HYDROSILYLATION CURABLE SILICONE RESIN

Abstract

A hydrosilylation curable polysiloxane comprising at least one of units of formula (I) and units of formula (II), wherein Ar is C6-C20 aryl, R1 is C2-C20 alkenyl, and R2, R3, R4 and R5 independently are C1-C20 hydrocarbyl.

Description

This invention relates to a hydrosilylation curable silicone resin having a good cure rate, while maximizing thermal stability.

Hydrosilylation curable silicone compositions comprising alkylsiloxane units are known, including encapsulants for light emitting diodes (LED), but the known compositions do not exhibit a combination of good cure speed and improved thermal stability. Typically increasing cure speed comes at the expense of reduced thermal stability since the catalysts and linking groups used in cure reduce stability. The current invention overcomes these limitations.

Hydrosilylation curable silicone compositions comprising both T^Vi and T^Ph units are known, e.g., in US20160208055. However, this reference does not teach the compositions of the present invention.

STATEMENT OF THE INVENTION

The present invention provides a hydrosilylation curable polysiloxane comprising at least one of units of formula (I) and units of formula (II)

wherein Ar is C₆-C₂₀ aryl, R¹ is C₂-C₂₀ alkenyl, and R², R³, R⁴ and R⁵ independently are C₁-C₂₀ hydrocarbyl.

DETAILED DESCRIPTION

Percentages are weight percentages (wt %) and temperatures are in ° C. unless specified otherwise. Operations were performed at room temperature unless specified otherwise. Alkyl groups are saturated hydrocarbyl groups that may be straight or branched. Preferably, alkyl groups have from one to six carbon atoms, preferably one or two. Alkenyl groups are hydrocarbyl groups that may be straight or branched and which have at least one aliphatic carbon-carbon double bond, preferably one aliphatic carbon-carbon double bond. Preferably, alkenyl groups have no aromatic rings. Preferably, alkyl and alkenyl groups are unsubstituted. Aryl groups are derived from aromatic compounds which can be mono- or poly-nuclear. Aryl groups may be substituted by alkyl or alkoxy groups. Preferably, aryl groups are unsubstituted. Preferably, aryl groups are hydrocarbyl groups.

As used herein, unless otherwise indicated, molecular weights, M_n, M_w and M_z have the conventional meanings and are determined by gel permeation chromatography. Molecular weights are reported herein in units of g/mol.

Preferably, the OSi(R²)(R³)— unit in formula (I) or (II) is part of a polysiloxane chain having from 10 to 500 of these units ([R²R³SiO_2/2] units or D units); preferably at least 20, preferably at least 30, preferably at least 35; preferably no more than 400, preferably no more than 300, preferably no more than 200, preferably no more than 150. Preferably, R² and R³ independently represent C₁-C₁₂ alkyl or C₆-C₁₂ aryl, preferably phenyl or C₁-C₁₂ alkyl, preferably phenyl or C₁-C₄ alkyl, preferably C₁-C₁₂ alkyl, preferably C₁-C₆ alkyl, preferably C₁-C₄ alkyl, preferably methyl or ethyl, preferably methyl. Preferably, R² and R³ represent the same alkyl group. Preferably, R⁴ and R⁵ independently represent C₁-C₁₂ alkyl or C₆-C₁₂ aryl, preferably phenyl or C₁-C₁₂ alkyl, preferably C₁-C₁₂ alkyl, preferably C₁-C₆ alkyl, preferably C₁-C₄ alkyl, preferably methyl or ethyl, preferably methyl. Bonds ending in “--” or “---” are understood as connecting to a silicon atom of another siloxane unit or to hydrogen.

Preferably, R¹ is C₂-C₁₂ alkenyl, preferably C₂-C₈ alkenyl, preferably C₂-C₆ alkenyl, preferably C₂-C₄ alkenyl, preferably vinyl. Preferably, when IV is larger than vinyl, the double bond is in the terminal position. Preferably, IV is acyclic. The siloxane units comprising R¹ are designated as [R¹SiO_3/2] units or T-alkenyl or T^alkenyl units.

Preferably, Ar is C₆-C₁₄ aryl, preferably C₆-C₁₂ aryl, preferably C₆-C₁₀ aryl, preferably phenyl. Preferably, Ar comprises no heterocyclic aromatic rings. Preferably, Ar comprises no heteroatoms. Preferably, Ar comprises no fused rings. Preferably, any substituents on Ar groups are limited to C₁-C₄ alkyl or alkoxy groups. Preferably, Ar groups are unsubstituted. The siloxane units comprising Ar are designated as [ArSiO_3/2] units or T-aryl or T^aryl units.

Preferably, the polysiloxane comprises from 0.5 to 4.5 mole % of C₁-C₂₀ hydrocarbyl groups comprising at least one carbon-carbon double bond, preferably from 0.8 to 4, preferably from 1 to 3, preferably from 1 to 2.5. Preferably, the polysiloxane comprises from 20 to 60 mole % T^aryl units; preferably at least 25 mole %, preferably at least 28 mole %; preferably no more than 55 mole %, preferably no more than 52 mole %. Preferably, the polysiloxane comprises from 0.5 to 4.5 mole % T^alkenyl units; preferably at least 0.8 mole %, preferably at least 1.0 mole %; preferably no more than 4 mole %, preferably no more than 3 mole %, preferably no more than 2.5 mole %. Preferably, the polysiloxane comprises from 40 to 80 mole % D units; preferably at least 45 mole %, preferably at least 48 mole %; preferably no more than 75 mole %, preferably no more than 72 mole %. Preferably, the T^aryl units are arranged in a non-linear block, preferably having a molecular weight of at least 500 g/mole. Preferably, the polysiloxane has a weight-average molecular weight of at least 20,000 g/mole. Preferably, at least 50 mole % of the units having carbon-carbon double bonds (this does not include aryl units) are present as T units, preferably at least 60 mole %, preferably at least 70 mole %, preferably at least 80 mole %, preferably at least 90 mole %.

Preferably, the hydrosilylation curable polysiloxane comprises units of formula (I). Preferably, less than 50 mole % of R¹ groups in the hydrosilylation curable polysiloxane is from units of formula (II), preferably less than 25 mole %, preferably less than 10 mole %, preferably less than 5 mole %, preferably less than 1 mole %.

In a preferred embodiment of the invention, the hydrosilylation curable polysiloxane comprises a unit of formula (III).

In a preferred embodiment of the invention, the hydrosilylation curable polysiloxane comprises a unit of formula (IV).

The present invention is further directed to a curable silicone composition comprising a hydrosilylation curable polysiloxane. Preferably, the composition further comprises a hydrosilylation catalyst and a crosslinker.

Preferably, the hydrosilylation catalyst is present in the curable silicone composition in a catalytic quantity along with the polysiloxane in an amount sufficient to promote curing of the composition. Suitable hydrosilylation catalysts include, without limitation, a platinum group metal which includes platinum, rhodium, ruthenium, palladium, osmium, or iridium metal or an organometallic compound thereof and a combination of any two or more thereof. In a preferred embodiment, the hydrosilylation catalyst is platinum black, platinum compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, a reaction product of chloroplatinic acid and a monohydric alcohol, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum dichloride, and complexes of the platinum compounds with olefins or low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core-shell type structure.

Preferably, the hydrosilylation catalyst is present in the composition in an amount from 0.1 to 5 ppm; preferably at least 0.2 ppm, preferably at least 0.25 ppm; preferably no more than 3 ppm, preferably no more than 2 ppm, preferably no more than 1.5 ppm, preferably no more than 1 ppm, preferably no more than 0.7 ppm, preferably no more than 0.5 ppm.

Preferably, the crosslinker is polysiloxane containing at least two silicon-bonded hydrogen atoms, preferably at least three. Preferably the silicon-bonded groups other than the silicon-bonded hydrogen are phenyl or C_1-10 alkyl, in an amount that provides about 0.8 moles to about 2.5 moles silicon-bonded hydrogen per 1 mole of the total alkenyl in the organopolysiloxane, preferably from 0.8 to 1.5, preferably from 0.9 to 1.2. Preferably, the crosslinking agent itself is an organopolysiloxane comprising about 0.3 mass % to 2.0 mass % silicon-bonded hydrogen. Preferably, a straight chain organopolysiloxane containing RSiO_3/2 units, R₂SiO_2/2 units, R₃SiO_1/2, and HR₂SiO_1/2 and/or HRSiO_2/2 wherein the silicon-bonded R groups are phenyl or C₁-C₁₀ alkyl, preferably phenyl or methyl. A preferred crosslinker is M^H_0.6 T^Ph_0.4 (any group not specified on an “M” unit is methyl, e.g. M^H is M^H(CH3)2).

EXAMPLES

Preparation of Siloxanes

Example 1

Same Process as Ex. 2, but with Higher Amount T-Phenyl as Shown in Table 3

Example 2

(T-Vinyl Incorporated at the Linear Capping Step (Using Optimal Method for Controlling Product Molecular Weight))

• • Composition: 45 wt % Ph-T (Dow Corning RSN-0217 Flake Resin: 217 flake in short)+55 wt % 101 dp PDMS+1.4 mol % T-Vinyl (from vinyl triacetoxysilane: VTA)
  • A 1 L 4 neck round bottom flask was loaded with 217 flake (90.0 g, 0.659 mols Si) and toluene (240.77 g). The flask was equipped with a thermometer, TEFLON stir paddle, and a Dean Stark apparatus attached to a water-cooled condenser. A nitrogen blanket was applied. A heating mantle was used for heating. Dean Stark was prefilled with toluene. Heated at reflux for 30 minutes. This step was done to remove any water that might be present. A solution of toluene (59.23 g)+silanol terminated PDMS (110.0 g, 1.478 mols Si, 0.0293 mols SiOH) was capped with vinyltriacetoxysilane (VTA). It was prepared in a glove box (same day) under nitrogen by adding VTA (7.14 g, 0.0307 mols Si) to the silanol terminated PDMS and mixing at room temperature for 1 hour.
  • Resin-Linear Coupling—Cooled a couple of degrees below reflux. The diacetoxy capped PDMS solution was added to the resin solution quickly. Heated at reflux for 2 hrs.
  • Resin-Resin Coupling CF=5.0 CF=[mols MTA/ETA/mols Si on phenyl-T]*100 Cooled to 106° C. and then added 50/50 MTA/ETA (7.49 g, 0.0330 mols) Heated at reflux for 1 hr.
  • Water Treatments 1 & 2—Repeated the following process 2×: [At ˜90° C. added DI water (23.0 g) and then removed the water by azeotropic distillation.] (each wash-20:1 molar ratio, water: total MTA/ETA+VTA)
  • Molecular Weight Control—Distilled off 100.2 g of volatiles to increase the solids content up to ˜50%. Heated at reflux for 4 hours. Molecular weight growth followed a 2^nd order polynomial.

Comparative Example 1

(T-Vinyl Incorporated in RR Coupling Step)

Composition: 56 wt % Ph-T (217 flake)+44 wt % 46dp PDMS+1.57 mol % T-vinyl

• • A 2 L 4 neck round bottom flask was loaded with 217 flake (Ph-T) (224.0 g, 1.64 mols Si) and toluene (394.12 g). The flask was equipped with a thermometer, TEFLON stir paddle, and a Dean Stark apparatus attached to a water-cooled condenser. A nitrogen blanket was applied. A heating mantle was used for heating. Dean Stark was prefilled with toluene. Heated at reflux for 30 minutes. This step was done to remove any water that might be present. A solution of toluene (94.77 g)+silanol terminated PDMS (176.0 g, 2.36 mols Si, 0.102 mols SiOH) was capped with a 50/50 molar ratio of methyltriacetoxysilane and ethyltriacetoxysilane (MTA/ETA). It was prepared in a glove box (same day) under nitrogen by adding MTA/ETA (24.45 g, 0.1076 mols Si) to the silanol terminated PDMS and mixing at room temperature for 1 hour.
    • Resin-Linear Coupling—Cooled a couple of degrees below reflux. The diacetoxy capped PDMS solution was added to the resin solution quickly. Heated at reflux for 2 hrs.
    • Resin-Resin Coupling CF=4.0 CF=[mols VTA/mols Si on phenyl-T]*100 Cooled to 106° C. and then added vinyltriacetoxysilane (15.23 g, 0.0656 mols) Heated at reflux for 1 hr.
    • Water Treatments 1 & 2—Repeated the following process 2×: [At ˜90° C. added DI water (46.8 g) and then removed the water by azeotropic distillation.]
    • Distilled off 224.1 g of volatiles targeting ˜60% solids content. This step was mainly done to remove some acetic acid to increase the efficiency of the final two water treatments.
    • Water Treatments 3 & 4—Repeated the following process 2×: [At ˜90° C. added DI water (46.8 g) and then removed the water by azeotropic distillation.]
    • Final Workup Distilled off 109.3 g of volatiles to increase the NVC to 70-75%. Cooled to room temperature and then pressure filtered through a Magna, Nylon, Supported, Plain 5.0 micron filter.

Comparative Example 2

(D-Vinyl Incorporated after the Resin-Linear Coupling Step (Using Optimal Method for Controlling Product Molecular Weight))

• • Composition: 45 wt % Ph-T (217 flake)+55 wt % 101dp PDMS+1.4 mol % D-Vinyl A 1 L 4 neck round bottom flask was loaded with 217 flake (90.0 g, 0.659 mols Si)+toluene (240.77 g). The flask was equipped with a thermometer, teflon stir paddle, and a Dean Stark apparatus attached to a water-cooled condenser. A nitrogen blanket was applied. A heating mantle was used for heating. Dean Stark was prefilled with toluene. Heated at reflux for 30 minutes. This was done to remove any water that might be present. A solution of toluene (59.23 g)+silanol terminated PDMS (110.0 g, 1.478 mols Si, 0.0293 mols SiOH) was capped with MTA/ETA. It was prepared in a glove box (same day) under nitrogen by adding 50/50 MTA/ETA (6.98 g, 0.0307 mols Si) to the silanol terminated PDMS and mixing at room temperature for 1 hour.
  • Resin-Linear Coupling—Cooled a couple of degrees below reflux. The diacetoxy capped PDMS solution was added to the resin solution quickly. Heated at reflux for 2 hrs.
  • Vinylmethyldiacetoxysilane Coupling—At 106° C. added vinylmethyldiacetoxysilane (5.83 g, 0.0310 mols Si). Heated at reflux for 1 hr.
  • VMDA Water Treatment—At ˜90° C. added DI water (27.0 g). Stoichiometry-20:1 molar ratio: water: total MTA/ETA+VMDA. Heated to reflux and removed water by azeotropic distillation.
  • Resin-Resin Coupling CF=2.0 CF=[mols MTA/ETA/mols Si on phenyl-T]*100—Cooled to 106° C. and then added 50/50 MTA/ETA (3.00 g, 0.0132 mols). Heated at reflux for 1 hr.
  • Water Treatments 1 & 2—Repeated the following process 2×: [At ˜90° C. added DI water (27.0 g) and then removed the water by azeotropic distillation.]
  • Molecular Weight Control—Distilled off 100.5 g of volatiles to increase the solids content to ˜50%. Heated at reflux for 2 hours and 50 minutes. Molecular weight growth followed a 2^nd order polynomial.
  • Water Treatments 3, 4, 5—Repeated the following process 3×: [At ˜90° C. added DI water (27.0 g) and then removed the water by azeotropic distillation.]
  • Distilled off some toluene under vacuum to increase the solids content to ˜75%. This was done on a rotovapor at an oil bath temperature of 50° C. in a 1 L round bottom flask. Increasing solids under vacuum was done to minimize molecular weight growth. Pressure filtered through a 142 mm diameter Magna, Nylon, Supported, Plain, 5.0 Micron filter.
  • Results: NVC samples were clear. Isolated Yield: 230.0 g solution (@76.1% NVC=175.0 g solids)
    Refractive Index of product film=1.468 (Measured on a Metricon 2010 Prism Coupler using 633 nm red light)

Comparative Example 3

(T-Vinyl Incorporated in RR Coupling Step)

Composition: 45 wt % Ph-T (217 flake)+55 wt % 101dp PDMS+1.4 mol % T-Vinyl

• • A 1 L 4 neck round bottom flask was loaded with 217 flake (90.0 g, 0.659 mols Si) and toluene (240.77 g). The flask was equipped with a thermometer, TEFLON stir paddle, and a Dean Stark apparatus attached to a water-cooled condenser. A nitrogen blanket was applied. A heating mantle was used for heating. Dean Stark was prefilled with toluene. Heated at reflux for 30 minutes. This step was done to remove any water that might be present. A solution of toluene (59.23 g)+silanol terminated PDMS (110.0 g, 1.478 mols Si, 0.0293 mols SiOH) was capped with a 50/50 molar ratio of methyltriacetoxysilane and ethyltriacetoxysilane (MTA/ETA). It was prepared in a glove box (same day) under nitrogen by adding MTA/ETA (6.98 g, 0.0307 mols Si) to the silanol terminated PDMS and mixing at room temperature for 1 hour.
  • Resin-Linear Coupling—Cooled a couple of degrees below reflux. The diacetoxy capped PDMS solution was added to the resin solution quickly. Heated at reflux for 2 hrs.
  • Resin-Resin Coupling CF=4.7 CF=[mols VTA/mols Si on phenyl-T]*100 Cooled to 106° C. and then added vinyltriacetoxysilane (7.14 g, 0.0307 mols) Heated at reflux for 1 hr.
  • Water Treatments 1 & 2—Repeated the following process 2×: [At ˜90° C. added DI water (22.1 g) and then removed the water by azeotropic distillation.]
  • Distilled off 100.1 g of volatiles targeting ˜50% solids content. Heated at reflux for 1.25 hours to increase the molecular weight.
  • Water Treatments 3, 4, & 5—Repeated the following process 3×: [At ˜90° C. added DI water (22.1 g) and then removed the water by azeotropic distillation.]
  • Final Workup Distilled off some volatiles (120.2 g) to increase the solids content up to ˜75% solids. Cooled to room temperature and then pressure filtered through a Magna, Nylon, Supported, Plain 5.0 micron filter.

Comparative Example 4

(D-Vinyl incorporated in RR Coupling Step, T^Ph-D^Vinyl-D^Me2)
Composition: 45 wt % Ph-T (217 flake)+55 wt % 101dp PDMS+1.4 mol % D-Vinyl

• • A 1 L 4 neck round bottom flask was loaded with 217 flake (90.0 g, 0.659 mols Si) and toluene (240.77 g). The flask was equipped with a thermometer, TEFLON stir paddle, and a Dean Stark apparatus attached to a water-cooled condenser. A nitrogen blanket was applied. A heating mantle was used for heating. Dean Stark was prefilled with toluene. Heated at reflux for 30 minutes. This step was done to remove any water that might be present. A solution of toluene (59.23 g)+silanol terminated PDMS (110.0 g, 1.478 mols Si, 0.0293 mols SiOH) was capped with vinyl methyl diacetoxysilane (VMDA, 5.78 g, 0.0307 mols Si). It was prepared in a glove box (same day) under nitrogen by adding VMDA to the silanol terminated PDMS and mixing at room temperature for 1 hour.
  • Resin-Linear Coupling—Cooled a couple of degrees below reflux. The capped PDMS solution was added to the resin solution quickly. Added 21.9 g toluene. Heated at reflux for 4 hrs. The reaction mixture turned very hazy while cooling to room temperature. This route therefore is ineffective in producing a useful material for optical applications.

Cure Speed Testing

a) with same amount of Pt—DSC thermograms were obtained at 10° C./min (open pan, He atmosphere) of 1.57 mol % Vinyl-T modified 56 wt % Ph-T 46dp PDMS resin-linears (formulation: M^H_0.6T^Ph_0.4 SiH cross-linker with SiH/Vinyl=1.0, 500 ppm DODS (dioctadecyl disulfide, 2/1 mol/mol TPP/Pt (triphenyl phosphine) and 1 ppm Pt) with the products of i) C. Ex. 1 and ii) Ex. 1.
The formulation containing the product of Ex. 1 exhibited a lower reaction exothermic peak (T_peak; 144.15° C.) than that exhibited by the formulation containing the product of C. Ex. 2 (160.98° C.), showing that the product of Ex. 1 produced a higher cure rate.
b) with varying amounts of Pt—DSC analysis (20° C./min in He atmosphere, open pan) of the hydrosilylation reaction exotherm on 56 wt % Ph-T (217)+44% 46dp PDMS, 1.57 mol % Vinyl-T sample as a function of Pt level; with the products of i) Ex. 1 and ii) C. Ex. 1; The temperature at the peak of the reaction exotherm (T_peak) was calculated; formulation: T-Vinyl resin-linear+M^H_0.6T^Ph_0.4 (SiH/Vinyl=1.0)+Pt.
The table below contains values of T_peak in ° C. at different levels of Pt. The data fit a logarithmic equation: T_peak=11.11 ln(ppm Pt)+142.46 with a correlation coefficient R²=0.9967.

	0.25 ppm Pt	0.5 ppm Pt	1 ppm Pt	2.5 ppm Pt
Ex. 1	158.2	150.3	142.1	132.9
C. Ex. 1			156.0

To achieve the same T_peak as C. Ex. 1 at 1 ppm, Ex. 1 would require only 0.31 ppm Pt.

TABLE 2
Vinyl functional Ph-T - PDMS examples and comparative examples. Compositions:
1 ppm Pt, 250 ppm DODS, 13.5 ppm TPP, RMS 356 SiH/Vi = 1
		Base resin-linear	mol %	Vinyl	Cure	Optical
		Composition	Vinyl	environment	speed	clarity
Ex. 1	26358-023	56 wt % Ph-T - 46 dp	1.57	TPh-TVinyl-DMe2	high	high
		PDMS
Ex. 2	26358-027	45 wt % Ph-T - 101 dp	1.40	TPh-TVinyl-DMe2	high	high
		PDMS
C.	26358-021	56 wt % Ph-T - 46 dp	1.57	TPh-TVinyl-TPh	low	high
Ex. 1		PDMS
C.	26358-035	45 wt % Ph-T - 101 dp	1.40	TPh-DVinyl-TPh	medium	high
Ex. 2		PDMS
C.	26358-037	45 wt % Ph-T -101 dp	1.40	TPh-TVinyl-TPh	low	high
Ex. 3		PDMS
C.	26358-033	45 wt % Ph-T - 101 dp	1.40	TPh-DVinyl-DMe2	n/a	low
Ex. 4		PDMS
Detailed results that form the basis of Table:
			Formulation (ppm),
			RMS 356 (SiH/Vi = 1)
mol %	wt %	Vinyl	Pt,	DODS	TPP,	Tonset-1	Tpeak-1	□Hreact-1	Tonset-2
vinyl	Ph-T	environment	ppm	ppm	ppm	° C.	° C.	J/g	° C.
1.57	56	TPh-TVinyl-DMe2	1	250	13.5,	116.9	150.8	5.74	247.1
					6 mo.
1.57	56	TPh-TVinyl-TPh	1	250	13.5	137.0	163.2	4.94	long tail
1.40	45	TPh-TVinyl-DMe2	1	250	13.5	119.0	152.9	4.47	long tail
1.40	45	TPh-TVinyl-TPh	1	250	13.5	136.4	169.6	4.78	long tail
1.40	45	TPh-DVinyl-DMe2	sample not optically clear (ineffective RL coupling ?) ***
1.40	45	TPh-DVinyl-TPh	1	250	13.5	122.4	156.2	6.60	weak
									shoulder

	TABLE 3
			Rate of change during
	Cured	500 h 225° C.	225° C. at 23° C.
	mol %	wt %	Vinyl	TS	EB	YM	TS	EB	YM	TS	EB	YM
	Vi.	Ph-T	environment	MPa	%	MPa	MPa	%	MPa	MPa/h	%/h	MPa/h
Ex. 1	1.57	56	TPh-TVinyl-DMe2	6.74	94	116	7.15	29	103	0.0008	−0.13	−0.026
Ex. 2	1.40	45	TPh-TVinyl-DMe2	5.41	171	19.6	4.39	56	17	−0.0021	−0.23	−0.005
C.	1.57	56	TPh-TVinyl-TPh	6.11	109	152	8.05	35	112	0.0039	−0.15	−0.081
Ex. 1
C.	1.40	45	TPh-DVinyl-TPh	4.88	211	37.8	5.01	70	31	0.0003	−0.28	−0.014
Ex. 2
C.	1.40	45	TPh-TVinyl-TPh	4.74	232	27.5	4.78	59	22	0.0001	−0.33	−0.010
Ex. 3

TABLE 4
Vinyl functional Ph-T - PDMS formulated with RMS 356, different levels
of Pt (no inhibitor) and comparative examples with results of cure
speed (from DSC) and thermal stability; composition only contains
the Vinyl functional resin-linear, RMS 356 (SiH/Vi = 1) and Pt
					Linear Tg	Change in
				DSC cure	change	E′(120° C.)
	mol %	Pt,	Vinyl	exotherm	after 500 h	during 225° C.
	Vinyl	ppm	environment	Temperature	@225° C.	aging
Ex. 3	1.57	1	TPh-TVinyl-DMe2	142° C.	18.6° C.	0.146 MPa/h
Ex. 4	1.57	0.31	TPh-TVinyl-DMe2	156° C.	6.0° C.	0.137 MPa/h
C.	1.57	1	TPh-TVinyl-TPh	156° C.	23.9° C.	0.150 MPa/h
Ex. 5

These results demonstrate that the composition of this invention is able to produce better thermal stability at lower platinum levels while maintaining cure speed.
Some additional experiments were performed to introduce D^Vi next to D^Me2 without the issue of incompatibility noted in the detailed results of Table 2:
Vinyl-D Next to D^Me2 vs. T^pH: Cure Speed

Another way to incorporate Vinyl-D next to D^Me2 is to cap with vinylmethyl diacetoxysilane followed by hydrolysis to turn the relatively unreactive second acetoxy group into silanol to ensure that further coupling with resin is possible. Since methyl/ethyl triacetoxysilane is needed to invoke resin-linear and resin-resin coupling this results in a relatively cumbersome synthesis and a vinyl environment of T^Ph-T^Me/Et-D^Vi-D^Me2 (Table 7 Example 3). Table 7 compares this system with the control where Vinyl-D is used as part of the RR coupling agent forming a T^Ph-D^Vi-T^Ph chain. Again, the data rheology and DSC data confirms that Vinyl moieties next to a D^Me2 unit exhibit higher cure speed as expected.

TABLE 1
Vinyl functional Ph-T - PDMS resin-linears with summarized
results as far as composition and cure speed; compositions:
1 ppm Pt, TPP (triphenylphosphine), RMS 352 SiH/Vi = 1.
ID	Example 5	Comp. Example 5
		PhT45-DP100	PhT45-DP100 new-2
Vi @		Linear ends	On resin
Chemical	Calc.	D65.0ViD1.1Me/EtT2.9PhT31.0	D65.0PhT31.0ViD1.1RT2.9
Compo-
sition
	(NMR)	ViD1.35D66.51RT1.39PhT30.75
Vi	Wt %	0.32	0.32
MW	GPC	43400	46900
min G′		13,320	885
max tan δ		1.295	4.445
time to tan	min	7.367	35.97
δ < 1
DSC T	° C.	143.0	146.7
peak

Example 5: T^pH-T^Me/Et-D^Vi-D^Me2: Resin Linear Containing D-Vinyl Capped Linear Followed by Hydrolysis and Further Coupling with T^Ph

Preparation of M^Vi(OH)-Terminated PDMS (Dp122)

A 300 mL 4-necked flask was equipped with thermometer, Dean-Stark trap attached to reflux condenser, and mechanical stirrer with Teflon stir paddle. OH-terminated PDMS (Dp103, 120 g, 15.7 mmol) and toluene (65 g) were loaded to the flask and stirred under reflux for 1 h for dehydration. After the solution was cooled to room temperature, excess ViMeSi(OAc)₂ (11.8 g, 62.8 mmol) was added and stirring was continued at room temperature for 0.5 h, then 2 h under reflux. Stripping of the residual ViMeSi(OAc)₂ and toluene under reduced pressure (2-3 torr, 100° C., N₂ bubbling) afforded M^Vi(OAc)₂-terminated PDMS as an intermediate. Then, the flask with the intermediate were added toluene (50 g), water (50 g), NaHCO₃ (6.44 g), and triethylamine (0.7 g) and stirring was continued for overnight at room temperature (progress of the reaction was monitored by IR (decrease of C═O/Si-Me)). After the aqueous layer was removed from the mixture, the organic layer was washed with water repeatedly (50 mL×3). Stripping of toluene and triethylamine under reduced pressure (2-3 torr, 50° C., N₂ bubbling) gave crude product which was purified by Zeta-plus filtration (40QSH) to afford M^Vi(OH)-terminated PDMS as clear oil (101.5 g, Dp 122 by ²⁹Si NMR)
Preparation of Resin-Linear (R/L=45/55) with M^Vi(OH)-Terminated PDMS (Dp122)

(Day 1)

A 200 mL 4-necked flask was equipped with thermometer, Dean-Stark trap attached to reflux condenser, and mechanical stirrer with Teflon stir paddle. The M^Vi(OH)-terminated PDMS (41.25 g) and toluene (22.5 g) were loaded to the flask under N₂ atmosphere and stirred under reflux for 0.5 h for dehydration. After the solution was cooled to room temperature, ETS900 (2.167 g) was added and stirring was continued for 0.5 h at room temperature to give a solution with ETS900 capped linear.
A 500 mL 4-necked flask (a flask with a drain on its bottom is favorable) was equipped with thermometer, Dean-Stark trap attached to reflux condenser, and mechanical stirrer with Teflon stir paddle. Toluene (90 g) and 217 flake (33.75 g) were loaded to the flask under N₂ atmosphere and stirred under reflux for 1 h for dehydration. After the solution was cooled to below 100° C., the above ETS900 capped linear solution was added to the flask and reflux was continued for 2 h (Resin-Linear coupling).

(Day 2˜)

The obtained solution was heated to 100° C. and added ETS900 (3.37 g, CF=6). Then the solution was heated under reflux for 2.5 h for Resin-Resin coupling (final viscosity was 28.29 cSt). After the solution was cooled to below 85° C., Dean-Stark trap was removed and reflux condenser was attached directly to the flask. To the flask was added 35 g of water and reflux was continued for 1 h. After the solution was cooled to below 85° C., aqueous layer was removed by syringe (or drain on the bottom of the flask, if available). The similar washing process was repeated for 7 times at 60-80° C. by water ×3, brine ×2, then water ×2. Dean-Stark trap was attached to the flask again and the solution was heated to remove residual water and toluene to concentrate NVC of the solution to ca. 60%. The solution was filtered through Zeta-plus filter (150GN) to afford 88.5 g of final product (NVC:64.43%). (If the solution was clear before filtration, heat it to 80° C. once to accelerate precipitation of T₈).

Comparative Example 5: T^Ph-D^Vi-T^Ph: Resin Linear where D-Vinyl is Used after Resin-Linear Coupling

Preparation of Resin-Linear (R/L=45/55) with OH-Terminated PDMS (Dp100)

(Day 1)

A 200 mL 4-necked flask was equipped with thermometer, Dean-Stark trap attached to reflux condenser. OH terminated PDMS (82.5 g) and toluene (45.0 g) were loaded to the flask under N₂ atmosphere and stirred by stir bar under reflux for 0.5 h for dehydration. After the solution was cooled to room temperature, ETS900 (5.300 g) was added and stirring was continued for 0.5 h at room temperature to give a solution with ETS900 capped linear.
A 1000 mL 4-necked flask (a flask with a drain on its bottom is favorable) was equipped with thermometer, Dean-Stark trap attached to reflux condenser, and mechanical stirrer with Teflon stir paddle. Toluene (180.0 g) and 217 flake (67.5 g) were loaded to the flask under N₂ atmosphere and stirred under reflux for 0.5 h for dehydration. After the solution was cooled to below 100° C., the above ETS900 capped linear solution was added to the flask and reflux was continued for 2 h (Resin-Linear coupling).

(Day 2˜)

The obtained solution was heated to 100° C. and added ETS900 (5.5057 g). Then the solution was heated under reflux for 1 h for Resin-Resin coupling (viscosity was 20.6 cSt). After the solution was cooled to below 100° C., vinylmethyldiacetoxysilane was added to the solution and reflux was continued for 2 h. After the solution was cooled to below 85° C., Dean-Stark trap was removed and reflux condenser was attached directly to the flask. To the flask was added 40 g of water and reflux was continued for 1 h. After the solution was cooled to below 85° C., aqueous layer was removed by syringe (or drain on the bottom of the flask, if available). The similar washing process was repeated for 7 times at 60-80° C. by water ×3, brine ×2, then water ×2. Dean-Stark trap was attached to the flask again and the solution was heated to remove residual water and toluene to concentrate NVC of the solution to ca. 70%. The solution was filtered through Zeta-plus filter (150GN) to afford 163.9 g of final product (NVC: 70.4%).

Claims

1. A hydrosilylation curable polysiloxane comprising at least one of units of formula (I) and units of formula (II)

wherein Ar is C6-C20 aryl, R1 is C2-C20 alkenyl, and R2, R3, R4 and R5 independently are C1-C20 hydrocarbyl.

2. The polysiloxane of claim 1 in which R2, R3, R4 and R5 independently represent C1-C4 alkyl.

3. The polysiloxane of claim 2 in which R1 is C2-C8 alkenyl.

4. The polysiloxane of claim 3 which comprises units of formula (I) and in which less than 25 mole % of R1 groups in the hydrosilylation curable polysiloxane is from units of formula (II).

5. The polysiloxane of claim 4 in which an [R2R3SiO2/2] unit in formula (I) or formula (II) is part of a polysiloxane chain having from 10 to 500 [R2R3SiO2/2] units.

6. The polysiloxane of claim 5 in which the polysiloxane comprises from 20 to 60 mole % [ArSiO3/2] units and from 40 to 80 mole % [R2R3SiO2/2] units.

7. The polysiloxane of claim 6 in which the polysiloxane further comprises from 0.5 to 4.5 mole % [R1SiO3/2] units.

8. The polysiloxane of claim 7 in which R2, R3, R4 and R5 independently represent methyl or ethyl.

9. The polysiloxane of claim 8 in which an [R2R3SiO2/2] unit in formula (I) is part of a polysiloxane chain having from 30 to 200 [R2R3SiO2/2] units.

10. The polysiloxane of claim 9 in which R2, R3, R4 and R5 are methyl, R1 is vinyl and Ar is phenyl.