Preparation of propylimine-functional organosilicon compounds and primary aminopropyl-functional organosilicon compounds

Abstract

Organosilicon compounds having primary aminopropyl functionality are prepared. A catalytic reductive amination process for combining a secondary propylimine-functional organosilicon compound with ammonia and hydrogen produces a primary aminopropyl-functional organosilicon compound.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the interests of U.S. Provisional Patent Application No. 63 / 252,639, filed on 6 October 2021, and U.S. Provisional Patent Application No. 63 / 330,571, filed on 13 April 2022, under Section 119(e) of the U.S. Patent Act. Both U.S. Provisional Patent Application No. 63 / 252,639 and U.S. Provisional Patent Application No. 63 / 330,571 are incorporated herein by reference.

[0002] (Field of invention) Processes for preparing propylimine-functional organosilicon compounds and primary aminopropyl-functional organosilicon compounds are disclosed. More specifically, the process includes protecting the propylaldehyde-functional organosilicon compound by forming a propylimine group from a propylaldehyde group, and the subsequent reductive amination of the propylimine-functional organosilicon compound using ammonia. [Background technology]

[0003] Introduction Certain amino-functional polyorganosiloxanes are useful, for example, in textile and leather processing applications. Other amino-functional polyorganosiloxanes, such as amine-terminated polydiorganosiloxanes, are useful in personal care applications such as hair care. Amine-terminated polydiorganosiloxanes may be useful, for example, in hair conditioning applications. Amino-functional polyorganosiloxanes produced by condensation may have the disadvantage of instability, as indicated by viscosity changes and / or the development of ammonia odor after aging, which is undesirable for personal care applications. Traditionally, amino-functional polyorganosiloxanes are expensive to produce by equilibration, as they require expensive starting materials and catalysts and multiple process steps to complete.

[0004] Another method for producing amino-functional polyorganosiloxanes involves using allylamine or derivatives that hydrolyze to allylamine. These are used to form amino-functional polyorganosiloxanes by performing hydrosilylation chemistry with SiH-functional polymers. However, this method has the drawback that the amino-functional polyorganosiloxane product may contain at least trace amounts of either SiH or allylamine, and due to the toxicity of allylamine and the reactivity of SiH, one of these must be removed before the product can be used for any personal care application.

[0005] Another method for producing amino-functional polyorganosiloxanes is by ammoniaxation of chloropropyl-terminated siloxanes. This expensive multi-step method has the drawback of potentially leaving residual salts (i.e., ammonium chloride) in the amine-terminated polyorganosiloxane product, which may require extensive washing to remove, making it less cost-effective and less sustainable. Furthermore, any residual ammonium chloride can produce an unpleasant odor, which is undesirable for personal care applications.

[0006] Therefore, in the organosilicon industry, there is an unmet need for synthetic methods to prepare a wide range of amino-functional organosilicon compounds with relatively high purity, high selectivity, and / or low cost. [Overview of the project]

[0007] A process for preparing a propylaldehyde-functional organosilicon compound is disclosed. The propylimine-functional organosilicon compound may be used to prepare a primary aminopropyl-functional organosilicon compound, comprising combining a propylaldehyde-functional organosilicon compound with a primary amine source as starting materials under conditions that result in a propylimine formation reaction, thereby forming a reaction product comprising the propylimine-functional organosilicon compound and water. The process further comprises forming a primary aminopropyl-functional organosilicon compound from the propylimine-functional organosilicon compound by reductive amination. [Modes for carrying out the invention]

[0008] In the processes described above and detailed below, the propylaldehyde-functional organosilicon compounds may be known propylaldehyde-functional organosilicon compounds and may be prepared by known methods as described in U.S. Patent No. 4,424,392 by Petty, U.S. Patent No. 5,021,601 by Frances et al., U.S. Patent No. 5,739,246 by Graiver et al., U.S. Patent No. 7,696,294 by Asirvatham, U.S. Patent No. 7,999,053 by Sutton et al., European Patent Application Publication No. 0392948(A1) by Frances, PCT Patent Application Publication No. 2006027074 by Kuhnle et al., and PCT Patent Application Publication No. 2022081444 by Fisk et al.

[0009] Hydroformylation Alternatively, the propylaldehyde-functional organosilicon compound may be prepared by a hydroformylation process as described in U.S. Provisional Patent Application No. 63 / 330571, filed on April 13, 2022, and incorporated herein by reference. This hydroformylation process comprises 1) combining starting materials under conditions that catalytically affect the hydroformylation reaction, wherein the starting materials comprise (A) a gas comprising hydrogen and carbon monoxide, (B) a vinyl-functional organosilicon compound, and (C) a hydroformylation reaction catalyst such as a rhodium / bisphosphoramidite ligand complex catalyst or a rhodium / tetraphosphoramidite ligand complex catalyst, thereby forming a hydroformylation reaction product comprising the propylaldehyde-functional organosilicon compound. The starting materials used in the hydroformylation process may optionally further comprise (D) a solvent.

[0010] (A) Synthesis gas The starting material (A), which is the gas used in the hydroformylation process, includes carbon monoxide (CO) and hydrogen gas (H2). For example, the gas may be synthesis gas. As used in this invention, "syngas" (from synthesis gas) refers to a gas mixture containing varying amounts of CO and H2. Methods of production are well known and include, for example, (1) steam reforming and partial oxidation of natural gas or liquid hydrocarbons, and (2) gasification of coal and / or biomass. While CO and H2 are typically the main components of synthesis gas, synthesis gas may also contain carbon dioxide and inert gases such as CH4, N2, and Ar. The molar ratio of H2 to CO (H2:CO molar ratio) varies greatly, but can range from 1:100 to 100:1, or alternatively from 1:10 to 10:1. Synthesis gas is commercially available and is often used as a fuel source or as an intermediate for producing other chemicals. Alternatively, CO and H2 from other sources (i.e., other than synthesis gas) may be used as starting material (A) as herein. Alternatively, the H2:CO molar ratio in starting material (A) for use herein may be 3:1 to 1:3, alternatively 2:1 to 1:2, or alternatively 1:1.

[0011] (B) Vinyl-functional organosilicon compound The vinyl-functional organosilicon compound has at least one vinyl group covalently bonded to silicon per molecule. Alternatively, the vinyl-functional organosilicon compound may have two or more vinyl groups covalently bonded to silicon per molecule. Starting material (B) may be a single vinyl-functional organosilicon compound. Alternatively, starting material (B) may comprise two or more different vinyl-functional organosilicon compounds. For example, the vinyl-functional organosilicon compound may comprise one or both of (B1) silane and (B2) polyorganosiloxane.

[0012] The vinyl-functional silane as starting material (B1) may be represented by formula (B1-1): R A x SiR 4 (4-x) wherein each R A is a vinyl group, each R 4 is independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an acyloxy group having 2 to 18 carbon atoms, and a hydrocarbonoxy functional group having 1 to 18 carbon atoms, and the subscript x is 1 to 4. Alternatively, the subscript x may be 1 or 2, alternatively 2, alternatively 1. Alternatively, each R 4 may be independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an acetoxy group having 2 to 18 carbon atoms, and an alkoxy functional group having 1 to 18 carbon atoms. Alternatively, each R 4 may be independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a hydrocarbonoxy functional group having 1 to 18 carbon atoms. Alternatively, each R 4 may be independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms. Alternatively, each R 4Each R in formula (B1-1) can be independently selected from the group consisting of alkyl groups with 1 to 8 carbon atoms and aryl groups with 6 to 8 carbon atoms. Alternatively, each R in formula (B1-1) 4 This can be independently selected from the group consisting of methyl and phenyl.

[0013] R 4 Suitable alkyl groups may be linear, branched, cyclic, or a combination of two or more of these. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and further examples of alkyl groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 4 The alkyl group can be selected from the group consisting of methyl, ethyl, propyl, and butyl, or alternatively, methyl, ethyl, and propyl, or alternatively, methyl or ethyl. Alternatively, R 4 The alkyl group can be methyl.

[0014] R 4 Suitable aryl groups can be monocyclic or polycyclic and may have a pendant hydrocarbyl group. For example, R 4 Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl, as well as aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, R 4 The aryl group can be monocyclic, such as phenyl, tolyl, or benzyl, or alternatively, R 4 The aryl group can be phenyl.

[0015] R 4 Suitable hydrocarbon oxy functional groups are those of the formula -OR 5 OR expression - OR 3 -OR 5 It may have, in the formula, each R 3R is a divalent hydrocarbyl group of 1 to 18 carbon atoms, which are independently selected. 5 These are independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms, and these are R 4 This is as described and illustrated above. 3 An example of a divalent hydrocarbyl group is the empirical formula -C r H 2r -Examples of alkane-diyl groups are given, where the subscript r is 2 to 8. The alkane-diyl group is a linear alkane-diyl, for example, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkane-diyl, for example,

[0016] [ka] It is possible. Alternatively, R 3 is an arylene group such as phenylene, or

[0017] [ka] These could be alkylarylene groups such as R. 3 This can be a linear alkane-diyl group such as ethylene. Alternatively, the hydrocarbon oxy functional group can be an alkoxy functional group such as methoxy, ethoxy, propoxy, or butoxy, or alternatively methoxy or ethoxy, or alternatively methoxy.

[0018] R 4 Suitable acyloxy groups are those in the formula

[0019] [ka] It may have, in the formula, R 5As stated above, a suitable example of an acyloxy group is acetoxy. Vinyl-functionalized acyloxysilanes and methods for preparing them are known in the art, for example, in U.S. Patent No. 5,387,706 by Rasmussen et al. and U.S. Patent No. 5,902,892 by Larson et al.

[0020] Suitable vinyl-functional silanes include vinyl-functional trialkylsilanes such as vinyltrimethylsilane and vinyltriethylsilane, vinyl-functional trialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and vinyltris(methoxyethoxy)silane, vinyl-functional dialkoxysilanes such as vinylphenyldiethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane, vinyl-functional monoalkoxysilanes such as trivinylmethoxysilane, vinyl-functional triacyloxysilanes such as vinyltriacetoxysilane, and vinyl-functional diacyloxysilanes such as vinylmethyldiacetoxysilane. All of these vinyl-functional silanes are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA). Furthermore, vinyl-functional silanes can be prepared by known methods, such as those disclosed in U.S. Patent No. 4,898,961 by Baile et al. and U.S. Patent No. 5,756,796 by Davern et al.

[0021] Alternatively, (B) vinyl-functional organosilicon compounds may include (B2) vinyl-functional polyorganosiloxanes. These polyorganosiloxanes may be cyclic, linear, branched, resinous, or a combination of two or more of these. The polyorganosiloxane has the unit formula (B2-1):(R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 RA SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h It may include, in the formula, R A and R 4 As described above, each Z independently consists of a hydrogen atom and R 5 (In the formula, R 5 The subscripts a, b, c, d, e, f, and g are selected from the group consisting of the above, and the subscripts a, b, c, d, e, f, and g represent the number of each unit in equation (B2-1), and have values ​​such that a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, the quantity (a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1, and the subscript h has a value such that 0≦h / (e+f+g)≦1.5. At the same time, the quantity (a+b+c+d+e+f+g) can be ≦10,000. Alternatively, if e=f=g=0, then h≧0. Alternatively, in equation (B-2-1), each R 4 R can be independently selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, and an aryl group with 6 to 18 carbon atoms. Alternatively, each R 4 R can be independently selected from the group consisting of alkyl groups with 1 to 12 carbon atoms and aryl groups with 6 to 12 carbon atoms. Alternatively, each R 4 R can be independently selected from the group consisting of alkyl groups with 1 to 8 carbon atoms and aryl groups with 6 to 8 carbon atoms. Alternatively, each R 4 Z can be independently selected from the group consisting of methyl and phenyl. Alternatively, each Z may be hydrogen or an alkyl group with 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen.

[0022] Alternatively, (B2) vinyl-functionalized polyorganosiloxanes may include (B2-2) linear polydiorganosiloxanes having at least one vinyl group per molecule, or alternatively, at least two vinyl groups (for example, in formula (B2-1) above, where subscripts e=f=g=0). For example, such polydiorganosiloxanes may have the unit formula (B2-3): (R 4 3SiO 1 / 2 ) a (R A R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R A R 4 SiO 2 / 2 ) d It may include, in the formula, R A and R 4 As stated above, subscript a is 0, 1, or 2, subscript b is 0, 1, or 2, subscript c ≥ 0, subscript d ≥ 0, where (b+d) ≥ 1, (a+b) = 2, and (a+b+c+d) ≥ 2. Alternatively, in unit formula (B2-3), the quantity (a+b+c+d) can be at least 3, alternatively at least 4, or alternatively > 50. At the same time, in unit formula (B2-3), the quantity (a+b+c+d) can be 10,000 or less, alternatively 4,000 or less, alternatively 2,000 or less, alternatively 1,000 or less, alternatively 500 or less, or alternatively 250 or less. Alternatively, in unit formula (B2-3), each R 4 These can be independently selected from the group consisting of alkyl and aryl compounds, and alternatively, methyl and phenyl compounds. Alternatively, each R in the unit formula (B2-3) 4 is an alkyl group, and alternatively, each R 4 It can be methyl.

[0023] Alternatively, the polydiorganosiloxane of unit formula (B2-3) is given by unit formula (B2-4): (R 4 2R A SiO 1 / 2 )2(R 4 2SiO 2 / 2 )m (R 4 R A SiO 2 / 2 ) n , Unit formula (B2-5): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R A SiO 2 / 2 ) p , or a combination of both (B2-4) and (B2-5).

[0024] In formulas (B2-4) and (B2-5), each R 4 and R A are as defined above. The subscript m can be 0 or a positive number. Alternatively, the subscript m can be at least 2. Alternatively, the subscript m can be 2 to 2,000. The subscript n can be 0 or a positive number. Alternatively, the subscript n can be 0 to 2000. The subscript o can be 0 or a positive number. Alternatively, the subscript o can be 0 to 2000. The subscript p is at least 2. Alternatively, the subscript p can be 2 to 2000.

[0025] The starting material (B2) is a vinyl-functionalized polydiorganosiloxane, for example, i) bis-dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), iii) bis-dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), v) bis-trimethylsiloxy-terminated polymethylvinylsiloxane, v i) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane), vii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viiii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl, vinyl-siloxy-terminated polydimethylsiloxane, and x) may include two or more combinations of i) to ix).

[0026] Methods for preparing the linear vinyl-functionalized polydiorganosiloxane described above with respect to the starting material (B2), such as hydrolysis and condensation of the corresponding organohalosilane and oligomer, or equilibration of the cyclic polydiorganosiloxane, are known in the art. See, for example, U.S. Patents 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having vinyl groups. Examples of linear polydiorganosiloxanes containing vinyl groups are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA) under trade names DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V-31, DMS-V33, DMS-V34, DMS-V35, DMS-V41, DMS-V42, DMS-V43, DMS-V46, DMS-V51, and DMS-V52.

[0027] Alternatively, (B2) vinyl-functionalized polyorganosiloxanes may be cyclic, for example, in the unit formula (B2-1) where the subscripts a=b=c=e=f=g=h=0. Cyclic vinyl-functionalized polydiorganosiloxanes are expressed in the unit formula (B2-7): (R 4 R A SiO 2 / 2 ) d It may have, in the formula, R A and R 4 As stated above, the subscript d can be 3-12, alternatively 3-6, or alternatively 4-5. Examples of cyclic vinyl-functionalized polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinyl-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexavinyl-cyclohexasiloxane. These cyclic vinyl-functionalized polydiorganosiloxanes are known in the art and are commercially available, for example, from Sigma-Aldrich (St. Louis, Missouri, USA), Milliken (Spartanburg, South Carolina, USA), and other manufacturers.

[0028] Alternatively, cyclic vinyl-functionalized polydiorganosiloxanes have the unit formula (B2-8):(R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d It may have, in the formula, R 4 and R A As stated above, the subscript c is >0 to 6, and the subscript d is >3 to 12. Alternatively, in equation (B2-8), c can be >3 to 6, and d can be >3 to 6.

[0029] Alternatively, (B2) vinyl-functionalized polyorganosiloxanes may be oligomers if, for example, the quantities (a+b+c+d+e+f+g) in the above unit formula (B2-1) are ≤ 50, ≤ 40, ≤ 30, ≤ 25, ≤ 20, ≤ 10, ≤ 5, ≤ 4, or ≤ 3. The oligomers may be cyclic, linear, branched, or a combination thereof. Cyclic oligomers are as described above as starting materials (B2-6).

[0030] An example of a linear vinyl-functionalized polyorganosiloxane oligomer is formula (B2-10):

[0031] [ka] It may have, in the formula, R 4 As stated above, each R 2 R is independent of R 4 and R A The group is selected from the following, but each molecule must have at least one R 2 R A The subscript z is 0 to 48. Alternatively, the subscript z can be 0 to 4, alternatively 0 or 1, or alternatively 0. Alternatively, in formula (B2-10), if z=0, the vinyl-functionalized polyorganosiloxane oligomer is given by formula (B2-10a).

[0032] [ka] It may have, in the formula, R A It is vinyl, R 4As stated above, examples of linear vinyl-functional polyorganosiloxane oligomers include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-vinyldisiloxane, and 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane (all of which are commercially available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA) or Sigma-Aldrich (St. Louis, Missouri, USA)).

[0033] Alternatively, vinyl-functionalized polyorganosiloxane oligomers may be branched. Branched oligomers have the general formula (B2-11):R A SiR 12 3 may be present, in the formula, R A This is vinyl as described above, and each R 12 R 13 and -OSi(R 14 ) Selected from 3, in the formula, each R 13 is a monovalent hydrocarbon group (for example, R 4 As described and illustrated above, each R is an alkyl group of 1 to 18 carbon atoms or an aryl group of 6 to 18 carbon atoms, and each R 14 R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 15 R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 16 R 13 and -[OSiR 13 2] ii OSiR 13 Selected from 3, the subscript ii has a value such that 0 ≤ ii ≤ 100. 12 At least two of them are -OSi(R 14 )3 is possible. Alternatively, R12 All three of them are -OSi(R 14 ) It could be 3.

[0034] Alternatively, in formula (B2-11), each R 12 R 13 In this case, the branched polyorganosiloxane oligomer has the following structure (B2-11a):

[0035] [ka] In the formula, R A and R 13 As stated above. Alternatively, in formula (B2-11a), each R 13 It can be methyl.

[0036] Alternatively, in formula (B2-11), each R 12 -OSi(R 14 )If it is 3, each R 14 -OSi(R 15 ) It could be in 3 parts,

[0037] [ka] In the formula, R A and R 15 As stated above, alternatively, each R 15 As mentioned above, R 13 This is possible, and each R 13 It can be methyl.

[0038] Alternatively, in formula (B2-11), each R 12 -OSi(R 14 )If it is 3, one R 14 Each R 12 ga-OSiR 13 (R 14 Each -OSi(R) is such that )2 14 )3 in R 13It is possible. Alternatively, -OSiR 13 (R 14 )2 R in 2 14 Each of these has the following branched polyorganosiloxane oligomer structure (B2-11c):

[0039] [ka] (In the formula, R A , R 13 , and R 15 -OSi(R 15 ) It could be in 3 parts. Alternatively, each R 15 R 13 This is possible, and each R 13 It can be methyl.

[0040] Alternatively, in equation (B2-11), one R 12 R 13 It could be, R 12 Two of them are -OSi(R 14 ) It could be 3. R 12 Two of them are -OSi(R 14 )If it is 3, one R 14 Each -OSi(R 14 )R in 3 13 And R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 The branched polyorganosiloxane oligomer has the following structure (B2-11d):

[0041] [ka] (In the formula, R A , R 13 , and R 15 -OSi(R 15 )3 is possible. Alternatively, each R 15R 13 This is possible, and each R 13 This can be methyl. Alternatively, vinyl-functionalized branched polyorganosiloxanes may have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, or alternatively 4 to 10 silicon atoms per molecule. An example of a vinyl-functionalized branched polyorganosiloxane oligomer is formula:

[0042] [ka] Vinyl-tris(trimethyl)siloxy)silane having formula

[0043] [ka] Methyl-vinyl-di((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane having, and formula

[0044] [ka] Examples include vinyl-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane having the above characteristics. The branched vinyl-functional polyorganosiloxane oligomers described above can be prepared by known methods, such as those disclosed in Grande et al., "Testing the Functional Tolerance of the Piers-Rubinsztajn Reaction: A New Strategy for Functional Silicones," Supplementary Material (ESI) for Chemical Communications, copyright The Royal Society of Chemistry 2010.

[0045] Alternatively, the (B2) vinyl-functional polyorganosiloxane may be branched, such as a branched vinyl-functional polyorganosiloxane (for example, in formula (B2-1), when the quantity (a+b+c+d+e+f+g)>50) which may have more vinyl groups and / or more polymer units per molecule than the above-mentioned branched oligomer and / or branched oligomer. The branched vinyl-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide >0~5 mol% trifunctional and / or tetrafunctional units in the (B2-1) branched vinyl-functional polyorganosiloxane.

[0046] For example, branched vinyl-functionalized polyorganosiloxanes have the unit formula (B2-13):(R 4 3SiO 1 / 2 ) q (R 4 2R A SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t It may contain a Q-type branched polyorganosiloxane, in which R 4 and R A As stated above, the subscripts q, r, s, and t have mean values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, and (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity >170 mPa·s to the branched polyorganosiloxane, as measured by a rotational viscometer (described below along with the test method). Alternatively, the viscosity may be >170 mPa·s to 1000 mPa·s, alternatively >170 mPa·s to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, or alternatively 190 mPa·s to 420 mPa·s. Suitable Q-type branched polyorganosiloxanes for the starting material (B2-12) are known in the art and can be prepared by known methods, as exemplified by Cray et al.'s U.S. Patent No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0047] Alternatively, branched vinyl-functionalized polyorganosiloxanes are given by formula (B2-14):[R A R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w It may include, in the formula, R A and R 4 As stated above, the subscripts v, w, and x have values ​​such that 200≧v≧1, 2≧w≧0, and 200≧x≧1. Alternatively, in this equation (B2-14), each R 4 The compound is independently selected from the group consisting of methyl and phenyl. Branched polyorganosiloxanes suitable as starting materials (B2-14) can be prepared by known methods, such as heating a mixture containing a polyorganosilicate resin and a cyclic polydiorganosiloxane or a linear polydiorganosiloxane in the presence of a catalyst such as an acid or a phosphazene base, and then neutralizing the catalyst.

[0048] Alternatively, a branched vinyl-functional polyorganosiloxane for the starting material (B2-11) is given by unit formula (B2-15): (R 4 3SiO 1 / 2 ) aa (R A R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R A R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd It may contain a T-branched polyorganosiloxane (silsesquioxane), in which R 4 and R AAs stated above, the subscript aa≧0, the subscript bb>0, the subscript cc is between 15 and 995, the subscript dd>0, and the subscript ee≧0. The subscript aa can be between 0 and 10. Alternatively, the subscript aa may have values ​​such as 12≧aa≧0, 10≧aa≧0, 7≧aa≧0, 5≧aa≧0, and 3≧aa≧0. Alternatively, the subscript bb≧1. Alternatively, the subscript bb≧3. Alternatively, the subscript bb may have values ​​such as 12≧bb>0, 12≧bb≧3, 10≧bb>0, 7≧bb>1, 5≧bb≧2, and 7≧bb≧3. Alternatively, the subscript cc can have a value such that 800≧cc≧15, or alternatively, 400≧cc≧15. Alternatively, the subscript ee can have a value such that 800≧ee≧0, 800≧ee≧15, or alternatively, 400≧ee≧15. Alternatively, the subscript ee can be 0. Alternatively, the quantity (cc+ee) can have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd can be 1 to 10. Alternatively, the subscript dd can have a value such that 10≧dd>0, alternatively, 5≧dd>0, or alternatively, dd=1. Alternatively, the subscript dd can be 1 to 10, and alternatively, the subscript dd can be 1 or 2. Alternatively, if subscript dd = 1, subscript bb may be 3 and subscript cc may be 0. The value of subscript bb may be sufficient to provide a silsesquioxane of unit formula (B2-15) having a vinyl content of 0.1% to 1%, or alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane. Suitable T-branched polyorganosiloxanes (silsesquioxanes) for the starting material (B2-15) are exemplified by those disclosed in U.S. Patent No. 4,374,967 by Brown et al., U.S. Patent No. 6,001,943 by Enami et al., U.S. Patent No. 8,546,508 by Nabeta et al., and U.S. Patent No. 10,155,852 by Enami.

[0049] Alternatively, (B2) vinyl-functionalized polyorganosiloxanes are given by formula R M 3SiO 1 / 2 The monofunctional unit ("M" unit) and formula SiO 4 / 2 The formula may include a vinyl-functional polyorganosilicate resin containing tetrafunctional silicate units ("Q" units), where each R M is an independently selected monovalent hydrocarbon group, and each R M This is independently of the above R 4 and R A A selection can be made from the group consisting of . Alternatively, each R M The R can be selected from the group consisting of alkyl, vinyl, and aryl. Alternatively, each R M R can be selected from methyl, vinyl, and phenyl. Alternatively, M At least one-third, and alternatively at least two-thirds, of the groups are methyl groups. Alternatively, the M group is (Me3SiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2ViSiO 1 / 2 Polyorganosilicate resins are soluble in solvents such as those described herein as starting materials (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low-viscosity linear and cyclic polydiorganosiloxanes.

[0050] When prepared, the polyorganosilicate resin comprises the above M units and Q units, and the polyorganosiloxane comprises silicon-bonded hydroxyl groups and / or the above portion (ZO 1 / 2 It further comprises units having hydrolyzable groups as described by the formula Si(OSiR M 3) May contain a neopentamer of 4, where R M As stated above, for example, the neopentamer may be a tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13Using 13C NMR spectroscopy, the hydroxyl and alkoxy content, as well as the molar ratio of M units to Q units, can be measured. This ratio is expressed as {M(resin)} / {Q(resin)}, where M units and Q units are excluded 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 0.5 / 1 to 1.5 / 1, or alternatively 0.6 / 1 to 0.9 / 1.

[0051] The Mn in polyorganosilicate resin is present in R M It varies depending on various factors, such as the type of hydrocarbon group represented. The Mn of polyorganosilicate resins refers to the number-average molecular weight measured using GPC when peaks representing neopentamers are excluded from the measurement. The Mn of polyorganosilicate resins can be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, or alternatively >3,000 Da to 8,000 Da. Alternatively, the Mn of polyorganosilicate resins may be 3,500 Da to 8,000 Da.

[0052] The fifth line of column 3 to the thirtieth line of column 4 of U.S. Patent No. 8,580,073, and paragraphs

[0023] to

[0026] of U.S. Patent Application Publication No. 2016 / 0376482 are incorporated herein by reference to disclose the MQ resin, which is a polyorganosilicate resin suitable for use as a starting material (B2). The polyorganosilicate resin can be prepared by any preferred method, such as co-hydrolysis of the corresponding silane or silica hydrosol capping. The polyorganosilicate resin can be prepared by silica hydrogel capping processes, such as those disclosed in U.S. Patent No. 2,676,182 by Daudt et al., U.S. Patent No. 4,611,042 by Rivers-Farrell et al., and U.S. Patent No. 4,774,310 by Butler et al. The method by Daudt et al. described above involves reacting a silica hydrosol with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a mixture thereof under acidic conditions, and recovering a copolymer having M and Q units. The resulting copolymer generally contains 2 to 5 weight percent of hydroxyl groups.

[0053] The intermediates used to prepare the polyorganosilicate resin may be a triorganosilane and a silane or alkali metal silicate containing four hydrolyzable substituents. The triorganosilane is of formula R M 3SiX may be present, in the formula, R M As described above, X represents a hydroxyl group, or, for example, a hydrolyzable substituent of the formula OZ above. A silane having four hydrolyzable substituents is given by the formula SiX ’ 4 may have, in the formula, each X ’ This is independently selected from the group consisting of halogens, alkoxys, and hydroxyls. A suitable alkali metal silicate is sodium silicate.

[0054] The polyorganosilicate resin prepared as described above is typically, for example, of the formula HOSiO 3 / 2It contains silicon-bonded hydroxyl groups. Polyorganosilicate resins may contain up to 3.5% silicon-bonded hydroxyl groups, as measured by FTIR and / or NMR spectroscopy as described above. For specific applications, the amount of silicon-bonded hydroxyl groups may be desirable to be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, or alternatively 0.3% to 0.8%. Silicon-bonded hydroxyl groups formed during the preparation of polyorganosilicate resins can be converted to trihydrocarbon siloxane groups or different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane, or disilazane containing appropriate terminal groups. Silanes containing hydrolyzable groups may be added in molar excess beyond the amount required to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0055] Alternatively, polyorganosilicate resins may contain 2% or less, 0.7% or less, 0.3% or less, or 0.3% to 0.8% hydroxyl groups, for example, formula XSiO 3 / 2 The formula may further include units that contain what is represented by, where R M As described above, X represents a hydrolyzable substituent, such as OH. The concentration of silanol groups (wherein X=OH) present in the polyorganosilicate resin can be determined using FTIR spectroscopy and / or NMR as described above.

[0056] For use herein, the polyorganosilicate resin further comprises one or more vinyl groups per molecule. Polyorganosilicate resins having vinyl groups can be prepared by reacting the product of Daudt et al. with a vinyl group-containing end-capping agent and an aliphatic unsaturated end-capping agent in an amount sufficient to provide 3 to 30 mole percent of vinyl groups in the final product. Examples of end-capping agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable end-capping agents are known in the art and are exemplified in U.S. Patent No. 4,584,355 by Blizzard et al., U.S. Patent No. 4,591,622 by Blizzard et al., and U.S. Patent No. 4,585,836 by Homan et al. Such resins can be prepared using a single end-capping agent or a mixture of such agents.

[0057] Alternatively, polyorganosilicate resins have the unit formula (B2-17):(R 4 3SiO 1 / 2 ) mm (R 4 2R A SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h It may include, in the formula, Z, R 4 , and R A , as well as the subscript h, are as described above, and the subscripts mm, nn, and oo have mean values ​​such that mm≧0, nn>0, oo>0, and 0.5≦(mm+nn) / oo≦4. Alternatively, 0.6≦(mm+nn) / oo≦4, alternatively, 0.7≦(mm+nn) / oo≦4, and alternatively, 0.8≦(mm+nn) / oo≦4.

[0058] Alternatively, (B2) vinyl-functionalized polyorganosiloxane is (B2-18) vinyl-functionalized silsesquioxane resin, i.e., unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b(R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h may comprise a resin containing a trifunctional (T) unit, wherein R 4 and R A are as defined above, and the subscripts satisfy f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0<h / (e+f)<1.5. Alternatively, the vinyl-functional silsesquioxane resin may have the unit formula (B2-19):(R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein R 4 , R A , Z, and the subscripts h, e, and f are as defined above. Alternatively, the vinyl-functional silsesquioxane resin may further comprise, in addition to the T units described above, a difunctional (D) unit of the formula R 4 2SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d , that is, a DT resin, wherein the subscripts c and d are as defined above. Alternatively, the vinyl-functional silsesquioxane resin may further comprise a monofunctional (M) unit of the formula (R 4 3SiO 1 / 2 ) a (R 4 2R A SiO 1 / 2 ) b , that is, an MDT resin, wherein the subscripts a and b are as defined above for the unit formula (B2-1).

[0059] Vinyl-functionalized silsesquioxane resins are commercially available, for example. The unit formula (B2-20) when dissolved in toluene is (Me2ViSiO2). 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 RMS-310, which contains D units, is commercially available from DSC. Vinyl-functionalized silsesquioxane resins can be produced by hydrolysis and condensation or mixtures of trialkoxysilanes using methods such as those described in Noll's "Chemistry and Technology of Silicone," Academic Press (1968), Chapter 5, pp. 190-245. Alternatively, vinyl-functionalized silsesquioxane resins can be produced by hydrolysis and condensation of trichlorosilanes using the methods described in U.S. Patent No. 6,281,285 by Becker et al. and U.S. Patent No. 5,010,159 by Bank et al. Vinyl-functionalized silsesquioxane resins containing D units can be prepared by known methods such as those disclosed in U.S. Patent Application No. 2020 / 0140619 and International Publication No. 2018 / 204068 by Swier et al.

[0060] Alternatively, the starting material (B), a vinyl-functionalized organosilicon compound, may include (B3) vinyl-functionalized silazanes. Vinyl-functionalized silazanes are given by formula (B3-1):[(R 1 (3-gg) R A gg Si) ff NH (3-ff) ] hh It may have, in the formula, R A As stated above, each R 1 The subscripts are independently selected from the group consisting of alkyl groups and aryl groups, each subscript ff is independently 1 or 2, and each subscript gg is independently 0, 1 or 2. <hh<10である。R 1 Regarding alkyl and aryl groups, 4may be the alkyl group and aryl group as described above. Alternatively, the subscript hh may have a value such that 1<hh<6. Examples of the vinyl-functional silazane include MePhViSiNH2, Me2ViSiNH2, (ViMe2Si)2NH, and (MePhViSi)2NH. The vinyl-functional silazane can be prepared by a known method, for example, reacting a vinyl-functional halosilane with ammonia under anhydrous or substantially anhydrous conditions, and then distilling the resulting reaction mixture to separate the cyclic vinyl-functional silazane and the linear vinyl-functional silazane, which are disclosed in, for example, U.S. Patent No. 2,462,635 to Haber, U.S. Patent No. 3,243,404 to Martellock, and International Publication No. WO 83 / 02948 to Dziark. Suitable vinyl-functional silazanes are commercially available, for example, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane (MeViSiNH)3 is available from Sigma-Aldrich (St. Louis, MO, USA), sym-tetramethyldivinyldisilazane (ViMe2Si)2NH is available from Alfa Aesar, and 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisilazane (MePhViSi)2NH is available from Gelest, Inc. (Morrisville, Pennsylvania, USA).

[0061] The starting material (B) may be any one of the above vinyl-functional organosilicon compounds. Alternatively, the starting material (B) may comprise a mixture of two or more of the vinyl-functional organosilicon compounds.

[0062] (C) Hydroformylation reaction catalyst The hydroformylation catalyst, which is the starting material (C) for use herein, comprises an active complex of rhodium and a ligand. The ligand may be symmetric or asymmetric. Alternatively, the ligand may be symmetric. The ligand may contain a bisphosphoamidite ligand, or alternatively, a bisphosphoamidite ligand. Alternatively, the ligand may contain a tetraphosphoamidite ligand, or alternatively, a tetraphosphoamidite ligand. Alternatively, the ligand may contain a phosphineamine ligand, or alternatively, a phosphineamine ligand. Alternatively, the ligand may contain a phosphine ligand, or alternatively, a phosphine ligand. Alternatively, the hydroformylation catalyst, which is the starting material (C), may comprise a combination of rhodium / ligand complexes containing different types of ligands.

[0063] The ligand has formulas (C1), (C2), and / or (C3), Equation (C1) is,

[0064] [ka] And, Equation (C2) is,

[0065] [ka] And, Equation (C3) is,

[0066] [ka] And, In the formula, R 101 ~R 122 Each is independently selected from hydrogen, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group, R 101 ~R 122 Two or more of these may be optionally combined to give one or more ring parts, X 1~X 4 Each of the following is independently selected from O, CH2, NH, NR, NSO2R, or NSO2A, where each R is independently selected substituted or unsubstituted alkyl or aryl group, and each A is independently selected aryl or heteroaryl group, Y 1 ~Y 8 Each of the elements is an independently selected nitrogen-containing heterocyclic moiety bonded to P via N, where each heterocyclic moiety may be substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO3H, sulfonate, amino, trifluoromethyl, and halogen.

[0067] The ligand may have formula (C1). Alternatively, the ligand may have formula (C2). Alternatively, the ligand may have formula (C3).

[0068] R 101 ~R 122The preferred hydrocarbyl groups may independently be linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is the aralkyl group. "Substitution" means that one or more hydrogen atoms may be replaced by atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, or bromine). Preferred alkyl groups are exemplified by, but are not limited to, 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, and branched saturated hydrocarbon groups with six carbon atoms. Suitable aryl groups include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, alkyl halides having 1 to 6 carbon atoms or aryl halides having 6 to 10 carbon atoms. Suitable alkyl halides include, but are not limited to, the alkyl groups mentioned above in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl.For example, fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples of suitable alkyl halogenated groups. Suitable aryl halogenated groups are exemplified by, but are not limited to, the above-mentioned aryl groups in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. For example, chlorobenzyl and fluorobenzyl are suitable aryl halogenated groups. Suitable heterocarbyl groups include any of the hydrocarbyl groups listed above, but contain one or more heteroatoms such as oxygen, sulfur, or nitrogen. Suitable halogen atoms include F, Cl, Br, I, At, and Ts, alternatively F, Cl, and Br, and alternatively Cl.

[0069] As mentioned above, R 101 ~R 122 Two or more of these can be optionally combined to give one or more ring sections. 101 ~R 122 The cyclic portion formed by any combination of these elements may be aliphatic or aromatic, and may be monocyclic, bicyclic, or polycyclic.

[0070] For example, if the ligand has formula (C1), R 101 , R 102 , R 107 , and R 108 If each of them is H, then R 103 and R 104 R forms an aliphatic ring, 105 and R 106 When they come together to form an aliphatic ring, the ligands of equation (C1) are given by the following equation (C1-1):

[0071] [ka] In the formula, X 1 , X 2 , and Y 1 ~Y 4 This is defined above.

[0072] As another example, if the ligand has formula (C1), R 101 R 102 , R 107 , and R 108 Each of these is H, and R 103 and R 104 R forms an aromatic ring, 105 and R 106 When they come together to form an aromatic ring, the ligand of formula (C1) is given by the following formula (C1-2):

[0073] [ka] In the formula, X 1 , X 2 , and Y 1 ~Y 4 This is defined above.

[0074] As yet another example, if the ligand has formula (C1), R 103 , R 104 , R 105 , and R 106 Each of these is H, and R 101 and R 102 This forms a bicyclic aromatic structure, R 107 and R 108 When these combine to form a bicyclic aromatic structure, the ligands of formula (C1) are given by the following formula (C1-3):

[0075] [ka] In the formula, X 1 , X2 , and Y 1 ~Y 4 This is defined above.

[0076] X 1 ~X 4 Each of the following is independently selected from O, CH2, NH, NR, NSO2R, or NSO2A, where each R is an independently selected substituted or unsubstituted alkyl or aryl group, and each A is an independently selected aryl or heteroaryl group. Alternatively, X 1 ~X 4 Each of these can be O.

[0077] Y 1 ~Y 8 Each of the is an independently selected nitrogen-containing heterocyclic moiety bonded to P via N, where each heterocyclic moiety may be substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO3H, sulfonate, amino, trifluoromethyl, and halogen. 1 ~Y 8 Each of these can independently be monocyclic, bicyclic, and / or polycyclic. Exemplary examples of nitrogen-containing heterocyclic groups include indole, isoindole, pyrrole, carbazole, and imidazole groups. As described above, any of the carbon atoms in these groups can be substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO3H, sulfonate, amino, trifluoromethyl, and halogen. Alternatively, Y 1 ~Y 8 At least one of these can be substituted with an alkoxy group having 1 to 8 carbon atoms. Alternatively, Y 1 ~Y 8 At least one of these is substituted with an alkyl group having 1 to 12 carbon atoms, such as a tert-butyl group.

[0078] Alternatively, the ligand may have the formula (C1), where R101 ~R 108 , X 1 ~X 2 , and Y 1 ~Y 4 The ligand is selected such that it is a bisphosphoamidite ligand having one of the following formulas (wherein Me represents methyl and tBu represents t-butyl):

[0079] [ka] 2,2'-Bis((di(1H-indole-1-yl)phosphanyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene

[0080] [ka] 2,2'-Bis((Bis(6-(4-methoxyphenyl)-1H-indole-1-yl)phosphanyl)oxy)-5,5',6,6',7,7',8,8'-Octahydro-1,1'-binaphthalene

[0081] [ka] 2,2'-Bis((Bis(6-(4-methoxyphenyl)-1H-indole-1-yl)phosphanyl)oxy)-5,5',6,6',7,7',8,8'-Octahydro-1,1'-binaphthalene

[0082] [ka] 2,2'-Bis((Bis(6-(3,5-di-tert-butylphenyl)-1H-indole-1-yl)phosphanyl)oxy)-1,1'-binaphthalene

[0083] [ka] 1,1',1'',1'''-(((4,4',5,5',6,6'-Hexamethyl-[1,1'-biphenyl]-2,2'-diyl)bis(oxy))bis(phosphantriyl))tetrakis(6-(3,5-di-tert-butylphenyl)-1H-indole), and

[0084] [ka] 2,2'-Bis((Bis(6-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indole-1-yl)phosphanyl)oxy)-5,5',6,6',7,7',8,8'-Octahydro-1,1'-binaphthalene A method for preparing the first ligand structure described in this section for formula (C1) is disclosed in U.S. Patent No. 9,795,952 by Diebolt et al., which is incorporated herein by reference in its entirety.

[0085] Alternatively, the ligand may have equation (C2), R 109 ~R 122 , X 1 ~X 2 , and Y 5 ~Y 8 The ligand is selected such that it is a bisphosphoamidite ligand having one of the following formulas: (C2-1):

[0086] [ka] 7,7'-Bis((bis(6-(3,5-di-tert-butylphenyl)-1H-indole-1-yl)phosphanyl)oxy)-2,2',3,3'-tetrahydro-1,1'-spirobio[indene] and (C2-2):

[0087] [ka] 7,7'-Bis((di(1H-indole-1-yl)phosphanyl)oxy)-2,2',3,3'-tetrahydro-1,1'-spirobio[indene].

[0088] Alternatively, the ligand may have equation (C3), R 101 ~R 106 , X 1 ~X 4 , and Y 1 ~Y 8 The ligand can be selected such that it is a tetraphosphoamidite ligand having one of the following formulas: (C3-1)

[0089] [ka] (C3-2)

[0090] [ka] Methods for preparing these ligand structures described above in this section for formula (C3) are disclosed in U.S. Patent No. 7,531,698 by Zhang et al., which is incorporated herein by reference in its entirety.

[0091] The rhodium / ligand complex catalyst, which is the starting material (C), can be prepared by changing the appropriate starting material by methods known in the art, such as those disclosed in U.S. Patent No. 4,769,498 by Billig et al., column 20, line 50 to column 21, line 40, and in U.S. Patent No. 10,023,516 by Brammer et al., column 11, line 35 to column 12, line 12. For example, the rhodium / ligand complex catalyst can be prepared by a process comprising combining a rhodium precursor with the ligand under conditions that form a complex, and the complex can then be introduced into a hydroformylation reaction medium containing one or both of the starting materials (A) and / or (B). Alternatively, for the in-situ formation of the rhodium / ligand complex catalyst, the rhodium catalyst precursor and ligand can be introduced into the reaction medium (e.g., before, during, and / or after the introduction of the rhodium catalyst precursor) to form the rhodium / ligand complex catalyst in situ. The rhodium / ligand complex catalyst can be activated by heating and / or exposure to the starting material (A) to form the (C) rhodium / ligand complex catalyst. The rhodium catalyst precursor is rhodium dicarbonylacetylacetonate, Rh2O3,Rh4(CO) 12 , Rh6(CO) 16 , and Rh(NO3)3 are exemplified. Further methods for preparing certain ligands are described herein in the attached examples.

[0092] For example, a rhodium precursor such as rhodium dicarbonylacetylacetonate, optionally a starting material (D), a solvent, and a ligand can be combined by any convenient means, such as mixing. The resulting rhodium / ligand complex catalyst can optionally be introduced into the reactor along with an excess ligand. Alternatively, the rhodium precursor, solvent (D), and ligand can be combined in the reactor with a vinyl-functional organosilicon compound which is a starting material (A) and / or (B), and a rhodium / ligand complex can be formed in situ. The relative amounts of ligand and rhodium precursor are sufficient to provide ligand / Rh molar ratios of 10 / 1 to 1 / 1, alternatively 5 / 1 to 1 / 1, alternatively 3 / 1 to 1 / 1, and alternatively 2.5 / 1 to 1.5 / 1. In addition to the rhodium / ligand complex catalyst, an excess (e.g., uncomplexed) ligand may be present in the reaction mixture. The excess ligand may be the same as or different from the ligand in the rhodium / ligand complex catalyst.

[0093] (C) The amount of rhodium / ligand complex catalyst (catalyst) is sufficient to catalytically catalyze the hydroformylation of (B) the vinyl-functional organosilicon compound. The exact amount of (C) rhodium / ligand complex catalyst depends on various factors, including the type of vinyl-functional organosilicon compound selected for the starting material (B), its exact vinyl content, and reaction conditions such as the temperature and pressure of the starting material (A). However, the amount of (C) rhodium / ligand complex catalyst may be sufficient to provide a rhodium metal concentration of at least 0.1 ppm, alternatively 0.15 ppm, alternatively 0.2 ppm, alternatively 0.25 ppm, or alternatively 0.5 ppm, based on the weight of the vinyl-functional organosilicon compound (B). At the same time, the amount of (C) rhodium / ligand complex catalyst may be sufficient to provide a rhodium metal concentration of up to 300 ppm, alternatively up to 100 ppm, alternatively up to 20 ppm, or alternatively up to 5 ppm, based on the same criteria. Alternatively, the amount of (C) catalyst may be sufficient to provide 0.1 ppm to 300 ppm, alternatively 0.2 ppm to 100 ppm, alternatively 0.25 ppm to 20 ppm, or alternatively 0.5 ppm to 5 ppm, based on the weight of (B) vinyl-functionalized organosilicon compound.

[0094] The hydroformylation process reaction can be carried out without additional solvents. Alternatively, the hydroformylation process reaction may be carried out with a solvent to facilitate the mixing and / or supply of one or more of the above starting materials, such as (C) a rhodium / ligand complex catalyst and / or a vinyl-functional organosilicon compound which is the starting material (B), for example, when a vinyl-functional polyorganosilicon resin is selected for the starting material (B). The solvent is exemplified by aliphatic or aromatic hydrocarbons that can dissolve the starting materials, such as toluene, xylene, benzene, hexane, heptane, decane, cyclohexane, or a combination of two or more of these. Additional solvents include THF, dibutyl ether, diglyme, and texanol. Although not intended to be constrained by theory, it is thought that solvents may be used to reduce the viscosity of the starting materials. The amount of solvent is not critical, but if present, the amount of solvent may be 5% to 70% based on the weight of the vinyl-functional organosilicon compound which is the starting material (B).

[0095] In the hydroformylation process described herein, the hydroformylation reaction in step 1) is carried out at a relatively low temperature. For example, step 1) may be carried out at a temperature of at least 30°C, alternatively at least 50°C, or alternatively at least 70°C. At the same time, the temperature in step 1) may be up to 150°C, alternatively up to 100°C, alternatively up to 90°C, or alternatively up to 80°C. While we do not wish to be constrained by theory, it is considered that lower temperatures, such as 30°C to 90°C, alternatively 40°C to 90°C, alternatively 50°C to 90°C, alternatively 60°C to 90°C, alternatively 70°C to 90°C, alternatively 80°C to 90°C, alternatively 30°C to 60°C, or alternatively 50°C to 60°C, may be desirable to obtain high selectivity and ligand stability.

[0096] In the hydroformylation process described herein, step 1) may be carried out at a pressure of at least 101 kPa (ambient pressure), alternatively at least 206 kPa (30 psi), or alternatively at least 344 kPa (50 psi). Simultaneously, the pressure in step 1) may be up to 6,895 kPa (1,000 psi), alternatively up to 1,379 kPa (200 psi), alternatively up to 1,000 kPa (145 psi), or alternatively up to 689 kPa (100 psi). Alternatively, step 1) may be carried out at a range of 101 kPa to 6,895 kPa, alternatively 344 kPa to 1,379 kPa, alternatively 101 kPa to 1,000 kPa, or alternatively 344 kPa to 689 kPa. While we do not wish to be constrained by theory, it is considered that using relatively low pressures, e.g., <~6,895 kPa, may be beneficial in the processes described herein, and the ligands described herein enable low-pressure hydroformylation processes, which have the advantages of being less costly and safer than high-pressure hydroformylation processes.

[0097] The hydroformylation process can be carried out in batch, semi-batch, or continuous manner using one or more suitable reactors, such as fixed-bed reactors, fluidized-bed reactors, continuous stirred tank reactors (CSTRs), or slurry reactors. The choice of (B) vinyl-functional organosilicon compounds, (C) catalysts, and (D) solvents may influence the size and type of reactor used. One reactor or two or more different reactors may be used. The hydroformylation process can be carried out in one or more steps, which may be influenced by balancing capital costs, achieving high catalyst selectivity, activity, lifetime, and ease of operation, as well as the reactivity of specific starting materials and the reaction conditions selected, and the desired product.

[0098] Alternatively, the hydroformylation process may be carried out in a continuous manner. For example, the process used may be one as described in U.S. Patent No. 10,023,516, wherein the olefin feed stream and catalyst described therein are replaced by (B) vinyl-functional organosilicon compounds and (C) rhodium / ligand complex catalysts as described herein, respectively.

[0099] Step 1) of the hydroformylation process forms a hydroformylation reaction product comprising a propylaldehyde-functional organosilicon compound. The hydroformylation reaction product may further include additional materials, such as those intentionally used during step 1) of the process or those formed in situ. Examples of such materials that may similarly be present include unreacted (B) vinyl-functional organosilicon compounds, unreacted (A) carbon monoxide and hydrogen gas, and / or by-products formed in situ, such as ligand decomposition products and their adducts, and high-boiling point liquid aldehyde condensation by-products, and (D) solvents, if used. The term “ligand decomposition products” includes, but is not limited to, any and all compounds obtained from one or more chemical transformations of at least one of the ligand molecules used in the process.

[0100] The process may further include one or more additional steps, such as 2) recovering (C) the rhodium / ligand complex catalyst from the reaction fluid containing the propylaldehyde-functional organosilicon compound. Recovery of (C) the rhodium / ligand complex catalyst may be carried out by methods known in the art, including but not limited to adsorption and / or membrane separation (e.g., nanofiltration). Preferred recovery methods are described, for example, in U.S. Patent No. 5,681,473 by Miller et al., Patent No. 8,748,643 by Priske et al., and Patent No. 10,155,200 by Geilen et al.

[0101] However, one advantage of the process described herein is that there is no need to remove and reuse the (C) catalyst. Due to the low required Rh level, not recovering and reusing the (C) catalyst may be more cost-effective, and the propylaldehyde-functional organosilicon compounds produced by the process may be stable even if the catalyst is not removed. Therefore, alternatively, the above process may be carried out without step 2).

[0102] Alternatively, the process may further include 3) purification of the hydroformylation reaction product. For example, the propylaldehyde-functional organosilicon compound can be isolated from the above additional material by any convenient means such as stripping and / or distillation, using optionally reduced pressure.

[0103] Propylaldehyde-functional organosilicon compounds The above-described propylaldehyde-functional organosilicon compounds are useful as starting materials in processes for preparing propylimine-functional organosilicon compounds and aminopropyl-functional organosilicon compounds. Starting material (E) is a propylaldehyde-functional organosilicon compound having at least one propylaldehyde functional group covalently bonded to silicon per molecule. Alternatively, the propylaldehyde-functional organosilicon compound may have two or more propylaldehyde functional groups covalently bonded to silicon per molecule. The propylaldehyde functional group covalently bonded to silicon is represented by formula:

[0104] [ka] It may have the formula, where G has the empirical formula -C2H4-. G is linear (-CH2CH-) or branched.

[0105] [ka] This is possible. Alternatively, the propylaldehyde-functional organosilicon compound may be a combination of propylaldehyde-functional organosilicon compound species in which some instances of group G are linear and some are branched. Alternatively, the propylaldehyde-functional organosilicon compound produced by the hydroformylation process described above may have most instances in which G is linear. The propylaldehyde-functional organosilicon compound may be a single propylaldehyde-functional organosilicon compound. Alternatively, two or more different propylaldehyde-functional organosilicon compounds may be used in the process described herein. For example, the propylaldehyde-functional organosilicon compound may comprise one or both of propylaldehyde-functional silane and propylaldehyde-functional polyorganosiloxane.

[0106] Propylaldehyde-functional organosilicon compounds are of formula (E1) (E1-1):R Ald x SiR 4 (4-x) It may contain a propylaldehyde-functionalized silane, in which each R Ald These are expressions that are selected independently.

[0107] [ka] It is the basis of the formula, where G is as described above, and R 4 And the subscript x is as described above. Alternatively, each R 4 This can be independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms. Alternatively, the subscript x can be 1 to 4.

[0108] Suitable propylaldehyde-functionalized silanes are exemplified by propylaldehyde-functionalized trialkylsilanes such as (propyl-aldehyde)-trimethylsilane and (propyl-aldehyde)-triethylsilane.

[0109] Alternatively, the propylaldehyde-functional organosilicon compound may include (E2) propylaldehyde-functional polyorganosiloxane. This propylaldehyde-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more of these. The unit formula of this propylaldehyde-functional polyorganosiloxane is (E2-1):(R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h It may include, in the formula, each R Ald The formula is as shown above.

[0110] [ka] The independently selected propylaldehyde group is G, R 4 Z, as well as the subscripts a, b, c, d, e, f, g, and h, are as described above.

[0111] Alternatively, the (E2) propylaldehyde-functionalized polyorganosiloxane may include a (E2-2) linear polydiorganosiloxane having at least one propylaldehyde functional group per molecule, or alternatively, at least two propylaldehyde functional groups (for example, in formula (E2-1) for the above propylaldehyde-functionalized polyorganosiloxane, where the subscripts e=f=g=0). For example, such polydiorganosiloxane may have the unit formula (E2-3): (R4 3SiO 1 / 2 ) a (R Ald R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R Ald R 4 SiO 2 / 2 ) d It may include, in the formula, R Ald and R 4 As stated above, subscript a is 0, 1, or 2, subscript b is 0, 1, or 2, subscript c ≥ 0, subscript d ≥ 0, where (b+d) ≥ 1, (a+b) = 2, and (a+b+c+d) ≥ 2. Alternatively, in the above unit formula (E2-3) for linear propylaldehyde-functional polyorganosiloxane, the quantity (a+b+c+d) may be at least 3, alternatively at least 4, or alternatively > 50. At the same time, in the formula, the quantity (a+b+c+d) may be 10,000 or less, alternatively 4,000 or less, alternatively 2,000 or less, alternatively 1,000 or less, alternatively 500 or less, or alternatively 250 or less. Alternatively, in the unit formula for linear propylaldehyde-functional polyorganosiloxanes, each R 4 Each R in the formula can be independently selected from the group consisting of alkyl and aryl, and alternatively, methyl and phenyl. 4 is an alkyl group, and alternatively, each R 4 It can be methyl.

[0112] Alternatively, a linear propylaldehyde-functional polydiorganosiloxane of unit formula (E2-3) is used, with unit formula (E2-4): (R 4 2R Ald SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R Ald SiO 2 / 2 ) n , Unit formula (E2-5): (R 4 3SiO1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R Ald SiO 2 / 2 ) p Alternatively, a combination of (E2-4) and (E2-5) may be selected from the group.

[0113] In equations (E2-4) and (E2-5), each R 4 and R Ald The above applies. The subscript m can be 0 or a positive number. Alternatively, the subscript m can be at least 2. Alternatively, the subscript m can be between 2 and 2,000. The subscript n can be 0 or a positive number. Alternatively, the subscript n can be between 0 and 2,000. The subscript o can be 0 or a positive number. Alternatively, the subscript o can be between 0 and 2,000. The subscript p is at least 2. Alternatively, the subscript p can be between 2 and 2,000.

[0114] The starting materials (E2) are: i) bis-dimethyl(propyl-aldehyde)siloxy-terminated polydimethylsiloxane, ii) bis-dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / methyl(propyl-aldehyde)siloxane), iii) bis-dimethyl(propyl-aldehyde)siloxy-terminated polymethyl(propyl-aldehyde)siloxane, iv) bis-trimethylsiloxane-terminated poly(dimethylsiloxane / methyl(propyl-aldehyde)siloxane), v) bis-trimethylsiloxane-terminated polymethyl(propyl-aldehyde)siloxane, vi) bis-dimethyl(propyl- The polydiorganosiloxanes may include propylaldehyde-functional polydiorganosiloxanes such as aldehyde)siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(propyl-aldehyde)siloxane), vii) bis-dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viiii) bis-dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl,(propyl-aldehyde)-siloxy-terminated polydimethylsiloxane, and combinations of two or more of x)i) to ix).

[0115] Alternatively, (E2) propylaldehyde-functional polyorganosiloxanes can be cyclic, for example, in the unit formula (E2-1), the subscripts a=b=c=e=f=g=h=0. (E2-6) Cyclic propylaldehyde-functional polydiorganosiloxanes have the unit formula (E2-7):(R 4 R Ald SiO 2 / 2 ) d It may have, in the formula, R Ald and R 4As stated above, the subscript d can be 3-12, alternatively 3-6, or alternatively 4-5. Examples of cyclic propylaldehyde-functional polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-tri(propyl-aldehyde)-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetra(propyl-aldehyde)-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-penta(propyl-aldehyde)-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexa(propyl-aldehyde)-cyclohexasiloxane.

[0116] Alternatively, (E2-6)cyclic propylaldehyde-functionalized polydiorganosiloxanes have the unit formula (E2-8):(R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d It may have, in the formula, R 4 and R Ald As stated above, the subscript c is >0 to 6, and the subscript d is >3 to 12. Alternatively, in equation (E2-8), the quantity (c+d) can be between 3 and 12. Alternatively, in equation (E2-8), c can be between 3 and 6, and d can be between 3 and 6.

[0117] Alternatively, (E2) propylaldehyde-functionalized polyorganosiloxanes may be (E2-9) oligomers, for example, if the quantities (a+b+c+d+e+f+g) in the above unit formula (E2-1) are ≤ 50, ≤ 40, ≤ 30, ≤ 25, ≤ 20, ≤ 10, ≤ 5, ≤ 4, or ≤ 3. The oligomers may be cyclic, linear, branched, or a combination thereof. The cyclic oligomers are as described above as starting materials (E2-6).

[0118] An example of a linear propylaldehyde-functionalized polyorganosiloxane oligomer is formula (E2-10):

[0119] [ka] It may have, in the formula, R 4 As stated above, each R 2’ R is independent of R 4 and R Ald Selected from the group consisting of, provided that at least one R per molecule 2’ However, R Ald The subscript z is given to be between 0 and 48. Alternatively, the subscript z can be between 0 and 4, between 0 and 1, or between 0. Alternatively, when z=0 in formula (E2-10), the propylaldehyde-functionalized polyorganosiloxane oligomer is given by formula (E2-10a):

[0120] [ka] It may have, in the formula, R 4 and R Ald As stated above, examples of linear propyl aldehyde-functional polyorganosiloxane oligomers include 1,3-di(propyl-aldehyde)-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-(propyl-aldehyde)-disiloxane, and 1,1,1,3,5,5,5-heptamethyl-3-(propyl-aldehyde)-trisiloxane.

[0121] Alternatively, propylaldehyde-functionalized polyorganosiloxane oligomers may be branched. Branched oligomers have the general formula (E2-11):R Ald SiR 12 3 may be present, in the formula, R Ald As stated above, each R 12 R 13 and -OSi(R 14 ) Selected from 3, each R 13 It is a monovalent hydrocarbon group, and each R 14 R 13, -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 15 R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 16 R 13 and -[OSiR 13 2] ii OSiR 13 Selected from 3, the subscript ii has a value such that 0 ≤ ii ≤ 100. 12 At least two of them are -OSi(R 14 )3 is possible. Alternatively, R 12 All three of them are -OSi(R 14 ) It could be 3.

[0122] Alternatively, in equation (E2-11), each R 12 R 13 In this case, the branched polyorganosiloxane oligomer has the following structure (E2-11a):

[0123] [ka] In the formula, R Ald and R 13 As stated above. Alternatively, in equation (E2-11a), each R 13 It can be methyl.

[0124] Alternatively, in equation (E2-11), each R 12 -OSi(R 14 )If it is 3, each R 14 -OSi(R 15 ) It could be in 3 parts,

[0125] [ka] In the formula, R Ald and R 15 As stated above, alternatively, each R 15 As mentioned above, R 13 This is possible, and each R 13 It can be methyl.

[0126] Alternatively, in equation (E2-11), each R 12 -OSi(R 14 )If it is 3, one R 14 Each R 12 ga-OSiR 13 (R 14 Each -OSi(R) is such that )2 14 )3 in R 13 It is possible. Alternatively, -OSiR 13 (R 14 )2 R in 2 14 Each of these branches a propylaldehyde-functional polyorganosiloxane oligomer with the following structure (E2-11c):

[0127] [ka] -OSi(R 15 ) It could be in 3 parts, In the formula, R Ald , R 13 , and R 15 As stated above, alternatively, each R 15 R 13 This is possible, and each R 13 It can be methyl.

[0128] Alternatively, in equation (B2-11), one R 12 R 13 It could be, R 12 Two of them are -OSi(R 14 ) It could be 3. R 12 Two of them are -OSi(R 14 )If it is 3, one R 14 Each -OSi(R 14)R in 3 13 And R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 The branched polyorganosiloxane oligomer has the following structure (E2-11d):

[0129] [ka] (In the formula, R Ald , R 13 , and R 15 -OSi(R 15 )3 is possible. Alternatively, each R 15 R 13 This is possible, and each R 13 This can be methyl. Alternatively, propylaldehyde-functionalized branched polyorganosiloxanes may have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, or alternatively 4 to 10 silicon atoms per molecule. An example of a propylaldehyde-functionalized branched polyorganosiloxane oligomer is formula:

[0130] [ka] It has 3-(3,3,3-trimethyl-1-λ) 2 -Disiloxanyl)propanal (also known as propyl-aldehyde-tris(trimethyl)siloxy)silane), formula

[0131] [ka] It has 3-(1,3,5,5,5-pentamethyl-1λ 3 ,3λ 3-Trisiloxaneyl)propanal (methyl-(propyl-aldehyde)-di((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane, and formula

[0132] [ka] It has 3-(3,5,5,5-tetramethyl-1λ 2 ,3λ 3 An example is trisiloxaneyl)propanal ((propyl-aldehyde)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane).

[0133] Alternatively, the (E2) propylaldehyde-functional polyorganosiloxane may be branched, such as a branched propylaldehyde-functional polyorganosiloxane (e.g., in formula (E2-1), when the number (a+b+c+d+e+f+g)>50) which may have more propylaldehyde groups and / or more polymer units per molecule than the branched oligomer described above, and / or more branched oligomer described above. The branched propylaldehyde-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide >0-5 mol% of trifunctional and / or tetrafunctional units in the branched propylaldehyde-functional polyorganosiloxane (in formula (E2-1)).

[0134] For example, branched propylaldehyde-functionalized polyorganosiloxanes have the unit formula (E2-13):(R 4 3SiO 1 / 2 ) q (R 4 2R Ald SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t It may contain a Q-type branched polyorganosiloxane, in which R4 and R Ald As stated above, the subscripts q, r, s, and t have mean values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, and (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity >170 mPa·s to the branched polyorganosiloxane, as measured by a rotational viscometer (described below along with the test method). Alternatively, the viscosity may be >170 mPa·s to 1000 mPa·s, alternatively >170 mPa·s to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, or alternatively 190 mPa·s to 420 mPa·s.

[0135] Alternatively, branched propylaldehyde-functionalized polyorganosiloxanes are derived from formula (E2-14):[R Ald R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w It may include, in the formula, R Ald and R 4 As stated above, the subscripts v, w, and x have values ​​such that 200≧v≧1, 2≧w≧0, and 200≧x≧1. Alternatively, in this equation (E2-14), each R 4 This is independently selected from the group consisting of methyl and phenyl.

[0136] Alternatively, a branched propylaldehyde-functional polyorganosiloxane for the starting material (E2-11) is given by the unit formula (E2-15): (R 4 3SiO 1 / 2 ) aa (R Ald R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R Ald R 4 SiO 2 / 2 ) ee (R4 SiO 3 / 2 ) dd It may contain a T-branched polyorganosiloxane (silsesquioxane), in which R 4 and R Ald As stated above, the subscript aa≧0, the subscript bb>0, the subscript cc is between 15 and 995, the subscript dd>0, and the subscript ee≧0. The subscript aa can be between 0 and 10. Alternatively, the subscript aa may have values ​​such as 12≧aa≧0, 10≧aa≧0, 7≧aa≧0, 5≧aa≧0, and 3≧aa≧0. Alternatively, the subscript bb≧1. Alternatively, the subscript bb≧3. Alternatively, the subscript bb may have values ​​such as 12≧bb>0, 12≧bb≧3, 10≧bb>0, 7≧bb>1, 5≧bb≧2, and 7≧bb≧3. Alternatively, the subscript cc can have a value such that 800≧cc≧15, or alternatively, 400≧cc≧15. Alternatively, the subscript ee can have a value such that 800≧ee≧0, 800≧ee≧15, or alternatively, 400≧ee≧15. Alternatively, the subscript ee can be 0. Alternatively, the quantity (cc+ee) can have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd can be 1 to 10. Alternatively, the subscript dd can have a value such that 10≧dd>0, alternatively, 5≧dd>0, or alternatively, dd=1. Alternatively, the subscript dd can be 1 to 10, and alternatively, the subscript dd can be 1 or 2. Alternatively, if the subscript dd = 1, the subscript bb may be 3 and the subscript cc may be 0. The value of the subscript bb may be sufficient to provide a silsesquioxane of unit formula (E2-15) having an aldehyde content of 0.1% to 1%, or alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane.

[0137] Alternatively, (E2) propylaldehyde-functional polyorganosiloxanes may include propylaldehyde-functional polyorganosilicate resins and / or propylaldehyde-functional silsesquioxane resins, among others. Such resins can be prepared, for example, by hydroformylation of vinyl-functional polyorganosiloxane resins as described above. Propylaldehyde-functional polyorganosilicate resins are of formula R M’ 3SiO 1 / 2 The monofunctional unit ("M" unit) and formula SiO 4 / 2 The formula includes a tetrafunctional silicate unit ("Q" unit), and each R M’ This is independently of the above R 4 and R Ald A selection can be made from the group consisting of . Alternatively, each R M’ The group can be selected from the group consisting of alkyl groups, propylaldehyde functional groups of the formula shown above, and aryl groups. Alternatively, each R M’ This can be selected from methyl, (propyl aldehyde), and phenyl. Alternatively, R M’ At least one-third, and alternatively at least two-thirds, of the groups are methyl groups. Alternatively, the M' unit is (Me3SiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2R Ald SiO 1 / 2 Polyorganosilicate resins are soluble in solvents such as those described herein as starting materials (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low-viscosity linear and cyclic polydiorganosiloxanes.

[0138] When prepared, the polyorganosilicate resin contains the above M' and Q units, and the polyorganosiloxane contains silicon-bonded hydroxyl groups and / or the above portion (ZO 1 / 2 It further comprises units having hydrolyzable groups as described by the formula Si(OSiR M’ 3) May contain a neopentamer of 4, where RM’ As stated above, for example, the neopentamer may be a tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13 Using 13C NMR spectroscopy, the hydroxyl and alkoxy content, as well as the molar ratio of M' units to Q units, can be measured. This ratio is expressed as {M'(resin)} / {Q(resin)}, where M' and Q units are excluded 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 0.5 / 1 to 1.5 / 1, or alternatively 0.6 / 1 to 0.9 / 1.

[0139] The Mn in polyorganosilicate resin is present in R M’ It varies depending on various factors, including the type of hydrocarbon group represented. The Mn of polyorganosilicate resins refers to the number-average molecular weight measured using GPC when peaks representing neopentamers are excluded from the measurements. The Mn of polyorganosilicate resins can be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, or alternatively >3,000 Da to 8,000 Da. Alternatively, the Mn of polyorganosilicate resins may be 3,500 Da to 8,000 Da.

[0140] Alternatively, polyorganosilicate resins have the unit formula (E2-17):(R 4 3SiO 1 / 2 ) mm (R 4 2R Ald SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h It may include, in the formula, Z, R 4 , and R Ald, and the subscript h is as defined above, and the subscripts mm, nn, and oo have average values such that mm≧0, nn>0, oo>0, and 0.5≦(mm+nn) / oo≦4. Alternatively, 0.6≦(mm+nn) / oo≦4, alternatively 0.7≦(mm+nn) / oo≦4, alternatively 0.8≦(mm+nn) / oo≦4.

[0141] Alternatively, the (E2) propionaldehyde-functional polyorganosiloxane may be (E2-18) a propionaldehyde-functional silsesquioxane resin, that is, a unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R Ald SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (ZO 1 / 2 ) h may comprise a resin containing trifunctional (T') units of, where R 4 and R Ald are as defined above, and the subscript f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0<h / (e+f)<1.5. Alternatively, the propionaldehyde-functional silsesquioxane resin may have a unit formula (E2-19): (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (ZO 1 / 2 ) h may comprise, where R 4 , R Ald, Z, and subscripts h, e, and f are as defined above. Alternatively, the propionaldehyde-functional silsesquioxane resin may comprise, in addition to the T units described above, a moiety of formula (R 4 ₂SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d difunctional (D') units, i.e., a D'T' resin, wherein the subscripts c and d are as defined above. Alternatively, the propionaldehyde-functional silsesquioxane resin may further comprise units of formula (R 4 ₃SiO 1 / 2 ) a (R 4 ₂R Ald SiO 1 / 2 ) b monofunctional (M') units, i.e., an M'D'T' resin, wherein the subscripts a and b are as defined above for unit formula (E2-1).

[0142] Alternatively, the starting material (E), which is the propionaldehyde-functional organosilicon compound, may have the unit formula (E3-1): [(R 1 (3-gg) R Ald gg Si) ff NH (3-ff) hh wherein R may be a propionaldehyde group as described above, each R Ald is a propionaldehyde group as described above, each R 1 is independently selected from the group consisting of alkyl groups and aryl groups as described above, each subscript ff is independently 1 or 2 as described above, subscript gg is independently 0, 1, or 2 as described above, and subscript h has a value such that 1 < hh < 10 as described above.

[0143] ​The starting material (E) may be any one of the above-described propylaldehyde-functional organosilicon compounds (whether prepared via the hydroformylation reaction process described herein or by any other method). Alternatively, the starting material (E) may comprise a mixture of two or more of the propylaldehyde-functional organosilicon compounds.

[0144] Alternatively, in the processes described herein, the starting material (E) may be a hydrolytically unstable propylaldehyde-functional organosilicon compound. A hydrolytically unstable propylaldehyde-functional organosilicon compound may, for example, have at least one R 4 The (E1) propylaldehyde-functional silane and / or (E2) propylaldehyde-functional polyorganosiloxane from the formulas shown above, any (E3) propylaldehyde-functional silazane, or any propylaldehyde-functional polyorganosiloxane oligomer of the formula (E2-10a) shown above, for example, 1,3-di(propyl-aldehyde)-1,1,3,3-tetramethyldisiloxane, or (E2-11a), for example, 1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)-3-vinyltrisiloxane.

[0145] Preparation of propylimine-functional organosilicon compounds and aminopropyl-functional organosilicon compounds The process for preparing propylamino-functional organosilicon compounds is: I) Combining starting materials under conditions that lead to the formation of a dehydrated imine, wherein the starting materials are (E) The above-mentioned propylaldehyde-functional organosilicon compound, (F1) Primary amine source, (G) Hydrogenation catalyst and Optionally, (J) solvent and, However, if (G) a hydrogenation catalyst is present in step I), step I) is carried out in the absence of hydrogen. This is done to form a reaction product containing a (L)propylimine-functional organosilicon compound and water, and to combine them. Optionally, II) remove the water produced by the dehydration imine formation reaction in step I), The process may optionally include isolating the (L)propylimine-functionalized organosilicon compound. The propylimine-functionalized organosilicon compound may be isolated by any convenient means such as stripping and / or distillation of the reaction product, and the propylimine-functionalized organosilicon compound may be used for purposes other than those described below. Alternatively, the (L)propylimine-functionalized organosilicon compound may be used to prepare an aminopropyl-functionalized organosilicon compound if the process further includes the following: III) Combining starting materials under conditions that catalyze a reductive amination reaction, wherein the starting materials are (L) The above-mentioned propylimine-functional organosilicon compound, (F2) Ammonia and, (G) Hydrogenation catalyst and (H) Hydrogen and, Optionally, a reaction product comprising (J) solvent and an aminopropyl-functional organosilicon compound is formed. However, the compounding is carried out on the condition that (G) the hydrogenation catalyst is added in at least one of steps I) and III).

[0146] The process may optionally further include, before step I), 1) combining the starting materials under conditions that catalyze the hydroformylation reaction, wherein the starting materials comprise (A) a gas containing hydrogen and carbon monoxide, (B) a vinyl-functional organosilicon compound, and (C) a rhodium / ligand complex catalyst, thereby forming a hydroformylation reaction product containing the propylaldehyde-functional organosilicon compound as described above. The process may optionally further include, before step I) and after step 1), step 2) recovering (C) the rhodium / ligand complex catalyst from the reaction product containing the propylaldehyde-functional organosilicon compound. However, step 2) is optional and may be unnecessary. For example, when hydroformylation is used to prepare (E) propylaldehyde-functional organosilicon compounds, although we do not wish to be bound by theory, the hydroformylation catalyst may not need to be removed if the amount of catalyst is not cost-effective to remove, and / or if the selection and amount of catalyst are not considered to adversely affect the dehydration imine formation reaction or the reductive amination reaction. The process may optionally further include step 3) of purifying the hydroformylation reaction product before step I) and after step 1) or step 2) (if any), thereby isolating the (E) propylaldehyde-functional organosilicon compound from the additional material as described above. However, this step 3) is optional and may not be necessary, for example, if a solvent is used in the hydroformylation reaction to prepare the (E) propylaldehyde-functional organosilicon compound, and the same solvent is used in a later step of the process.

[0147] Step I) Protection of Aldehydes In step I) of the above process, a dehydration imine formation reaction occurs, protecting the aldehyde group and forming an imine group. In step I), the starting materials, comprising (E) a propylaldehyde-functional organosilicon compound and (F1) a primary amine source, can be combined by any convenient means, such as mixing. Mixing can be carried out by any convenient means, for example, at RT and under ambient pressure and atmosphere. The mixing time is sufficient for the imine group to be formed from the aldehyde group under selected conditions. Step I) can be carried out in batch mode or continuous mode. The time is not critical and is sufficient for the imine group to be formed, for example, 1 second to 1 hour.

[0148] (F) Amine source In the process described herein, a primary amine source (F1) is used in step I). The primary amine source may be any primary amine source that is inexpensive and separable from the aminopropyl-functional organosilicon compound prepared by the process. The primary amine source may be an organic primary amine. An organic primary amine is an organic primary amine of formula: R 18 It may contain NH2, in the formula, R 18 R is an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms. 18 Suitable alkyl groups may be linear, branched, cyclic, or a combination of two or more of these. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and further examples of alkyl groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. 18 Suitable aryl groups may be, for example, phenyl, tolyl, xyl, phenylethyl, and benzyl. Alternatively, R 18 The alkyl group can be selected from the group consisting of ethyl, propyl, and butyl, or alternatively, ethyl or propyl, or alternatively, propyl and butyl. Alternatively, R18 The alkyl group can be propyl. Alternatively, R 18 It can be an aryl group, and alternatively, R 18 This could be benzyl. Alternatively, an organic primary amine may have two or more primary amine groups per molecule. Organic primary amines are known and commercially available in the art. For example, ethylamine, propylamine, n-butylamine, isobutylamine, and benzylamine are available from various suppliers such as Acros Organics or Sigma Aldrich, Inc. (St. Louis, Missouri, USA). Alternatively, the primary amine source may include a primary amino-functional organosilicon compound. The primary amino-functional organosilicon compound used as the primary amine source in step I) can be any primary amino-functional organosilicon compound, and for example, the primary amine source may have the same formula as the primary amino-functional organosilicon compound prepared by this process. For example, the primary amine source may be 2-aminopropyltrimethylsilane or 3,3'-(1,1,3,3,-tetramethyldisiloxane-1,3-diyl)propane-diamine. The formation of imine-functional organosilicon compounds using primary amino-functional organosilicon compounds as primary amine sources is shown in Scheme 1 below.

[0149] [ka]

[0150] The primary amine source used in step I) may be used with a superstoichiometric amount of amine functionality relative to the aldehyde functionality of the (E) propylaldehyde-functionalized organosilicon compound. For example, the primary amine source may be used in an amount sufficient to provide a molar ratio of amine group:aldehyde group of 10:1 to 1:1.

[0151] Propylimine-functional organosilicon compounds The propylimine-functional organosilicon compound prepared in step I) of the above process has at least one propylimine functional group covalently bonded to silicon per molecule. Alternatively, the propylimine-functional organosilicon compound may have two or more propylimine functional groups covalently bonded to silicon per molecule. This propylimine functional group, R I The formula is:

[0152] [ka] The formula may have, where G is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms as described and illustrated above, and R 19 R 18 (When an organic primary amine is used as a primary amine source, the alkyl group or aryl group as described above) and the organosilicon moiety (when an amino-functional organosilicon compound is used as a primary amine source) are selected. The propylimine-functional organosilicon compound may have any of the above formulas for (E) propylaldehyde-functional organosilicon compound, provided that there is at least one R per molecule. Ald R I It is assumed that it is replaced by R. Alternatively, Ald All or substantially all of the cases are R I It can be replaced with.

[0153] Propylimine-functional organosilicon compounds are (L1) formula (L1-1):R I x SiR 4 (4-x) It may contain a propylimine-functionalized silane, in which R I , R 4 The subscript x is as described above.

[0154] Alternatively, the propylimine-functional organosilicon compound may include (L2)propylimine-functional polyorganosiloxane. The propylimine-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more of these. The unit formula of the propylimine-functional polyorganosiloxane is (L2-1):(R 4 3SiO 1 / 2 ) a (R 4 2R I SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R I SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R I SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h It may include, in the formula, each R I R is an imine group of the above formula that is independently selected, 4 Z, and the subscripts a, b, c, d, e, f, g, and h are as described above for formula (B2-1).

[0155] Alternatively, the (L2) propylimine-functionalized polyorganosiloxane may include a (L2-2) linear polydiorganosiloxane having at least one propylimine functional group, or alternatively, at least two propylimine functional groups per molecule (for example, when the subscripts e=f=g=0 in formula (L2-1) for the above propylimine-functionalized polyorganosiloxane). For example, the polydiorganosiloxane has the unit formula (L2-3): (R 4 3SiO 1 / 2 ) a (R I R 4 2SiO 1 / 2 ) b (R 4 2SiO2 / 2 ) c (R I R 4 SiO 2 / 2 ) d It may include, in the formula, R I As stated above, R 4 Furthermore, the subscripts a, b, c, and d are as described above for formula (E2-3).

[0156] Alternatively, a linear propylimine-functional polydiorganosiloxane of unit formula (L2-3) is given by unit formula (L2-4): (R 4 2R I SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R I SiO 2 / 2 ) n Unit formula (L2-5): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R I SiO 2 / 2 ) p Alternatively, a combination of (L2-4) and (L2-5) may be selected from the group.

[0157] In equations (L2-4) and (L2-5), R I As stated above, R 4 Furthermore, the subscripts m, n, o, and p are as described above for formulas (E2-4) and (E2-5).

[0158] Alternatively, (L2) propylimine-functional polyorganosiloxanes may be cyclic, for example, if the subscripts a=b=c=e=f=g=h=0 in the unit formula (L2-1). (L2-6) Cyclic propylimine-functional polydiorganosiloxanes have the unit formula (L2-7): (R 4 R I SiO 2 / 2 ) d It may have, in the formula, R I and R4 As stated above, the subscript d can be 3-12, alternatively 3-6, or alternatively 4-5.

[0159] Alternatively, (L2-6) cyclic imine-functional polydiorganosiloxanes have the unit formula (L2-8): (R 4 2SiO 2 / 2 ) c (R 4 R I SiO 2 / 2 ) d It may have, in the formula, R 4 and R I As stated above, the subscript c is >0 to 6, and the subscript d is >3 to 12. Alternatively, in equation (L2-8), the quantity (c+d) can be between 3 and 12. Alternatively, in equation (L2-8), c can be between 3 and 6, and d can be between 3 and 6.

[0160] Alternatively, (L2) imine-functionalized polyorganosiloxanes can be (L2-9) oligomers if, for example, the quantities (a+b+c+d+e+f+g) in the above unit formula (L2-1) are ≤ 50, ≤ 40, ≤ 30, ≤ 25, ≤ 20, ≤ 10, ≤ 5, ≤ 4, or ≤ 3. The oligomers can be cyclic, linear, branched, or a combination thereof. The cyclic oligomers are as described above as starting materials (L2-6).

[0161] An example of a linear propylimine-functionalized polyorganosiloxane oligomer is formula (L2-10):

[0162] [ka] It may have, in the formula, R 4 As stated above, each R 2’’’ R is independent of R 4 and R I Selected from the group consisting of, provided that at least one R per molecule 2’’’ However, R IThe subscript z is given to be between 0 and 48. Alternatively, the subscript z can be between 0 and 4, between 0 and 1, or between 0. Alternatively, when z=0 in formula (L2-10), the propylimine-functionalized polyorganosiloxane oligomer is given by formula (L2-10a):

[0163] [ka] It may have, in the formula, R 4 and R I This is as stated above.

[0164] Alternatively, propylimine-functionalized polyorganosiloxane oligomers may be branched. Branched oligomers have the general formula (L2-11):R I SiR 12 3 may be present, in the formula, R I As stated above, each R 12 R 13 and -OSi(R 14 ) Selected from 3, each R 13 It is a monovalent hydrocarbon group, and each R 14 R 13 , -OSi(R 15 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 15 R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 16 R 13 and -[OSiR 13 2] ii OSiR 13 Selected from 3, the subscript ii has a value such that 0 ≤ ii ≤ 100. 12 At least two of them are -OSi(R 14 )3 is possible. Alternatively, R 12 All three of them are -OSi(R 14 ) It could be 3.

[0165] Alternatively, in formula (L2-11), each R 12 is R 13 , the branched polyorganosiloxane oligomer has the following structure (L2-11a):

[0166]

Chemical Formula

[0167] Alternatively, in formula (L2-11), each R 12 is -OSi(R 14 )3, each R 14 can be a -OSi(R 15 )3 moiety such that the branched polyorganosiloxane oligomer has the following structure (L2-11b):

[0168]

Chemical Formula

[0169] Alternatively, in formula (L2-11), each R 12 is -OSi(R 14 )3, one R 14 can be R in each -OSi(R 12 )3 such that each R 13 is -OSiR 14 (R 14 )2. 13 Alternatively, the two R groups in -OSiR 13 (R 14 )214 Each of these has the following structure (L2-11c):

[0170] [ka] -OSi(R 15 ) It could be in 3 parts, In the formula, R I , R 13 , and R 15 As stated above, alternatively, each R 15 R 13 This is possible, and each R 13 It can be methyl.

[0171] Alternatively, in equation (L2-11), one R 12 R 13 It could be, R 12 Two of them are -OSi(R 14 ) It could be 3. R 12 Two of them are -OSi(R 14 )If it is 3, one R 14 Each -OSi(R 14 )R in 3 13 And R 12 Two of them are -OSiR 13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 The branched polyorganosiloxane oligomer has the following structure (L2-11d):

[0172] [ka] -OSi(R 15 ) It can be 3, and in the formula, R I , R 13 , and R 15 As stated above, alternatively, each R 15 R 13 This is possible, and each R 13It can be methyl. Alternatively, branched polyorganosiloxanes may have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, or alternatively 4 to 10 silicon atoms per molecule. An example of an imine-functionalized branched polyorganosiloxane oligomer is given by formula:

[0173] [ka] (E)-N-butyl-3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propane-1-imine, and formula

[0174] [ka] An example is (E)-3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)-N-propylpropane-1-imine, which has the following properties.

[0175] Alternatively, the (L2) propylimine-functional polyorganosiloxane may be branched, such as the branched oligomer described above, and / or a branched propylimine-functional polyorganosiloxane that may have more propylimine groups and / or more polymer units per molecule than the branched oligomer described above (for example, in formula (L2-1), when the number (a+b+c+d+e+f+g)>50). The branched propylimine-functional polyorganosiloxane may have a number (e+f+g) sufficient to provide >0-5 mol% of trifunctional and / or tetrafunctional units in the (L2-1) branched propylimine-functional polyorganosiloxane.

[0176] For example, branched propylimine-functionalized polyorganosiloxanes have the unit formula (L2-13):(R 4 3SiO 1 / 2 ) q (R 42R I SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t of the Q-type branched polyorganosiloxane, where in the formula, R I is as defined above, and R 4 as well as the subscripts q, r, s, and t are as defined above for (E2-13).

[0177] Alternatively, the branched propylimine-functional polyorganosiloxane may have the formula (L2-14):[R I R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w where in the formula, R I is as defined above, and R 4 as well as the subscripts v, w, and x are as defined above with respect to formula (E2-14). Alternatively, in this formula (L2-14), each R 4 is independently selected from the group consisting of methyl and phenyl, each R I has the formula described above, where G has 2, 3, or 6 carbon atoms.

[0178] Alternatively, the branched propylimine-functional polyorganosiloxane for (L2-11) may have the unit formula (L2-15):(R 4 3SiO 1 / 2 ) aa (R I R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R I R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 )dd It may contain a T-branched polyorganosiloxane (silsesquioxane), in which R I As stated above, R 4 Furthermore, the subscripts aa, bb, cc, dd, and ee are as described above for the unit formula (E2-15).

[0179] Alternatively, (L2)propylimine-functional polyorganosiloxanes may include propylimine-functional polyorganosilicate resins and / or propylimine-functional silsesquioxane resins, among others. Propylimine-functional polyorganosilicate resins are of formula R M’’’ 3SiO 1 / 2 The monofunctional unit ("M'''" unit) and formula SiO 4 / 2 The formula includes a tetrafunctional silicate unit ("Q" unit), and each R M’’’ This is independently of the above R 4 and R I A selection can be made from the group consisting of . Alternatively, each R M’’’ R is an alkyl group, as shown above. I The formula can be selected from the group consisting of a propylimine functional group and an aryl group. The polyorganosilicate resin is soluble in solvents such as those described herein as starting material (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low-viscosity linear and cyclic polydiorganosiloxanes.

[0180] The propylimine-functionalized polyorganosilicate resin comprises the above-mentioned M''' and Q units, and the polyorganosilicate resin comprises silicon-bonded hydroxyl groups and / or the above-mentioned portion (ZO 1 / 2 It further comprises units having hydrolyzable groups as described by the formula Si(OSiR M’’’ 3) May contain a neopentamer of 4, where R M’’’ As stated above, for example, the neopentamer may be a tetrakis(trimethylsiloxy)silane. 29 Si NMR and13 Using 13C NMR spectroscopy, the hydroxyl and alkoxy content, as well as the molar ratio of M''' units to Q units, can be measured. This ratio is expressed as {M'''(resin)} / {Q(resin)}, where M''' units and Q units are excluded 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 range from 0.5 / 1 to 1.5 / 1, or alternatively from 0.6 / 1 to 0.9 / 1.

[0181] The Mn in polyorganosilicate resin is present in R M’’’ It varies depending on various factors, including the type of hydrocarbon group represented. The Mn of polyorganosilicate resins refers to the number-average molecular weight measured using GPC when peaks representing neopentamers are excluded from the measurements. The Mn of polyorganosilicate resins can be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, or alternatively >3,000 Da to 8,000 Da. Alternatively, the Mn of polyorganosilicate resins may be 3,500 Da to 8,000 Da.

[0182] Alternatively, polyorganosilicate resins have the unit formula (L2-17):(R 4 3SiO 1 / 2 ) mm (R 4 2R I SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h It may include, in the formula, Z, R 4 , and R I , as well as the subscript h, are as described above, and the subscripts mm, nn, and oo have mean values ​​such that mm≧0, nn>0, oo>0, and 0.5≦(mm+nn) / oo≦4. Alternatively, 0.6≦(mm+nn) / oo≦4, alternatively, 0.7≦(mm+nn) / oo≦4, and alternatively, 0.8≦(mm+nn) / oo≦4.

[0183] Alternatively, (L2) the propylimine-functional polyorganosiloxane may comprise (L2-18) a propylimine-functional silsesquioxane resin, that is, a resin containing trifunctional (T''') units of the unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R I SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R I SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R I SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein R 4 and R I are as defined above, and the subscripts satisfy f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0<h / (e+f)<1.5. Alternatively, the propylimine-functional silsesquioxane resin may comprise the unit formula (L2-19):(R 4 SiO 3 / 2 ) e (R I SiO 3 / 2 ) f (ZO 1 / 2 ) h wherein R 4 , R I , Z, and the subscripts h, e, and f are as defined above. Alternatively, the propylimine-functional silsesquioxane resin may further comprise difunctional (D''') units, and the imine-functional silsesquioxane resin, in addition to the T units described above, may have the formula (R 4 2SiO 2 / 2 ) c (R 4 R I SiO 2 / 2 ) dunits, i.e., a D'''T''' resin, where the subscripts c and d are as defined above. Alternatively, the propylimine-functional silsesquioxane resin may be of the formula (R 4 3SiO 1 / 2 ) a (R 4 2R I SiO 1 / 2 ) b monofunctional (M''') units, i.e., an M'''D'''T''' resin, where the subscripts a and b are as defined above for the unit formula (E2-1).

[0184] Alternatively, the (L) propylimine-functional organosilicon compound may have the unit formula (L3-1): [(R 1 (3-gg) R I gg Si) ff NH (3-ff) hh where R I is a propylimine group as described above, each R 1 is independently selected from the group consisting of alkyl groups and aryl groups as described above, each subscript ff is independently 1 or 2 as described above, subscript gg is independently 0, 1, or 2 as described above, and subscript h has a value such that 1 < hh < 10 as described above.

[0185] The propylimine-functional organosilicon compound (L) prepared in Step I) that may be used in Step III) of the process described herein may be any one of the propylimine-functional organosilicon compounds described above. Alternatively, (L) the propylimine-functional organosilicon compound may comprise a mixture of two or more of the propylimine-functional organosilicon compounds.

[0186] Alternatively, in the process described herein, (L) the propylimine-functional organosilicon compound may be a hydrolysis-labile propylimine-functional organosilicon compound. The hydrolysis-labile propylimine-functional organosilicon compound is, for example, at least one R 4 ​The (L1) propylimine-functional silane and / or (L2) propylimine-functional polyorganosiloxane from any of the formulas shown above, any (L3) propylimine-functional silazane, or any propylimine-functional polyorganosiloxane oligomer of formula (L2-10a) or (L2-11a) shown above, for example, (E)-N-butyl-3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propane-1-imine or (E)-3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)-N-propylpropane-1-imine.

[0187] Step II) Drying The above process may optionally further include step II) removing water produced by the dehydration imine formation reaction in step I). Step II) may be carried out during and / or after step I), during and / or after step III), or in combination thereof. Alternatively, step II) may be present and carried out during and / or after step I), for example, when a hydrolysis-unstable propylaldehyde-functional organosilicon compound is used, and / or when a hydrolysis-unstable propylimine-functional organosilicon compound or a hydrolysis-unstable aminopropyl-functional organosilicon compound is formed during the process.

[0188] In step II), water can be removed by any convenient means, such as stripping, distillation, and / or contact of the reaction mixture and / or reaction product of step I) with a desiccant (K). The desiccant may include an adsorbent which may contain inorganic fine particles. The adsorbent may have a particle size of 10 micrometers or less, alternatively 5 micrometers or less. The adsorbent may have an average pore size sufficient to adsorb water, for example, 10 Å (angstroms) or less, alternatively 5 Å or less, or alternatively 3 Å or less. Examples of adsorbents include molecular sieves such as zeolites such as szeolites, mordenite and analzolite, alkali metal aluminosilicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide and combinations thereof.

[0189] Examples of commercially available adsorbents include dry molecular sieves, such as 3 Å molecular sieves sold by Grace Davidson under the trade name SYLOSIV (trademark) and by Zeochem (Louisville, Kentucky, USA) under the trade name PURMOL, as well as 4 Å molecular sieves such as Doucil zeolite 4A available from Ineos Silicas (Warrington, England). Other useful molecular sieves include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A (all commercially available from UOP (Illinois, USA)), SILIPORITE NK 30AP and 65xP (Atofina (Philadelphia, Pennsylvania, USA)), and molecular sieves available from WRGrace (Maryland, USA).

[0190] Alternatively, desiccants may include chemicals that form complexes with water, such as calcium chloride (CaCl2), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), or magnesium sulfate (MgSO4), all of which are commercially available.

[0191] The amount of desiccant is not particularly limited and will vary depending on various factors, including the type of desiccant selected. Those skilled in the art will be able to select a suitable desiccant and conditions for removing water in step II). If a desiccant is used, the process described herein may further include removing the desiccant before step III). The desiccant may then be removed by any convenient means, such as filtration. Alternatively, the desiccant may be used during and / or after step III). The desiccant may then be removed after step III).

[0192] The process for producing aminopropyl-functional organosilicon compounds may optionally further include an additional step (G) of pre-treating the hydrogenation catalyst prior to step III). The pre-treatment may be carried out to activate the catalyst and / or to enhance its activity. The pre-treatment may be carried out by any convenient means, such as exposing the hydrogenation catalyst to hydrogen before initiating the reductive amination reaction in step III). For example, the packed bed of the hydrogenation catalyst may be purged with hydrogen before introducing the (L) propylimine-functional organosilicon compound and (F2) ammonia.

[0193] In step III) of the process, (F2) ammonia having the formula NH3, for example, anhydrous ammonia, is used. Ammonia is known in the art and is commercially available from various suppliers, including Air Products (Allentown, Pennsylvania, USA). The amount of (F2) ammonia used in step III) may be sufficient to provide ammonia:imine groups in a molar ratio greater than 1:1, alternatively 5:1 or greater, and alternatively 10:1 to 40:1.

[0194] (G) Hydrogen catalyst The hydrogenation catalyst used in step III) of the process for preparing aminopropyl-functional organosilicon compounds may be a heterogeneous hydrogenation catalyst, a homogeneous hydrogenation catalyst, or a combination thereof. Alternatively, the hydrogenation catalyst may be a heterogeneous hydrogenation catalyst. Suitable heterogeneous hydrogenation catalysts include metals selected from the group consisting of cobalt (Co), copper (Cu), iron (Fe), nickel (Ni), iridium (Ir), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), and combinations of two or more of these. Alternatively, the hydrogenation catalyst may include Co, Cu, Ni, Pd, Pt, Ru, or combinations of two or more of these. Alternatively, the hydrogenation catalyst may include Co, Cu, Ni, or a combination of two or more of these. The hydrogenation catalyst may include a support such as alumina (Al2O3), silica (SiO2), silicon carbide (SiC), or carbon (C). Alternatively, the hydrogenation catalyst may be selected from the group consisting of Rh / C, Raney nickel, Raney copper, Raney cobalt, Ru / C, Ru / Al2O3, Pd / C, Pd / Al2O3, Pd / CaCO3, Cu / C, Cu / Al2O3, Cu / SiO2, Cu / SiC, Cu / C, nickel catalysts on the above supports, and combinations of two or more of these.

[0195] Alternatively, heterogeneous hydrogenation catalysts for the reductive amination of the imine group of (L)propylimine-functionalized organosilicon compounds may comprise a support material in which copper, chromium, nickel, rhodium, or two or more of these as active components. Exemplary catalysts include 0.3–15% copper, 0.3–15% nickel, and 0.05–3.5% chromium. The support material may be, for example, porous silicon dioxide or aluminum oxide. Barium may be optionally added to the support material. Alternatively, chromium-free hydrogenation catalysts may be used. For example, Ni / Al2O3 or Co / Al2O3, or copper oxide / zinc oxide-containing catalysts (which further contain potassium, nickel, and / or cobalt), in addition to alkali metals, may be used. Suitable hydrogenation catalysts are disclosed, for example, in U.S. Patent No. 7,524,997 or U.S. Patent No. 9,567,276 and the references cited therein. Alternatively, heterogeneous hydrogenation catalysts can be commercially available, such as the Rh / C catalyst available from Sigma-Aldrich, Ni-5256P available from BASF, and Co-179, which is also commercially available.

[0196] Other examples of heterogeneous hydrogenation catalysts suitable for use herein include Raney nickel, e.g., Raney nickel 2400, Ni-3288, Raney copper, Hysat 401 salt (Cu), ruthenium on carbon (Ru / C), rhodium on carbon (Rh / C), platinum on carbon (Pt / C), and copper on silicon carbide (Cu / SiC).

[0197] Alternatively, homogeneous hydrogenation catalysts may be used herein. These homogeneous hydrogenation catalysts may be metal complexes, the metals of which may be selected from the group consisting of Co, Fe, Ir, Rh, and Ru. Examples of suitable homogeneous hydrogenation catalysts include [RhCl(PPh3)3] (Wilkinson catalyst), [Rh(NBD)(PR'3)2]+ClO4- (wherein R' is an alkyl group, e.g., Et), [RuCl2(diphosphine)(1,2-diamine)] (Noyori catalyst), RuCl2(TRIPHOS) (wherein TRIPHOS=PhP[(CH2CH2PPh2)2], Ru(II)(dppp)(glycine) complex (wherein dppp=1,3-bis(diphenylphosphino)propane), RuCl2(PPh3)3, RuCl2(CO)2(PPh3)2, IrH3(PPh3)3, [Ir(H2)(CH3COO)(PPh3)3], cis-[Ru-Cl2(ampy)(PP)] (wherein ampy=2-(aminomethyl)pyridine, and PP Examples include HCNNR (=1,4-bis-(diphenylphosphino)butane, 1,1'-ferrocendiyl-bis(diphenylphosphine)), pincer RuCl(CNNR)(PP) complex [wherein PP = 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-ferrocendiyl-bis(diphenylphosphine)], and HCNNR = 4-substituted aminomethyl-benzo[h]quinoline, R = Me, Ph], [RuCl2(dppb)(ampy)] (wherein dppb = 1,4-bis(diphenylphosphino)butane, ampy = 2-aminomethylpyridine), [Fe(PNPMeiPr)(CO)(H)(Br)], [Fe(PNPMe-iPr)(H)2(CO)], and combinations thereof.

[0198] The amount of hydrogenation catalyst used in the process varies depending on various factors, including whether the process is run in batch mode or continuous mode, the type of propylimine-functionalized organosilicon compound, whether a heterogeneous or homogeneous hydrogenation catalyst is selected, and the reductive amination reaction conditions such as temperature and pressure. However, when the process is run in batch mode, the amount of catalyst can be less than 1% by weight to 50% by weight, alternatively 5% to 30% by weight, based on the weight of the propylimine-functionalized organosilicon compound. Alternatively, the amount of catalyst can be at least 1%, alternatively at least 4, alternatively at least 6.5, alternatively at least 8% by weight, and simultaneously, the amount of catalyst can be up to 50%, alternatively up to 20, alternatively up to 14, alternatively up to 13, alternatively up to 10, alternatively up to 9% by weight, based on the same criteria. Alternatively, when the process is run in continuous mode, for example by filling the reactor with a heterogeneous hydrogenation catalyst, the amount of heterogeneous hydrogenation catalyst can be 10 hours -1 The reactor volume (filled with hydrogenation catalyst) required to achieve the space-time, or 1 m³ of catalyst 2 This may be sufficient to provide enough catalyst surface area to achieve a substrate flow rate of 10 kg / hour per unit.

[0199] (H) Hydrogen Hydrogen is known in the art and is commercially available from various suppliers, such as Air Products. Hydrogen can be used in superstoichiometric amounts relative to the imine group of (L)propylimine-functionalized organosilicon compounds to enable a complete reaction.

[0200] (J) Solvent The solvent (J) that may be optionally used in the process for preparing propylimine-functional organosilicon compounds and / or aminopropyl-functional organosilicon compounds may be selected from solvents that are neutral to the dehydration imine formation reaction when used in step I) above, and / or neutral to the reductive amination reaction when used in step III) of the process. Specific examples of such solvents are: monohydric alcohols such as methanol, ethanol, and isopropyl alcohol; ethers such as dioxane and THF; aliphatic hydrocarbons such as hexane, heptane, and paraffinic solvents; aromatic hydrocarbons such as benzene, toluene, and xylene; and chlorinated hydrocarbons. These solvents may be used individually or in combination of two or more. The amount of solvent is not critical and may vary depending on various factors such as the type and amount of each starting material used. For example, if the propylaldehyde-functional organosilicon compounds and / or propylimine-functional organosilicon compounds are resinous rather than oligomeric, more solvent may be used. However, the amount of solvent may be between 0 and 99% based on the total weight of all starting materials used in the process.

[0201] During or after step III) of the process, water may be removed as described above for step II). For example, a desiccant such as (K) an adsorbent or a water complexing agent may be optionally used to remove water produced as a by-product. Suitable desiccants and their usage conditions are as described above. The desiccant selected for use during or after step III) may be the same as or different from the desiccant selected for use during or after step I). Alternatively, if a desiccant is used during or after step I), the desiccant may be omitted during or after step III).

[0202] Step III) Reductive Amination Reaction The reductive amination reaction in step III) may be carried out using pressurized hydrogen. The hydrogen (gauge) pressure may be 10 psig (68.9 kPa) to 3000 psig (20,685 kPa), alternatively 10 psig to 2000 psig (13,790 kPa), alternatively 10 psig to 1500 psig (10,342 kPa), or alternatively 200 psig (1379 kPa) to 1200 psig (8274 kPa). The reaction may be carried out at a temperature of 0 to 200°C. Alternatively, a temperature of 50 to 150°C may be preferred to shorten the reaction time. Alternatively, the hydrogen (gauge) pressure used may be at least 25 psig, alternatively at least 50 psig, alternatively at least 100 psig, alternatively at least 150 psig, or alternatively at least 164 psig, while the hydrogen gauge pressure may be up to 800 psig, alternatively up to 400 psig, alternatively up to 300 psig, alternatively up to 200 psig, or alternatively up to 194 psig. The temperature for the reaction may be at least 40°C, alternatively at least 50°C, alternatively at least 65°C, or alternatively at least 80°C, while the temperature may be up to 200°C, alternatively up to 150°C, or alternatively up to 120°C.

[0203] The reductive amination reaction can be carried out in batch mode or continuous mode. In batch mode, the reductive amination reaction time varies depending on various factors including the amount of catalyst and the reductive amination reaction temperature, but step III) of the process for preparing aminopropyl-functional organosilicon compounds can be carried out for 1 minute to 24 hours. Alternatively, the reductive amination reaction can be carried out for at least 1 minute, alternatively at least 2 minutes, alternatively at least 1 hour, alternatively at least 2 hours, alternatively at least 3 hours, alternatively at least 3.3 hours, alternatively at least 3.7 hours, alternatively at least 4 hours, alternatively at least 4.5 hours, alternatively at least 5.5 hours, or alternatively at least 6 hours, and simultaneously, the reductive amination reaction can be carried out for up to 24 hours, alternatively up to 23 hours, alternatively up to 22.5 hours, alternatively up to 22 hours, alternatively up to 17.5 hours, alternatively up to 17 hours, or alternatively up to 16.5 hours.

[0204] Alternatively, in batch mode, the endpoint of a reductive amination reaction can be considered to be the time after continuing the reaction for a further 1-2 hours at which no further decrease in reactor pressure is observed. If the reactor pressure decreases during the reaction, it may be desirable to repeat the introduction of hydrogen and amine sources and maintain it under high pressure to shorten the reaction time. Alternatively, the reactor can be repressurized once or more times with hydrogen and ammonia to achieve a sufficient supply of hydrogen and ammonia for the reaction of the imine functional group while maintaining a reasonable reactor pressure.

[0205] In continuous mode, the reductive amination reaction may be carried out in a trickle bed reactor. A trickle bed reactor may provide reduced capital investment and / or increased yield in step III) of the process, and / or easier handling for the separation of the aminopropyl-functional organosilicon compound from the catalyst after step III). Alternatively, a high-pressure reactor (e.g., a reactor capable of withstanding pressures up to 3000 psig (20,685 kPa) as described above) may be used for the reductive amination reaction in step III) in either batch mode or continuous mode.

[0206] After the reductive amination reaction is complete, (G) the hydrogenation catalyst can be separated in a pressurized inert (e.g., nitrogen) atmosphere by any convenient means such as filtration or adsorption using diatomaceous earth or activated carbon, sedimentation, centrifugation, or by maintaining the hydrogenation catalyst in a structured packing or other immobile structure, or by a combination thereof.

[0207] The reductive amination reaction in step III) may also produce byproducts containing a primary amine source (as described above for use in step I). The primary amine source can be recovered from the reductive amination reaction product produced in step III) by any convenient means such as stripping and / or distillation. The primary amine source thus recovered can be reused in the process of step I). An exemplary reaction scheme illustrating the above process is described and shown below.

[0208] Example reaction scheme In an optional first step, a vinyl-functional organosilicon compound (e.g., 1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)-3-vinyltrisiloxane) undergoes a hydroformylation reaction to form a propylaldehyde-functional organosilicon compound (e.g., 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal). In step I), a propylaldehyde-functional organosilicon compound (e.g., 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal) combines with an organic primary amine (e.g., N-butylamine) to form a propylimine-functional organosilicon compound (e.g., N-butyl-3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propane-1-imine) and water as a byproduct. In step II), water may be removed, and in step III), a propylimine-functional organosilicon compound (e.g., N-butyl-3-(1,1,1,5,5,5,-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propan-1-imine) may be combined with hydrogen, ammonia, and a hydrogenation catalyst under conditions that catalyze the reductive amination reaction. N-butylamine is formed as a byproduct of the reductive amination reaction, and the N-butylamine can optionally be reused by returning to step I). The desired product, e.g., 3-(1,1,1,5,5,5,-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propan-1-amine) is also formed in step III).

[0209] Optional process - an example of hydroformylation for forming aldehyde-functional organosilicon compounds.

[0210] [ka]

[0211] Step I) - Example of Dehydration Imine Formation Reaction

[0212] [ka]

[0213] Step II) Remove water and optionally isolate N-butyl-3-(1,1,1,5,5,5,-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propane-1-imine.

[0214] Step III) Example of a reductive amination reaction

[0215] [ka]

[0216] Aminopropyl-functional organosilicon compounds The aminopropyl-functional organosilicon compounds prepared as described above have at least one primary aminopropyl functional group covalently bonded to silicon per molecule. Alternatively, the aminopropyl-functional organosilicon compounds may have two or more primary aminopropyl functional groups covalently bonded to silicon per molecule. Primary aminopropyl functional group, R N The formula is:

[0217] [ka] The formula may have, where G is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms, as described and illustrated above. The aminopropyl functional organosilicon compound has at least one R I R N The (L)propylimine-functionalized organosilicon compound may have any one of the above formulas, which is preplaced.

[0218] The aminopropyl-functional organosilicon compound prepared as described above is (N1) formula (N1-1):R N x SiR4 (4-x) It may contain an aminopropyl functional silane, in which R N , R 4 , and the subscript x are as described above. Aminopropyl-functionalized silanes are exemplified by aminopropyl-functionalized trialkylsilanes such as (aminopropyl)-trimethylsilane and (aminopropyl)-triethylsilane.

[0219] Alternatively, aminopropyl-functional organosilicon compounds may include (N2)aminopropyl-functional polyorganosiloxanes. These aminopropyl-functional polyorganosiloxanes may be cyclic, linear, branched, resinous, or a combination of two or more of these. The aminopropyl-functional polyorganosiloxane has the unit formula (N2-1):(R 4 3SiO 1 / 2 ) a (R 4 2R N SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R N SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R N SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h It may include, in the formula, each R N R is an independently selected primary aminopropyl functional group of the above formula, 4 Z, and the subscripts a, b, c, d, e, f, g, and h are as described above for formula (B2-1).

[0220] Alternatively, (N2) aminopropyl-functionalized polyorganosiloxane may include (N2-2) linear polydiorganosiloxane having at least one primary aminopropyl functional group per molecule, or alternatively, at least two primary aminopropyl functional groups (for example, in formula (N2-1) for the above aminopropyl-functionalized polyorganosiloxane, the subscripts e=f=g=0). For example, the polydiorganosiloxane has the unit formula (N2-3): (R 4 3SiO 1 / 2 ) a (R N R 4 2SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R I R 4 SiO 2 / 2 ) d It may include, in the formula, R N As stated above, R 4 Furthermore, the subscripts a, b, c, and d are as described above for formula (E2-3).

[0221] Alternatively, a linear aminopropyl-functional polydiorganosiloxane with unit formula (N2-3) is given by unit formula (N2-4): (R 4 2R N SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) m (R 4 R N SiO 2 / 2 ) n , Unit formula (N2-5): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) o (R 4 R N SiO 2 / 2 ) p Alternatively, the group may be selected from the combination of both (N2-4) and (N2-5).

[0222] In equations (N2-4) and (N2-5), RN As stated above, R 4 Furthermore, the subscripts m, n, o, and p are as described above for formulas (E2-4) and (E2-5).

[0223] Aminopropyl-functionalized polyorganosiloxanes (N2) include i) bis-dimethyl(aminopropyl)siloxy-terminated polydimethylsiloxane, ii) bis-dimethyl(aminopropyl)siloxy-terminated poly(dimethylsiloxane / methyl(aminopropyl)siloxane), iii) bis-dimethyl(aminopropyl)siloxy-terminated polymethyl(aminopropyl)siloxane, iv) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methyl(aminopropyl)siloxane), v) bis-trimethylsiloxy-terminated polymethyl(aminopropyl)siloxane, vi) bis-dimethyl( The aminopropyl functional polydiorganosiloxanes may include aminopropyl)siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(aminopropyl)siloxane), vii) bis-dimethyl(aminopropyl)siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viiii) bis-dimethyl(aminopropyl)siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl,methyl,(aminopropyl)-siloxy-terminated polydimethylsiloxane, and combinations of two or more of x)i) to ix).

[0224] Alternatively, (N2) aminopropyl-functional polyorganosiloxanes can be cyclic, for example, if the subscripts a=b=c=e=f=g=h=0 in the unit formula (N2-1). (N2-6) Cyclic aminopropyl-functional polydiorganosiloxanes have the unit formula (N2-7): (R 4 R N SiO 2 / 2 ) d It may have, in the formula, R N and R 4As stated above, the subscript d can be 3-12, alternatively 3-6, or alternatively 4-5. Examples of cyclic aminopropyl-functional polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-tri(aminopropyl)-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetra(aminopropyl)-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-penta(aminopropyl)-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexa(aminopropyl)-cyclohexasiloxane.

[0225] Alternatively, (N2-6)cyclic aminopropyl functional polydiorganosiloxanes have the unit formula (N2-8):(R 4 2SiO 2 / 2 ) c (R 4 R N SiO 2 / 2 ) d It may have, in the formula, R 4 and R N As stated above, the subscript c is >0 to 6, and the subscript d is >3 to 12. Alternatively, in equation (N2-8), the quantity (c+d) can be between 3 and 12. Alternatively, in equation (N2-8), c can be between 3 and 6, and d can be between 3 and 6.

[0226] Alternatively, (N2) aminopropyl-functionalized polyorganosiloxanes can be (N2-9) oligomers, for example, if the quantities (a+b+c+d+e+f+g) in the above unit formula (N2-1) are ≤ 50, ≤ 40, ≤ 30, ≤ 25, ≤ 20, ≤ 10, ≤ 5, ≤ 4, or ≤ 3. The oligomers can be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as (N2-6).

[0227] An example of a linear aminopropyl-functionalized polyorganosiloxane oligomer is formula (N2-10):

[0228] [ka] It may have, in the formula, R 4 As stated above, each R 2’’ R is independent of R 4 and R N Selected from the group consisting of, provided that at least one R per molecule 2’’ However, R N The subscript z is given to be between 0 and 48. Alternatively, the subscript z can be between 0 and 4, between 0 and 1, or between 0. Alternatively, in formula (N2-10), if z=0, the aminopropyl functional polyorganosiloxane oligomer is given by formula (N2-10a):

[0229] [ka] It may have, in the formula, R 4 and R N As stated above, examples of linear aminopropyl-functional polyorganosiloxane oligomers include 1,3-di(aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-(aminopropyl)-disiloxane, and 1,1,1,3,5,5,5-heptamethyl-3-(aminopropyl)-trisiloxane.

[0230] Alternatively, aminopropyl-functionalized polyorganosiloxane oligomers may be branched. Branched oligomers have the general formula (N2-11):R N SiR 12 3 may be present, in the formula, R N As stated above, each R 12 R 13 and -OSi(R 14 ) Selected from 3, each R 13 It is a monovalent hydrocarbon group, and each R 14 R 13 , -OSi(R 15 )3, and -[OSiR 13 2]ii OSiR 13 Selected from 3, each R 15 R 13 , -OSi(R 16 )3, and -[OSiR 13 2] ii OSiR 13 Selected from 3, each R 16 R 13 and -[OSiR 13 2] ii OSiR 13 Selected from 3, the subscript ii has a value such that 0 ≤ ii ≤ 100. 12 At least two of them are -OSi(R 14 )3 is possible. Alternatively, R 12 All three of them are -OSi(R 14 ) It could be 3.

[0231] Alternatively, in equation (L2-11), each R 12 R 13 In this case, the branched polyorganosiloxane oligomer has the following structure (N2-11a):

[0232] [ka] In the formula, R N and R 13 As stated above. Alternatively, in equation (N2-11a), each R 13 It can be methyl.

[0233] Alternatively, in equation (N2-11), each R 12 -OSi(R 14 )If it is 3, each R 14 -OSi(R 15 ) It could be in 3 parts,

[0234] [ka] In the formula, RN and R 15 As stated above, alternatively, each R 15 As mentioned above, R 13 This is possible, and each R 13 It can be methyl.

[0235] Alternatively, in equation (N2-11), each R 12 -OSi(R 14 )If it is 3, one R 14 Each R 12 ga-OSiR 13 (R 14 Each -OSi(R) is such that )2 14 )3 in R 13 It is possible. Alternatively, -OSiR 13 (R 14 )2 R in 2 14 Each of these is a branched aldehyde-functional polyorganosiloxane oligomer with the following structure (N2-11c):

[0236] [ka] -OSi(R 15 ) It could be in 3 parts, In the formula, R N , R 13 , and R 15 As stated above, alternatively, each R 15 R 13 This is possible, and each R 13 It can be methyl.

[0237] Alternatively, in equation (N2-11), one R 12 R 13 It could be, R 12 Two of them are -OSi(R 14 ) It could be 3. R 12 Two of them are -OSi(R 14 )If it is 3, one R 14 Each -OSi(R 14 )R in 3 13 And R 12 Two of them are -OSiR13 (R 14 )2. Alternatively, -OSiR 13 (R 14 ) Each R in 2 14 The branched polyorganosiloxane oligomer has the following structure (N2-11d):

[0238] [ka] -OSi(R 15 ) It can be 3, and in the formula, R N , R 13 , and R 15 As stated above, alternatively, each R 15 R 13 This is possible, and each R 13 It can be methyl. Alternatively, branched polyorganosiloxanes may have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, or alternatively 4 to 10 silicon atoms per molecule. An example of an aminopropyl-functionalized branched polyorganosiloxane oligomer is 3-(3,3,3-trimethyl-1l2-disiloxanyl)propan-1-amine, which has the formula

[0239] [ka] It has.

[0240] Alternatively, the (N2) aminopropyl-functional polyorganosiloxane may be branched, such as the branched oligomer described above, and / or a branched aminopropyl-functional polyorganosiloxane that may have more aminopropyl groups and / or more polymer units per molecule than the branched oligomer described above (for example, in formula (N2-1), when the number (a+b+c+d+e+f+g)>50). The branched aminopropyl-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide >0-5 mol% of trifunctional and / or tetrafunctional units in the branched aminopropyl-functional polyorganosiloxane (in formula (N2-1)).

[0241] For example, branched aminopropyl-functional polyorganosiloxanes have the unit formula (N2-13):(R 4 3SiO 1 / 2 ) q (R 4 2R N SiO 1 / 2 ) r (R 4 2SiO 2 / 2 ) s (SiO 4 / 2 ) t It may contain a Q-type branched polyorganosiloxane, in which R N As stated above, R 4 Furthermore, the subscripts q, r, s, and t are as described above for (E2-13).

[0242] Alternatively, branched aminopropyl-functional polyorganosiloxanes are given by formula (N2-14):[R N R 4 2Si-(O-SiR 4 2) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3] w It may include, in the formula, R N As stated above, R 4Furthermore, the subscripts v, w, and x are as described above with respect to equation (E2-14). Alternatively, in this equation (N2-14), each R 4 This is independently selected from the group consisting of methyl and phenyl.

[0243] Alternatively, the branched aminopropyl-functional polyorganosiloxane for (N2-11) has the unit formula (N2-15): (R 4 3SiO 1 / 2 ) aa (R N R 4 2SiO 1 / 2 ) bb (R 4 2SiO 2 / 2 ) cc (R N R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd It may contain a T-branched polyorganosiloxane (silsesquioxane), in which R N As stated above, R 4 Furthermore, the subscripts aa, bb, cc, dd, and ee are as described above for the unit formula (E2-15).

[0244] Alternatively, (N2)aminopropyl-functional polyorganosiloxane may include aminopropyl-functional polyorganosilicate resins and / or aminopropyl-functional silsesquioxane resins, among others. The aminopropyl-functional polyorganosilicate resin is of formula R M’’ 3SiO 1 / 2 The monofunctional unit ("M''" unit) and formula SiO 4 / 2 The formula includes a tetrafunctional silicate unit ("Q" unit), and each R M’’ This is independently of the above R 4 and R N A selection can be made from the group consisting of . Alternatively, each R M’’ R is an alkyl group, as shown above. NThe formula for can be selected from the group consisting of aminopropyl functional groups and aryl groups. Alternatively, each R M’’ R can be selected from methyl, (aminopropyl), (aminobutyl), and phenyl. Alternatively, M’’ At least one-third, and alternatively at least two-thirds, of the groups are methyl groups. Alternatively, the M'' unit is (Me3SiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2R N SiO 1 / 2 Polyorganosilicate resins are soluble in solvents such as those described herein as starting materials (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low-viscosity linear and cyclic polydiorganosiloxanes.

[0245] The aminopropyl functionalized polyorganosilicate resin comprises the above M'' and Q units, and the polyorganosilicate resin comprises silicon-bonded hydroxyl groups and / or the above portion (ZO 1 / 2 It further comprises units having hydrolyzable groups as described by the formula Si(OSiR M’’ 3) May contain a neopentamer of 4, where R M’’ As stated above, for example, the neopentamer may be a tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13 Using 13C NMR spectroscopy, the hydroxyl and alkoxy content, as well as the molar ratio of M'' units to Q units, can be measured. This ratio is expressed as {M''(resin)} / {Q(resin)}, where M'' and Q units are excluded 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 range from 0.5 / 1 to 1.5 / 1, or alternatively from 0.6 / 1 to 0.9 / 1.

[0246] The Mn in aminopropyl-functionalized polyorganosilicate resins is present in the R M’’ It varies depending on various factors, such as the type of hydrocarbon group represented. The Mn of polyorganosilicate resins refers to the number-average molecular weight measured using GPC when peaks representing neopentamers are excluded from the measurements. The Mn of polyorganosilicate resins can be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, or alternatively >3,000 Da to 8,000 Da. Alternatively, the Mn of polyorganosilicate resins may be 3,500 Da to 8,000 Da.

[0247] Alternatively, polyorganosilicate resins have the unit formula (N2-17):(R 4 3SiO 1 / 2 ) mm (R 4 2R N SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h It may include, in the formula, Z, R 4 , and R N , as well as the subscript h, are as described above, and the subscripts mm, nn, and oo have mean values ​​such that mm≧0, nn>0, oo>0, and 0.5≦(mm+nn) / oo≦4. Alternatively, 0.6≦(mm+nn) / oo≦4, alternatively, 0.7≦(mm+nn) / oo≦4, and alternatively, 0.8≦(mm+nn) / oo≦4.

[0248] Alternatively, (N2)aminopropyl-functionalized polyorganosiloxane is (N2-18)aminopropyl-functionalized silsesquioxane resin, i.e., unit formula: (R 4 3SiO 1 / 2 ) a (R 4 2R N SiO 1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 R N SiO2 / 2 ) d (R 4 SiO 3 / 2 ) e (R N SiO 3 / 2 ) f (ZO 1 / 2 ) h may comprise a resin containing a trifunctional (T'') unit of, wherein R 4 and R N are as defined above, and the subscripts satisfy f>1, 2<(e+f)<10,000, 0<(a+b) / (e+f)<3, 0<(c+d) / (e+f)<3, and 0<h / (e+f)<1.5. Alternatively, the aminopropyl-functional silsesquioxane resin may have the unit formula (N2-19):(R 4 SiO 3 / 2 ) e (R N SiO 3 / 2 ) f (ZO 1 / 2 ) h may comprise, wherein R 4 , R N , Z, and the subscripts h, e, and f are as defined above. Alternatively, the aminopropyl-functional silsesquioxane resin may further comprise difunctional (D'') units, and the aminopropyl-functional silsesquioxane resin, in addition to the T units described above, may comprise units of the formula (R 4 2SiO 2 / 2 ) c (R 4 R N SiO 2 / 2 ) d that is, a D''T'' resin, wherein the subscripts c and d are as defined above. Alternatively, the aminopropyl-functional silsesquioxane resin may further comprise monofunctional (M'') units of the formula (R 4 3SiO 1 / 2 ) a (R 4 2R N SiO 1 / 2 ) b that is, a M''D''T'' resin, wherein the subscripts a and b are as defined above for unit formula (E2-1).

[0249] Alternatively, the (N) aminopropyl-functional organosilicon compound has the unit formula (N3-1): [(R 1 (3-gg) R N gg Si) ff NH (3-ff) hh may include, where R in the formula N is as described above, each R 1 is independently selected from the group consisting of alkyl groups and aryl groups as described above, each subscript ff is independently 1 or 2 as described above, subscript gg is independently 0, 1, or 2 as described above, and subscript h has a value such that 1<hh<10 as described above.

[0250] The aminopropyl-functional organosilicon compound prepared in Step III) of the process described herein may be any one of the aminopropyl-functional organosilicon compounds described above. Alternatively, the reductive amination reaction product may comprise a mixture of two or more of the aminopropyl-functional organosilicon compounds.

[0251] Alternatively, the processes described herein may be used to produce hydrolysis-labile aminopropyl-functional organosilicon compounds. The hydrolysis-labile aminopropyl-functional organosilicon compound is, for example, at least one R 4 is a hydrocarbyloxy group or an acyloxy group, any one of (N1) aminopropyl-functional silanes and / or (N2) aminopropyl-functional polyorganosiloxanes of any of the formulas shown above, any (N3) aminopropyl-functional silazane, or any aminopropyl-functional polyorganosiloxane oligomer of formula (N2-10a) or (N2-11a) as described and exemplified above. [Examples]

[0252] ​These examples are provided to those skilled in the art to illustrate the present invention and should not be construed as limiting the scope of the invention as described in the claims. The starting materials used in the examples are listed in Table 1 below.

[0253] [Table 1]

[0254] In this example 1, the formula

[0255] [ka] 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal was synthesized as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (25.2 mg), ligand 1 (150.5 mg), and toluene (17.07 g) were added to a 30 mL glass vial using a magnetic stirrer. The mixture was stirred on a stirring plate until a homogeneous solution was formed. This catalyst solution was transferred to an airtight syringe equipped with a metal valve and then removed from the glove box. In a ventilated fume hood, 1,3-divinyltetramethyldisiloxane (1000 g) was packed into a 2 L autoclave reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psig (689.5 kPa) with nitrogen via an immersion tube and the pressure was carefully released through a valve connected to the headspace. This process was repeated three times to deactivate the reactor headspace. The reactor was then pressure-tested by pressurizing it with nitrogen to 300 psig (2068.4 kPa). After releasing the pressure, the catalyst solution was added to the reactor through the sample-filled port. The reactor was pressurized with synthesis gas to 100 psig (689.5 kPa), then depressurized three times, and finally pressurized to 80 psig (551.6 kPa) via the immersion tube. The reaction temperature was set to 50°C until gas intake slowed, and then to 80°C. The stirring speed was set to 800 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing synthesis gas. The pressure was set to 100 psig (689.5 kPa). The progress of the reaction was monitored by a data logger measuring the pressure in a 300 mL intermediate cylinder as synthesis gas was supplied to the reactor via a pressure regulator. A conversion rate of over 98% was observed after 22.5 hours. The n / i ratio of the final product 1 This was determined by 1H NMR analysis.

[0256] In this Comparative Example 2, 18 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, was packed into a 300 mL autoclave reactor with toluene (18 g) and Ni-5256P catalyst (4.1 g). The reactor was sealed and the headspace was inactivated with nitrogen. Ammonia (74.6 g, 30 equivalents) was added, and the reactor was pressurized with hydrogen to 550 psig (3792.1 kPa). The reactor was heated to 90°C, and hydrogen was added until the pressure was 100 psig (689.5 kPa) higher than the reactor pressure at the reaction temperature. The reaction pressure was observed to be 940 psig (6481.1 kPa). Reductive amination was carried out at 90°C and 825 RPM for 4 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 17.0 g of concentrated product. The concentrated product was analyzed using GC-FID and was found to be 59.7 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0257] This reference example 3 uses 560 DP and equations.

[0258] [ka] A bis(propylaldehyde-terminated) polydimethylsiloxane (wherein the formula, the subscript pp represents the average number of difunctional siloxane units per molecule, with a value of 558) having the following properties was prepared: In a nitrogen-filled glove box, Rh(acac)(CO)2 (90.6 mg, 0.350 mmol), ligand 1 (550 mg, 0.656 mmol), and toluene (51.43 g, 558 mmol) were added to a 120 mL glass bottle using a magnetic stirrer. The mixture was stirred on a stirring plate until a homogeneous solution was formed. A portion of this solution (1.45 g) was transferred to an airtight syringe equipped with a metal valve and then removed from the glove box. In a ventilated fume hood, the average dimethylsiloxy(D) units (M) of 558 per molecule were added.Vi 2D 558 Bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (195.3 g, 4.68 mmol) having ) was packed into a 300 mL Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi (689.5 kPa) with nitrogen via an immersion tube, and the pressure was carefully released three times through a valve connected to the headspace. The reactor was then pressure-tested by pressurizing it to 300 psi (2068.4 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample-filling port. The reactor was pressurized to 100 psi (689.5 kPa) with synthesis gas, and after releasing the pressure three times, it was pressurized to 80 psi (551.6 kPa) via an immersion tube. The reaction temperature was set to 90°C. The stirring speed was set to 600 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing synthesis gas. The pressure was set to 100 psi (689.5 kPa). The progress of the reaction was monitored by a data logger that measured the pressure in a 300 ml intermediate cylinder when synthesis gas was supplied to the reactor via a pressure regulator. The reaction was run for 4 hours. The resulting product contained bis(propylaldehyde-terminated) polydimethylsiloxane with 560 DP. 1 H and 29 The samples were characterized by Si NMR.

[0259] In this comparative example 4, the formula is:

[0260] [ka] A bis(3-aminopropyl)-terminated poly(dimethylsiloxane) having 560 DP (wherein the subscript qq was 558) was prepared as follows: In a 2 L autoclave reactor, the terminal dipropion siloxane prepared as described in Reference Example 3, (poly[oxy(dimethylsilylene)], α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy], or (C2H6OSi) n C 10 H22 O3Si2 (wherein n=560) (595g), toluene (399g), and 5 wt% Rh / C (36.5g) were packed into the reactor. The reactor was sealed and the headspace was inactivated with nitrogen. The mixture was stirred at 820 rpm, ammonia (44g) was added, and the mixture was stirred for 18 minutes. The reactor was pressurized with hydrogen to 615 psig (4240.3 kPa) and heated to 60°C. The reactor pressure was 683 psig (4709.1 kPa). The reactor pressure was increased with hydrogen to 795 psig (5481.3 kPa), and the reaction was carried out for 4 hours with continuous addition of hydrogen. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by a rotary evaporator to collect 595.8g of product. 29 The characteristics were evaluated by Si analysis, GPC, and viscosity. The octamethylcyclotetrasiloxane content was measured by GC analysis. 29 Si NMR analysis revealed 78% -propyl-NH2 terminally capped polydimethylsiloxane.

[0261] In this Reference Example 5, 3-1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal was prepared as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (13.6 mg, 0.0525 mmol), ligand 1 (84.5 mg, 0.101 mmol), and toluene (10.0 g, 108.5 mmol) were added to a 30 mL glass vial using a magnetic stirring bar. The mixture was stirred on a stirring plate until a homogeneous solution was formed. This solution was transferred to an airtight syringe equipped with a metal valve and then removed from the glove box. In a ventilated fume hood, vinylmethylbis(trimethylsiloxy)silane (MD Vi1000g, 4.02mol of M) was packed into a 2L autoclave reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi (689.5 kPa) with nitrogen via an immersion tube, and the pressure was carefully released three times through a valve connected to the headspace. The reactor was then pressure-tested by pressurizing it to 300 psi (2068.4 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample-filling port. The reactor was pressurized to 100 psi (689.5 kPa) with synthesis gas, and after releasing the pressure three times, it was pressurized to 80 psi (551.6 kPa) via an immersion tube. The reaction temperature was set to 75°C. The stirring speed was set to 800 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing synthesis gas. The pressure was set to 100 psi (689.5 kPa). The progress of the reaction was monitored by a data logger that measured the pressure in the intermediate cylinder when synthesis gas was supplied to the reactor via a vacuum regulator. The resulting product was 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD Pr-ald It contained M). Crude 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD Pr-ald A portion of M) was purified by vacuum distillation. The vacuum distillation apparatus consisted of a 500 three-neck round-bottom flask with a PTFE-coated magnetic stirrer, an electrically heated mantle whose internal temperature, measured by a thermoprobe, was controlled by J-CHEM®, and a 12-inch (30.48 cm) Vigreux column connected to a 250 mL pre-tare-weighted collection flask. A vacuum manifold was connected to a system including a vacuum gauge and a nitrogen line to regulate pressure and break the vacuum. Water cooling was used on the distillate condenser, and a dry eye trap was placed between the distillation system and the diaphragm vacuum pump to capture lower boiling point components. A thermometer was installed to measure the temperature of the overhead vapor. Crude 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD) Pr-aldDistillation was performed by filling a 500 mL reboiler with (M) (341.5 g). Distillation was carried out at a pressure of 2 Tor (266.6 Pa). The light cut (13 g) was collected at a pot temperature of 76 °C and an overhead temperature of 66 °C. The purified 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD) Pr-ald The main fraction containing M) (243g) was collected at a pot temperature of 80-85°C and an overhead temperature of 67-69°C. 55g of bottom material was also recovered.

[0262] In this Comparative Example 6, N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl)butan-1-amine was synthesized as follows: A 300 mL autoclave reactor was packed with 12.0 g of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal, prepared as described in Reference Example 5, toluene (48.5 g), n-butylamine (3.8 g), and 5% by weight of Rh / C (1.4 g). The reactor was sealed and the headspace was inactivated with nitrogen. The mixture was stirred at 800 rpm for 5 minutes. The reactor was pressurized with hydrogen to 463 psig (3192.3 kPa) and heated to 60°C. The reactor pressure was 452 psig (3116.4 kPa). The reactor pressure was increased to 651 psig (4488.5 kPa) with hydrogen, and the reaction was carried out for 4 hours while continuously adding hydrogen. The reactor was cooled and evacuated. The reaction product was collected, the reactor was rinsed with toluene, and 75.2 g of material was collected. A portion of the material was filtered through a syringe filter, the solvent was stripped, and gas chromatography and 1 H and 13 Characterization by 13C NMR analysis confirmed the presence of N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl)butan-1-amine. GC analysis showed that the N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl)butan-1-amine product was present at 86 area %.

[0263] In this Example 7, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propan-1-amine and N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl)butan-1-amine were synthesized as follows: A 300 mL autoclave reactor was packed with 11.7 g of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal prepared as described in Reference Example 5, toluene (48.4 g), n-butylamine (3.9 g, 1.25 equivalents), and 5% by weight of Rh / C (1.2 g). The reactor was sealed and the headspace was inactivated with nitrogen. Ammonia (18.3 g, 25 equivalents) was added to the mixture, and the reactor pressure was 114 psig (786 kPa). The mixture was stirred at 800 rpm for 7 minutes. Hydrogen was added to the reactor to 480 psig (3309.5 kPa), and the hydrogenation was stopped. The reactor was heated to 60°C, at which point the reaction pressure was 580 psig (3999 kPa). The reactor pressure was increased to 798 psig (5502 kPa) with hydrogen, and the reaction was carried out for 4 hours while hydrogen was continuously added. The reactor was cooled and evacuated. The reaction product was collected, and the reactor was rinsed with toluene to collect 109.6 g of liquid. A portion of the liquid was filtered through a syringe filter, the solvent was stripped, and gas chromatography and 1 H and 13 Characterization was performed by 13C NMR analysis, and as a result, 67.4 GC / FID area % of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propan-1-amine and 18.6 GC / FID area % of N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl)butan-1-amine are shown, and together these are 86 area % of the product by GC.

[0264] In this Comparative Example 8, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propan-1-amine was synthesized as follows: A 300 mL autoclave reactor was packed with 12.1 g of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal, prepared as described in Reference Example 30, toluene (48.4 g), and 5% by weight of Rh / C (1.3 g). The reactor was sealed and the headspace was inactivated with nitrogen. Stirring was started at 800 rpm, and ammonia (19.9 g, 26.9 equivalents) was added to the mixture, and the reactor pressure was 117 psig (806.7 kPa). Hydrogen was added to the reactants to 444 psig (3061.3 kPa), and the hydrogenation valve was closed. The reactor was heated to 60°C, at which point the reaction pressure was 610 psig (4205.8 kPa). The reactor was pressurized with hydrogen to 463 psig (3192.3 kPa) and heated to 60°C. The reactor pressure was increased with hydrogen to 816 psig (5626.1 kPa), and the reaction was carried out for 4.5 hours while continuously adding hydrogen. The reactor was cooled and evacuated. The desired product was collected to obtain 60.6 g of liquid. A portion of the liquid was filtered through a syringe filter, the solvent was stripped, and gas chromatography and 1 H and 13 Characterization by 13C NMR and GC / FID analysis confirmed the presence of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propan-1-amine in the reaction product. GC analysis showed 79 area % of the 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propan-1-amine product.

[0265] Example 7 showed an improved yield compared to Comparative Example 8 using the process of the present invention.

[0266] In this example 9, the formula is:

[0267] [ka] A bis(3-aminopropyl)-terminated poly(dimethylsiloxane) having 560 DP (wherein the subscript qq was 558) was prepared as follows: In a glass container, the terminal dipropionsiloxane prepared as described in Reference Example 3, (poly[oxy(dimethylsilylene)], α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy], or (C2H6OSi) n C 10 H 22 A solution was formed by filling a container with O3Si2 (wherein n=558) (70.0 g) and toluene (71.0 g). n-butylamine (0.51 g, 2.1 equivalents) was added to this solution and mixed thoroughly. The mixture became turbid. MgSO4 (3.0 g) was added and mixed, and the mixture was held for 16 hours. The mixture was filtered to remove the MgSO4, and 140 g of clear liquid was obtained. 1 The presence of butylimine was confirmed by analysis using 1H NMR.

[0268] In a 300 mL autoclave reactor, the terminal diiminesiloxane prepared in Example 9, (poly[oxy(dimethylsilylene)]), α-[dimethyl(3-(butylimino)propylsilyl)]-ω-[[dimethyl(3-(butylimino)propylsilyl]oxy], or (C2H6OSi) n C 18 H 40 A solution of O3N2Si2 (wherein n=558) (140 g) and 5 wt% Rh / C (3.5 g) were packed into the reactor. The reactor was sealed and the headspace was inactivated with nitrogen. The mixture was stirred at 800 rpm, ammonia (7.1 g) was added, and the mixture was stirred for 13 minutes. The reactor was pressurized with hydrogen to 259 psig (1785.7 kPa) and heated to 60°C. The reactor pressure was 290 psig (1999.5 kPa). The reactor pressure was increased with hydrogen to 790 psig (5446.9 kPa), and the reaction was carried out for 4 hours while continuously adding hydrogen. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by a rotary evaporator to collect 70.7 g of product. 29 Si and1 The characteristics were determined by 1H NMR analysis. 29 Si NMR analysis revealed 91% primary amino-functionalized, terminally capped polydimethylsiloxane.

[0269] In this Example 10, 50.33 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, was packed into a 300 mL autoclave reactor with methanol (15.1 g), Ni-5256P (6.01 g), and n-butylamine (29.7 g). The reactor was sealed, stirring was started at 400 RPM, and the headspace was inactivated with nitrogen. The stirring speed was increased to 800 RPM, and ammonia (35.3 g, 10 equivalents) was added. The reactor was pressurized to 505 psig with hydrogen. The reactor was heated to 90°C, and hydrogen was added until the pressure reached 805 psig. Reductive amination was carried out at 90°C for approximately 16 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 49.8 g of concentrated product. The concentrated product was analyzed using GC-FID and was found to be 72.4 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0270] In this Example 11, 50.07 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, was packed into a 300 mL autoclave reactor with methanol (15.05 g), Ni-5256P (6.02 g), and isobutylamine (29.72 g). The reactor was sealed, stirring was started at 400 RPM, and the headspace was inactivated with nitrogen. The stirring speed was increased to 820 RPM, and ammonia (35.3 g, 10 equivalents) was added. The reactor was pressurized to 506 psig with hydrogen. The reactor was heated to 90°C, and hydrogen was added until the pressure reached 802 psig. Reductive amination was carried out at 90°C for approximately 16 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 48.7 g of concentrated product. The concentrated product was analyzed using GC-FID and was found to be 79.2 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0271] In Example 12, 25.1 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, was packed into a glass container with methanol (25.1 g) and 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) (30.0 g) to form an imine solution. This solution was packed into a 300 mL autoclave reactor, and Ni-5256P (2.76 g) was added. The reactor was sealed, stirring was started at 820 RPM, and the headspace was inactivated with nitrogen. The stirring speed was continued at 820 RPM, and ammonia (37.3 g) was added. The reactor was pressurized with hydrogen to 519 psig. The reactor was heated to 90°C, and hydrogen was added until the pressure reached 773 psig. Reductive amination was carried out at 90°C for approximately 16 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 48.7 g of concentrated product. The concentrated product was analyzed using GC-FID and was found to be 79.2 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0272] Hydroformylation of branched organosilicon oligomers to produce aldehydes

[0273] [ka] In this Reference Example 13, 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal of formula (above) was synthesized as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (47.5 mg), ligand 1 (294 mg), and toluene (60.2 g) were added to a glass bottle using a magnetic stirrer. The mixture was stirred on a stirring plate until a homogeneous solution was formed. A portion of this catalyst solution (2.88 g) was transferred to an airtight syringe equipped with a metal valve and then removed from the glove box. In a ventilated fume hood, 1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)-3-vinyltrisiloxane (180 g) was packed into a 300 mL pressure reactor. The reactor was sealed. While stirring at 600 RPM, the reactor was pressurized to 100 psig with nitrogen via an immersion tube, and the pressure was carefully released through a valve connected to the headspace. This process was repeated three times to deactivate the reactor headspace. The reactor was then pressure-tested by pressurizing it to 300 psig with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample-filled port. The reactor was pressurized to 100 psig with synthesis gas, then released three times, and then pressurized to 100 psig via an immersion tube. The reaction temperature was set to 80°C. The stirring speed was set to 600 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing synthesis gas. The pressure was set to 100 psig. The progress of the reaction was monitored by a data logger measuring the pressure in a 300 mL intermediate cylinder as synthesis gas was supplied to the reactor via a pressure regulator. A conversion rate of over 99% was observed after 16 hours. The n / i ratio was the final product. 1 ¹H NMR analysis determined the ratio to be 7.5:1.

[0274] [ka]

[0275] In this Comparative Example 14, 40 g of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal, prepared as described in Example 13, was packed into a 300 mL autoclave reactor along with THF (40.03 g) and Ni-5256P (3.99 g). The reactor was sealed and the headspace was inactivated with nitrogen. Ammonia (29.0 g, 15 equivalents) was added, and the reactor was pressurized with hydrogen to 530 psig. The reactor was heated to 100°C, and hydrogen was added until the pressure was 100 psig higher than the reactor pressure at the reaction temperature. Reductive amination was carried out at 100°C, 920 psig, and 800 RPM for 16 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 33.8 g of concentrated product. The concentrated product was analyzed using GC-FID and was found to be 44.1 wt% 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propan-1-amine.

[0276] [ka]

[0277] In this Example 15, 30 g of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propanal, prepared as described in Example 13, was packed into a glass round-bottom flask. 60 g of THF solvent was added to form a solution. While stirring with a PTFE-coated magnetic stirrer, N-butylamine (6.53 g, 1.05 equivalents) was added to the solution. A mild exothermic reaction was observed. MgSO4 was added to adsorb water from the solution. MgSO4 was removed by filtration to obtain 95 g of a solution containing N-butyl-3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propan-1-imine. The imine-containing solution was packed into a 300 mL autoclave reactor along with Ni-5256P catalyst (3.01 g). The reactor was sealed and the headspace was inactivated with nitrogen. Ammonia (21.7 g, 15 equivalents) was added, and the reactor was pressurized with hydrogen to 520 psig. The reactor was heated to 100 °C, and hydrogen was added until the pressure was 100 psig higher than the reactor pressure at the reaction temperature. Reductive amination was carried out at 100 °C, 925 psig, and 800 RPM for 20 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 25.0 g of concentrated product. The concentrated product, when analyzed using GC-FID, was 75.9 wt% 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propan-1-amine. This example and the immediately preceding comparative example demonstrate that using the process of the present invention dramatically increases yields compared to attempting to directly form primary amino-functional organosilicon compounds from corresponding aldehyde-functional organosilicon compounds using ammonia.

[0278] In this example 16, the formula, M 0.24 M プロパナールアルデヒド 0.139 T Ph 0.62The T-phenyl resin propanal was synthesized as follows: In a nitrogen-filled glove box, Rh(acac)(CO)2 (48.0 mg), ligand 1 (311.9 mg), and toluene (59.9 g) were combined to form a homogeneous catalyst solution. A portion (5.8 g) of this catalyst solution was transferred to an airtight syringe equipped with a metal valve, and then removed from the glove box. In a ventilated fume hood, M dissolved in toluene (90 g) was prepared. 0.24 M Vi 0.139 T Ph 0.62 90g of the catalyst was packed into a 300mL pressure reactor. The reactor was sealed. While stirring at 600 RPM, the reactor was pressurized to 100 psig with nitrogen via an immersion tube, and the pressure was carefully released through a valve connected to the headspace. This process was repeated three times to deactivate the reactor headspace. The reactor was then pressure-tested by pressurizing it to 300 psig with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample-filling port. The reactor was pressurized to 100 psig with synthesis gas, then released three times, and then pressurized to 100 psig via an immersion tube. The reaction temperature was set to 70°C. The stirring speed was set to 600 RPM. Once the desired temperature was reached, an intermediate cylinder containing synthesis gas was connected to the reactor. The pressure was set to 100 psig. The progress of the reaction was monitored by a data logger that measured the pressure in the 300mL intermediate cylinder as synthesis gas was supplied to the reactor via a pressure regulator. Final product 1 A conversion rate of over 99%, determined by 1H NMR analysis, was observed after 16 hours. Toluene was removed, leaving the product as a viscous liquid.

[0279] In this Example 17, 25.8 g of M, as described in Example 16, was used. 0.24 M プロパナールアルデヒド 0.14 T Ph 0.62The mixture was packed into a glass round-bottom flask. THF solvent (51.6 g) was added to form a solution. N-butylamine (2.55 g, 1.1 equivalents) was added to the solution while stirring with a PTFE-coated magnetic stirrer. MgSO4 was added to adsorb water from the solution. MgSO4 was removed by filtration to obtain a solution containing the corresponding N-butylimine. The imine-containing solution was packed into a 300 mL autoclave reactor along with a 5% Ru / C catalyst (2.6 g). The reactor was sealed and the headspace was inactivated with nitrogen. Ammonia (8.3 g, approximately 15 equivalents) was added and the reactor was pressurized with hydrogen to 530 psig. The reactor was heated to 80°C and hydrogen was added until the pressure reached 880 psig. Reductive amination was carried out at 80°C, 880 psig, and 800 RPM for 18.5 hours. The reactor was cooled and evacuated. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 27.2 g of concentrated product. The concentrated product was: 1 H and 13 If determined by 13C NMR, M 0.24 M プロピルアミン 0.139 T Ph 0.52 This example 17 demonstrates that a primary amino-functional polyorganosiloxane resin can be produced using the process of the present invention.

[0280] In this Example 18, 299.1 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, was packed into a glass round-bottom flask. 898.1 g of isopropanol solvent was added to form a solution. Iso-butylamine (196.1 g, 2.1 equivalents) was added to the solution while stirring with a mechanical stirrer. The resulting imine-functional organosilicon compound, along with ammonia and hydrogen, in the isopropanol solution were passed through a continuous tubular (trickle bed) reactor at flow rates of 0.18 mL / min, 0.036 mL / min, and 8.6 sccm, respectively. The inner diameter of the tubular reactor was 3 mm and contained 6.03 g of Ni-5256E catalyst. The reactor was controlled at 100°C. The reactor effluent was collected, and volatile substances were removed under vacuum, leaving a liquid. The liquid, when analyzed using GC-FID, contained more than 50% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine). This example demonstrates that the reductive amination reaction of the present invention can be carried out in continuous mode without occlusion.

[0281] In this Comparative Example 19, 300.0 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, was packed into a glass round-bottom flask. 1200 g of isopropanol solvent was added to form a solution. The resulting aldehyde-functional organosilicon compound, along with ammonia and hydrogen, in the isopropanol solution were passed through a continuous tubular (trickle bed) reactor at flow rates of 0.30 mL / min, 0.056 mL / min, and 14 sccm, respectively. The inner diameter of the tubular reactor was 3 mm and contained 6.0 g of Ni-5256E catalyst. The reactor was controlled at 100°C. The reactor became blocked immediately after the feed flow was started due to solid formation inside the reactor, and the reactor effluent was not collected.

[0282] Example 18 demonstrates the advantage of improved processability when using the process of the present invention compared to Comparative Example 19.

[0283] In this hypothetical Example 20, methanol (30 g) and Ni-5256P (6.0 g) are packed into a 300 mL autoclave reactor, and the reactor is inactivated with nitrogen. Ammonia (35 g, 10 equivalents) is added. The mixture is heated to 110°C, and then hydrogen is added until the pressure reaches 1000 psig. To the stirred reaction mixture (800 RPM), 50 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal, prepared as described in Example 1, is pumped in over 60 minutes. During this time, hydrogen is continuously supplied at 1000 psig. After the addition of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal is complete, the reaction is continued at 110°C and 1000 psig for 2 hours. The reactor is cooled and evacuated. The reaction product is collected, filtered to remove the catalyst, and the solvent is removed using a rotary evaporator to collect the concentrated product.

[0284] Industrial applicability When reductive amination of propylaldehyde-functional organosilicon compounds using ammonia, a primary imine-functional organosilicon compound is initially formed, which is then converted to the desired primary aminopropyl-functional organosilicon compound via reductive amination. However, the primary imine group is relatively unstable and can cause self-condensation of the propylimine-functional organosilicon compound, forming higher molecular weight byproducts such as triazines and secondary amines, often resulting in significant yield loss. Furthermore, the formation of these byproducts often increases the viscosity of the product and / or leads to solid formation, which makes catalytic separation difficult and limits the opportunity to carry out reductive amination reactions using continuous reactor equipment. Methods to minimize the formation of these byproducts are desirable to improve the yield and process robustness of reductive amination reactions for producing aminopropyl-functional organosilicon compounds. The process described herein addresses this problem by producing a secondary propylimine-functional organosilicon compound using a primary amine source. Next, the secondary imine is treated with excess ammonia, hydrogen, and a hydrogenation catalyst to obtain a primary aminopropyl-functional organosilicon compound, thereby regenerating the primary amine source, which can then be reused and used in subsequent dehydration imine production reactions.

[0285] Furthermore, during the reductive amination reaction of propylaldehyde-functional organosilicon compounds with ammonia, 1 molar equivalent of water per mole of aldehyde-functional compound is produced as a byproduct of primary imine group formation. Certain aminopropyl-functional organosilicon compounds are unstable to hydrolysis and react with water under the conditions used in this reductive amination reaction, and this instability can lead to side reactions that produce further undesirable byproducts. Silanes, silazanes, and branched and linear oligomeric siloxanes functionalized with alkoxy or acyloxy groups, such as the oligomeric aminopropyl-functional siloxane derived from the branched propylaldehyde-functional siloxane oligomer (E2-10) or (E2-11) mentioned above, are more susceptible to side reactions in the presence of water than other aminopropyl-functional polyorganosiloxanes.

[0286] While we do not wish to be constrained by theory, the ability to remove water in step II) of the process described herein (i.e., after the formation of secondary imine groups and water via the dehydration imine formation reaction is initiated in step I) and before the reductive amination reaction in step III) of the process described herein) is considered to improve the yield of primary aminopropyl-functional organosilicon compounds as products, even when using hydrolysis-unstable propylaldehyde-functional organosilicon compounds as starting materials, and / or when producing hydrolysis-unstable propylimine-functional organosilicon compounds and hydrolysis-unstable aminopropyl-functional organosilicon compounds. Furthermore, since the stability of secondary imine groups is improved compared to primary imine groups, the present invention offers an opportunity to improve the yield and robustness of the reductive amination reaction by providing options to address the above problems. Secondary imine groups are less prone to decomposition via self-condensation, which increases the process yield while also allowing alternative processing options such as the use of continuous reactors. In addition, the increased stability of the secondary imine-functional organosilicon compound intermediate allows for the selective removal of water generated during secondary imine group formation using various techniques, including distillation or the use of drying agents. The ability to remove water during the early stages of the process minimizes or eliminates the formation of certain by-products when using organosilicon compounds with lower hydrolysis stability in the process. Finally, the formation of the secondary imine-functional organosilicon compound as an intermediate protects the aldehyde group (of the starting material for the aldehyde-functional organosilicon compound) from oxidative decomposition.

[0287] While we do not wish to be constrained by theory, the process is also thought to offer fewer or no salt byproduct streams, shorter reaction times, and / or lower production of cyclic siloxane byproducts compared to conventional condensation reaction processes. Furthermore, hydroformylation and reductive amination can be carried out in a single reactor without the need to isolate intermediates, and may have minimal process steps.

[0288] While we do not wish to be constrained by theory, another advantage of the present invention is that the resulting aminopropyl-functional organosilicon compounds have a high proportion of linear aminopropyl functional groups, and this is because propylaldehyde-functional organosilicon compounds having branched propylaldehyde moieties react and decompose during the processes described herein, thereby allowing for their easy removal. Furthermore, the resulting aminopropyl-functional organosilicon compounds may have a reduced cyclic siloxane (e.g., octamethylcyclotetrasiloxane, D4) content compared to aminopropyl-functional organosilicon compounds produced via condensation chemistry using a carboxylic acid catalyst or equilibration chemistry using a base catalyst.

[0289] Definitions and Use of Terms All quantities, ratios, and percentages are based on weight unless otherwise specified. The total amount of all starting materials in a composition is 100% by weight. The "Summary of the Invention" and "Abstract" are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more unless specifically indicated by the context of the specification. The singular form includes the plural form unless otherwise specified. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as described 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 term "hydrolysis-unstable" refers to any organosilicon compound that reacts with water at temperatures below 120°C. The hydrolysis-unstable organosilicon compounds described herein include any organosilicon compounds used or produced that react with water at temperatures below 120°C. Examples include any (B) alkenyl-functional organosilicon compounds, any (E) aldehyde-functional organosilicon compounds, any (L) imine-functional organosilicon compounds, and any primary amino-functional organosilicon compounds prepared as described herein that satisfy one or more of the following criteria: i) one or more R per molecule 4 i) the organosilicon compound is a silazane, and / or ii) any oligomeric polyorganosiloxane of formula (B2-10a), (E2-10a), (L2-10a), (N2-10a) as shown above, e.g., 1,3-di(aminopropyl)-1,1,3,3-tetramethyldisiloxane, (B2-11a), (E2-11a), (L2-11a), or (N2-11a), e.g., 3-(3,3,3-trimethyl-1l2-disiloxanyl)propan-1-amine. Abbreviations used herein have their definitions in Table Z.

[0290] [Table 2]

[0291] In this specification, the following test methods were used: FTIR: The concentration of silanol groups present in polyorganosiloxane resins (e.g., polyorganosilicate resins and / or silsesquioxane resins) was determined by FTIR spectroscopy according to ASTM standard E-168-16. GPC: The molecular weight distribution of polyorganosiloxanes was determined by GPC using an Agilent Technologies 1260 Infinity chromatograph and toluene as the solvent. The instrument had three columns: a 5 μm PL gel, 7.5 × 50 mm guard column, and two 5 μm PL gel, Mixed-C 7.5 × 300 mm columns. Calibration was performed using polystyrene standards. Samples were prepared by dissolving polyorganosiloxanes in toluene (approximately 1 mg / mL), and the solutions were immediately analyzed by GPC (flow rate of 1 mL / min, column temperature of 35°C, run time of 25 minutes). 29 Si NMR: The alkenyl content of the starting material (B) can be measured by the technique described in "The Analytical Chemistry of Silicones," edited by A. Lee Smith, Chemical Analysis, Vol. 112, John Wiley & Sons, Inc. (1991). Viscosity: Viscosity can be measured for polymers having viscosities of, for example, 120 mPa·s to 250,000 mPa·s (e.g., certain (B2) alkenyl-functionalized polyorganosiloxanes and (E2) aldehyde-functionalized polyorganosiloxanes) using a Brookfield DV-III cone and plate viscometer with a #CP-52 spindle at 25°C and 0.1 to 50 RPM. Those skilled in the art will recognize that the rotation speed decreases as viscosity increases, and that an appropriate spindle and rotation speed can be selected.

[0292] The mixture of the aldehyde-functional organosilicon compound and the reductive amination reaction product in the above examples is 1 H,13 1C NMR and 29 The analysis was performed by Si NMR, GC / MS, GPC, and viscosity. The conversion rate and yield in the above examples were mainly 1 It was based on 1H NMR data.

[0293] Embodiments of the present invention In the first embodiment, the process for preparing an imine-functional organosilicon compound is as follows: I) Combining starting materials under conditions that lead to the formation of a dehydrated imine, wherein the starting materials are (E) Propylaldehyde-functional organosilicon compounds, (F1) Primary amine source, (G) Hydrogenation catalyst and Optionally, (J) solvent and Optionally, (K) a desiccant and, This is done to form a dehydrated imine reaction product containing a (L)propylimine-functional organosilicon compound and water, and to combine them. Optionally, II) remove water, This includes optionally isolating (L)imine-functionalized organosilicon compounds.

[0294] In the second embodiment, the process for producing an aminopropyl-functional organosilicon compound involves carrying out the process of the first embodiment. III) Combining starting materials under conditions that catalyze a reductive amination reaction, wherein the starting materials are (L) Propylimine-functional organosilicon compounds, (F2) Ammonia and, (G) Hydrogenation catalyst and (H) Hydrogen and, Optionally, (J) solvent and Optionally, (K) a desiccant and, However, (G) the hydrogenation catalyst is compounded in at least one of steps I) and III), This includes compounding to form a reductive amination reaction product containing an aminopropyl functional organosilicon compound and a primary amine source.

[0295] In a third embodiment, the process of the first or second embodiment further comprises preparing an (E)propylaldehyde-functional organosilicon compound by a hydroformylation process, the hydroformylation process is 1) Combining starting materials under conditions that catalyze the hydroformylation reaction, wherein the starting materials are (A) A gas containing hydrogen and carbon monoxide, (B) Vinyl-functional organosilicon compounds, (C) A rhodium / phosphoamidite ligand complex catalyst is included, thereby forming a hydroformylation reaction product containing (E) a propylaldehyde-functional organosilicon compound. Optionally, 2) (E) recover the (C) rhodium / phosphoamidite ligand complex catalyst from the hydroformylation reaction product containing a propylaldehyde-functional organosilicon compound, Optionally, this includes 3) isolating a propylaldehyde-functional organosilicon compound.

[0296] In the fourth embodiment, in any one of the processes of the first to third embodiments, the propylaldehyde-functional organosilicon compound is unstable to hydrolysis, for example, as defined above.

[0297] In the fifth embodiment, in the process of the fourth embodiment, the aldehyde-functional organosilicon compound is of the formula

[0298] [ka] It has, in the formula, each R 4 Each R is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms, AldThese are expressions that are selected independently.

[0299] [ka] It is a group of which, in the formula, G is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms.

[0300] In the sixth embodiment, in the process of the fifth embodiment, each R 4 It is methyl, and R Ald It is a linear propyl aldehyde.

[0301] In the seventh embodiment, in any one of the processes of the first to fourth embodiments, the propylaldehyde-functional organosilicon compound is of the formula

[0302] [ka] It has, in the formula, each R 13 Each R is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms, Ald These are expressions that are selected independently.

[0303] [ka] It is a group of which, in the formula, G is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms.

[0304] In the eighth embodiment, in the process of the seventh embodiment, each R 13 It is methyl, and R Ald It is a linear propyl aldehyde.

[0305] In the ninth embodiment, in any one of the processes of the first to third embodiments, the propylimine-functional organosilicon compound is unstable to hydrolysis, for example, as defined above.

[0306] In the tenth embodiment, in the process of the ninth embodiment, the propylimine-functional organosilicon compound is of the formula

[0307] [ka] It has, in the formula, each R 4 Each R is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms, I These are expressions that are selected independently.

[0308] [ka] The group is a non-aliphatic unsaturated divalent hydrocarbon group having 2, and R 19 The group is selected from alkyl groups with 1 to 18 carbon atoms, aryl groups with 6 to 18 carbon atoms, and organosilicon moieties.

[0309] In the 11th embodiment, in the process of the 10th embodiment, each R 4 is methyl, G is linear, and each R 19 These are alkyl groups with 1 to 4 carbon atoms.

[0310] In the twelfth embodiment, in the process of the eleventh embodiment, the propylimine-functional organosilicon compound is of the formula

[0311] [ka] It has, in the formula, each R 13 R is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms. I is, formula

[0312] [ka] The group is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms, and R 19 This is selected from the group consisting of alkyl groups with 1 to 18 carbon atoms, aryl groups with 6 to 18 carbon atoms, and organosilicon moieties.

[0313] In the 13th embodiment, in the process of the 12th embodiment, each R 13 is methyl, G is linear, and each R 19 These are alkyl groups with 1 to 4 carbon atoms.

[0314] In the fourteenth embodiment, in the process of the second embodiment, the aminopropyl-functional organosilicon compound is unstable to hydrolysis, for example, as defined above.

[0315] In the 15th embodiment, in the process of the 14th embodiment, the aminopropyl functional organosilicon compound is of the formula

[0316] [ka] It has, in the formula, each R 4 Each R is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms, N These are expressions that are selected independently.

[0317] [ka] It is a primary amino group, where G is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms.

[0318] In the sixteenth embodiment, in the process of the fifteenth embodiment, each R 4 G is methyl, and G is linear.

[0319] In the 17th embodiment, in the process of the 14th embodiment, the amino-functional organosilicon compound is of the formula

[0320] [ka] It has, in the formula, each R 13 R is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms and aryl groups with 6 to 18 carbon atoms. N is, formula

[0321] [ka] It is a primary amino group, where G is a non-aliphatic unsaturated divalent hydrocarbon group having two carbon atoms.

[0322] In the 18th embodiment, in the process of the 17th embodiment, each R 13 G is methyl, and G is linear.

Claims

1. A process for preparing a propylimine-functional organosilicon compound, wherein the process comprises: I) Combining starting materials under conditions that lead to a dehydration imine formation reaction, wherein the starting materials are Propylaldehyde-functional organosilicon compounds, Primary amine source, Optionally, it includes a hydrogenation catalyst, This forms a reaction product containing a propylimine-functional organosilicon compound and water. However, if the hydrogenation catalyst is present in step I), the compounding is carried out under the condition that step I) is performed in the absence of hydrogen. III) Combining starting materials under conditions that catalyze a reductive amination reaction, wherein the starting materials are The aforementioned imine-functional organosilicon compound, Ammonia and, Hydrogen and, Optionally, the hydrogenation catalyst is included, However, provided that the hydrogenation catalyst is combined in at least one of steps I) and III), A process comprising compounding, thereby forming a reaction product containing an aminopropyl functional organosilicon compound.

2. The process further includes forming the propylaldehyde-functional organosilicon compound by a process that, prior to step I), involves compounding the starting materials under conditions that catalyze the hydroformylation reaction, wherein the starting materials are (A) A gas containing hydrogen and carbon monoxide, (B) Alkenyl-functional organosilicon compounds, (C) A rhodium / ligand complex catalyst comprising, wherein the ligand has formula (C1), (C2), and / or (C3), Equation (C1) is, 【Chemistry 1】 And, Equation (C2) is, 【Chemistry 2】 And, Equation (C3) is, 【Transformation 3】 And, During the ceremony, R １０１ ~R １２２ Each of these is independently selected from hydrogen, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group, R １０１ ~R １２２ Two or more of these may be optionally combined to give one or more ring sections. X １ to X ４ each independently represent O, CH ２ , NH, NR, NSO ２ R, or NSO ２ A, wherein each R is an independently selected substituted or unsubstituted alkyl or aryl group, and each A is an independently selected aryl or heteroaryl group, Y １ ~Y ８ Each of the elements is an independently selected nitrogen-containing heterocyclic moiety bonded to P via N, where each heterocyclic moiety is alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, or -SO ３ The process according to claim 1, which may be substituted with one or more groups or atoms selected from H, sulfonates, aminos, trifluoromethyls, and halogens.

3. The process according to claim 1 or 2, further comprising recovering the propylaldehyde-functional organosilicon compound before step I).

4. The aforementioned primary amine source Formula: R １８ NH ２ (In the formula, R １８ (which is an organic primary amine of an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms), The process according to claim 1 or 2, selected from the group consisting of primary amino-functional organosilicon compounds.

5. The process according to claim 1 or 2, wherein the hydrogenation catalyst is a heterogeneous hydrogenation catalyst comprising a metal selected from the group consisting of Co, Cu, Fe, Ni, Ir, Pd, Pt, Rh, Ru, and combinations of two or more of these.

6. The process according to claim 1 or 2, wherein the amount of the hydrogenation catalyst is less than 1% by weight to 50% by weight, based on the weight of the aldehyde-functional organosilicon compound.

7. In step III), one or both of conditions (i) and (ii) are met, and condition (i) is H ２ The process according to claim 1, wherein the pressure is between 10 psig (68.9 kPa) and 1500 psig (10,342 kPa), and condition (ii) is that the temperature is between 0°C and 200°C.

8. The process according to claim 1 or 7, further comprising pre-treating the hydrogenation catalyst before step III).

9. The process according to claim 1 or 7, further comprising recovering the aminopropyl functional organosilicon compound from the reaction product during and / or after step IV) III).

10. The process according to claim 1, 2, or 7, further comprising v) recovering the primary amine source generated in step III) and optionally reusing the primary amine source in step I).

11. The process according to claim 1, 2, or 7, wherein step III) is carried out in continuous mode.

12. The process according to claim 1 or 2, wherein step II) exists, and step II) is performed before and / or during step I).

13. The process according to claim 12, wherein the propylaldehyde-functional organosilicon compound reacts with water at a temperature of less than 120°C.

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