POLYDIORGANOSILOXANES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No.

62/722345 filed 24 Aug 2018 under 35 U.S.C. §1 19 (e). U.S. Provisional Patent Application No. 62/722345 is hereby incorporated by reference.

TECHNICAL FIELD

[0002] This invention relates to a method for condensation polymerization of hydroxyl- terminated polydiorganosiloxanes. The method employs a trifluoromethane sulfonate (triflate) compound as a catalyst that minimizes production of cyclic polydiorganosiloxane by-products.

BACKGROUND

[0003] Organosiloxane oligomers and short chain polymers having hydroxyl groups may be polymerized via condensation reaction to high molecular weight, high degree of polymerization (DP), polymers by polymerization in the presence of a suitable condensation reaction catalyst. Condensation polymerization of hydroxyl functional organosiloxanes occurs with the elimination of water as a by-product. Previous methods employed Bronsted acids, Bronsted bases, or phosphonitriles as catalysts. Although these catalysts can be highly active (to produce product with high DP), they tend to produce large quantities (>1000 ppm) of the cyclic by-product, octamethylcyclotetrasiloxane (D4), in the resulting hydroxyl-functional polydiorganosiloxane product.

PROBLEM TO BE SOLVED

[0004] There is an industry need to produce high molecular weight, high degree of

polymerization polyorganosiloxanes with lower D4 content than achieved with previous methods, described above.

SUMMARY

[0005] A method for polymerizing polydiorganosiloxanes comprises:

1 ) heating, at a temperature of 50°C to 200°C, a reaction mixture prepared by mixing starting materials comprising

A) a polydiorganosiloxane of unit formula [(HO)R2SiO-|/2]2(R2Si02 2)n’ where subscript n is 0 to 2000, and each R is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; and

B) 10 ppm to 500 ppm, based on weight of starting material A), of a trifluoromethane sulfonate compound selected from the group consisting of

B-1 ) aluminum(lll) trifluoromethane sulfonate, B-2) bismuth(lll) trifluoromethane sulfonate,

B-3) gallium(lll) trifluoromethane sulfonate,

B-4) iron(lll) trifluoromethane sulfonate,

B-5) indium(lll) trifluoromethane sulfonate,

B-6) scandium(lll) trifluoromethane sulfonate, and

B-7) dicyclohexylboron trifluoromethane sulfonate;

2) quenching the reaction mixture; and

3) recovering a product from the reaction mixture, where the product has unit formula

[(HO)R2SiO-|/2]2(R2Si02/2)m’ where m > n.

DETAILED DESCRIPTION

[0006] A method for polymerizing polydiorganosiloxanes to produce a hydroxyl-terminated polydiorganosiloxane product having higher DP than the starting material and low D4 content comprises:

optionally, pre-1 ) mixing B) a trifluoromethane sulfonate compound and C) a chelating ligand for the trifluoromethane sulfonate compound before step 1 );

1 ) heating, at a temperature of 50°C to 200°C, a reaction mixture prepared by mixing starting materials comprising

A) a polydiorganosiloxane of unit formula [(HO)R2SiO-|/2]2(R2Si02/2)n’ where subscript n is 0 to 2000, and each R is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; and

B) 10 ppm to 500 ppm, based on weight of starting material A), of the

trifluoromethanesulfonate compound, which is selected from the group consisting of

B-1 ) aluminum(lll) trifluoromethanesulfonate,

B-2) bismuth(lll) trifluoromethanesulfonate,

B-3) gallium(lll) trifluoromethanesulfonate,

B-4) iron(lll) trifluoromethanesulfonate,

B-5) indium(lll) trifluoromethanesulfonate,

B-6) scandium(lll) trifluoromethanesulfonate, and

B-7) dicyclohexylboron trifluoromethanesulfonate;

optionally C) the chelating ligand; and

optionally D) a solvent;

2) quenching the reaction mixture; and

3) recovering the product from the reaction mixture, where the product has unit formula

[(HO)R2SiO-|/2]2(R2Si02/2)m’ where m > n. In step 1 ), B) the trifluoromethane sulfonate compound and, when present, C) the chelating ligand may be combined. Alternatively, when step pre-1 ) is present, B) the trifluoromethane sulfonate compound and C) the chelating ligand may be combined to form a chelate before step 1 ).

[0007] The method may be performed using a batch reactor or a continuous reactor, such as a gas liquid reactor. Residence time depends on various factors including the temperature selected and the type of reactor. However, step 1 ) may be performed by heating at a temperature of 80°C to 105°C for 30 seconds to 2 hours. The method may be performed at ambient pressure and does not require an inert atmosphere. However, conditions that enable by-product water to be removed may facilitate increasing DP of the product or improving selectivity (minimizing D4 in the product), or both. Therefore, the method may further comprise removing water during and/or after step 1 ). Selectivity may also be improved when starting material C), the ligand, is added. Alternatively, the method may be performed under conditions in which water is not removed during step 1 ). Step 2) may be performed by adding E) an amine and cooling the reaction mixture to a temperature less than 50°C. Step 3) may be performed by a method comprising filtering, stripping and/or distilling the reaction mixture.

[0008] The method described above can produce a hydroxyl-terminated polydiorganosiloxane having a DP higher than that of starting material A) and a low D4 content. For example, D4 content in the product may be < 400 ppm, alternatively < 300 ppm. The minimum amount of D4 may be 0, alternatively 100 ppm. And, when starting material A) has a DP < 50, DP of the product may be > 300, alternatively > 400, alternatively > 500, alternatively > 1000, alternatively > 1500, and alternatively > 2000. Alternatively, when starting material A) has a DP < 50, DP of the product may be 300 to 3000, alternatively 400 to 2500, alternatively 500 to 2000.

Starting Material A) Polydiorganosiloxane

[0009] Starting material A) is a polydiorganosiloxane comprising unit formula

[(HO)R2SiO-|/2]2(R2Si02/2)n’ where subscript n is 0 to 2000, and each R is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms. Suitable monovalent hydrocarbon groups for R may be selected from the group consisting of alkyl, alkenyl, and aryl. Exemplary alkyl groups include methyl, ethyl, propyl (including n-propyl and iso-propyl), butyl (including n-butyl, t-butyl, iso-butyl and sec-butyl), and hexyl groups (including branched and linear isomers thereof). Exemplary alkenyl groups include vinyl, allyl, and hexenyl (including branched and linear isomers thereof). Exemplary aryl groups include phenyl, tolyl, xylyl, naphthyl, and benzyl. Alternatively, each alkyl may be methyl, each alkenyl may be selected from the group consisting of vinyl, allyl, and hexenyl, and each aryl may be phenyl.

Alternatively, 50% to 100%, alternatively 80% to 100%, and alternatively 90% to 100% of all instances of R are alkyl groups such as methyl. Alternatively, the R groups on starting material A) may be methyl and phenyl. Alternatively, the R groups on starting material A) may be methyl and vinyl. In starting material A), subscript n is 0 to 2000. Alternatively, subscript n may be 5 to 2000, alternatively 5 to 200, alternatively 10 to 150, alternatively 15 to 100, alternatively 20 to 50, and alternatively 25 to 35. One skilled in the art would recognize that starting material A) may be substantially linear, alternatively starting material A) is linear. Furthermore, starting material A) may contain a small number of additional siloxane units, such as those of formula (H0RSi02/2) _> (RS1O3/2) and/or (S1O4/2) provided that starting material A) is substantially linear. Examples of starting material A) include bis-hydroxy terminated polydimethylsiloxane. Suitable polydiorganosiloxanes for starting material (A) may be prepared by methods known in the art such as the addition of diorganodichlorosilanes to a water/solvent mixture to yield a mixture of low molecular weight hydroxy end-blocked polydiorganosiloxanes and cyclic siloxanes in solvent. The mixture may be purified to separate hydroxy end-blocked

polydiorganosiloxanes and cyclic polysiloxanes. Alternatively, suitable bis-hydroxy terminated polydimethylsiloxane are commercially available from Dow Silicones Corporation of Midland, Michigan, USA.

Starting Material B) Trifluoromethane sulfonate Compound

[0010] Starting material B) is a trifluoromethane sulfonate compound (triflate compound). Starting material B) is used in the method in an amount of 10 ppm to 500 ppm, based on the weight of starting material A). Starting material B) is selected from the group consisting of: B-1 ) aluminum(lll) trifluoromethane sulfonate, B-2) bismuth(lll) trifluoromethane sulfonate, B-3) gallium(lll) trifluoromethane sulfonate, B-4) iron(lll) trifluoromethane sulfonate, B-5) indium(lll) trifluoromethane sulfonate, B-6) scandium(lll) trifluoromethane sulfonate, and B-7)

dicyclohexylboron trifluoromethane sulfonate. Alternatively, starting material B) may be selected from the group consisting of B-1 ) aluminum(lll) trifluoromethane sulfonate, B-2) bismuth(lll) trifluoromethane sulfonate, B-3) gallium(lll) trifluoromethane sulfonate, B-4) iron(lll) trifluoromethane sulfonate, and B-5) indium(lll) trifluoromethane sulfonate. Alternatively, starting material B) may be a metal trifluoromethane sulfonate, i.e., starting material B) may be any one of B1 ), B2), B3), B4), B5), and B6). Alternatively, starting material B) may be selected from the group consisting of B-2) bismuth(lll) trifluoromethane sulfonate, B-3) gallium(lll) trifluoromethane sulfonate, and B-4) iron(lll) trifluoromethane sulfonate. Alternatively, starting material B) may be selected from the group consisting of B-1 ) aluminum(lll) trifluoromethane sulfonate, B-5) indium(lll) trifluoromethane sulfonate, and B-6) scandium(lll) trifluoromethane sulfonate. Alternatively, starting material B) may be selected from the group consisting of B-1 ) aluminum(lll) trifluoromethane sulfonate and B-5) indium(lll) trifluoromethane sulfonate. In one embodiment, starting material B) may be combined with starting material C), a ligand, before step 1 ) of the method described herein. Suitable trifluoromethane sulfonate compounds are commercially available, e.g., from Sigma-Aldrich, Fischer Scientific, or Alfa Aesar.

Starting Material C) Ligand

[0011] Starting material C) may optionally be added in the method described herein. In this embodiment, starting material C) and starting material B) may be combined before step 1 ) by any convenient means, such as mixing. In one embodiment, starting material C) may be a bisimine ligand. Starting material C) may have general formula:

are an independently selected alkyl groups of 1 to 8 carbon atoms, alternatively 1 to 6 carbon atoms, and alternatively 2 to 5 carbon atoms. Alternatively, R ¹ and R ² may each be a butyl group, such as a tert-butyl group. Suitable bisimine ligands such as 1 ,2-bis-(2-di-iso-propylphenyl) imino)ethane or 1 ,2-bis(2-di-tert-butylphenyl)imino)ethane are commercially available, e.g., from Sigma-Aldrich.

[0012] Alternatively, starting material C) may be

represents a t-butyl group.

The amount of ligand added depends on various factors including which triflate compound is selected for starting material B) and the DP desired in the product, however, the amount of ligand may be 1 molar equivalent to 2 molar equivalents based on the amount of starting material B).

Starting Material D) Solvent

[0013] Starting material D), a solvent, may optionally be used in the method described herein. The solvent may be used to deliver one or more of the other starting materials. For example, the ligand may be dissolved in a solvent before combining the ligand and the metal triflate. Alternatively, the metal triflate may be dissolved in a solvent before combining with the metal triflate in step pre-1 ) described above, or before combining with starting material A) in step 1 ). The solvent may be an aprotic solvent, such as tetrahydrofuran, toluene, or dichloromethane. Alternatively, the solvent may be a low molecular weight trimethylsiloxy-terminated

polydimethylsiloxane, such as an OS Fluid, which is commercially available from Dow Silicones Corporation of Midland, Michigan, U.S.A. The solvent may be used to deliver one or more starting materials (i.e., one or more starting materials may be dissolved in solvent before step 1 ), the reaction may proceed in solvent, or both. The amount of solvent depends on various factors including the type and amount of starting materials A), B), and C) selected and whether one or more starting materials is being delivered in a solvent, or whether the reaction will proceed in a solvent. For example, when present, the amount may be sufficient to form a reaction mixture with a concentration of starting material A) of 0.1 M - 0.5 M.

Starting Material E) Amine

[0014] Starting material E) the amine is used to quench the reaction mixture in step 2) of the method described herein. The amine may be an alkyl amine such as trimethylamine, triethylamine, or A/,A/-dimethylcyclohexylamine. The amount of amine may be 100 ppm to 100,000 ppm of amine based on total weight of all starting materials used in the method.

Alternatively, the amount of amine may be 100 ppm to 1000 ppm on the same basis. Suitable amines are commercially available, e.g., from Sigma-Aldrich or Fisher Scientific.

Product

[0015] The product of the method described herein is a bis-hydroxyl terminated

polydiorganosiloxane of unit formula [(HO)R2SiO-|/2]2(R2Si02/2)m’ where R is as described above for starting material A), and subscript m has a value greater than subscript n in starting material A). For example, in the product described above, subscript m may have a value ranging from (n + 250) to (n + 2500), alternatively (n + 300) to (n + 2400), alternatively (n + 350) to (n + 2300), alternatively (n + 400) to (n + 2000), alternatively (n + 450) to (n + 1500).

EXAMPLES

[0016] These examples are intended to illustrate some embodiments of the invention and should not be interpreted as limiting the scope of the invention set forth in the claims.

Comparative Example 1 - Polymerization of Bis-Hydroxyl-Terminated Polydimethylsiloxane with trifluoromethanesulfonic acid (Entry 12 in Table 1).

[0017] A 40 mL glass vial was filled with 10 g of bis-hydroxy terminated poly(dimethylsiloxane) having an average DP of 35 and equipped with a stir bar. The bis-hydroxy terminated poly(dimethylsiloxane) was obtained from Dow Silicones Corporation of Midland, Ml, USA. The vial was heated to 80°C, and 71 pL of trifluoromethanesulfonic acid (as a 0.01 M solution in anhydrous dichloromethane) was added to the bis-hydroxy terminated poly(dimethylsiloxane) to initiate polymerization. Stirring was continued for 2 hr at 80°C with open caps before the solutions were quenched by adding 2 drops of A/,A/-dimethylcyclohexylamine (as a 1% solution in toluene), and cooling to room temperature. Analysis of the crude reaction mixture by GPC indicated a final degree of polymerization of 1 1 17, while headspace GC measured 3,678 ppm of residual D4.

Reference Example 2 - General Procedure

\ / \ / catalyst \ / \ /

HO ^S V ^S }qH HO ^S V ^S }qH n ~ 35 m > n

[0018] Samples were prepared as follows. A 40 ml. glass vial was filled with 10 g of bis- hydroxy terminated poly(dimethylsiloxane) having an average DP of 35 and equipped with a sandwich-style rare earth magnet stirbar. The vial was heated to 80°C or 105°C, and a trifluoromethane sulfonate compound (as a 0.01 M solution in anhydrous THF) was added to the bis-hydroxy terminated poly(dimethylsiloxane) to initiate polymerization. Stirring was continued for 2 hr at 80°C or 105°C with open caps before the resulting solution was quenched by adding 2 drops of A/,A/-dimethylcyclohexylamine (as a 1 % solution in toluene), and cooling to room temperature. Analysis of the resulting crude reaction mixture by GPC indicated a final degree of polymerization, while headspace GC measured residual octamethylcyclotetrasiloxane. The trifluoromethane sulfonate compound, temperature, concentration of metal triflate, degree of polymerization of the bis-hydroxy terminated polydimethylsiloxane prepared by the method, residual D4 in the bis-hydroxy terminated polydimethylsiloxane prepared by the method and DP/D4 ratio are shown below in Table 1. Other catalysts tested were Nonafluorobutane-1 - sulfonic acid, Dicyclohexylboron trifluoromethanesulfonate, and Phosphonitrilic Chloride

Catalyst were used instead of the metal triflate catalyst.

Table 1 - Comparison of Metal Triflates and Other Catalysts

[0019] ^* The phosphonitrilic chloride catalyst is a mixture of [CI ₃ P=N-PCI ₂ =N- PCI ₃ ] ⁺ [PxCI ₅ x ₊ i ]- and [CI ₃ P=N-PCI ₂ =N-PCI ₂ =N-PCI ₃ ]+[P _x CI _{5x+ 1} ]-

[0020] The DP/D4 ratio shown in the tables herein was calculated by dividing the difference in DP between the final product and starting material A) by the amount of D4 generated.

Generally, high DP/D4 ratio is desired, provided that DP increased sufficiently.

Example 3 - General Procedure.

[0021] Samples were prepared as described above in Reference Example 2, except that heating was performed for 2 hr at 105°C and loading of the triflate was 25 ppm. Table 2, below, shows the degree of polymerization for each catalyst with bis-hydroxy terminated

poly(dimethylsiloxane) after 2 hr at 105°C.

Table 2

[0022] Tables 1 and 2 show that under the conditions tested, only certain metal triflates produced a bis-hydroxy terminated polydimethylsiloxane with sufficient chain extension (as shown by increase in DP) and low D4 content. For example, Copper(ll) triflate, Yttrium (III) triflate, Cerium (IV) triflate, Cerium (III) triflate, Ytterbium (III) triflate, Zinc (II) triflate, and Samarium(lll) triflate did not produce sufficient increase in DP of the product under the conditions tested.

Example 4 - Addition of Ligands

[0023] Samples were prepared as follows. A metal triflate and 1 or 2 molar equivalents of a ligand were dissolved in anhydrous THF to prepare a metal triflate· ligand solution. A 40 mL glass vial was filled with 10 g of bis-hydroxy terminated poly(dimethylsiloxane) having an average DP of 35 and equipped with a sandwich-style rare earth magnet stirbar. The vial was heated to 105°C, and metal triflate· ligand solution at a concentration of 0.01 M was added to the bis-hydroxy terminated poly(dimethylsiloxane) to initiate polymerization. Stirring was continued for 2 hr at 105°C with open caps before the resulting solutions were quenched by adding 2 drops of A/,A/-dimethylcyclohexylamine (as a 1% solution in toluene) to each vial, and cooling to room temperature. Analysis of the resulting crude reaction mixtures by gel permeation chromatography (GPC) indicated a final degree of polymerization, and headspace gas chromatography (GC) measured residual D4. Table 3, below, shows the metal triflate or metal triflate· ligand tested, the concentration at which it was added, DP, and amount of D4 in the product. [0024] Ligands tested were as follows.

E F G

Table 3

[0025] Table 3 shows that the ligand of formula

improved performance (with higher DP and lower D4) than bismuth(lll) triflate alone under the conditions tested in Example 3.

Example 5 - Addition of Ligands

[0026] Samples were prepared as follows. A metal triflate and 1 or 2 molar equivalents of ligand D were dissolved in anhydrous THF to prepare a metal triflate· ligand solution. A 40 mL glass vial was filled with 10 g of bis-hydroxy terminated poly(dimethylsiloxane) having an average DP of 35 and equipped with a sandwich-style rare earth magnet stirbar. The vial was heated to 105°C, and metal triflate· ligand solution at a concentration of 0.01 M was added to the bis-hydroxy terminated poly(dimethylsiloxane) to initiate polymerization. Stirring was continued for 2 hr at 105 °C with open caps before the resulting solutions were quenched by adding 2 drops of A/,A/-dimethylcyclohexylamine (as a 1% solution in toluene) to each vial, and cooling to room temperature. Analysis of the resulting crude reaction mixtures by GPC indicated a final degree of polymerization, and headspace GC measured residual D4. Table 4, below, shows the metal triflate or metal triflate· ligand tested, the concentration at which it was added, DP, and amount of D4 in the product.

Table 4

Reference Example 6 - Molecular distribution

[0027] Molecular distribution of starting materials can be analyzed by GPC equipped with triple detector array (Refractive Index, Right Angle Light Scattering, and Viscometer). 0.5% of samples were used for GPC analysis. Mw of Polystyrene standards were in the range of 580 to 100,000, and a 3 ^rcl order calibration curve was used for molecular weight determination. Both samples and standards were diluted in HPLC grade ethyl acetate.

Reference Example 7 - D4 Concentration [0028] D4 Concentration measurements were made using the following instruments, procedures, and quantitation methods.

GC HP 6890

[0029] Gradient: 50 °C (1 min) - 220 °C @ 10 °C/min (no hold); Inlet: Split 1 :20, 9.68 psi, 150 °C; Flow: 2 mL/min

FID: Flydrogen 40 mL/min, Air 450 mL/min, Makeup 45 mL/min, Temperature 260 °C; Column:

RTX-1 , 30 m / 320 pm / 0.25 pm

Headspace Unit Perkin-Elmer TurboMatrix 40

[0030] Incubation: 120 °C for 10 min with shaking; Syringe: 125 °C; Transfer Line: 130 °C; Pressurize: 3 min; Withdraw: 0.5 min; Column pressure: 20 psi; Injection: 0.15 min / 0.3 mL; GC cycle: 25 min

Sample preparation

[0031] Internal standards were prepared to be 0.01 % dodecane by weight in Fisher Brand 19 fluid vacuum oil. 1 mL of internal standard solution was added to a 20 mL headspace vial (with Eppendorf repeater pipet). 100 mg of D4 standard (usually 100 ppm standard used) or 100 mg of experimental sample was added to the headspace vial.

Quantitation:

[0032] Quantitation of the D4 content was by the single point internal standard method. A relative response factor (RRF) of D4 relative to dodecane was established and updated every time a new batch of internal standard solution was prepared. The amount of D4 in the samples was determined within the Thermo Atlas data system according to an equation of the same type as the one below:

Conc _D4

Industrial Applicability

[0033] Bis-hydroxy terminated silicone polymers produced by Dow Silicones Corporation can contain approximately 1000 ppm D4 as a by-product. The inventors surprisingly found that several triflate compounds generate significantly less octamethylcyclotetrasiloxane than the conventional catalysts used under the conditions tested in the examples above. The inventors further found that several ligands can improve the selectivity in silanol condensation

polymerizations when combined with a metal triflate salt under the conditions tested in the examples above. In each case the selectivity for each catalyst was determined by dividing the change in the degree of polymerization by the amount of D4 produced in the reaction (ADP/AD4). The initial ligand screen identified bisimine D as the optimal ligand for reducing D4 generation, increasing ADP/AD4 from 2.5 for Bi(OTf)3 to 4.9 for the Bi(OTf)3 _* 2D complex (Table 3).

Definitions and Usage of Terms

[0034] All amounts, ratios, and percentages are by weight unless otherwise indicated by the context of the specification. The SUMMARY and the 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 disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 0 to 2000 includes not only the range of 0 to 2000, but also 1 , 2, 5, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 100, 200, 300, 400, 500, 600, 800, 1000, 1250, 1500, 1750, and 2000 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, 0 to 2000 includes the subsets of, for example, for example, 10 to 1500, 16 to 750, 20 to 450, 5 to 50, and 10 to 40, as well as any other subset subsumed in the range. Table 5, below, defines abbreviations used throughout this application.

Table 5 - Abbreviations

Embodiments of the Invention

[0035] In a first embodiment, a method for polymerizing polydiorganosiloxanes comprises:

Pre-1 ) combining starting materials comprising:

B) a metal trifluoromethane sulfonate selected from the group consisting of B-1 ) aluminum(lll) trifluoromethanesulfonate, B-2) bismuth(lll) trifluoromethane sulfonate, B-3) gallium(lll) trifluoromethane sulfonate, B-4) iron(lll) trifluoromethanesulfonate, and B-5) indium(lll) trifluoromethane sulfonate; and C) a ligand of general formula

each R ² and each R ¹ are an independently selected alkyl groups of 1 to 8 carbon atoms, thereby forming a catalyst;

1 ) heating, at a temperature of 50°C to 200°C, a reaction mixture prepared by mixing the catalyst with starting materials comprising

A) a polydiorganosiloxane of unit formula [(HO)R2SiO-|/2]2(R2Si02/2)n’ where subscript n is 0 to 2000, and each R is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; and

optionally D) a solvent;

2) quenching the reaction mixture; and

3) recovering a product from the reaction mixture, where the product has unit formula

[(HO)R2SiO-|/2]2(R2Si02/2)m’ where m > n.

[0036] In a second embodiment, in the method of the first embodiment, each R is

independently selected from the group consisting of alkyl, alkenyl, and aryl.

[0037] In a third embodiment, in the method of the second embodiment, each alkyl is methyl, each alkenyl is selected from the group consisting of vinyl, allyl, and hexenyl, and each aryl is phenyl.

[0038] In a fourth embodiment, in the method of the first embodiment, subscript n is 5 to 2000, alternatively 5 to 200, alternatively 10 to 150, alternatively 15 to 100, alternatively 20 to 50, and alternatively 25 to 35.

[0039] In a fifth embodiment, in the method of the first embodiment, the metal

trifluoromethane sulfonate is present in an amount of 10 ppm to 500 ppm based on the weight of starting material A).

[0040] In a sixth embodiment, in the method of the first embodiment, the metal

trifluoromethane sulfonate is selected from the group consisting of B-2) bismuth(lll)

trifluoromethane sulfonate, B-3) gallium(lll) trifluoromethane sulfonate, and B-4) iron(lll) trifluoromethanesulfonate.

[0041] In a seventh embodiment, in the method of the first embodiment, the metal

trifluoromethane sulfonate is selected from the group consisting of B-1 ) aluminum(lll) trifluoromethane sulfonate and B-5) indium(lll) trifluoromethane sulfonate. [0042] In an eighth embodiment, in the method of the first embodiment, starting material C) is

[0043] In a ninth embodiment, in the first embodiment starting material D), a solvent, is present.

[0044] In a tenth embodiment, in the method of the ninth embodiment, the solvent is selected from the group consisting of aprotic solvents and trimethylsiloxy-terminated

polydimethylsiloxanes.

[0045] In an eleventh embodiment, in the method of the first embodiment, step pre-1 ) is performed by mixing at ambient pressure and temperature.

[0046] In a twelfth embodiment, in the method of the first embodiment, step 1 ) is performed by heating at a temperature of 80°C to 105°C for 30 seconds to 2 hours at ambient pressure.

[0047] In a thirteenth embodiment, in the method of the first embodiment, the method further comprises removing water during and/or after step 1 ).

[0048] In a fourteenth embodiment, in the method of the first embodiment, step 2) is performed by adding an amine and cooling the reaction mixture to a temperature less than 50°C.

[0049] In a fifteenth embodiment, in the method of the fourteenth embodiment, the amine is A/,A/-dimethylcyclohexylamine.

[0050] In a sixteenth embodiment, in the method of the first embodiment, step 3) is performed by a method comprising filtering, stripping and/or distilling the reaction mixture.

[0051] In a seventeenth embodiment, a method for polymerizing polydiorganosiloxanes comprises:

optionally Pre-1 ) combining starting materials comprising:

B) dicyclohexylboron trifluoromethane sulfonate; and

C) a ligand of general formula each R ² and each R ¹ are an independently selected alkyl groups of 1 to 8 carbon atoms, thereby forming a catalyst;

1 ) heating, at a temperature of 50°C to 200°C, a reaction mixture prepared by mixing B) dicyclohexylboron trifluoromethane sulfonate, or the catalyst when step pre-1 ) is used, with starting materials comprising

A) a polydiorganosiloxane of unit formula [(HO)R2SiO-|/2]2(R2Si02/2)n’ where subscript n is 0 to 2000, and each R is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; and

optionally D) a solvent;

2) quenching the reaction mixture; and

3) recovering a product from the reaction mixture, where the product has unit formula

[(HO)R2SiO-|/2]2(R2Si02/2)m’ where m > n.

[0052] In an eighteenth embodiment, in the method of the seventeenth embodiment, each R is independently selected from the group consisting of alkyl, alkenyl, and aryl.

[0053] In a nineteenth embodiment, in the method of the eighteenth embodiment, each alkyl is methyl, each alkenyl is selected from the group consisting of vinyl, allyl, and hexenyl, and each aryl is phenyl.

[0054] In a twentieth embodiment, in the method of the seventeenth embodiment, subscript n is 5 to 2000, alternatively 5 to 200, alternatively 10 to 150, alternatively 15 to 100, alternatively 20 to 50, and alternatively 25 to 35.

[0055] In a twenty-first embodiment, in the method of the seventeenth embodiment, starting

material

[0056] In a twenty-second embodiment, in the seventeenth embodiment starting material D), a solvent, is present. [0057] In a twenty-third embodiment, in the method of the twenty-second embodiment, the solvent is selected from the group consisting of aprotic solvents and trimethylsiloxy-terminated polydimethylsiloxanes.

[0058] In an twenty-fourth embodiment, in the method of the seventeenth embodiment, step pre-1 ) is performed by mixing at ambient pressure and temperature.

[0059] In a twenty-fifth embodiment, in the method of the seventeenth embodiment, step 1 ) is performed by heating at a temperature of 80°C to 105°C for 30 seconds to 2 hours at ambient pressure.

[0060] In a twenty-sixth embodiment, in the method of the seventeenth embodiment, the method further comprises removing water during and/or after step 1 ).

[0061] In a twenty-seventh embodiment, in the method of the seventeenth embodiment, step 2) is performed by adding an amine and cooling the reaction mixture to a temperature less than 50°C.

[0062] In a twenty-eighth embodiment, in the method of the twenty-seventh embodiment, the amine is A/,A/-dimethylcyclohexylamine.

[0063] In a twenty-ninth embodiment, in the method of the seventeenth embodiment, step 3) is performed by a method comprising filtering, stripping and/or distilling the reaction mixture.