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WO2025165569A1 - Composition avec un pré-catalyseur de platine (iv) à fonctionnalisé par un siloxane - Google Patents

Composition avec un pré-catalyseur de platine (iv) à fonctionnalisé par un siloxane

Info

Publication number
WO2025165569A1
WO2025165569A1 PCT/US2025/011562 US2025011562W WO2025165569A1 WO 2025165569 A1 WO2025165569 A1 WO 2025165569A1 US 2025011562 W US2025011562 W US 2025011562W WO 2025165569 A1 WO2025165569 A1 WO 2025165569A1
Authority
WO
WIPO (PCT)
Prior art keywords
phenyl
independently
compound
composition
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/011562
Other languages
English (en)
Inventor
Mary E. Garner
Jonathan AXTELL
Souvagya BISWAS
Bizhong Zhu
Myoungbae LEE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Dow Silicones Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC, Dow Silicones Corp filed Critical Dow Global Technologies LLC
Publication of WO2025165569A1 publication Critical patent/WO2025165569A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
    • 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
    • C08G77/12—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

  • the present invention relates to a composition comprising a photoactivated siloxane- functionalized platinum (IV) (Pt(IV)) pre-catalyst, particularly useful in hydrosilylation reactions.
  • Hydrosilylation is commonly used in the silicones industry for the synthesis of silicone polymers and cross-linked materials.
  • UV-initiated hydrosilylation using a photoactive pre-catalyst is becoming more popular as the energy input needed to trigger the reaction is low relative to thermally activated approaches.
  • Pt(IV) species such as cyclopentadienyltrimethylplatinum and its analogs are known as photoactive pre-catalysts (see US 4,510,094; US 8,088,878; and US 10,392,479) for hydrosilylation; Pt(IV) decompose under UV irradiation to form the catalytically active Pt(0) species. Nevertheless, these known pre- catalysts are often undesirably volatile and reactions using these pre-catalysts tend to be sluggish.
  • Pt(IV) species such as cyclopentadienyltrimethylplatinum and its analogs are known as photoactive pre-catalysts (see US 4,510,094; US 8,088,878; and US 10,392,479) for hydrosilylation; Pt(IV) decompose under UV irradiation to form the catalytically active Pt(0) species. Nevertheless, these known pre-catalysts are often undesirably volatile and reactions using these pre-catalysts tend to be sluggish.
  • the present invention is a composition
  • the present invention addresses a need in the art by providing a Pt(IV) pre-catalyst that decomposes rapidly to the catalytically active Pt(0) state under light irradiation.
  • the present invention is a) a compound functionalized with at least one Si-H group; b) a compound functionalized with at least one olefin group; and c) a compound of Formula 1: where Ar is phenyl, naphthyl, or anthracenyl; X is a C2-C12 hydrocarbyl diradical; each R 1 is independently C 1 -C 6 -alkyl or phenyl; each R 2 is independently C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, Ar, NO2, acetyl, trifluoromethyl, or halo; each R 3 is independently C1-C6-alkyl, C1-C6-alkoxy, phenyl, or -(
  • the compound with at least one Si-H group preferably has at least two Si-H groups.
  • the polyorganosiloxane of Formula 2 is an example of such a compound: Formula 2 where each R′ is independently C1-C6-alkyl, phenyl, or H; the sum of m + n is in the range of from 2 or from 3 to 400 or to 200 or to 3000 or to 1000 or to 500 or 100 or to 50, and wherein n is from 0, or from 2 or from 3 to preferably 100 or to 50 or to 20; with the proviso that when n is 0, each R′ is H.
  • the compound functionalized with at least one olefin group preferably is functionalized with at least two terminal olefin groups.
  • the compound functionalized with at least one olefin group may also be a Q-branched polyorganosiloxane, as illustrated in Formula 3: R'' O R '' where each R′′ is represented by Fragment 1: where the dashed lines represent the point of attachment to the oxygen atoms; each q is in the range of from 0 to 2000 or to 1000 or to 500 or to 250; each R a is independently C1-C6-alkyl or phenyl; and each R b is R a or a C2-C8-alkenyl group; with the proviso that at least one of the R b groups is a C2-C6-alkenyl group.
  • the compound with at least one olefin group may also be a combination of polyorganosiloxanes of Formulas 3 and 4, where the weight-to-weight ratio of the polyorganosiloxane of Formula 3 to the polyorganosiloxane of Formula 4 is preferably in the range of from 60:40 to 95:5.
  • the compound functionalized with at least one olefin group may further comprise a polyorganosiloxane resin, as illustrated in Formulas 5 and 6: Formula 5 Formula 6 where R° is methyl, ethyl, or phenyl, and the dashed lines represent the points of attachment to other groups.
  • the mole:mole ratio of Si-H groups to olefin groups is in the range of from 0.1:1 or from 0.5:1, to 20:1 or to 10:1 or to 5:1 or to 1.5:1.
  • the compound of Formula 1 is advantageously prepared using the following steps.
  • an alkali metal cyclopentadiene such as sodium cyclopentadiene (Na-Cp) is contacted with R 1 -Br to form an alkyl or phenyl substituted cyclopentadiene (R 1 )x-Cp.
  • R 1 groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups.
  • (R 1 )x-Cp is then contacted with an alkali metal bis(trimethylsilyl)amide such as potassium or sodium bis(trimethylsilyl)amide or with an alkyl lithium such as n-butyl lithium to form the alkali metal salt of (R 1 )x-Cp
  • an alkali metal bis(trimethylsilyl)amide such as potassium or sodium bis(trimethylsilyl)amide
  • an alkyl lithium such as n-butyl lithium
  • a dibromomethylaryl compound such as dibromomethylbenzene is contacted with an alkenyl-functionalized Grignard reagent to form an alkenyl-functionalized bromomethylaryl compound, preferably an alkenyl-functionalized bromomethylbenzene (Intermediate B): where n is from 0 to 9.
  • Intermediate B can be used as precursor to prepare an intermediate for the compound of Formula 1 where X is a C3-C12 hydrocarbyl diradical.
  • An analogous intermediate can be prepared where X is a C2 hydrocarbyl diradical by using the commercially available bromomethylstyrene as Intermediate B.
  • a tolyl-functionalized Grignard reagent such as (p-tolyl)magnesium bromide is contacted with a halide-functionalized dimethyl(vinyl)silyl compound such as chlorodimethyl(vinyl)silane to form a tolyl-functionalized dimethyl(vinyl)silyl compound:
  • the tolyl- brominating agent such as N-bromosuccinimide (NBS) in the presence of a radical initiator such as azobisisobutyronitrile (AIBN) to generate a dimethyl(vinyl)silyl-functionalized bromomethylbenzene (Intermediate B′), where each R 7 is H and m is 1: N N N B ' in the presence of a platinum catalyst to form Intermediate C:
  • Intermediate C Norbornadiene dimethyl platinum (II) ((NBD)PtMe2) is dissolved in suitable donor solvent such as pyridine, then contacted with Intermediate C under conditions
  • R 5 is preferably methyl, phenyl, or -OSi(OCH3)3; each R 6 is preferably methyl; each R 7 is preferably H; and the sum of z + w is preferably from 1 to 15. In another aspect, w is 0; in another aspect, z is from 1 to 15.
  • compounds of the present invention include the following: a trimethoxy silane, which is advantageously mixed with the pre-catalyst prior to admixing with compounds a) and b).
  • the compound of Formula 1 is a Pt(IV) pre-catalyst that exhibits excellent efficiency for promoting UV-triggered hydrosilylation chemistry. This efficiency is believed to arise from both the presence of the Pt-(R 7 )2Ar fragment, which provides a mechanism for a more facile homolytic cleavage and concomitant transformation of the pre-catalyst to the catalytically active Pt(0) state, and siloxane functionality, which promotes improved dispersion of the pre-catalyst in a siloxane medium.
  • the resulting gray suspension was allowed to warm to ambient temperature and stirred vigorously for 72 h.
  • the reaction mixture was then removed from the glovebox and diluted with deionized water (25 mL) causing the heterogenous mixture to become homogeneous.
  • the resulting biphasic mixture was transferred to a separatory funnel and the organic layer was washed with water (2 x 10 mL) and brine (2 x 10 mL).
  • the organic layer was collected, dried over MgSO 4 , filtered, and concentrated to a nearly colorless oil by rotary evaporation.
  • the crude material was purified by flash chromatography using 100% hexanes as the solvent system. The desired product was collected in fractions 7 - 24. 1 H NMR and GC-MS was used to confirm purity.
  • Karstedt's catalyst was added (3 drops of a 2 wt% Pt in xylenes solution) and the mixture was heated to 50 °C, followed by the dropwise addition of 1,1,1,3,3-pentamethyldisiloxane (MM') (0.87 mL, 4.44 mmol, 1 equiv). Stirring was continued at 50 °C for 24 h. The mixture was cooled to room temperature then diluted with hexanes (4 mL) and stirred with activated carbon for 5 – 10 min. The mixture was then passed through a 0.45- ⁇ m PTFE syringe filter and the volatiles were removed by rotary evaporation to afford a nearly colorless liquid.
  • MM' 1,1,1,3,3-pentamethyldisiloxane
  • Karstedt's catalyst was added (2 drops of a 2wt% Pt in xylenes) and the mixture was heated to 50 °C followed by the dropwise addition of 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) (0.217 mL, 0.80 mmol, 1 equiv). After 2 h, the mixture was cooled to ambient temperature, and the reaction mixture was diluted with hexanes (4 mL) and stirred with activated carbon for 5 – 10 min. The mixture was then passed through a 0.45- ⁇ m PTFE syringe filter and the volatiles were removed by rotary evaporation to afford a nearly colorless liquid. Yield: 0.338 g, 94.4 %.
  • MD′M 1,1,1,3,5,5,5-heptamethyltrisiloxane
  • reaction mixture was then heated a total of 18 h at 70 °C, after which time the reaction mixture was cooled to ambient temperature and then concentrated in vacuo onto silica gel and purified by ISCO chromatography using 100 % hexanes as the solvent system.
  • the desired product was isolated from fractions 5 - 11. Yield: 0.360 g, 22.6 %.
  • Karstedt's catalyst was added (1 drop of a 2 wt% Pt in xylenes) and the mixture was heated to 50 °C followed by the dropwise addition of 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) (0.112 mL, 0.41 mmol, 1 equiv). After 2 h, the mixture was cooled to ambient temperature, and the reaction mixture was diluted with hexanes (4 mL) and stirred with activated carbon for 5 min. The mixture was then passed through a 0.45- ⁇ m PTFE syringe filter and the volatiles were removed by rotary evaporation to afford a nearly colorless liquid. Yield: 0.183 g, 93.1 %.
  • MD′M 1,1,1,3,5,5,5-heptamethyltrisiloxane
  • the reaction mixture was stirred at ambient temperature for 18 h.
  • the volatiles were removed in vacuo and the residue was triturated with dichloromethane (DCM, 2 x 4 mL), extracted into DCM (3 x 5 mL), and filtered through a Celite pad, which was then washed with additional DCM (10 mL).
  • the combined extracts were then concentrated in vacuo to afford a red/maroon oil.
  • the material was then removed from the glovebox and extracted again into DCM (10 mL) and filtered through a Florisil pad, which was then washed with additional DCM.
  • the filtrate was concentrated to a red oil by rotary evaporation.
  • Li (CH3)5Cp (0.070 g, 0.49, 1.2 equiv) was added to the reaction mixture directly as a solid at ambient temperature. Additional pyridine (2 mL) was added to facilitate quantitative transfer of all the Cp salt into the reaction vial. The reaction mixture was stirred at ambient temperature for another 2 h, after which time the reaction mixture was passed through a Celite pad atop a Florisil pad contained within a 0.45- ⁇ m PTFE syringe filter. The pads and filter were rinsed with hexanes (4 x 3 mL) and combined with the filtrate.
  • Table 1 illustrates the formulations.
  • Formulation 1 used the compound of Intermediate Example 6;
  • Formulation 2 used the compound of Intermediate Example 7, etc.
  • Pre-catalyst + Solvent amounts were tuned to achieve a concentration of elemental Pt of 18 ppm for each formulation.
  • the pre-catalyst concentration in MTM refers to the weight % concentration of the pre-catalyst.
  • Table 1 Polyorganosiloxane Formulations Formulation Example No 1 2 3 4 5 78 90 33 % 45

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

La présente invention est une composition comprenant a) un composé fonctionnalisé par au moins un groupe Si-H ; b) un composé fonctionnalisé par au moins un groupe oléfine ; et c) un composé représenté par la formule 1 : dans laquelle Ar, x, R1, R2, R3, R4, R7, m, x, y et z sont tels que définis dans la description. La composition fournit un pré-catalyseur qui se décompose rapidement à un état de platine qui favorise l'hydrosilylation lors de l'irradiation avec de la lumière de la longueur d'onde appropriée.
PCT/US2025/011562 2024-01-31 2025-01-14 Composition avec un pré-catalyseur de platine (iv) à fonctionnalisé par un siloxane Pending WO2025165569A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463627494P 2024-01-31 2024-01-31
US63/627,494 2024-01-31

Publications (1)

Publication Number Publication Date
WO2025165569A1 true WO2025165569A1 (fr) 2025-08-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2025/011562 Pending WO2025165569A1 (fr) 2024-01-31 2025-01-14 Composition avec un pré-catalyseur de platine (iv) à fonctionnalisé par un siloxane

Country Status (2)

Country Link
TW (1) TW202532423A (fr)
WO (1) WO2025165569A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510094A (en) 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
US8088878B2 (en) 2008-01-25 2012-01-03 Wacker Chemie Ag Hydrosilylation reactions activated through radiation
US10392479B2 (en) 2014-08-26 2019-08-27 Wacker Chemie Ag Platinum complexes and their use in compounds that can be cross-linked by a hydrosilylation reaction
WO2021168056A1 (fr) * 2020-02-19 2021-08-26 Momentive Performance Materials Inc. Compositions de silicone photodurcissables et procédé de fabrication de revêtements anti-adhésifs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510094A (en) 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
US8088878B2 (en) 2008-01-25 2012-01-03 Wacker Chemie Ag Hydrosilylation reactions activated through radiation
US10392479B2 (en) 2014-08-26 2019-08-27 Wacker Chemie Ag Platinum complexes and their use in compounds that can be cross-linked by a hydrosilylation reaction
WO2021168056A1 (fr) * 2020-02-19 2021-08-26 Momentive Performance Materials Inc. Compositions de silicone photodurcissables et procédé de fabrication de revêtements anti-adhésifs

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE REAXYS [online] 1 January 2021 (2021-01-01), MOMENTIVE PERFORMANCE MATERIALS: "PHOTOCURABLE SILICONE COMPOSITIONS AND PROCESS FOR MANUFACTURE OF RELEASE LINERS - WO2021/168056", XP093254868, Database accession no. XRN = 52075105, 52075113 *
EUR. J. INORG. CHEM., vol. 2015, 2015, pages 226 - 239

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