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Title:
RADIATION CURABLE POLYORGANYLOXY-SILOXANE COMPOSITIONS
Document Type and Number:
WIPO Patent Application WO/2021/126178
Kind Code:
A1
Abstract:
The present invention is a curable silicone composition comprising a linear polyorganyloxy-siloxane component (A) of the following general formula (I) R1 aR2 3-aSiO(R2 2SiO)b(R3HSiO)c(R3R4OSiO)dSiR1 aR2 3-a (I) wherein, R1, R2, R3, a, b, c are as defined above and R4 is a hydrocarbon derivative, which has from 1 to 30 carbon atoms having linear, branched, or cyclic arrangements, and may be substituted by OH groups, halogen atoms, silyl groups, siloxy groups, -CN, -COOR6, -OCOOR7, -CONR8R9, -OCONR10R11, -NR12CONR13R14, -SO2-R15, -OSO2-R16, -OP(OR17) (OR18), 1,3-dioxolan-2-one, wherein the carbon may be interrupted by nonadjacent groups which are selected from -(CO)-, -O-, -S- or -NR19-,R6 to R19 are each a monovalent hydrocarbon radical which has from 1 to 18 carbon atoms and may be substituted by halogen atoms, and d comprises up to 60 mol % of the silicon atoms of the organosilicon compound (A) of the general formula (I); a mercapto group containing component (B) containing at least two carbon bonded SH groups per molecule; and a photoiniator component (C). The present invention further relates to a process for curing the curable silicone composition by energetic radiation.

Inventors:
YOUNG JOHN (US)
ACHENBACH FRANK (DE)
STEPP MICHAEL (AT)
ZHENG TIANYUE (US)
Application Number:
PCT/US2019/067043
Publication Date:
June 24, 2021
Filing Date:
December 18, 2019
Export Citation:
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Assignee:
WACKER CHEMIE AG (DE)
YOUNG JOHN (US)
International Classes:
C08L83/04; C08G77/20
Foreign References:
EP0776943A11997-06-04
US9879126B22018-01-30
Other References:
SUN, Z. ET AL.: "Structure and Properties of Silicone Rubber/Styrene-Butadiene Rubber Blends with in Situ Interface Coupling by Thiol-ene Click Reaction", IND. ENG. CHEM. RES., vol. 56, no. 6, 2017, pages 1471 - 1477
SUN, H. ET AL.: "The role of dipole structure and their interaction on the electromechanical and actuation performance of homogeneous silicone dielectric elastomers", POLYMER, vol. 165, 2019, pages 1 - 10
Attorney, Agent or Firm:
CONGER, William G. et al. (US)
Download PDF:
Claims:
WHAT IS CLAIMED IS:

1. A curable silicone composition, comprising: a linear polyorganyloxy-siloxane component (A) of the following general formula (I)

R1aR23-aSiO(R22SiO)b(R3HSiO)c(R3R4OSiO)dSiR1aR23-a (I) wherein,

R1 is a hydrocarbon possessing aliphatically unsaturated groups which are selected from alkenyl and alkynyl groups which has from 1 to 18 carbon atoms with the proviso that at least one R1 per molecule is a hydrocarbon possessing aliphatically unsaturated groups,

R2 is an aliphatically saturated hydrocarbon which has from 1 to 30 carbon atoms,

R3 is an aliphatically saturated hydrocarbon which has from 1 to 30 carbon atoms,

R4 is a hydrocarbon derivative, which has from 1 to 30 carbon atoms having linear, branched, or cyclic arrangements, and may be substituted by OH groups, halogen atoms, silyl groups, siloxy groups, -CN, -COOR6, -OCOOR7, -CONR8R9, - OCONR10RU, -NR12CONR13R14, -SO2-R15, -0S02-R16, -OP(OR17) (OR18), 1,3- dioxolan-2-one, wherein the carbon may be interrupted by nonadjacent groups which are selected from -(CO)-, -0-, -S- or -NR19-,

R6 to R19 are each a monovalent hydrocarbon radical which has from 1 to 18 carbon atoms and may be substituted by halogen atoms, a is 1, 2 or 3, b is a positive integer number of at least 5, c is 0 or a positive integer number and d is a positive integer number which is chosen so that (R3R4SiO)c comprises up to 60 mol % of the silicon atoms of the organosilicon compound (A) of the general formula (I); a mercapto group containing component (B) containing at least two carbon bonded SH groups per molecule; and a photoiniator component (C).

2. The curable silicone composition according to claim 1, wherein R1 is selected from vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, ethinyl and octenyl.

3. The curable silicone composition according to any one of the preceding claims wherein at least 10 mol % of the groups R4 are substituted by groups which are selected from OH groups, halogen atoms, silyl groups, siloxy groups, -CN, -COOR6, -OCOOR7, - CONR8R9, -OCONR10Ru, -NR12C0NR13R14, -SO2-R15, -OSO2-R16, -OP(OR17) (OR18), 1,3- dioxolan-2-one.

4. The curable silicone composition according to any one of the preceding claims wherein a is 1.

5. The curable silicone composition according to any one of the preceding claims wherein the mercapto group containing component (B) is a mercapto functional polyorganosiloxane (Bl).

6. The curable silicone composition according to any one of the preceding claims wherein the mercapto group containing component (B) is a mercapto organic component (B2).

7. The curable silicone composition according to any one of the preceding claims wherein the constituents (A) and (B) are present in such an amount in the crosslinkable compositions of the invention that the molar ratio of SH groups to aliphatically unsaturated groups is 0.1 to 20.

8. The curable silicone composition according to any one of the preceding claims wherein the photoiniator component (C) is selected from 2,2-dimethoxy-l -hydroxy - cyclohexyl - phenyl - ketone, 1- [4- (2-hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-l- propan-l-one, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholinopropan-l-one , 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) - butanone-1, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, 2-hydroxy- 1- (4- [4- (2-hydroxy-2-methyl - propionyl) - benzyl] - phenyl} - 2-methyl - propane, 1,2-octanedione, 1- [4- (phenyl ene Thio) -, 2- (O-benzoyl oxime)], 2- hydroxy-2-methyl-l -phenyl - propane- 1 -one, phenyl glyoxylate butyric acid methyl ester, thioxanthone in combination with triethylamine, 2,4,6-trimethyl benzoyl - diphenyl, or combinations thereof. 9. The curable silicone composition according to any one of the preceding claims wherein the curable silicone composition contains an actively reinforcing filler component (D).

10. A process for curing the curable silicone composition according to any one of the preceding claims by energetic radiation.

11. The process of claim 10, wherein the energetic radiation is ultraviolet light having a wave length of from 200 to 400 nanometers.

Description:
RADIATION CURABLE POLYORGANYLOXY-SILOXANE COMPOSITIONS

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to mixtures that are crosslinkable to give vulcanizates, which mixtures comprise a linear polyorganyloxy-siloxane component (A), a mercapto group containing component (B) and a photoinitiator component (C); and a process for curing the curable silicone composition by energetic radiation.

2. Description of the Related Art

Photoinduced crosslinking is especially attractive. Organopolysiloxanes are well known to cured through addition, condensation, and radiation mechanisms, but vulcanization using sulfur or thiol containing reagents may also be sufficient in generating a cured elastomer (Sun, Z., et ak, “Structure and Properties of Silicone Rubber/Styrene-Butadiene Rubber Blends with in Situ Interface Coupling by Thiol-ene Click Reaction.” Ind. Eng. Chem. Res. 56 (6), pp. 1471-1477, (2017)).

Furthermore, thiol-ene click chemistry has been reported to be suitable for curing of organopolysiloxanes possessing polar functional groups (Sun, H., et al. (2019), "The role of dipole structure and their interaction on the electromechanical and actuation performance of homogeneous silicone dielectric elastomers." Polymer 165: 1-10). Herein, polar functionalized poly-organyloxy-siloxanes are found to cure using thiol-ene click chemistry, and the resulting elastomers, for those skilled in the art, may find benefits in consumer care, coatings, electronics, electro-active polymers, the medical sector, the pharmaceutical sector, as sealants, and for soft robotics applications.

SUMMARY OF THE INVENTION

The present invention is a curable silicone composition comprising: a linear polyorganyloxy-siloxane component (A) of the following general formula (I) R 1 aR 2 3-aSiO(R 2 2 SiO) b (R 3 HSiO)c(R 3 R 4 OSiO)dSiR 1 aR 2 3-a (I) wherein,

R 1 is a hydrocarbon possessing aliphatically unsaturated groups which are selected from alkenyl and alkynyl groups which has from 1 to 18 carbon atoms with the proviso that at least one R 1 per molecule is a hydrocarbon possessing aliphatically unsaturated groups, R 2 is an aliphatically saturated hydrocarbon which has from 1 to 30 carbon atoms,

R 3 is an aliphatically saturated hydrocarbon which has from 1 to 30 carbon atoms,

R 4 is a hydrocarbon derivative, which has from 1 to 15 carbon atoms, and may be substituted by OH groups, halogen atoms, silyl groups, siloxy groups, -CN, -COOR 6 , - OCOOR 7 , -CONR 8 R 9 , -OCONR 10 R u , -NR 12 C0NR 13 R 14 , -SO2-R 15 , -OSO2-R 16 , - OP(OR 17 ) (OR 18 ), l,3-dioxolan-2-one, wherein the carbon may be interrupted by nonadjacent groups which are selected from -(CO)-, -0-, -S- or -NR19-,

R 6 to R 19 are each a monovalent hydrocarbon radical which has from 1 to 18 carbon atoms and may be substituted by halogen atoms, a is 1, 2 or 3, b is a positive integer number of at least 1, c is 0 or a positive integer number and d is a positive integer number which is chosen so that (R 3 R 4 SiO) c comprises up to 60 mol % of the silicon atoms of the organosilicon compound (A) of the general formula (I); a mercapto group containing component (B) containing at least two carbon bonded SH groups per molecule; and a photoinitiator component (C).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The polyorganyloxy-siloxane component (A) possessing vinyl termini and polar pendent functionalization has not been available until now.

The component (A) can be prepared while avoiding issues with hydrosilylation as taught in the prior art, by using a novel two-set approach of combining equilibration/ring-opening polymerization with dehydrogenative or reductive coupling reactions. With this approach, siloxane polymers possessing both vinyl (CC-unsaturated) terminated and polar pendent groups can be obtained without the problems of molecular weight and gelation. Using dehydrogenative or reductive coupling may avoid the use of precious metal catalysts, such as Rh, Pd, or Pt, which are typically used in hydrosilylation chemistry, as well as avoiding the use of olefmic containing materials, thereby increasing the number of functionalized siloxane polymers. A dehydrogenative or reductive pathway enables chemical feedstocks possessing alcohol, aldehyde, or ketone groups to be used as a method of functionalizing the siloxane polymer. It was unexpectedly discovered that polar polyorganyloxy-siloxane components (A) are stable up to 150 °C and have high resistance to humidity. An advantage of thiol-ene click curing chemistry versus Pt-based addition curing as described in US9879126, is that depending on the thiol content of the crosslinker, component (B), it may allow a lower weight percentage of crosslinker which enables better compatibility with the polarity of component (A). An additional advantage of this invention compared to Pt curing methods, as described in US9879126, is better functional group tolerance and activity of the photoinitiator component (C) with respect to the polarity in the polyorganyloxy-siloxane component (A). Thiol-ene click chemistry may facilitate faster curing speed than with addition curing processes.

R 1 can be an alkenyl, alkenylaryl, arylalkenyl, alkynyl, alkynylaryl or arylalkynyl group. Preferably R 1 is an alkenyl group. Preferably R 1 has from 1 to 10 carbon atoms. Preferably R 1 is selected from vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, ethynyl and octenyl, with vinyl groups being the most preferred. Preferably one R 1 in every terminal position of the molecule is a hydrocarbon possessing aliphatically unsaturated groups. Preferably the curable silicone composition has 0.01 to 2 percent by weight of R 1 .

R 2 and R 3 independently are preferably selected from alkyl groups. Preferably R 2 and R 3 are hydrocarbon groups from 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl and decyl; aryl group such as phenyl, tolyl, xylyl and naphthyl. Also included are halogenated alkyl radicals in which some hydrogen atoms are substituted by halogen atoms, such as trifluoropropyl and nonafluorooctyl. Of these, alkyl and fluoroalkyl radicals of 1 to 6 carbon atoms are preferred. Methyl and ethyl are most preferred. It is especially preferred that at least 80 mol percent of R 2 be methyl or ethyl. R 6 to R 14 preferably are each a monovalent hydrocarbon radical which has from 1 to 6 carbon atoms, in particular from 1 to 6 carbon atoms.

In a preferred embodiment R 4 is a hydrocarbon derivative, which has from 1 to 15 carbon atoms.

In a preferred embodiment the groups R 4 are substituted by groups which are selected from OH groups, halogen atoms, silyl groups, siloxy groups, -CN, -COOR 6 , -OCOOR 7 , -CONR 8 R 9 , - OCONR 10 R U , -NR 12 CONR 13 R 14 , -SO2-R 15 , -OSOi-R 16 , -OP(OR 17 ) (OR 18 ), l,3-dioxolan-2- one.

Examples of hydrocarbon derivatives R 4 include polar groups of linear carbonate, cyclic carbonate, l,6-anhydro-3,4-dideoxyhexopyranose, cyano, linear sulfone, cyclic sulfone, linear sulfoxide, cyclic sulfoxide, linear phosphate, cyclic phosphate, linear phosphonate, cyclic phosphonate, linear carbamate, cyclic carbamate, linear urea, cyclic urea, linear thiourea, cyclic thiourea, linear thiocarbonate, cyclic thiocarbonate, linear thiocarbamate, cyclic thiocarbamate, linear phosphonothioate, cyclic phosphonothioate, linear phosphoramide, cyclic phosphoramide, malonate, ketone or lactone, or epoxy.

Preferably a is 1. Preferably b is a positive integer number of 10 to 1000, more preferably 20 to 500 and most preferably 40 to 200. c is preferably 0 or a positive integer number of at most 20 more preferably at most 10 and most preferably at most 5. Preferably the unit (R 2 2 SiO) b ranges from 30% to 99 mol% of the component (A). Preferably d is a positive integer number of 5 to 500, more preferably 10 to 200 and most preferably 15 to 100.

Preferably d is chosen so that the unit (R 3 R 4 SiO) d comprises up to 60 mol %, more preferably 5 to 40 mol% of the silicon atoms of the organosilicon component (A) of general formula (1), preferably determined based on standard analytical Nuclear Magnetic Spectroscopy 29 Si (NMR) techniques.

Preferably the molecular weight of component (A) is in the range of from 5,000 to 30,000. Number average molecular weight (Mw) of the component (A) is preferably in the range of 300 to 30,000. Moreover, no particular limitation is placed on viscosity measured under 10 (s- 1) shear rate conditions at 25 degrees centigrade using a rheometer equipped with a cone plate of 20 mm diameter, although this viscosity is preferably in the range of 1 to 50,000 mPa s, and particularly preferably is in the range of 5,000 to 20,000 mPa s.

A preferred polyorganyloxy-siloxane component (A) has the following general formula (II) wherein R 1 , R 2 , R 3 and R 4 have the meanings as defined above, x is a positive integer number of at least 5 and y is a positive integer number which is chosen so that (R 3 R 4 SiO) y comprises up to 60 mol

% of the silicon atoms of the organosilicon compound (A) of the general formula (II).

The mercapto group containing component (B) is the crosslinker. Component (B) can be either a mercapto functional polyorganosiloxane (Bl), a mercapto organic component (B2) or mixtures thereof. The mercapto functional crosslinkers are preferably selected such that the component (A) and mercapto group containing component (B) are compatible. The combination of components (A) and (B) are compatible when specific polymers or components are combined in the amounts to be used, and the resulting mixture does not separate into phases. A cloudy mixture can indicate separate phases and may separate on standing, such combinations are usually not used, however, a cloudy mixture can be used if the storage, viscosity stability, and cure properties are met. The selection for compatibility can readily be determined for any specific polymer or component. The amount of components (A) and (B) used will influence the overall compatibility with component (A).

The mercapto functional component (B) should have at least two mercapto groups per molecule, preferably the number of mercapto groups is three or more. Preferably component (B) has three or more mercapto groups per molecule promote a crosslinked structure with suitable elastomeric properties. The mercapto functional polyorganosiloxane (Bl) is exemplified using gamma- mercaptopropyl or mercaptoisobutyl functional polyorganosiloxanes wherein the polymer has 3 to 20 mercapto containing siloxane units in either terminal or pendent positions.

The mercapto organic component (B2) is also known in the art by terms such as "polythiols" and "polymercaptans". These mercapto organic compounds contain at least 2 mercapto groups (-SH) and consist of atoms selected from sulfur, hydrogen, and carbon, and optionally oxygen. Preferably, these mercapto organic compounds contain from 2 to 6 mercapto groups. Some examples are 2, 2'-dimercaptodi ethyl ether, dipentaerythritolhexa(3-mercaptopropionate), glycol dimercaptoacetate, glycol dimercaptopropionate, pentraerythritol tetrakis(3- mercatopropionate), pentaerythritol tetrakis(3-mercaptobutanoate) (commercially available from Showa Denko under trade name Karenz MT™ PEI, contains pentaerythritol tris(3- mercaptobutanoate)), polyethylene glycol dimercaptoacetate of the formula ElSCEhCOOCE^CEhOCEy n CEhOOCCEhSIT, polyethylene glycol di(3-mercaptopropionate) of the formula

HSCH 2 CH 2 C00CH 2 (CH 2 0CH 2 ) n CH 2 00CCH 2 CH 2 SH with n being from 2 to 20, trimethyl ol ethane tri(3-mercaptopropionate), trimethyl ol ethane trithioglycolate, trimethyl olpropane tri(3-mercaptopropionate), and trimethyl olpropane trithioglycolate.

The amount of mercapto functional component (B) in the curable silicone composition according to the invention is preferably in the range of from 0.1 to 10 percent by weight, more preferably 0.5 to 5 percent by weight, and most preferably between 1 to 3 percent by weight.

Preferably, constituents (A) and (B) are present in such an amount in the crosslinkable compositions of the invention that the molar ratio of SH groups to aliphatically unsaturated groups is 0.1 to 20, more preferably 1.0 to 5.0.

The photoiniator component (C) is a known photopolymerization initiator that includes but is not limited to 2,2-dimethoxy-l -hydroxy - cyclohexyl - phenyl - ketone, 1- [4- (2- hydroxyethoxy) - phenyl] -2-hy droxy-2-m ethyl- 1 -propan- 1 -one, 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropan-l-one , 2-benzyl-2-dimethylamino-l- (4-morpholinophenyl) - butanone-1, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, 2-hydroxy-l- (4- [4- (2- hydroxy-2-methyl - propionyl) - benzyl] - phenyl} -2-methyl - propane, 1,2-octanedione, 1- [4- (phenyl ene Thio) 2- (O-benzoyl oxime)], 2-hy droxy-2-m ethyl- 1 -phenyl - propane- 1 -one, phenylglyoxylate butyric acid methyl ester, thioxanthone in combination with triethylamine, 2,4,6-trimethyl benzoyl - diphenyl, or combinations thereof. Although phosphine oxide and the like, as long as it is able to absorb the light generated from the light sourced used for photocuring.

The above compounds are commercially available, IRGACURE ® 651, 184, 2959, the 907, the 369, the 379, the 819, the 127, the OXE01,02, DAROCUR ® 1173, the MBF, the TPO (manufactured by BASF Japan Co., Ltd.), ESACURE ® KIP150, same TZT, same KT046, the 1001M, the KB1, the KS300, the KL200, the TPO, the ITX, the EDB (manufactured by Japan Siber Hegner Co., Ltd.), and the like.

The content of the photoiniator component (C) in the curable composition of the present invention is preferably from 0.5 to 20% by weight relative to the polymerizable compound, and more preferably in the amount be in the range of 0.1 to 5 percent.

The curable silicone composition according to the invention can optionally contain an actively reinforcing filler component (D). The content of filler (D) is in the range of from 0 to 70 percent by weight, preferably 0 to 50 percent by weight, and more preferably between 0 to 30 weight of the curable silicone composition.

Examples of reinforcing fillers which can be used as component (D) are fumed or precipitated silicas with BET surface areas of at least 50 m 2 /g, as well as carbon blacks and activated carbons such as furnace black and acetylene black, where fumed and precipitated silicas with BET surface areas of at least 50 m 2 /g are preferred. The specified silica fillers can have hydrophilic character or be hydrophobicized by known processes. Fillers (D) having been surface-treated are most preferred. The surface treatment is achieved by known processes for hydrophobicizing finely divided fillers. The hydrophobicization can take place, for example, either prior to the incorporation into the polyorganosiloxane, or else in the presence of a polyorganosiloxane after the in-situ process. Both processes can be carried out either in the batch process or continuously. Preferably used hydrophobicizing agents are organosilicon compounds which are able to react with the filler surface to form covalent bonds or are physisorbed permanently onto the filler surface. Examples of hydrophobicizing agents are alkylchlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, octylmethyldichlorosilane, octadecylmethyldichlorosilane, octyldimethylchlorosilane, octadecyldimethylchlorosilane and tert-butyldimethylchlorosilane: alkenylchlorosilanes such as vinyltrichlorosilane; alkylalkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane; trimethylsilanol, 3- methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane; alkenylalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane; cyclic diorgano(poly)siloxanes such as octamethylcyclotetrasiloxane, dekamethylcyclopentasiloxane; linear diorganopolysiloxanes such as dimethylpolysiloxanes with trimethylsiloxy end groups, and dimethylpolysiloxanes with silanol or alkoxy end groups; disilazanes such as hexaalkyldisilazanes, most preferably hexamethyldisilazane, divinyltetramethyldisilazane, bis(trifluoropropyl)tetramethyldisilazane; cyclic dimethylsilazanes such as hexamethylcyclotrisilazane. It is also possible to use mixtures of the aforementioned hydrophobicizing agents. In order to accelerate the hydrophobicization, it is also possible, where appropriate, to add catalytically active additives such as, for example, amines, metal hydroxides and water.

As a consequence of a surface treatment, preferred fillers (D) have a carbon content of at least 0.01 to at most 20 percent by weight, preferably between 0.1 and 10 percent by weight, most preferably between 0.5 to 5 percent by weight.

The curable silicone composition can, if desired, include, as constituents, further additives to a fraction of up to 70 percent by weight, preferably 0.0001 to 40 percent by weight. These additives can be e.g. inactive fillers, resin-like polyorganosiloxanes which are different from the components (A) and (B), antimicrobial additives e.g. fungicides, fragrances, rheological additives, antistats, hydrophilizing additives, corrosion inhibitors, oxidation inhibitors, light protection agents, anti-inflammatory agents and agents for influencing the electrical properties, dispersion auxiliaries, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers etc. These include additives such as quartz flour, diatomaceous earth, clays, chalk, lithopone, carbon blacks, graphite, metal oxides, metal carbonates and sulfates, metal salts of carboxylic acids, fibers such as glass fibers, plastic fibers, plastic powders, dyes, pigments etc. These fillers can moreover be heat-conducting. Examples of heat-conducting fillers are aluminum nitride; aluminum oxide; boron nitride; diamond; carbon nanotubes, graphite; magnesium oxide; silicon carbide; tungsten carbide; zinc oxide and a combination thereof. Heat-conducting fillers are known and commercially available.

The curable silicone composition can, if desired, include, optionally solvent inter alia one or more solvents (E). However, it is to be ensured that the solvent has no disadvantageous effects on the overall system. Suitable solvents are known and are commercially available. The solvent can be, for example, an organic solvent with 3 to 20 carbon atoms. Examples of solvents include aliphatic hydrocarbons such as, for example, nonane, decalin and dodecane; aromatic hydrocarbons such as, for example, mesitylene, xylene and toluene; chlorinated hydrocarbons such as dichloromethane and trichloromethane; esters such as, for example, ethyl acetate and butyrolactone; ethers such as, for example, n-butyl ether and polyethylene glycol monomethyl ether; ketones such as, for example, methyl isobutyl ketone, methyl pentyl ketone, and dihydrolevoglucosenone which is commercially available under the trade name Cyrene™ from Sigma-Aldrich; alcohols such as glycol and glyercol cyclocarbonate; silicone fluids such as, for example, linear, branched and cyclic polydimethylsiloxanes and combinations of these solvents. The optimal concentration of a specific solvent in the curable silicone composition can be determined easily through routine experiments. The amount of solvent can be between 0 and 95 percent or between 1 and 95 percent.

The present invention further relates to a process for curing the curable silicone composition described above by energetic radiation.

Energetic radiation, for the purposes of this invention, is radiation selected from the group consisting of actinic radiation such as ultraviolet light, X-rays and gamma rays and particulate radiation such as alpha particles and electron beams. The length of time that the compositions of this invention should be exposed to the energetic radiation, in order to cure said composition and to adhere it to the substrate, will depend upon the energy of the radiation and the intensity of the radiation that is incident on the composition. Furthermore, the effectiveness of incident radiation is dependent upon several factors. For example, low energy electron beams are known to be more effective in an inert atmosphere such as nitrogen, than in air. Of course, it is well known that the intensity of the incident radiation is also inversely proportional to the distance between the energy source and the composition. Whatever form of energetic radiation is used in the method of this invention, the compositions of this invention are exposed to it for a length of time sufficient to cure the composition and to adhere it to the substrate.

Ultraviolet light is a preferred form of energetic radiation for curing the compositions of this invention because of its relative safety, lower cost and lower power requirements. Furthermore, ultraviolet light that contains radiation having a wave length of from 200 to 400 nanometers is highly preferred for the method of this invention.

The curing temperatures preferably are from 0°C to 80°C, more preferably 10 to 50°C.

The curing time preferably is from 0.1 second to 1 hour, more preferably 0.5 second to 1 minute.

The polyorganyloxy-siloxane compound (A) of the general formula (I), may be prepared by a process, in which a linear polyorganyloxy-siloxane compound of the following general formula (IV)

R I bR 2 3-hSiO(R 2 2SiO)i(R 3 HSiO)j SiR'hRVh (IV) wherein R 1 R 2 and R 3 are as defined above, h is 1, 2 or 3, i is a positive integer number of at least 1 and j is positive integer number of at least 1, is reacted with an alcohol of the general formula (III) R 4 OH, wherein R 4 is as defined in general formula (I), in the presence of a catalyst (K) which is [CuH(PPh3)3]6.

The polyorganyloxy-siloxane compound (A) prepared by said process is free of precious metal catalysts. Examples of alcohols of the general formula (III) are methanol, ethanol, 2-propanol, 1- propanol, 1 -butanol, 2-butanol, cyclohexanol, 2-methyl -2-propanol, 2-methyl- 1 -propanol, 1- pentanol, 1-hexanol, 1,2-ethanediol, 1-m ethyl- 1,2-ethanediol, 2,5-dimethyl-2,5-hexanediol, 2- butene-l,4-diol, 2-butyne-l,4-diol, 3-hexyne-2,5-diol, the neopentyl glycol ester of hydroxypivalinic acid, neopentyl glycol, poly-THF-1000(R)(BASF) (- H[OCH2CH2CH2CH2]nOH), 1-ethynyl-l -cyclohexanol, 2-methyl-3-butyn-2-ol, 4-ethyl- 1- octyn-3-ol, 2-chloro-ethanol, propargyl alcohol, t-amyl alcohol, N-(2 -hydroxy ethyl)-2- pyrrolidone, 1,4-butanediol, 2,4-butanediol, 2-ethylhexanol, furfuryl alcohol, glycerol, 1,3- propanediol, 10-undecen-l-yl, 1-dodecanol, 1-octadecanol, allyl alcohol, allyl-PEG-OH having an average of 3 PEG units, 2-hydroxy- 1 -ethyl methacrylate, ethyl lactate, glycerol cyclocarbonate and glycerol glycide, 3-hydroxypropionitrile, 3 -hydroxy-3 -phenylpropionitrile,

, cyclohexanone cyanohydrin, acetone cyanohydrin, N-methyl-N-2-hydroethyl- cyanoacetamide. Use of glycerolglycide is noteworthy, for those skill in the art, including epoxy groups into the polymer may be further reacted with carbon dioxide to yield a cyclocarbonate. HO-CHi-SiMei-O-SiMei-CHi-OH, H0-CH 2 CH 2 CH 2 -SiMe 2 -0-SiMe 2 - CH2CH2CH2-OH. To suppress the secondary reaction of Si-H to Si-OH, it is advantageous to dry the alcohols used before use, particularly when using polyether alcohols. This can be affected by known methods, for example by means of desiccants or vacuum distillation.

Optionally, the dehydrogenative or reductive coupling approach can also use to include unsaturated alcohols, may also include alkenyl or alkynyl radicals. Example of alcohols possessing unsaturated functionality capable of undergoing crosslinking are allylpropargyl ether, allyl alcohol, 1-hexynol or 1-hexenol.

In the process for preparing polyorganyloxy-siloxane compound (A) the above-mentioned solvents (E) with the exception of alcohols can be used. The temperatures in the process preferably are from 20°C to 150°C, more preferably 40 to 120°C.

All of the symbols in the formulae, above have their meaning in each case independently of one another. In all of the formulae, the silicon atom is tetravalent. The composition of this invention can be coated on metal, paper, or plastic, and depending on thickness of the coating, curing times can be as short as thirty seconds, as detailed in the following examples.

In the examples below, unless stated otherwise, all amounts and percentages are based on the weight and all conversions are carried out at a pressure of 0.10 MPa (abs.).

The above viscosities relate to the measurement method described below. In the examples, the viscosities were measured on a "MCR 302" rheometer from Anton Paar in accordance with DIN EN ISO 3219: 1994 and DIN 53019, using a cone-plate system (cone CP50-2) with an opening angle of 2 degrees. Calibration of the instrument was carried out using standard oil 10,000 from the Physikalisch-Technischen Bundesanstalt [National Metrology Institute of the Federal Republic of Germany] The measurement temperature is 25.00 degrees centigrade plus or minus 0.05 degrees centigrade, the measurement time 3 min. The viscosity stated is the arithmetic mean of three independently performed individual measurements. The measurement uncertainty of the dynamic viscosity is 1.5 percent. The shear rate gradient was selected depending on the viscosity and is designated separately for each stated viscosity.

Examples

Preparation of Component (A)

Example la

Preparation of a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3- dioxolan-4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Preparation of vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi / 2]2[MeRSiO]i5[Me2SiO]85, R = H or (2-oxo-l,3-dioxolan-4-yl)methoxy First, vinyl terminated poly(methylsiloxane-co-dimethylsiloxane) (ViPHMS) was synthesized. To an oven dried round bottom flask equipped with a reflux condenser and a magnetic stirrer, 7.3 g of ViSi 20 (commercially available from Wacker), 0.3 g of Me-Siloxane (commercially available from Wacker), 14.3 g of octamethylcyclotetrasiloxane (D4, commercially available from Gelest), 3.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane (TV, commercially available from Gelest) was added. The mixture was stirred vigorously under nitrogen atmosphere and heated to 80 °C, when 1 g of Amberlyst ® 15 (commercially available from Sigma- Aldrich, USA) was added. The reaction was heated to 120 °C and kept for 12 hours. After that, the Amberlyst ® 15 was filtered off and the volatiles were distilled off at 0.12 mbar / 150 °C to obtain 22.6 g colorless fluid as the product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR. The molecular weight was measured by SEC.

In another oven dried four-necked round bottom flask equipped with a reflux condenser, a magnetic stirrer and a thermometer, 0.4 g Stryker’s Reagent [CuH(PPh3)3]6 (commercially available from Sigma-Aldrich, USA) was dissolved in 20 mL anhydrous toluene (commercially available from Sigma-Aldrich, USA). 8.2 g 4-hydroxymethyl-l,3-dioxolan-2- one (commercially available from Spectrum or Innospec) was added and air was bubbled through the mixture for 5 minutes with vigorous stirring. Afterwards, 19.4 g of ViPHMS of the average formula [Me2(CH2=CH)SiOi / 2]2[MeHSiO]i5[Me2SiO]85 was added. The reaction was heated to 110 °C and monitored by FT-IR. After 1.5 h, FT-IR showed the disappearance of SiH signal. Then the mixture was cooled down to room temperature, diluted with heptane, filtered through Celite (commercially available from Sigma-Aldrich, USA). The solvent was removed in rotary evaporator to obtain 27 g colorless to light tanned fluid as the final product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR.

Example lb

Preparation of a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3- dioxolan-4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Preparation of vinyl terminated polydimethylsiloxane with 30% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi / 2]2[MeRSiO]3o[Me2SiO]7o, R = H or (2-oxo-l,3-dioxolan-4-yl)methoxy Example la was repeated. To an oven dried round bottom flask equipped with a reflux condenser and a magnetic stirrer, 7.5 g of ViSi 20 (commercially available from Wacker), 0.3 g of Me-Siloxane (commercially available from Wacker), 10.9 g of octamethylcyclotetrasiloxane (D4, commercially available from Gelest), 6.3 g of 1, 3,5,7- tetramethylcyclotetrasiloxane (DF, commercially available from Gelest) was added. The mixture was stirred vigorously under nitrogen atmosphere and heated to 80 °C, when 1 g of Amberlyst ® 15 (commercially available from Sigma-Aldrich, USA) was added. The reaction was heated to 120 °C and kept for 12 hours. Afterwards, the Amberlyst ® 15 was filtered off and the volatiles were distilled off at 0.16 mbar / 150 °C to obtain 21.8 g colorless fluid as the product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR. The molecular weight was measured by SEC.

In another oven dried four-necked round bottom flask equipped with a reflux condenser, a magnetic stirrer and a thermometer, 0.48 g Stryker’s Reagent [CuH(PPli3)3]6 (commercially available from Sigma-Aldrich, USA) was dissolved in 20 mL anhydrous toluene (commercially available from Sigma-Aldrich, USA). 11.4 g 4-hydroxymethyl-l,3-dioxolan-2- one (commercially available from Spectrum or Innospec) was added and air was bubbled through the mixture for 5 minutes with vigorous stirring. After that, 18.6 g of ViPHMS of the average formula [Me2(CH2=CH)SiOi / 2]2[MeHSiO]3o[Me2SiO]7o was added. The reaction was heated to 110 °C and monitored by FT-IR. After 1.5 h,FT-IR showed the disappearance of SiH signal. Then the mixture was cooled down to room temperature, diluted with heptane, filtered through Celite (commercially available from Sigma-Aldrich, USA). The solvent was removed in rotary evaporator to obtain 25 g colorless to light tanned fluid as the final product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR.

Example lc

Preparation of a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3- dioxolan-4-yl)methoxy] siloxane-co-dimethylsiloxane}

(Preparation of vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 200 chain length) [Me2(CH2=CH)SiOi / 2]2[MeRSiO]3o[Me2SiO]i7o, R = H or (2-oxo-l,3-dioxolan-4-yl)methoxy

Example la was repeated. To an oven dried round bottom flask equipped with a reflux condenser and a magnetic stirrer, 7.5 g of ViSi 20 (commercially available from Wacker), 0.5 g of Me-Siloxane (commercially available from Wacker), 36.1 g of octamethylcyclotetrasiloxane (D4, commercially available from Gelest), 6.3 g of 1, 3,5,7- tetramethylcyclotetrasiloxane (DF, commercially available from Gelest) was added. The mixture was stirred vigorously under nitrogen atmosphere and heated to 80 °C, when 1.8 g of Amberlyst ® 15 (commercially available from Sigma-Aldrich, USA) was added. The reaction was heated to 120 °C and kept for 5.5 hours. After that, the Amberlyst ® 15 was filtered off and the volatiles were distilled off at 0.19 mbar / 150 °C to obtain 43.9 g colorless fluid as the product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR. The molecular weight was measured by SEC.

In another oven dried four-necked round bottom flask equipped with a reflux condenser, a magnetic stirrer and a thermometer, 0.6 g Stryker’s Reagent [CuH(PPli3)3]6 (commercially available from Sigma-Aldrich, USA) was dissolved in 40 mL anhydrous toluene (commercially available from Sigma-Aldrich, USA). 13 g 4-hydroxymethyl-l,3-dioxolan-2- one (commercially available from Spectrum or Innospec) was added and air was bubbled through the mixture for 5 minutes with vigorous stirring. Afterwards, 41 g of ViPHMS of the average formula [Me2(CH2=CH)SiOi / 2]2[MeHSiO]3o[Me2SiO]i7o was added. The reaction was heated to 110 °C and monitored by FT-IR. After 2 h, FT-IR showed the disappearance of SiH signal. Then the mixture was cooled down to room temperature, diluted with heptane, filtered through Celite (commercially available from Sigma-Aldrich, USA). The solvent was removed in rotary evaporator to obtain 45 g colorless to light tanned fluid as the final product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR.

Example Id

Preparation of a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3- dioxolan-4-yl)methoxy] siloxane-co-dimethylsiloxane} (Preparation of vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 300 chain length)

[Me2(CH2=CH)SiOi / 2]2[MeRSiO]45[Me2SiO]255, R = H or (2-oxo-l,3-dioxolan-4-yl)methoxy

Example la was repeated. To an oven dried round bottom flask equipped with a reflux condenser and a magnetic stirrer, 2.5 g of ViSi 20 (commercially available from Wacker), 0.3 g of Me-Siloxane (commercially available from Wacker), 19.2 g of octamethylcyclotetrasiloxane (D 4 , commercially available from Gelest), 3.1 g of 1, 3,5,7- tetramethylcyclotetrasiloxane (D 4 ’, commercially available from Gelest) was added. The mixture was stirred vigorously under nitrogen atmosphere and heated to 80 °C, when 1 g of Amberlyst ® 15 (commercially available from Sigma-Aldrich, USA) was added. The reaction was heated to 120 °C and kept for 7.5 hours. After that, the Amberlyst ® 15 was filtered off and the volatiles were distilled off at 0.2 mbar / 150 °C to obtain 21.9 g colorless fluid as the product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR. The molecular weight was measured by SEC.

In another oven dried four-necked round bottom flask equipped with a reflux condenser, a magnetic stirrer and a thermometer, 0.4 g Stryker’s Reagent [CuH(PPli3)3]6 (commercially available from Sigma-Aldrich, USA) was dissolved in 20 mL anhydrous toluene (commercially available from Sigma-Aldrich, USA). 8.2 g 4-hydroxymethyl-l,3-dioxolan-2- one (commercially available from Spectrum or Innospec) was added and air was bubbled through the mixture for 5 minutes with vigorous stirring. Afterwards, 18.8 g of ViPHMS of the average formula [Me2(CH2=CH)SiOi / 2]2[MeHSiO]45[Me2SiO]255 was added. The reaction was heated to 110 °C and monitored by FT-IR. After 1 h, FT-IR showed the disappearance of SiH signal. Then the mixture was cooled down to room temperature, diluted with heptane, filtered through Celite (commercially available from Sigma-Aldrich, USA). The solvent was removed in rotary evaporator to obtain 24 g off-white to light brown gel as the final product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR.

Example le Preparation of a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3- dioxolan-4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Preparation of vinyl terminated polydimethylsiloxane with 30% cyclocarbonate functionality and 300 chain length)

[Me2(CH2=CH)SiOi / 2]2[MeRSiO]9o[Me2SiO]2io, R = H or (2-oxo-l,3-dioxolan-4-yl)methoxy

Example la was repeated. To an oven dried round bottom flask equipped with a reflux condenser and a magnetic stirrer, 8.2 g of ViSi 20 (commercially available from Wacker), 0.9 g of Me-Siloxane (commercially available from Wacker), 50.7 g of octamethylcyclotetrasiloxane (D4, commercially available from Gelest), 20.6 g of 1, 3,5,7- tetramethylcyclotetrasiloxane (DF, commercially available from Gelest) was added. The mixture was stirred vigorously under nitrogen atmosphere and heated to 80 °C, when 3.1 g of Amberlyst ® 15 (commercially available from Sigma-Aldrich, USA) was added. The reaction was heated to 120 °C and kept for 6 hours. After that, the Amberlyst ® 15 was filtered off and the volatiles were distilled off at 0.2 mbar / 1500 °C to obtain 66.3 g colorless fluid as the product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR. The molecular weight was measured by SEC.

In another oven dried four-necked round bottom flask equipped with a reflux condenser, a magnetic stirrer and a thermometer, 1.86 g Stryker’s Reagent [CuH(PPli3)3]6 (commercially available from Sigma-Aldrich, USA) was dissolved in 60 mL anhydrous toluene (commercially available from Sigma-Aldrich, USA). 43.3 g 4-hydroxymethyl-l,3-dioxolan-2- one (commercially available from Spectrum or Innospec) was added and air was bubbled through the mixture for 5 minutes with vigorous stirring. Afterwards, 63.4 g of ViPHMS of the average formula [Me2(CH2=CH)SiOi / 2]2[MeHSiO]9o[Me2SiO]2io was added. The reaction was heated to 110 °C and monitored by FT-IR. After 2 h, FT-IR showed the disappearance of SiH signal. Then the mixture was cooled down to room temperature, diluted with heptane, filtered through Celite (commercially available from Sigma-Aldrich, USA). The solvent was removed in rotary evaporator to obtain 104 g orange gel as the final product. The structure was confirmed by 1 HNMR, 29 SiNMR and FTIR. Curing of the silicone composition Example 1 using Component la

UV thiol-ene curing of polymer using Darocur 1173

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi/2]2[MeRSiO]i5[Me2SiO]85, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 9.9 g, 0.33 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 0.36 g Darocur 1173 (purchased from Sigma- Aldrich) and 1.9 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 30 seconds.

Example 2 using Component la

UV thiol-ene curing of polymer using thioxanthone and triethylamine

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi/2]2[MeRSiO]i5[Me2SiO]85, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy Polymer 31.4 g, 0.82 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 10 mg thioxanthone (purchased from Sigma- Aldrich) and 4.8 mg triethylamine (purchased from Sigma-Aldrich) and 5.7 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 5 minutes. The resulting elastomer shows a storage modulus of 11.9 kPa, a loss modulus of 8.8 kPa, and a loss factor of 0.74 (Anton Paar, Model: MCR 302; test method: oscillation mode at 5Hz frequency, 5% amplitude and 25 °C).

Example 3 using Component lb

UV thiol-ene curing of polymer using Darocur 1173

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 30% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi/2]2[MeRSiO]3o[Me2SiO]7o, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 6.9 g, 0.28 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 0.31 g Darocur 1173 (purchased from Sigma- Aldrich) and 1.8 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 60 seconds.

Example 4 using Component lb

UV thiol-ene curing of polymer using thioxanthone and triethylamine Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 30% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi/2]2[MeRSiO]3o[Me2SiO]7o, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 6.5 g, 0.17 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 2 mg thioxanthone (purchased from Sigma- Aldrich) and 1 mg triethylamine (purchased from Sigma-Aldrich) and 1.2 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 2 minutes.

Example 5 using Component lb

UV thiol-ene curing of polymer using thioxanthone and triethylamine

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 30% cyclocarbonate functionality and 100 chain length)

[Me2(CH2=CH)SiOi/2]2[MeRSiO]3o[Me2SiO]7o, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 30.1 g, 1.0 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 14 mg thioxanthone (purchased from Sigma- Aldrich) and 7 mg triethylamine (purchased from Sigma-Aldrich) and 5.5 g SKS 130 are mixed using aSpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 5 minutes. The resulting elastomer shows a storage modulus of 14.3 kPa, a loss modulus of 10.4 kPa, and a loss factor of 0.73 (Anton Paar, Model: MCR 302; test method: oscillation mode at 5Hz frequency, 5% amplitude and 25 °C).

Example 6 using Component lc

UV thiol-ene curing of polymer using Darocur 1173

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 200 chain length)

[Me2(CH2=CH)SiOi/2]2[MeRSiO]3o[Me2SiO]i7o, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 9.5 g, 0.17 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 0.2 g Darocur 1173 (purchased from Sigma- Aldrich) and 1.8 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 30 seconds.

Example 7 using Component Id

UV thiol-ene curing of polymer using thioxanthone and triethylamine

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 15% cyclocarbonate functionality and 300 chain length) [Me2(CH2=CH)SiOi/2]2[MeRSiO]45[Me2SiO]255, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 32.1 g, 0.43 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 6 mg thioxanthone (purchased from Sigma- Aldrich) and 3 mg triethylamine (purchased from Sigma-Aldrich) and 5.4 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 50 minutes. Example 8 using Component le

UV thiol-ene curing of polymer using thioxanthone and triethylamine

Polymer: a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly{methy l[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane}

(Vinyl terminated polydimethylsiloxane with 30% cyclocarbonate functionality and 300 chain length) [Me2(CH2=CH)SiOi / 2]2[MeRSiO]9o[Me2SiO]2io, R = (2-oxo-l, 3 -dioxolan-4-yl)m ethoxy

Polymer 30 g, 0.43 g Pentaerythritol tetrakis(3-mercaptobutanoate) (purchased from Showa Denko under trade name Karenz MT™ PEI), 6 mg thioxanthone (purchased from Sigma- Aldrich) and 3 mg triethylamine (purchased from Sigma-Aldrich) and 5.4 g SKS 130 are mixed using a SpeedMixer™ (FlackTech, inc., Model: DAC 600.1 FVZ). Residual solvent is removed under vacuum. The mixture is then prepared into a film, and cured under UV (Honle UV America, inc., Model: UVAPRINT 100-200 HPV E2) for 20 minutes.