylamine over 1.5 hours. Two small additional fractions (total = about 1.1 g) were removed under vacuum distillation. Then 0.059 g (0.44 mmol) of 100% dimethylaminopropane was removed. 1) of ammonium sulfate was added to the crude mixture. The pot was then heated to about 113° C. to distill the product. 27.54 g of 96.1% pure cyclic siloxazane was collected. The receiving flask was replaced, and then 27.54 g (84.2% yield) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane product fraction was collected over 2 hours. However, GC-MS showed that this material was only 96% pure and contained 3.5% allylamine. It is believed that better yields and purity could have been obtained using the reactive distillation process of the present invention.

[0173] In this Example 14, the synthesis of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was carried out as follows: In a N2-containing glove box, a 1 L three-necked reaction flask was connected at the top joint to 1) a high efficiency condenser cooled to about -15°C with silicone fluid; 2) a compression fitting (Kalrez O-ring) with a thermowell; and 3) a glass stopper. The top of the condenser was open to the glove box. To the reactor was added 161.4 g (2.83 mol) of allylamine and 0.82 g of a stock catalyst solution in xylene containing about 1.8% Pt and about 16.6% of the hydrosilylation promoter, allyloxy-diphenylsilane (APP). Using a heating mantle, the reactor was heated to about 52°C to reflux the solution. Next, 343.7 g (2.56 mol) of TMDSO was fed in portions over three days using a syringe. On day 1, 137 g of TMDSO was added in intermittent aliquots over 6.25 hours (fed at 1-4 g / min). After gas evolution ceased, the pot temperature virtually stopped increasing. The pot temperature increased from 52 to 63°C. The reaction mixture was allowed to cool overnight. On day 2, 195 g of TMDSO was added via syringe over 9 hours. On day 3, the final 11.7 g of TMDSO was added, and then the crude mixture was heated to approximately 102°C for 6 hours. The average pot temperature was 80°C on days 2 and 3.

[0174] Example 14 (continued): Purification of (1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane) was carried out using a simple Vigreux distillation column as follows. The condenser on the reactor in the above synthesis was replaced with about 15 cm of Vigreux distillation column connected to a distillation head with the condenser chilled to about -15°C connected to a receiver. 1.6 g (12.6 mmol) of ammonium sulfate was added and the reactor was heated to about 95°C and then placed under vacuum. A forerun of 48.75 g was slowly collected over 3 hours. The receiving flask was exchanged and then 291.5 g (60.1% yield) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane product fraction was collected over 1 hour. Quantitative UHPLC-MS analysis revealed that the 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane contained approximately 59.1 ppm allylamine. This comparative example demonstrated the limited ability to separate allylamine using a simple distillation column. This comparative example also showed a 10-15% yield loss for the distillation method of the present invention.

[0175] In this Example 15, the synthesis of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was carried out as follows: The reactor described in Comparative Example 14 was placed in a N2-containing glove box. To the reactor was added 150.1 g (2.63 mol) of allylamine and 2.51 g of a stock catalyst solution in xylene containing about 0.5% Pt and about 5.4% of the hydrosilylation promoter M2APP. Using a heating mantle, the reactor was heated to about 53° C. and the solution was refluxed. Then, using a syringe, 346.2 g (2.58 mol) of TMDSO was intermittently fed over 11 hours, where the average pot temperature was about 80° C. After about 80% of the TMDSO had been added, there was an exotherm of 5+° C. The solution was then heated to about 110° C. for 2.5 hours and then cooled to ambient temperature.

[0176] Example 15 (continued) Purification of allylamine from 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was carried out using a five tray column as follows: The condenser on the reactor in Example 14 (synthesis) was replaced with a five tray Oldershaw distillation column connected to a distillation head, the condenser was refrigerated to about -15°C and connected to a receiver. 10.0 g of crude mixture from Example 15 was removed for analysis. 1.3 g (9.8 mmol) of ammonium sulfate was added and the reactor was heated to about 95°C and then placed under vacuum. 28.04 g of forerunate was slowly collected over 2 hours. The receiver flask was replaced and then 264.2 g (55.2% yield) of cyclic siloxazane product fraction was collected over 1 hour. Quantitative UHPLC-MS analysis revealed that the cyclic siloxazane contained about 32.7 ppm of allylamine. Example 14 showed that the use of a five tray column provided a limited improvement over the Vigreux column used in Example 13. Furthermore, this Example 15 also provided a 15-20% decrease in yield relative to the reactive distillation process described herein.

[0177] In this Example 16, the synthesis of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was carried out using a continuous feed of TMDSO as follows: In a fume hood, a 1 L 4-neck flask was connected to: 1) a high efficiency condenser cooled to about -15°C with silicone fluid at the top joint; 2) a compression fitting (Kalrez O-ring) adapter supplied with Tygon™ tubing connected to a 1 L flask containing 1,1,3,3-tetramethyldisiloxane with a peristaltic pump to feed the siloxane; 3) a compression fitting with a thermowell; 4) a compression adapter connected to an in situ Raman probe. The top of the condenser was connected to Schlenk lines upstream and downstream of an oil bubbler, followed by a solution of about 0.75 M HCl (aq) to wash any remaining amine vapors into the stream. The reactor was inerted with N2. To the reactor was added 156 g (2.73 mol) of allylamine and 9 g of a stock catalyst solution in toluene solution containing about 0.25% Pt and about 2.06% of the hydrosilylation promoter M2APP. Using a heating mantle, the reactor was heated to about 51° C. and the solution was heated to reflux. A peristaltic pump was then used to feed 273 g (2.03 mol) of TMDSO over 8 hours, initially at a feed rate of 0.54 g / min for the first 3 hours, which was shown to accumulate SiH in the system. The feed was paused for 2 hours while the SiH was gradually consumed. The remaining TMDSO was then fed initially at a rate of 0.98 g / min at a temperature of about 70-80° C. After about 60% of the TMDSO had been fed, there was a significant exotherm resulting in an increase in temperature and a distinct >5° C. exotherm. After the feeds were completed, the mixture was heated to about 109° C. for 2.5 hours and then cooled to ambient temperature. The synthesis in Example 15 demonstrated that a continuous feed of SiH-terminated siloxane oligomers is not suitable for an industrial-scale process for preparing cyclic siloxazanes due to a high exotherm >5°C.

[0178] Example 16 (continued): The reaction mixture prepared above was purified as follows: The feed line of the reaction flask was replaced with a gas adapter connected to a Schlenk line. Under nitrogen flow, the condenser was replaced with a 5 tray Oldershaw distillation column connected to a distillation head with the condenser chilled to about -15°C. A magnet connected to a timed actuator was used to direct the flow into and away from the receiver. A thermocouple was used to monitor the temperature of the distillation. The reaction was stripped under vacuum at about 115°C for 4 hours with a reflux ratio of 3 to 6, until the column was nearly dry. The overhead contained only 20% cyclic siloxazane.

[0179] The solution was cooled and 0.5 g (3.78 mmol) of ammonium sulfate was added. The vacuum was then restored. A second forerunate (61.6 g) was collected at a reflux ratio of 46 over 4 hours to give a 97% pure cyclic siloxazane containing 42.5 ppm residual allylamine. The reflux ratio was then set to 3-6 and a product fraction of 226.6 g (1.20 mol) of cyclic siloxazane was collected. Quantitative UHPLC-MS analysis revealed that the cyclic siloxazane contained 0.6 ppm allylamine.

[0180] In this Example 17, the synthesis of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was carried out using a continuous feed of HMDSO as follows. The reactor described in Example 16 was modified to increase the number of trays to 10, with a distillation column, head, and receiver already attached to the reactor. The reactor was inerted with N2. The reactor was charged with 1175 g (3.06 mol) of allylamine and 10 g of a stock catalyst solution in toluene solution containing about 0.25% Pt and about 3.78% of the hydrosilylation promoter M2APP. Using a heating mantle, the reactor was heated to about 53° C. and the solution was refluxed. Then, using a peristaltic pump, 369.7 g (2.75 mol) of TMDSO was fed over 7 hours. For the first 5.5 hours, TMDSO was fed at about 0.78 g / min. After approximately 65-70% of the TMDSO had been added, the reaction exotherm accelerated rapidly, resulting in a temperature increase of >40° C. After cooling to 70-90° C., the remaining TMDSO was fed to the reactor at a rate of 1.22 g / min for 1.5 hours, during which time there was no SiH accumulation and a clear, constant, mild exotherm. The solution was then heated to approximately 109° C., mixed for 2.5 hours, and finally cooled to ambient temperature.

[0181] In this Example 18, the cyclic siloxazane was purified by reactive distillation.

[0182] The feed lines of the reaction flask described in the synthesis section of Example 17 were replaced with glass stoppers. 0.5 g (3.78 mmol) of ammonium sulfate was added and the flask was placed under vacuum. A time-based distillation was carried out as described herein. The reaction mixture in the flask was heated under vacuum for 0.75 hours to layer in the distillation column, and then an initial fraction (43.4 g) was collected over about 5 hours at a reflux ratio of about 33 to allow time for the allylamine to reform via transamination equilibrium and be removed along with other low boiling impurities. For the product fraction, the reflux ratio was switched from 1 to 3 and 292.2 g (56.1% yield) of the cyclic siloxazane was collected over 1.5 hours. Quantitative UHPLC-MS analysis revealed that the cyclic siloxazane contained about 12.7 ppm of allylamine, a clear improvement over the previous comparative example. Example 18 demonstrated that the cyclic siloxazane could be distilled to low levels of allylamine.

[0183] In this Example 19, the reactor setup described in Example 17 was used for the synthesis. To the reactor, 1175 g (3.06 mol) of allylamine and 10 g of a stock catalyst solution in toluene containing about 0.25% Pt and about 3.78% of the hydrosilylation promoter M2APP were added. Using a heating mantle, the reactor was heated to about 52° C., where the solution was refluxed. Then, using a peristaltic pump, 144.3 g (1.07 mol) of TMDSO was fed slowly at about 0.5 g / min over the first 2 hours, then paused for 1 hour, then fed for 1 hour, then paused for 1.5 hours, then fed another 30 g over 30 minutes. Unlike the other comparative examples, the SiH consumption rate decreased significantly over this time, resulting in the accumulation of SiH in the system. The feed was interrupted to allow time for the SiH to be safely consumed, and the process was stopped only when the pot temperature reached 70° C.

[0184] In this Example 20, the reactor configuration described in Example 17 was used in this process, but modified to include a nitrogen purge line into the reaction flask to slowly feed inert gas into and through the apparatus, including the reaction flask and distillation column, to push out any residual hydrogen. To the flask was added 1175 g (3.06 mol) of allylamine and 10.7 g of a stock catalyst solution in xylene containing about 0.25% Pt and about 2.06% of the hydrosilylation promoter, M2APP, and 33.0 g (0.311 mol) of xylene. Using a heating mantle, the flask was heated to about 54° C. to reflux the solution. Then, using a peristaltic pump, 331.4 g (2.47 mol) of TMDSO was fed into the reaction flask over a period of two days. On the first day, TMDSO was fed at an average rate of about 0.5 g / min in pulses lasting 0.8 to 1.5 hours, with intermittent pauses of 0.6 to 0.8 hours each. The flask was cooled overnight and then reheated to a reflux temperature of about 72°C and the remaining 137g of TMDSO was fed at a rate of about 0.92g / min over 2.75 hours during which there was no SiH accumulation and a clear, constant, mild exotherm. The reaction temperature was held at 80-90°C during this process. The reactor was then heated to about 122°C for 2.5 hours. Example 20 shows that the reactor can be flushed with an inert gas such as nitrogen to minimize or eliminate the accumulation of H2 in the reactor atmosphere and in the solution. Without wishing to be bound by theory, it is believed that H2 appears to slowly poison the catalyst if it is not flushed from the system. This also shows that the use of shorter pulses is more effective to avoid SiH accumulation.

[0185] Example 20 (continued) In the synthesis carried out in Example 20, the feed lines of the reaction flask described above were replaced with glass stoppers. 0.4 g (3.02 mmol) of ammonium sulfate was added and the flask was placed under vacuum. A time-based distillation was carried out as described above. The crude mixture was heated under vacuum for 1.5 hours to allow stratification in the distillation column, and then early fractions were collected for 1.5 hours at a reflux ratio of 25, then for 4 hours at a reflux ratio of 50 to allow time for the allylamine to reform via equilibration and be removed along with other low boiling impurities. 54.03 g of fore-cut material was collected. To test the efficiency of the allylamine separation, a comparable amount (59.8 g) of the product cyclic siloxazane was collected over 30 minutes using a reflux ratio of 2. Quantitative UHPLC-MS analysis revealed that the cyclic siloxazane contained approximately 1.5 ppm of allylamine. The receiving flask was replaced again and another 295.66 g (76.1%) of cyclic siloxazane was collected at a reflux ratio of about 2 for 2 hours, then at a reflux ratio of 6 for an additional 4.5 hours. The cyclic siloxazane collected from this step was shown to contain about 1.5 ppm allylamine. Example 20 demonstrated that pure cyclic siloxazane products with low allylamine content and good yields can be prepared by the process described herein.

[0186] In this Example 21, the reactor configuration described in Example 20 was used in the process. To the flask was added 1175 g (3.06 mol) of allylamine and 10.2 g of a stock catalyst solution in toluene containing about 0.25% Pt and about 2.06% of the hydrosilylation promoter, M2APP, and 48.6 g (0.526 mol) of toluene. Using a heating mantle, the flask was heated to about 54° C. to reflux the solution in the flask. Then, using a peristaltic pump, 311.5.4 g (2.32 mol) of TMDSO was fed into the reaction flask over a period of two days. On the first day, TMDSO was fed at an average rate of about 0.85 g / min in pulses lasting about 20 minutes each, with intermittent pauses of 20 minutes over a period of seven hours. The average feed rate was then increased to 1.2 g / min for an additional hour, with intermittent pauses of 10 and 15 minutes each. The flask was allowed to cool overnight and then reheated to a reflux temperature of about 72°C and the remaining 138 g of TMDSO was fed at an average rate of about 1.30 g / min in successive 20 minute pulses with 20 minute pauses over 4.5 hours during which there was no SiH accumulation and a clear, constant, mild exotherm. The reaction temperature was held at 75-90°C during this process. The reactor was then heated to about 118°C for 2.5 hours. Working Example 20 demonstrated that the use of intermittent feeds of SiH terminated siloxane oligomer at 10-20 minute intervals resulted in a quasi-continuous dehydrocoupling and hydrosilylation reaction with little SiH accumulation as shown by in-situ Raman analysis.

[0187] Example 21 (continued). The feed lines of the reaction flask described in Example 21 (synthesis description above) were replaced with glass stoppers. 0.4 g (3.02 mmol) ammonium sulfate was added and the flask was placed under vacuum. The reaction distillation was carried out as described herein. The mixture in the flask was heated under vacuum for 0.5 hours to allow stratification in the distillation column, and then early fractions were collected for 6 hours at a reflux ratio of 20, then for 1 hour at a reflux ratio of 50 to allow time for the allylamine to reform via equilibration and be removed along with other low boiling impurities. 50.56 g of fore-cut material was collected. The receiving flask was replaced and 317 g (70.9% yield) of the product cyclic siloxazane was collected over 6.5 hours at a reflux ratio of about 2. Quantitative UHPLC-MS analysis revealed that the cyclic siloxazane collected from this process showed to contain about 0.3 ppm of allylamine. This Example 21 showed that allylamine can be removed using the process described herein, even with a different solvent. Nearly an order of magnitude lower allylamine concentrations were achieved.

[0188] Without being bound by theory, it is believed that the above examples illustrate the following advantages of the present invention: If by-product H2 is not adequately removed, the catalyst can become poisoned during the synthesis of cyclic siloxazanes as described herein. Furthermore, a comparative (non-reactive) distillation utilizing a simple Vigreux column without a redistribution catalyst generated a 99% pure cyclic siloxazane product in 60% yield containing 60 ppm or more allylamine. However, switching to a five tray column with controlled reflux according to the process of the present invention described above improved the purity of the cyclic siloxazane product to ≥ 99.5% at 59% yield with significantly lower (e.g., 0.6-12 ppm allyl functional amine). With 10 trays, a reflux ratio of 50 during allyl functional amine removal followed by a reflux ratio of only 2 for the product fraction gave a purity of 99.8% at 76% yield with an average allyl functional amine concentration of 0.4-1.5 ppm. The inventors surprisingly found that the addition of a redistribution catalyst (e.g., ammonium sulfate in the above examples) and the resulting rearrangement requires a distillation column due to the high boiling point difference, but surprisingly found that close-boiling impurity chain-extended siloxanes are formed during the rearrangement, the formation of which was previously unknown. The application of high reflux reactive distillation to remove the close-boiling impurities during the rearrangement generated products of superior purity not previously achieved.

[0189] Part II. Preparation of Amino-Functional Polyorganosiloxanes

[0190] [Table 9]

[0191] The starting materials in Table 2, which have the DOWSIL™, SYL-OFF™, and SILASTIC™ brands, are commercially available from Dow Silicones Corporation (Midland, Mich., USA).

[0192] In this Example I, a single source of cyclic-SiMe2OSiMe2C3H6NH in MeOH solution was converted to MeO-SiMe2OSiMe2C3H6NH2 as follows: A 12 mL scintillation vial was charged with approximately 0.50 g of a crude mixture consisting of approximately 55% cyclic-SiMe2OsiMe2C3H6NH-, with the remainder consisting of hydrocarbon and siloxane materials and traces of platinum. A condenser was added to the top of the flask and cooled to approximately -15°C. Approximately 61.0 mL of methanol was added to the flask over 30 minutes, resulting in a mild exotherm of 21.3°C. The solution was refluxed at 72°C for 7 hours.

[0193] In this Working Example II, MeO-SiMe2OSiMe2C3H6NH2 was purified by distillation. The condenser on the flask from Working Example I was replaced with a 15 cm Vigreux column, a distillation head, and a receiving flask. The flask was heated to about 115°C without vacuum to remove excess methanol and other components with a boiling point lower than MeO-SiMe2OSiMe2C3H6NH2. MeO-SiMe2OSiMe2C3H6NH2 was collected under a vacuum of -20 in Hg to -28 in Hg heated to about 130°C. About 38% of the theoretical yield of MeO-SiMe2OSiMe2C3H6NH2 was collected.

[0194] In this Example III, 1,13-diamino-4,4,6,6,8,8,10,10-octamethyl-5,7,9-trioxa-4,6,8,10-tetrasilatridecane (bis-aminopropyl-tetrasiloxane), the hydrolysis product of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (cyclic-SiMe2OSiMe2C3H6NH-), was synthesized as follows: 60.15 g (0.318 mol) of cyclic-SiMe2OSiMe2C3H6NH- was added to a N2-inerted 250 mL three-neck round bottom flask equipped with a thermocouple, magnetic stir bar, gas adapter, and septum. 3.0 g (0.16 mol) of HO was added. (l)was added to the flask in four aliquots over 50 minutes with vigorous stirring, resulting in a reaction exotherm that heated the mixture from ambient temperature to approximately 50°C. The solution was stirred for 1 hour and a GC-FID / -MS sample was taken, which indicated that there was 69% conversion to bis-aminopropyl-tetrasiloxane. The mixture was stirred at ambient temperature for an additional 20 hours and another GC-FID sample was taken, which indicated 95% conversion. To speed up the process, 0.2 g (0.11 mol) of HO was added. (l) was added and the mixture was heated to about 82°C for 3 hours, cooled to ambient temperature over 1 hour and another GC-FID was taken which indicated that 99+% conversion to bis-aminopropyl-tetrasiloxane had occurred. The flask was heated to 55°C under vacuum for 75 minutes to remove excess water. The composition was confirmed by GC-FID / -MS, 1 H, 13 C, and 29 Confirmed by Si NMR.

[0195] In this Example IV, a bis-aminopropyl polydimethylsiloxane with Mw 1,400 g / mol and DP=16 was synthesized as follows: Approximately 100 g (0.1 mol) of bis-silanol terminated polydimethylsiloxane (average Mw 1,000 g / mol) (OH-PDMS2) was added to a 250 mL three-neck round bottom flask equipped with a thermocouple, a magnetic stir bar, and a condenser with a gas adapter. The flask was continuously purged with N2 and the OH-PDMS2 was vigorously stirred. The flask was then heated to approximately 64°C, at which point 39.16 g (0.207 mol) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (cyclic-SiMe2OSiMe2C3H6NH-) was added over a period of 10 minutes. The reaction mixture in the flask was heated to a maximum temperature of approximately 74°C and then began to cool. The applied heat was increased to hold the reaction mixture at 75° C. and stirred for 30 minutes. The heat was then turned off and the reaction mixture was cooled to room temperature and stirred overnight while flushing the headspace with nitrogen. The composition was: 1 H NMR, 29 Confirmed by Si NMR, the liquid had a viscosity of 8 mPa·s to 10 mPa·s.

[0196] In this Example V, the general procedure for preparing a bis-aminopropyl terminated polydimethylsiloxane was carried out as follows.

[0197] [ka]

[0198] A 20 mL vial was charged with the following starting materials: bis-silanol terminated polydimethylsiloxane and 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane. The resulting mixture was mixed at reaction temperature until homogeneous. The resulting product was bis-aminopropyl terminated polydimethylsiloxane. 29 The progress of the reaction was monitored using Si-NMR. The polymer was stable for at least 6 months after aging at 45° C. The selection and amount of bis-hydroxy terminated polydimethylsiloxane (silanol), amount of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (endcapping agent), reaction conditions, and results are shown in Table X below.

[0199] [Table 10] * Capping efficiency is 29 Analyzed by Si-NMR

[0200] Industrial Applicability Problems to be solved: Without being bound by theory, it is believed that when both hydrosilylation and dehydrocoupling reactions occur with allyl-functional amines in a process for making a reaction product containing cyclic siloxazanes, the hydrosilylation reaction is inhibited. Inhibition of one reaction can lead to excessive accumulation of both silicon-bonded hydrogen and allyl groups. It is believed that a runaway reaction can occur due to the promotion of the hydrosilylation reaction when the primary amine concentration is reduced by dehydrocoupling. It is further believed that when making cyclic siloxazanes, high boiling oligomers are formed due to multiple reactive sites on the SiH-terminated siloxane oligomers. Furthermore, hydrolyzable allyl-functional amines can bond to intermediates with close boiling points, resulting in the formation of potentially toxic amines when the resulting reaction product is exposed to air or moisture.

[0201] It is known that hydrosilylation reaction is inhibited by primary amine.The inventors have found that as long as there is SiH-terminated siloxane oligomer available for dehydrocoupling, hydrosilylation actually slows down and barely reacts, making it impractical to continuously and slowly feed SiH-terminated siloxane oligomer to eliminate the accumulation of SiH and allyl groups in one reactor.That is, when the SiH-terminated siloxane oligomer described herein is fed into a reactor containing allyl-functional amine and platinum catalyst, it is believed that only one end dehydrocoupling, and therefore the SiH of the other end does not dehydrocoupling, resulting in the accumulation of SiH.

[0202] Solution: The above working example (W) demonstrated that cyclic siloxazanes can be efficiently prepared by the process described herein. By intermittently feeding the SiH-terminated siloxane oligomer, the problem of SiH accumulation to dangerous levels can be prevented. Furthermore, using the process described herein, the yield of cyclic siloxazanes can be improved by reactive distillation under the conditions described herein by eliminating the loss of product in the head fraction of the distillation.

[0203] Cyclic siloxazanes can be used as capping agents for silanol-functional organosilicon compounds, including silanol-functional polyorganosiloxanes such as silanol-terminated polydiorganosiloxanes.Polydiorganosiloxanes with terminal amino functional groups can be prepared, and these polydiorganosiloxanes can have improved stability over amino-functional siloxanes prepared by conventional methods (e.g., as disclosed in U.S. Pat. No. 7,238,768), as demonstrated by, for example, Example XII above, which shows that the aminopropyl-terminated polydimethylsiloxane prepared as described herein has low ammonia concentration after aging at both room temperature and 45°C, and Example XIII, which shows that the viscosity of the aminopropyl-terminated polydimethylsiloxane prepared as described herein remains constant after aging at both room temperature and 45°C.

[0204] Definitions and Use of Terms Unless otherwise indicated by the context herein, all amounts, ratios, and percentages herein are by weight; the articles "a," "an," and "the" each refer to one or more; the singular includes the plural. The Summary and Abstract are incorporated herein by reference. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in Sections §2111.03 I., II., and III of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. The use of "for example," "eg," "such as," and "including" to list examples is not limiting to only the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples. Abbreviations used herein have the definitions in Table 8.

[0205] [Table 11]

[0206] The following test methods were used to determine the properties of the starting materials herein.

[0207] The viscosity of each polydiorganosiloxane (such as bis-hydroxyl terminated polydiorganosiloxanes and / or amino-functional polydiorganosiloxanes prepared therewith) having a viscosity up to 250,000 mPa·s was measured on a Brookfield DV-III cone and plate viscometer with a #CP-52 spindle at 0.1 to 50 RPM. One skilled in the art will recognize that as the viscosity increases, the rotation speed decreases and will be able to select the appropriate rotation speed when measuring the viscosity using this test method.

[0208] The Williams Plasticity of any polyorganosiloxane that is considered a gum may be determined by American Society for Testing and Materials (ASTM) Test Method 926D as described in US Pat. No. 8,877,293 (B2).

[0209] 29 Si NMR and 13 C NMR spectroscopy can be used to characterize the hydrocarbon groups in the polydiorganosiloxane (e.g., R 8 and / or R 9 The content of R groups such as 29 Si NMR spectra should be obtained using the methodology outlined by Taylor et al. in Chapter 12, pages 347-417, Section 5.5.3.1, of The Analytical Chemistry of Silicones, edited by A. Lee Smith, Chemical Analysis Vol. 112 (1991), John Wiley & Sons. In this chapter, the authors discuss the general parameters specific to obtaining quantitative NMR spectra of silicon nuclei. Each NMR spectrometer differs in terms of electronics, capabilities, sensitivity, frequency, and operating procedures. 29 Si and 13 The instrument manual of the spectrometer used must be consulted in order to tune, shim and calibrate a pulse sequence sufficient for quantitative 1D measurements of C nuclei.

[0210] The key output of an NMR analysis is the NMR spectrum. In the absence of a standard, a signal-to-noise ratio of 10:1 or greater (signal height to average baseline noise) is recommended to be considered quantitative. A properly acquired and processed NMR spectrum results in signals that can be integrated using any commercially available NMR processing software package.

[0211] From these integrals, the weight percent of the total R group content is 29 From the Si NMR spectrum, the following (I M )·(U M )=G M ;(I M(R) )·(U M(R’) )=G M(R) ;(I D )·(U D )=G D ;(I D(R) )·(U D(R) )=G D(R) ;U R / U M(R) =Y R’ ;U R / U D(R) =Y R’’ ; Y R’’ · [G M(R) / (G M +G M(R) +G D +G D(R) )·100]=W R’ ; Y R’’’ · [G D(R) / (G M +G M(R) +G D +G D(R) )·100]=W R’’ ; and W R’ +W R’’ = Total W Rwhere I is the integral signal of the indicated siloxy group, U is the unit molecular weight of the indicated siloxy group, G is a placeholder representing units in grams, W is the weight percent of the indicated siloxy units, Y is the ratio value of the specified siloxy units, R is as above, R' represents R groups from only M(R) groups, and R'' represents R groups from only D(R) groups.

[0212] -1H-NMR and 195 Pt NMR was evaluated using the following equipment and solvents: a Varian 400 MHz mercury spectrometer is used, and C6D6 is used as the solvent.

[0213] Gas Chromatography-Flame Ionization Detector (GC-FID) conditions: The capillary column was 30 m long, had an internal diameter of 0.32 mm, and contained a 0.25 μm thick stationary phase in the form of a coating on the inner surface of the capillary column, the stationary phase containing phenylmethylsiloxane. The carrier gas was helium gas at a flow rate of 105 mL per minute. The GC instrument was an Agilent Model 7890A gas chromatograph. The inlet temperature was 200°C. The GC experimental temperature profile consisted of a 2 min soak (hold) at 50°C, a ramp to 250°C at a rate of 15°C / min, and a 10 min soak (hold) at 250°C.

[0214] GC-MS Instrumentation and Conditions. Samples are analyzed by electron impact ionization and chemical ionization gas chromatography-mass spectrometry (EI GC-MS and CI GC-MS). Agilent 6890GC conditions include a DB-1 column with a 30 meter (m) x 0.25 millimeter (mm) x 0.50 micrometer (μm) membrane configuration, an inlet temperature of 200°C, an oven program of 2 min at 50°C, a 15°C / min ramp to 250°C, and 10 min at 250°C. Helium carrier gas flows at a constant flow rate of 1 mL / min and a 50:1 split injection. Agilent 5973MSD conditions include an MS scan range of 15-800 Daltons, using a custom CI gas mixture of 5% NH3 and 95% CH4 for EI and CI ionization.

[0215] The number average molecular weight of the polyorganosiloxane starting material (e.g., starting material D described herein) and the amino-functional polyorganosiloxane product) can be measured by GPC according to the test method of U.S. Patent No. 9,593,209, column 31, reference example 1. The transmittance of the amino-functional polydimethylsiloxanes prepared in the above examples was measured using a Spectronic 21: Milton Roy on a water basis.

[0216] The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of terms of description rather than of limitation. With respect to any Markush group on which the description of an individual feature or aspect herein relies, different, unusual and / or unexpected results may result from each element of the respective Markush group, independent of all other Markush group elements. Each element of a Markush group may be relied upon individually and / or in combination to provide adequate support for specific embodiments within the scope of the appended claims.

[0217] Moreover, any ranges and subranges relied upon in describing the present invention are understood to be individually and inclusively within the scope of the appended claims and to describe and contemplate the entire range encompassing all and / or partial values ​​therein, even if all and / or partial values ​​therein are not expressly set forth herein. Those skilled in the art will readily recognize that the recited ranges and subranges fully describe and enable various embodiments of the present invention, and that such ranges and subranges may be further delineated into relevant halves, thirds, fourths, fifths, etc. By way of example only, the range "1-18" may be further delineated into a lower third (i.e., 1-6), a middle third (i.e., 7-12), and an upper third (i.e., 13-18), which are individually and collectively within the scope of the appended claims, and which may be relied upon and provide appropriate justification for specific embodiments within the scope of the appended claims, individually and / or collectively. In addition, with respect to words defining or modifying a range, such as "at least," "greater than," "less than," "less than," etc., such words should be understood to include subranges and / or upper or lower limits.

Claims

1. 1. A process for preparing a cyclic siloxazane comprising: １） a) an allyl-functional amine, b) a platinum catalyst capable of catalyzing hydrosilylation reactions; c) Formula 【Chemistry 1】 (In the formula, 【Chemistry 2】 represents a bond selected from the group consisting of a double bond and a triple bond, subscript a is 1 or 2, and subscript b is 0 or 1, with the proviso that 【Chemistry 3】 is a double bond, a=2 and b=1; 【Chemistry 4】 is a triple bond, a=1 and b=0, and each R １ are independently selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R ２ is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R ３ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ４ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ５ is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; R ６ is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; Thereby forming a reaction mixture and thereafter 2) adding to the reaction mixture: d) Formula 【Chemistry 5】 (In the formula, each R ８ is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and subscript x is 1 or 2), thereby forming a cyclic siloxazane and a hydrogen (H ２ preparing a reaction product comprising a by-product comprising Optionally, 3) removing at least a portion of said hydrogen during step 2); and Optionally, 4) after step 2), heating the reaction mixture at a temperature of 110° C. to 150° C. for 1 to 6 hours; Optionally, 5) performing a reactive distillation of said reaction product, thereby purifying said cyclic siloxazane.

2. 1. A process for preparing a cyclic siloxazane comprising: １） a) an allyl-functional amine, b) a catalyst capable of catalyzing a hydrosilylation reaction; c) Formula 【Chemistry 6】 (In the formula, 【Chemistry 7】 represents a bond selected from the group consisting of a double bond and a triple bond, subscript a is 1 or 2, and subscript b is 0 or 1, with the proviso that 【Chemistry 8】 is a double bond, a=2 and b=1; 【Chemistry 9】 is a triple bond, a=1 and b=0, and each R １ are independently selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R ２ is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R ３ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ４ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ５ is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; R ６ is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; Thereby forming a reaction mixture and thereafter 2) adding to the reaction mixture: d) Formula 【Chemistry 10】 (In the formula, each R ８ is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and subscript x is 1 or 2, thereby preparing a reaction product comprising said cyclic siloxazane and a by-product comprising hydrogen; Optionally, 3) removing at least a portion of said hydrogen during step 2); and Optionally, 4) after step 2), heating the reaction mixture at a temperature of 110° C. to 150° C. for 1 to 6 hours; 5) performing a reactive distillation of said reaction product, thereby purifying said cyclic siloxazane.

3. The allyl-functional amine starting material a) is represented by the formula 【Chemistry 11】 (In the formula, each R ９ 3. The process of claim 1 or 2, wherein:

4. The process of claim 3, wherein the allyl-functional amine is selected from the group consisting of 2-methyl-allylamine and allylamine.

5. The promoter starting material c) is 【Chemistry 12】 (1,1,-dimethyl-2-propenyl)oxydiphenylsilane, 【Chemistry 13】 (1-methyl-2-propenyl)oxydiphenylsilane, 【Chemistry 14】 【Chemistry 15】 3. The process according to claim 1 or 2, wherein the compound is selected from the group consisting of:

6. 3. The process of claim 1 or 2, wherein the starting material d), the SiH-terminated siloxane oligomer, is selected from the group consisting of 1,1,3,3-tetramethyldisiloxane and 1,1,3,3,5,5-hexamethyltrisiloxane.

7. 3. The process according to claim 1 or 2, wherein the starting material e) a solvent is added during and / or after step 1).

8. 3. The process of claim 1 or 2, wherein the combining in step 1) is carried out by mixing the starting materials a), b), and c) and heating the reaction mixture to a temperature of up to 110° C.

9. 3. The process of claim 1 or 2, wherein starting materials c), the hydrosilylation reaction accelerator, and starting materials b), the platinum catalyst, are combined prior to combining starting material a), the allyl-functional amine.

10. Step 2) is carried out at a temperature of 20° C. to 200° C., and in step 2), d) adding the SiH-terminated siloxane oligomer; i) providing to the reaction mixture a first aliquot of d) the SiH terminated siloxane oligomer sufficient to provide a first SiH concentration of from 100 ppm to 1000 ppm based on the weight of the reaction mixture; ii) ceasing to feed the SiH terminated siloxane oligomer until a second SiH concentration is measured that is less than the first SiH concentration; and iii) delivering a second aliquot of said SiH terminated siloxane oligomer to said reaction mixture sufficient to provide a third SiH concentration in said reaction mixture greater than said second concentration, said third SiH concentration being between 100 ppm and 1000 ppm by weight of said reaction mixture; iv) d) repeating steps ii) and iii) one or more times until addition of the SiH terminated siloxane oligomer is completed.

11. 3. The process of claim 1 or 2, wherein step 3) is present and step 3) comprises purging with an inert gas.

12. Step 5) is carried out in a distillation apparatus comprising a distillation column having a top and a bottom with at least five theoretical trays therebetween, a reboiler connected to the bottom, and a reflux condenser connected to the top, the process comprising: i) combining a redistribution catalyst with the reaction product in the reboiler, thereby forming a redistribution reaction mixture; ii) heating said redistribution reaction mixture to reflux in said distillation column and collecting an overhead fraction comprising allyl-functional amines via said reflux condenser at a reflux ratio of from 5 to 200; iii) distilling the redistribution reaction mixture at a reflux ratio of 40 to 200 for 1 hour to 48 hours; and thereafter iv) collecting the cyclic siloxazane as an overhead fraction; 3. The process of claim 1 or 2, optionally comprising: v) recycling the overhead fraction collected in step ii) and / or the overhead fraction collected in step iii) when repeating step i).

13. 1. A process for preparing an amino-functional organosilicon compound comprising: pre-1) １） a) an allyl-functional amine, b) a platinum catalyst capable of catalyzing hydrosilylation reactions; Optionally, c) a compound of formula 【Chemistry 16】 (In the formula, 【Chemistry 17】 represents a bond selected from the group consisting of a double bond and a triple bond, subscript a is 1 or 2, and subscript b is 0 or 1, with the proviso that 【Chemistry 18】 is a double bond, a=2 and b=1; 【Chemistry 19】 is a triple bond, a=1 and b=0, and each R １ are independently selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R ２ is selected from the group consisting of hydrogen, alkyl groups of 1 to 15 carbon atoms, and aryl groups of 6 to 20 carbon atoms; R ３ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ４ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ５ is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; R ６ is an independently selected monovalent hydrocarbon radical of 1 to 15 carbon atoms; thereby forming a reaction mixture, and thereafter 2) adding to the reaction mixture: d) Formula 【Chemistry 20】 (In the formula, each R ８ is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and subscript x is 1 or 2), thereby forming a cyclic polysiloxazane and a hydrogen (H ２ preparing a reaction product comprising a by-product comprising Optionally, 3) removing at least a portion of said hydrogen during step 2); Optionally, 4) after step 2), heating the reaction mixture at a temperature of 110° C. to 150° C. for 1 to 6 hours; and A) preparing a cyclic siloxazane by carrying out a process comprising: 5) carrying out a reactive distillation of said reaction product, thereby purifying said cyclic siloxazane; １） A) the cyclic siloxazane, and D) combining starting materials including a silanol-functional organosilicon compound, thereby preparing a reaction product including said amino-functional organosilicon compound; Optionally, 2) recovering said amino-functional organosilicon compound; and Optionally, prior to step 2), adding to the reaction mixture E) an acid pre-catalyst.

14. A process for preparing an α-alkoxy-ω-amino functional polysiloxane comprising the steps of: pre-I) A) preparing a cyclic siloxazane by carrying out the process according to claim 1 or 2; I) A) the cyclic siloxazane, and B) Formula R １０ OH (in the formula, R １０ is an alkyl group of 1 to 8 carbon atoms, Thereby, the formula 【Chemistry 21】 C) preparing a reaction product comprising the α-alkoxy-ω-amino functional polysiloxane; Optionally, II) purifying said reaction product to C) recover said α-alkoxy-ω-amino functional polysiloxane.

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