WO2021126178A1 - Compositions de polyorganyloxy-siloxane durcissables par rayonnement - Google Patents

Compositions de polyorganyloxy-siloxane durcissables par rayonnement Download PDF

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WO2021126178A1
WO2021126178A1 PCT/US2019/067043 US2019067043W WO2021126178A1 WO 2021126178 A1 WO2021126178 A1 WO 2021126178A1 US 2019067043 W US2019067043 W US 2019067043W WO 2021126178 A1 WO2021126178 A1 WO 2021126178A1
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groups
silicone composition
curable silicone
component
composition according
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PCT/US2019/067043
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John Young
Frank Achenbach
Michael Stepp
Tianyue Zheng
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Wacker Chemie Ag
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • 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.
  • A linear polyorganyloxy-siloxane component
  • B mercapto group containing component
  • C photoinitiator component
  • 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)).
  • 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).
  • 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.
  • the present invention is a curable silicone composition
  • 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).
  • 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.
  • 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.
  • R 1 is an alkenyl group.
  • R 1 has from 1 to 10 carbon atoms.
  • R 1 is selected from vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, ethynyl and octenyl, with vinyl groups being the most preferred.
  • one R 1 in every terminal position of the molecule is a hydrocarbon possessing aliphatically unsaturated groups.
  • 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.
  • 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.
  • halogenated alkyl radicals in which some hydrogen atoms are substituted by halogen atoms, such as trifluoropropyl and nonafluorooctyl.
  • 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.
  • R 4 is a hydrocarbon derivative, which has from 1 to 15 carbon atoms.
  • 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.
  • 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.
  • a is 1.
  • 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.
  • the unit (R 2 2 SiO) b ranges from 30% to 99 mol% of the component (A).
  • d is a positive integer number of 5 to 500, more preferably 10 to 200 and most preferably 15 to 100.
  • 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.
  • NMR Nuclear Magnetic Spectroscopy 29 Si
  • 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.
  • 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
  • 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 MTTM PEI, contains pentaerythritol tris(3- mercaptobutanoate)), polyethylene glycol dimercaptoacetate of the formula ElSCEhCOOCE ⁇ CEhOCEy n CEhOOCCEhSIT, polyethylene glycol di(3-mercaptopropionate) of the formula
  • 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.
  • 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-
  • 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.
  • 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.
  • 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.
  • 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.
  • 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- methacryloxypropyltrimeth
  • 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.
  • 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.
  • 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.
  • 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 CyreneTM 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 present invention further relates to a process for curing the curable silicone composition described above by energetic radiation.
  • Energetic radiation 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.
  • actinic radiation such as ultraviolet light, X-rays and gamma rays
  • 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.
  • 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.
  • 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)
  • the polyorganyloxy-siloxane compound (A) prepared by said process is free of precious metal catalysts.
  • 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) (-
  • the dehydrogenative or reductive coupling approach can also use to include unsaturated alcohols, may also include alkenyl or alkynyl radicals.
  • 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.
  • 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.
  • 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.
  • the above viscosities relate to the measurement method described below.
  • 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 Bundesweg [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.
  • ViSi 20 commercially available from Wacker
  • Me-Siloxane commercially available from Wacker
  • Me-Siloxane commercially available from Wacker
  • octamethylcyclotetrasiloxane D4, commercially available from Gelest
  • DF 1, 3,5,7- tetramethylcyclotetrasiloxane
  • 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.
  • ViSi 20 commercially available from Wacker
  • Me-Siloxane commercially available from Wacker
  • D4 octamethylcyclotetrasiloxane
  • DF 1, 3,5,7- tetramethylcyclotetrasiloxane
  • 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.
  • 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.
  • ViSi 20 commercially available from Wacker
  • Me-Siloxane commercially available from Wacker
  • D 4 octamethylcyclotetrasiloxane
  • D 4 3.1 g of 1, 3,5,7- tetramethylcyclot
  • 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.
  • 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.
  • ViSi 20 commercially available from Wacker
  • Me-Siloxane commercially available from Wacker
  • D4 octamethylcyclotetrasiloxane
  • DF 1, 3,5,7- tetramethylcyclotetrasiloxane
  • 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.
  • Polymer a-(dimethylvinylsilyloxy)-co-(dimethylvinylsilyl)-poly ⁇ methyl[(2-oxo-l,3-dioxolan- 4-yl)methoxy]siloxane-co-dimethylsiloxane ⁇
  • 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).

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  • Silicon Polymers (AREA)

Abstract

La présente invention concerne une composition de silicone durcissable comprenant un composant polyorganyloxy-siloxane linéaire (A) de formule générale suivante (I) : R1 aR2 3 - aSiO(R2 2SiO)b(R3HSiO)c (R3R4OSiO)dSiR1 aR2 3 - a (I) dans laquelle, R1, R2, R3, a, b, c sont tels que définis ci-dessus et R4 est un dérivé hydrocarboné, qui comporte 1 à 30 atomes de carbone présentant un agencement linéaire, ramifié ou cyclique et qui peut être substitué par des groupes OH, des atomes d'halogène, des groupes silyle, des groupes siloxy, -CN, -COOR6, -OCOOR7, -CONR8R9, -OCONR10R11, -NR12CONR13R14, -SO2-R15, -OSO2-R16, -OP(OR17) (OR18), la 1,3-dioxolan-2-one, le carbone pouvant être interrompu par des groupes non adjacents qui sont choisis parmi -(CO)-, -O-, -S- ou -NR19-, R6 à R19 représentent chacun un radical hydrocarboné monovalent qui comporte 1 à 18 atomes de carbone et peut être substitué par des atomes d'halogène, et d comprend jusqu'à 60 % en moles des atomes de silicium du composé d'organosilicium (A) de formule générale (I) ; un composant contenant un groupe mercapto (B) contenant au moins deux groupes SH liés à du carbone par molécule ; et un composant photo-initiateur (C). La présente invention concerne en outre un procédé de durcissement de la composition de silicone durcissable par un rayonnement énergétique.
PCT/US2019/067043 2019-12-18 2019-12-18 Compositions de polyorganyloxy-siloxane durcissables par rayonnement WO2021126178A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0776943A1 (fr) * 1995-11-30 1997-06-04 Dow Corning Toray Silicone Company, Limited Catalyseur de vulcanisation pour des composés organopolysiloxanes et des composés organopolysiloxanes susceptibles d'être vulcanisées
US9879126B2 (en) 2012-12-28 2018-01-30 Dow Corning Corporation Curable organopolysiloxane composition for transducers and applications of such curable silicone composition for transducers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0776943A1 (fr) * 1995-11-30 1997-06-04 Dow Corning Toray Silicone Company, Limited Catalyseur de vulcanisation pour des composés organopolysiloxanes et des composés organopolysiloxanes susceptibles d'être vulcanisées
US9879126B2 (en) 2012-12-28 2018-01-30 Dow Corning Corporation Curable organopolysiloxane composition for transducers and applications of such curable silicone composition for transducers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
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
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

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