Preparation of Amino-Functional Organosilicon Compounds

Abstract

An amino-functional organosilicon compound is prepared by a catalytic reductive amination process for combining an aldehyde-functional organosilicon compound with an amine source and hydrogen to produce the amino-functional organosilicon compound.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 63 / 252,639, filed October 6, 2021. U.S. Provisional Application No. 63 / 252,639 is incorporated herein by reference.

[0002] A process for preparing an amino-functional organosilicon compound is disclosed. More specifically, the process for preparing an amino-functional organosilicon compound comprises the reductive amination of an aldehyde-functional organosilicon compound with an amine source.

[0003] Introduction Certain amino-functional polyorganosiloxanes are useful, for example, in textile and leather treatment applications. Other amino-functional polyorganosiloxanes, such as amine-terminated polydiorganosiloxanes, are useful in personal care applications, such as hair care. Amine-terminated polydiorganosiloxanes can be useful, for example, in hair conditioning applications. Amino-functional polyorganosiloxanes made by condensation can suffer from 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 make by equilibration, as they require expensive starting materials and catalysts and require multiple process steps to complete.

[0004] Another method for making amino-functional polyorganosiloxanes uses allylamines or derivatives that hydrolyze to allylamines, which are used with SiH-functional polymers to perform hydrosilylation chemistry to form amino-functional polyorganosiloxanes; however, this method suffers from the drawback that the amino-functional polyorganosiloxane product may contain at least trace amounts of either SiH or allylamine, either of which must be removed before the product can be used in any personal care application due to the toxicity of allylamine and the reactivity of SiH.

[0005] Another method of making amino-functional polyorganosiloxanes is by ammonolysis of chloropropyl-terminated siloxanes. This expensive multi-step method can suffer from the drawback of leaving residual salts (i.e., ammonium chloride) in the amine-terminated polyorganosiloxane product that may require extensive washing to remove, which is less cost-effective and less sustainable. Also, any residual ammonium chloride may produce a malodor, which is undesirable for personal care applications.

[0006] Thus, there is an unmet need in the organosilicon industry for synthetic methods for preparing a wide range of amino-functional organosilicon compounds with relatively high purity, high selectivity, and / or low cost. Summary of the Invention

[0007] The process for preparing amino-functional organosilicon compounds includes combining starting materials, including an aldehyde-functional organosilicon compound, an amine source, hydrogen, and a hydrogenation catalyst, under conditions to catalyze a reductive amination reaction, thereby forming a reductive amination reaction product comprising the amino-functional organosilicon compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In the process for preparing the amino-functional organosilicon compound introduced above, the aldehyde-functional organosilicon compound can be a known aldehyde-functional organosilicon compound, and can be made by known methods, such as those described in U.S. Patent No. 4,424,392 to Petty, U.S. Patent No. 5,021,601 to Frances et al., U.S. Patent No. 5,739,246 to Graiver et al., U.S. Patent No. 7,696,294 to Asirvatham, and U.S. Patent No. 7,999,053 to Sutton et al., European Patent Application Publication No. 0392948(A1) to Frances, and PCT Patent Application Publication No. WO2006027074 to Kuhnle et al.

[0009] Hydroformylation Alternatively, the aldehyde-functional organosilicon compound can be prepared by a hydroformylation process, which comprises: 1) combining starting materials, including (A) a gas comprising hydrogen and carbon monoxide, (B) an alkenyl-functional organosilicon compound, and (C) a hydroformylation catalyst, such as a rhodium / bisphosphite ligand complex catalyst, under conditions that catalyze a hydroformylation reaction, thereby forming a hydroformylation reaction product comprising the aldehyde-functional organosilicon compound.

[0010] The hydroformylation process described herein employs starting materials comprising (A) a gas comprising hydrogen and carbon monoxide, (B) an alkenyl-functional organosilicon compound, and (C) a rhodium / bisphosphite ligand catalyst. The starting materials may optionally further comprise (D) a solvent.

[0011] (A) Synthetic gas The gaseous starting material (A) used in the hydroformylation process is carbon monoxide (CO) and hydrogen gas (H 2 For example, the gas may be synthesis gas. As used herein, "syngas" (from synthesis gas) refers to gas that contains varying amounts of CO and H. 2It refers to a gas mixture containing CO and H. 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. 2 is typically the major component of synthesis gas, which also contains carbon dioxide as well as CH 4 , N 2 , and inert gases such as Ar. 2 and CO molar ratio (H 2 The CO and H molar ratio (CO / H) varies widely but can range from 1:100 to 100:1, alternatively 1:10 to 10:1. Syngas is commercially available and is often used as a fuel source or as an intermediate to produce other chemicals. Alternatively, CO and H from other sources (i.e., other than syngas) can be used. 2 may be used as starting material (A) herein. Alternatively, H in starting material (A) for use herein 2 The H:CO molar ratio can be from 3:1 to 1:3, alternatively from 2:1 to 1:2, alternatively 1:1.

[0012] (B) Alkenyl-functional organosilicon compounds The alkenyl-functional organosilicon compound has at least one alkenyl group covalently bonded to silicon per molecule. Alternatively, the alkenyl-functional organosilicon compound can have two or more alkenyl groups covalently bonded to silicon per molecule. The starting material (B) can be one alkenyl-functional organosilicon compound. Alternatively, the starting material (B) can include two or more alkenyl-functional organosilicon compounds that are different from each other. For example, the alkenyl-functional organosilicon compound can include one or both of (B1) silane and (B2) polyorganosiloxane.

[0013] The starting material (B1), an alkenyl-functional silane, has the formula (B1-1): R A x SiR 4 (4-x) wherein each R A is an independently selected alkenyl group of 2 to 8 carbon atoms, and each R 4is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscript x is 1 to 4. Alternatively, the subscript x can be 1 or 2, alternatively 2, alternatively 1. Alternatively, each R 4 may be independently selected from the group consisting of alkyl groups of 1 to 12 carbon atoms, and aryl groups of 6 to 12 carbon atoms. Alternatively, each R 4 may be independently selected from the group consisting of alkyl groups of 1 to 8 carbon atoms and aryl groups of 6 to 8 carbon atoms. 4 may be independently selected from the group consisting of methyl and phenyl.

[0014] R A The alkenyl group of R may have a terminal alkenyl functionality, e.g., A is the formula

[0015] [ka] where subscript y is 0 to 6. Alternatively, each R A may be independently selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, each R A may be independently selected from the group consisting of vinyl and allyl. Alternatively, each R A Alternatively, each R A can be allyl.

[0016] R 4Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by 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 the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 4 The alkyl group of R may be selected from the group consisting of methyl, ethyl, propyl, and butyl, alternatively methyl, ethyl, and propyl, alternatively methyl or ethyl. 4 The alkyl group in may be methyl.

[0017] R 4 Suitable aryl groups for may be monocyclic or polycyclic and may have pendant hydrocarbyl groups. For example, R 4 Aryl groups of R include phenyl, tolyl, xylyl, and naphthyl, as well as aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. 4 The aryl group of R may be monocyclic, such as phenyl, tolyl, or benzyl; alternatively, R 4 The aryl group can be phenyl.

[0018] Suitable alkenyl-functional silanes are exemplified by alkenyl-functional trialkylsilanes such as vinyltrimethylsilane, vinyltriethylsilane, and allyltrimethylsilane, all of which are commercially available, for example, from Gelest Inc. (Morrisville, Pennsylvania, USA).

[0019] Alternatively, (B) the alkenyl-functional organosilicon compound may comprise (B2) an alkenyl-functional polyorganosiloxane. The polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The polyorganosiloxane may have a unit formula (B2-1): (R 4 3 SiO 1 / 2 ) a (R 4 2 R A SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein R A and R 4 is as defined above, and each Z is independently selected from a hydrogen atom and R 5 (In the formula, R 5 are as above), and the subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (B2-1), with values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, and subscript 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, when e=f=g=0, then h≧0. Alternatively, in formula (B-2-1), each R 4 may be independently selected from the group consisting of a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, and an aryl group of 6 to 18 carbon atoms.4 may be independently selected from the group consisting of alkyl groups of 1 to 12 carbon atoms, and aryl groups of 6 to 12 carbon atoms. Alternatively, each R 4 may be independently selected from the group consisting of alkyl groups of 1 to 8 carbon atoms, and aryl groups of 6 to 8 carbon atoms. 4 may be independently selected from the group consisting of methyl and phenyl. Alternatively, each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen.

[0020] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may comprise (B2-2) a linear polydiorganosiloxane having at least one alkenyl group per molecule, alternatively at least two alkenyl groups (e.g., in formula (B2-1) above, where subscripts e=f=g=0). For example, the polydiorganosiloxane may have the unit formula (B2-3): (R 4 3 SiO 1 / 2 ) a (R A R 4 2 SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R A R 4 SiO 2 / 2 ) d wherein R A and R 4is as above, subscript a is 0, 1, or 2, subscript b is 0, 1, or 2, subscript c≧0, and subscript d≧0, provided that the quantity (b+d)≧1, the quantity (a+b)=2, and the quantity (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, and 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, and alternatively 250 or less. Alternatively, in unit formula (B2-3), each R 4 may be independently selected from the group consisting of alkyl and aryl, alternatively methyl and phenyl. Alternatively, each R in the unit formula (B2-3) 4 can be an alkyl group, alternatively, each R 4 can be methyl.

[0021] Alternatively, the polydiorganosiloxane of the unit formula (B2-3) may be a polydiorganosiloxane of the unit formula (B2-4): (R 4 2 R A SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) m (R 4 R A SiO 2 / 2 ) n , Unit formula (B2-5): (R 4 3 SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) o (R 4 R A SiO 2 / 2 ) p or a combination of both (B2-4) and (B2-5).

[0022] In formulas (B2-4) and (B2-5), each R 4 and RA are as above. Subscript m may be 0 or a positive number. Alternatively, subscript m may be at least 2. Alternatively, subscript m may be from 2 to 2,000. Subscript n may be 0 or a positive number. Alternatively, subscript n may be from 0 to 2000. Subscript o may be 0 or a positive number. Alternatively, subscript o may be from 0 to 2000. Subscript p is at least 2. Alternatively, subscript p may be from 2 to 2000.

[0023] The starting material (B2) is 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, vi) bis-dimethylvinylsiloxy terminated Poly(dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane), vii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxane, x) bis-dimethylhexenylsiloxy terminated polydimethylsiloxane, xi) bis-dimethylhexenylsiloxy terminated polydimethylsiloxane, xii) bis-dimethylhexenylsiloxy terminated polymethylhexenylsiloxane, xiii) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane), xiv) bis-trimethylsiloxy terminated polymethylhexenylsiloxane, xv) bis-dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methylhexenyl xvi) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvii) bis-dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), and xix) combinations of two or more of i)-xviii).

[0024] Methods for preparing the above-mentioned linear alkenyl-functional polydiorganosiloxanes for starting material (B2), such as the hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or the equilibration of cyclic polydiorganosiloxanes, are known in the art, see, for example, U.S. Pat. Nos. 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Examples of linear polydiorganosiloxanes having alkenyl groups are commercially available, for example, under the 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, DMS-V52 from Gelest Inc., Morrisville, Pennsylvania, USA.

[0025] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may be cyclic, for example, where in the unit formula (B2-1), the subscripts a=b=c=e=f=g=h=0. Cyclic alkenyl-functional polydiorganosiloxanes are represented by the unit formula (B2-7): (R 4 R A SiO 2 / 2 ) d wherein R A and R 4is as above, and subscript d can be 3 to 12, alternatively 3 to 6, alternatively 4 to 5. Examples of cyclic alkenyl functional 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 alkenyl-functional 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 vendors.

[0026] Alternatively, the cyclic alkenyl-functional polydiorganosiloxane may be represented by the unit formula (B2-8): (R 4 2 SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d wherein R 4 and R A is as above, and subscript c is >0 to 6, and subscript d is 3 to 12. Alternatively, in formula (B2-8), c can be 3 to 6, and d can be 3 to 6.

[0027] Alternatively, (B2) the alkenyl-functional polyorganosiloxane can be an oligomer, for example, where the quantity (a+b+c+d+e+f+g) in the above unit formula (B2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer can be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as the starting material (B2-6).

[0028] An example of a linear alkenyl-functional polyorganosiloxane oligomer is represented by the formula (B2-10):

[0029] [ka] wherein R 4 is as above, and each R 2 are independently 4 and R A with the proviso that at least one R 2 is R A with the proviso that the subscript z is 0 to 48. Alternatively, the subscript z can be 0 to 4, alternatively 0 or 1, alternatively 0. Alternatively, when z=0 in formula (B2-10), the alkenyl-functional polyorganosiloxane oligomer has the formula (B2-10a):

[0030] [ka] Examples of linear alkenyl-functional polyorganosiloxane oligomers can include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-vinyl-disiloxane, 1,1,1,3,5,5,5-heptamethyl-3-vinyl-trisiloxane (all of which are commercially available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA) or Sigma-Aldrich (St. Louis, Missouri, USA)).

[0031] Alternatively, the alkenyl-functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (B2-11): R A SiR 12 3 wherein R A is as above, and each R 12 is R 13 and -OSi(R14 ) 3 wherein each R 13 is a monovalent hydrocarbon group (e.g., R 4 an alkyl or aryl group as described and exemplified above for R 14 is R 13 , -OSi(R 15 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 15 is R 13 , -OSi(R 16 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 16 is R 13 and -[OSiR 13 2 ] ii OSiR 13 3 where the subscript ii has a value such that 0≦ii≦100. 12 At least two of -OSi(R 14 ) 3 Alternatively, R 12 All three of the -OSi(R 14 ) 3 It could be.

[0032] Alternatively, in formula (B2-11), each R 12 -OSi(R 14 ) 3 If, then, for each R 14 The branched polyorganosiloxane oligomer has the following structure (B2-11a):

[0033] [ka] R such that 13 moiety, where R13 is as above, and R A is an alkenyl group as described above. Alternatively, each R A may be vinyl, and each R 13 can be methyl.

[0034] Alternatively, in formula (B2-11), each R 12 -OSi(R 14 ) 3 If, then, for each R 14 is -OSi(R) such that the branched polyorganosiloxane oligomer has the following structure (B2-11b): 15 ) 3 It may be a part

[0035] [ka] In the formula, R A and R 15 is as described above. Alternatively, each R 15 is R as above 13 Each R 13 can be methyl.

[0036] Alternatively, in formula (B2-11), each R 12 -OSi(R 14 ) 3 If so, then one R 14 is each R 12 -OSiR 13 (R 14 ) 2 For each -OSi(R 14 ) 3 In R 13 Alternatively, -OSiR 13 (R 14 ) 2 Two R's in 14 each of which is a branched polyorganosiloxane oligomer having the following structure (B2-11c):

[0037] [ka] (In the formula, R A , R 13 , and R 15 is as described above) 15 ) 3 Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0038] Alternatively, in formula (B2-11), one R 12 is R 13 R 12 Two of them are -OSi(R 14 ) 3 It can be. R 12 Two of them are -OSi(R 14 ) 3 If so, then one R 14 Each -OSi(R 14 ) 3 R in 13 and R 12 Two of them are -OSiR 13 (R 14 ) 2 Alternatively, -OSiR 13 (R 14 ) 2 Each R in 14 is a branched polyorganosiloxane oligomer having the following structure (B2-11d):

[0039] [ka] (In the formula, R A , R 13 , and R 15 is as described above) 15 ) 3 Alternatively, each R 15 is R 13 Each R 13may be methyl. Alternatively, the alkenyl functional branched polyorganosiloxane may have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, alternatively 4 to 10 silicon atoms per molecule. Examples of alkenyl functional branched polyorganosiloxane oligomers include those having the formula:

[0040] [ka] vinyl-tris(trimethylsiloxy)silane having the formula formula

[0041] [ka] Methyl-vinyl-di(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane having the formula formula

[0042] [ka] and vinyl-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane having the formula

[0043] [ka] (Hex-5-en-1-yl)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane having (Si10Hex). The branched alkenyl-functional polyorganosiloxane oligomers can be prepared by known methods such as those disclosed in "Testing the Functional Tolerance of the Piers-Rubinsztajn Reaction: A new Strategy for Functional Silicones" by Grande et al., Supplementary Material (ESI) for Chemical Communications, copyright The Royal Society of Chemistry 2010.

[0044] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may be branched, such as the branched oligomers described above, and / or branched alkenyl-functional polyorganosiloxanes that may have, for example, more alkenyl groups and / or more polymer units per molecule than the branched oligomers described above (e.g., in formula (B2-1), the amount (a+b+c+d+e+f+g)>50). The branched alkenyl-functional polyorganosiloxane may have an amount (e+f+g) sufficient to provide the branched alkenyl-functional polyorganosiloxane (in formula (B2-1)) with >0-5 mol% trifunctional and / or tetrafunctional units.

[0045] For example, the branched alkenyl-functional polyorganosiloxane may be represented by the unit formula (B2-13): (R 4 3 SiO 1 / 2 ) q (R 4 2 R A SiO 1 / 2 ) r (R 4 2 SiO 2 / 2 ) s (SiO 4 / 2 ) t In one embodiment, the branched polyorganosiloxane may be of the formula:4 and R A is as above, and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to the branched polyorganosiloxane a viscosity of >170 mPa·s 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, alternatively 190 mPa·s to 420 mPa·s. Q-type branched polyorganosiloxanes suitable for the starting material (B2-12) are known in the art and can be made by known methods, exemplified by those disclosed in U.S. Pat. No. 6,806,339 to Cray et al. and U.S. Patent Application Publication No. 2007 / 0289495 to Cray et al.

[0046] Alternatively, the branched alkenyl-functional polyorganosiloxane may be represented by the formula (B2-14): [R A R 4 2 Si-(O-SiR 4 2 ) x -O] (4-w) -Si-[O-(R 4 2 SiO) v SiR 4 3 ] w wherein R A and R 4 is as above, and the subscripts v, w, and x have values ​​such that 200 ≧ v ≧ 1, 2 ≧ w ≧ 0, and 200 ≧ x ≧ 1. Alternatively, in this formula (B2-14), each R 4 is independently selected from the group consisting of methyl and phenyl; Ais independently selected from the group consisting of vinyl, allyl, and hexenyl. Suitable branched polyorganosiloxanes for starting material (B2-14) can be prepared by known methods such as by heating a mixture containing a polyorganosilicate resin and a cyclic or linear polydiorganosiloxane in the presence of a catalyst such as an acid or a phosphazene base, followed by neutralization of the catalyst.

[0047] Alternatively, the branched alkenyl-functional polyorganosiloxane for the starting material (B2-11) may have the unit formula (B2-15): (R 4 3 SiO 1 / 2 ) aa (R A R 4 2 SiO 1 / 2 ) bb (R 4 2 SiO 2 / 2 ) cc (R A R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd In the formula, R 4 and R Ais as above, with subscript aa≧0, subscript bb>0, subscript cc is from 15 to 995, subscript dd>0, and subscript ee≧0. Subscript aa may be from 0 to 10. Alternatively, subscript aa may have a value such that 12≧aa≧0, alternatively 10≧aa≧0, alternatively 7≧aa≧0, alternatively 5≧aa≧0, alternatively 3≧aa≧0. Alternatively, subscript bb≧1. Alternatively, subscript bb≧3. Alternatively, subscript bb may have a value such that 12≧bb>0, alternatively 12≧bb≧3, alternatively 10≧bb>0, alternatively 7≧bb>1, alternatively 5≧bb≧2, alternatively 7≧bb≧3. Alternatively, the subscript cc may have a value such that 800≧cc≧15, alternatively 400≧cc≧15. Alternatively, the subscript ee may have a value such that 800≧ee≧0, 800≧ee≧15, alternatively 400≧ee≧15. Alternatively, the subscript ee may be 0. Alternatively, the quantity (cc+ee) may have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd may be 1 to 10. Alternatively, the subscript dd may have a value such that 10≧dd>0, alternatively 5≧dd>0, alternatively dd=1. Alternatively, the subscript dd may be 1 to 10, alternatively the subscript dd may be 1 or 2. Alternatively, when subscript dd=1, subscript bb can be 3 and subscript cc can be 0. The value of subscript bb can be sufficient to provide a silsesquioxane of formula (B2-15) having an alkenyl content of 0.1% to 1%, 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 to Brown et al., U.S. Patent No. 6,001,943 to Enami et al., U.S. Patent No. 8,546,508 to Nabeta et al., and U.S. Patent No. 10,155,852 to Enami.

[0048] Alternatively, (B2) the alkenyl-functional polyorganosiloxane may be represented by the formula R M 3 SiO 1 / 2 and monofunctional units ("M" units) of formula SiO 4 / 2 wherein each R M are independently selected monovalent hydrocarbon radicals, and each R M are independently R as above 4 and R A Alternatively, each R M may be selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, each R M may be selected from methyl, vinyl, and phenyl. Alternatively, R M At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M units are (Me 3 SiO 1 / 2 ), (Me 2 PhSiO 1 / 2 ), and (Me 2 ViSiO 1 / 2 The polyorganosilicate resins are 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.

[0049] When prepared, the polyorganosilicate resin contains the M and Q units described above, and the polyorganosiloxane contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M 3 ) 4 wherein R M is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and13 C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M and Q units, expressed as {M(resin)} / {Q(resin)}, excluding the M and Q units from the neopentamer. The M / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M:Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0050] The Mn of the polyorganosilicate resin is determined by the R M The Mn of the polyorganosilicate resins varies depending on various factors such as the type of hydrocarbon group represented by Mn. The Mn of the polyorganosilicate resins refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resins can be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, alternatively >3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resins can be 3,500 Da to 8,000 Da.

[0051] U.S. Patent No. 8,580,073, column 3, line 5 to column 4, line 31, and U.S. Patent Application Publication No. 2016 / 0376482, paragraphs

[0023] to

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

[0052] The intermediates used to prepare the polyorganosilicate resins can be triorganosilanes and silanes or alkali metal silicates containing four hydrolyzable substituents. The triorganosilanes are represented by the formula R M 3 SiX, where R M is as above, and X represents a hydroxyl group or a hydrolyzable substituent, for example of the formula OZ above. A silane having four hydrolyzable substituents has the formula SiX 2 4 wherein each X 2 is independently selected from the group consisting of halogen, alkoxy, and hydroxyl. Suitable alkali metal silicates include sodium silicate.

[0053] The polyorganosilicate resins prepared as described above typically have the formula, for example, HOSiO 3 / 2of silicon-bonded hydroxyl groups. The polyorganosilicate resin may contain up to 3.5% silicon-bonded hydroxyl groups as measured by FTIR spectroscopy and / or NMR spectroscopy as described above. In certain applications, it may be desirable for the amount of silicon-bonded hydroxyl groups to be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively between 0.3% and 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin can be converted to trihydrocarbon siloxane groups or different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane or disilazane containing the appropriate end group. The silane containing the hydrolyzable group can be added in a molar excess over the amount required to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0054] Alternatively, the polyorganosilicate resin has no more than 2%, alternatively no more than 0.7%, alternatively no more than 0.3%, alternatively between 0.3% and 0.8% hydroxyl groups, e.g., of the formula XSiO 3 / 2 wherein R M is as above, and 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.

[0055] For use herein, polyorganosilicate resins further comprise one or more terminal alkenyl groups per molecule. Polyorganosilicate resins having terminal alkenyl groups can be prepared by reacting the product of Daudt et al. with an alkenyl-containing endblocking agent and an endblocking agent free of aliphatic unsaturation in an amount sufficient to provide 3 to 30 mole percent alkenyl groups in the final product. Examples of endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and are exemplified in U.S. Patents 4,584,355 to Blizzard et al., 4,591,622 to Blizzard et al., and 4,585,836 to Homan et al. A single endblocking agent or a mixture of such agents can be used to prepare such resins.

[0056] Alternatively, the polyorganosilicate resin may be represented by the unit formula (B2-17): (R 4 3 SiO 1 / 2 ) mm (R 4 2 R A SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h wherein Z, R 4 , and R A , and subscript h are as 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.

[0057] Alternatively, the (B2) alkenyl-functional polyorganosiloxane may be (B2-18) an alkenyl-functional silsesquioxane resin, i.e., a polyorganosiloxane having the unit formula: (R 4 3 SiO 1 / 2 ) a (R4 2 R A SiO 1 / 2 ) b (R 4 2 SiO 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 contain a resin containing trifunctional (T) units of the formula, where R 4 and R A are as defined above, 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 alkenyl-functional silsesquioxane resin may contain the unit formula (B2-19): (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h where R 4 , R A , Z, and subscripts h, e, and f are as defined above. Alternatively, in addition to the above T units, the alkenyl-functional silsesquioxane resin may further contain difunctional (D) units of the formula R 4 2 SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d , i.e., a DT resin, where subscripts c and d are as defined above. Alternatively, the alkenyl-functional silsesquioxane resin has the formula (R 4 3 SiO 1 / 2 ) a (R 4 2 R ASiO 1 / 2 ) b wherein the subscripts a and b are as defined above for unit formula (B2-1).

[0058] Alkenyl-functional silsesquioxane resins are commercially available, for example, of the formula (B2-20): (Me 2 ViSiO 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 RMS-310, which contains DSC, is commercially available. Alkenyl-functional silsesquioxane resins can be produced by hydrolysis and condensation of trialkoxysilanes or mixtures using methods such as those described in Noll, "Chemistry and Technology of Silicone," Academic Press (1968), Chapter 5, pages 190-245. Alternatively, alkenyl-functional silsesquioxane resins can be produced by hydrolysis and condensation of trichlorosilanes using methods described in U.S. Pat. No. 6,281,285 to Becker et al. and U.S. Pat. No. 5,010,159 to Bank et al. Alkenyl-functional silsesquioxane resins containing D units can be prepared by known methods such as those disclosed in U.S. Patent Application No. 2020 / 0140619 and WO 2018 / 204068 to Swier et al.

[0059] The starting material (B) can be any one of the alkenyl-functional organosilicon compounds described above. Alternatively, the starting material (B) can include a mixture of two or more of the alkenyl-functional organosilicon compounds.

[0060] (C) Hydroformylation reaction catalyst The starting material (C), which is a hydroformylation catalyst for use herein, comprises an active complex of rhodium with a closed-end bisphosphite ligand. The bisphosphite ligand can be symmetric or asymmetric. Alternatively, the bisphosphite ligand can be symmetric. The bisphosphite ligand has the formula (C1):

[0061] [ka] wherein R 6 and R 6’ are each independently selected from the group consisting of hydrogen, an alkyl group of at least one carbon atom, a cyano group, a halogen group, and an alkoxy group of at least one carbon atom; R 7 and R 7’ are each independently an alkyl group of at least 3 carbon atoms, and a group of the formula -SiR 17 3 wherein each R 17 is an independently selected monovalent hydrocarbon radical of 1 to 20 carbon atoms; R 8 , R 8’ , R 9 , and R 9’ are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group; R 10 , R 10’ , R 11 , and R 11’ are each independently selected from the group consisting of hydrogen and alkyl groups. 7 and R 7’ One of the groups may be hydrogen.

[0062] In formula (C1), R 6 and R 6’ R can be an alkyl group of at least 1 carbon atom, alternatively 1 to 20 carbon atoms. 6 and R 6’Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by 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 20 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 6 and R 6’ The alkyl group of R may be selected from the group consisting of ethyl, propyl, and butyl, alternatively, propyl and butyl. 6 and R 6’ The alkyl group in R may be butyl. 6 and R 6’ may be an alkoxy group, the alkoxy group being of the formula -OR 6’’ wherein R 6’’ is R 6 and R 6 is an alkyl group as described above.

[0063] Alternatively, in formula (C1), R 6 and R 6’ may be independently selected from alkyl groups of 1 to 6 carbon atoms and alkoxy groups of 1 to 6 carbon atoms. 6 and R 6’ can be an alkyl group of 2 to 4 carbon atoms. Alternatively, R 6 and R 6’ may be an alkoxy group of 1 to 4 carbon atoms. 6 and R 6’ may be a butyl group, alternatively a tert-butyl group. 6 and R 6’ can be a methoxy group.

[0064] In formula (C1), R 7 and R 7’R can be an alkyl group of at least 3 carbon atoms, alternatively 3 to 20 carbon atoms. 7 and R 7’ Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by 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 20 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 7 and R 7’ The alkyl group of R may be selected from the group consisting of propyl and butyl. 7 and R 7’ The alkyl group can be butyl.

[0065] Alternatively, in formula (C1), R 7 and R 7’ is represented by the formula -SiR 17 3 where each R 17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms. The monovalent hydrocarbon group is 6 and R 6 can be an alkyl group of 1 to 20 carbon atoms as described above.

[0066] Alternatively, in formula (C1), R 7 and R 7’ may each be an independently selected alkyl group, alternatively an alkyl group of 3 to 6 carbon atoms. 7 and R 7’ can be an alkyl group of 3 to 4 carbon atoms. Alternatively, R 7 and R 7’ may be a butyl group, alternatively a tert-butyl group.

[0067] In formula (C1), R8 , R 8’ , R 9 , R 9’ is R 6 and R 6’ may be an alkyl group of at least one carbon atom as described above. Alternatively, R 8 and R 8’ may be independently selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms. 8 and R 8’ Alternatively, in formula (C1), R 9’ and R 9’ may be independently selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms. 9 and R 9’ can be hydrogen.

[0068] In formula (C1), R 10 and R 10’ R may be a hydrogen atom or an alkyl group of at least one carbon atom, alternatively from 1 to 20 carbon atoms. 10 and R 10’ The alkyl group of R 6 and R 6 ' may be as described above. Alternatively, each R 10 and R 10’ Alternatively, each R 10 and R 10’ can be hydrogen.

[0069] In formula (C1), R 11 and R 11’ R may be a hydrogen atom or an alkyl group of at least one carbon atom, alternatively from 1 to 20 carbon atoms. 11 and R 11’ The alkyl group of R 6 and R 6 ' may be as described above. Alternatively, each R 11 and R 11’ can be hydrogen.

[0070] Alternatively, the ligand of formula (C1) may be selected from the group consisting of: (C1-1) 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepine; (C1-2) 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine); and a combination of both (C1-1) and (C1-2).

[0071] Alternatively, the ligand may include 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepine, as disclosed in column 11 of U.S. Pat. No. 10,023,516 (see also U.S. Pat. No. 7,446,231, which discloses this compound as Ligand D in column 22, and U.S. Pat. No. 5,727,893, which discloses this compound as Ligand F in column 20, lines 40-60).

[0072] Alternatively, the ligand may include biphephos, commercially available from Sigma Aldrich, and may be prepared as described in U.S. Patent No. 9,127,030. (See also U.S. Patent No. 7,446,231, column 21 for Ligand B, and U.S. Patent No. 5,727,893, column 20, lines 5-18 for Ligand D).

[0073] The rhodium / bisphosphite ligand complex catalyst, starting material (C), can be prepared by methods known in the art, such as those disclosed in U.S. Patent No. 4,769,498 to Billig et al., column 20, line 50 to column 21, line 40, and U.S. Patent No. 10,023,516 to Brammer et al., column 11, line 35 to column 12, line 12, by varying the appropriate starting materials. For example, the rhodium / bisphosphite ligand complex can be prepared by a process comprising combining a rhodium precursor with the above-described bisphosphite ligand (C1) under conditions to form a complex, which can then be introduced into a hydroformylation reaction medium containing one or both of the above-described starting materials (A) and / or (B). Alternatively, for in situ formation of the rhodium / bisphosphite ligand complex, the rhodium / bisphosphite ligand complex may be formed in situ by introducing a rhodium catalyst precursor to the reaction medium and (C1) introducing a bisphosphite ligand to the reaction medium (e.g., before, during, and / or after the introduction of the rhodium catalyst precursor). The rhodium / bisphosphite ligand complex may be activated by heating and / or exposure to starting material (A) to form (C) the rhodium / bisphosphite ligand complex catalyst. The rhodium catalyst precursor may be rhodium dicarbonyl acetylacetonate, Rh. 2 O 3 ,Rh 4 (CO) 12 , Rh 6 (CO) 16 , and Rh(NO 3 ) 3 As exemplified by:

[0074] For example, the rhodium precursor, such as rhodium dicarbonyl acetylacetonate, optionally the starting material (D), the solvent, and (C1) the bisphosphite ligand can be combined by any convenient means, such as, for example, by mixing. The resulting rhodium / bisphosphite ligand complex can be introduced into a reactor, optionally with an excess of the bisphosphite ligand. Alternatively, the rhodium precursor, (D) the solvent, and the bisphosphite ligand can be combined with the starting material (A) and / or (B), the alkenyl functional organosilicon compound, in the reactor, and the rhodium / bisphosphite ligand complex can be formed in situ. The relative amounts of the bisphosphite ligand and the rhodium precursor are sufficient to provide a molar ratio of bisphosphite ligand / Rh of 10 / 1 to 1 / 1, alternatively 5 / 1 to 1 / 1, alternatively 3 / 1 to 1 / 1, alternatively 2.5 / 1 to 1.5 / 1. In addition to the rhodium / bisphosphite ligand complex, excess (e.g., uncomplexed) bisphosphite ligand may be present in the reaction mixture. The excess bisphosphite ligand may be the same as or different from the bisphosphite ligand in the complex.

[0075] The amount of (C) rhodium / bisphosphite ligand complex catalyst (catalyst) is sufficient to catalyze the hydroformylation of (B) alkenyl-functional organosilicon compound. The exact amount of catalyst depends on various factors, including the type of alkenyl-functional organosilicon compound selected for starting material (B), its exact alkenyl content, and reaction conditions such as temperature and pressure of starting material (A). However, the amount of (C) 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, alternatively 0.5 ppm, based on the weight of (B) alkenyl-functional organosilicon compound. At the same time, the amount of (C) 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, alternatively up to 5 ppm, on the same basis. Alternatively, the amount of (C) catalyst may be sufficient to provide from 0.1 ppm to 300 ppm, alternatively from 0.2 ppm to 100 ppm, alternatively from 0.25 ppm to 20 ppm, alternatively from 0.5 ppm to 5 ppm, based on the weight of the (B) alkenyl functional organosilicon compound.

[0076] solvent The hydroformylation reaction may be carried out without additional solvent. Alternatively, the hydroformylation reaction may be carried out with a solvent to facilitate mixing and / or feeding one or more of the above starting materials, such as (C) catalyst and / or starting material (B), for example, when an alkenyl-functional polyorganosilicate resin is selected for the starting material (B). Solvents are exemplified by aliphatic or aromatic hydrocarbons capable of dissolving the starting materials, such as toluene, xylene, benzene, hexane, heptane, decane, cyclohexane, or combinations of two or more of these. Additional solvents include THF, dibutyl ether, diglyme, and texanol. Without wishing to be bound by theory, it is believed that a solvent may be used to reduce the viscosity of the starting material. 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 starting material (B), which is an alkenyl-functional organosilicon compound.

[0077] Hydroformylation reaction conditions In the process described herein, step 1) is carried out at a relatively low temperature. For example, step 1) can be carried out at a temperature of at least 30°C, alternatively at least 50°C, alternatively at least 70°C. At the same time, the temperature in step 1) can be up to 150°C, alternatively up to 100°C, alternatively up to 90°C, alternatively up to 80°C. Without wishing to be bound by theory, it is believed that lower temperatures, for example, 30°C-90°C, alternatively 40°C-90°C, alternatively 50°C-90°C, alternatively 60°C-90°C, alternatively 70°C-90°C, alternatively 80°C-90°C, alternatively 30°C-60°C, alternatively 50°C-60°C, may be desirable to obtain high selectivity and ligand stability.

[0078] In the 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), alternatively at least 344 kPa (50 psi). At the same time, 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 1000 kPa (145 psi), alternatively up to 689 kPa (100 psi). Alternatively, step 1) may be carried out at 101 kPa to 6,895 kPa, alternatively 344 kPa to 1,379 kPa, alternatively 101 kPa to 1000 kPa, alternatively 344 kPa to 689 kPa. Without wishing to be bound by theory, it is believed that it may be beneficial to use relatively low pressures in the processes herein, e.g., <-6,895 kPa, and the ligands described herein enable low pressure hydroformylation processes, which have the benefits of lower cost and better safety than high pressure hydroformylation processes.

[0079] The hydroformylation process may be carried out in batch, semi-batch, or continuous mode using one or more suitable reactors, such as fixed bed reactors, fluidized bed reactors, continuous stirred tank reactors (CSTRs), or slurry reactors. (B) The choice of alkenyl-functional organosilicon compound, (C) the catalyst, and (D) whether a solvent is used may affect the size and type of reactor used. One reactor, or two or more different reactors may be used. The hydroformylation process may be carried out in one or more steps, which may be influenced by balancing capital costs, achieving high catalyst selectivity, activity, life, and ease of operation, as well as the reactivity of the particular starting materials and the reaction conditions selected, and the desired products.

[0080] Alternatively, the hydroformylation process can be carried out in a continuous manner.For example, the process used can be as described in U.S. Patent No. 10,023,516, except that the olefin feed stream and catalyst described therein are replaced with (B) the alkenyl-functional organosilicon compound and (C) the rhodium / bisphosphite ligand complex catalyst described herein, respectively.

[0081] Step 1) of the hydroformylation process forms a reaction fluid containing an aldehyde-functional organosilicon compound. The reaction fluid may further include additional materials, such as those either intentionally used during step 1) of the process or those formed in situ. Examples of such materials that may also be present include unreacted (B) alkenyl-functional organosilicon compound, 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 liquid aldehyde condensation by-products, and (D) solvent, if used. The term "ligand decomposition products" includes, but is not limited to, any and all compounds resulting from one or more chemical transformations of at least one of the ligand molecules used in the process.

[0082] The hydroformylation process may further include one or more additional steps, such as 2) recovering (C) the rhodium / bisphosphite ligand complex catalyst from the reaction fluid containing the aldehyde-functional organosilicon compound. (C) Recovering the rhodium / bisphosphite 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). Suitable recovery methods are described, for example, in U.S. Patent No. 5,681,473 to Miller et al., U.S. Patent No. 8,748,643 to Priske et al., and U.S. Patent No. 10,155,200 to Geilen et al.

[0083] However, one benefit of the process described herein is that it is not necessary to remove and reuse (C) catalyst.Due to the low level of Rh required, it may be more cost-effective not to recover and reuse (C) catalyst, and the aldehyde-functional organosilicon compound produced by the process may be stable even if catalyst is not removed.Therefore, alternatively, the above process may be carried out without step 2).

[0084] Alternatively, the hydroformylation process may further include 3) purification of the reaction product. For example, the aldehyde-functional organosilicon compound may be isolated from the additional materials described above by any convenient means, such as stripping and / or distillation, optionally using reduced pressure.

[0085] Aldehyde-functional organosilicon compounds Aldehyde-functional organosilicon compounds are useful as starting materials in the process for preparing amino-functional organosilicon compounds. The starting material (E) is an aldehyde-functional organosilicon compound having at least one aldehyde functional group covalently bonded to silicon per molecule. Alternatively, the aldehyde-functional organosilicon compound may have two or more aldehyde functional groups covalently bonded to silicon per molecule. The aldehyde functional group covalently bonded to silicon is represented by the formula:

[0086] [ka] where G is a divalent hydrocarbon group free of aliphatic unsaturation having 2 to 8 carbon atoms. G can be linear or branched. Examples of divalent hydrocarbyl groups for G include those having the empirical formula -C r H 2r -, where the subscript r is 2 to 8. The alkane-diyl group includes linear alkane-diyl, for example, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - or branched alkane-diyl, for example

[0087] [ka] Alternatively, each G can be an alkane-diyl group of 2 to 6 carbon atoms, alternatively 2, 3, or 6 carbon atoms. The aldehyde-functional organosilicon compound can be one aldehyde-functional organosilicon compound. Alternatively, two or more aldehyde-functional organosilicon compounds different from each other can be used in the process described herein. For example, the aldehyde-functional organosilicon compound can include one or both of an aldehyde-functional silane and an aldehyde-functional polyorganosiloxane.

[0088] The aldehyde-functional organosilicon compound has the formula (E1-1): Ald x SiR 4 (4-x)(E1) an aldehyde-functional silane of the formula: Ald are independently selected formulas as above

[0089] [ka] is a group of R 4 and the subscript x is as follows, for example, each R 4 is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscript x is 1 to 4.

[0090] Suitable aldehyde-functional silanes are exemplified by aldehyde-functional trialkylsilanes such as (propyl-aldehyde)-trimethylsilane, (propyl-aldehyde)-triethylsilane, and (butyl-aldehyde)trimethylsilane.

[0091] Alternatively, the aldehyde-functional organosilicon compound may comprise (E2) an aldehyde-functional polyorganosiloxane. The aldehyde-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The aldehyde-functional polyorganosiloxane may have a unit formula (E2-1): (R 4 3 SiO 1 / 2 ) a (R 4 2 R Ald SiO 1 / 2 ) b (R 4 2 SiO 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 (ZO1 / 2 ) h wherein each R Ald is the formula above.

[0092] [ka] and G, R are independently selected aldehyde groups. 4 , Z, and subscripts a, b, c, d, e, f, g, and h are as defined above.

[0093] Alternatively, the (E2) aldehyde-functional polyorganosiloxane may comprise (E2-2) a linear polydiorganosiloxane having at least one aldehyde functional group per molecule, alternatively at least two aldehyde functional groups (e.g., where subscripts e=f=g=0 in formula (E2-1) for the aldehyde-functional polyorganosiloxane above). For example, the polydiorganosiloxane may comprise a unit of formula (E2-3): (R 4 3 SiO 1 / 2 ) a (R Ald R 4 2 SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R Ald R 4 SiO 2 / 2 ) d wherein R Ald and R 4is as above, subscript a is 0, 1, or 2, subscript b is 0, 1, or 2, subscript c≧0, and subscript d≧0, with the proviso that the quantity (b+d)≧1, the quantity (a+b)=2, and the quantity (a+b+c+d)≧2. Alternatively, in the unit formula (E2-3) for the linear aldehyde-functional polyorganosiloxane above, the quantity (a+b+c+d) can be at least 3, alternatively at least 4, and alternatively >50. At the same time, in the formula, 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, and alternatively 250 or less. Alternatively, in the unit formula for the linear aldehyde-functional polyorganosiloxane, each R 4 may be independently selected from the group consisting of alkyl and aryl, alternatively, methyl and phenyl. Alternatively, each R 4 can be an alkyl group, alternatively, each R 4 can be methyl.

[0094] Alternatively, the linear aldehyde-functional polydiorganosiloxane of the unit formula (E2-3) may be represented by the unit formula (E2-4): (R 4 2 R Ald SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) m (R 4 R Ald SiO 2 / 2 ) n , Unit formula (E2-5): (R 4 3 SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) o (R 4 R Ald SiO 2 / 2 ) p or a combination of both (E2-4) and (E2-5).

[0095] In formulae (E2-4) and (E2-5), each R 4 and R Ald are as above. Subscript m may be 0 or a positive number. Alternatively, subscript m may be at least 2. Alternatively, subscript m may be from 2 to 2,000. Subscript n may be 0 or a positive number. Alternatively, subscript n may be from 0 to 2000. Subscript o may be 0 or a positive number. Alternatively, subscript o may be from 0 to 2000. Subscript p is at least 2. Alternatively, subscript p may be from 2 to 2000.

[0096] The starting material (E2) is 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-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(propyl-aldehyde)siloxane), v) bis-trimethylsiloxy terminated polymethyl(propyl-aldehyde)siloxane. siloxane, vi) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(propyl-aldehyde)siloxane), vii) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethyl(propyl-aldehyde)siloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl,methyl,(propyl-aldehyde)siloxy terminated polydimethylsiloxane, x) bis-dimethyl tyl(heptyl-aldehyde)siloxy terminated polydimethylsiloxane, xi) bis-dimethyl(heptyl-aldehyde)siloxy terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xii) bis-dimethyl(heptyl-aldehyde)siloxy terminated polymethyl(heptyl-aldehyde)siloxane), xiii) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xiv) bis-trimethylsiloxy terminated polymethyl(heptyl-aldehyde)siloxane, xv) bis xvi) bis-dimethyl(heptyl-aldehyde)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(heptyl-aldehyde)siloxane), xvii) bis-dimethyl(heptyl-aldehyde)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) dimethyl(heptyl-aldehyde)-siloxy terminated poly(dimethylsiloxane / diphenylsiloxane),and xix) a combination of two or more of i) to xviii).

[0097] Alternatively, (E2) the aldehyde-functional polyorganosiloxane may be cyclic, for example, in the unit formula (E2-1), the subscripts a=b=c=e=f=g=h=0. (E2-6) The cyclic aldehyde-functional polydiorganosiloxane may be represented by the unit formula (E2-7): (R 4 R Ald SiO 2 / 2 ) d wherein R Ald and R 4 is as above, and subscript d can be 3 to 12, alternatively 3 to 6, alternatively 4 to 5. Examples of cyclic aldehyde 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.

[0098] Alternatively, the (E2-6) cyclic aldehyde-functional polydiorganosiloxane may be represented by the unit formula (E2-8): (R 4 2 SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d wherein R 4 and R Ald is as above, where subscript c is >0 to 6, and subscript d is 3 to 12. Alternatively, in formula (E2-8), the quantity (c+d) can be 3 to 12. Alternatively, in formula (E2-8), c can be 3 to 6, and d can be 3 to 6.

[0099] Alternatively, (E2) aldehyde-functional polyorganosiloxane may be (E2-9) oligomer, for example, where the quantity (a+b+c+d+e+f+g) in the above formula (E2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer may be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as starting material (E2-6).

[0100] An example of a linear aldehyde-functional polyorganosiloxane oligomer is represented by the formula (E2-10):

[0101] [ka] wherein R 4 is as above, and each R 2’ are independently 4 and R Ald with the proviso that at least one R 2 But R Ald with the proviso that the subscript z is 0 to 48. Alternatively, the subscript z can be 0 to 4, alternatively 0 to 1, alternatively 0. Alternatively, when z=0 in formula (E2-10), the aldehyde-functional polyorganosiloxane oligomer has the formula (E2-10a):

[0102] [ka] wherein R 4 and R AldExamples of linear 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.

[0103] Alternatively, the aldehyde-functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (E2-11): R Ald SiR 12 3 wherein R Ald is as above, and each R 12 is R 13 and -OSi(R 14 ) 3 Each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 15 is R 13 , -OSi(R 16 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 16 is R 13 and -[OSiR 13 2 ] ii OSiR 13 3 where the subscript ii has a value such that 0≦ii≦100. 12 At least two of -OSi(R 14 ) 3 Alternatively, R 12All three of the -OSi(R 14 ) 3 It could be.

[0104] Alternatively, in formula (E2-11), each R 12 -OSi(R 14 ) 3 If, then, for each R 14 The branched polyorganosiloxane oligomer has the following structure (E2-11a):

[0105] [ka] R such that 13 moiety, where R 13 is as above, and R Ald is an aldehyde group as described above. Alternatively, each R Ald can be propanal, and each R 13 can be methyl.

[0106] Alternatively, in formula (E2-11), each R 12 -OSi(R 14 ) 3 If, then, for each R 14 is a branched polyorganosiloxane oligomer having the structure -OSi(R 15 ) 3 It may be a part

[0107] [ka] In the formula, R Ald and R 15 is as described above. Alternatively, each R 15 is R as above 13 Each R 13 can be methyl.

[0108] Alternatively, in formula (E2-11), each R 12 -OSi(R 14 ) 3If so, then one R 14 is each R 12 -OSiR 13 (R 14 ) 2 For each -OSi(R 14 ) 3 In R 13 Alternatively, -OSiR 13 (R 14 ) 2 Two R's in 14 each of which is a branched aldehyde-functional polyorganosiloxane oligomer having the following structure:

[0109] [ka] -OSi(R 15 ) 3 It may be a part In the formula, R Ald , R 13 , and R 15 is as described above. Alternatively, each R 15 is R 13 Each R 13 can be methyl.

[0110] Alternatively, in formula (B2-11), one R 12 is R 13 R 12 Two of them are -OSi(R 14 ) 3 It can be. R 12 Two of them are -OSi(R 14 ) 3 If so, then one R 14 Each -OSi(R 14 ) 3 R in 13 and R 12 Two of them are -OSiR 13 (R 14 ) 2 Alternatively, -OSiR 13 (R 14 ) 2 Each R in 14The branched polyorganosiloxane oligomer has the following structure:

[0111] [ka] (In the formula, R Ald , R 13 , and R 15 is as described above) 15 ) 3 Alternatively, each R 15 is R 13 Each R 13 can be methyl. Alternatively, the aldehyde-functional branched polyorganosiloxane can have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, alternatively 4 to 10 silicon atoms per molecule. Examples of aldehyde-functional branched polyorganosiloxane oligomers include those having the formula:

[0112] [ka] 3-(3,3,3-trimethyl-1-lambda 2 -disiloxanyl)propanal (which may also be referred to as propyl-aldehyde-tris(trimethyl)siloxy)silane); formula

[0113] [ka] 3-(1,3,5,5,5-pentamethyl-1λ 3 ,3λ 3 -trisiloxaneyl)propanal (which may also be referred to as methyl-(propyl-aldehyde)-di((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane); formula

[0114] [ka] 3-(3,5,5,5-tetramethyl-1λ 2 ,3λ 3 -trisiloxaneyl)propanal (which may also be referred to as (propyl-aldehyde)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-silane); formula

[0115] [ka] 7-(3,5,5,5-tetramethyl-1λ 2 ,3λ 3 -trisiloxanyl)heptanal (which may also be referred to as (heptyl-aldehyde)-tris((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-silane).

[0116] Alternatively, the (E2) aldehyde-functional polyorganosiloxane can be branched, such as the branched oligomers described above, and / or branched aldehyde-functional polyorganosiloxanes that can have, for example, more aldehyde groups and / or more polymer units per molecule than the branched oligomers described above (e.g., in formula (E2-1), the amount (a+b+c+d+e+f+g)>50). The branched aldehyde-functional polyorganosiloxane can have an amount (e+f+g) sufficient to provide the branched aldehyde-functional polyorganosiloxane (in formula (E2-1)) with >0-5 mol% trifunctional and / or tetrafunctional units.

[0117] For example, the branched aldehyde-functional polyorganosiloxane may be represented by the unit formula (E2-13): 4 3 SiO 1 / 2 ) q (R 4 2 R Ald SiO 1 / 2 ) r (R 4 2 SiO2 / 2 ) s (SiO 4 / 2 ) t In one embodiment, the branched polyorganosiloxane may be of the formula: 4 and R Ald is as above, and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to the branched polyorganosiloxane a viscosity of >170 mPa·s 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, alternatively 190 mPa·s to 420 mPa·s.

[0118] Alternatively, the branched aldehyde-functional polyorganosiloxane may be represented by the formula (E2-14): [R Ald R 4 2 Si-(O-SiR 4 2 ) x -O] (4-w) -Si-[O-(R 4 2 SiO) v SiR 4 3 ] w wherein R Ald and R 4 is as above, and the subscripts v, w, and x have values ​​such that 200≧v≧1, 2≧w≧0, and 200≧x≧1. Alternatively, in this formula (E2-14), each R 4 is independently selected from the group consisting of methyl and phenyl; Ald has the formula above, where G has 2, 3, or 6 carbon atoms.

[0119] Alternatively, the branched aldehyde-functional polyorganosiloxane for the starting material (E2-11) may have the unit formula (E2-15): (R 4 3 SiO 1 / 2 )aa (R Ald R 4 2 SiO 1 / 2 ) bb (R 4 2 SiO 2 / 2 ) cc (R Ald R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd In the formula, R 4 and R Aldis as above, with subscript aa≧0, subscript bb>0, subscript cc is from 15 to 995, subscript dd>0, and subscript ee≧0. Subscript aa may be from 0 to 10. Alternatively, subscript aa may have a value such that 12≧aa≧0, alternatively 10≧aa≧0, alternatively 7≧aa≧0, alternatively 5≧aa≧0, alternatively 3≧aa≧0. Alternatively, subscript bb≧1. Alternatively, subscript bb≧3. Alternatively, subscript bb may have a value such that 12≧bb>0, alternatively 12≧bb≧3, alternatively 10≧bb>0, alternatively 7≧bb>1, alternatively 5≧bb≧2, alternatively 7≧bb≧3. Alternatively, the subscript cc may have a value such that 800≧cc≧15, alternatively 400≧cc≧15. Alternatively, the subscript ee may have a value such that 800≧ee≧0, 800≧ee≧15, alternatively 400≧ee≧15. Alternatively, the subscript ee may be 0. Alternatively, the quantity (cc+ee) may have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd may be 1 to 10. Alternatively, the subscript dd may have a value such that 10≧dd>0, alternatively 5≧dd>0, alternatively dd=1. Alternatively, the subscript dd may be 1 to 10, alternatively the subscript dd may be 1 or 2. Alternatively, when subscript dd=1, subscript bb can be 3 and subscript cc can be 0. The value of subscript bb can be sufficient to provide a silsesquioxane of unit formula (E2-15) having an aldehyde content of 0.1% to 1%, alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane.

[0120] Alternatively, (E2) the aldehyde-functional polyorganosiloxane may comprise an aldehyde-functional polyorganosiloxane resin, such as an aldehyde-functional polyorganosilicate resin and / or an aldehyde-functional silsesquioxane resin. Such resins may be prepared, for example, by hydroformylating an alkenyl-functional polyorganosiloxane resin, as described above. The aldehyde-functional polyorganosilicate resin may be represented by the formula R M’ 3 SiO 1 / 2 and monofunctional units ("M" units) of formula SiO 4 / 2 "R" is a tetrafunctional silicate unit ("Q" unit) of the formula M’ are independently R as above 4 and R Ald Alternatively, each R M’ may be selected from the group consisting of alkyl groups, aldehyde functional groups of the formula shown above, and aryl groups. Alternatively, each R M’ may be selected from methyl, (propyl-aldehyde), and phenyl. Alternatively, R M’ At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M' units are (Me 3 SiO 1 / 2 ), (Me 2 PhSiO 1 / 2 ), and (Me 2 R Ald SiO 1 / 2 The polyorganosilicate resins are 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.

[0121] When prepared, the polyorganosilicate resin contains the M' and Q units described above, and the polyorganosiloxane contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M’3 ) 4 wherein R M’ is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13 C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M' and Q units, expressed as {M'(resin)} / {Q(resin)}, excluding the M' and Q units from the neopentamer. The M' / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M' units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M' / Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0122] The Mn of the polyorganosilicate resin is determined by the R M’ The Mn of the polyorganosilicate resins varies depending on various factors including the type of hydrocarbon group represented by. The Mn of the polyorganosilicate resins refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resins may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da, alternatively >3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resins may be 3,500 Da to 8,000 Da.

[0123] Alternatively, the polyorganosilicate resin may be represented by the unit formula (E2-17): (R 4 3 SiO 1 / 2 ) mm (R 4 2 R Ald SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h wherein Z, R 4 , and R Ald、and the subscript h is as described 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.

[0124] Alternatively, the (E2) aldehyde-functional polyorganosiloxane may include an (E2-18) aldehyde-functional silsesquioxane resin, i.e., the unit formula: (R 4 3 SiO 1 / 2 ) a (R 4 2 R Ald SiO 1 / 2 ) b (R 4 2 SiO 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 of a resin containing trifunctional (T') units, where R 4 and R Ald are as described 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 aldehyde-functional silsesquioxane resin may have the unit formula (E2-19): (R 4 SiO 3 / 2 ) e (R Ald SiO 3 / 2 ) f (ZO 1 / 2 ) h and may include, where R 4 and R Ald, Z, and subscripts h, e, and f are as defined above. Alternatively, the alkenyl-functional silsesquioxane resin may contain, in addition to the T units described above, units of the formula (R 4 2 SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d where subscripts c and d are as defined above. Alternatively, the alkenyl-functional silsesquioxane resin may further comprise a difunctional (D') unit of the formula (R 4 3 SiO 1 / 2 ) a (R 4 2 R Ald SiO 1 / 2 ) b wherein the subscripts a and b are as defined above for unit formula (E2-1).

[0125] The starting material (E) can be any one of the aldehyde-functional organosilicon compounds described above. Alternatively, the starting material (E) can include a mixture of two or more of the aldehyde-functional organosilicon compounds.

[0126] Preparation of Amino-Functional Organosilicon Compounds The process for preparing the amino-functional organosilicon compound comprises: I) combining starting materials under conditions to catalyze a hydrogenation reaction, the starting materials comprising: (E) an aldehyde-functional organosilicon compound as described above; and (F) an amine source; (G) a hydrogenation catalyst; (H) hydrogen; and optionally, (J) a solvent, thereby forming a reaction product comprising an amino-functional organosilicon compound.

[0127] The process may optionally further comprise, prior to step I), 1) combining starting materials under conditions that catalyze the hydroformylation reaction, the starting materials comprising (A) a gas comprising hydrogen and carbon monoxide, (B) an alkenyl-functional organosilicon compound, and (C) a rhodium / bisphosphite ligand complex catalyst, thereby forming a hydroformylation reaction product comprising an aldehyde-functional organosilicon compound as described above. Optionally, the method may further comprise, prior to step I) and after step 1), step 2) recovering (C) the rhodium / bisphosphite ligand complex catalyst from the reaction product comprising the aldehyde-functional organosilicon compound. However, step 2) is optional and may not be required. For example, when hydroformylation is used to prepare (E) aldehyde-functional organosilicon compound, it may not be necessary to remove the hydroformylation reaction catalyst, since, without wishing to be bound by theory, it is believed that the amount of catalyst is not cost-effective to remove and / or the selection and amount of catalyst does not adversely affect the reductive amination reaction.Optionally, the process may further include 3) purifying the reaction product before step I) and after step 1), thereby isolating the aldehyde-functional organosilicon compound from additional materials as described above.However, this step 3) is optional and may not be necessary, for example, when a solvent is used in the hydroformylation reaction to prepare (E) aldehyde-functional organosilicon compound, and the same solvent is used as starting material (J).

[0128] The process may optionally further comprise pretreating (G) the hydrogenation catalyst before step I). Pretreatment may be carried out to activate the catalyst and / or to increase the activity of the catalyst. Pretreatment may be carried out by any convenient means, such as exposing the hydrogenation catalyst to hydrogen before starting the reaction. For example, the packed bed of the hydrogenation catalyst may be purged with hydrogen before introducing (E) the aldehyde-functional organosilicon compound and (F) the amine source.

[0129] (F) Amine source The amine source as used herein may include (F1) a primary amine, (F2) ammonia, (F3) a polyetheramine, (F4) a diamine, or a combination of two or more of (F1), (F2), (F3), and (F4). A primary amine is a amine having the formula: R 18 NH 2 wherein R 18 is an alkyl group of 1 to 18 carbon atoms. 18 Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by 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 the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 18 The alkyl group of R may be selected from the group consisting of ethyl, propyl, and butyl, alternatively ethyl or propyl, alternatively propyl and butyl. 18 The alkyl group in the formula can be propyl. Primary amines are known in the art and commercially available. For example, ethylamine, propylamine, n-butylamine, and isobutylamine are available from a variety of sources, such as Acros Organics or Sigma Aldrich, Inc. (St. Louis, Missouri, USA). Alternatively, the (F) amine source can be a compound of the formula NH 3 (F2) ammonia, such as anhydrous ammonia, having a C 1 H 2 O 2 , 2 H 2 O 3 , 3 H 2 O 4 , 4 H 2 O 5 , 5 H 2 O 6 , 6 H 2 O 7 , 7 H 2 O 8 , 8 H 2 O 9 , 9 H 3 Ammonia is known in the art and is commercially available from a variety of sources, including Air Products (Allentown, Pennsylvania, USA).

[0130] Alternatively, the (F) amine source may comprise (F3) a polyetheramine. Polyetheramines are known in the art and are commercially available, for example, from Huntsman Corporation (The Woodlands, Texas, USA) under the trade name JEFFAMINE™ M series. Polyetheramines have the unit formula (H 2 N)(C 2 H 4 O) jj (C 3 H 6 O) kk (H), where the subscripts jj and kk represent the average number of ethylene oxide units and propylene oxide units (respectively) per molecule, jj≧0, kk≧0, and the amount (jj+kk) is sufficient to give the polyetheramine a molecular weight of from 600 g / mol to 3000 g / mol, alternatively from 600 g / mol to 1000 g / mol.

[0131] Alternatively, the (F) amine source may comprise a (F4) diamine. The diamine may be represented by the formula H 2 ND-NH 2 where D represents a divalent hydrocarbyl group. Examples of divalent hydrocarbyl groups for D include alkane-diyl groups, arylene groups, such as phenylene, or alkylarylene groups, such as

[0132] [ka] An example of an alkane-diyl group for D is the empirical formula -C r H 2r -, where the subscript r is 2 to 6. The alkane-diyl group can be a straight chain alkane-diyl, for example, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - or branched alkane-diyl, for example

[0133] [ka] Alternatively, each D can be an alkane-diyl group of 2, 3, or 6 carbon atoms. Alternatively, (F4) diamine can be ethylenediamine. Diamines such as ethylenediamine are commercially available from a variety of sources, such as Alfa Aesar and Acros Organics.

[0134] One amine source may be used herein. Alternatively, the (F) amine source may comprise a combination of two or more of the above amine sources, for example, two or more species of (F1) primary amines, a combination of (F1) primary amines and (F2) ammonia, or a combination of (F2) ammonia and (F3) polyetheramine. The amine source may be used with a superstoichiometric amount of amine functionality relative to the aldehyde functionality of the (E) aldehyde-functional organosilicon compound. For example, when the starting material (F) is a primary amine or diamine as described above, the amount may be sufficient to provide a molar ratio of amine groups:aldehyde groups of 10:1 to 1:1. Alternatively, when the starting material (F) is ammonia, the amount may be sufficient to provide a molar ratio of ammonia:aldehyde groups of more than 1:1, alternatively 5:1 or more, alternatively 10:1 to 40:1.

[0135] (G) Hydrogenation catalyst The hydrogenation catalyst used in the process for preparing amino-functional organosilicon compounds can be a heterogeneous hydrogenation catalyst, a homogeneous hydrogenation catalyst, or a combination thereof. Alternatively, the hydrogenation catalyst can 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 thereof. Alternatively, the hydrogenation catalyst can include Co, Cu, Ni, Pd, Pt, Ru, or combinations of two or more thereof. Alternatively, the hydrogenation catalyst can include Co, Cu, Ni, Pd, or combinations of two or more thereof. Alternatively, the hydrogenation catalyst may include Co, Cu, Ni, or a combination of two or more thereof. 2 O 3 ), silica (SiO 2 Alternatively, the hydrogenation catalyst may comprise a support such as Rh / C, Raney nickel, Raney copper, Raney cobalt, Ru / C, Ru / Al 2 O 3 , Pd / C, Pd / Al 2 O 3 , Pd / CaCO 3 , Cu / C, Cu / Al 2 O 3 , Cu / SiO 2 , Cu / SiC, Cu / C, nickel catalysts on the above supports, and combinations of two or more thereof.

[0136] Alternatively, the heterogeneous hydrogenation catalyst for hydrogenation of the imine intermediate formed via the reaction of the aldehyde group of the (E) aldehyde-functional organosilicon compound with the amine group of the (F) amine source may comprise copper, chromium, nickel, rhodium, or a support material to which two or more of these are applied as active components. An exemplary catalyst comprises 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 optionally be added to the support material. Alternatively, a chromium-free hydrogenation catalyst may be used. For example, Ni / Al 2 O 3 or Co / Al 2 O 3 or copper oxide / zinc oxide containing catalysts (which further contain potassium, nickel, and / or cobalt), plus alkali metals, may be used. Suitable hydrogenation catalysts are disclosed, for example, in U.S. Pat. No. 7,524,997 or U.S. Pat. No. 9,567,276 and the references cited therein. Alternatively, heterogeneous hydrogenation catalysts may be commercially available, such as Rh / C catalyst available from Sigma-Aldrich, Ni-5256P available from BASF, and Co-179, which is also commercially available.

[0137] 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), copper on silicon carbide (Cu / SiC).

[0138] Alternatively, homogeneous hydrogenation catalysts may be used herein. The homogeneous hydrogenation catalyst may be a metal complex, and the metal may be selected from the group consisting of Co, Fe, Ir, Rh, and Ru. An example of a suitable homogeneous hydrogenation catalyst is [RhCl(PPh 3 )3 ](Wilkinson's catalyst), [Rh(NBD)(PR' 3 ) 2 ]+ClO 4 - (wherein R' is an alkyl group, e.g., Et), [RuCl 2 (diphosphine)(1,2-diamine)] (Noyori catalyst), RuCl 2 (TRIPHOS)(where TRIPHOS=PhP[(CH 2 CH 2 PPh 2 ) 2 ], Ru(II)(dppp)(glycine) complex (where dppp=1,3-bis(diphenylphosphino)propane), RuCl 2 (PPh 3 ) 3 , RuCl 2 (CO) 2 (PPh 3 ) 2 , IrH 3 (PPh 3 ) 3 , [Ir(H 2 )(CH 3 COO)(PPh 3 ) 3 ], cis-[Ru-Cl2(ampy)(PP)][where ampy = 2-(aminomethyl)pyridine and PP = 1,4-bis-(diphenylphosphino)butane, 1,1'-ferrocenediyl-bis(diphenylphosphine)], pincer RuCl(CNNR)(PP) complexes [where PP = 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-ferrocenediyl-bis(diphenylphosphine)] and HCNNR = 4-substituted aminomethyl-benzo[h]quinolines, R = Me, Ph], [RuCl 2 (dppb)(ampy)] (where dppb = 1,4-bis(diphenylphosphino)butane, ampy = 2-aminomethylpyridine), [Fe(PNPMeiPr)(CO)(H)(Br)], [Fe(PNPMe-iPr)(H)2(CO)], and combinations thereof.

[0139] The amount of hydrogenation catalyst used in the process varies depending on various factors including whether the process is run in batch or continuous mode, the selection of the aldehyde-functional organosilicon compound, whether a heterogeneous or homogeneous hydrogenation catalyst is selected, and 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% to 50% by weight, alternatively 5% to 30% by weight, based on the weight of the aldehyde-functional 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, while 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, on the same basis. Alternatively, when the process is run in continuous mode, for example by filling the reactor with a heterogeneous hydrogenation catalyst, the amount of hydrogenation catalyst can be less than 10% by weight, based on the weight of the aldehyde-functional organosilicon compound. -1 Reactor volume (filled with hydrogenation catalyst) to achieve a space time of 1 m 2 The catalyst surface area may be sufficient to achieve 10 kg / hr of substrate per hour.

[0140] (H) Hydrogen Hydrogen is known in the art and is commercially available from a variety of sources, such as Air Products. Hydrogen may be used in superstoichiometric amounts relative to the aldehyde functionality of the (E) aldehyde-functional organosilicon compound to allow for complete reaction.

[0141] (J) Solvent The solvent (J) that may be optionally used in the process for preparing the amino-functional organosilicon compound may be selected from solvents that are neutral to the reaction. The following are specific examples of such solvents: monohydric alcohols such as methanol, ethanol, and isopropyl alcohol; ethers such as dioxane, THF; aliphatic hydrocarbons such as hexane, heptane, and paraffinic solvents; and aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons, and water. 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 aldehyde-functional organosilicon compound is a resin rather than an oligomer, more solvent may be used. However, the amount of solvent may be 0-99% based on the total weight of all starting materials.

[0142] (K) Adsorbent In step I) of the process, an adsorbent may be optionally added to remove water produced as a by-product during the reaction. An example of a suitable adsorbent may be inorganic particulates. 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, alternatively 3 Å or less. Examples of adsorbents include zeolites such as chabazite, mordenite and analcime, alkali metal aluminosilicates, silica gel, silica magnesia gel, activated carbon, activated alumina, calcium oxide and molecular sieves such as combinations thereof.

[0143] Examples of commercially available desiccants include desiccated molecular sieves, such as 3 Å (angstrom) molecular sieves available from Grace Davidson under the trade name SYLOSIV™ and Zeochem (Louisville, Kentucky, USA) under the trade name PURMOL™, and 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 available from UOP (Illinois, USA)), SILIPORITE™ NK 30AP and 65xP (Atofina (Philadelphia, Pennsylvania, USA)), and molecular sieves available from WRGrace (Maryland, USA). Other suitable desiccants include MgSO 4 The amount of adsorbent is not critical and depends on various factors, including the amount of carbinol groups in the starting material (C).

[0144] The reductive amination reaction may be carried out using pressurized hydrogen. The hydrogen (gauge) pressure may be from 10 psig (68.9 kPa) to 3000 psig (20,685 kPa), alternatively from 10 psig to 2000 psig (13,790 kPa), alternatively from 10 psig to 1500 psig (10,342 kPa), alternatively from 200 psig (1379 kPa) to 1200 psig (8274 kPa). The reaction may be carried out at a temperature of 0 to 200° C. Alternatively, to shorten the reaction time, a temperature of 50 to 150° C. may be suitable. Alternatively, the hydrogen (gauge) pressure used can be at least 25 psig, alternatively at least 50 psig, alternatively at least 100 psig, alternatively at least 150 psig, alternatively at least 164 psig, while the hydrogen gauge pressure can be up to 800 psig, alternatively up to 400 psig, alternatively up to 300 psig, alternatively up to 200 psig, alternatively up to 194 psig. The temperature for the reaction can be at least 40° C., alternatively at least 50° C., alternatively at least 65° C., alternatively at least 80° C., while the temperature can be up to 200° C., alternatively up to 150° C., alternatively up to 120° C.

[0145] This reaction can be carried out as a batch process or as a continuous process. In a batch process, step I) of the process for preparing amino-functional organosilicon compounds can be carried out for 1 minute to 24 hours, although the reaction time depends on various factors including the amount of catalyst and the reaction temperature. Alternatively, the 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, alternatively at least 6 hours, while the reaction can be carried out for up to 24 hours, alternatively at least 23 hours, alternatively at least 22.5 hours, alternatively at least 22 hours, alternatively at least 17.5 hours, alternatively at least 17 hours, alternatively at least 16.5 hours.

[0146] Alternatively, in a batch process, the end point of the reaction may be considered to be the time when a decrease in reactor pressure is no longer observed after continuing the reaction for an additional 1-2 hours. If the reactor pressure decreases during the course of the reaction, it may be desirable to repeat the introduction of hydrogen and amine sources and maintain it under elevated pressure to shorten the reaction time. Alternatively, the reactor may be repressurized with hydrogen and amine sources one or more times to achieve an adequate supply of hydrogen and amine sources for the reaction of the aldehyde functional groups while maintaining a reasonable reactor pressure.

[0147] After completion of the reaction, the hydrogenation catalyst may be separated by any convenient means, such as filtration or adsorption, for example with diatomaceous earth or activated carbon, sedimentation, centrifugation, in a pressurized inert (e.g., nitrogen) atmosphere, by maintaining the catalyst in structured packing or other fixed structure, or by combinations of these.

[0148] The amino-functional organosilicon compounds prepared as described above have at least one amino-functional group covalently bonded to silicon per molecule. Alternatively, the amino-functional organosilicon compounds may have two or more amino-functional groups covalently bonded to silicon per molecule. The amino-functional group R covalently bonded to silicon N is the expression:

[0149] [ka] where G is a divalent hydrocarbon group free of aliphatic unsaturation having 2 to 8 carbon atoms, as described and exemplified above, and R 19 is R 18 (which is an alkyl group as above), H, 2 where D is a divalent hydrocarbyl group as defined above, and for example units of the formula -(C 2 H 4 O) jj (C 3 H 6 O) kk(H) polyether groups, where the subscripts jj and kk are as defined above. The amino-functional organosilicon compound is selected from the group consisting of at least one R Ald R N The (E) aldehyde-functional organosilicon compound may have any one of the formulas above for the aldehyde-functional organosilicon compound, preplaced with: EXAMPLES

[0150] These examples are provided to illustrate the invention to one of ordinary skill in the art and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials used in the examples are listed in Table 1 below.

[0151] [Table 1]

[0152] In this Example 1, the formula

[0153] [ka] 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal was synthesized as follows: In a nitrogen-filled glovebox, 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 stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The catalyst solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glovebox. In a ventilated fume hood, 1,3-divinyltetramethyldisiloxane (1000 g) was charged to 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 a dip tube and carefully released through a valve connected to the headspace. This process was repeated three times for reactor headspace inerting. The reactor was then pressure tested by pressurizing with nitrogen to 300 psig (2068.4 kPa). After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized with syngas to 100 psig (689.5 kPa) and then released three times before pressurizing to 80 psig (551.6 kPa) through the dip tube. The reaction temperature was set to 50°C until gas uptake slowed, then the temperature was set to 80°C. The agitation speed was set to 800 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing syngas. The pressure was set to 100 psig (689.5 kPa). The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. A conversion of over 98% was observed after 22.5 hours. The n / i ratio of the final product 1 Determined by 1 H NMR analysis.

[0154] In this Example 2, 120 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 2 L autoclave reactor along with methanol (120 g) and 5 wt% Rh / C catalyst (18 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (398 g, 24 equiv.) was added and the reactor was pressurized to 519 psig (3578.4 kPa) with hydrogen. 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 900 psig (6205.3 kPa). The reductive amination was carried out at 90°C and 810 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 116.0 g of product, which was analyzed by GC-FID, 1 H, 13 C, and 29 The analysis was carried out using Si NMR.

[0155] In this Example 3, 120 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 2 L autoclave reactor along with toluene (120 g) and 5 wt% Rh / C catalyst (18 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (398 g, 24 equiv.) was added and the reactor was pressurized to 354 psig (2440.7 kPa) with hydrogen. 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 1021 psig (7039.5 kPa). The reductive amination was carried out at 90°C and 802 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 110.9 g of product, which was analyzed by GC-FID, 1 H, 13 C, and 29 The analysis was carried out using Si NMR.

[0156] In this Example 4, 120 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 2 L autoclave reactor along with heptane solvent (120 g) and 5 wt% Rh / C catalyst (18 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (398 g, 24 equiv.) was added and the reactor was pressurized to 338 psig (2330.4 kPa) with hydrogen. 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 1044 psig (7198.1 kPa). The reductive amination was carried out at 90°C and 800 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 102.2 g of product, which was analyzed by GC-FID, 1 H, 13 C, and 29 The analysis was carried out using Si NMR.

[0157] In this Example 5, 140 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 2 L autoclave reactor along with methanol (140 g) and Ni-5256P catalyst (21.0 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (580.5 g, 30 equiv.) was added and the reactor was pressurized to 650 psig (4481.6 kPa) with hydrogen. 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 850 psig (5860.5 kPa). The reductive amination was carried out at 90°C and 780 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 131.6 g of concentrated product. The concentrated product was 64.4% by weight 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) when analyzed using GC-FID. 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) has the formula:

[0158] [ka] had.

[0159] In this Example 6, 18 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 300 mL autoclave reactor along with toluene solvent (18 g) and Ni-5256P catalyst (4.1 g). The reactor was sealed and the headspace was inerted with nitrogen. Ammonia (74.6 g, 30 equiv.) was added and the reactor was pressurized to 550 psig (3792.1 kPa) with hydrogen. 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). The reductive amination was carried out at 90° C. and 825 RPM for 4 hours. The reactor was cooled and vented. 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, which was 59.7 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0160] In this Example 7, a reductive amination experiment was carried out in a 300 mL autoclave reactor using Co-0179 at 110° C. and 800 RPM for 4 hours. 3,3′-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal (16 g), prepared as described in Example 1, was charged with methanol (16 g) and Co catalyst (4.9 g). The reactor was sealed and the headspace was inerted with nitrogen. Ammonia (74.6 g, 30 equiv.) was added and the reactor was pressurized to 600 psig (4136.8 kPa) with hydrogen. 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 1200 psig (8273.7 kPa). The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 16.0 g of concentrated product, which was 65.7 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) when analyzed using GC-FID.

[0161] Examples 2-7 demonstrated that reductive amination could be successfully carried out using different catalysts under the conditions tested.

[0162] The effect of ammonia equivalent was studied in the following Examples 8 to 14. Reductive amination reactions were carried out in 300 mL and 2 L autoclave reactors at 90° C. with 5 wt % Rh / C.

[0163] In this Example 8, 5 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 300 mL autoclave reactor along with methanol (35.6 g) and 5 wt% Rh / C catalyst (1.5 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (41.5 g, 60 equiv.) was added and the reactor was pressurized to 600 psig (4136.9 kPa) with hydrogen. 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 810 psig (5584.8 kPa). The reductive amination was carried out at 90°C and 840 RPM for 2 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator.

[0164] In this Example 9, 10 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 300 mL autoclave reactor along with methanol (2.5 g) and 5 wt% Rh / C catalyst (2.9 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (41.5 g, 30 equiv.) was added and the reactor was pressurized to 680 psig (4688.4 kPa) with hydrogen. 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 980 psig (6756.9 kPa). The reductive amination was carried out at 90°C and 830 RPM for 2 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator.

[0165] In this Example 10, 120 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 2 L autoclave reactor along with methanol (120 g) and 5 wt% Rh / C catalyst (18 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (398 g, 24 equiv.) was added and the reactor was pressurized to 519 psig (3578.4 kPa) with hydrogen. 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 reaction temperature. The reaction pressure was observed to be 900 psig (6205.3 kPa). The reductive amination was carried out at 90°C and 810 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator.

[0166] Examples 8-10 show the synthesis of NH using the Rh / C hydrogenation catalyst under the conditions tested. 3 As the equivalent weight decreased, the GC-FID area % of the desired product, 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine), decreased while the GC-FID area % of the dimeric by-product, (bis(3-(3-(3-aminopropyl)-1,1,3,3-tetramethyldisiloxaneyl)propyl)amine) increased. These results are shown in Table 2 below. Desired product in Table 2 refers to 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0167] [Table 2]

[0168] Reductive amination reactions were also carried out with Ni-5256P catalyst at various ammonia equivalents in a 2 L autoclave reactor at 90° C. as follows.

[0169] In this Example 11, 279.8 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a reactor along with methanol (279.8 g) and Ni-5256P catalyst (63 g). Reductive amination chemistry was carried out using ammonia (386.7 g, 10 equivalents). The reactor was pressurized to 576 psig (3971.4 kPa) with hydrogen. 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 610 psig (4205.8 kPa). The reductive amination was carried out at 90°C and 847 RPM for 16.5 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation. The concentrated product was 68.6 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0170] In this Example 12, 186.3 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a reactor along with methanol and Ni-5256P catalyst (41.9 g). Reductive amination chemistry was carried out using ammonia (514.8 g, 20 equivalents). The reactor was pressurized to 576 psig (3971.4 kPa) with hydrogen. 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 reaction temperature. The reaction pressure was observed to be 680 psig (4688.4 kPa). The reductive amination was carried out at 90°C and 839 RPM for 17 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation. The concentrated product was 68.5 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0171] In this Example 13, 139.6 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a reactor along with methanol (139.6 g) and Ni-5256P catalyst (31.4 g). Reductive amination chemistry was carried out using ammonia (578.8 g, 30 equivalents). The reactor was pressurized to 562 psig (3874.9 kPa) with hydrogen. 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 820 psig (5653.7 kPa). The reductive amination was carried out at 90°C and 832 RPM for 17 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation. The concentrated product was 70.1 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0172] In this Example 14, 111.6 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged along with methanol (111.6 g) and Ni-5256P catalyst (25.11 g). Reductive amination chemistry was carried out using ammonia (616.9 g, 40 equivalents). The reactor was pressurized to 550 psig (3792.1 kPa) with hydrogen. 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 920 psig (6343.2 kPa). The reductive amination was carried out at 90°C and 815 RPM for 17.5 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation. The concentrated product was 69.6 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0173] Examples 11-14 show that little difference was observed in the selectivity to 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) when the equivalent amount of ammonia was varied using a Ni catalyst under the conditions tested. Good selectivity was obtained over a wide range of ammonia concentrations.

[0174] In this Example 15, 13 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 300 mL autoclave reactor along with methanol (52 g) and Ni-5256P catalyst (2.0 g). The reactor was sealed and the headspace inerted with nitrogen. Ammonia (53.9 g, 30 equiv.) was added and the reactor was pressurized to 554 psig (3819.7 kPa) with hydrogen. 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 724 psig (4991.8 kPa). The reductive amination was carried out at 90° C. and 828 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 12.8 g of concentrated product, which was 70.3 wt % 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0175] In this Example 16, 140 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 2 L autoclave reactor along with methanol (140 g) and Ni-5256P catalyst (21.0 g, BASF). The reactor was sealed and the headspace was inerted with nitrogen. Ammonia (580.5 g, 30 equiv.) was added and the reactor was pressurized to 648 psig (4467.8 kPa) with hydrogen. 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 845 psig (5826.1 kPa). The reductive amination was carried out at 90°C and 820 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 131.3 g of concentrated product, which was 69.8 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0176] In this Example 17, 19 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 300 mL autoclave reactor along with methanol (4.8 g) and Ni-5256P (2.9 g). The reactor was sealed and the headspace was inerted with nitrogen. Ammonia (78.8 g, 30 equiv.) was added and the reactor was pressurized to 566 psig (3902.4 kPa) with hydrogen. 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 970 psig (6687.9 kPa). The reductive amination was carried out at 90° C. and 823 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 19.4 g of concentrated product, which was 64.0 wt % 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0177] Examples 15-17 were carried out using varying amounts of solvent. In each example, a large amount of the desired product, 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine), was formed. However, Examples 16-18 showed that under the conditions tested, a higher proportion of methanol solvent (Examples 15 and 16) provided somewhat better selectivity to 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) than a lower proportion of solvent (Example 17).

[0178] In this Example 18, Example 17 was repeated with the same results.

[0179] In this Example 19, 19 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged to a 300 mL autoclave reactor along with methanol (4.8 g) and Ni-5256P (2.9 g). The reactor was sealed and the headspace was inerted with nitrogen. Ammonia (78.8 g, 30 equiv.) was added and the reactor was pressurized to 660 psig (4550.5 kPa) with hydrogen. The reactor was heated to 120°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 1200 psig (8273.7 kPa). The reductive amination was carried out at 120°C and 822 RPM for 4 hours. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator to collect 18.7 g of concentrated product, which was 66.7 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) as analyzed using GC-FID.

[0180] Varying reaction temperatures were studied in Examples 18 and 19. These examples show that varying the reaction temperature from 90° C. to 120° C. had little effect on selectivity, and both samples had good selectivity to 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) under the conditions tested.

[0181] Reductive amination experiments using 5 wt% Rh / C were designed to screen solvents in a 2L autoclave reactor equipped with a cooling coil. All experiments were carried out at 90°C using 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal (dialdehyde) prepared as described in Example 1 and solvent in amounts to provide a 1:1 mass ratio of dialdehyde and solvent. After the reactor cooled and vented the ammonia and hydrogen, the crude product was collected and stripped of the solvent using a rotary evaporator. Table 3 lists the product masses. Each of these products was purified using a Vigreux distillation process to obtain a main fraction containing 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0182] [Table 3]

[0183] In Examples 20-22, a 12-inch Vigreux fractional distillation apparatus was used to separate the light and bottom fractions, and each of these products yielded a main fraction of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine). In Example 20, 116.0 g of the product was charged to a reboiler (250 mL, three-neck round bottom flask). The reboiler temperature was set at 150° C. and a vacuum of less than 1 Torr (less than 0.13 kPa) was applied to the apparatus. The fractions - light (1.2 g), main (41.1 g), and bottom (65.5 g) were obtained from the distillation. Similar results were obtained for the distillation of the other two products. GC-FID analysis of the main fraction showed 95 area % 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine).

[0184] The combined main fraction (126.8 g) from these three distillations was further purified using packed column distillation. A 1 inch ID, 20 inch long vacuum jacketed column was packed with 0.16 inch Pro-Pak random packing. A reflux splitter and condenser were attached to the top of the packed column. The reboiler (250 mL, 3-neck round bottom flask) was heated to 140° C. and the condenser was maintained at 22° C. The reflux ratio was set to 5:1 and a vacuum was applied to less than 5 Torr (less than 0.67 kPa). High purity 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) (91.8 g, 99.4 GC-FID area %) was collected at an overhead temperature of 117° C. and approximately 3 Torr (0.4 kPa).

[0185] Three reactions (Examples 23, 24, and 25) were carried out in a 2 L autoclave reactor. In each, 140 g of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal prepared as described in Example 1 was charged along with methanol (140 g) and Ni-5256P (31.5 g). The reductive amination reaction was carried out using ammonia (580.5 g, 30 equivalents). The reactor was pressurized to 600 psig (4136.9 kPa) with hydrogen. 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 1000 psig (6894.8 kPa). The reactions were carried out at 90°C for 3 hours. After the reactor was cooled to room temperature, the ammonia was vented. The reactor was then pressurized with 800 psig (5515.8 kPa) hydrogen and hydrogenation was carried out at 110°C. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed using a rotary evaporator. GC-FID analysis of the concentrated product showed an average 63 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) purity. Two replicate reactions were performed. The concentrated products from these three reactions were mixed and purified using short path distillation.

[0186] A typical short path distillation apparatus was used to separate the light and heavy fractions, resulting in a 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) main fraction. A total of 379 g of concentrated product from these three reactions was fed to a reboiler (500 mL, three-neck round bottom flask). The reboiler was set at 150° C. and maintained at a vacuum of less than 1 Torr (less than 0.13 kPa). After collecting 10.5 g of the light fraction, a new distillate receiver was switched to for the main fraction. The main fraction (259 g) was analyzed using GC-FID, which showed a purity of 90.3 wt% 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine). The bottoms fraction (94.4 g) contained high boilers and leached Ni catalyst.

[0187] The main fraction (259 g) from the short path distillation was the feed to the reboiler (500 mL, three-neck round bottom flask) for the packed column distillation. A vacuum jacketed column with 1 inch internal diameter and 20 inch length was packed with 0.16 inch Pro-Pak random packing. A multiple receiver system was used to collect several light fractions. The process conditions for the packed column distillation were a heating mantle powered with 85 W constant power, a vacuum of less than 1 Torr (less than 0.13 kPa), and a reflux ratio of 5:1. From this distillation, a 102 g sample of 99.6 wt% pure 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) (GC-FID assay) was obtained.

[0188] In this Example 26, a DP of 560 and a

[0189] [ka] A bis(propylaldehyde terminated) polydimethylsiloxane having the formula: where the subscript pp represents the average number of difunctional siloxane units per molecule and has a value of 558, was prepared as follows: 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 stir bar. The mixture was stirred on a stir 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 subsequently removed from the glove box. In a ventilated fume hood, the dimethylsiloxy (D) units (M) on average per molecule were analyzed. Vi 2 D 558 Bis-dimethylvinylsiloxy terminated polydimethylsiloxane (195.3 g, 4.68 mmol) with dimethylvinylsiloxy was charged 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 through a dip tube and carefully released three times through the valve connected to the head space. The reactor was then pressure tested by pressurizing to 300 psi (2068.4 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample load port. The reactor was pressurized to 100 psi (689.5 kPa) with syngas and then released three times before pressurizing to 80 psi (551.6 kPa) through a dip tube. The reaction temperature was set to 90° C. The agitation speed was set to 600 RPM. Once the desired temperature was reached, an intermediate cylinder containing syngas was connected to the reactor. The pressure was set at 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 as syngas was fed to the reactor through a pressure reducing regulator. The reaction was run for 4 hours. The resulting product contained bis(propylaldehyde terminated) polydimethylsiloxane with a DP of 560. The product was 1 H and 29 It was characterized by Si NMR.

[0190] In this Example 27, a compound of the formula:

[0191] [ka] A bis(3-aminopropyl) terminated poly(dimethylsiloxane) having a DP of 560 (where the subscript qq was 558) was prepared as follows: In a 300 mL autoclave reactor was added 10 mL of dipropionoterminated poly(dimethylsiloxane), (poly[oxy(dimethylsilylene)], α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy], or (C 2 H 6 OSi) n C 10 H 22 O 3 S 2 The reactor was charged with 5,2'-tetramethylphenylacetamide (90.0 g), toluene (63.7 g), and 5 wt. % Rh / C (4.5 g). The reactor was sealed and the headspace was inerted with nitrogen. The mixture was stirred at 800 rpm, ammonia (9.2 g) was added, and the mixture was stirred for 30 minutes. The reactor was pressurized to 250 psig (1723.7 kPa) with hydrogen and heated to 60° C. The reactor pressure was 340 psig (2344.2 kPa). The reactor pressure was increased to 716 psig (4936.7 kPa) with hydrogen and the reaction was run for 4 hours with continuous addition of hydrogen. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation to collect 83.9 g of product. The product was 29 Characterized by Si analysis, GPC, and viscosity. Octamethylcyclotetrasiloxane content was determined by GC analysis.

[0192] In this Example 28, the formula

[0193] [ka] where the subscript rr represents the average number of difunctional siloxane units per molecule and has a value of 328. (poly[oxy(dimethylsilylene)], α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy], or (C 2 H 6 OSi) n C 10 H 22 O 3 S 2 (wherein n=328) was prepared as follows: 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 stir bar. The mixture was stirred on a stir plate until a homogeneous solution was formed. A portion of this solution (1.5 g) was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, the dimethylsiloxy (D) units (M) of 328 on average per molecule were mixed together to obtain a 120 mL glass bottle. Vi 2 D 328Bis-dimethylvinylsiloxy terminated polydimethylsiloxane (196 g, 7.95 mmol) with dimethylvinylsiloxy was charged to 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 through a dip tube and carefully released three times through the valve connected to the head space. The reactor was then pressure tested by pressurizing to 300 psi (2068.4 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample load port. The reactor was pressurized to 100 psi (689.5 kPa) with syngas and then released three times before pressurizing to 80 psi (551.6 kPa) through a dip tube. The reaction temperature was set to 90° C. The agitation speed was set to 600 RPM. Once the desired temperature was reached, an intermediate cylinder containing syngas was connected to the reactor. The pressure was set at 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 as syngas was fed to the reactor through a pressure reducing regulator. The reaction was run for 4 hours. The resulting product contained bis(propylaldehyde terminated) polydimethylsiloxane with a DP of 330. 1 H and 29 It was characterized by Si NMR.

[0194] In this Example 29, the formula

[0195] [ka] (wherein the subscript ss represents the average number of difunctional siloxane units per molecule and has a value of 328), bis(3-aminopropyl)-terminated poly(dimethylsiloxane) poly[oxy(dimethylsilylene)], α-[(3-aminopropyl)dimethylsilyl]-ω-[[(3-aminopropyl)dimethylsilyl]oxy], or (C 2 H 6 OSi) n C 10 H 28 N 2 OSi 2(where n=approximately 330) was prepared as follows: A 300 mL autoclave reactor was charged with 90.6 g of dipropionaldehyde siloxane prepared as described in Example 28, toluene (60.3 g), and 5 wt. % Rh / C (4.5 g). The reactor was sealed and the headspace was inerted with nitrogen. The mixture was stirred at 800 rpm, ammonia (14.9 g) was added, and the mixture was stirred for 30 minutes. The reactor was pressurized to 233 psig (1606.5 kPa) with hydrogen and heated to 60° C. The reactor pressure was 317 psig (2185.6 kPa). The reactor pressure was increased to 728 psig (5019.4 kPa) with hydrogen and the reaction was run for 4 hours with continuous addition of hydrogen. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation to collect 83.4 g of product. 29 Characterized by Si NMR analysis, GPC, and viscosity. Octamethylcyclotetrasiloxane content was determined by GC analysis.

[0196] In this Example 30, 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 stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, vinylmethylbis(trimethylsiloxy)silane (MD ViM) (1000 g, 4.02 mol) was loaded into a 2 L autoclave reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi (689.5 kPa) with nitrogen through a dip tube and carefully released three times through the valve connected to the head space. The reactor was then pressure tested by pressurizing to 300 psi (2068.4 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi (689.5 kPa) with syngas and then released three times before pressurizing to 80 psi (551.6 kPa) through a dip tube. The reaction temperature was set at 75°C. Once the desired temperature was reached, with the agitation speed set at 800 RPM, an intermediate cylinder containing syngas was connected to the reactor. The pressure was set at 100 psi (689.5 kPa). The progress of the reaction was monitored by a data logger that measured the pressure in the intermediate cylinder as synthesis gas was fed to the reactor through a pressure reducing regulator. The resulting product was 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD Pr-ald Containing crude 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD Pr-ald A portion of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD) was purified by vacuum distillation. The vacuum distillation apparatus consisted of a 500 three-neck round bottom flask with a PTFE coated magnetic stir bar, an electric heating mantle with internal temperature controlled by a J-CHEM™ as measured by a thermoprobe, and a 12 inch (30.48 cm) Vigreux column connected to a 250 mL pre-tared collection flask. A vacuum manifold was connected to a system that included a vacuum gauge and a nitrogen line to regulate pressure and break vacuum. Water cooling was used on the distillate condenser, and a dry ice trap was placed between the distillation system and the diaphragm vacuum pump to capture lower boiling components. A thermometer was installed to measure the temperature of the overhead vapors. Crude 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MD) was purified by vacuum distillation. Pr-aldDistillation was carried out by charging 341.5 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MDM) to a 500 mL reboiler. The distillation was carried out at a pressure of 2 Torr (266.6 Pa). A light cut (13 g) was collected at a pot temperature of 76° C. and an overhead temperature of 66° C. Purified 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propanal (MDM) was obtained. Pr-ald A main fraction containing 243 g of dimethylformamide (M) was collected at a pot temperature of 80-85° C. and an overhead temperature of 67-69° C. 55 g of bottoms material was also collected.

[0197] In this Example 31, N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl)butan-1-amine was synthesized as follows: A 300 mL autoclave reactor was charged with 12.0 g of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal prepared as described in Example 30, toluene (48.5 g), n-butylamine (3.8 g), and 5 wt. % Rh / C (1.4 g). The reactor was sealed and the headspace was inerted with nitrogen. The mixture was stirred at 800 rpm for 5 minutes. The reactor was pressurized to 463 psig (3192.3 kPa) with hydrogen 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 run for 4 hours with continuous addition of hydrogen. The reactor was cooled and vented. The reaction product was collected and the reactor was rinsed with toluene to collect 75.2 g of material. A portion of the material was filtered through a syringe filter, stripped of solvent, and analyzed by gas chromatography as well as HPLC. 1 H and 13 Characterization was performed by C NMR analysis, which confirmed the presence of N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl)butan-1-amine.

[0198] In this Example 32, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propan-1-amine and N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl)butan-1-amine were synthesized as follows: A 300 mL autoclave reactor was charged with 11.7 g of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal prepared as described in Example 30, toluene (48.4 g), n-butylamine (3.9 g, 1.25 equiv.), and 5 wt. % Rh / C (1.2 g). The reactor was sealed and the headspace was inerted 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. The reactor was charged with hydrogen to 480 psig (3309.5 kPa) and hydrogen addition 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 run for 4 hours with continuous addition of hydrogen. The reactor was cooled and vented. 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, stripped of solvent, and analyzed by gas chromatography as well as HPLC. 1 H and 13 Characterization was performed using C NMR analysis, which revealed that 67.4 GC / FID area % of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propan-1-amine 18.6 GC / FID area % of N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl)butan-1-amine.

[0199] In this Example 33, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propan-1-amine was synthesized as follows: A 300 mL autoclave reactor was charged with 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal (12.1 g), toluene (48.4 g), and 5 wt. % Rh / C (1.3 g). The reactor was sealed and the headspace was inerted with nitrogen. Agitation at 800 rpm was started, ammonia (19.9 g, 26.9 equiv.) was added to the mixture, and the reactor pressure was 117 psig (806.7 kPa). The reaction was charged with hydrogen 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 to 463 psig (3192.3 kPa) with hydrogen and heated to 60° C. The reactor pressure was increased to 816 psig (5626.1 kPa) with hydrogen and the reaction was run for 4.5 hours with continuous addition of hydrogen. The reactor was cooled and vented. The desired product was collected to give 60.6 g of liquid. A portion of the liquid was filtered through a syringe filter, stripped of solvent, and analyzed by gas chromatography as well as HPLC. 1 H and 13 Characterization by C NMR and GC / FID analysis confirmed the presence of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propan-1-amine in the reaction product.

[0200] In this Example 34, N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl)-58,61-dimethyl-2,5,8,11,14,17,20,23,26,29,32,35,38,41,44,47,50,53,56,59,62-heneicosaoxapentahexacontan-64-amine (MDM-M1000) was prepared as follows. A 300 mL autoclave reactor was charged with 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal (21.1 g), isopropanol (41.4 g), Jeffamine™ M1000 (77.1 g), and 5 wt.% Rh / C (1.0 g). The reactor was sealed and the headspace inerted with nitrogen. The mixture was stirred at 900 rpm, and the reactor was pressurized to 105 psig (724 kPa) with hydrogen and heated to 60° C. Hydrogen was fed to a reactor pressure of 315 psig (2171.9 kPa) and the reaction was run for 4 hours with continuous addition of hydrogen. The reactor was cooled and sampled. An additional 5 wt. % Rh / C catalyst (1.0 g) was added and the reaction continued for 4 hours at 60° C. and 315 psig (2171.9 kPa) hydrogen pressure. The reactor was cooled and vented. The reaction product was filtered to remove the catalyst and the solvent was removed under vacuum using a rotary evaporator to give 82.6 g of product. 1 H, 29 Si, and 13 It was analyzed by C NMR analysis.

[0201] In this Example 35, N-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl)-7,10,13,16,19,22,25,28-octamethyl-2,5,8,11,14,17,20,23,26,29-decaoxadotriacontan-31-amine (MDM-M600) was prepared as follows: A 300 mL autoclave reactor was charged with 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal (25.0 g), isopropanol (50.0 g), Jeffamine™ M600 (54.7 g), and 5 wt. % Rh / C (1.3 g). The reactor was sealed and the headspace was inerted with nitrogen. The mixture was stirred at 900 rpm for 10 minutes and the reactor was pressurized with hydrogen to 102 psig (703.3 kPa) and heated to 60°C. Hydrogen was fed to a reactor pressure of 309 psig (2130.5 kPa) and the reaction was run for 4 hours with continuous addition of hydrogen. The reaction mixture was cooled and vented. The reaction product was filtered to remove the catalyst and the solvent was removed under vacuum using a rotary evaporator to give 67.9 g of product. 1 H, 29 Si, and 13 It was analyzed by C NMR analysis.

[0202] In this Example 36, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)dipropanal (M Pr-ald D 7 M Pr-ald ) was prepared as follows: In a nitrogen-filled glove box, Rh(acac)(CO) 2(9.3 mg, 0.0359 mmol), Ligand 1 (58.1 mg, 0.069 mmol), and heptane (10.0 g, 99.8 mmol) were added to a 30 mL glass vial using a magnetic stir bar. The mixture was stirred on a stir plate until a homogenous solution was formed. The solution was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)divinyl (M Vi D 7 M Vi ) (700 g, 1.027 mol) was charged into a 2 L autoclave reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi (689.5 kPa) with nitrogen through a dip tube and carefully released three times through the valve connected to the head space. The reactor was then pressure tested by pressurizing to 300 psi (2068.4 kPa) with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psi (689.5 kPa) with syngas and then released three times before pressurizing to 80 psi (551.6 kPa) through a dip tube. The reaction temperature was set at 70°C. Once the desired temperature was reached, the agitation speed was set at 800 RPM, and an intermediate cylinder containing syngas was connected to the reactor. The pressure was set at 100 psi (689.5 kPa). The progress of the reaction was monitored by a data logger that measured the pressure in the intermediate cylinder as synthesis gas was fed to the reactor through a pressure reducing regulator. The resulting product was 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)dipropanal (M Pr-ald D 7 M Pr-ald ) was contained.

[0203] In this Example 37, N,N'-((1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)bis(propane-3,1-diyl))bis(58,61-dimethyl-2,5,8,11,14,17,20,23,26,29,32,35,38,41,44,47,50,53,56,59,62-heneicosaoxapentahexacontan-64-amine) was prepared as follows: In a 300 mL autoclave reactor, 29.9 g of 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)dipropanal (M Pr-ald D 7 M Pr-ald ), isopropanol (54.9 g), Jeffamine™ M1000 (79.8 g), and 5 wt. % Rh / C (3.3 g). The reactor was sealed and the headspace inerted with nitrogen. The mixture was stirred at 900 rpm and the reactor was pressurized to 113 psig (779.1 kPa) with hydrogen and heated to 60° C. Additional hydrogen was fed to the reactor to reach a pressure of 315 psig (2171.9 kPa) and the reaction was run for 5 hours with continuous addition of hydrogen. The hydrogen pressure was increased to 400 psig (2757.9 kPa) and the reaction was continued for 23 hours. The reaction mixture was cooled and the reactor was vented. The reaction product was filtered to remove the catalyst and the solvent was removed under vacuum using a rotary evaporator to give 94.4 g of product. The product was 1 H, 29 Si, and 13 It was analyzed by C NMR analysis.

[0204] In this Example 38, a compound of the formula:

[0205] [ka] A bis(3-aminopropyl) terminated poly(dimethylsiloxane) having a DP of 560 (where the subscript qq was 558) was prepared as follows: In a glass container was added 100 mL of either dipropionoterminated poly(dimethylsiloxane), (poly[oxy(dimethylsilylene)], α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy], or (C 2 H 6 OSi) n C 10 H 22 O 3 S 2 Where n=558 (70.0 g) and toluene (71.0 g) were charged to form a solution. To this solution was charged n-butylamine (0.51 g, 2.1 eq) and mixed thoroughly. The mixture became cloudy. MgSO 4 (3.0 g) was added, mixed, and the mixture was held for 16 hours. The mixture was filtered and treated with MgSO 4 The liquid was removed to obtain 140 g of a transparent liquid. 1 Analysis by 1 H NMR confirmed the presence of butylimine.

[0206] In a 300 mL autoclave reactor, was added either the diimine-terminated siloxane prepared in Example 38, (poly[oxy(dimethylsilylene)], α-[dimethyl(3-(butylimino)propylsilyl]-ω-[[dimethyl(3-(butylimino)propylsilyl]oxy], or (C 2 H 6 OSi) n C 18 H 40 O 3 N 2 S 2The reactor was charged with 140 g of 5 wt.% Rh / C (3.5 g), where n=558, and 1.0 g of 5 wt.% Rh / C. The reactor was sealed and the headspace was inerted 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 to 259 psig (1785.7 kPa) with hydrogen and heated to 60° C. The reactor pressure was 290 psig (1999.5 kPa). The reactor pressure was increased to 790 psig (5446.9 kPa) with hydrogen and the reaction was run for 4 hours with continuous addition of hydrogen. The reactor was cooled and vented. The reaction product was collected, filtered to remove the catalyst, and the solvent was removed by rotary evaporation to collect 70.7 g of product. 29 Si and 1 It was characterized by 1 H NMR analysis.

[0207] In this Example 39, poly[oxy(dimethylsilylene)] having a DP of 203, α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy], or (C 2 H 6 OSi) n C 10 H 22 O 3 S 2 where n=201 was prepared by hydroformylation reaction of a bis-vinyl terminated polydimethylsiloxane with a DP of 203 using the procedure described above.

[0208] In this Example 40, a compound of the formula:

[0209] [ka] A siloxane having a DP of 203 (where the subscript qq was 201) was prepared as follows: In a nitrogen glove box, 5.000 g of (poly[oxy(dimethylsilylene)], α-[dimethyl(3-oxopropyl)silyl]-ω-[[dimethyl(3-oxopropyl)silyl]oxy] from Example 39, or (C 2 H6 OSi) n C 10 H 22 O 3 S 2 (where n=201), 88 μL of ethylenediamine (Sigma Aldrich), 0.2508 g of 5% Rh / C (Sigma Aldrich), and 18.723 g of 2-propanol (anhydrous, Sigma Aldrich) were added to a 60 mL wide-mouth vial. The vial was inverted and shaken until visibly homogenous, then transferred to a fume hood where the viscous slurry was dumped into the bottom of a 100 mL Parr reactor. Once the reactor was sealed and all connections were made, the reactor was inerted using nitrogen and leak checked at 550 psig (3792.1 kPa). The reactor was deemed leak-free and the reactor was heated to 90° C., which was achieved within 10 minutes. Hydrogen was added 30 minutes after heating / stirring began. A stable reactor pressure of 30 psig (206.8 kPa) was observed and the hydrogen mass flow controller was set to 430 psig (400 psig H 2 )(2964.8kPa, (2757.9kPa H 2 The reactor was kept stirring and heated for 2 hours before cooling and venting. After cooling the reactor and purging the headspace with nitrogen, the reactor was opened in the fume hood and 21.13 g of reaction material was collected in a glass vial. The collected material was filtered through a 2 inch (5.08 cm) plug of powdered celite to remove the catalyst and the vial / column was rinsed twice with about 12 mL of propanol. An aliquot of the filtered material was concentrated for preliminary proton, carbon, and silicon NMR analysis. The remainder was then concentrated and placed under high vacuum to remove residual propanol and stirred slowly while heated to 60° C. After 1 day under vacuum the sample weighed 2.4082 g, but NMR analysis indicated the presence of the siloxane with a DP of 203 shown above and some residual propanol.

[0210] [ka]

[0211] In this Example 41, 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 (31.6 mg), Ligand 1 (165.2 mg), and toluene (40.02 g) were combined to form a homogeneous solution. A portion of this catalyst solution (2.88 g) was transferred to an airtight syringe equipped with a metal valve and subsequently 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 charged to a 300 mL pressure reactor. The reactor was sealed. With stirring at 600 RPM, the reactor was pressurized to 100 psig with nitrogen through a dip tube and carefully released through a valve connected to the headspace. This process was repeated three times for reactor headspace inerting. The reactor was then pressure tested by pressurizing to 300 psig with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psig with syngas and then released three times before pressurizing to 100 psig through a dip tube. An intermediate cylinder containing syngas was connected to the reactor. The reaction temperature was set to 65°C and then increased to 70°C. The stirring speed was set to 600 RPM. The pressure was set to 100 psig. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. After 18 hours, 2.5 g of additional catalyst solution was added. After an additional 24 h reaction time, a conversion rate of over 99% was observed. 1 The ratio was determined to be 4.5 to 1 by 1 H NMR analysis.

[0212] In this example 42, the synthesis of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propan-1-amine was carried out as follows. In a nitrogen purged glove box, a 1,2-dichlorophenyl ether (1,2-dichlorophenyl ether) of the formula (1,2-dichlorophenyl ether), prepared as described above in Example 41, having an approximate linear to branched ratio of 4:1, was prepared.

[0213] [ka] Aldehyde (6 g) containing 5% Ru / C (0.3 g, 5 wt%) was added to a glass vial and then diluted with methanol (28 mL). The mixture was shaken and transferred to an open Parr reactor. The reactor was sealed and then connected to associated heating / cooling / agitation / venting / thermocouple / pressure transducer / knockout pot. The reactor was pressurized / vented three times using low pressure nitrogen (approximately 35 psig) followed by leak checking of the reactor and associated ancillary equipment using high pressure (approximately 550 psig) nitrogen. The reactor was considered leak-free if a pressure drop of less than 3 psig / min was observed. The 30 minute inter-addition time was defined by the time between the start of heating (immediately after the ammonia addition was completed) and the first hydrogen addition. Generally, the reactor was at the heat set point 5-10 minutes after the ammonia addition was completed. The reactor timer was started when hydrogen was added and the reactor maintained pressure / temperature and added hydrogen as needed until the run timer had elapsed. The reaction temperatures are the reaction set points, with the first temperature of 60° C. referring to the temperature maintained between ammonia addition (approximately 60 equivalents) and after hydrogen addition, and the second temperature of 105° C. referring to the temperature set point established after the hydrogen pressure is achieved at the initial set point.

[0214] After 2 hours, the reactor was turned off the heat and began to cool. Cooling was accomplished via an internal cooling coil fed with DI water and continued until below 30°C or until the operator began depressurizing the reactor. Once the reactor pressure was below 10 psig, low pressure nitrogen was used to sweep the reactor and purge to the exhaust line for 5 minutes. At this point, the reactor was isolated and opened to manually collect the reaction product. The reaction product was collected in a fume hood and additional reaction solvent was used if the reaction product did not move easily. An equal or greater volume of solvent rinse was used to wash the reactor and in some cases, an alternative solvent was used for subsequent washes.

[0215] The reaction product was filtered through Celite™ and then concentrated under reduced pressure for NMR analysis. 6 Prepare samples using 150-200 mg of material in 0.04 M CrAcAc in benzene-d for silicon spectrum acquisition. 6 Samples were prepared at higher concentrations using solution. In cases where the samples concentrated by rotary evaporation were not clear (e.g., contained residual catalyst) or the NMR peaks were broad, the samples were filtered and transferred to an NMR tube. 3-(1,1,1,5,5,5-Hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propan-1-amine formation was confirmed by NMR.

[0216] In this Example 43, 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)-N-methylpropan-1-amine was prepared using a procedure similar to that of Example 42, in which two different batches of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propanal were used, with linear to branched isomer ratios of 4:1 and 5:1 (as determined by proton NMR). In a nitrogen purged glovebox, the aldehyde (50 g) and Ni 5256 (5 g, 10 wt%) were added to a glass vial and then combined with a solution of methylamine (35.3 g, 8 eq, 33 wt% in ethanol). No additional solvent was added. The resulting solution was stirred in the glove box for an unspecified time (generally less than 10 minutes) and transferred to an open Parr reactor. Three reaction batches of 50 g each of starting aldehyde were carried out in a 300 mL reactor. All three were analyzed by NMR and GC before mixing and concentration. After concentration, approximately 125 g of crude reaction product was collected, which was analyzed before distillation. The crude sample was a light sea-green color.

[0217] The crude reaction product was filtered and distilled using a packed bed with Propak distillation packing (2.5 cm x 29 cm) to give a main product fraction of 57.06 g at 0.5 Torr and an overhead temperature of 75-80° C. NMR analysis confirmed the presence of 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)-N-methylpropan-1-amine.

[0218] In this Example 44, the formula: M 0.24 M プロパナールアルデヒド 0.14 T Ph 0.62T-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 of this catalyst solution (5.8 g) was transferred to an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M dissolved in toluene (90 g) was 0.24 M Vi 0.14 T Ph 0.62 (90 g) was loaded into a 300 mL pressure reactor. The reactor was sealed. With stirring at 600 RPM, the reactor was pressurized to 100 psig with nitrogen through a dip tube and carefully released through a valve connected to the headspace. This process was repeated three times for reactor headspace inerting. The reactor was then pressure tested by pressurizing to 300 psig with nitrogen. After releasing the pressure, the catalyst solution was added to the reactor through the sample loading port. The reactor was pressurized to 100 psig with syngas and then released three times before pressurizing to 100 psig through a dip tube. The reaction temperature was set to 70° C. The stirring speed was set to 600 RPM. Once the desired temperature was reached, the reactor was connected to an intermediate cylinder containing syngas. The pressure was set to 100 psig. The progress of the reaction was monitored by a data logger that measured the pressure in the 300 mL intermediate cylinder as syngas was fed to the reactor through a pressure reducing regulator. The final product 1 More than 99% conversion, as determined by H NMR analysis, was observed after 16 h. Removal of the toluene afforded the product of formula M 0.24 M プロパンアルデヒド 0.14 T Ph 0.62 The product of T-phenylpropanal remained as a viscous liquid.

[0219] M 0.24 M プロピルアミン 0.139 T Ph 0.52 Synthesis of In this Example 45, 25.8 g of M0.24 M プロパナールアルデヒド 0.14 T Ph 0.62 was charged into a glass round bottom flask. THF solvent (51.6 g) was added to form a solution. N-butylamine (2.55 g, 1.1 equiv.) was added to the solution while stirring with a PTFE coated magnetic stir bar. MgSO 4 MgSO was added to adsorb water from the solution. 4 The N-butylimine functionalized phenylsilsesquioxane resin was removed by filtration to obtain a solution containing the corresponding N-butylimine functionalized phenylsilsesquioxane resin. The imine-containing solution was charged to a 300 mL autoclave reactor along with 5% Ru / C catalyst (2.6 g). The reactor was sealed and the headspace was inerted with nitrogen. Ammonia (8.3 g, approximately 15 equivalents) was added and the reactor was pressurized to 530 psig with hydrogen. The reactor was heated to 80° C. and hydrogen was added until the pressure was 880 psig. The reductive amination was carried out at 80° C., 880 psig, and 800 RPM for 18.5 hours. The reactor was cooled and vented. The reductive amination 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 reaction product. The concentrated product was 1 H and 13 As determined by C NMR, the formula M 0.24 M プロピルアミン 0.14 T Ph 0.62 of propylamine functional phenyl silsesquioxane resin.

[0220] Industrial Applicability The above working examples show that a variety of aldehyde-functional organosilicon compounds can be successfully used to form amino-functional organosilicon compounds using the process described herein. The process described herein is flexible in that it can prepare a wide variety of polymeric polyorganosiloxanes and organosilicon small molecules with pendant and / or terminal amino functional groups. In addition, the process can have one or more of the following advantages: low cost, simple process, low temperature below 150°C (less likely to decompose sensitive molecules, lower capital cost, safer), minimal by-products, almost complete recovery of heterogeneous catalyst. In addition, the process described herein can provide one or more of the additional advantages of producing high purity amino-functional organosilicon compounds with little or no side reactions, and has easy post-treatment to recover amino-functional organosilicon compounds (e.g., simple filtration and distillation to recover heterogeneous catalyst). It is also believed that the process can provide less or no salt by-product streams, short reaction times, and / or low cyclic siloxane by-product production than conventional condensation reaction processes. Furthermore, the hydroformylation and reductive amination can be carried out in one single reactor without the need to isolate intermediates and with minimal process steps.

[0221] Without wishing to be bound by theory, it is believed that another advantage of the present invention is that the amino-functional organosilicon compound produced has a high proportion of linear amino functional groups, and this is because the aldehyde-functional organosilicon compound with branched aldehyde moieties reacts and decomposes during the process described herein, thereby allowing them to be easily removed.In addition, the amino-functional organosilicon compound produced can have reduced cyclic siloxane (e.g., octamethylcyclotetrasiloxane, D4) content compared to the amino-functional organosilicon compound produced via condensation chemistry using carboxylic acid catalyst or equilibration chemistry using base catalyst.

[0222] Definitions and Use of Terms All amounts, ratios, and percentages are by weight unless otherwise specified. The amounts of all starting materials in the composition total 100% by weight. The Summary and Abstract are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more, unless otherwise indicated by the context of the specification. The singular includes the plural unless otherwise indicated. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in Sections §2111.03 I., II., and III of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. Abbreviations used herein have the definitions in Table Z.

[0223] [Table 4]

[0224] The following test methods were used herein: FTIR: The concentration of silanol groups present in polyorganosiloxane resins (e.g., polyorganosilicate resins and / or silsesquioxane resins) was determined using 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 was equipped with three columns, a PL Gel 5 μm, 7.5×50 mm guard column, and two PL Gel 5 μm, Mixed-C 7.5×300 mm columns. Calibration was performed using polystyrene standards. Samples were made by dissolving polyorganosiloxanes in toluene (approximately 1 mg / mL), and then the solution was immediately analyzed by GPC (flow rate of 1 mL / min, column temperature of 35° C., run time of 25 minutes). 29Si NMR: The alkenyl content of the starting material (B) can be measured by the techniques described in "The Analytical Chemistry of Silicones," edited by A. Lee Smith, Vol. 112 of Chemical Analysis, John Wiley & Sons, Inc. (1991). Viscosity: Viscosity can be measured, for example, for polymers (e.g., certain (B2) alkenyl-functional polyorganosiloxanes and (E2) aldehyde-functional polyorganosiloxanes) having a viscosity of 120 mPa·s to 250,000 mPa·s on a Brookfield DV-III cone & plate viscometer equipped with a #CP-52 spindle at 25°C and 0.1 to 50 RPM. Those skilled in the art will recognize that as the viscosity increases, the rotation speed decreases and that appropriate spindles and rotation speeds can be selected.

[0225] The mixture of the aldehyde-functional organosilicon compound and the reductive amination reaction product from the above examples is 1 H, 13 C NMR and 29 The conversion and yield in the above examples were mainly analyzed by Si NMR, GC / MS, GPC, and viscosity. 1 The results were based on 1 H NMR data.

[0226] EMBODIMENTS OF THE PRESENT DISCLOSURE In a first embodiment, the process for preparing an amino-functional organosilicon compound comprises: 1) combining starting materials under conditions to catalyze a hydroformylation reaction, the starting materials being: (A) a gas containing hydrogen and carbon monoxide; (B) an alkenyl-functional organosilicon compound; and (C) a rhodium / bisphosphite ligand complex catalyst, wherein the bisphosphite ligand is represented by the formula

[0227] [ka] wherein R 6 and R 6’ are each independently selected from the group consisting of hydrogen, an alkyl group of 1 to 20 carbon atoms, a cyano group, a halogen group, and an alkoxy group of 1 to 20 carbon atoms; R 7 and R 7’ each independently represents an alkyl group having 3 to 20 carbon atoms, and a group of the formula -SiR 17 3 wherein each R 17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms; R 8 , R 8’ , R 9 , and R 9’ are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group; R 10 , R 10’ , R 11 , and R 11’ are each independently selected from the group consisting of hydrogen or and alkyl groups, thereby forming a hydroformylation reaction product comprising (E) an aldehyde-functional organosilicon compound; 2) combining starting materials under conditions to catalyze a reductive amination reaction, the starting materials including (E) an aldehyde-functional organosilicon compound, (F) an amine source, (G) a hydrogenation catalyst, (H) hydrogen, and optionally, (J) a solvent, and optionally, (K) an adsorbent, thereby forming a reaction product including an amino-functional organosilicon compound.

[0228] In a second embodiment, in the process of the first embodiment, the starting material (B) is a compound represented by the formula (B1): R A x SiR 4 (4-x) wherein each R A is an independently selected alkenyl group of 2 to 8 carbon atoms, and each R 4is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscript x is 1-4.

[0229] In a third embodiment, in the process of the first embodiment or the second embodiment, the alkenyl-functional organosilicon compound has the unit formula: (R 4 3 SiO 1 / 2 ) a (R 4 2 R A SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h wherein each R A is an independently selected alkenyl group of 2 to 8 carbon atoms, and each R 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 5 wherein each R 5are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (B2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has values ​​such that 0≦h / (e+f+g)≦1.5, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

[0230] In a fourth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is cyclic and (R 4 R A SiO 2 / 2 ) d (wherein the subscript d is 3 to 12), (R 4 2 SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d (wherein c is >0 to 6, and d is 3 to 12), and combinations thereof.

[0231] In a fifth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is linear and has the unit formula (B3): (R 4 3 SiO 1 / 2 ) a (R 4 2 R A SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R 4 R A SiO 2 / 2 ) d where the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2.

[0232] In a sixth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is represented by the unit formula: (R 4 3 SiO 1 / 2 ) mm (R 4 2 R A SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h where the subscripts mm, nn, and oo represent the mole percent of each unit in the polyorganosilicate resin, 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.

[0233] In a seventh embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is represented by the unit formula: (R 4 3 SiO 1 / 2 ) a (R 4 2 R A SiO 1 / 2 ) b (R 4 2 SiO 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 wherein 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である。

[0234] In an eighth embodiment, in the process of the third embodiment, subscripts b=2, a=c=d=e=f=h=0, and the alkenyl-functional organosilicon compound is

[0235] [ka] Includes.

[0236] In the ninth embodiment, in any one of the processes of the third to eighth embodiments, each R A is independently selected from the group consisting of vinyl, allyl, and hexenyl.

[0237] In the tenth embodiment, in any one of the processes of the third to ninth embodiments, each R 4 is independently selected from the group consisting of methyl and phenyl.

[0238] In an eleventh embodiment, in the process of any one of the first to tenth embodiments, in the bisphosphite ligand, R 6 and R 6’ are each selected from the group consisting of a methoxy group and a t-butyl group; R 7 and R 7’ are each a t-butyl group, and R 8 , R 8’ , R 9 , R 9’ , R 10 , R 10’ , R 11 , and R 11’ are each hydrogen.

[0239] In a twelfth embodiment, in the process of any one of the first to eleventh embodiments, starting material (C) is present in an amount sufficient to provide from 0.1 ppm to 300 ppm Rh, based on the combined weight of starting materials (A), (B), and (C).

[0240] In a thirteenth embodiment, in the process of any one of the first to twelfth embodiments, the starting material (C) has a molar ratio of bisphosphite ligand / Rh of 1 / 1 to 10 / 1.

[0241] In a fourteenth embodiment, in the process of any one of the first to thirteenth embodiments, the conditions of step 1) are: i) a temperature of 30° C. to 150° C.; ii) a pressure of 101 kPa to 6,895 kPa; iii) a CO / H ratio in the synthesis gas of 3 / 1 to 1 / 3. 2 and iv) a combination of two or more of conditions i), ii), and iii).

[0242] In a fifteenth embodiment, in the process of any one of the first to fourteenth embodiments, (C) the rhodium / bisphosphite ligand complex catalyst is formed by combining a rhodium precursor with a bisphosphite ligand to form a rhodium / bisphosphite ligand complex, and combining the rhodium / bisphosphite ligand complex with starting material (A) using heating prior to step 1).

[0243] In a sixteenth embodiment, the aldehyde-functional organosilicon compound prepared by the process of the first or second embodiment has the formula (E1): R Ald x SiR 4 (4-x) where each R Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R 4 is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscript x is 1-4.

[0244] In a seventeenth embodiment, the aldehyde-functional organosilicon compound prepared by the process of the first or second embodiment has the unit formula (E2-1): (R 4 3 SiO 1 / 2 ) a (R4 2 R Ald SiO 1 / 2 ) b (R 4 2 SiO 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 wherein each R Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 5 wherein each R 5 are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (E2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has values ​​such that 0≦h / (e+f+g)≦1.5, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

[0245] In an eighteenth embodiment, in the process of the seventeenth embodiment, the aldehyde-functional polyorganosiloxane is cyclic and (R 4 R Ald SiO 2 / 2 ) d (wherein the subscript d is 3 to 12), (R 4 2 SiO 2 / 2 ) c (R4 R Ald SiO 2 / 2 ) d (wherein c is >0 to 6, and d is 3 to 12), and combinations thereof.

[0246] In a nineteenth embodiment, in the process of the seventeenth embodiment, the aldehyde-functional polyorganosiloxane is linear and has the unit formula (E3): (R 4 3 SiO 1 / 2 ) a (R 4 2 R Ald SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R 4 R Ald SiO 2 / 2 ) d where the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2.

[0247] In a twentieth embodiment, in the process of the seventeenth embodiment, the aldehyde-functional polyorganosiloxane is represented by the unit formula: (R 4 3 SiO 1 / 2 ) mm (R 4 2 R Ald SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h where the subscripts mm, nn, and oo represent the mole percent of each unit in the polyorganosilicate resin, 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.

[0248] In a twenty-first embodiment, in the process of the seventeenth embodiment, the aldehyde-functional polyorganosiloxane is represented by the unit formula: (R 4 3 SiO 1 / 2 ) a (R 4 2 R Ald SiO 1 / 2 ) b (R 4 2 SiO 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 where 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である。

[0249] In a twenty-second embodiment, in the process of the seventeenth embodiment, the aldehyde-functional polyorganosiloxane is branched and has the unit formula: R Ald SiR 12 3 wherein each R 12 is R 13 and -OSi(R 14 ) 3 Each R 13 is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 15 is R 13 , -OSi(R 16 ) 3 , and -[OSiR13 2 ] ii OSiR 13 3 Each R 16 is R 13 and -[OSiR 13 2 ] ii OSiR 13 3 where subscript ii has a value such that 0≦ii≦100, with the proviso that R 12 At least two of -OSi(R 14 ) 3 This is subject to the condition that:

[0250] In a twenty-third embodiment, in the process of the seventeenth embodiment, subscripts b=2, a=c=d=e=f=h=0, and the aldehyde functional organosilicon compound is

[0251] [ka] Includes.

[0252] In the twenty-fourth embodiment, in any one of the processes of the seventeenth to twenty-third embodiments, each R Ald is independently selected from the group consisting of propylaldehyde, butyraldehyde, and heptylaldehyde.

[0253] In the 25th embodiment, in any one of the processes of the 17th to 24th embodiments, each R 4 is independently selected from the group consisting of methyl and phenyl.

[0254] In a twenty-sixth embodiment, the process of any one of the first through twenty-fifth embodiments further comprises recovering the aldehyde-functional organosilicon compound prior to step 2).

[0255] In a twenty-seventh embodiment, in the process of any one of the first to twenty-sixth embodiments, the (F) amine source is represented by the formula (F1): R 18 NH 2 wherein R 18 is an alkyl group of 1 to 18 carbon atoms.

[0256] In a twenty-eighth embodiment, in the process of any one of the first to twenty-seventh embodiments, the (F) amine source comprises (F2) ammonia.

[0257] In a twenty-ninth embodiment, in the process of any one of the first to twenty-sixth embodiments, the (F) amine source comprises (F3) a polyetheramine.

[0258] In a thirtieth embodiment, in the process of any one of the first to twenty-ninth embodiments, the (F) amine source comprises an (F4) diamine.

[0259] In a thirty-first embodiment, in the process of any one of the first to thirtieth embodiments, 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 thereof.

[0260] In a thirty-second embodiment, in the process of the thirty-first embodiment, the heterogeneous hydrogenation catalyst comprises a metal selected from the group consisting of Co, Cu, Ni, Pd, Pt, Rh, Ru, and combinations of two or more thereof.

[0261] In a thirty-third embodiment, in the process of the thirty-second embodiment, the heterogeneous hydrogenation catalyst comprises Co, Ni, or Rh.

[0262] In a thirty-fourth embodiment, in step 2) of the process of any one of the first to thirty-third embodiments, the amount of hydrogenation catalyst is 1% to 50% by weight, based on the weight of the aldehyde-functional organosilicon compound.

[0263] In the 35th embodiment, in step 2) of the process of any one of the first to 34th embodiments, H 2 The pressure is 10 psig (68.9 kPa) to 1500 psig (10342 kPa).

[0264] In a thirty-sixth embodiment, in step 2) of the process of the thirty-fifth embodiment, H 2 The pressure is 200 psig (1379 kPa) to 1200 psig (8274 kPa).

[0265] In the thirty-seventh embodiment, in step 2) of the process of any one of the first to thirty-sixth embodiments, the temperature is 0°C to 200°C.

[0266] In a thirty-eighth embodiment, in step 2) of the process of the thirty-seventh embodiment, the temperature is from 50°C to 150°C.

[0267] In a thirty-ninth embodiment, the process of any one of the first to thirty-eighth embodiments further comprises pretreating the hydrogenation catalyst prior to step 2).

[0268] In a fortieth embodiment, the process of any one of the first through thirty-ninth embodiments further comprises 3) recovering the amino-functional organosilicon compound from the reaction product after step 2).

[0269] In a forty-first embodiment, in the process of the second embodiment, the amino functional organosilicon compound is represented by the formula: R N x SiR 4 (4-x) wherein each R N are independently selected expressions

[0270] [ka] G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms, and each R 19 is R 18 , H, DNH 2 wherein D is a divalent hydrocarbyl group, and a polyether group; 4 is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscript x is 1-4.

[0271] In a forty-second embodiment, in the process of the second embodiment, the amino-functional organosilicon compound is represented by the unit formula: 4 3 SiO 1 / 2 ) a (R 4 2 R N SiO 1 / 2 ) b (R 4 2 SiO 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 wherein each R N are independently selected expressions

[0272] [ka] G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms, and each R 19 is R 18 , H, D-DNH 2wherein D is a divalent hydrocarbyl group, and a polyether group; 4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R 5 wherein each R 5 are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (E2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has values ​​such that 0≦h / (e+f+g)≦1.5, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

[0273] In a forty-third embodiment, in the process of the forty-second embodiment, the amino-functional polyorganosiloxane is cyclic and (R 4 R N SiO 2 / 2 ) d (wherein the subscript d is 3 to 12), (R 4 2 SiO 2 / 2 ) c (R 4 R N SiO 2 / 2 ) d wherein c is >0-6 and d is 3-12.

[0274] In a forty-fourth embodiment, in the process of the forty-second embodiment, the amino-functional polyorganosiloxane is linear and has the unit formula: (R 4 3 SiO 1 / 2 ) a (R 4 2 R N SiO 1 / 2 ) b (R 42 SiO 2 / 2 ) c (R 4 R N SiO 2 / 2 ) d where the quantity (a+b)=2, the quantity (b+d)≧1, and the quantity (a+b+c+d)≧2.

[0275] In a forty-fifth embodiment, in the process of the forty-second embodiment, the amino-functional polyorganosiloxane is represented by the unit formula: (R 4 3 SiO 1 / 2 ) mm (R 4 2 R N SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h where the subscripts mm, nn, and oo represent the mole percent of each unit in the polyorganosilicate resin, 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.

[0276] In a forty-sixth embodiment, in the process of the forty-second embodiment, the amino-functional polyorganosiloxane is represented by the unit formula: (R 4 3 SiO 1 / 2 ) a (R 4 2 R N SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R 4 R N SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (R N SiO 3 / 2 ) f (ZO1 / 2 ) h wherein 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である。

[0277] In a forty-seventh embodiment, in the process of the forty-second embodiment, the amino functional organosilicon compound is

[0278] [ka] where R N is as defined above and each R 13 is a monovalent hydrocarbon group selected from alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms.

[0279] In a forty-eighth embodiment, in the process of the forty-fourth embodiment, the amino-functional organosilicon compound is represented by the unit formula: (R 4 2 R N SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) m (R 4 R N SiO 2 / 2 ) n , Unit formula: (R 4 3 SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) o (R 4 R N SiO 2 / 2 ) p or a combination thereof, wherein each R is 4 and R Nis as above, m is 0 or a positive number, and n is 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.

[0280] In a forty-ninth embodiment, in the process of the forty-eighth embodiment, the linear amino-functional polyorganosiloxane has the formula:

[0281] [ka] wherein each R 2’’ are independently N and R 4 wherein R N and R 4 is as above, and the subscript z is 0 to 48.

[0282] In a fifty-first embodiment, in the process of the forty-ninth embodiment, the linear amino-functional polyorganosiloxane has the formula:

[0283] [ka] wherein R 4 and R N is as stated above.

[0284] In a fifty-first embodiment, in the process of the forty-second embodiment, the amino-functional polyorganosiloxane is branched and has the general formula: R N SiR 12 3 wherein R N is as above, and each R 12 is R 13 and -OSi(R 14 ) 3 Each R 13is a monovalent hydrocarbon group, and each R 14 is R 13 , -OSi(R 15 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 15 is R 13 , -OSi(R 16 ) 3 , and -[OSiR 13 2 ] ii OSiR 13 3 Each R 16 is R 13 and -[OSiR 13 2 ] ii OSiR 13 3 where the subscript ii has a value such that 0≦ii≦100.

[0285] In a fifty-second embodiment, in the process of the fifty-first embodiment, the amino-functional polyorganosiloxane is

[0286] [ka] (In the formula, R N and R 15 is as above),

[0287] [ka] (In the formula, R N , R 13 , and R 15 is as above), and

[0288] [ka] (In the formula, R N, R 13 , and R 15 is as defined above).

[0289] In a fifty-third embodiment, in the process of the fifty-second embodiment, the amino-functional polyorganosiloxane is

[0290] [ka] wherein R 19 is as stated above.

[0291] In a fifty-fourth embodiment, in the process of the forty-second embodiment, the amino-functional organosilicon compound is represented by the unit formula: (R 4 3 SiO 1 / 2 ) q (R 4 2 R N SiO 1 / 2 ) r (R 4 2 SiO 2 / 2 ) s (SiO 4 / 2 ) t wherein R 4 and R N where the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity as measured by a rotational viscometer of >170 mPa s.

[0292] In a fifty-fifth embodiment, in the process of the fifty-fourth embodiment, the amino-functional organosilicon compound is a compound having the unit formula [R N R 4 2 Si-(O-SiR 4 2 ) x -O] (4-w) -Si-[O-(R 4 2SiO) v SiR 4 3 ] w wherein R N and R 4 where the subscripts v, w, and x have values ​​such that 200≧v≧1, 2≧w≧0, and 200≧x≧1.

[0293] In a fifty-sixth embodiment, in the process of the forty-second embodiment, the amino-functional organosilicon compound is represented by the unit formula: (R 4 3 SiO 1 / 2 ) aa (R N R 4 2 SiO 1 / 2 ) bb (R 4 2 SiO 2 / 2 ) cc (R N R 4 SiO 2 / 2 ) ee (R 4 SiO 3 / 2 ) dd wherein R 4 and R N is as above, with subscript aa≧0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee≧0.

[0294] In the 57th embodiment, in any one of the processes of the 41st embodiment to the 56th embodiment, each R N is, independently, -(C 3 H 6 )NH 2 , -(C 4 H 8 )NH 2 , -(C 2 H 4 )N(H)(C 2 H 5 ), -(C 3 H 6 )N(H)(C 2 H 5), -(C 4 H 8 )N(H)(C 2 H 5 ), -(C 2 H 4 )N(H)(C 3 H 7 ), -(C 3 H 6 )N(H)(C 3 H 7 ), -(C 4 H 8 )N(H)(C 3 H 5 ), -(C 2 H 4 )N(H)(C 4 H 9 ), -(C 3 H 6 )N(H)(C 4 H 9 ), -(C 4 H 8 )N(H)(C 4 H 9 ), -(C 2 H 4 )N(H)(C 2 H 4 O) jj (C 3 H 6 O) kk (H), -(C 3 H 6 )N(H)(C 2 H 4 O) jj (C 3 H 6 O) kk (H), and -(C 4 H 8 )N(H)(C 2 H 4 O) jj (C 3 H 6 O) kk (H), wherein the subscripts jj≧0, kk≧0, and the quantity (jj+kk) is selected from the group consisting of R N is sufficient to give a molecular weight of 600 g / mol to 3000 g / mol, alternatively 600 g / mol to 1000 g / mol.

[0295] In the 58th embodiment, in any one of the processes of the 41st embodiment to the 57th embodiment, each R 4 is independently selected from the group consisting of methyl and phenyl.

Claims

1. A process for preparing an amino-functional organosilicon compound, said process comprising: I) combining starting materials under conditions to catalyze a reductive amination reaction, said starting materials having the formula: 【Chemistry 1】 wherein G is a divalent hydrocarbon group free of aliphatic unsaturation having from 2 to 8 carbon atoms, with an amine source, a hydrogenation catalyst, hydrogen, and optionally a solvent, thereby forming a reaction product comprising said amino-functional organosilicon compound.

2. The aldehyde-functional organosilicon compound has the formula: R Ａｌｄ ｘ SiR ４ （４－ｘ） wherein each R Ａｌｄ is independently selected from the group consisting of propylaldehyde, butyraldehyde, and heptylaldehyde; ４ are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and subscript x is 1 to 4.

3. A process for preparing an amino-functional organosilicon compound, the process comprising: I) combining starting materials under conditions to catalyze a reductive amination reaction, the starting materials comprising an aldehyde-functional organosilicon compound, an amine source, a hydrogenation catalyst, hydrogen, and optionally a solvent, thereby forming a reaction product comprising the amino-functional organosilicon compound; The aldehyde-functional organosilicon compound has the unit formula: (R ４ ３ SiO １／２ ) ａ (R ４ ２ R Ａｌｄ SiO １／２ ) ｂ (R ４ ２ SiO 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 wherein each R Ａｌｄ are independently selected aldehyde groups of 3 to 9 carbon atoms, and each R ４ is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R ５ wherein each R ５ are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent the number of each unit in said unit formula and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, subscript g≧0; and subscript h has values ​​such that 0≦h / (e+f+g)≦1.5, 10,000≧(a+b+c+d+e+f+g)≧2, and the quantity (b+d+f)≧1.

4. The aldehyde-functional polyorganosiloxane is i) (R ４ R Ａｌｄ SiO ２／２ ) ｄ (wherein the subscript d is 3 to 12), (R ４ ２ SiO ２／２ ) ｃ (R ４ R Ａｌｄ SiO ２／２ ) ｄ wherein c is 0 to 6 and d is 3 to 12, and combinations thereof; ii) Unit formula: (R ４ ３ SiO １／２ ) ａ (R ４ ２ R Ａｌｄ SiO １／２ ) ｂ (R ４ ２ SiO ２／２ ) ｃ (R ４ R Ａｌｄ SiO ２／２ ) ｄ wherein the number (a+b)=2, the number (b+d)≧1, and the number (a+b+c+d)≧2; iii) Unit formula: (R ４ ３ SiO １／２ ) ｍｍ (R ４ ２ R Ａｌｄ SiO １／２ ) ｎｎ (SiO ４／２ ) ｏｏ (ZO １／２ ) ｈ wherein the subscripts mm, nn, and oo represent the mole percentage of each unit in said polyorganosilicate resin, 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; iv) Unit formula: (R ４ ３ SiO １／２ ) ａ (R ４ ２ R Ａｌｄ SiO １／２ ) ｂ (R ４ ２ SiO 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 wherein 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; v) Formula: R Ａｌｄ SiR １２ ３ wherein each R １２ is R １３ and -OSi(R １４ ) ３ and each R １３ is a monovalent hydrocarbon group, and each R １４ is R １３ , -OSi(R １５ ) ３ , and -[O SiR １３ ２ ] ｉｉ OSiR １３ ３ and each R １５ is R １３ , -OSi(R １ ６ ) ３ , and -[OSiR １３ ２ ] ｉｉ OSiR １３ ３ and each R １６ is R １ ３ and -[OSiR １３ ２ ] ｉｉ OSiR １３ ３ where subscript ii has a value such that 0≦ii≦100, with the proviso that R １２ At least two of the groups are —OSi(R １４ ) ３ 4. The process of claim 3, wherein the branched aldehyde-functional polyorganosiloxane is selected from the group consisting of:

5. Subscript b=2 and a=c=d=e=f=g=h=0, and said aldehyde-functional organosilicon compound is 【Chemistry 2】 4. The process of claim 3, comprising:

6. Each R Ａｌｄ 4. The process of claim 3, wherein is independently selected from the group consisting of propyl aldehyde, butyraldehyde, and heptyl aldehyde.

7. Each R ４ 3. The process of claim 2, wherein is independently selected from the group consisting of methyl and phenyl.

8. Prior to step I), the method further comprises forming said aldehyde-functional organosilicon compound by a process comprising combining starting materials under conditions to catalyze a hydroformylation reaction, said starting materials comprising: (A) a gas containing hydrogen and carbon monoxide; (B) an alkenyl-functional organosilicon compound; and (C) a rhodium / bisphosphite ligand complex catalyst, wherein the bisphosphite ligand is represented by the formula 【Transformation 3】 wherein R ６ and R ６’ are each independently selected from the group consisting of hydrogen, an alkyl group of 1 to 20 carbon atoms, a cyano group, a halogen group, and an alkoxy group of 1 to 20 carbon atoms; R ７ and R ７’ each independently represents an alkyl group of 3 to 20 carbon atoms, and a group of the formula -SiR １７ ３ wherein each R １７ is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms; R ８ , R ８’ , R ９ , and R ９’ are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group; R １０ , R １０’ , R １１ , and R １１’ are each independently selected from the group consisting of hydrogen or and alkyl groups, thereby forming a hydroformylation reaction product comprising said aldehyde-functional organosilicon compound.

9. 9. The process of claim 8, further comprising recovering the aldehyde-functional organosilicon compound prior to step I).

10. (F) the amine source is (F1) Formula: R １８ NH ２ (In the formula, R １８ is an alkyl group of 1 to 18 carbon atoms; (F2) ammonia, (F3) polyetheramines, (F4) Formula H ２ N-D-NH ２ wherein D is a divalent hydrocarbyl group, and (F5) A combination of two or more of (F1), (F2), (F3), and (F4).

11. 6. The process of any one of claims 1 to 5, 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 thereof.

12. The process of any one of claims 1 to 5, wherein the amount of the hydrogenation catalyst is from less than 1 to 50 weight percent based on the weight of the aldehyde-functional organosilicon compound.

13. In step I), one or both of the conditions (i) and (ii) are satisfied, and the condition (i) is H ２ The process of any one of claims 1 to 5, wherein the pressure is from 10 psig (68.9 kPa) to 1500 psig (10,342 kPa) and condition (ii) is the temperature is from 0°C to 200°C.

14. The process of any one of claims 1 to 5, further comprising pretreating the hydrogenation catalyst prior to step I).

15. II) The process of any one of claims 1 to 5, further comprising recovering said amino-functional organosilicon compound from said reaction product during and / or after step I).

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