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WO2025170712A1 - Copolymère de polyorganosiloxane linéaire-résine à fonction époxy, composition contenant le copolymère, et procédés pour leur préparation et leur utilisation - Google Patents

Copolymère de polyorganosiloxane linéaire-résine à fonction époxy, composition contenant le copolymère, et procédés pour leur préparation et leur utilisation

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Publication number
WO2025170712A1
WO2025170712A1 PCT/US2025/011356 US2025011356W WO2025170712A1 WO 2025170712 A1 WO2025170712 A1 WO 2025170712A1 US 2025011356 W US2025011356 W US 2025011356W WO 2025170712 A1 WO2025170712 A1 WO 2025170712A1
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WO
WIPO (PCT)
Prior art keywords
alternatively
carbon atoms
copolymer
group
linear
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Pending
Application number
PCT/US2025/011356
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English (en)
Inventor
Yanhu WEI
Steven Swier
John Horstman
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Dow Silicones Corp
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Dow Silicones Corp
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Publication of WO2025170712A1 publication Critical patent/WO2025170712A1/fr
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    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/55—Boron-containing compounds
    • 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
    • C08L83/06—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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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

Definitions

  • An epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer and methods for its preparation and use are provided.
  • a curable composition containing the epoxy-functional resin-linear polyorganosiloxane copolymer is useful for forming an encapsulant film.
  • LED Light emitting diode
  • materials are required with high performance such as high optical transmission, high thermal and photothermal stability, strong adhesion, and good mechanical properties.
  • Epoxy based resins have been considered as candidates because of their advantages including good optical clarity, high mechanical strength, strong adhesion and fast cure, but epoxy based resins are limited by their poor thermal and photo/photothermal stability and discoloration.
  • Silicone materials have been broadly applied in LED packaging because of their excellent thermal and photothermal stability, however some of their limitations may restrict the applications, such as weak adhesion and high gas permeability because of their highly flexible siloxane backbone.
  • An epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer and methods for preparation and use of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer are provided.
  • the epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer comprises linear blocks and non - linear blocks, wherein each linear block comprises 10 to 400 disiloxy units of formula (R ⁇ SiOz/r), wherein each R 2 is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each non - linear block has a molecular weight of at least 500 g/mol; the non - linear blocks comprise trisiloxy units and hydrolyzable groups; and the non - linear blocks further comprise epoxycycloalkyl - functional groups bonded to silicon atoms. At least 30 mol % of the non - linear blocks may be crosslinked with each other, and each linear block is linked to at least one non - linear block.
  • the copolymer may have a Mw of at least 20,000 g/mol measured by GPC.
  • Linear polyorganosiloxanes typically comprise mostly D units, which results in polydiorganosiloxanes that are fluids of varying viscosity, depending on the DP, indicated by the number of D units in the polydiorganosiloxanes.
  • Linear polydiorganosiloxanes typically have Tg lower than 25 °C, alternatively lower than 0 °C, and alternatively lower than -20 °C.
  • “Resin” polysiloxane results when a majority of the siloxy units are T, Q, or both units.
  • T siloxy units When T siloxy units are predominant, the resulting polysiloxane can be referred to as a “silsesquioxane resin”.
  • Q units When Q units are predominant, the resulting polysiloxane can be referred to as a silicate.
  • Increasing the amount of T and/or Q siloxy units typically results in polysiloxanes having increasing hardness and/or glass like properties.
  • resin - linear polyorganosiloxane block copolymer refers to polyorganosiloxanes containing polydiorganosiloxane blocks comprising, alternatively consisting essentially of, alternatively consisting of, D units in combination with resin blocks comprising T units.
  • the resin - linear polyorganosiloxane block copolymer is a block copolymer (not a random copolymer).
  • the D units are primarily bonded together to form polymeric polydiorganosiloxane chains having 10 to 400 D units, referred to herein as linear blocks.
  • the T units are primarily bonded to each other to form branched polymeric chains, and these are included in the non - linear blocks.
  • a significant number of these non - linear blocks may aggregate to form nano-domains when solid forms of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer are provided.
  • the disiloxy units of formula (R 2 2 SiO 2/2 ) that are arranged in linear blocks have an average of 10 to 400 units of formula (R 2 2 SiO 2 / 2 ) per linear block.
  • each linear block may have an average of at least 10, alternatively at least 50, alternatively at least 100, alternatively at least 150, and alternatively at least 200 disiloxy units; while at the same time each linear block may have up to 400, alternatively up to 300, and alternatively up to 200, disiloxy units per linear block.
  • each linear block may have 100 to 150 disiloxy units, alternatively 115 to 125 disiloxy units, alternatively 90 to 170 disiloxy units.
  • the linear blocks are covalently bonded to the non - linear blocks.
  • the trisiloxy units are arranged in the non - linear blocks.
  • the non - linear blocks each have a molecular weight of at least 500 g/mol, alternatively 500 g/mol to 4,000 g/mol per block.
  • each non - linear block may have a Mn of at least 500 g/mol, alternatively at least 1,000 g/mol, alternatively at least 1,500 g/mol; while at the same time each non - linear block may have a Mn of up to 4,000 g/mol, alternatively up to 3,000 g/mol; alternatively up to 2,500 g/mol; alternatively up to 2,000 g/mol; and alternatively up to 1,500 g/mol.
  • the epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may further comprise hydrolyzable groups in the non - linear blocks.
  • the hydrolyzable groups may have formula (ZO1/2), wherein each Z is independently selected from H or a monovalent hydrocarbyl group of 1 to 30 carbon atoms.
  • the monovalent hydrocarbyl group for Z may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms, and alternatively methyl.
  • each Z may be H.
  • the epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may comprise up to 50 mol % of the hydrolyzable groups, alternatively at least 0.5 mol%, alternatively at least 1 mol%, alternatively at least 5 mol %, alternatively at least 10 mol%, and alternatively at least 15 mol%; while at the same time the epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may comprise up to 50 mol %, alternatively up to 35 mol %, alternatively up to 30 mol%, alternatively up to 25 mol%, and alternatively up to 20 mol % of the hydrolyzable groups.
  • the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may have a Mw of 20,000 g/mol to 500,000 g/mol.
  • the epoxycycloalkyl- functional resin - linear polyorganosiloxane block copolymer may have a Mw of at least 20,000 g/mol, alternatively at least 40,000 g/mol, alternatively at least 50,000 g/mol, alternatively at least 60,000 g/mol, alternatively at least 70,000 g/mol, and alternatively at least 80,000 g/mol; while at the same time Mw may be up to 500,000 g/mol, alternatively up to 450,000 g/mol, alternatively up to 400,000 g/mol, alternatively up to 350,000 g/mol, alternatively up to 300,000 g/mol; alternatively up to 250,000 g/mol; alternatively up to 200,000 g/mol; alternatively up to 150,000 g/mol and alternatively up to 100,000
  • Starting material (al-1) used in the method above is an aryltrialkoxy silane of formula R 6 Si(OR 5 )3, where R 6 is an aryl group of 6 to 30 carbon atoms, and each R 5 is an independently selected alkyl group of 1 to 6 carbon atoms. Suitable aryl groups for R 6 are as described and exemplified above. Alternatively, R 6 may be selected from phenyl or naphthyl, alternatively phenyl. R 5 is an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively 1 to 2 carbon atoms. Alternatively, each R 5 may be methyl.
  • [2-(3,4- Epoxycyclohexyl)ethyl]triethoxysilane also called 2-(7-Oxabicyclo[4.1.0]hept-3-yl)ethyl- triethoxysilane, with Cas No. 10217-34-2); both of which are commercially available from sources such as Gelest, Inc.
  • the amount of (al -2) the epoxycycloalkyl - functional trialkoxy silane used may be 3 mol % to 20 mol % based on amounts of starting materials (al- 1), (al-2), and (al-3), combined.
  • R 7 may be selected from the group consisting of vinyl, allyl, or hexenyl; alternatively vinyl and hexenyl; alternatively vinyl.
  • Subscript g may be 0, alternatively at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4; while at the same time, g may be up to 9, alternatively up to 8, alternatively up to 7, alternatively up to 6, and alternatively up to 5.
  • R 1 and R 2 may be alkyl groups, alternatively methyl. Examples of oligomers suitable for use as starting material (al-3) include l,3-divinyl-l,l,3,3-tetramethyldisiloxane (CAS No.
  • the amount of (al-3) the bis-alkenyl- terminated diorganosiloxane oligomer used may be 5 mol % to 10 mol % based on amounts of starting materials (al- 1), (al-2), and (al-3), combined.
  • Starting material (a 1-4) is water.
  • the water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and/or solvents), and/or pure (i.e., free from, or substantially free from, minerals and/or other impurities).
  • the water may be processed or unprocessed prior to the hydrolysis reaction. Examples of processes that may be used for purifying the water include reverse osmosis, distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and/or filtered.
  • the water may be unprocessed (e.g. may be tap water, i.e., provided by a municipal water system or well water, used without further purification).
  • Starting material (cl) is a catalyst capable of forming a hydrolysis product of starting materials (al-1), (al-2), (al-3), and (al-4).
  • Starting material (cl) may be an acid catalyst, such as a carboxylic acid exemplified by acetic acid, ethanoic acid, propionic acid, octanoic acid, decanoic acid, lauric acid, lactic acid, fluoroacetic acid, and 4,4,4-trifluorobutanoic acid;
  • Bronstedt acids Lewis acids such as HC1, acidic phosphoric esters, or a sulphonic acid such as trifluoromethane sulfonic acid. Suitable acids are known in the art and are commercially available.
  • the amount of acid catalyst depends on various factors including the species selected and the species and amounts of starting materials (al-1), (al-2), (al-3) and the hydrolysis reaction conditions, such as temperature. However, the amount of acid catalyst may be, for example 100 to 1,000 ppm based on weights of starting materials (al-1) and (al-3) combined. Alternatively, the amount of acid catalyst may be 200 ppm to 900 ppm, alternatively 250 ppm to 750 ppm, alternatively 500 ppm, on the same basis.
  • Step (Al) may be performed by any convenient means such as mixing optionally with heating.
  • starting materials (al-1), (al-2), (al-3) and (cl) may be combined in a reactor with mixing and heating to a temperature of 50 °C to ⁇ 100 °C.
  • Starting material (al-4) the water may be added slowly over time, either continuously or intermittently in two or more aliquots.
  • the resulting mixture may then be heated, optionally with stirring for an additional time period such as 1 hour to 12 hours, alternatively 2 hours to 4 hours, and alternatively 3 hours.
  • the method above optionally comprises neutralizing (cl) the acid catalyst after step (Al).
  • Neutralizing may be performed by combining (e.g., by simple mixing) a neutralizing agent with the hydrolysis product formed in step (Al).
  • the neutralizing agent is not critical and may be, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, or potassium hydroxide.
  • the amount of neutralizing agent depends on various factors including the type and amount of catalyst used in step (Al), however, the amount of neutralizing agent may be, for example 500 ppm to 2,000 ppm based on weight of the silsesquioxane resin to be produced in step (Al).
  • the neutralizing agent may be removed by filtration after neutralizing is complete, e.g., before or after step (A2).
  • a solvent may optionally be included during and/or after step (Al) and/or step (A2) of the method described above to facilitate mixing of the starting materials and the aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane resin produced in step (Al).
  • the solvent is not critical and may be, for example, an aromatic hydrocarbon exemplified by benzene, toluene, xylene, or a combination thereof.
  • step (Al) starting materials (al-1) the aryltrialkoxysilane, (al-3) the bis-alkenyl-terminated dialkylsiloxane oligomer, (cl) the catalyst, and (a 1-4) the water may be combined and heated, optionally with solvent. Thereafter, the neutralizing agent described above may be added, for example, when a strong acid catalyst such as trifluoromethane sulfonic acid is used for starting material (c2).
  • the neutralizing agent may be a strong base, such as KOH.
  • (a 1-2) the epoxycycloalkyl - functional trialkoxysilane may then be added, and additional water may be added, with heating.
  • the strong acid catalyst may be neutralized and thereby prevented from catalyzing a ring opening reaction of the epoxy- moiety of starting material (al -2). And, when a molar excess of the strong base is used, this may function as a catalyst to react starting material (al -2) with the reaction product described above. Thereafter, step (A2) of the method may be performed.
  • step (A2) of the method the aryl-, epoxy cycloalkyl-, alkenyl- functional silsesquioxane resin prepared in step (Al) (which silsesquioxane resin will form the non - linear block of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer described above), is combined with additional starting materials under conditions to effect hydrosilylation reaction to bond the linear block to the non - linear block.
  • the block with subscript c, shown above in unit Formula (A) forms via the hydrosilylation reaction in step (A2) (i.e., of the alkenyl group from the aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane (e.g., M V1 T) resin formed in step (Al) with a silicon bonded hydrogen atom of starting material (a2-l) and/or (a2-2) in step (A2) of the method described above).
  • Hydrosilylation may be performed by any convenient means, such as heating under inert atmosphere.
  • the hydrosilylation may be performed in the same reactor as step (Al) or a different reactor.
  • Starting material (a2-l) used in step (A2) of the method described above is a linear polyorganohydrogensiloxane that may be used to form the linear blocks of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer of unit formula (R 1 2 HSiOi/2)2(R 2 2SiO 2 /2)h, where each R 1 and each R 2 are the independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms, subscript h represents an average number of disiloxy units per molecule, and subscript h is an integer with a value of 8 to 398.
  • each R 1 may be alkyl, alternatively methyl.
  • each R 2 may be alkyl or aryl; alternatively methyl or phenyl.
  • subscript h may have a value of at least 8, alternatively at least 10, alternatively at least 20, alternatively at least 48, alternatively at least 98, alternatively at least 148, alternatively at least 198; while at the same time, subscript h may be up to 398, alternatively up to 298, alternatively up to 198.
  • Starting material (a2-l) may be used to form the linear blocks of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer.
  • suitable linear polyorganohydrogensiloxanes suitable as starting material (a2-l) are exemplified by bis-dimethylhydridosiloxy-terminated polydimethylsiloxanes with varying degrees of polymerization, as described above.
  • Linear polyorganohydrogensiloxanes suitable as starting material (a2-l) are commercially available, such as those available from Gelest, Inc., for example, hydride terminated polydimethylsiloxanes with product codes DMS-H03, DMS-H05, DMS-H11, DMS-H21, DMS-H25, DMS-H31, or DMS-H41.
  • Methods of preparing linear polyorganohydrogensiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in: US Patent 3957713 to Jeram et al. and US Patent 4329273 to Hardman, et al.
  • Starting material (a2-2) is an organohydrogensiloxane crosslinker that crosslinks non - linear blocks of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer, as described above.
  • This crosslinker may comprise an organohydrogensiloxane comprising two or more siloxane units selected from, HR ⁇ SiOic, R SiO , HR 2 SiC>2/2, R 2 2SiO /2, R 2 SiO3/2, HSiO3/2 and SiC>4/2 units, with the proviso that at least 2 units per molecule contain a silicon bonded hydrogen atom.
  • each R 1 and each R 2 are a monovalent hydrocarbyl groups as described above.
  • each R 1 may be alkyl such as methyl.
  • each R 2 may be alkyl such as methyl or aryl such as phenyl.
  • This organohydrogensiloxane crosslinker may be linear, branched, cyclic, resinous, or a combination thereof.
  • the organohydrogensiloxane crosslinker may be linear or branched.
  • the organohydrogensiloxane may be linear.
  • the linear organohydrogensiloxane crosslinker may comprise an aryl- functional siloxane oligomer of unit formula (R 1 HSiOi/2)2(R 8 2SiO2/2)j, where each R 1 is the independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms, as described above; each R 8 is an independently selected aryl group of 6 to 30 carbon atoms as described above; and subscript j represents average number of disiloxy units per molecule, and subscript j is an integer with a value of 1 to 3.
  • each R 1 may be alkyl such as methyl.
  • each R 8 may be aryl such as phenyl.
  • Subscript j may be 1, 2, or 3; alternatively 1 or 2, and alternatively ] may be 1.
  • the crosslinker may be, for example l,l,5,5-tetramethyl-3,3-diphenyltrisiloxane (CAS No. 17875-55-7) which is commercially available from Sigma Aldrich, Inc.
  • Starting material (c2) is a hydrosilylation reaction catalyst.
  • the hydrosilylation reaction catalyst will promote a reaction between the alkenyl groups of the silsesquioxane resin and the silicon bonded hydrogen atoms of starting materials (a2-l) and (a2-2), described above.
  • the hydrosilylation reaction catalyst comprises a platinum group metal.
  • the platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum.
  • the hydrosilylation reaction catalyst may be the platinum group metal or a compound or complex of the platinum group metal.
  • the hydrosilylation reaction catalyst may be a compound such as chloridotris(triphenylphosphane)rhodium(I) (Wilkinson’s Catalyst), a rhodium diphosphine chelate such as [l,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [l,2-bis(diethylphospino)ethane]dichlorodirhodium, chloroplatinic acid (Speier’s Catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an organopolysiloxane such as l,3-diethenyl-l,l,3,3-tetramethyldisiloxane complexes with platinum (Karstedt’s Catalyst) or Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (
  • the compound or complex may be microencapsulated in a matrix or coreshell type structure.
  • Hydrosilylation reaction catalysts are known in the art, for example, as described in PCT Patent Application Publication WO2021/081822 to Guo, et al. and the references cited therein. Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFFTM 4000 Catalyst and SYL-OFFTM 2700 are available from Dow Silicones Corporation of Midland, Michigan, USA.
  • the amount of hydrosilylation reaction catalyst depends on various factors including the selections and SiH contents of starting materials (a2-l) and (a2-2), the alkenyl content of the silsesquioxane resin, and the hydrosilylation reaction conditions, such as temperature, however the amount may be sufficient to provide 0.1 to 5,000 ppm of platinum group metal, alternatively 1 to 1,000 ppm, alternatively 1 to 100 ppm, and alternatively 1 to 10 ppm, based on combined weights of the silsesquioxane resin and starting materials (a2-l) and (a2-2).
  • the silsesquioxane resin and starting materials (a2-l), (a2-2), and (c2) and optionally a solvent to aid mixing may be combined in a reactor with heating to a temperature of 50 °C to 150 °C, alternatively 90 °C to 110 °C.
  • the silsesquioxane resin is used in a molar excess such that the resulting epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may have residual silicon bonded alkenyl groups, and does not contain unreacted SiH.
  • step (A3) of the method described above recovering the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may be performed by any convenient means, such as stripping and/or distillation, optionally with reduced pressure.
  • the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may comprise unit Formula (B) as follows
  • the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer comprising unit Formula (B) may be prepared by a method comprising:
  • (b 1-1) an alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer comprising difunctional siloxy units and trifunctional siloxy units, wherein (bl -1 ) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer comprises unit formula (R 14 2SiO 2 /2)t(R 15 SiO 3 /2)u(ZOi/2)v, wherein each R 14 and each R 15 are independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and a monovalent hydrocarbyl group of 1 to 30 carbon atoms; subscripts t and u represent mole fractions of siloxy units in (bl - 1 ) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer, and subscripts t and u have values such that
  • each R 15 may be independently selected from alkyl, alkenyl, and aryl; alternatively each R 1S may be independently selected from alkenyl and aryl.
  • the alkyl group and the aryl group for R 15 may be as described above for R 1 and R 2 .
  • the alkenyl for R 15 may be as described above for R 3 .
  • the alkyl group for R 15 may be methyl.
  • the aryl group for R 15 may be phenyl or naphthyl, alternatively phenyl.
  • the alkenyl group for R 15 may be vinyl, allyl, or hexenyl; alternatively vinyl or hexenyl; alternatively vinyl or allyl; and alternatively vinyl.
  • the alkenyl-, aryl- functional resin - linear copolymer may comprise 0.5 mol% to 5 mol% of alkenyl groups.
  • the balance of instances of R 15 that are not alkenyl groups may be aryl groups.
  • the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer is a block copolymer (not a random copolymer).
  • the difunctional units of formula (R 14 2SiO 2 / 2 ) are primarily bonded together to form polymeric polydiorganosiloxane chains having 10 to 400 (R 14 2 SiO 2 / 2 ) units, which are linear blocks.
  • the (R 15 SiO3/2) units are primarily bonded to each other to form branched polymeric chains, which are non - linear blocks.
  • a significant number of these non - linear blocks may aggregate to form nano-domains when solid forms of the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer are provided.
  • the disiloxy units of formula (R 14 2SiO2/2) that are arranged in linear blocks have an average of 10 to 400 units of formula (R 14 2SiO2/2) per linear block.
  • each linear block may have an average of at least 10, alternatively at least 50, alternatively at least 100, alternatively at least 150, and alternatively at least 200 units of formula (R 14 2SiO2/2): while at the same time each linear block may have up to 400, alternatively up to 300, and alternatively up to 200, units of formula (R 14 2 SiO 2/2 ) per linear block.
  • each linear block may have 100 to 150 (R 14 2 SiO 2 /2) units, alternatively 115 to 125 (R 14 2 SiO 2 / 2 ) units, alternatively 90 to 170 (R 14 2 SiO 2 / 2 ) units.
  • the linear blocks are covalently bonded to the non - linear blocks.
  • the (R 15 SiO3/ 2 ) units are arranged in the non - linear blocks.
  • the non - linear blocks each have a molecular weight of at least 500 g/mol, alternatively 500 g/mol to 4,000 g/mol per block.
  • the hydrolyzable groups may allow the alkenyl-, aryl- functional resin - linear copolymer to further react or cure or to crosslink.
  • Crosslinking of the non - linear blocks may be accomplished via a variety of chemical mechanisms and/or moieties.
  • crosslinking of the non - linear blocks within the copolymer may result from condensation of residual silanol and/or alkoxy groups present in the non - linear blocks.
  • At least 30% of the non - linear blocks in the copolymer may be crosslinked with each other, alternatively at least 40%, alternatively at least 50%, alternatively at least 60%, alternatively at least 70%, and alternatively at least 80%.
  • 30% to 80% of the non - linear blocks may be crosslinked with each other, alternatively 30% to 70%, alternatively 30% to 60%, alternatively 30% to 40%, and alternatively 30% to 40% of the non - linear blocks are crosslinked with each other.
  • the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may have a Mw of 20,000 g/mol to 500,000 g/mol.
  • the copolymer may have a Mw of at least 20,000 g/mol, alternatively at least 40,000 g/mol, alternatively at least 50,000 g/mol, alternatively at least 55,000 g/mol, alternatively at least 60,000 g/mol, and alternatively at least 65,000 g/mol; while at the same time Mw may be up to 500,000 g/mol, alternatively up to 450,000 g/mol, alternatively up to 400,000 g/mol, alternatively up to 350,000 g/mol, alternatively up to 300,000 g/mol; alternatively up to 250,000 g/mol; alternatively up to 200,000 g/mol; alternatively up to 150,000 g/mol and alternatively up to 125,000 g/mol.
  • the alkenyl-, aryl- functional resin - linear copolymer may have a Mn of 15,000 to 50,000 g/mol.
  • the alkenyl-, aryl- functional resin - linear copolymer may have Mn of at least 15,000 g/mol, alternatively at least 20,000 g/mol; while at the same time Mn may be up to 50,000 g/mol, alternatively up to 30,00 g/mol, alternatively up to 25,000 g/mol.
  • Mw and Mn may be measured by GPC using the test method described in the EXAMPLES, below.
  • the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may be isolated in a solid form, for example, by casting a film of a solution of the alkenyl-, aryl- functional resin - linear copolymer in an organic solvent (e.g., benzene, toluene, xylene, or combinations thereof) and allowing the solvent to evaporate.
  • the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may be provided in a solution in an organic solvent in an amount of 50% to 80%, alternatively 60% to 80%, copolymer solids with the balance being organic solvent in the solution.
  • the curable composition may be prepared by any convenient means.
  • the curable composition may be prepared by a method comprising: mixing starting materials comprising (I) the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer and (II) the catalyst under ambient conditions, and if present, any of the optional additional starting materials described above.
  • the method may further comprise preparing the epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer by the method described above, before mixing said epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer with the other starting materials of the curable composition.
  • the Tpeak value for a composition should increase relative to the Tpeak for an identical amine-free composition if the proper amine is present, but desirably remains below 130 °C, alternatively below 120 °C, alternatively below 110 °C so as to reflect dissociation sufficient to rapidly cure at 90 °C.
  • the amines have at least one, alternatively at least two, and can have three conjugated moieties attached to the nitrogen of the amine through a conjugated carbon so that the free electron pair on the nitrogen can dissociate with the conjugated moiety and weaken the amine as a Lewis base.
  • the conjugated moieties are aromatic moieties.
  • Triaryl amines have three aromatic conjugated moieties attached to the amine nitrogen each through a conjugated carbon.
  • triaryl amines are examples of amines that optimally delocalize the nitrogen free electrons to create a weak Lewis base.
  • triaryl amines have been surprisingly discovered to have a blocking effect on Lewis acid catalysts at 23 °C and inhibit Lewis acid catalyzed reaction at 23 °C and are in scope of the broadest scope of the amines suitable for use in the catalyst used in the thermally curable composition described herein.
  • the amines used herein are stronger Lewis bases than triaryl amines in order to achieve greater blocking effect (hence, longer shelf stability) at 23 °C.
  • the composition can be free of amidines and guanidines.
  • the amine has the following formula: R n R 12 R 13 N; wherein each of R 11 ,
  • the amount of inhibited arylborane Lewis acid catalyst in the thermally curable composition may be > 100 ppm, alternatively at least 200 ppm, alternatively at least 300 ppm; while at the same time the amount may be up to 1,000 ppm, alternatively up to 500 ppm, alternatively up to 400 ppm, based on weight of the epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer.
  • EP-M H intermediate (described above in Table 1) was prepared as follows: To a 500 mL flask were added 24.8 g (0.2 mol) 4-Vinyl-cyclohexane 1.2- epoxide, 80.4 g (0.6 mol) M H M H , 60 mL toluene and Karstedt’s catalyst (in an amount sufficient to provide 3 ppm Pt), followed by stirring at 80 °C for 3 hours. Sampling to NMR after 3 hours and NMR results showed all vinyl groups converted. The solvent and excess M H M H were removed by rotary evaporator to obtain 103 g product EP-M H , with formula:
  • a vinyl-functional resin - linear polyorganosiloxane block copolymer intermediate (T V1 -RL) was prepared as follows: A 3L 4 neck round bottom flask was equipped with a thermocouple, Teflon stir paddle attached to a glass stir shaft, and a Dean Stark apparatus attached to a water-cooled condenser. The flask was loaded with: 217 Flake (270.00g, 1.977mols Si), toluene (722.31g) + an amount of toluene equal to the volume of the Dean Stark apparatus. A nitrogen blanket was applied. The flask was heated at reflux for 30 minutes to remove trace water from the 217 Flake. The flask was cooled to a couple of degrees below reflux and contained a resin solution.
  • NMR spectra showed 96% of vinyl groups converted to epoxycyclohexyl - functional groups of formula .
  • the epoxycyclohexyl - functional resin linear polyorganosiloxane produced in this example had Mw of 56,300 g/mol and Mn of 21,800 g/mol.
  • BCF-TEA catalysts were prepared as follows:
  • BCF stock solution typically 5 weight % BCF in toluene
  • Adhesion testing was performed as follows: The adhesion data for each sample were measured according to ASTM method D3359 by using a Gardco PA-2000 adhesion test kit after cure (according to the thermal cure or UV cure test method described above) and aging. After scratching the film surface by using a Crosshatch tool, the amount of the coating materials remained on the Al panel surface indicated the adhesion capability of the film. The higher the remained%, the stronger the adhesion of the materials to the substrate. The adhesion was not acceptable if the amount that remained was ⁇ 80%.
  • Table 3 shows data for thermally cured epoxy - functional resin - linear polyorganosiloxane block copolymers.
  • Cl and C2 are two comparative examples which contained Vinyl functional groups and were curable by Pt catalyzed hydrosilylation.
  • C3 is a comparative example which contained physically blended epoxy-functional phenyl-T resin (the resin intermediate prepared in synthesis example 3, above, with unit formula M V1 o.iT PEP o.o7T Ph o.83) and epoxy terminated PDMS (M CEP DIOOM CEP ). Note: all samples were cured at 150 °C for 30 minutes.
  • Table 3 displays the key data measured for thermally cured epoxy - functional resin - linear polyorganosiloxane block copolymers prepared as described above.
  • the copolymer SAMPLE 7-1, SAMPLE 4-2 and SAMPLE 4-3 each contained 7 mol% Si atoms attached with cyclohexyl epoxide (CEP) functional groups, but SAMPLE 4-1 contained only 3.5 mol% Si atoms attached with cyclohexyl epoxide (CEP).
  • SAMPLE 4-4 (Cl) contained 7 mol% propylene epoxide (PEP) - functional groups, which was less reactive than CEP.
  • TAS-SbR is triarylsulfonium hexafluoroantimonate salt (from Aldrich)
  • Ci2Ar2l-SbF6 is 4,4’-didodecyldiphenyliodonium antimonate salt (from GE)
  • Ar2l-BCF4 is 4-isopropyl-4’-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (bought from Gelest).
  • Table 5 shows data for UV cured epoxy - functional resin - linear polyorganosiloxane copolymers. All examples cured by 10 second irradiation of 365 nm LED UV light with UV power of 2 J/cm 2 .
  • C4 is a comparative example SAMPLE 4-4 with 7 mol% propyl epoxy.
  • C5 was a comparative example, which comprised Vi-RL (the vinyl -functional resin - linear polyorganosiloxane block copolymer intermediate prepared in Synthesis Example 6) and was curable via hydrosilylation in the presence of UV activated Pt catalyst Pt(acac)2.
  • C6 was a comparative example which contained physically blended epoxy-functional phenyl-T resin (intermediate prepared in synthesis example 3 with unit formula M V1 o.iT PEP o.o7T Ph o.83) and epoxy terminated PDMS (M CEP 2DIOO).
  • C7 is a comparative example of only epoxy terminated PDMS (M CEP 2D o).
  • C8 is another comparative example containing APZ-55 (M V1 2sD PEP 4oT Ph 75).
  • compositions to test the UV cure efficiency and the thermal stability of the UV curable EP-RL copolymers were developed. Table 5 above shows the data measured for U V cured compositions. All examples comprised a cyclohexyl epoxide functional resin-linear (CEP-RL) (either SAMPLE 7-1, SAMPLE 4-2, SAMPLE 4-1, or SAMPLE 4-3) and photoacid generator (PAG-Dow).
  • C4 was a comparative example of propylene epoxide functional resin-linear polyorganosiloxane copolymer (PEP-RL, SAMPLE 4-4 above).
  • the gel swelling test indicated that (1) all CEP functional resin - linear polyorganosiloxane copolymer composition examples cured well with 2J/cnr UV power (cure% > 90%); (2) all CEP functional resin - linear polyorganosiloxane copolymer composition examples cured much faster and better than hydrosilylation cured Vi-RL (in comparative example C5); (3) PEP functional resin - linear polyorganosiloxane block copolymer composition examples cured slightly less than CEP functional resin - linear polyorganosiloxane block copolymer composition (see comparative example C4)); (4) SAMPLE 7-1, SAMPLE 4-2 and SAMPLE 4-3 with higher epoxy contents cured better than SAMPLE 4-1 with less epoxy content; (5) the shelf life of the prepared films from each example was over 30 days at RT and under dark storage conditions.
  • C6 was very hazy before and after UV irradiation.
  • the gel swelling test showed the cure% of C6 after UV cure was 50%.
  • Table 6 The cure and adhesion data (Extractable% and ROR%) for release coating compositions prepared from UV cured epoxy - functional resin - linear polyorganosiloxane block copolymers or Vi-RL (the vinyl-functional resin - linear polyorganosiloxane block copolymer intermediate prepared at the beginning of Synthesis Example 6) were measured on thermal paper substrates (Lintec/Mactac thermal paper).
  • CEP functional resin - linear polyorganosiloxane block copolymers were applied as UV curable release coatings on thermal paper substrates (e.g., Lintec/Mactac thermal paper used here) to compare their performance vs that of hydrosilylation curable Vi-RL composition.
  • Extractable% and ROR% are two data measured to show their performance as release coatings for thermal paper. Extractable% is the weight percentage extracted from the cured film and was measured and calculated as the weight loss percentage of the film after 30 min immersing in a MIBK (methyl isobutyl ketone) solution.
  • ROR% is the percentage of rub off resistance which was measured and calculated as the weight percentage of the film remained on the substrate after a rubbing off test.
  • Table 7 has results of thermal aging and adhesion tests, which showed that (i) PAG- Dow cured composition examples 10-14 had good thermal stability indicated by the little change of the color (or b* value) and the high toughness and flexibility of the aged samples; (ii) Epoxycycloakyl - functional resin - linear polyorganosiloxane block copolymers showed better cure and much higher adhesions on substrates (thermal paper, F4 boards or Al) than hydrosilylation curable Vi-RL (comparative examples C5 and C7).
  • the good thermal stability of the UV cured epoxycycloakyl - functional resin - linear polyorganosiloxane block copolymers was also confirmed by the only slightly changed Young’s modulus and the remained high elongation% measured for examples 17, 18 and 19 in Table 7 after aging at 150 °C for 5 days.
  • the mechanical properties of the UV cured epoxycycloakyl - functional resin - linear polyorganosiloxane block copolymer compositions can be easily tuned by adding epoxyfunctional crosslinkers such as M CEP M CEP used in examples 18 and 19.
  • the Young’s modulus of the UV cured compositions according to this invention were from 45.2 to 68.7 to 84 MPa with the increase of the M CEP M CEP content from 0 to 2 % to 5 %.
  • Epoxy containing materials may suffer from yellowing issues during high temperature applications (e.g., temperature over 100 °C).
  • the comparative example C8 in Table 5 (containing APZ-55) showed much higher b* value after aging.
  • the epoxycycloalkyl - functional resin - linear polyorganosiloxane copolymers described herein did not show much yellowing issues, which was proved by the low b* values measured for thermally aged composition samples cured by either thermal or UV cure, e.g., as shown above in Table 5.

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Abstract

L'invention concerne un copolymère séquencé de résine à fonction époxycyclohexylalkyle-polyorganosiloxane linéaire et des procédés pour sa préparation et son utilisation. Le copolymère séquencé de résine à fonction époxycyclohexylalkyle-polyorganosiloxane linéaire est utile à la fois dans des compositions thermodurcissables et dans des compositions durcissables par UV.
PCT/US2025/011356 2024-02-07 2025-01-13 Copolymère de polyorganosiloxane linéaire-résine à fonction époxy, composition contenant le copolymère, et procédés pour leur préparation et leur utilisation Pending WO2025170712A1 (fr)

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