CA3006651A1 - Near cyclic siloxane-free silicones - Google Patents

Abstract

The present application provides a method for the preparation of siloxane oligomers or polymers essentially without the attendant co-generation of cyclic silicone oligomers by the addition of water, alcohols or alkoxysilanes to hydridosiloxanes in the presence of a Lewis acid, of which B(C6F5)3 is particularly suitable example.
The mild and selective reaction permits the preparation of small linear and branched siloxane oligomers or polymers. Silicone oligomers provide alternatives to cyclomethicones in personal care applications.

Description

NEAR CYCLIC SILOXANE-FREE SILICONES
FIELD
[0001] The present application relates to the preparation of linear or branched silicone oligomers and polymers essentially without the co-generation of low molecular weight cyclic silicone by-products, by the addition of water, alcohols or alkoxysilanes to hydride-containing silanes or siloxanes in the presence of an appropriate Lewis acid.
BACKGROUND

[0002] Silicone polymers, particularly, polydimethylsiloxanes (PDMS), are widely used in the form of fluids, oils, elastomers and resins due to their characteristics, which include high thermal and electrical stability, optical transparency, high flexibility, low biological activity, and, in the case of elastomers, ease of fabrication and the ability to take complex shapes in molds, etc.1 Their good 'skin feel' has made them widely used constituents in personal care products in the form of medium to high viscosity oils, oil swollen elastomers, elastomers and, particularly, low viscosity oils. In the latter case, cyclomethicones ¨ typically a mixture of D4 and D5 in various ratios (D =
Me2SiO) ¨
constitute a particularly broadly used class of molecules that benefit from low heats of vaporization, optical transparency and good skin feel.

[0003] The data for the safety of D4 is very strong following extensive exposure studies of various animal populations including humans.2-3 However, because of selected studies on rats, which indicated D4 could be a reproductive toxin in certain circumstances, its use was mostly supplanted in personal care compositions by D5, which has a lower vapor pressure and is understood to be safe for human exposure by inhalation or other routes of contact.

[0004] Strong evidence has similarly been produced for the safety of D4 and D5 in the environment; efficient pathways to environmental and microbial degradation exist, ultimately leading to the formation of sand, water and CO2.4-7 In spite of the data, certain regulators have expressed concern that the cyclic compounds could be PBT
(persistent, bioaccumulative and toxic), particularly D4. To avoid concerns by regulators and consumers alike, there is a desire to replace, in personal care and other products, cyclomethicones in their various forms by other ingredients that deliver comparable levels of performance, but are 'cyclic silicone free.8

[0005] The classic method for the preparation of linear dimethylsilicone polymers involves first the hydrolysis and then condensation of active silane monomers, among which Me2SiCl2 is an important example.9 In all such processes, the primary products of hydrolysis and condensation are mixtures of linear and cyclic siloxane materials; the specific ratios of cyclics are dependent upon reaction conditions (primarily D4 (Me2Si0)4 with lower quantities of D3 and higher homologues).19 Note that analogous processes may be used to produce silicone polymers in which one or more methyl groups is substituted with other (functional) alkyl or aryl residues.

[0006] Upon exposure to acids or bases, both linear and cyclic silicones undergo equilibration between linear and cyclic forms. For example, the neat reaction of D4 (Me2Si0)4 and Me3SiOSiMe3 (MM) in the presence of acid gives a mixture of about 85%
linear polymers and 15% cyclic siloxanes." A similar outcome results from base catalysis, once equilibrium is achieved. The reverse reaction similarly occurs, such that exposure of linear or elastomeric silicone polymers to acid or base leads, among other degradation products, to the formation of cyclic siloxane monomers. As a consequence of this equilibrium, most silicone oils, elastomers and even more highly reticulated elastomers and resins contain measureable and in some cases significant quantities of cyclic materials.

[0007] The classic methods to remove cyclics from silicones include distillation techniques with heat and, optionally, vacuum. In the case of fluids or gels, high surface area evaporation, for example, with a wiped film evaporator, may be required.12 Such a process is typically inefficient with elastomers, such that solvent extraction and/or thermal processing may instead be utilized. For example, post cure baking for - 4 hours at 200 C to remove volatiles is required by regulators for certain types of products, such as biomaterials.13-18 Thus, traditional methods for silicone synthesis and processing lend themselves to contamination by cyclic silicones. It is difficult to remove cyclic siloxanes from their linear analogues of comparable molecular weight because of the similarity of boiling points.

[0008] The Piers-Rubinsztajn reaction ("PR reaction") involves the condensation of hydrosilanes, including hydrosiloxanes ("HSi compounds"), with alkoxysilanes (Figure 1). The product is a siloxane and alkane. The PR reaction is described in US
patent 7,064,173,16. Analogous processes operate between HSi compounds and borates,17 phenols,18 silanols,19 and alkoxybenzene derivatives,29 respectively, all of which generate new siloxane bonds.21 The catalyst most commonly used for these processes is B(C6F5)3 (BCF) including a photoactivated version.22 Other relatively water stable and hydrophobic Lewis acid catalysts known in the art, particularly based on arylboranes, will similarly promote these reactions, as reviewed by Oestreich et al. 23

[0009] An analogous Piers-Rubinsztajn reaction occurs between hydrosilanes or hydrosiloxanes and silanols, as has been reported by Kawakami et al.19 (Figure 1).
Ganachaud et al. reported, starting from MHM" (HSiMe20SiMe2H) with B(C6F5)3 as catalyst, the formation of cyclic silicones and subsequent acid-catalyzed ring-opening polymerization into silicone polymers in water as solvent.24 SUMMARY

[0010] It has now been discovered that the formation of silanols from hydrosilanes may be initiated simply by exposing hydrosilanes to water or alcohols (sometimes higher temperatures are required) in the presence of B(C6F5)3 and that, under appropriate reaction conditions, formation of cyclic siloxane is not efficient.

[0011] Hydrosilanes and hydrosiloxanes (HSiR3) can be used for the preparation of linear, branched and network silicones by reaction with alkoxysilanes in the presence of boron-based Lewis acids, typically B(C6F5)3 (Figure 3). It is reported herein that an analogous process can occur simply with the addition of equimolar amounts of water (or selected alcohols) to hydrosilanes to give low molecular weight siloxanes without significant, concomitant cyclic siloxane formation. This reaction was previously reported using water as a reaction medium,24 the authors noted, "the reaction is too fast and non-controlled." This prior report did not disclose the use of water in amounts and under conditions for it to act as a chain extender.

[0012] Note that while carboxylic acids and like active OH and SH
compounds26 can similarly convert silanes into siloxanes, the efficiency of these processes is compromised by the presence of carbonyl and related functional groups with which the HSi compounds can also react (that is, much higher quantities of SiH compounds are required), as is described by Piers,26-28 and others,29 which are included in total by reference.

[0013]
The present application therefore includes a process for preparing siloxane oligomers or polymers containing low levels of cyclic siloxanes comprising combining a compound of Formula I or a compound of Formula II:

/ R210010R8/oly R3 R5 y R9 R12 R14 ¨rn (I) or - P (II) wherein R1-R5, R7-R9, R10, R12 and r-114 are independently selected from Ci-walkyl, C2-/
ioalkenyl, C2-ioalkynyl, aryl, R17 and linear and branched siloxanes;
R6 and R13 are independently selected from Ci_walkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;

R161i,o_L
R11 is selected from H, C21oalkenyl, C2-ioalkynyl, aryl, R17 and linear and branched siloxanes;
R15-R17 are independently selected from Ci-valkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;
Y is H;
n is 0, 1 or 2;
m is 1 or 2; and (CA 3006651 2018-05-30 p is 1,2 or 3;
with (a) a chain extender selected from:
(i) H20, D20 and HOD;
(ii) Ci-loalkylOH;
(iii) a compound of Formula III:

D19 0 1 vSi / 0 \
R20 R22 Y' R26 wherein R18-R22 and R24-R26 are independently selected from Ci-ioalkyl, C2-ioalkenyl, ioalkynyl, aryl, R29 and linear and branched siloxanes;
R23 is selected from Ci-malkyl, C2-ioalkenyl, C2-loalkynyl and aryl;
R27-R29 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;
Y is OH, OD or and OCi_ioalkyl; and q is 0, 1 or 2; and and (iv) a compound of Formula IV:

s (IV) wherein R30, R32 and R34 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, aryl, R3' and linear and branched siloxanes;

R361 \ 0 4_ R31 is selected from Y", Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, aryl, R37 and linear and branched siloxanes;
R33 is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;
R35-R37 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;
Y" is OH, OD or and OCi-loalkyl;
s is 1, 2 or 3; and (b) a Lewis acid selected from B(C6F5)3 and ArB(C6F5)2, where Ar is an aryl group, that is optionally fluoro-substituted, wherein the amount of the chain extender is equimolar with the amount of the compound of Formula I or II.

[0014]
The present application also includes a siloxane oligomer containing low levels of cyclic siloxanes prepared using a process of the application as described herein.

[0015]
The present application also includes a siloxane polymer containing low levels of cyclic siloxanes prepared using a process of the application as described herein.

[0016]
The present application also includes a method of preparing a personal care product comprising combining one or more siloxane oligomers prepared using a process of the application as described herein with components for the personal care product.

[0017]
The present application also includes a personal care product comprising one or more of the siloxane oligomers prepared using a process of the application as described herein with components for the personal care product.

[0018] The present application also includes a personal care product comprising one or more siloxane oligomers containing low levels of cyclic siloxanes prepared using a process of the application as described herein.

[0019] Other features and advantages of the present application will become apparent from the following detailed description. However, it should be understood that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments, but should be given the broadest interpretation consistent with the description as a whole.
BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The embodiments of the application will now be described in greater detail with reference to the attached drawings in which:

[0021] Figure 1 shows selected Pier- Rubinsztajn-type reactions known in the art.

[0022] Figure 2 shows dimerization reactions of monofunctional siloxanes in exemplary embodiments of the application.

[0023] Figure 3 shows chain extension of di- or poly-functional siloxanes in exemplary embodiments of the application.
DETAILED DESCRIPTION OF THE APPLICATION
Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art.

[0024] The present application refers to a number of chemical terms and abbreviations used by those skilled in the art. Nevertheless, definitions of selected terms are provided for clarity and consistency.

[0025] As used herein, the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "include" and "includes") or "containing" (and any form of containing, such as "contain" and "contains"), are inclusive or open-ended and do not exclude additional, unrecited elements or process/method steps.

[0026] As used herein, the word "consisting" and its derivatives, are intended to be close ended terms that specify the presence of stated features, elements, components, groups, integers, and/or steps, and also exclude the presence of other unstated features, elements, components, groups, integers and/or steps.

[0027] The term "consisting essentially of", as used herein, is intended to specify the presence of the stated features, elements, components, groups, integers, and/or steps as well as those that do not materially affect the basic and novel characteristic(s) of these features, elements, components, groups, integers, and/or steps.

[0028] Terms of degree such as "substantially", "about" and "approximately" as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least 5% of the modified term if this deviation would not negate the meaning of the word it modifies.

[0029] As used in this application, the singular forms "a", "an" and "the" include plural references unless the content clearly dictates otherwise. For example, an embodiment including "a compound" should be understood to present certain aspects with one compound or two or more compounds. In embodiments comprising an "additional" or "second" component, such as an additional or second compound, the second component as used herein is chemically different from the other components or first component. A "third" component is different from the other, first, and second components, and further enumerated or "additional" components are similarly different.

[0030] The term "and/or" as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that "at least one of" or "one or more" of the listed items is used or present.

[0031] The term "alkyl" as used herein, whether it is used alone or as part of another group, means straight or branched chain, saturated alkyl groups. The number of carbon atoms that are possible in the referenced alkyl group are indicated by the prefix "Cn1-n2". For example, the term Ci-ioalkyl means an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0032]
The term "alkenyl" as used herein, whether it is used alone or as part of another group, means straight or branched chain, unsaturated alkyl groups containing at least one double bond. The number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix "Cni-n2". For example, the term C2-ioalkenyl means an alkenyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and at least one double bond.

[0033]
The term "alkynyl" as used herein, whether it is used alone or as part of another group, means straight or branched chain, unsaturated alkyl groups containing at least one triple bond. The number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix "Cni-n2". For example, the term C2-ioalkynyl means an alkynyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and at least one triple bond.

[0034]
The term "aryl" as used herein, whether it is used alone or as part of another group, refers to cyclic groups containing from 6 to 20 carbon atoms and at least one aromatic ring. In an embodiment of the application, the aryl group contains from 6, 9 or carbon atoms, such as phenyl, indanyl or naphthyl.

[0035]
The term monomer is used to describe a silane or siloxane moiety that is possible of undergoing reactions to give siloxane products of increased molecular weight.

[0036]
The term oligomer is used to describe a siloxane moiety that is prepared by reactions of lower molecular weight siloxanes or silanes (monomers). The number of monomers contained in an oligomer is <20.

[0037]
The term "linear siloxane" as used herein refers to a group comprising R R"
14' units, wherein R, R', R" and R" are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2_10alkynyl and aryl, arranged in linear fashion. The number of units may R""---be between 1 and 10 with the terminal group being 14 , wherein R" is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl.

[0038]
The term "branched siloxane" as used herein refers to a group comprising R R"
units, wherein R, R', R" and R" are as defined above, with the exception that at least one of R, R', R" and R" is k . The number of units may be between 1 and with any terminal group being R , wherein R" is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl.

[0039]
The present application includes a process for preparing siloxane oligomers or polymers containing low levels of cyclic siloxanes comprising combining a compound of Formula 1 or a compound of Formula 11:

/2 Rh10 I y -n- (I) or - P (II) wherein R1-R5, R7-R9, R10, R12 and Ru are independently selected from Ci-ioalkyl, C2-"
ioalkenyl, C2-ioalkynyl, aryl, R17 and linear and branched siloxanes;
R6 and R13 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;

=

/ R160__ is selected from H, Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, aryl, R17 and linear and branched siloxanes;
R16-R17 are independently selected from Ci-ioalkyl, C2_ioalkenyl, C2-ioalkynyl and aryl;
Y is H;
n is 0, 1 or 2;
m is 1 0r2; and p is 1,2 or 3;
with (a) a chain extender selected from:
(i) H20, D20 and HOD;
(ii) Ci-loalkylOH;
(iii) a compound of Formula Ill:

R19/ 01 ol 0R25\
R20 R22 Y' R26 (Ill) wherein R.18-R22 and R24-R26 are independently selected from Ci-ioalkyl, C2-ioalkenyl, loalkynyl, aryl, R29 and linear and branched siloxanes;
R23 is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;
R27-R29 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl;
Y' is OH, OD or and OCi-loalkyl; and q is 0, 1 or 2; and (iv) a compound of Formula IV:

031--Si " / 0 - -s (IV) wherein R30, R32 and R34 are independently selected from Ci-walkyl, C2-walkenyl, C2-R361 0__ walkynyl, aryl, R37 ' and linear and branched siloxanes;

R36 --Si R31 is selected from Y", Ci-walkyl, C2-walkenyl, C2-walkynyl, aryl, R37 and linear and branched siloxanes;
R33 is selected from Ci-walkyl, C2-walkenyl, C2-walkynyl and aryl;
R35-R37 are independently selected from Ci-walkyl, C2-walkenyl, C2-walkynyl and aryl;
Y" is OH, OD or and 0C-i-walkyl;
s is 1,2 0r3; and (b) a Lewis acid selected from B(C6F5)3 and ArB(C6F5)2, where Ar is an aryl group, that is optionally fluoro-substituted, wherein the amount of the chain extender is equimolar with the amount of the compound of Formula I or II.

[0040] In some embodiments, the process is for the preparation of siloxane oligomers and polymers containing between 0 wt% and 10 wt%, 0.01 wt% and 5 wt%, 0.1 wt% and 1 wt%, or less than 100 ppm cyclic siloxanes.

[0041] In some embodiments, the Lewis acid is B(C6F6)3.

[0042] In some embodiments, m is 1; R11 is selected from Ci-walkyl, C2-walkenyl, C2-loalkynyl, aryl, R17 and linear and branched siloxanes; and R360__ R31 is selected from Ci-walkyl, C2-walkenyl, C2-walkynyl, aryl, R37 and linear and branched siloxanes; and the process is for the preparation of siloxane oligomers.

[0043] In some embodiments, m is 2; R11 is H; and R31 is Y"; and the process is for the preparation of siloxane polymers.

[0044] In some embodiments, Y' and Y" are OH or and OD or and OCi-walkyl.

[0045] In some embodiments, R1-R14 are the same and are selected from Ci-ioalkyl C2-walkenyl, C2-walkynyl and aryl. In some embodiments, R1-R14 are the same and are selected from Ci-salkyl. In some embodiments, R1-R14 are the same and are CH3.

[0046] In some embodiments, R18-R26 or R30-R34 are the same and are selected from Ci-walkyl. In some embodiments, R18-R26 or R30-R34 are the same and are selected from C1-6a1ky1. In some embodiments, R18-R26 or R30-R34 are the same and are CH3.

[0047] In some embodiments, the chain extender is H20. In some embodiments, the H20 is in the form of: i) atmospheric water; ii) bulk water droplets; iii) water dispersed in an organic solvent; or iv) water dissolved in an organic solvent.

[0048] In some embodiments, the chain extender is a compound of Formula III or IV.

[0049] In some embodiments, the cyclic siloxanes are selected from one or more of D3, D4 and D5.

[0050] In some embodiments, the compound of Formula II is Me3SiOSiMe2H.
In some embodiments, the compound of Formula I is Me3SiOSiMeHOSiMe3. In some embodiments, the compound of Formula I is Me3SiOMe2SiOSiMeHOSiMe3.

[0051] In some embodiments, the amount of the Lewis acid is about 0.01 mol% to about 1 mol% or about 0.05 mol% to about 0.2 mol%.

[0052] The present application also includes a siloxane oligomer containing low levels of cyclic siloxanes prepared using a process of the application as described herein.

[0053] The present application also includes a siloxane polymer containing low levels of cyclic siloxanes prepared using a process of the application as described herein.

[0054] The present application also includes a method of preparing a personal care product comprising combining one or more siloxane oligomers prepared using a process of the application as described herein with components for the personal care product.

[0055] The present application also includes a personal care product comprising one or more of the siloxane oligomers prepared using a process of the application as described herein with components for the personal care product.

[0056] The present application also includes a personal care product comprising one or more siloxane oligomers containing low levels of cyclic siloxanes prepared using a process of the application as described herein.

[0057] The following non-limiting examples are illustrative of the present application. As is apparent to those skilled in the art, many of the details of the examples may be changed while still practicing the methods, compositions and kits described herein.
EXAMPLES
Materials

[0058] Pentamethyldisiloxane (MM"), bis(trimethylsiloxy)methylsilane (MDHM), tris(trimethylsiloxy)silane (M3TH) and tetramethyldisiloxane (MHMH) were purchased from Gelest and dried over molecular sieves before use. a,(0-Hydride-terminated poly(dimethylsiloxane) (H-PDMS-H, DMS-H03 (450 g mo1-1, 2-3 cSt), DMS-H11 (1,600 g mo1-1, 7-10 cSt), DMS-H25 (16,000 g mol-1, 500 cSt), DMS-H31 (27,600 g m01-1, 1,000 cSt), DMS-H41 (62,700 g m01-1, 10,000 cSt)), a,w-hydroxyl-terminated poly(dimethylsiloxane) (HO-PDMS-OH, DMS-S14 (1,270 g mo1-1, 35-45 cSt), DMS-(21,600 g mol-1, 1,000 cSt)) and a,co-hydride-terminated polyphenylmethylsiloxane (PMS-H03 (340 g mo1-1, 2-5 cSt)) were purchased from Gelest and were purified using kugelrohr distillation before use. Tetramethylcyclotetrasiloxane (D14) was purchased from Sigma Aldrich and used as received. Ultrapure water (18 MD-cm) was obtained from Easy pure RF (Barnstead). The B(C6F5)3 catalyst was provided by Alfa Aesar. Toluene (Caledon) was dried over an activated alumina column.
Methods

[0059] 1H and 29Si NMR spectra were recorded on a Bruker Advance 600 MHz nuclear magnetic resonance spectrometer using deuterated solvent chloroform-d.

[0060] Polymer molecular weights were established by gel permeation chromatography (GPC) using a Waters Alliance GPC System 2695 calibrated with a polystyrene calibration kit S-M-10 (Lot 85) from Polymer Laboratories.

[0061] GC-MS analyses were performed using an Agilent 6890N gas chromatograph (Santa Clara, CA, USA), equipped with a DB-17ht column (30 m x 0.25 mm i.d. x 0.15 pm film, J & W Scientific) and a retention gap (deactivated fused silica, 5 m x 0.53 mm i.d.), and coupled to an Agilent 5973 MSD single quadruple mass spectrometer. One microliter of sample was injected using Agilent 7683 autosampler with a 10:1 split and slit flow of 7.0 ml/min. The injector temperature was 250 C
and carrier gas (helium) flow was 0.7 ml/min. The transfer line was 280 C and the MS
source temperature was 230 C. The column temperature started at 50 C and raised to at 8 C/min, and then held at 300 C for 10 min for a total run time of 41.25 min. Full scan mass spectra between m/z 50 and 800 were acquired after five min solvent delay.

[0062] FTIR data was collected on a Nicolet 6700 FTIR using Thermo Electron's OMNIC software.

Hydrolysis reaction using pentamethyldisiloxane WWI + H20 ([0HF[SiH]=4;
[BCFJ/[SiEl]=0.1 mol%))

[0063] Pentamethyldisiloxane (11.9 g, 0.08 mol) and H20 droplets (2.88 ml, 0.16 mol) were placed in a 1L three-neck round-bottomed flask which was connected to a condenser under nitrogen protection and to which was added B(C6F5)3 (0.1M, 0.72 ml, 0.072 mmol) diluted in toluene at room temperature. After 3 h the reaction was quenched by a small quantity of neutral alumina, the product was collected by filtration through Celite under reduced pressure. The mass balance of the reaction is 86% 10.76 g due to volatility of some of the ingredients.

[0064] Pentamethyldisiloxane: 1H NMR (600 MHz, chloroform-d): 6 4.676-4.68 (sept, J = 2.8 Hz, 1H), 0.17 (d, J = 2.8 Hz, 6H), 0.09 (s, 9H) ppm. 29Si NMR
(600 MHz, chloroform-d, 119 MHz, trace Cr(acac)3): 6 9.71 (s, 1Si), -6.76 (s, 1Si) ppm.
GC-MS:
C5I-1160Si2, calculated: 148, found: [M-15]=133.1 (100).

[0065] Hydrolysis products of pentamethyldisiloxane: 1H NMR (600 MHz, chloroform-d): 6 1.54 (s, 0.2H), 0.09 (s, 6H), 0.05 (s, 4H) ppm. 29Si NMR (600 MHz, chloroform-d, 119MHz, trace Cr(acac)3): 6 9.24 (s, 1 Si), -21.49 (s, 1Si) ppm.
GC-MS:
C1oH3003Si4, calculated: 310, found: [M-15]=295.1 (40), 207.1(100), 73.1 (30).

C12H3604Si5, calculated: 384, found: [M-15]= 369.2 (40), 281.1 (100), 147.1 (55), 73.2 (25). C14H4205Si6, calculated: 458, found: [M-15]=443.2 (20), 355.1 (40), 281.1 (60), 221.1 (100), 207.1 (45), 147.1 (70), 91.1 (50), 73.1 (60). C16H4806Si7, calculated: 532, found: [M-15]=517.2 (5), 341.0 (20), 207.1 (80), 91.2 (100).
Hydrolysis products of Bis(trimethylsiloxy)methylsilane - MDFIRA + H20 ([0H]I[SiH]=4; [BCF]/[SiH]=0.1 mol%)

[0066] Bis(trimethylsiloxy)methylsilane (17.8 g, 0.08 mol) and H20 droplets (2.88 ml, 0.16 mol) were placed in a 1L three-neck round-bottomed flask which was connected to a condenser under nitrogen protection and to which was added B(C6F5)3 (0.1M, 0.72 ml, 0.072 mmol) diluted in toluene at room temperature. After 3 h the reaction was quenched by alumina. The yield of the reaction is 95% (17.44 g).

[0067] Bis(trimethylsiloxy)methylsilane: 1H NMR (600 MHz, chloroform-d):
6 4.63 (d, J = 1.5 Hz, 1H), 1.54 (s, 0.3H), 0.12 (s, 18H), 0.10 (d, J = 1.6 Hz, 3H) ppm. 29Si NMR
(600 MHz, chloroform-d, 119MHz, trace Cr(acac)3): 69.36 (s, 2Si), -36.40 (s, 1Si) ppm.
GC-MS: C7H2202Si3, calculated: 222, found: [M-15]=207.2 (100), 73.1 (50)

[0068] Hydrolysis products of Bis(trimethylsiloxy)methylsilane: 1H NMR
(600 MHz, chloroform-d): 6 1.55 (s, 0.1H), 0.10 (s, 36H), 0.02 (s, 6H) ppm.29Si NMR (600 MHz, chloroform-d, 119MHz, trace Cr(acac)3): 67.59 (s, 4Si), -54.51 (s, 0.17Si), -65.93 (s, 2Si) ppm. GC-MS: compound insufficient sensitivity to characterize the peak to characterize the peak, [M-15]=355.0 (5), 207.1 (100), 106.1 (100), 77.1 (80), 51.1 (30).
C14H4205S16, calculated: 458, found: [M-15]=443.2 (50), 355.1 (50), 281.1 (55), 221.1 (100), 147.1 (70), 73.1 (75).
Hydrolysis reaction using a mixture of pentamethyldisiloxane (MM") and bis(trimethylsiloxy)methylsilane (MDHM)-MA/1" + MIDHM + H20 ([OH]/[Sill]=4;
[BCF]![S1H]=0.1 mol%)

[0069] Pentamethyldisiloxane (1.50 g, 0.01 mol), bis(trimethylsiloxy)methylsilane (2.24 g, 0.01 mol) and H20 droplets (0.72 ml, 0.04 mol) were placed in a 50 ml plastic test tube that was connected to a condenser under nitrogen protection and to which was added B(C6F5)3 (0.1M, 0.18m1, 0.018 mmol) diluted in toluene at room temperature. After 3 h the reaction was quenched by alumina, the product was collected by filtration through Celite under reduced pressure.

[0070] Hydrolysis products using pentamethyldisiloxane with bis(trimethylsiloxy)methylsilane: 1H NMR (600 MHz, Chloroform-d): 6 2.04 (s, 0.03H), 0.13 (s, 1H), 0.10 (d, J = 5.0 Hz, 15H), 0.05 (s, 3H), 0.03 (s, 2H) ppm. 29Si NMR (600 MHz, Chloroform-d, 119MHz, trace Cr(acac)3): 6 8.66 (s, 1Si), 7.58 (s, 20Si), 7.23 (s, 10Si), -21.50 (s, 9Si), -21.68 (s,1Si), -54.50(s, 2Si), -65.37 (s, 2Si), -65.93 (s, 11Si) ppm.
GC-MS: C1oH3003Si4, calculated: 310, found: [M-151=295.1 (50), 207.1(100), 73.1 (50).
C12H3604Si5, calculated: 384, found: [M-15]=369.1 (30), 281.1 (100), 207.0 (90), 147.1 (40), 91.1 (25). C14H4205Si6, calculated: 458, found: [M-15]=443.2 (60), 355.1 (60), 281.1 (70), 221.1 (100),147.1 (70), 73.1 (75).

Hydrolysis reaction using tris(trimethylsiloxy)silane - M3TH + H20 ([0H1/[SiH]=4;
[BCF]/[S11-11=0.1 mol%)

[0071] Tris(trimethylsiloxy)silane (23.7 g, 0.08 mol) and H20 droplets (2.88 ml, 0.16 mol) were placed in a 1L three-neck round-bottomed flask that was connected to a condenser under nitrogen protection and to which was added B(C6F5)3 (0.1M, 0.72 ml, 0.072 mmol) diluted in toluene at room temperature. After 3 h the reaction was quenched by alumina, the product was collected by filtration through Celite under reduced pressure.
The characterizations are shown as below:

[0072] Tris(trimethylsiloxy)silane: 1H NMR (600 MHz, chloroform-d): 6 4.23 (s, 1H), 1.51 (s, 0.20H), 0.12 (s, 27H) ppm. 29Si NMR (600 MHz, chloroform-d, 119 MHz, trace Cr(acac)3): 6 9.41 (s, 3S1), -82.74 (s, 1Si) ppm. no reaction products were observed.

[0073] Monofunctional silanes or silicone monomers, oligomers, and polymers are, in some cases, commercially available, or can be readily synthesized.39 Exposure of monofunctional silicones to water in the form of: i) atmospheric water, ii) bulk water droplets, iii) water dispersed in an organic solvent or water dissolved in an organic solvent, in the presence of a Lewis acid catalyst such as B(C6F5)3 leads to dimerization in good to excellent yield. Exposure of small, monofunctional hydrosilanes or hydrosiloxanes to water or alcohols in the presence of an appropriate Lewis acid, such as B(C6F5)3, leads to dimerization to form disiloxanes and hydrogen gas. Note: hydrogen gas is a by-product of these reactions and appropriate caution must be exercised both with respect to flammability and buildup of pressure.

[0074] Sterics affected the outcome of the process. Using water droplets (bulk water), the bulkiest silane (M3TH) did not appreciably react within 3 hours (Figure 2A), whereas the less branched analogues Me3SiOSiMe2H and (Me3Si0)2SiMeH underwent complete reaction in 2-3 hours to give homodimers Me3SiOSiMe20SiMe20SiMe3 and (Me3Si0)2SiMe0SiMe(SiOMe3)2, respectively (Figure 2B,D); hydrogen bubble evolution was easily seen to occur at the water/silicone oil interface. A competition reaction between Me3SiOSiMe2H and (Me3Si0)2SiMeH, surprisingly, led mostly to the homodimers, with about 10-20% formation of the crossproduct as shown by GC/MS
(Figure 2C). Note that the cross-product (Me3Si0)2SiMe0SiMe2SiOMe3 is readily available using a standard Piers-Rubinsztajn reaction by combining an SiH-containing reagent with an alkoxysilane under the same conditions, for example, MMI1 +
M2Dme (Figure 2E).2531

[0075] The Me3SiOSiMe20SiMe20SiMe3, (Me3Si0)2SiMe0SiMe2SIOMe3 and (Me3Si0)2SiMe0SiMe(SiOMe3)2 produced by the hydrolysis method are essentially cyclic siloxane free, with a good skin feel and low heat of vaporization, that is, with the attributes the find utility in personal care products but without the use of cyclomethicones. The concentration of the cyclic monomers D3, D4 and D5 in the product mixtures was found to be much less than 1% (Table 1, in optimized experiments, none of these cyclics was observed (the limit of detection in these experiments was ¨100 ppm)).

Table 1 GC-MS results for low cyclic-containing silicone oils by hydrolysis of monofunctional hydrosiloxanes MM" +H20 ([0H]/[SiH]=4) Structure Nomenclature Relative Product ratio (%) ratio by GC 29Si NMR
(% 5%) Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si MIDHM +H20 ([0HMSH]=4) Unknown low boiling 3 compound a Si i Si 0 \00 õLa., ./õ0,1,-Si T T
mmH ___________________________ A
mu-im + H20 ([0H1/[SiH]=4) Si Si Si Si Si Si Si -Si--Si-\

Si Si Si o' I ,o, Si T Si a Approximately a pentasiloxane, based on retention time.

[0076]
Water can be replaced in these reactions by alcohols, of which linear aliphatic alcohols such as octanol or chloroethanol serve as non-limiting examples; note elevated temperatures may be required for a facile reaction to occur. One skilled in the art will understand that the rate of reaction can be controlled by changes in temperature, the specific reagents, and the concentrations of the reagents or catalyst. But even without optimization, the reaction is efficient at room temperature. For example, the dimerization of 11.9 g of (Me3Si0)2SiMeH (Me3Si0)2SiMe0SiMe(OSiMe3)2 (M2D11 M2TTM2) was efficient at room temperature, with isolated yields after distillation of 85-95% using 0.1 mol% of BCF and water droplets as a source of water (Figure 2B).

[0077]
A series of experiments was undertaken to establish optimal concentrations of both water and BCF. Concentrations of B(C6F5)3 of 0.01-0.1mol% with respect to [SiH]
are sufficient for efficient reaction (over 90% yield in less than 3 hours).
Higher concentrations may be associated with other processes, including metathesis involving the formation of Me2SiH2, as reported in US Patent 7148370.32-33 The reaction is typically sluggish at lower catalyst concentrations. When the concentration of water is too high -over 2-3wt% - the catalytic activity of B(C6F5)3 is compromised. If an excess of water is provided at the outset, or over time, silanol-terminated oligomers or polymers can form.
Chain extension of telechelic H-terminated silicones

[0078]
General procedure for chain extension using hydrolysis - water droplets (Table 2, 1-4, 7-9): To a mixture of hydride-terminated H-PDMS-H (Mn 500 g m01-1 2.03 g, 4.06 mmol) and distilled water (230 1.11, 13 mmol) in a 100.0 ml round-bottomed flask that was connected to a condenser under a nitrogen blanket, was added tris(pentafluorophenyl)borane diluted in toluene (0.1M, 0.016 ml, 1.6 p.mol).
The mixture was stirred at room temperature. After 3 h, alumina (-0.5 g) was added to the mixture to quench the reaction. The product was collected by filtration through Celite under reduced pressure. Mn 46,000 Mw 86,200, Dm 1.88, Table 2 entry 4. Note: 1H NMR and 29Si NMR
are diagnostic for loss of SiH groups but are otherwise not helpful.
Representative NMR
data is provided; the other samples differ only in the relative magnitude of the SiMe2 peak.

[0079] 1H NMR (600 MHz, chloroform-d): 6 1.54 (s, 20H), 0.17 (m, 6H), 0.14 (s, 1H), 0.07 (m, 258H), -0.03 (s, 1H) ppm. 29Si NMR (600 MHz, chloroform -d, 119MHz, trace Cr(acac)3): 8 -21.94 (s, 1Si) ppm.

[0080] General procedure for chain extension using hydrolysis by moisture in an open flask (Table 2, entry 5): To a 10.0 ml round-bottomed flask was added hydride-terminated H-PDMS-H (500 g mol-1, 2.05 g, 4.1 mmol) with B(C6F5)3 diluted in toluene (0.1M, 0.040 ml, 4 mop ([BCF]/[SiH]=0.05 mol%, humidity: 15%). The mixture was stirred at room temperature open to atmosphere, and after 10 hours alumina (-0.5 g) was added to the mixture to quench the reaction. The product was collected by filtration through Celite under reduced pressure.

[0081] General procedure for chain extension using hydrolysis by moisture in an open flask augmented with wet toluene (Table 2): To a 100.0 ml round-bottomed flask was added hydride-terminated H-PDMS-H (500 g moll, 1.53 g, 3.1 mmol) diluted in 15.0 ml toluene. The mixture was added tris(pentafluorophenyl)borane diluted in toluene (0.04 M, 0.020 ml, 0.771Amol) ([BCF]/[SiH]=0.05 mol%, [OH]/[SiH]=0.08) and stirred at room temperature in an open vessel. After 24 h, alumina (-0.5 g) was added to the mixture to quench the reaction. The product was collected by filtration through Celite under reduced pressure.

[0082] Copolymerization of HMe2SKOSiMe2)nSiMe2H
HOMe2Si(OSiMe2)nSiMe2OH (Table 2, entry 10): To a mixture of hydride-terminated H-PDMS-H (Mn 27,600 g m01-1 1.23 g, 0.045 mmol) and hydroxyl-terminated HO-PDMS-OH
(Mn 21,600 g m01-1 1.05 g, 0.049 mmol) in a 100.0 ml round-bottomed flask that was connected to a condenser under a nitrogen blanket, was added tris(pentafluorophenyl)borane diluted in toluene (0.01M, 0.013 ml, 0.13 [and).
The mixture was stirred at room temperature. After 24 h, alumina (-0.5 g) was added to the mixture to quench the reaction. The product was collected by filtration through Celite under reduced pressure.

[0083] Copolymerization of HMe2Si(OSiMePh)3SiMe2H
HOMe2Si(OSiMe2)nSiMe2OH (Table 2, entry 11): To an oven-dried 100.0 ml round-bottomed flask under nitrogen atmosphere was added dry toluene (5 ml). Si0H-terminated polysiloxane (MW: 1200 g mo1-1, 1.500 g, 1.25 mmol) was added, followed by addition of SiH-terminated polysiloxane (MW: 400, 0.500, 1.25 mmol). To this stirring mixture was added tris(pentafluorophenyl)borane (10 I of a 25.6 mg m1-1 solution in toluene, 0.02 mol% relative to SiH) followed by the lowering of the flask into an oil bath preheated to 50 C. Bubbling commenced quickly, tapering off over 10 min.
Note: if catalyst concentrations higher than 0.02 mol /0 are used, it is advisable to add one of the reagents (SiH or SiOH) dropwise to safely control the rate of gas evolution.
As reaction viscosity increased over the first 2 h, and additional 5-10 ml of dry toluene was added to allow stirring to continue. After 24 h, 0.500 g of neutral alumina was added to quench the catalyst. The reaction mixture was stirred for a further 2 h, filtered through Celite under reduced pressure, and concentrated to afford the product, a colorless oil.
Table 2: Polymerization of HSi-Telechelic Silicones Using Water or HOSi-Telechelic Silicones Entry na [OM/ [BU]! t H20c Mn Mw Dm Copolymer [SiH] [SH]b (h) 1 0 3 200 3 L 50,100 76,300 1.52 2 5 3 200 3 L 27,800 52,600 1.89 3 370 3 200 3 L 33400 50,900 1.53 4 5 3 200 24 L 46,000 86,200 1.88 5 NA 500 24 0 20,000 30,000 1.50 6 5 0.08 500 24 S 183,000 349,000 1.91 7 0 1 80 20 L 20,700 32,500 1.57 8 0 3 200 3 L 50,100 76,300 1.52 9 0 0.6 400 22 L 77,200 140,800 1.83 370 1 500 24 NA 251,000 471,500 1.88 HOSiMe20-(SiMe20)371H
11 MePhd 1 200 24 NA 15,500 24,000 1.55 HOSiMe20-(SiMe20)16H
a n in HSiMe20(SiMe20)nSiMe2H. b in ppm: [BCF]i[SiH] x 106. c L = bulk liquid water (closed system), 0 open system 56% relative humidity, S 230 ppm water in toluene and the flask was open to the atmosphere. d HSiMe20(SiMePh0)3SiMe2H, at 50 C.
Silicone resin preparation using hydrolysis

[0084] Procedure for silicone resin preparation using DH4 and water: DH4 (5.00 g, 20.8 mmol) was placed in a 100.0 ml round bottle flask with B(C6F5)3 (0.078M, 0.625 ml, 0.049 mmol) diluted in toluene. The mixture was stirred at room temperature open to the atmosphere.

[0085] 29Si NMR (850 MHz): 8 -35.78 (s, 5 Si), -56.87 (s, 1 Si), -65.79 (s, 5 Si) ppm.
13C NMR (850 MHz): 6 -2.12 (s, 1 C), -6.19 (s, 1 C) ppm.

[0086] General procedure for silicone elastomer/foam preparation using SiH

compounds and water: Preparation of DH4 stock solution: DH4 (0.12 g, 0.48 mmol) was weighed in a 25.0 ml vial and dissolved in hexane (13.56 ml) to prepare a stock solution of DH4 (8.6 mg m1-1). Preparation of silicone foam using DH4+ DMS-H11 ([BCF]/[SiH]=0.02 mol%) An oven dried round bottom flask was charged with DH4 (2.00 g, 8.31 mmol), DMS-H11 (2.03 g, 1.818 mmol), distilled water (0.055 mol, 997 I), B(C6F5)3 (0.02 mol%, 0.0074 mmol, 73 I). A water condenser was placed on top and a nitrogen balloon was used to maintain a positive pressure of nitrogen, the reaction was stirred for three hours. The resulting foam was removed from the flask and extracted using a Soxhlet extraction device.

[0087] Preparation of silicone foam using H-PDMS-H and DH4 with hexane ([BCF]/[SiH]=0.9 mol%): DMS-H41 (1.53 g, 0.048 mmol) with DH4 (142.7 mM, 34.3 mg m1-1, 0.76 ml) were poured into a Teflon-coated 12 wellplate with B(C6F5)3 (0.078M, 8 I, 0.62 mmol). Once the B(C6F5)3 was added, the mixture was vigorously stirred by hand (-30 s), then placed on the bench at room temperature overnight.

[0088] Preparation of silicone elastomer ([BCF]/[SiH]=0.3 mol%): To a mixture of DMS-H25 (1.53 g, 0.10 mmol), DH4 (35.8 mM, 8.6 mg m1-1, 1 ml) and hexane (1 ml) in a polystyrene Petri dish (10 mm thick 35 mm diameter), B(C6F5)3(0.078M, 15 I, 1.17 mmol) was added. The contents were rapidly stirred at room temperature (-30 s), then moved to a 40 C oven under vacuum (571 Torr) overnight. The Shore 00 hardness of the silicone foam was 8.5.

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Claims (26)

CLAIMS:

1.
A process for preparing siloxane oligomers or polymers containing low levels of cyclic siloxanes comprising combining a compound of Formula I or a compound of Formula II:
wherein R1-R5, R7-R9, R10, R12 and R14 are independently selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl, aryl, and linear and branched siloxanes;
R6 and R13 are independently selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl and aryl;
R11 is selected from H, C2-10alkenyl, C2-10alkynyl, aryl, and linear and branched siloxanes;
R15-R17 are independently selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl and aryl;
Y is H;
n is 0, 1 or 2;
m is 1 or 2; and p is 1, 2 or 3;
with (a) a chain extender selected from:

(i) H2O, D2O and HOD;
(ii) C1-10alkylOH, (iii) a compound of Formula III:
wherein R18-R22 and R24-R26 are independently selected from C1-10alkyl, C2-10alkenyl, 10alkynyl, aryl, and linear and branched siloxanes;
R23 is selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl and aryl;
R27- R29 are independently selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl and aryl;
Y' is OH, OD or and OC1-10alkyl; and q is 0, 1 or 2; and (iv) a compound of Formula IV:
wherein R30, R32 and R34 are independently selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl, aryl, and linear and branched siloxanes;

R31 is selected from Y", C1-10alkyl, C2-10alkenyl, C2-10alkynyl, aryl, and linear and branched siloxanes;
R33 is selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl and aryl;
R35-R37 are independently selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl and aryl;
Y" is OH, OD or and OC1-10alkyl, s is 1, 2 or 3; and (b) a Lewis acid selected from B(C6F5)3 and ArB(C6F5)2, where Ar is an aryl group, that is optionally fluoro-substituted, wherein the amount of the chain extender is equimolar with the amount of the compound of Formula I or II.

2. The process of claim 1, wherein the siloxane oligomers and polymers contain between 0 wt% and 10 wt% cyclic siloxanes.

3. The process of claim 2, wherein the siloxane oligomers and polymers contain between 0.01 wt% and 5 wt% cyclic siloxanes.

4. The process of claim 3, wherein the siloxane oligomers polymers contain between 0.1 wt% and 1 wt% cyclic siloxanes.

5. The process of claim 1, wherein the siloxane oligomers and polymers contain less than 100 ppm cyclic siloxanes.

6. The process of any one of claims 1 to 5, wherein the Lewis acid is B(C6F5)3.

7. The process of any one of claims 1 to 6, wherein m is 1;

R11 is selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl, aryl, and linear and branched siloxanes;
R31 is selected from C1-10alkyl, C2-10alkenyl, C2-10alkynyl, aryl, and linear and branched siloxanes; and the process is for the preparation of siloxane oligomers.

8. The process of any one of claims 1 to 6, wherein m is 2;
R11 is H;
R31 is Y"; and the process is for the preparation of siloxane polymers.

9. The process of any one of claims 1 to 8, wherein Y' and Y" are OH or and OD or and OC1-10alkyl.

10. The process of any one of claims 1 to 9, wherein R1-R14 are the same and are selected from C1-10alkyl C2-10alkenyl, C2-10alkynyl and aryl.

11. The process of claim 10, wherein R1- R14 are the same and are selected from C1-6alkyl.

12. The process of claim 11, wherein R1-R14 are the same and are CH3.

13. The process of any one of claims 1 to 12, wherein R18-R26 or R30-R34 are the same and are selected from C1-10alkyl.

14. The process of claim 13, wherein R18- R26 or R30-R34 are the same and are selected from C1-6alkyl.

15. The process of claim 14, wherein R18-R26 or R30-R34 are the same and are CH3.

16. The process of any one of claims 1 to 15, wherein the chain extender is H2O, for example wherein H2O is in the form of: i) atmospheric water; ii) bulk water droplets; iii) water dispersed in an organic solvent; or iv) water dissolved in an organic solvent.

17. The process of any one of claims 1 to 15, wherein the chain extender is a compound of Formula III or IV.

18. The process of any one of claims 1 to 7 and 9 to 17, wherein the cyclic siloxanes are selected from one or more of D3, D4 and D5.

19. The process of any one of claims 1 to 7 and 9 to 18, wherein the compound of Formula II is Me3SiOSiMe2H.

20. The process of any one of claims 1 to 7 and 9 to 18, wherein the compound of Formula I is Me3SiOSiMeHOSiMe3.

21. The process of any one of claims 1 to 7 and 9 to 18, wherein the compound of Formula I is Me3SiOMe2SiOSiMeHOSiMe3.

22. The process of any one of claims 1 to 21, wherein the amount of the Lewis acid is about 0.01 mol% to about 1 mol% or about 0.05 mol% to about 0.2 mol%.

23. A siloxane oligomer containing low levels of cyclic siloxanes prepared using the process of any one of claims 1 to 7 and 9 to 22.
24. A siloxane polymer containing low levels of cyclic siloxanes prepared using the process of claim 8.

24. A method of preparing a personal care product comprising combining one or more siloxane oligomers of claim 23 with components for the personal care product.

25. A personal care product comprising one or more of the siloxane oligomers of claim 24.

26. A personal care product comprising one or more siloxane oligomers containing low levels of cyclic siloxanes prepared using the process of any one of claims 1 to 7 and 9 to 22.