PREPARATION OF ORGANOSILICON COMPOUNDS WITH CARBOXY FUNCTIONALITY

Abstract

An organosilicon compound with carboxy-functional groups is prepared. An oxidation process in which an aldehyde-functional organosilicon compound and an oxygen source are combined produces the carboxy-functional organosilicon compound.

Claims

1. A process for preparing a carboxy-functional organosilicon compound, the process comprising: forming an aldehyde-functional organosilicon compound before step I) by a process comprising combining, under conditions to catalyze hydroformylation reaction, 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, where the bisphosphite ligand has formula ##STR00049## where R.sup.6 and R.sup.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.sup.7 and R.sup.7 are each independently selected from the group consisting of an alkyl group of 3 to 20 carbon atoms, and a group of formula SiR.sup.17.sub.3, where each R.sup.17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms; R.sup.8, R.sup.8, R.sup.9, and R.sup.9 are each independently selected form the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group, and R.sup.10, R.sup.11, and R.sup.11 are each independently selected from the group consisting of hydrogen or and alkyl group; thereby forming a hydroformylation reaction product comprising the aldehyde-functional organosilicon compound; and thereafter I) combining, under conditions to conduct oxidation reaction, starting materials comprising the aldehyde-functional organosilicon compound and an oxygen source, thereby forming an oxidation reaction product comprising the carboxy-functional organosilicon compound.

2. The process of claim 1, where the aldehyde-functional organosilicon compound comprises an aldehyde-functional silane of formula: R.sup.Ald.sub.xSiR.sup.4.sub.(4-x), where each R.sup.Ald is an independently selected aldehyde group of 3 to 9 carbon atom having formula ##STR00050## where G is a linear or branched divalent hydrocarbon group of 2 to 8 carbon atoms that is free of aliphatic unsaturation; each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and an hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4.

3. The process of claim 1, where the aldehyde-functional organosilicon compound comprises an aldehyde-functional polyorganosiloxane of unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.c(R.sup.AldSiO.sub.3/2).sub.f(SiO.sub.4/2).sub.g(ZO.sub.1/2).sub.h; where each R.sup.Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R.sup.5, where each R.sup.5 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; subscripts a, b, c, d, e, f, and g represent numbers of each unit in the unit formula and have values such that subscript a0, subscript b0, subscript c0, subscript d0, subscript e0, subscript f0, subscript g0; and subscript h has a value such that 0h/(e+f+g)1.5, with the proviso that when e=f=g=0, then h0; 10,000(a+b+c+d+e+f+g)2, and a quantity (b+d+f)1.

4. The process of claim 3, where the aldehyde-functional polyorganosiloxane is selected from the group consisting of: i) a cyclic aldehyde-functional polyorganosiloxane having a unit formula selected from the group consisting of (R.sup.4R.sup.AldSiO.sub.2/2).sub.d, where subscript d is 3 to 12; (R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d, where c is >0 to 6 and d is 3 to 12; and a combination thereof; ii) a linear aldehyde-functional polyorganosiloxane comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d, where a quantity (a+b)=2, a quantity (b+d)1, and a quantity (a+b+c+d)2; iii) an aldehyde-functional polyorganosilicate resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.mm(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.nn(SiO.sub.4/2).sub.oo(ZO.sub.1/2).sub.h, where subscripts mm, nn, and oo represent mole percentages of each unit in the polyorganosilicate resin; and subscripts mm, nn and oo have average values such that mm0, nn0, oo>0, and 0.5(mm+nn)/oo4; iv) an aldehyde-functional silsesquioxane resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.c(R.sup.AldSiO.sub.3/2).sub.f(ZO.sub.1/2).sub.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; v) a branched aldehyde-functional polyorganosiloxane comprising unit formula: R.sup.AldSiR.sup.12.sub.3, where each R.sup.12 is selected from R.sup.13 and OSi(R.sup.14).sub.3; where each R.sup.13 is a monovalent hydrocarbon group; where each R.sup.14 is selected from R.sup.13, OSi(R.sup.15).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.15 is selected from R.sup.13, OSi(R.sup.16).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.16 is selected from R.sup.13 and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; and where subscript ii has a value such that 0ii100, with the proviso that at least two of R.sup.12 are OSi(R.sup.14).sub.3; vi) a Q branched aldehyde-functional polyorganosiloxane oligomer comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.q(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.r(R.sup.4.sub.2SiO.sub.2/2).sub.s(SiO.sub.4/2).sub.t, where subscripts q, r, s, and t have average values such that 2q0, 4r0, 995s4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity>170 mPa.Math.s measured by rotational viscometry (as described below with the test methods) to the Q branched polyorganosiloxane; and vii) a T branched aldehyde-functional polyorganosiloxane comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.aa(R.sup.AldR.sup.4.sub.2SiO.sub.1/2).sub.bb(R.sup.4.sub.2SiO.sub.2/2).sub.cc(R.sup.AldR.sup.4SiO.sub.2/2).sub.ee(R.sup.4SiO.sub.3/2).sub.dd, where subscript aa0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee0.

5. The process of claim 2, where each R.sup.Ald is independently selected from the group consisting of propyl aldehyde, butyl aldehyde, and heptyl aldehyde.

6. The process of a claim 2, where each R.sup.4 is independently selected from the group consisting of methyl and phenyl.

7. The process of claim 1, further comprising: II) equilibrating the carboxy-functional organosilicon compound with a cyclic polydiorganosiloxane in the presence of an equilibration catalyst.

8. The process of claim 1, further comprising recovering the aldehyde-functional organosilicon compound before step I).

9. The process of claim 1, were the oxygen source is selected from the group consisting of air, oxygen gas, and a peroxide compound.

10. The process of claim 9, where the oxygen source is used at a partial pressure from 3 psia (20 kPa) to 100 psia (690 kPa).

11. The process of claim 1, where the starting materials in step I) further comprise an additional material selected from the group consisting of an oxidation reaction catalyst, a solvent, and both the oxidation reaction catalyst and the solvent.

12. The process of claim 11, where the oxidation reaction catalyst is present and comprises a transition metal complex comprising a metal selected from the group consisting of Co, Cu, Mn, Ni, Rh, and a combination of two or more thereof.

13. The process of claim 11, where the oxidation reaction catalyst is present and comprises an organocatalyst comprising N-hydroxy functionality.

14. The process of claim 11, where the oxidation reaction catalyst is present in an amount of 0.001 to 1 mole % based on moles of aldehyde-functional groups from the aldehyde-functional organosilicon compound.

15. The process of claim 11, where the solvent is present and is selected from the group consisting of a ketone, an ester, a carboxylic acid, an aliphatic hydrocarbon, an aromatic hydrocarbon, and a combination of two or more thereof.

16. The process of claim 2, where the carboxy-functional organosilicon compound comprises a carboxy-functional silane of formula: R.sup.Car.sub.xSiR.sup.4.sub.(4-x), where each R.sup.Car is an independently selected carboxy-functional group of 3 to 9 carbon atoms; each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and an hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4.

17. The process of claim 3, where the carboxy-functional organosilicon compound comprises a carboxy-functional polyorganosiloxane of unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.CarSiO.sub.3/2).sub.f(SiO.sub.4/2).sub.g (ZO.sub.1/2).sub.h; where each R.sup.Car is an independently selected carboxy-functional group of 3 to 9 carbon atoms, and each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R.sup.5, where each R.sup.5 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; subscripts a, b, c, d, e, f, and g represent numbers of each unit in the unit formula and have values such that subscript a0, subscript b0, subscript c0, subscript d0, subscript e0, subscript f0, subscript g0; and subscript h has a value such that 0h/(e+f+g)1.5, with the proviso that when e=f=g=0, then h0, 10,000(a+b+c+d+e+f+g)2, and a quantity (b+d+f)1.

18. The process of claim 17, where the carboxy-functional polyorganosiloxane is selected from the group consisting of: i) a cyclic carboxy-functional polyorganosiloxane having a unit formula selected from the group consisting of (R.sup.4R.sup.CarSiO.sub.2/2).sub.d, where subscript d is 3 to 12; (R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d, where c is >0 to 6 and d is 3 to 12; ii) a linear carboxy-functional polyorganosiloxane comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d, where a quantity (a+b)=2, a quantity (b+d)1, and a quantity (a+b+c+d)2; iii) a carboxy-functional polyorganosilicate resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.mm(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.nn(SiO.sub.4/2).sub.oo(ZO.sub.1/2).sub.h, where subscripts mm, nn, and oo represent mole percentages of each unit in the polyorganosilicate resin; and subscripts mm, nn and oo have average values such that mm0, nn0, oo>0, and 0.5(mm+nn)/oo4; iv) a carboxy-functional silsesquioxane resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.CarSiO.sub.3/2).sub.f(ZO.sub.1/2).sub.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; and a branched carboxy-functional polyorganosiloxane comprising unit formula: R.sup.CarSiR.sup.12.sub.3, where each R.sup.12 is selected from R.sup.13 and OSi(R.sup.14).sub.3; where each R.sup.13 is a monovalent hydrocarbon group; where each R.sup.14 is selected from R.sup.13, OSi(R.sup.15).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.15 is selected from R.sup.13, OSi(R.sup.16).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.16 is selected from R.sup.13 and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; and where subscript ii has a value such that 0ii100, with the proviso that at least two of R.sup.12 are OSi(R.sup.14).sub.3; v) a Q branched carboxy-functional polyorganosiloxane oligomer comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.q(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.r(R.sup.4.sub.2SiO.sub.2/2).sub.s(SiO.sub.4/2).sub.t, where subscripts q, r, s, and t have average values such that 2q0, 4r0, 995s4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity>170 mPa.Math.s measured by rotational viscometry (as described below with the test methods) to the Q branched polyorganosiloxane; and vi) a T branched carboxy-functional polyorganosiloxane comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.aa(R.sup.CarR.sup.4.sub.2SiO.sub.1/2).sub.bb(R.sup.4.sub.2SiO.sub.2/2).sub.cc(R.sup.CarR.sup.4SiO.sub.2/2).sub.ee(R.sup.4SiO.sub.3/2).sub.dd, where subscript aa0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee0.

19. The process of claim 1, where step I) is conducted at a temperature of 0 to 100 C.

20. The process of claim 1, where step I) is conducted in the presence of UV radiation.

Description

EXAMPLES

[0119] These examples are provided to illustrate the invention to one of ordinary skill in the art and should not be construed to limit the scope of the invention set forth in the claims. Starting Materials used in the examples are described below in Table 1.

TABLE-US-00001 TABLE 1 Starting Materials Type Name Chemical Description Source Solvent Toluene C.sub.7H.sub.8 Fisher Chemical Solvent Heptane C.sub.7H.sub.16 Fisher Chemical Solvent 3-pentanone CH.sub.3CH.sub.2COCH.sub.2CH.sub.3 Sigma- Aldrich Catalyst N-hydroxyphthalimide C.sub.8H.sub.5NO.sub.3 Sigma- Aldrich Cyclosiloxane D4 DSC Hydroformylation (Acetylacetonato) Rh(acac)(CO)2 Unknown Catalyst dicarbonylrhodium(I) Precursor Ligand 1 6,6-[[3,3,5,5-tetrakis(1,1- TDCC dimethylethyl)-1,1-biphenyl]-2,2- diyl]bis(oxy)]bis-dibenzo[d,f] [1,3,2]dioxaphosphepin Vinylsiloxane vinylmethylbis(trimethylsiloxy)silane MD.sup.ViM DSC 1 Vinylsiloxane 1,3-divinyltetramethyldisiloxane M.sup.ViM.sup.Vi DSC 2 Vinylsiloxane 2,4,6,8-Tetramethyl-2,4,6,8- D.sup.Vi.sub.4 DSC 3 tetravinylcyclotetrasiloxane Vinylsiloxane 3,3- M.sup.ViD.sub.7M.sup.Vi DSC 4 (1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15, 17,17-octadecamethylnonasiloxane- 1,17-diyl)divinyl Vinylsiloxane Bis-trimethylsioxy-terminated MD.sub.8.2 D.sup.vi.sub.3.7M DSC 5 poly(dimethyl/methylvinyl)siloxane with an average, per molecule, of 8.2 dimethyl siloxy units and an average of 3.7 methylvinylsiloxy units Vinylsiloxane Bis-dimethylvinylsiloxy-terminated M.sup.Vi.sub.2D.sub.180 DSC 6 polydimethylsiloxane with average DP = 180 5-((1,1,1,3,5,5,5- Si10 Vi Synthesized heptamethyltrisiloxan-3-yl)oxy)- internally 1,1,1,3,7,9,9,9-octamethyl-3,7- at DSC, bis((trimethylsilyl)oxy)-5- using the vinylpentasiloxane synthesis described above 5-((1,1,1,3,5,5,5- Si10 Hex Synthesized heptamethyltrisiloxan-3-yl)oxy)-5- internally (hex-5-en-1-yl)-1,1,1,3,7,9,9,9- at DSC, octamethyl-3,7- using the bis((trimethylsilyl)oxy)pentasiloxane synthesis described above Vinylsiloxane Bis-dimethylvinylsiloxy-terminated M.sup.Vi.sub.2D.sub.329 DSC 7 polydimethylsiloxane with an average of 329 dimethylsiloxy (D) units per molecule Vinylsiloxane Bis-dimethylvinylsiloxy-terminated M.sup.Vi.sub.2D.sub.25 DSC 8 polydimethylsiloxane with an average of 25 dimethylsiloxy (D) units per molecule Vinylsiloxane Bis-dimethylvinylsiloxy-terminated M.sup.Vi.sub.2D.sub.77 DSC 16 polydimethylsiloxane with an average of 77 dimethylsiloxy (D) units per molecule Vinyl Silane 1 Vinyltrimethylsilane Me.sub.3SiCHCH.sub.2 Gelest Vinyl Ethoxydimethyl(vinyl)silane Me.sub.2Si(OEt)Vi Gelest Alkoxysilane 1 Aldehyde- 3-(1,1,1,3,5,5,5- MD.sup.Pr-AldM, Synthesis siloxane 1 heptamethyltrisiloxan-3-yl)propanal C10H26O3Si3 Example 1, below. Aldehyde- 3,3-(1,1,3,3-tetramethyldisiloxane- M.sup.Pr-AldM.sup.Pr-Ald, Synthesis siloxane 2 1,3-diyl)dipropanal C10H22O3Si2 Example 2, below. Aldehyde- Tetrapropanal- D.sup.Pr-Ald.sub.4, Synthesis siloxane 3 tetramethylcyclotetrasiloxane C16H32O8Si4 Example 3, below. Aldehyde- Propylaldehyde terminated PDMS M.sup.Pr-aldD.sub.7M.sup.Pr-ald Synthesis siloxane 4 (DP = 7) Example 7 Aldehyde- Hydroformylation products of MD.sub.8.2D.sup.Pr-ald.sub.3.7M Synthesis siloxane 5 MD.sub.8.2D.sup.vi.sub.3.7M Example 9 Aldehyde- Propyl-aldehyde terminated PDMS M.sup.Pr-ald.sub.2D.sub.180 Synthesis siloxane 6 (DP = 180) Example 8 Aldehyde- Propyl-aldehyde terminated PDMS M.sup.Pr-ald.sub.2D.sub.329 Synthesis siloxane 7 (DP = 329) Example 10 Aldehyde- Propyl-aldehyde terminated PDMS M.sup.Pr-ald.sub.2D.sub.25 Synthesis siloxane 8 (DP = 25) Example 11 Aldehyde- Propyl-aldehyde terminated PDMS M.sup.Pr-ald.sub.2D.sub.77 Synthesis siloxane 9 (DP = 77) Example 12 Aldehyde- (M.sub.2T).sub.3T Propionaldehyde See Synthesis siloxane Example 13 Aldehyde- (M.sub.2T).sub.3T heptanealdehyde See Synthesis siloxane Example 14 Hexenyl- Q branched-hexenyl-siloxane Q-(D.sub.36M.sup.hex)4 Synthesis siloxane Example 4, below. Allyl-Siloxane Allyl terminated PDMS (DP = 102) Synthesis Example 5, below. Vi-MQ resin DOWSIL 6-3444, Resin of unit Methyl- and vinyl- DSC formula functional (Me.sub.3SiO.sub.1/2).sub.40(Me.sub.2ViSiO.sub.1/2).sub.4(SiO.sub.4/2).sub.56 polyorganosilicate resin with an average of 40 trimethylsiloxy (M) units, 4 dimethylvinylsiloxy (MVi) units and 56 tetrasiloxy units per molecule Aldehyde-MQ Hydroformylation products of MQ Synthesis resin resin (DOWSIL 6-3444 Int) Example 6. D4 Octamethylcyclotetrasiloxane (Me.sub.2SiO.sub.2/2).sub.4 DSC Acid DOWEX DR-2030 Acid ion exchange TDCC Equilibration resin Catalyst 1 Acid Triflic Acid CF.sub.3SO.sub.3H Sigma- Equilibration Aldrich Catalyst 2 Aldehyde 3-(ethoxydimethylsilyl)propanal Me.sub.2Si(OEt)CH.sub.2CH.sub.2CHO, Synthesis Alkoxysilane 1 C7H16O2Si Example 15 Aldehyde 3-(trimethylsilyl)propanal Me.sub.3SiCH.sub.2CH.sub.2CHO Synthesis Silane 1 Example 16. Oxidant 1 3-chloroperbenzoic acid C.sub.7H5ClO.sub.3 Sigma- Aldrich Oxidant 2 Tert-butyl peroxide C.sub.8H.sub.18O.sub.2 Sigma- Aldrich Oxidant 3 Tert-butyl hydroperoxide (5-6M in Hydroperoxide Sigma- decane) formula: C.sub.4H.sub.10O.sub.2 Aldrich

[0120] In this Synthesis Example 1, the procedure for making 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal (Aldehyde siloxane 1) was performed as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (6.7 mg, 0.026 mmol), Ligand 1 (30.2 mg, 0.0360 mmol) and toluene (5.0 g, 0.054 mmol) were added into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, vinylmethylbis(trimethylsiloxy)silane (20.2 g, 81.2 mmol) and the toluene (57.7 g, 627 mmol) were loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized 80 psi via the dip-tube. Reaction temperature was set to 90 C. Agitation rate was set to 500 RPM. The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi. The reaction progress was monitored by a data logger which measured the pressure in the 300 ml intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. N/I ratio was determined by .sup.1H NMR analysis of the final product.

[0121] In this Synthesis Example 2, the procedure for making 3,3-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal (Aldehyde siloxane 2) was performed as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (18.1 mg, 0.0699 mmol), Ligand 1_(88.0 mg, 0.105 mmol) and toluene (5.0 g, 0.054 mmol) were added into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, 1,3-divinyltetramethyldisiloxane (44.8 g, 240 mmol) and the toluene (40.0 g, 488 mmol) were loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized 80 psi via the dip-tube. Reaction temperature was set to 90 C. Agitation rate was set to 500 RPM. The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi. The reaction progress was monitored by a data logger which measured the pressure in the 300 ml intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. N/I ratio was determined by .sup.1H NMR analysis of the final product.

[0122] In this Synthesis Example 3, the procedure for making Tetrapropanal-tetramethylcyclotetrasiloxane (Aldehyde siloxane 3) was performed as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (5.9 mg, 0.019 mmol), Ligand 1 (28.6 mg, 0.0341 mmol) and toluene (5.0 g, 0.054 mmol) were added into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, 2,4,6,8-Tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (45.0 g, 130 mmol) and the toluene (40.0 g, 488 mmol) were loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized 80 psi via the dip-tube. Reaction temperature was set to 90 C. Agitation rate was set to 500 RPM. The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi. The reaction progress was monitored by a data logger which measured the pressure in the 300 ml intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. N/I ratio was determined by .sup.1H NMR analysis of the final product.

[0123] In this Synthesis Example 4, the syntheses of Q branched hexenyl polyorganosiloxane polymers were performed as follows:

A. Synthesis of Hexenyl Neopentamer

##STR00026##

[0124] In a typical procedure, a 500 ml multi-neck reactor was equipped with a thermocouple, overhead stirrer, nitrogen-sweep and a dean-stark trap with condenser. The reactor was charged with 1,3-di-5-hexenyl-1,1,3,3-tetramethyldisiloxane (78.84 g, 0.26 mol, 0.55 equivalent) and acetic acid (129.7 g, 2.16 mol, 4.5 equivalent) were charged into and purged with overhead nitrogen. Triflic acid (0.3089 g, 2.1 mmol, 0.1 wt %) was added dropwise into the reactor using a syringe. Then the mixture in the reactor was stirred and heated to 45 C. under N.sub.2. Tetraethoxysilane (TEOS, 100 g, 0.48 mol, 1 equivalent) was added dropwise into the reaction mixture via an addition funnel and the reaction mixture temperature maintained at 45-50 C. during TEOS addition. After TEOS addition was done, the reaction proceeded at 80 C. until the reaction was complete. The reaction was monitored by GC-MS. The reaction mixture was cooled down to room temperature after reaction was complete, followed by washing with DI water twice, saturated NaHCO.sub.3 solution three times and DI water twice again. The raw product was dried over anhydrous Na.sub.2SO.sub.4 and then stripped at 180 C. to remove the residual volatiles. A pale yellow oil was obtained (yield=88%).

B. Synthesis of Q-branched Hexenyl Polyorganosiloxane Q-(D.sub.36M.sup.hex)4

##STR00027##

or more

[0125] In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (75.5 mg, 0.292 mmol), Ligand 1(489.1 mg, 0.58 mmol) and toluene (10.0 g, 0.108 mmol) were added into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, Q-branched hexenyl siloxane (150 g, 13.59 mmol) was loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized 80 psi via the dip-tube. Reaction temperature was set to 70 C. Agitation rate was set to 600 RPM. The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi. The reaction progress was monitored by a data logger which measured the pressure in the 300 ml intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. N/I ratio was determined by .sup.1H NMR analysis of the final product.

[0126] In this Synthesis Example 5, Allyl-Siloxane described in Table 1 was prepared as follows: In a typical procedure, a 500 ml multi-neck reactor was equipped with a thermocouple, overhead stirrer, nitrogen-sweep and a dean-stark trap with condenser. The reactor was charged with 1,3-diallyltetramethyldisiloxane(13.81 g, 64.38 mmol, 1 equivalent) and octamethylcyclotetrasiloxane (D4, 487 g, 1.64 mol, 25.5 equivalent) and purged with overhead nitrogen. The mixture in the reactor was stirred and heated to 140 C. under nitrogen atmosphere and dilute potassium silanolate (10 wt % in D4, 1.2809 g) was then added into the reactor. The reaction proceeded at 140 C. for 4 hours and was monitored by offline NMR. When the reaction was complete, octylsilyl phosphonate (2.5 wt % in D4, 2.967 g) was added into the reactor to neutralize the reaction. Then the heat was turned off to allow the reactor to cool to ambient temperature. The final Allyl-Siloxane was obtained by stripping off the volatile cyclics under vacuum.

[0127] In this Synthesis Example 6, Aldehyde-MQ resin described in Table 1 was prepared as follows: In a nitrogen filled glovebox, Rh(acac)(CO)2 (3.8 mg, 0.0147 mmol), Ligand 1 (27.28 mg, 0.0325 mmol) and toluene (5.0 g, 57.9 mmol) were added into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, vinyl-MQ resin (DOWSIL 6-3444 Int) (37.5 g) and the toluene (112.5 g, 1.22 mol) were loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized 80 psi via the dip-tube. Reaction temperature was set to 70 C. Agitation rate was set to 500 RPM. The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi. The reaction progress was monitored by a data logger which measured the pressure in the 300 ml intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. N/I ratio was determined by .sup.1H NMR analysis of the final product.

[0128] In this Synthesis Example 7, 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.sup.Pr-aldD.sub.7M.sup.Pr-ald) was prepared as follows. In a nitrogen filled glovebox, Rh(acac)(CO).sub.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 into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe 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.sup.ViD.sub.7M.sup.Vi) from DSC (700 g, 1.027 mol) was loaded to a 2-L Autoclave-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized 80 psi via the dip-tube. Reaction temperature was set to 70 C. Agitation rate was set to 800 RPM The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi. The reaction progress was monitored by a data logger which measured the pressure in the intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. The resulting product contained 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.sup.Pr-aldD.sub.7M.sup.Pr-ald), Aldehyde-siloxane 4 in Table 1.

[0129] In this Synthesis Example 8, M.sup.Vi.sub.2D.sub.180, was hydroformylated to form M.sup.Pr-aldD.sub.180M.sup.Pr-ald, as follows. In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (0.0050 g), Ligand 1 (0.0326 g) and toluene (5.0 g) were added into a 60 mL vial with a magnetic stir bar. The mixture was stirred at RT on a stir plate until a homogeneous solution was formed. The solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M.sup.Vi.sub.2D.sub.180 (200 g) from DSC was loaded to the Parr-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa) below the desired pressure via the dip-tube. Reaction temperature was set to 70 C. Heater and agitation were turned on. The 300 mL intermediate cylinder containing the syngas for the reaction and the reactor were connected when the desired temperature was reached. Pressure drop from a 300 mL intermediate cylinder was used to monitor the reaction progress and was recorded by a data logger. Full conversion of vinyl groups was observed after 3.5 hours reaction time as monitored by .sup.1H NMR.

[0130] In this Synthesis Example 9, MD.sub.8.2 D.sup.Pr-Ald.sub.3.7M was synthesized as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (0.0191 g), Ligand 1 (0.1324 g) and toluene (76.74 g) were added into a 125 mL bottle with a magnetic stir bar. The mixture was stirred at room temperature on a stir plate until a homogeneous solution was formed. 3.65 g of the solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, MD.sub.8.2D.sup.vi.sub.3.7M (180 g) from DSC was loaded to the Parr-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa) below the desired pressure via the dip-tube. Reaction temperature was set to 70 C. Heater and agitation were turned on. The 300 mL intermediate cylinder containing the syngas for the reaction and the reactor were connected when the desired temperature was reached. Pressure drop from a 300 mL intermediate cylinder was used to monitor the reaction progress and was recorded by a data logger. Full conversion of vinyl groups was observed after 24 hours reaction time as monitored by .sup.1H NMR.

[0131] In this Synthesis Example 10, hydroformylation of Vinylsiloxane 7, M.sup.vi.sub.2D.sub.329, was performed, as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (0.380 g), Ligand 1 (2.45 g) and toluene (90 g) were added into a 125 mL vial with a magnetic stir bar. The mixture was stirred at RT on a stir plate until a homogeneous solution was formed. Then 8.6 g of the solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M.sup.vi.sub.2D.sub.329 (1394 g) was loaded to a 2 liter Autoclave-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa) below the desired pressure via the dip-tube. Reaction temperature was set to 90 C. Heater and agitation were turned on. The cylinder containing the syngas for the reaction and the reactor were connected when the desired temperature was reached. A mass flow totalizer was used to monitor the reaction progress. Full conversion of vinyl groups was observed after stirring overnight as determined by .sup.1H NMR; M.sup.Pr-Ald.sub.2D.sub.329 formed.

[0132] In this Example 11, hydroformylation of Vinylsiloxane 8, M.sup.Vi.sub.2D.sub.25, was performed, as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (0.0252 g), Ligand 1 (1.63 g) and toluene (50 g) were added into a 125 mL vial with a magnetic stir bar. The mixture was stirred at RT on a stir plate until a homogeneous solution was formed. The solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M.sup.Vi.sub.2D.sub.25 (1000 g) was loaded to a 2 liter Autoclave-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa) below the desired pressure via the dip-tube. Reaction temperature was set to 80 C. Heater and agitation were turned on. The cylinder containing the syngas for the reaction and the reactor were connected when the desired temperature was reached. A mass flow totalizer was used to monitor the reaction progress. Full conversion of vinyl groups was observed after 2 hours reaction time as monitored by .sup.1H NMR; M.sup.Pr-Ald.sub.2D.sub.25 formed.

[0133] In this Synthesis Example 12, hydroformylation of Vinylsiloxane 16, M.sup.Vi.sub.2D.sub.77, was performed, as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (0.0050 g), Ligand 1 (0.0227 g) and toluene (30.09 g) were added into a 60 mL vial with a magnetic stir bar. The mixture was stirred at RT on a stir plate until a homogeneous solution was formed. The solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, M.sup.Vi.sub.2D.sub.77 (140.12 g) and toluene (46.92 g) were loaded to the Parr-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa) below the desired pressure via the dip-tube. Reaction temperature was set to 90 C. Heater and agitation were turned on. The 300 mL intermediate cylinder containing the syngas for the reaction and the reactor were connected when the desired temperature was reached. Pressure drop from a 300 mL intermediate cylinder was used to monitor the reaction progress and was recorded by a data logger. Full conversion of vinyl groups was observed after 10 hours reaction time as monitored by .sup.1H NMR; M.sup.Pr-Ald.sub.2D.sub.77 formed.

[0134] In this Synthesis Example 13, hydroformylation of a branched oligomer was performed as follows:

##STR00028##

In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (15.1 mg, 0.0583 mmol), Ligand 1 (76.4 mg, 0.0911 mmol) and toluene (7.49 g, 0.0814 mmol) were added into a 30 mL glass vial with a magnetic stir bar. The mixture was stirred on a stir plate until a homogeneous solution formed. This solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, 5-((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)-5-vinylpentasiloxane (145.0 g, 189.2 mmol) was loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace for three times. The reactor was then pressure tested by pressurizing to 300 psi (2068 kPa) with nitrogen. After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psi (689 kPa) and then released for three times prior to being pressurized to 80 psi (552 kPa) via the dip-tube. Reaction temperature was set to 100 C. Agitation rate was set to 500 RPM. The intermediate cylinder containing syngas and the reactor were connected when the desired temperature was reached. The pressure was set to 100 psi (689 kPa). The reaction progress was monitored by a data logger which measured the pressure in the 300 mL intermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator. >98% conversion was observed after 200 minutes. N/I ratio was determined by .sup.1H NMR analysis of the final product.

[0135] In this Synthesis Example 14, hydroformylation of a branched oligomer was performed as follows:

##STR00029##

In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (25.5 mg, 0.0984 mmol), Ligand 1 (122.3 mg, 0.1457 mmol) and toluene (5.0 g) were added into a 30 mL vial with a magnetic stir bar. The mixture was mixed on a magnetic stir plate until a homogeneous solution formed. The solution was transferred to an air-tight syringe with a metal valve and removed from the glove box. In a fume hood, Si10 Hex (100.0 g, 121.6 mmol) was added to the Parr reactor. The reactor was sealed and loaded into the holder. The reactor was pressurized with nitrogen up to 100 psi (690 kPa) via the dip-tube and was carefully released through headspace for three times. After pressure testing, the catalyst solution was added to the reactor. The reactor was pressurized with syngas to 100 psi and then released for three times prior to being pressurized to 80 psi via the dip-tube. Agitation and heating were initiated. The intermediate cylinder containing syngas and the reactor were connected when the reaction reached 110 C. The pressure of the intermediate cylinder was monitored by a data logger. After the reaction was done, the reactor was purged with nitrogen for three times and the material was transferred to a glass container as a colorless liquid, which turned light yellow over time.

[0136] In this Synthesis Example 15, the procedure to make 3-(ethoxydimethylsilyl)propanal (Aldehyde Alkoxysilane 1) was performed, as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (14.3 mg, 0.055 mmol), Ligand 1 (100.9 mg, 0.12 mmol) and toluene (70 g) were added into a 60 mL vial with a magnetic stir bar. The mixture was stirred at RT on a stir plate until a homogeneous solution was formed. The 3.5 g of the solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, Vinyl Alkoxysilane 1, Me.sub.2Si(OEt)Vi, (40 g, 307 mmol) was loaded to the Parr-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (690 kPa) and then vented for three times prior to being pressurized to 109 psig (752 kPa) via the dip-tube. Reaction temperature was set to 70 C. Heater and agitation were turned on. The 300 mL intermediate cylinder containing the syngas for the reaction and the reactor were connected when the desired temperature was reached. Pressure drop from a 300 mL intermediate cylinder was used to monitor the reaction progress and was recorded by a data logger. Full conversion of vinyl groups was observed after 23 hours reaction time as monitored by .sup.1H NMR; 3-(ethoxydimethylsilyl)propanal formed.

[0137] In this Synthesis Example 16, hydroformylation of Vinyltrimethylsilane, was performed, as follows: In a nitrogen filled glovebox, Rh(acac)(CO).sub.2 (0.0007 g), Ligand 1 (0.0043 g) and toluene (0.90 g) were added into a vial with a magnetic stir bar. The mixture was stirred at RT on a stir plate until a homogeneous solution was formed. The solution was transferred to an air-tight syringe with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, Vinyltrimethylsilane (53.0 g) was loaded to a 300 mL Parr-reactor. The reactor was sealed and pressurized with nitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valve connected to the headspace. The pressure/vent cycle with nitrogen was repeated three times. Pressure testing was subsequently performed by pressurizing the reactor with nitrogen to up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was added to the reactor via the sample loading port. The reactor was pressurized with syngas to 100 psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa) below the desired pressure via the dip-tube. The reaction temperature was set to 70 C. The heater and agitation were turned on. The reaction was run at 100 psig (689 kPa) syngas pressure. 99.5% conversion of vinyl groups was observed after 20 hours reaction time as monitored by .sup.1H NMR; propyl-aldehyde functional trimethylsilane was formed.

[0138] In this Reference Example A, oxidation of aldehyde-functional organosilicon compounds was performed as follows. In a typical procedure, a 250 ml glass reactor was charged with 150 g of an Aldehyde-siloxane. The aldehyde-siloxane was stirred with a mechanical stirrer or magnetic stirrer and air is continuously injected below the liquid surface with a stainless-steel needle at a rate of 50-200 cc/min. Reaction progress was determined using .sup.1H NMR analysis and the reactions were continued until high conversion was attained. The aldehyde starting materials and the reaction products mixtures were analyzed by .sup.1H, .sup.13C NMR and .sup.29Si NMR, GC/MS and GPC. The conversion and yield were mainly based on .sup.1H NMR data.

[0139] In this Working Example 1, oxidation of MD.sup.Pr-AldM (the hydroformylation product of MD.sup.viM prepared as described in Synthesis Example 1) was performed according to the procedure in Reference Example A, with the following results.

##STR00030##

TABLE-US-00002 TABLE 3 The results of oxidation batches of MD.sup.Pr-AldM with crude and distilled aldehyde. Mass Rxn Conversion of Linear Acid/ Aldehyde Air rate Tem. Time Aldehyde branched acid/ Expt. No. (g) (cc/min) ( C.) (hr) (%) total acid 20CF2124 118 (crude) 50 25 118 99.7 82.3/8.2/90.5 20CF2130 94 (distilled) 50 25 68 98.4 83.0/7.3/90.4

[0140] In this Working Example 2, oxidation of MD.sub.8.2 D.sup.Pr-Ald.sub.3.7M (the hydroformylation products of Vinylsiloxane 5, MD.sub.8.2D.sup.vi.sub.3.7M, prepared according to Synthesis Example 9) was performed as follows.

##STR00031##

Aldehyde-siloxane 5 (100.4 g) was loaded to a 250 mL reaction flask equipped with a PTFE coated stir bar. Air was bubbled into the liquid subsurface using a needle at 50 cc/min at ambient temperature 20-25 C. The reaction was run for 244 hours to produce 101 g of clear slightly yellow colored product. Product analysis by NMR was conducted using CDCl.sub.3 solvent. 96.8% aldehyde conversion was attained. The product contained 83 mole % linear carboxy-propyl groups and 6.8 mole % branched carboxy-propyl groups (89.8% total acid).

[0141] In this Working Example 3, oxidation of Aldehyde-siloxane 2, M.sup.Pr-AldM.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 2, M.sup.viM.sup.vi prepared as described in Synthesis Example 2), was performed as follows.

##STR00032##

Crude Aldehyde-siloxane 2 (309 g) and 3-pentanone solvent (76 g) were added to a 500 mL reaction flask equipped with an overhead paddle stirrer and a needle for subsurface addition of air. The oxidation reaction was run with an air addition rate of 100 cc/min with 400 rpm agitation. The reaction was continued for 187 hr. 340.9 g of clear, slightly yellow product solution was collected. .sup.1H NMR analysis showed 96% aldehyde conversion, 91.3 mole % carboxylic acid and 5 mole % formyl ester.

[0142] In this Working Example 4, oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald a (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 was performed as follows.

##STR00033##

Crude Aldehyde-siloxane 4 (195.3 g) was loaded to a 250 mL European style flask equipped with a PTFE coated magnetic stir bar. Air was sparged subsurface with a needle at 100 cc/min and the mixture was stirred with the magnetic stirrer at maximum speed. The reaction was analyzed by .sup.1H NMR at 16, 40, and 64 hr. The reaction was stopped after 64 hours. The clear slightly yellow product liquid (194.6 g) was collected. The reaction reached 96.6% aldehyde conversion with 89.7% acid, and 4.0% formyl ester.

[0143] In this Working Example 5, oxidation of Aldehyde-siloxane 3, D.sup.Pr-Ald.sub.4 (the hydroformylation product of Vinylsiloxane 3, D.sup.vi.sub.4) prepared according to Synthesis Example 3, was performed as follows.

##STR00034##

The oxidation reaction was run in 250 mL European style flask with magnetic stirring. 50.25 g of Aldehyde-siloxane 3 was loaded. The reaction was run starting with 80 cc/min air bubbled in sub-surface through a needle at ambient temperature 20-25 C. After 2 hours, 3-pentanone solvent (50 mL) was added and the air rate was increased to 100 cc/min. After 46 hours, additional 3-pentanone (50 mL) was added. After 69 hours, additional 3-pentanone (25 mL) was added. After 77 hours, additional 3-pentanone (50 mL) was added, and the air rate was decreased to 10 cc/min due to sample viscosity. After 165 hours, the reaction was stopped. The reaction was sparged with nitrogen overnight to remove 2.74 g of solvent and 52.17 g of slightly yellow viscous oil was collected.

[0144] In this Working Example 6, oxidation of Aldehyde-siloxane 6, M.sup.Pr-AldD.sub.180M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 6, M.sup.Vi.sub.2D.sup.180) prepared according to Synthesis Example 8 was performed as follows.

##STR00035##

Crude M.sup.Pr-AldD.sub.180M.sup.Pr-Ald solution (189.27 g) was loaded to a 250 mL tapered side glass flask with mechanical overhead stirring. The reaction was run with 100 cc/min air starting at ambient temperature of 21.9 C. The reaction was stopped after 67 hours and 98.6% aldehyde conversion. The oxidation reaction product contained 91.8% acid, 2% formyl ester, and 1.4% unreacted aldehyde.

[0145] In this Working Example 7, the M.sup.acid-D.sub.7-M.sup.acid prepared according to Working Example 4 was equilibrated with D4 in the presence of DOWEX DR-2030 as follows. The D4 was dried over molecular sieves. M.sup.acid-D.sub.7-M.sup.acid was dried over molecular sieves and filtered through a 0.45 m PTFE syringe filter. To a 250 mL reaction flask equipped with an overhead stirrer, thermoprobe, water cooled condenser, nitrogen headspace purge, and heating mantle was added DOWEX DR-2030 (0.40 g) and D4 (65.2 g) and heated to 60 C. The M.sup.acid-D.sub.7-M.sup.acid (13.37 g) was added via syringe. The resulting clear mixture was then stirred at 60 C. overnight for 21 hr to give a clear flowable fluid which was analyzed by Si NMR to show a DP of 74.7. The reaction was continued an additional 3 hours, and while warm, the reaction mixture was filtered through a medium disposable filter funnel to remove catalyst, which gave 75.32 g of clear, slightly viscous liquid. The fluid was stripped on a rotary evaporator at 16 torr and 95 C. for 30 minutes to yield 70.51 g of product fluid. Si NMR analysis of the product fluid showed a DP of 76 and 16% D4.

[0146] In this Working Example 8, D4 was dried over molecular sieves. To a 250 mL reaction flask equipped with an overhead stirrer, thermoprobe, heating mantle bar was added DOWEX DR-2030 (0.5 g) and D4 (108 g) and heated to 80 C. Using a syringe pump the bis-trimethylsiloxy-terminated poly(dimethyl/methyl, carboxypropyl)siloxane copolymer prepared in Working Example 2 (MD.sub.8.2D.sup.acid.sub.3.7M, 9 g) was added in dropwise over 3 hours. The mixture was then stirred at 80 C. overnight for 14 hrs to give a thick liquid. The reaction mixture contained some gelled material. While warm, the reaction mixture was filtered through a coarse sintered glass funnel to remove gelled material and catalyst and gave 101 g of clear thick liquid. Si NMR indicated a DP of 259.

[0147] In this Working Example 9, oxidation of (M2T)3T Propionaldehyde (prepared as described in Synthesis Example 13 was performed as follows.

##STR00036##

Crude (M2T)3T Propionaldehyde (90 g, 77:1 n:i ratio) was loaded to a 240 mL septa cap bottle equipped with a PTFE coated stir bar. Air was sparged subsurface with a needle at 50 cc/min and the mixture was stirred for 64 hr. The clear slightly yellow liquid (90.0 g) was collected. .sup.1H NMR analysis of this liquid showed acid, formyl ester, and unreacted aldehyde in a 97.8, 1.82, and 0.39 mole % ratio, respectively.

[0148] In this Working Example 10, oxidation of MD.sup.Pr-AldM (prepared as shown in Synthesis Example 1) with 3-pentanone and/or N-hydroxyphthalimide was studied as follows. Four oxidation experiments were set up for oxidation MD.sup.Pr-AldM under different conditions. Experiment A used 3.0 g of neat MD.sup.Pr-AldM. Experiment B used 4.5 g of neat MD.sup.Pr-AldM with 0.04 g (1 wt %) N-hydroxyphthalimide. Experiment C used 3.0 g MD.sup.Pr-AldM and 3.0 g 3-pentanone. Experiment D used 2.8 g MD.sup.Pr-AldM, 2.8 g 3-pentanone, and 0.015 g N-hydroxyphthalimide (0.5 wt % relative to MD.sup.Pr-AldM). Each oxidation was run with 10 cc/min air and 500 rpm agitation for 24 hours. The results are shown below in Table 3.

TABLE-US-00003 TABLE 3 Starting Materials and Results of Working Example 10 With N- With N-hydroxy- Neat hydroxy- With 3- phthalimide MD.sup.Pr-AldM phthalimide Pentanone and 3-Pentanone A B C D linear Ald 1.9% 3.6% 8.0% 0.6% branched ald 0.2% 0.3% 0.7% 0.0% Formyl Ester 3.4% 2.9% 2.3% 2.3% Ester dimer 0.5% 0.5% 0.1% 0.6% B-silanol 0.1% 0.4% 0.3% 1.1% Acid n 88.1% 86.7% 83.3% 89.2% Acid i 5.8% 5.7% 5.4% 6.2% Total Acid 93.9% 92.4% 88.7% 95.3% Acid/ 23.91 24.71 33.45 23.70 impurity selectivity Conversion 97.8% 96.1% 91.3% 99.4%

[0149] In this Working Example 11, oxidation of aldehyde-functional MQ Resin (hydroformylation product prepared according to Synthesis Example 6) was performed as follows. To a 40 mL septa cap vial equipped with a PTFE coated magnetic stir bar was loaded with 25 g of aldehyde-MQ resin from synthesis example 6. Air was bubbled into the solution subsurface at a rate of 20 cc/min at a temperature of 22 C. while stirred with a magnetic stir plate at 1000 RPM. The reaction was continued for 184 hours and the liquid product was collected. Quantitative .sup.13C NMR analysis of the product revealed 95% conversion with 83% acid and 12% formyl ester.

[0150] In this Working Example 12, oxidation of 3-(ethoxydimethylsilyl)propanal (hydroformylation product prepared according Synthesis Example 15) was performed as follows. A 40 mL vial was charged with a magnetic stirrer and 3-(ethoxydimethylsilyl)propanal [Me.sub.2Si(OEt)CH.sub.2CH.sub.2CHO] (7.16 g, 44.7 mmol). Air was bubbled, subsurface at 40 cc/min. A stir plate was used and set at 1000 RPM. The reaction was monitored by .sup.1H NMR spectroscopy at 2 h, 21 h, 42 h, and 116 h. The reaction was stopped after 116 h. 4.31 g of pale yellow liquid was collected. Analysis by .sup.1H NMR spectroscopy revealed 96.2% aldehyde conversion with 95.2% acid and 1.0% formyl ester. The result was further supported by .sup.13C NMR spectroscopy data.

[0151] In this Working Example 13, oxidation of 3-(ethoxydimethylsilyl)propanal (hydroformylation product prepared according Synthesis Example 15) was performed as follows. A 40 mL vial was charged with a magnetic stirrer and 3-(ethoxydimethylsilyl)propanal [Me.sub.2Si(OEt)CH.sub.2CH.sub.2CHO] (6.96 g, 43.4 mmol). Air was bubbled, subsurface at 5 cc/min. A stir plate was used and set at 1000 RPM. The reaction was monitored by .sup.1H NMR spectroscopy at 16 h, 24 h, 51 h, 62 h, and 144 h. The reaction was stopped after 144 h. 5.56 g of pale yellow liquid was collected. Analysis by .sup.1H NMR spectroscopy revealed 93.5% aldehyde conversion with 92.6% acid and 0.9% formyl ester.

##STR00037##

[0152] In this Working Example 14, RT oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 was performed as follows. A 40 mL vial was charged with a magnetic stirrer and M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (10.1 g, 13.2 mmol). Air was bubbled, subsurface at 40 cc/min. The reaction was conducted at RT, and a stir plate was used and set at 1000 RPM. The reaction was monitored by .sup.1H NMR spectroscopy at 30 min, 1 h, 2 h, 4 h, 7 h, and 23 h. The reaction was stopped after 23 h. 9.35 g of a colorless liquid was obtained. Analysis by .sup.1H NMR spectroscopy revealed 96.5% aldehyde conversion with 87.0% acid and 6.1% formyl ester.

[0153] In this Working Example 15, 60 C. oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 was performed as follows. A 40 mL vial was charged with a magnetic stirrer and M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (9.99 g, 13.1 mmol). Air was bubbled, subsurface at 40 cc/min. The reaction was conducted at 60 C., and a stir plate was used and set at 1000 RPM. The reaction was monitored by .sup.1H NMR spectroscopy at 30 min, 1 h, 2 h, 4 h, 7 h, and 23 h. The reaction was stopped after 23 h. 9.12 g of a colorless liquid was obtained. Analysis by .sup.1H NMR spectroscopy revealed 98.3% aldehyde conversion with 84.7% acid and 10.2% formyl ester.

[0154] In this Working Example 16, 100 C. oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 was performed as follows. A 40 mL vial was charged with a magnetic stirrer and M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (10.1 g, 13.2 mmol). Air was bubbled, subsurface at 40 cc/min. The reaction was conducted at 100 C., and a stir plate was used and set at 1000 RPM. The reaction was monitored by .sup.1H NMR spectroscopy at 30 min, 1 h, 2 h, 4 h, 7 h, and 23 h. The reaction was stopped after 23 h. 8.55 g of a colorless liquid was obtained. Analysis by .sup.1H NMR spectroscopy revealed 98.4% aldehyde conversion with 80.0% acid and 16.0% formyl ester. Working Examples 14 to 16 showed that the oxidation reaction could be conducted at different temperatures.

[0155] In this Working Example 17, 0 C. oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald a (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 was performed as follows. A 250 mL jacketed glass reactor was charged with M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (91.1 g, 119 mmol). Air was bubbled, subsurface at 100 cc/min. The reaction was conducted at 0 C. an overhead stirrer was used for agitation and was set to 500 RPM. The reaction was monitored by .sup.1H NMR spectroscopy at 20 h, 23 h, 44 h, 67 h, and 140 h. The reaction was stopped after 140 h. 78.6 g of a colorless liquid was obtained. Analysis by .sup.1H NMR spectroscopy revealed 92.3% aldehyde conversion with 88.7% acid and 2.5% formyl ester.

##STR00038##

[0156] In this Working Example 18, oxidation of aldehyde-functional silane (hydroformylation product prepared according to Synthesis Example 16) was performed as follows. To a 40 mL septa cap vial equipped with a PTFE coated magnetic stir bar was loaded with 5.7 g of propyl-aldehyde functional trimethylsilane from synthesis example 16. Air was bubbled into the solution subsurface at a rate of 5 cc/min at a temperature of 22 C. while stirred with a magnetic stir plate at 1400 RPM. The reaction was continued for 22 hours and 5.8 g of liquid product was collected. .sup.1H NMR analysis of the product revealed 97.6% conversion with 91.2% acid and 6.4% formyl ester.

[0157] In this Working Example 19, oxidation of Aldehyde-siloxane 7, M.sup.Pr-AldD.sub.329M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 7, M.sup.vi.sub.2D.sub.329) prepared according to Synthesis Example 10 was performed as follows.

##STR00039##

Crude M.sup.Pr-AldD.sub.329M.sup.Pr-Ald solution (1315 g) was loaded to a 2 L 3-neck glass flask with mechanical overhead stirring and a temperature controlled heating mantle. The reaction was run with 200 cc/min air added with two subsurface needles. The reaction temperature was controlled at 30 C. and the reaction was stirred at 400 RPM. The reaction was run for 115 hours. .sup.1H NMR analysis of the product revealed 96.4% conversion with 91.6% acid and 4.8% formyl ester.

[0158] In this Working Example 20, the M.sup.acid-D.sub.7-M.sup.acid prepared according to Working Example 4 was equilibrated with D4 in the presence of trifluoromethanesulfonic acid to generate a terminal carboxy-functionalized PDMS as follows. To a 40 mL septa cap vial equipped with a PTFE coated stir bar was added M.sup.acid-D.sub.7-M.sup.acid (3.3 g) and D4 (7.95 g) to form a homogeneous solution. The mixture was heated to 90 C. A solution of 1 wt % triflic acid in dichloromethane (100 uL) was added vial syringe. The mixture was stirred at 90 C. for 16 h with a headspace nitrogen purge (50 cc/min). The product was analyzed by NMR and GPC. Si NMR showed a DP of 42.

[0159] In this Working Example 21, the MD.sup.pr-acidM prepared according to Working Example 1 was equilibrated with D4 in the presence of trifluoromethanesulfonic acid to generate a pendant carboxy-functionalized PDMS as follows. To a 40 mL septa cap vial equipped with a PTFE coated stir bar was added MD.sup.Pr-acidM (0.95 g) and D4 (9.5 g) to form a homogeneous solution. The mixture was heated to 90 C. and the vial was purged with nitrogen. A solution of 1 wt % triflic acid in dichloromethane (100 uL) was added vial syringe. The mixture was stirred at 90 C. with a headspace nitrogen purge for 17 hours. At 25 hours reaction time, the nitrogen purge was removed and replaced with a static nitrogen headspace pad. The reaction was stopped at 113 hours. The product was analyzed by NMR and GPC. Si NMR showed a DP of 57.

[0160] In this Working Example 22, the MD.sub.8.2 D.sup.Pr-Acid.sub.3.7M prepared according to Working Example 2 was equilibrated with D4 in the presence of trifluoromethanesulfonic acid to generate a pendant carboxy functionalized PDMS as follows. To a 40 mL septa cap vial equipped with a PTFE coated stir bar was added MD.sub.8.2 D.sup.Pr-Acid.sub.3.7M (0.8 g) and D4 (12 g) to form a cloudy mixture. The mixture was heated to 90 C. and was cloudy. A solution of 1 wt % triflic acid in dichloromethane (120 uL) was added vial syringe. After 3 minutes the mixture became clear. The mixture was stirred at 90 C. with a headspace nitrogen pad for 15 hours. The product was analyzed by NMR and GPC. Si NMR showed a DP of 290.

[0161] In this Working Example 23, the MD.sub.8.2 D.sup.Pr-Acid.sub.3.7M prepared according to Working Example 2 and M.sup.acid-D.sub.7-M.sup.acid prepared according to Working Example 4 were equilibrated with D4 in the presence of trifluoromethanesulfonic acid to generate a PDMS functionalized with pendant and terminal carboxy groups as follows. To a 40 mL septa cap vial equipped with a PTFE coated stir bar was added MD.sub.8.2 D.sup.Pr-Acid.sub.3.7M (1.1 g), M.sup.acid-D.sub.7-M.sup.acid (0.73 g), and D4 (16 g) to form a mixture. The mixture was heated to 90 C. and a solution of 1 wt % triflic acid in dichloromethane (150 uL) was added vial syringe. The mixture was stirred at 90 C. with a headspace nitrogen purge for 19 hours. 0.53 g of material was collected from the headspace purge. The product was analyzed by NMR and GPC. Si NMR showed a DP of 160.

[0162] In this Working Example 24, oxidation of Aldehyde-siloxane 9, M.sup.Pr-AldD.sub.77M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 16, M.sup.Vi.sub.2D.sub.77) prepared according to Synthesis Example 12 was performed as follows.

##STR00040##

Crude M.sup.Pr-AldD.sub.77M.sup.Pr-Ald solution (185 g) was loaded to a 250 mL European style tapered wall flask with mechanical overhead stirring. The reaction was run with 50-100 cc/min air at ambient temperature 20-25 C. The oxidation was run for 68 hrs. .sup.1H NMR analysis of the product revealed 96.9% conversion with 87.5% acid and 9.3% formyl ester. The end of reaction mixture contained 1.5 wt % toluene. 139.17 g of yellow liquid was collected.

[0163] In this Working Example 25, oxidation of (M2T)3T Heptanaldehyde (prepared as described in Synthesis Example 14 was performed as follows. Crude (M2T)3T Heptanealdehyde (100 g) which contained approximately 5 wt % toluene was loaded to a one-neck round bottom flask equipped with a PTFE coated stir bar and a septa cap. The liquid was stirred on a magnetic stir plate at 1150 rpm as plant air was sparged subsurface through a needle. The reaction mixture was analyzed by 1H NMR until complete. The reaction was stopped after 24 hours and the (M2T)3T-Heptanoic acid product was collected as a clear orange liquid.

[0164] In this Working Example 26, oxidation of Aldehyde-siloxane 8, M.sup.Pr-AldD.sub.25M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 8, M.sup.Vi.sub.2D.sub.25) prepared according to Synthesis Example 11 was performed as follows.

##STR00041##

Crude M.sup.Pr-AldD.sub.25M.sup.Pr-Ald solution (572 g) containing approximately 3 wt % toluene was loaded to a 500 mL European style tapered wall flask with mechanical overhead stirring. The reaction was run with 200 cc/min air at ambient temperature starting at 22 C. The oxidation was run for 72 hrs. .sup.1H NMR analysis of the product revealed 98.4% conversion with 91.2% acid and 7.2% formyl ester. 550.7 g of clear slightly colored liquid was collected.

[0165] In this Working Example 27, RT oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald a (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 in the presence of 285 nm UV light was performed as follows. A 20 mL quartz test tube was charged with M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (5.00 g, 6.5 mmol). Air was bubbled, subsurface at 20 cc/min. The reaction was conducted at RT and was not stirred. A 285 nm UV LED was used to irradiate the sample for a specified time. The reaction was monitored by .sup.1H NMR spectroscopy at 15 min, 1 h, 3 h, 5 h, 8 h, and 13 h. The reaction was stopped after 13 h. 3.84 g of a colorless liquid was obtained. Analysis by .sup.1H NMR spectroscopy revealed 97.1% aldehyde conversion with 90.3% acid and 4.5% formyl ester. The reaction was repeated in the absence of UV light using the same amount of M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (5.00 g, 6.5 mmol) and the same air bubbling rate (20 cc/min). After 13 h under these conditions .sup.1H NMR spectroscopy revealed 64.2% aldehyde conversion with 60.6% acid and 3.0% formyl ester. .sup.1H NMR spectroscopy revealed 97.1% aldehyde conversion with 90.3% acid and 4.5% formyl ester.

[0166] The reaction described above was repeated except without UV irradiation. After 13 h under these conditions, .sup.1H NMR spectroscopy revealed 64.2% aldehyde conversion with 60.6% acid and 3.0% formyl ester, showing that the reaction was still performed, but at a slower rate.

##STR00042##

[0167] In this Working Example 28, RT oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 in the presence of a peroxy acid (3-chloroperbenzoic acid, oxidant 1) was performed as follows. A 40 mL vial was charged with a magnetic stirrer and M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (2.22 g, 2.9 mmol). A separate 40 mL vial was charged with 3-chloroperbenzoic acid (1.22 g, 7.13 mmol) and deuterated benzene (2.58 g) to form a white slurry. The slurry was added to the vial containing M.sup.Pr-AldD.sub.7M.sup.Pr-Ald over 2 min. An aliquot from the reaction was analyzed by .sup.1H NMR spectroscopy after 15 min. Analysis by .sup.1H NMR spectroscopy revealed 87.9% aldehyde conversion with 58.8% acid and 29.1% formyl ester.

##STR00043##

[0168] In this Working Example 29, 100 C. oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 in the presence of a organic peroxide (di-tert-butyl peroxide, oxidant 2) was performed as follows. A 40 mL vial was charged with a magnetic stirrer and M.sup.Pr-AldD.sub.7M.sup.Pr-Ald(0.95 g, 1.2 mmol) and tert-butyl peroxide (0.50 mL, 0.40 g, 2.72 mmol). The reaction was stirred under N.sub.2 atmosphere and heated at 100 C. Aliquots were removed after 15 min, 1.5 h, and 3 h and analyzed by .sup.1H NMR spectroscopy to determine the molar ratio between the desired acid and the starting material. A control experiment was performed using M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (0.95 g, 1.2 mmol) with no added oxidant and heating at 100 C. under N.sub.2. Aliquots of this reaction were acquired after 15 min, 1.5 h, and 3 h and analyzed by .sup.1H NMR spectroscopy to determine the molar ratio between the desired acid and the starting material. The results from these experiments are presented in Table 4. After 3 h, the reaction was stopped. 0.72 g of a colorless liquid was obtained.

TABLE-US-00004 TABLE 4 Oxidation of M.sup.Pr-AldD.sub.7M.sup.Pr-Ald using tert-butyl peroxide at 100 C. Molar ratio (mmol acid/mmol Oxidant Time starting material) Di-tert-butyl peroxide 0 min 0 15 min 0 1.5 h 0.04 3 h 0.31 None (control) 0 min 0 15 min 0 1.5 h 0.01 3 h 0.01

##STR00044##

[0169] In this Working Example 30, 100 C. oxidation of Aldehyde-siloxane 4, M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (the hydroformylation product of Vinylsiloxane 4 M.sup.viD.sub.7M.sup.vi) prepared according to Synthesis Example 7 in the presence of a organic hydroperoxide (tert-butyl hydroperoxide, oxidant 3) was performed as follows. A 40 mL vial was charged with a magnetic stirrer and M.sup.Pr-AldD.sub.7M.sup.Pr-Ald a (0.95 g, 1.2 mmol) and tert-butyl hydroperoxide (0.50 mL, 5.5 mmol/mL, 2.75 mmol). The reaction was stirred under N.sub.2 atmosphere and heated at 100 C. Aliquots were removed after 15 min, 1.5 h, and 3 h and analyzed by .sup.1H NMR spectroscopy to determine the molar ratio between the desired acid and the starting material. A control experiment was performed using M.sup.Pr-AldD.sub.7M.sup.Pr-Ald (0.95 g, 1.2 mmol) with no added oxidant and heating at 100 C. under N.sub.2. Aliquots of this reaction were acquired after 15 min, 1.5 h, and 3 h and analyzed by .sup.1H NMR spectroscopy to determine the molar ratio between the desired acid and the starting material. The results from these experiments are presented in Table 5. After 3 h, the reaction was stopped. 0.73 g of a colorless liquid was obtained.

TABLE-US-00005 TABLE 5 Oxidation of M.sup.Pr-AldD.sub.7M.sup.Pr-Ald using tert-butyl hydroperoxide at 100 C. Molar ratio (mmol acid/mmol Oxidant Time starting material) Tert-butyl hydroperoxide 0 min 0 15 min 0.51 1.5 h 1.91 3 h 4.83 None (control) 0 min 0 15 min 0 1.5 h 0.01 3 h 0.01

##STR00045##

INDUSTRIAL APPLICABILITY

[0170] The working examples above show that a variety of aldehyde-functional organosilicon compounds can successfully undergo oxidation reaction to form carboxy-functional organosilicon compounds using the process of this invention. The process described herein is flexible in that a wide variety of polymeric polyorganosiloxanes and organosilicon small molecules, with both pendant and/or terminal carboxy functionality) can be prepared. The process described herein is capable of forming carboxy-functional organosilicon compounds with two or more carboxy-groups per molecule. In addition, the process may have one or more of the following benefits: low cost, simple process, minimal by-product formation, relatively low pressure, low temperature of 50 C. or less (less likely to degrade sensitive molecules, lower capital cost, and safer), minimal side products, and good control of the reaction. Furthermore, the process does not require purification or separation of the starting materials before use.

Definitions and Usage of Terms

[0171] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The amounts of all starting materials in a composition total 100% by weight. The SUMMARY and ABSTRACT are hereby incorporated by reference. The articles a, an, and the each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated. The transitional phrases comprising, consisting essentially of, and consisting of are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section 2111.03 I., II., and III. The abbreviations used herein have the definitions in Table Z.

TABLE-US-00006 TABLE Z Abbreviations Abbreviation Definitions acac acetyl acetonate C. degrees Celsius cc cubic centimeters D Difunctional siloxy unit, trimethylsiloxy unit of formula Me.sub.2SiO.sub.2/2 D.sup.al Difunctional siloxy unit, allylmethylsiloxy unit of formula (Allyl)(Me)SiO.sub.2/2 D.sup.hex Difunctional siloxy unit, hexenylmethylsiloxy unit of formula (Hex)(Me)SiO.sub.2/2 D.sup.Pr-ald Difunctional siloxy unit, propylaldehyde, methylsiloxy unit of formula (Pr-ald)(Me)SiO.sub.2/2 D.sup.vi Difunctional siloxy unit, vinylmethylsiloxy unit of formula (Vi)(Me)SiO.sub.2/2 DP degree of polymerization DSC Dow Silicones Corporation of Midland, Michigan, USA Et ethyl FTIR Fourier transform infra-red g gram GPC gel permeation chromatography h or hr hour Hex hexenyl iPr isopropyl kPa kiloPascals M Monofunctional siloxy unit, trimethylsiloxy unit of formula R.sub.3SiO.sub.1/2 or Me.sub.3SiO.sub.1/2 M.sup.al Monofunctional siloxy unit, allyldimethylsiloxy unit of formula (Allyl)(Me.sub.2)SiO.sub.1/2 M.sup.hex Monofunctional siloxy unit, hexenyldimethylsiloxy unit of formula (Hex)(Me.sub.2)SiO.sub.1/2 M.sup.Pr-ald Monofunctional siloxy unit, propyladehyde, dimethylsiloxy unit of formula (Pr-ald)(Me.sub.2)SiO.sub.1/2 M.sup.vi Monofunctional siloxy unit, vinyldimethylsiloxy unit of formula (Vi)(Me.sub.2)SiO.sub.1/2 Me methyl mg milligram min minute mL milliliter mm millimeter Mmol millimole Mn number average molecular weight measured by GPC Mw weight average molecular weight measured by GPC mPa .Math. s milliPascal seconds NBD norbornadiene NMR nuclear magnetic resonance PDI Polydispersity index (calculated as Mw/Mn) PDMS polydimethylsiloxane Ph phenyl ppm parts per million by weight Pr propyl Pr-ald propyl-aldehyde psi pounds per square inch PTFE polytetrafluoroethylene Q tetrafunctional siloxy unit of formula SiO.sub.4/2 RPM or rpm revolutions per minute RT room temperature of 25 5 C. TDCC The Dow Chemical Company of Midland, Michigan, USA THF tetrahydrofuran or u micro m micrometer Vi vinyl

[0172] The following test methods were used herein. FTIR: The concentration of silanol groups present in the 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 the polyorganosiloxanes was determined by GPC using an Agilent Technologies 1260 Infinity chromatograph and toluene as a solvent. The instrument was equipped with three columns, a PL gel 5 m 7.550 mm guard column and two Plgel 5 m Mixed-C 7.5300 mm columns. Calibration was made using polystyrene standards. Samples were made by dissolving polyorganosiloxanes in toluene (1 mg/mL) and then immediately analyzing the solution by GPC (1 m/min flow, 35 C. column temperature, 25-minute run time). .sup.29Si NMR: Alkenyl content of starting material (B) can be measured by the technique described in The Analytical Chemistry of Silicones ed. A. Lee Smith, Vol. 112 in Chemical Analysis, John Wiley & Sons, Inc. (1991). Viscosity: Viscosity may be measured at 25 C. at 0.1 to 50 RPM on a Brookfield DV-III cone & plate viscometer with #CP-52 spindle, e.g., for polymers (such as certain (B2) alkenyl-functional polyorganosiloxanes) with viscosity of 120 mPa.Math.s to 250,000 mPa.Math.s. One skilled in the art would recognize that as viscosity increases, rotation rate decreases and would be able to select appropriate spindle and rotation rate.

EMBODIMENTS OF THE INVENTION

[0173] In a first embodiment, a process for preparing a carboxy-functional organosilicon compound comprises: [0174] 1) combining, under conditions to conduct hydroformylation reaction, starting materials comprising [0175] (A) a gas comprising hydrogen and carbon monoxide, [0176] (B) an alkenyl-functional organosilicon compound, and [0177] (C) a rhodium/bisphosphite ligand complex catalyst, where the bisphosphite ligand has formula

##STR00046## [0178] where [0179] R.sup.6 and R.sup.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; [0180] R.sup.7 and R.sup.7 are each independently selected from the group consisting of an alkyl group of 3 to 20 carbon atoms, and a group of formula SiR.sup.17.sub.3, where each R.sup.17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms; [0181] R.sup.8, R.sup.8, R.sup.9, and R.sup.9 are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group, and [0182] R.sup.10 R.sup.10, R.sup.11, and R.sup.11 are each independently selected from the group consisting of hydrogen or and alkyl group; thereby forming a hydroformylation reaction product comprising an aldehyde-functional organosilicon compound; and [0183] 2) combining, under conditions to conduct oxidation reaction, starting materials comprising (E) the aldehyde-functional organosilicon compound and (F) an oxygen source, thereby forming an oxidation reaction product comprising (I) the carboxy-functional organosilicon compound.

[0184] In a second embodiment, in the process of the first embodiment, starting material (B) comprises an alkenyl-functional silane of formula (B1): R.sup.A.sub.xSiR.sup.4.sub.(4-x), where each R.sup.A is an independently selected alkenyl group of 2 to 8 carbon atoms; each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and an hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4.

[0185] In a third embodiment, in the process of the first embodiment, the alkenyl-functional organosilicon compound comprises an alkenyl-functional polyorganosiloxane of unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.ASiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.ASiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.ASiO.sub.3/2).sub.f(SiO.sub.4/2).sub.g(ZO.sub.1/2).sub.h; where each R.sup.A is an independently selected alkenyl group of 2 to 8 carbon atoms, and each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R.sup.5, where each R.sup.5 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; subscripts a, b, c, d, e, f, and g represent numbers of each unit in formula (B2-1) and have values such that subscript a0, subscript b0, subscript c0, subscript d0, subscript e0, subscript f0, subscript g0; and subscript h has a value such that 0h/(e+f+g)1.5, with the proviso that when e=f=g=0, then h0; 10,000(a+b+c+d+e+f+g)2, and a quantity (b+d+f)1.

[0186] In a fourth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is cyclic and has a unit formula selected from the group consisting of: (R.sup.4R.sup.ASiO.sub.2/2).sub.d, where subscript d is 3 to 12; (R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.ASiO.sub.2/2).sub.d, where c is >0 to 6 and d is 3 to 12; and a combination thereof.

[0187] In a fifth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is linear and comprises unit formula (B3): (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.ASiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.ASiO.sub.2/2).sub.d, where a quantity (a+b)=2, a quantity (b+d)1, and a quantity (a+b+c+d)2.

[0188] In a sixth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is an alkenyl-functional polyorganosilicate resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.mm(R.sup.4.sub.2R.sup.ASiO.sub.1/2).sub.nn(SiO.sub.4/2).sub.oo(ZO.sub.1/2).sub.h, where subscripts mm, nn, and oo represent mole percentages of each unit in the polyorganosilicate resin; and subscripts mm, nn and oo have average values such that mm0, nn0, oo>0, and 0.5(mm+nn)/oo4.

[0189] In a seventh embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is an alkenyl-functional silsesquioxane resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.ASiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.ASiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.ASiO.sub.3/2).sub.f(ZO.sub.1/2).sub.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.

[0190] In an eighth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane is a branched oligomer comprising general formula: R.sup.ASiR.sup.12.sub.3, where R.sup.A is as described above and each R.sup.12 is selected from R.sup.13 and OSi(R.sup.14).sub.3; where each R.sup.13 is a monovalent hydrocarbon group; where each R.sup.14 is selected from R.sup.13, OSi(R.sup.15).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.15 is selected from R.sup.13, OSi(R.sup.16).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.16 is selected from R.sup.13 and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; and where subscript ii has a value such that 0ii100.

[0191] In a ninth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane comprises a Q branched polyorganosiloxane of unit formula (B2-13): (R.sup.4.sub.3SiO.sub.1/2).sub.q(R.sup.4.sub.2R.sup.ASiO.sub.1/2).sub.r(R.sup.4.sub.2SiO.sub.2/2).sub.s(SiO.sub.4/2).sub.t, where subscripts q, r, s, and t have average values such that 2q0, 4r0, 995s4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity>170 mPa.Math.s measured by rotational viscometry (as described below with the test methods) to the branched polyorganosiloxane.

[0192] In a tenth embodiment, in the process of the third embodiment, the alkenyl-functional polyorganosiloxane comprises a T branched polyorganosiloxane (silsesquioxane) of unit formula (B2-15): (R.sup.4.sub.3SiO.sub.1/2).sub.aa(R.sup.AR.sup.4.sub.2SiO.sub.1/2).sub.bb(R.sup.4.sub.2SiO.sub.2/2).sub.cc(R.sup.AR.sup.4SiO.sub.2/2).sub.ee(R.sup.4SiO.sub.3/2).sub.dd, where subscript aa0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee0.

[0193] In an eleventh embodiment, in any one of the third to tenth embodiments, each R.sup.A is independently selected from the group consisting of vinyl, allyl, and hexenyl.

[0194] In a twelfth embodiment, in the process of any one of the third to eleventh embodiments, each R.sup.4 is independently selected from the group consisting of methyl and phenyl.

[0195] In a thirteenth embodiment, the process of the first embodiment further comprises: II) equilibrating the carboxy-functional organosilicon compound with a cyclic polydiorganosiloxane in the presence of an equilibration catalyst.

[0196] In a fourteenth embodiment, in the process of any one of the first to thirteenth embodiments, in the bisphosphite ligand, R.sup.6 and R.sup.6 are each selected from the group consisting of a methoxy group and a t-butyl group, R.sup.7 and R.sup.7 are each a t-butyl group, and R.sup.8, R.sup.8, R.sup.9, R.sup.9, R.sup.10 R.sup.10, R.sup.11, and R.sup.11 are each hydrogen.

[0197] In a fifteenth embodiment, in the process of any one of the first to fourteenth embodiments, starting material (C) is present in an amount sufficient to provide 0.1 ppm to 300 ppm Rh based on combined weights of starting materials (A), (B), and (C).

[0198] In a sixteenth embodiment, in the process of any one of the first to fifteenth embodiments, starting material (C) has a molar ratio of bisphosphite ligand/Rh of 1/1 to 10/1.

[0199] In a seventeenth embodiment, in the process of any one of the first to sixteenth embodiments, the conditions in step 2) are selected from the group consisting of: i) a temperature of 20 C. to 50 C.; ii) a pressure of 3 psia to 100 psia; iii) the oxygen source has 21% to 100% oxygen; and iv) a combination of two or more of conditions i), ii) and iii).

[0200] In an eighteenth embodiment, in the process of any one of the first to seventeenth embodiments, (C) the rhodium/bisphosphite ligand complex catalyst is formed by combining a rhodium precursor and the bisphosphite ligand to form a rhodium/bisphosphite ligand complex and combining the rhodium/bisphosphite ligand complex and starting material (A) with heating before step 1).

[0201] In a nineteenth embodiment, the aldehyde-functional organosilicon compound prepared by the process of the first embodiment or the second embodiment is an aldehyde-functional silane of formula (E1): R.sup.Ald.sub.xSiR.sup.4.sub.(4-x), where each R.sup.Ald is an independently selected aldehyde group of 3 to 9 carbon atoms; each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and an hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4.

[0202] In a twentieth embodiment, the aldehyde-functional organosilicon compound prepared by the process of the first embodiment or the second embodiment is an aldehyde-functional polyorganosiloxane of unit formula (E2-1): (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.AldSiO.sub.3/2).sub.f(SiO.sub.4/2).sub.g(ZO.sub.1/2).sub.h; where each R.sup.Ald is an independently selected aldehyde group of 3 to 9 carbon atoms, and each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R.sup.5, where each R.sup.5 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; subscripts a, b, c, d, e, f, and g represent numbers of each unit in formula (E2-1) and have values such that subscript a0, subscript b0, subscript c0, subscript d0, subscript e0, subscript f0, subscript g0; and subscript h has a value such that 0h/(e+f+g)1.5, with the proviso that when e=f=g=0, then h0, 10,000(a+b+c+d+e+f+g)2, and a quantity (b+d+f) 1.

[0203] In a twenty-first embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is cyclic and has a unit formula selected from the group consisting of: (R.sup.4R.sup.AldSiO.sub.2/2).sub.d, where subscript d is 3 to 12; (R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d, where c is >0 to 6 and d is 3 to 12; and a combination thereof.

[0204] In a twenty-second embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is linear and comprises unit formula (E3): (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d, where a quantity (a+b)=2, a quantity (b+d)1, and a quantity (a+b+c+d)2.

[0205] In a twenty-third embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is an aldehyde-functional polyorganosilicate resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.mm(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.nn(SiO.sub.4/2).sub.oo(ZO.sub.1/2).sub.h, where subscripts mm, nn, and oo represent mole percentages of each unit in the polyorganosilicate resin; and subscripts mm, nn and oo have average values such that mm0, nn0, oo>0, and 0.5(mm+nn)/oo4.

[0206] In a twenty-fourth embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is an aldehyde-functional silsesquioxane resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.AldSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.AldSiO.sub.3/2).sub.f(ZO.sub.1/2).sub.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.

[0207] In a twenty-fifth embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is branched and comprises unit formula: R.sup.AldSiR.sup.12.sub.3, where each R.sup.12 is selected from R.sup.13 and OSi(R.sup.14).sub.3; where each R.sup.13 is a monovalent hydrocarbon group; where each R.sup.14 is selected from R.sup.13, OSi(R.sup.15).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.15 is selected from R.sup.13, OSi(R.sup.16).sub.3, and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; where each R.sup.16 is selected from R.sup.13 and [OSiR.sup.13.sub.2].sub.iiOSiR.sup.13.sub.3; and where subscript ii has a value such that 05 ii100, with the proviso that at least two of R.sup.12 are OSi(R.sup.14).sub.3.

[0208] In a twenty-sixth embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is a Q branched aldehyde-functional polyorganosiloxane oligomer comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.q(R.sup.4.sub.2R.sup.AldSiO.sub.1/2).sub.r(R.sup.4.sub.2SiO.sub.2/2).sub.s(SiO.sub.4/2).sub.t, where subscripts q, r, s, and t have average values such that 2q0, 4r0, 995s4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart a viscosity>170 mPa.Math.s measured by rotational viscometry (as described below with the test methods) to the Q branched polyorganosiloxane; and

[0209] In a twenty-seventh embodiment, in the process of the twentieth embodiment, the aldehyde-functional polyorganosiloxane is a T branched aldehyde-functional polyorganosiloxane comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.aa(R.sup.AldR.sup.4.sub.2SiO.sub.1/2).sub.bb(R.sup.4.sub.2SiO.sub.2/2).sub.cc(R.sup.AldR.sup.4SiO.sub.2/2).sub.ee(R.sup.4SiO.sub.3/2).sub.dd, where subscript aa0, subscript bb>0, subscript cc is 15 to 995, subscript dd>0, and subscript ee0.

[0210] In a twenty-eighth embodiment, in the process of any one of the twentieth to twenty-seventh embodiments, each R.sup.Ald is independently selected from the group consisting of propyl aldehyde, butyl aldehyde, and heptyl aldehyde.

[0211] In a twenty-ninth embodiment, in the process of any one of the twentieth to twenty-eighth embodiments, each R.sup.4 is independently selected from the group consisting of methyl and phenyl.

[0212] In a thirtieth embodiment, the process of any one of the first to twenty-ninth embodiments further comprises recovering the aldehyde-functional organosilicon compound before step 2).

[0213] In a thirty-first embodiment, in step 2) of the process of any one of the first to thirtieth embodiments an oxidation reaction catalyst is added.

[0214] In a thirty-second embodiment, in the process of the thirty-first embodiment, the oxidation reaction catalyst comprises a transition metal complex.

[0215] In a thirty-third embodiment, in the process of the thirty-second embodiment, the transition metal complex comprises a transition metal selected from the group consisting of Co, Cu, Ni, Mn, and Rh.

[0216] In a thirty-fourth embodiment, in the process of the thirty-first embodiment, the oxidation reaction catalyst is an organocatalyst containing N-hydroxy functionality.

[0217] In a thirty-fifth embodiment, in the process of the thirty-fourth embodiment, the organocatalyst is selected from the group consisting of N-hydroxyphthalimide and 2,2,6,6-Tetramethylpiperidin-1-yl)oxyl.

[0218] In a thirty-sixth embodiment, the process of any one of the first to thirty-fifth embodiments, further comprises 3) recovering the carboxy-functional organosilicon compound from the oxidation reaction product after step 2).

[0219] In a thirty-seventh embodiment, in the process of the second embodiment, the carboxy-functional organosilicon compound comprises a carboxy-functional silane of formula: R.sup.Car.sub.xSiR.sup.4.sub.(4-x), where each R.sup.Car is an independently selected carboxy group of 3 to 9 carbon atoms of formula

##STR00047##

where G is a divalent hydrocarbon group free of aliphatic unsaturation that has 2 to 8 carbon atoms; each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and an hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4.

[0220] In a thirty-eighth embodiment, in the process of the third embodiment, the carboxy-functional organosilicon compound comprises a carboxy-functional polyorganosiloxane of unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.CarSiO.sub.3/2).sub.f(SiO.sub.4/2).sub.g(ZO.sub.1/2).sub.h; where each R.sup.Car is an independently selected carboxy group of 3 to 9 carbon atoms of formula

##STR00048##

where G is a divalent hydrocarbon group free of aliphatic unsaturation that has 2 to 8 carbon atoms; each R.sup.4 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R.sup.5, where each R.sup.5 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; subscripts a, b, c, d, e, f, and g represent numbers of each unit in the unit formula and have values such that subscript a0, subscript b0, subscript c0, subscript d0, subscript e0, subscript f0, subscript g0; and subscript h has a value such that 0h/(e+f+g)1.5, with the proviso that when e=f=g=0, then h0,10,000(a+b+c+d+e+f+g)2, and a quantity (b+d+f)1.

[0221] In a thirty-ninth embodiment, in the process of the thirty-eighth embodiment, the carboxy-functional polyorganosiloxane is cyclic and has a unit formula selected from the group consisting of (R.sup.4R.sup.CarSiO.sub.2/2).sub.d, where subscript d is 3 to 12; (R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d, where subscript c is >0 to 6 and subscript d is 3 to 12.

[0222] In a fortieth embodiment, in the process of the thirty-eighth embodiment, the carboxy-functional polyorganosiloxane is linear and comprises unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d, where a quantity (a+b)=2, a quantity (b+d)1, and a quantity (a+b+c+d)2.

[0223] In a forty-first embodiment, in the process of the thirty-eighth embodiment, the carboxy-functional polyorganosiloxane is a carboxy-functional polyorganosilicate resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.mm(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.nn(SiO.sub.4/2).sub.oo(ZO.sub.1/2).sub.h, where subscripts mm, nn, and oo represent mole percentages of each unit in the polyorganosilicate resin; and subscripts mm, nn and oo have average values such that mm0, nn0, oo>0, and 0.5(mm+nn)/oo4.

[0224] In a forty-second embodiment, in the process of the thirty-eighth embodiment, the carboxy-functional polyorganosiloxane is a carboxy-functional silsesquioxane resin comprising unit formula: (R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2R.sup.CarSiO.sub.1/2).sub.b(R.sup.4.sub.2SiO.sub.2/2).sub.c(R.sup.4R.sup.CarSiO.sub.2/2).sub.d(R.sup.4SiO.sub.3/2).sub.e(R.sup.CarSiO.sub.3/2).sub.f(ZO.sub.1/2).sub.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.

[0225] In a forty-third embodiment, in the process of the thirty-eighth embodiment, where the carboxy-functional polyorganosiloxane is branched.

[0226] In a forty-fourth embodiment, in the process of any one of the thirty-seventh embodiment to the forty-third embodiment, each R.sup.Car is independently selected from the group consisting of (C.sub.2H.sub.4)C(O)OH, (C.sub.3H.sub.6)C(O)OH, and (C.sub.6H.sub.12)C(O)OH.

[0227] In a forty-fifth embodiment, in the process of any one of the thirty-seventh embodiment to the forty-fourth embodiment, where each R.sup.4 is independently selected from the group consisting of methyl and phenyl.

[0228] In a forty-sixth embodiment, in the process of any one of the preceding embodiments, the oxidation reaction is conducted at a temperature of 0 to 100 C.

[0229] In a forty-seventh embodiment, in the process of any one of the preceding embodiments, the starting materials are exposed to ultra-violet radiation during the oxidation reaction in step 2).