WO2020243834A1 - Durcissement de silicone sans catalyseur - Google Patents

Durcissement de silicone sans catalyseur Download PDF

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Publication number
WO2020243834A1
WO2020243834A1 PCT/CA2020/050770 CA2020050770W WO2020243834A1 WO 2020243834 A1 WO2020243834 A1 WO 2020243834A1 CA 2020050770 W CA2020050770 W CA 2020050770W WO 2020243834 A1 WO2020243834 A1 WO 2020243834A1
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formula
process according
compound
independently
ioalkynyl
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PCT/CA2020/050770
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English (en)
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Michael A. Brook
Andrea FEINLE
Jose Moran-Mirabal
Ayodele FATONA
Michael Yin WONG
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Mcmaster University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present application relates to the preparation of silicone elastomers without the need for catalysts.
  • Silicone elastomers are widely used because of the properties they possess, which are typically not matched by organic analogues, including low surface energy, low Tg, high thermal stability, etc.
  • silicone elastomers are created principally through three methods: radical cure at elevated temperature of silicone oils, or vinyl-modified silicone oils; condensation (moisture cure) crosslinking of telechelic silanol polymers with small organofunctional silanes (sometimes referred to as room temperature vulcanization); and hydrosilylation cure in which a vinylsilicone and HSi-containing silicone are combined to give a two carbon spacer between silicone chains (this process may be‘inhibited’ such that elevated temperatures are required for cure; in the case of hydrosilylation cure at room temperature, sometimes this process is also called RTV). 1
  • Catalysts are used for all three cure strategies. Radical cure often uses peroxides; RTV (moisture) typically exploits tin or titanium-derived catalysts, and hydrosilylation is mostly facilitated by platinum.
  • RTV moisture
  • platinum platinum
  • the present application relates to the preparation of silicone elastomers without the need for catalysts.
  • the present disclosure relates to treating silicone possessing SiH groups with heat and oxygen which leads to silicone elastomers via formation of both SiO bonds and ethers.
  • reaction of aminoalkyl- or hydroxyalkyl-modified organic chemical linkages with a crosslinker such as cyanuric acid, or anhydrides bridges silicone chains at polymer termini and/or pendant to the chain to form elastomers.
  • the properties of the resulting elastomers including modulus, extension at break, depend on the spacing between crosslinkers and the specific organic functional groups formed during cure. In other embodiments, small changes in the fraction of organic groups can significantly affect the physical properties of the elastomer product.
  • the present application includes a process for preparing elastomers comprising combining a compound of Formula I or a compound of Formula II:
  • R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or simultaneously selected from Ci-
  • R 6 and R 13 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl;
  • R 11 is selected from H, Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, . linear and branched siloxanes, and Y;
  • Y is a hydroxy-modified group, in which the hydroxy group is a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R 19 , wherein the linker R 19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and the hydroxy group is connected to the linker via a sp 3 hybridized carbon; or wherein the compound of Formula I or Formula II is reacted with a multifunctional organic molecule that crosslinks the compound of Formula I or Formula II to form the silicone elastomer.
  • the linker R 19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkyn
  • the multifunctional organic molecule is cyanuric chloride, EDTA anhydride or pyromellitic dianhydride:
  • Y when Y is an amino-modified group, there may be more than one nitrogen in Y, or a sulfur atom.
  • Y is -R 18 -NH2, and for example
  • Y is: where a, b are 0-30.
  • silicones bearing aminoalkyl or hydroxyalkyl groups can react with either di- or oligoanhydrides and/or cyanuric chloride 11 to form di-, tri- or higher order organic linkages at room temperature or slightly elevated temperatures ( ⁇ 60 °C).
  • the network structure and resulting properties of the elastomer depends on the number of linkages to a given crosslinker.
  • carboxylic acids are generated that further affect the physical properties of the elastomer.
  • the properties of the resulting elastomers are additionally affected by the presence of residual amines, and of ammonium ions.
  • Silicone polymers containing both aminoalkyl and hydroxyalkyl groups are produced by several manufacturers.
  • these silicone polymers are readily crosslinked into silicone elastomers at room temperatures in the absence of catalyst.
  • the crosslinking molecules include cyanuric chloride, di-anhydrides, including pyromellitic dianhydride, EDTA dianhydride and others. 19
  • triazines result from the reaction of monofunctional, telechelic, or pendant modified aminoalkylsilicones or hydroxypropylsilicones with cyanuric chloride.
  • the reactions with amines are favored over alcohols, because the HCI produced in the reaction can be self-neutralized if sufficient amines are present ( Figure 4).
  • the properties of the elastomers formed depend on total crosslink density, the number of linkages to the triazine moiety(ies), the fraction of residual amines or ammonium ions and the relative quantity of pendant, telechelic and monofunctional silicones used in the reaction.
  • dianhydrides also react spontaneously with monofunctional, telechelic, or pendant modified aminoalkylsilicones or hydroxyalkylsilicones.
  • network structures are formed with pendently modified functional silicones, and may be tuned by using telechelic silicones for chain extension and/or monofunctional entities to reduce the modulus ( Figure 4).
  • crosslinking is accompanied by carboxylic acid formation which, in the acid form and even more in the carboxylate form, strongly influence the physical properties of the elastomer.
  • Figure 1 shows organic cure reactions of silicones using catalyzed organic chemistry.
  • Figure 2 shows organic cure reactions of silicones without catalysts.
  • Figure 3 shows silicone elastomer formation through crosslinking aminoalkyl and hydroxyalkyl-modified silicone polymers with dianhydrides or cyanuric chloride.
  • Figure 4 A: aminoalkylsilicones crosslinked with cyanuric chloride (HCI complexed with residual amines) and B: hydroxyalkylsilicone crosslinked with EDTA dianhydride in one embodiment of the disclosure.
  • the words“comprising” (and any form of comprising, such as“comprise” and“comprises”),“having” (and any form of having, such as“have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as“contain” and“contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process/method steps.
  • alkyl as used herein, whether it is used alone or as part of another group, means straight or branched chain, saturated alkyl groups. The number of carbon atoms that are possible in the referenced alkyl group are indicated by the prefix “Cni-n2”.
  • Ci-ioalkyl means an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • alkenyl as used herein, whether it is used alone or as part of another group, means straight or branched chain, unsaturated alkyl groups containing at least one double bond.
  • the number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix“C ni -n 2”.
  • C2-ioalkenyl means an alkenyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and at least one double bond.
  • alkynyl as used herein, whether it is used alone or as part of another group, means straight or branched chain, unsaturated alkyl groups containing at least one triple bond.
  • the number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix“Cni-n2”.
  • C2-ioalkynyl means an alkynyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and at least one triple bond.
  • alkenylene means divalent hydrocarbon radicals having straight, branched or cyclic moieties or combinations thereof.
  • aryl refers to cyclic groups containing from 6 to 20 carbon atoms and at least one aromatic ring. In an embodiment of the application, the aryl group contains from 6, 9 or 10 carbon atoms, such as phenyl, indanyl or naphthyl.
  • aminoalkylsilicone refers to a primary or secondary amine connected to the silicone polymer through a linker R 18 .
  • hydroxyalkylsilicone refers to a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R 19 .
  • the term“monomer” is used to describe a silane or siloxane moiety that has the possibility of undergoing reactions to give siloxane products of increased molecular weight.
  • oligomer is used to describe a siloxane moiety that is prepared by reactions of lower molecular weight siloxanes or silanes (monomers). The number of monomers contained in an oligomer is about ⁇ 20.
  • linear siloxane refers to a group comprising
  • R' R'" units wherein R, R', R" and R'" are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl, arranged in linear fashion.
  • the number of units may be selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl, arranged in linear fashion. The number of units may
  • R" is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl.
  • branched siloxane refers to a group comprising
  • R' R' units, wherein R, R', R" and R'" are as defined above, with the exception that
  • R at least one of R, R', R" and R'" is R' .
  • the number of units may be between 1 and R
  • R" is selected from Ci-ioalkyl, C2- loalkenyl, C2-ioalkynyl and aryl.
  • the present application includes a process for preparing elastomers comprising combining a compound of Formula I or a compound of Formula II:
  • R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or simultaneously selected from Ci-
  • R 6 and R 13 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl;
  • R 11 is selected from H, Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, C6-2oaryl, . linear and branched siloxanes, and Y;
  • Y is a hydroxy-modified group, in which the hydroxy group is a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R 19 , wherein the linker R 19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and the hydroxy group is connected to the linker via a sp 3 hybridized carbon; wherein the compound of Formula I or Formula II is reacted with a multifunctional organic molecule that crosslinks the compound of Formula I or Formula II to form the silicone elastomer.
  • the linker R 19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkyny
  • p is about 0-2000, or about 10-2000, or about 10- 1000, or about 50-1000, or about 100-1000.
  • R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or
  • Ci-6alkyl C2-6alkenyl, C2-6alkynyl, C6-ioaryl
  • R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or
  • Ci-6alkyl C2-6alkenyl, C2-6alkynyl, C6-ioaryl
  • R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or simultaneously selected from Ci-3alkyl or phenyl. In one embodiment, R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are CH3.
  • R 6 and R 13 are independently selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In one embodiment, R 6 and R 13 are independently selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In one embodiment, R 6 and R 13 are independently selected from Ci-3alkyl or phenyl. In one embodiment, R 6 and R 13 are Chb.
  • R 1 1 is selected from H, Ci-6alkyl, C2-6alkenyl, C2-
  • R 1 1 is selected from H, Ci-6alkyl, , linear and branched siloxanes, and Y. In another embodiment, R 1 1 is selected from H, Ci-3alkyl, CH3, or phenyl.
  • R 15 -R 17 are independently or simultaneously selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In another embodiment, R 15 -R 17 are independently or simultaneously selected from Ci-3alkyl or phenyl In one embodiment, R 15 -R 17 are CH3.
  • Y is an amino-modified group having one or more amine groups, in which the amine is a primary or secondary amine connected to the silicone polymer through a linker R 18 , wherein the linker R 18 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6- 2oarylalkyl, and wherein the nitrogen atom(s) of the primary or secondary amine is connected to the linker via a sp 3 hybridized carbon, and wherein one or more carbons in R 18 may be replaced with one or more nitrogen atoms (NH or N-(Ci-6alkyl)) or sulfur atoms.
  • the linker R 18 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkyn
  • Y is -R 18 -NH2 or -R 18 -NHR a , wherein R a is Ci-6alkyl optionally substituted with amino (Nhte).
  • R 18 is selected from Ci- 6alkyl, Ci-6alkylene, C2-6alkenyl, C2-6alkenylene, C2-6alkynyl, C2-6alkynylene, C6-ioaryl, or C6-ioarylalkyl.
  • R 18 is selected from Ci-6alkyl, or Ci-6alkylene, wherein one or more of the carbon atom is replaced with one or more oxygen atoms.
  • Y is -R 18 -NH2 or -R 18 -(NH2)2 and for example
  • Y is a hydroxy-modified group, in which the hydroxy group is a primary or secondary or tertiary alcohol connected to the silicone polymer through a linker R 23 , wherein the linker R 23 is selected from Ci-ioalkyl, Ci-ioalkylene, C2- ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl and the hydroxy group is connected to the linker via a sp 3 hybridized carbon and wherein one or more carbons in R 23 may be replaced with one or more oxygen atoms.
  • the linker R 23 is selected from Ci-ioalkyl, Ci-ioalkylene, C2- ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl and the hydroxy
  • R 23 is selected from Ci-6alkyl, Ci-6alkylene, C2-6alkenyl, C2-6alkenylene, C2- 6alkynyl, C2-6alkynylene, C6-ioaryl, or C6-ioarylalkyl.
  • R 23 is selected from Ci-6alkyl, or Ci-6alkylene, wherein one or more of the carbon atoms is replaced with one or more oxygen atoms.
  • Y is wherein a, b are 0-30.
  • the multifunctional organic molecule crosslinker is an organic molecule having functional groups which are able to react with the amino or hydroxyl groups of the Y moiety to form the silicone elastomers.
  • the multifunctional organic molecule crosslinker has two or three functional groups (i.e. a difunctional or trifunctional crosslinker).
  • the functional groups are leaving groups, such as halo groups or anhydrides.
  • the multifunctional organic molecule is cyanuric chloride, EDTA anhydride or pyromellitic dianhydride:
  • the cyanuric chloride is combined with amionalkylsilicone at a ratio such that there is at least one free amine is present for each amine that forms a bond with cyanuric chloride, such amine can act to neutralize HCI generated.
  • the crosslinker is a dianhydride, selected from EDTA dianhydride and pyromellitic dianhydride.
  • the compound formula (II) is a compound of formula
  • the properties of the elastomer are controlled by varying the amount of Y groups on the compounds of formula (I) or (II), and by the amount and nature of the crosslinking.
  • the compound of formula (I) is a silicone polymer comprised of a terminal monomer of formula (A)
  • each X is independently a leaving group such that, after polymerization, X is replaced with 0 (oxygen) to form a compound of formula (I),
  • the monomers of formula (B) and (C) are present at a molar ratio of between about 1 : 1000 to about 1000: 1 , or about 1 :500 to about 500: 1 , or about 1 : 100 to about 100: 1.
  • the compound of formula (I) is a silicone polymer formed from a monomer of formula (E)
  • each X is independently a leaving group such that, after polymerization, X is replaced with 0 (oxygen) to form a compound of formula (II), wherein Y and R 10 -R 14 are as defined above in any embodiment.
  • any residual functional groups on the elastomer is used in a second step to link the elastomer to other materials, such as substrates or solid supports.
  • the degree of crosslinking is controlled by stoichiometry of the functional group to the crosslinker.
  • the compound of formula (I) or (II) is crosslinked with the crosslinker without the need for a catalyst at an appropriate temperature, for example 0-100°C, or about room temperature.
  • the crosslinker such as cyanuric chloride
  • FTIR data was collected on a Nicolet 6700 FTIR using Thermo Electron’s OMNIC software
  • GC-MS analyses were performed using an Agilent 6890N gas chromatograph (Santa Clara, CA, USA), equipped with a DB-17ht column (30 m c 0.25 mm i.d. x 0.15 pm film, J & W Scientific) and a retention gap (deactivated fused silica, 5 m x 0.53 mm i.d.), and coupled to an Agilent 5973 MSD single quadruple mass spectrometer.
  • One microliter of sample was injected using Agilent 7683 autosampler with a 10: 1 split and slit flow of 7.0 ml/min.
  • the injector temperature was 250 °C and carrier gas (helium) flow was 0.7 ml/min.
  • the transfer line was 280 °C and the MS source temperature was 230 °C.
  • the column temperature started at 50 °C and raised to 300 °C at 8 °C/min, and then held at 300 °C for 10 min for a total run time of 41 .25 min.
  • Full scan mass spectra between m/z 50 and 800 were acquired after five min solvent delay.
  • a Shore OO durometer (Rex Gauge Company, Inc. U.S.) was used to characterize the hardness of the elastomer.
  • Example 1 Full crosslinking of both anhydride groups: [0076]
  • Crosslinked silicone elastomers were prepared from telechelic 3- (aminopropyl)-terminated polydimethylsiloxane or pendant 3-
  • EDTAD (0.04 g, 0.17 mmol) was dispersed in IPA (0.51 g) and stirred with a magnetic stir bar (450 rpm) for 3 h.
  • IPA (0.5 g) was added on top of the thus obtained viscous mixture and the sample was placed into an oven at 60 °C for 24 h. Subsequently, the cured elastomer was cooled to room temperature and characterized.
  • Example 2 Partial crosslinking of the anhydride groups:
  • Crosslinked silicone elastomers comprising anhydride groups were prepared using telechelic 3-(aminopropyl)-terminated polydimethylsiloxane and EDTAD in IPA at room temperature.
  • EDTAD 0.08 g, 0.34 mmol
  • IPA distilled water
  • a magnetic stir bar 450 rpm
  • Example 3 Molecular Characterization: Full crosslinking of both anhydride groups:
  • IR ATR-IR, cm- 1 : 2962, 2904, 1714, 1677, 1648, 1577, 1444, 1412, 1257, 1077, 1009, 864, 786, 699, 685, 660.
  • Example 4 Partial crosslinking of the anhydride groups:
  • IR ATR-IR, cm- 1 ): 2962, 2906, 1805, 1745, 1680, 1653, 1572, 1465, 1443, 1413, 1345, 1321 , 1257, 1009, 927, 864, 786, 701 , 685, 661 , 614.
  • Example 5 Elastomer preparation using triazinyl-crosslinked silicones
  • a representative curing procedure for the synthesis of amino-triazinyl functional silicone networks based on cyanuric chloride is provided below.
  • (Aminopropyl)methylsiloxane-dimethylsiloxane copolymer (PDMS-NFte, AMS-162, 1 g, 0.876 mmol of amino groups) was weighed into a polypropylene mixing cup (FlackTek, size 10) followed by the addition of cyanuric chloride (27 mg, 0.146 mmol dissolved in 500 pL of dichloromethane).
  • Example 6 Elastomer preparation using pre-grafted triazinyl crosslinked silicones a) Synthesis of 4,6-dichloro-s-triazinyl modified aminosilicones
  • Table 2 Formulations for the preparation of EDTAD-crosslinked aminosilicones comprising anhydride groups.
  • Table 4 Shore 00 hardness of EDTAD-crosslinked silicones comprising anhydride groups.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'élastomères de siloxane sans avoir besoin de catalyseurs par la réaction de silicones à modification aminoalkyle ou hydroxyalkyle avec du chlorure cyanurique ou des dianhydrides tels que le dianhydride d'EDTA ou le dianhydride pyromellitique.
PCT/CA2020/050770 2019-06-04 2020-06-04 Durcissement de silicone sans catalyseur WO2020243834A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808686A (en) * 1987-06-18 1989-02-28 General Electric Company Silicone-polyimides, and method for making
US5916688A (en) * 1997-02-18 1999-06-29 Nippon Steel Chemical Co., Ltd. Resin solution compositions for electronic materials and protective membranes prepared therefrom for circuits in printed wiring boards
US20110086204A1 (en) * 2009-10-09 2011-04-14 Usa As Represented By The Administrator Of The National Aeronautics And Space Administration Modification of Surface Energy Via Direct Laser Ablative Surface Patterning
WO2012020068A2 (fr) * 2010-08-10 2012-02-16 Universität Paderborn Surfaces autostructurantes par séparations de phases de polydiméthylsiloxanes dans des revêtements polymères durs
US20130153261A1 (en) * 2010-08-10 2013-06-20 Schwering & Hasse Elektrodraht Gmbh Electrical Insulation Enamels Composed of Modified Polymers and Electrical Conductors Produced Therefrom and Having Improved Sliding Capacity
US20180230269A1 (en) * 2017-02-16 2018-08-16 Samsung Sdi Co., Ltd. Photosensitive resin composition, black pixel defining layer using the same and display device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808686A (en) * 1987-06-18 1989-02-28 General Electric Company Silicone-polyimides, and method for making
US5916688A (en) * 1997-02-18 1999-06-29 Nippon Steel Chemical Co., Ltd. Resin solution compositions for electronic materials and protective membranes prepared therefrom for circuits in printed wiring boards
US20110086204A1 (en) * 2009-10-09 2011-04-14 Usa As Represented By The Administrator Of The National Aeronautics And Space Administration Modification of Surface Energy Via Direct Laser Ablative Surface Patterning
WO2012020068A2 (fr) * 2010-08-10 2012-02-16 Universität Paderborn Surfaces autostructurantes par séparations de phases de polydiméthylsiloxanes dans des revêtements polymères durs
US20130153261A1 (en) * 2010-08-10 2013-06-20 Schwering & Hasse Elektrodraht Gmbh Electrical Insulation Enamels Composed of Modified Polymers and Electrical Conductors Produced Therefrom and Having Improved Sliding Capacity
US20180230269A1 (en) * 2017-02-16 2018-08-16 Samsung Sdi Co., Ltd. Photosensitive resin composition, black pixel defining layer using the same and display device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PINTEALA, M. ET AL.: "Functional Polysiloxanes, 2. On the reaction of hydroxypropyl- and aminoalklyl-terminated polydimethysiloxanes with cyclic anhydrides", POLYMER BULLETIN, vol. 32, 1994, pages 173 - 178, XP000425948, DOI: 10.1007/BF00306385 *

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