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WO2024242750A1 - Silicone - (meth)acrylate - polyether copolymer and synthesis method - Google Patents

Silicone - (meth)acrylate - polyether copolymer and synthesis method Download PDF

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Publication number
WO2024242750A1
WO2024242750A1 PCT/US2024/021023 US2024021023W WO2024242750A1 WO 2024242750 A1 WO2024242750 A1 WO 2024242750A1 US 2024021023 W US2024021023 W US 2024021023W WO 2024242750 A1 WO2024242750 A1 WO 2024242750A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
copolymer
independently selected
formula
Prior art date
Application number
PCT/US2024/021023
Other languages
French (fr)
Inventor
Fang Zhang
Matthew Carter
Scott BOELTER
Jodi Mecca
Nanguo Liu
Weijun Zhou
Hai Wang
Original Assignee
Dow Global Technologies Llc
Dow Silicones Corporation
Rohm And Haas Company
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 Corporation, Rohm And Haas Company filed Critical Dow Global Technologies Llc
Publication of WO2024242750A1 publication Critical patent/WO2024242750A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • 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
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes

Definitions

  • a silicone - (meth)acrylate - polyether copolymer and method for its preparation are provided. More particularly, the silicone - (meth) acrylate - poly ether copolymer comprises a linear siloxane backbone and a pendant (meth) acrylate - polyether moiety.
  • the silicone - (meth) acrylate - polyether copolymer can be prepared via free radical polymerization reaction.
  • SPEs Silicone polyethers
  • SPEs may suffer from various drawbacks, such as containing impurities including aldehydes and ketones produced as side products in processes for manufacturing SPEs, resulting in SPEs that may contain undesirable amounts of formaldehyde or other small molecule volatile organic compounds.
  • Silicone - (meth)acrylate copolymers have been disclosed as additives in various applications, such as pressure sensitive adhesives, coating compositions such as conformal coatings for electronic devices, silicone elastomers, and personal care compositions.
  • a silicone - (meth)acrylate - polyether copolymer comprises a linear backbone comprising a silicone moiety and a pendant (meth) acrylate - polyether moiety.
  • the Copolymer may be prepared via a method comprising a free radical polymerization reaction of a mercapto-functional polydiorganosiloxane and a (meth)acrylate - poly(alkylene glycol).
  • the silicone - (meth)acrylate - polyether copolymer comprises the linear backbone (comprising the silicone moiety) and the pendant (meth) acrylate - polyether moiety.
  • the (meth)acrylate group in the pendant (meth) acrylate - polyether moiety is covalently bonded to a sulfur atom in a mercapto-alkyl linker, where the alkyl group in the linker is covalently bonded to a silicon atom in the silicone moiety.
  • the pendant (meth) acrylate - poly ether moiety comprises a (meth)acrylate - poly(alkylene glycol) unit and may optionally further comprise an additional (meth)acrylate monomer unit.
  • the silicone moiety is derived from A) a mercapto-functional polydiorganosiloxane.
  • the (meth)acrylate - poly(alkylene glycol) unit is derived from B) a (meth)acrylate - poly(alkylene glycol), and the additional (meth) acrylate monomer unit is derived from C) a (meth)acrylate monomer, when present.
  • the Copolymer may comprise at least 20 wt%, alternatively at least 29 wt%, alternatively at least 29.9 wt%, alternatively at least 30 wt%, alternatively at least 35 wt%, and alternatively at least 39.9 wt% of the silicone moiety, based on combined weights of reactants used to prepare the Copolymer; while at the same time the Copolymer may comprise up to 90 wt%, alternatively up to 80 wt%, alternatively up to 70 wt%, alternatively up to 60 wt%, alternatively at up to 50 wt%, and alternatively up to 42.9 wt% of the silicone moiety on the same basis.
  • the Copolymer may comprise 20 wt% to 90 wt% of the silicone moiety, alternatively 20 wt% to 80 wt%, and alternatively 20 wt% to 50 wt% of the silicone moiety, on the same basis.
  • the Copolymer further comprises the (meth)acrylate - polyether moiety in an amount of 10 wt% to 80 wt%, based on combined weights of the reactants used to prepare the Copolymer.
  • the (meth) acrylate - poly ether moiety may be present in an amount of at least 10 wt%, alternatively at least 20 wt%, alternatively, at least 30 wt%, and alternatively at least 40 wt%, on the same basis; while at the same time the (meth)acrylate - polyether moiety may comprise up to 80 wt%, alternatively up to 71 wt%, alternatively up to 70 wt%, alternatively up to 66 wt%, alternatively up to 61 wt%, alternatively up to 58 wt%, and alternatively up to 50 wt% of the (meth)acrylate - polyether moiety on the same basis.
  • the pendant (meth)acrylate - polyether moiety comprises a (meth)acrylate - poly(alkylene glycol) unit and may optionally further comprise the additional (meth)acrylate monomer unit.
  • the Copolymer may comprise at least 10 wt%, alternatively at least 20 wt%, alternatively at least 30 wt%, alternatively at least 33 wt%, alternatively at least 39 wt%, and alternatively at least 40 wt% of the (meth)acrylate - poly(alkylene glycol) unit based on combined weights of the reactants used to make the Copolymer; while at the same time, the Copolymer may comprise up to 80 wt%, alternatively up to 65 wt%, alternatively up to 64 wt%, alternatively up to 60 wt%, alternatively up to 56 wt%, alternatively up to 52 wt%, and alternatively up to 40 wt% of the (meth)acrylate - poly(alkylene
  • the Copolymer may further comprise 0 to 30 wt% of the additional (meth)acrylate monomer unit, based on combined weights of reactants used to the Copolymer.
  • the Copolymer may comprise at least 1 wt%, alternatively at least 2 wt %, alternatively at least 4 wt%, alternatively at least 8 wt%, and alternatively at least 10 wt% of the additional (meth) acrylate monomer unit on the same basis; while at the same time the Copolymer may comprise up to 30 wt%, alternatively up to 23 wt%, alternatively up to 20 wt%, alternatively up to 16 wt%, alternatively up to 15 wt%, alternatively up to 14 wt%, and alternatively up to 13 wt% of the (meth)acrylate monomer unit on the same basis.
  • the Copolymer may comprise 0 to 23 wt%, alternatively 8 wt% to 23 wt%
  • R 10 comprises formula each
  • R 3 is an endblocker of a poly(meth)acrylate chain in the pendant (meth)acrylate - polyether moiety
  • each R 4 is independently selected from H or methyl
  • each D 2 is independently selected alkane-diyl group of 2 to 4 carbon atoms
  • each subscript n is independently 1 to 25
  • each R s is independently selected from H and an alkyl group of 1 to 4 carbon atoms
  • each subscript w is independently > 0 to 20, alternatively 1 to 20, and alternatively 1 to 15, and with the provisos that in at least one instance of R 10 , per molecule, subscript n is 5 to 25.
  • each R 1 is an independently selected alkyl group of 1 to 10 carbon atoms, such as methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n- butyl, t-butyl, iso-butyl, and sec-butyl), pentyl, hexyl, heptyl, octyl, nonyl and decyl (each including linear and branched alkyl groups, i.e., of 5 to 10 carbon atoms).
  • each R 1 may be methyl.
  • each D 1 is an independently selected alkane-diyl group of 1 to 16, alternatively 2 to 16, and alternatively 2 to 10, carbon atoms.
  • the alkane-diyl group may be linear or branched and has empirical formula -CTh, where subscript r is 1 to 16, alternatively 2 to 16, alternatively 2 to 10, alternatively 2 to 6, and alternatively 2 to 4.
  • suitable alkane- diyl groups for D 1 include -C2H4-, -C3H6-, -C4H8-.
  • D 1 may be -C3H6- (e.g., propanediyl).
  • Subscripts x and y represent average numbers of each difunctional siloxane unit per molecule.
  • Subscript x may be 1 to 1,000.
  • subscript x may be at least 10, alternatively at least 15, alternatively at least 20, alternatively at least 24; while at the same time, subscript x may be up to 1,000, alternatively up to 950, alternatively up to 900, alternatively up to 750, alternatively up to 500, alternatively up to 250, alternatively up to 100, alternatively up to 90, alternatively up to 85, alternatively up to 39, alternatively up to 38, alternatively up to 37, and alternatively up to 36.
  • Subscript y may be 1 to 100. Alternatively, subscript y may be at least 1 , alternatively at least 2, alternatively at least 2.2, alternatively at least 2.4; while at the same time, subscript y may be up to 10, alternatively up to 8, alternatively up to 6.
  • the Copolymer may have any distribution of the pendant (meth) acrylate - polyether moiety, R 2 , such as block or random. Alternatively, the Copolymer may have a random distribution of pendant (meth)acrylate - polyether moieties, R 2 .
  • R 3 is an endblocker of the poly (meth) acrylate chain in the pendant (meth)acrylate - polyether moiety.
  • R 3 may be H.
  • R 3 may be another structure resulting from termination of the free radical polymerization to make the Copolymer, as described below.
  • each D 2 is an independently selected alkane-diyl group of 2 to 4 carbon atoms.
  • the alkane-diyl group may be linear or branched and has empirical formula -C 3 H2s, where subscript s is 2 to 4, alternatively 2 to 3, and alternatively 2.
  • suitable alkane- diyl groups for D 1 include -C2H4-, -C3H6-, -C4H8-.
  • D 1 may be -C2H4- or -C3H6-.
  • each R 5 is hydrogen or an alkyl group of 1 to 4 carbon atoms.
  • the alkyl group for R 5 may be methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, t-butyl, iso-butyl, and sec-butyl).
  • each R 5 may be independently selected from the group consisting of H and methyl.
  • each R 5 may be an alkyl group; alternatively methyl.
  • subscript w represents the average number of (meth) acrylate - poly(alkylene glycol) units (and, when present, the average number of additional (meth) acrylate monomer units) per group R 10 .
  • Each subscript w independently has a value > 0, alternatively, each subscript w has a value of at least 1, alternatively 1 to 20, alternatively 1 to 15, alternatively 1 to 10, alternatively 2 to 15.
  • subscript a may be 0 to 10
  • subscript b may be > 0 to 10, alternatively 1 to 10, and alternatively 1 to 5.
  • the additional (meth)acrylate monomer units with subscript a and (meth)acrylate - poly(alkylene glycol) units with subscript b may be in any order and when a > 1 and b > 1 , these units are not necessarily in blocks as shown in general formula (HI) above, e.g., the units may have a random distribution.
  • Copolymer described herein may be prepared by a method comprising:
  • B) a (meth) acrylate - poly(alkylene glycol) of formula (V): are each as described and exemplified above for formula (II), and subscript n’ is as described above for formula (III);
  • Hty optionally C) a (meth)acrylate monomer of formula (VI): where D 2 and R 4 are each as described and exemplified above for formula (II);
  • Step 1) of the method described herein may be performed by any convenient means.
  • the starting materials may be combined in any order in any suitable reactor.
  • starting materials comprising A) the mercapto-functional polydiorganosiloxane and B) the (meth) aery late- poly(alkylene glycol) (and when used C) the (meth)acrylate monomer and E) the solvent) may be combined in a reactor, e.g., with mixing means such as an impeller or baffles.
  • Starting material D the free radical initiator
  • One or more of starting materials A), B), C) and D) may optionally be dissolved in E) the solvent before mixing with the other starting materials.
  • the starting materials may be combined under an inert atmosphere, such as nitrogen.
  • Step 1) may further comprise mixing and optionally heating the starting materials.
  • the temperature may depend on various factors such as the selection of solvent, however, step 1) may be performed at a temperature of up to 150 °C, alternatively RT to ⁇ 100 °C, and alternatively RT to 65 °C.
  • Reaction time depends on various factors such as the type and amount of free radical initiator selected for starting material D), however, the reaction time may be 30 mins to 24 hours, alternatively 30 mins to 8 hours.
  • Step 1) produces a reaction product comprising the Copolymer.
  • the reaction product may further comprise one or more additional components, such as an unreacted starting material, D) the free radical initiator, E) the solvent, if used, and a side product, such as a poly(meth)acrylate polymer, e.g., formed by polymerizing the (meth)acrylate groups of a portion of starting material B) and/or copolymerizing the (meth)acrylate groups of portions of starting materials B) and/or C), when starting material C) is present.
  • a side product such as a poly(meth)acrylate polymer, e.g., formed by polymerizing the (meth)acrylate groups of a portion of starting material B) and/or copolymerizing the (meth)acrylate groups of portions of starting materials B) and/or C), when starting material C) is present.
  • the method may optionally further comprise step 2): purifying the reaction product, thereby recovering the Copolymer.
  • Purifying may be performed by any convenient means, such as precipitation, filtration, stripping and/or distillation with heating and optionally under reduced pressure.
  • the product of step 2) is the Copolymer having minimized or eliminated content of the one or more additional components of the reaction product, described above.
  • the starting materials used in the method are described in detail, below.
  • Starting material A) is a reactant used in the method is the mercapto-functional polydiorganosiloxane.
  • the mercapto-functional polydiorganosiloxane comprises unit formula (IV): (R 1 2SiO2/2)x(R 1 R 10 SiO2/2) y (R 1 3SiOi/2)z, where subscripts x, y, and z each represent average numbers of each unit in the unit formula, and subscripts x, y, and z have average values as defined above for the Copolymer, each R 1 is an independently selected alkyl group of 1 to 10 carbon atoms; and each R 10 is an independently selected mercapto-alkyl group of formula -D -SH, where each D 1 is an independently selected alkane-diyl group of 1 to 16 carbon atoms, wherein R 1 and D 1 are as described and exemplified above for the Copolymer.
  • the mercapto-functional polydiorganosiloxane may have any distribution of the pendant mercapto-alkyl groups R 10 , such as block or random.
  • the copolymer may have a random distribution of pendant mercapto-alkyl groups, R 10 .
  • Examples of mercapto-functional polydiorganosiloxanes suitable for use herein include bis-trimethylsiloxy-terminated poly(dimethyl/methyl,mercaptopropyl)siloxanes. Methods for preparing mercapto-functional polydiorganosiloxanes are known as disclosed, for example, in U.S. Patent 5,202,190 and the references cited therein. Pendant mercapto-functional polydiorganosiloxanes are commercially available and are exemplified by poly(dimethyl/methylmercaptoalkyl) siloxanes.
  • GP-367, GP-71-SS, GP-800, and GP- 710 are available from available from Genesee Polymers Corporation of Burton, Michigan, USA; KF-2001 and KF-2004 are available from Shin-Etsu Silicone; SMS-022, SMS-142, and SMS-992 are available from Gelest Inc. of Morrisville, Pennsylvania, USA; and PS848, PS849, and PS850 are available from UCT, Inc. of Bristol, Pennsylvania USA..
  • Starting material B) is a reactant used in the method for making the Copolymer is a
  • the (meth) acrylate - poly(alkylene glycol) may comprise polyethylene glycol) methyl ether (meth)acrylate with average Mn of 300 to 480.
  • (Meth) acrylate - poly(alkylene glycols) are known in the art and are commercially available.
  • polyethylene glycol)methyl ether acrylate and poly(ethylene glycol) methyl ether methacrylate are commercially available from various sources such as Millipore Sigma of St. Eouis, Missouri, USA (Sigma) and TCI America of Portland, Oregon, USA, and poly(ethylene glycol) methyl ether methacrylate compounds with molecular weights of 1,000 to 13,000 are commercially available from Fisher Scientific.
  • Starting material C) is a (meth) acrylate monomer, which is an optional additional reactant that may be used to make the Copolymer herein.
  • Starting material C) has formula (VI): each D 2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, and each R 4 is independently selected from H or methyl, each as described and exemplified above.
  • suitable (meth)acrylate monomers include hydroxybutyl (meth)acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth)acrylate, all of which are known in the art and are commercially available, e.g., from BASF SE or Sigma.
  • the additional (meth)acrylate monomer may comprise hydroxyethylmethacrylate.
  • Starting materials A) and B), and C), when present described above are the reactants used in amounts to provide the Copolymer with the amounts of silicone moieties and pendant (meth)acrylate polyether moieties and the units thereof, described above.
  • Starting material D) used in the method is a free radical initiator.
  • Free radical initiators are known in the art and are exemplified by peroxides, azo compounds, peracids, and peresters.
  • the peroxide may be an organic peroxide or a hydroperoxide, such as benzoyl peroxide; 4- monochlorobenzoyl peroxide; t-butylperoctoate; t-butyl peroxybenzoate, tert-butylperoxybenzoate, tert-butyl cumyl peroxide, tert-butyloxide 2,5-dimethyl-2,5-di-tert-butylperoxyhexane; 2,4- dichlorobenzoyl peroxide; di-tertbutylperoxy-diisopropyl benzene; l,l-bis(tert-butylperoxy)-3,3,5- trimethylcyclohexane; 2,5-di-tert-butylperoxyhexane-3,2,5-dimethyl-2,5-bis(tert-butylperoxy) hexane; cumyl-tert-butyl peroxide;
  • di -peroxide radical initiators may be used alone or in combination with other radical initiators.
  • Such di-peroxide radical initiators include, but are not limited to, l,4-bis-(t-butyl peroxycarbo)cyclohexane; 1 ,2-di(t-butyl peroxy)cyclohexane; and 2,5-di(t-butyl peroxy)-3-hexyne.
  • Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma.
  • the azo compound may be an aliphatic azo compound such as 1-t-amylazo-l- cyanocyclohexane; azo-bis-isobutyronitrile; and 1-t-butylazo-cy anocyclohexane; 2,2'-azo- bis-(2- methyl)butyronitrile; 2,2’ -azobis(2-methylpropionitrile); 2,2’ -azobis(2-methylpropionamidine) dihydrochloride; 2,2’-azobis(cyanovaleric acid); or a combination of two or more thereof.
  • aliphatic azo compound such as 1-t-amylazo-l- cyanocyclohexane; azo-bis-isobutyronitrile; and 1-t-butylazo-cy anocyclohexane; 2,2'-azo- bis-(2- methyl)butyronitrile; 2,2’ -azobis(2-methylpropionitrile); 2,2’ -azobis(2-
  • Azo compounds are known in the art and are commercially available, e.g., under the tradename VAZOTM WSP from The Chemours Company of Wilmington, Delaware, USA. Furthermore, peroxides and azo compounds are disclosed at paragraphs [0057] to [0063] of U.S. Patent Application Publication 2014/0287642. Initiators are also disclosed in U.S. Patent 5,202,190.
  • the initiator used in the method described herein may be an azo compound, such as 2,2'-azobis(2-methylpropionitrile), which is commercially available from Sigma.
  • the amount of free radical initiator depends on various factors including the type of initiator and reaction conditions, such as temperature, selected. Alternatively, the amount of initiator may be 0.1 wt% to 5 wt%, alternatively 0.4 wt% to 2 wt%, based on combined weights of starting materials A), B), and C).
  • Starting material E) is a solvent that may optionally be used in the method described herein to dissolve or disperse one or more of the starting materials before and/or during step 1).
  • D) the free radical initiator may be dissolved in the solvent before or during mixing with the other starting materials, described herein.
  • Suitable solvents may be organic solvents including aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin; hydrocarbon solvents such as industrial gasoline, petroleum benzene, and solvent naphtha; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutylketone, acetonylacetone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; ether solvent
  • the solvent may comprise a siloxane solvent such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; and mixtures thereof, which are commercially available from various sources such as Gelest, Inc. of Morrisville, Pennsylvania, USA and from Dow.
  • the amount of solvent is not critical, and may be, for example 1 wt% to 99 wt% based on combined weights of starting materials A), B), C), D) and E).
  • the Copolymer described above is useful may find use in a myriad of end use applications and compositions.
  • the Copolymer may be used as a surfactant, wetting agent, formulation aid, and/or dispersant.
  • the Copolymer may be useful as a defoamer for coatings, oil and gas applications and/or pulp and paper applications.
  • the Copolymer may be useful as an additive for adjusting adhesion and/or release force in paper coatings such as pressure sensitive adhesive and/or release coating compositions.
  • the Copolymer may be added to compositions such as coating compositions, pressure sensitive adhesive compositions, and/or release coating compositions by any convenient means such as mixing at RT.
  • the Copolymer may be added to a pressure sensitive adhesive composition, such as that disclosed in U.S. Patent Application Publication 2022-0056317, U.S. Patent App Pub 2022-0073800, U.S. Patent Application Publication 2023-0103925 or PCT Publication WO2022/066261, in addition to, or instead of, the silicone - (meth)acrylate copolymer described therein.
  • the Copolymer described herein may be added to a coating composition such as that disclosed in U.S. Patent Application Publication 2023-0086870, U.S.
  • the Copolymer described herein may be used in a personal care composition, such as that described in U.S. Patent 8,258,243 or PCT Publication WO2022/093497 in addition to, or instead of, the silicone - (meth)acrylate copolymer described therein.
  • 3-mercaptopropylmethyldimethoxysilane had formula:
  • Each Mercapto-functional PDMS in Table 2 has the x and y are as shown above in Table 2, and where the difunctional units with subscripts x and y are not necessarily in blocks, but may be randomly or semi-randomly distributed in the polydiorganosiloxane.
  • the reactor contents were then placed under a N2 blanket, and heated from 25 °C to 65 °C over 30 mins, while stirring at 250 RPM. The reactor contents were then stirred for 6 hrs at 65 °C. After cooling to RT, the reactor contents were evacuated under reduced pressure on a rotary evaporator, and then transferred to a pear-shaped flask equipped with a stir bar and placed in a water bath at 50 °C. The contents of the flask were stirred vigorously, and placed under high vacuum ( ⁇ 50 milliTorr, 6.67 Pa) for ⁇ 4 hr. The contents of the flask were then left overnight under high vacuum at RT and collected for use. Additional samples were made using modifications to this procedure, by varying the relative composition of starting materials, as listed in Table 3.
  • % Silicone refers to the weight % of Mercapto-functional PDMS used based on combined weights of Mercapto-functional PDMS, PEG(M)A, and HEMA used to prepare the copolymer.
  • %PEG(M)A refers to the weight % of polyethylene glycol (meth) acrylate based on combined weights of Mercapto-functional PDMS, PEG(M)A, and HEMA used to prepare the copolymer.
  • the method for manufacturing the Copolymer described herein provides the benefit of being capable of producing Copolymer species with varying amounts of silicone and pendant (meth)acrylate - polyether moieties, as well as varying amounts of (meth)acrylate - poly(alkylene glycol) and additional (meth) acrylate monomer units in the pendant (meth) acrylate - poly ether moiety. Furthermore, the method for manufacturing the Copolymer described herein may minimize or avoid the generation of aldehyde by-products, such as formaldehyde, resulting in improved foam formulations over foam formulations containing SPEs with formaldehyde impurities.
  • aldehyde by-products such as formaldehyde

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Abstract

A silicone - (meth)acrylate - polyether copolymer includes a linear siloxane backbone with pendant (meth)acrylate - polyether moieties. The siloxane backbone is made up of a silicone moiety having a silicon bonded mercapto-alkyl linker (wherein the alkyl group in the linker is bonded to a silicon atom in the silicone moiety). The pendant (meth)acrylate - polyether moiety is covalently bonded to a sulfur atom in the mercapto-alkyl linker. The pendant (meth)acrylate - polyether moiety includes a (meth)acrylate - poly(alkylene glycol) unit. The silicone - (meth)acrylate - polyether copolymer is useful as a surfactant, formulation aid, and/or dispersant. The silicone - (meth)acrylate - polyether copolymer may be useful as a defoamer for coatings, oil and gas applications and/or pulp and paper applications. Furthermore, the silicone - (meth)acrylate - polyether copolymer may be useful as an additive for adjusting adhesion and/or release force in paper coatings such as pressure sensitive adhesive and/or release coating compositions.

Description

SILICONE - (METH)ACRYLATE - POLYETHER COPOLYMER AND SYNTHESIS
METHOD
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No.
63/468,281 filed on 23 May 2023 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No. 63/468,281 is hereby incorporated by reference.
FIELD
[0002] A silicone - (meth)acrylate - polyether copolymer and method for its preparation are provided. More particularly, the silicone - (meth) acrylate - poly ether copolymer comprises a linear siloxane backbone and a pendant (meth) acrylate - polyether moiety. The silicone - (meth) acrylate - polyether copolymer can be prepared via free radical polymerization reaction.
INTRODUCTION
[0003] Silicone polyethers (SPEs) are known for use as surfactants in various applications. However, SPEs may suffer from various drawbacks, such as containing impurities including aldehydes and ketones produced as side products in processes for manufacturing SPEs, resulting in SPEs that may contain undesirable amounts of formaldehyde or other small molecule volatile organic compounds.
[0004] Silicone - (meth)acrylate copolymers have been disclosed as additives in various applications, such as pressure sensitive adhesives, coating compositions such as conformal coatings for electronic devices, silicone elastomers, and personal care compositions.
SUMMARY
[0005] A silicone - (meth)acrylate - polyether copolymer (Copolymer) comprises a linear backbone comprising a silicone moiety and a pendant (meth) acrylate - polyether moiety. The Copolymer may be prepared via a method comprising a free radical polymerization reaction of a mercapto-functional polydiorganosiloxane and a (meth)acrylate - poly(alkylene glycol).
DETAILED DESCRIPTION
[0006] As introduced above, the silicone - (meth)acrylate - polyether copolymer (Copolymer) comprises the linear backbone (comprising the silicone moiety) and the pendant (meth) acrylate - polyether moiety. The (meth)acrylate group in the pendant (meth) acrylate - polyether moiety is covalently bonded to a sulfur atom in a mercapto-alkyl linker, where the alkyl group in the linker is covalently bonded to a silicon atom in the silicone moiety. The pendant (meth) acrylate - poly ether moiety comprises a (meth)acrylate - poly(alkylene glycol) unit and may optionally further comprise an additional (meth)acrylate monomer unit. As described below, in the method for making the Copolymer, the silicone moiety is derived from A) a mercapto-functional polydiorganosiloxane. The (meth)acrylate - poly(alkylene glycol) unit is derived from B) a (meth)acrylate - poly(alkylene glycol), and the additional (meth) acrylate monomer unit is derived from C) a (meth)acrylate monomer, when present.
[0007] The Copolymer may comprise at least 20 wt%, alternatively at least 29 wt%, alternatively at least 29.9 wt%, alternatively at least 30 wt%, alternatively at least 35 wt%, and alternatively at least 39.9 wt% of the silicone moiety, based on combined weights of reactants used to prepare the Copolymer; while at the same time the Copolymer may comprise up to 90 wt%, alternatively up to 80 wt%, alternatively up to 70 wt%, alternatively up to 60 wt%, alternatively at up to 50 wt%, and alternatively up to 42.9 wt% of the silicone moiety on the same basis. Alternatively, the Copolymer may comprise 20 wt% to 90 wt% of the silicone moiety, alternatively 20 wt% to 80 wt%, and alternatively 20 wt% to 50 wt% of the silicone moiety, on the same basis.
[0008] The Copolymer further comprises the (meth)acrylate - polyether moiety in an amount of 10 wt% to 80 wt%, based on combined weights of the reactants used to prepare the Copolymer. Alternatively, the (meth) acrylate - poly ether moiety may be present in an amount of at least 10 wt%, alternatively at least 20 wt%, alternatively, at least 30 wt%, and alternatively at least 40 wt%, on the same basis; while at the same time the (meth)acrylate - polyether moiety may comprise up to 80 wt%, alternatively up to 71 wt%, alternatively up to 70 wt%, alternatively up to 66 wt%, alternatively up to 61 wt%, alternatively up to 58 wt%, and alternatively up to 50 wt% of the (meth)acrylate - polyether moiety on the same basis.
[0009] The pendant (meth)acrylate - polyether moiety comprises a (meth)acrylate - poly(alkylene glycol) unit and may optionally further comprise the additional (meth)acrylate monomer unit. The Copolymer may comprise at least 10 wt%, alternatively at least 20 wt%, alternatively at least 30 wt%, alternatively at least 33 wt%, alternatively at least 39 wt%, and alternatively at least 40 wt% of the (meth)acrylate - poly(alkylene glycol) unit based on combined weights of the reactants used to make the Copolymer; while at the same time, the Copolymer may comprise up to 80 wt%, alternatively up to 65 wt%, alternatively up to 64 wt%, alternatively up to 60 wt%, alternatively up to 56 wt%, alternatively up to 52 wt%, and alternatively up to 40 wt% of the (meth)acrylate - poly(alkylene glycol) unit on the same basis. Alternatively, the Copolymer may comprise 28.8 wt% to 64 wt%, alternatively 20 wt% to 80 wt% of the (meth)acrylate - poly(alkylene glycol) unit on the same basis.
[0010] The Copolymer may further comprise 0 to 30 wt% of the additional (meth)acrylate monomer unit, based on combined weights of reactants used to the Copolymer. Alternatively, the Copolymer may comprise at least 1 wt%, alternatively at least 2 wt %, alternatively at least 4 wt%, alternatively at least 8 wt%, and alternatively at least 10 wt% of the additional (meth) acrylate monomer unit on the same basis; while at the same time the Copolymer may comprise up to 30 wt%, alternatively up to 23 wt%, alternatively up to 20 wt%, alternatively up to 16 wt%, alternatively up to 15 wt%, alternatively up to 14 wt%, and alternatively up to 13 wt% of the (meth)acrylate monomer unit on the same basis. Alternatively, the Copolymer may comprise 0 to 23 wt%, alternatively 8 wt% to 23 wt%, and alternatively 8 wt% to 12 wt% of the (meth)acrylate monomer unit on the same basis.
[0011] The Copolymer may comprise unit formula (I): (R12SiO2/2)x(R1R2SiO2/2)y(R13SiOi/2)z, where subscripts x, y, and z each represent average numbers of each unit in the unit formula, and subscripts x, y, and z have values such that z = 2, x = 1 to 1,000, and y = 1 to 100; each R1 is an independently selected alkyl group of 1 to 10 carbon atoms; each R2 is an independently selected group of formula: -D'-S-R10, where each D1 is an independently selected alkane-diyl group of 1 to
16 carbon atoms, and R10 comprises formula
Figure imgf000004_0001
each
R3 is an endblocker of a poly(meth)acrylate chain in the pendant (meth)acrylate - polyether moiety, each R4 is independently selected from H or methyl, each D2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, each subscript n is independently 1 to 25, each Rs is independently selected from H and an alkyl group of 1 to 4 carbon atoms, each subscript w is independently > 0 to 20, alternatively 1 to 20, and alternatively 1 to 15, and with the provisos that in at least one instance of R10, per molecule, subscript n is 5 to 25.
[0012] In unit formula (I) above, each R1 is an independently selected alkyl group of 1 to 10 carbon atoms, such as methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n- butyl, t-butyl, iso-butyl, and sec-butyl), pentyl, hexyl, heptyl, octyl, nonyl and decyl (each including linear and branched alkyl groups, i.e., of 5 to 10 carbon atoms). Alternatively, each R1 may be methyl.
[0013] In unit formula (I) above, each D1 is an independently selected alkane-diyl group of 1 to 16, alternatively 2 to 16, and alternatively 2 to 10, carbon atoms. The alkane-diyl group may be linear or branched and has empirical formula -CTh, where subscript r is 1 to 16, alternatively 2 to 16, alternatively 2 to 10, alternatively 2 to 6, and alternatively 2 to 4. Examples of suitable alkane- diyl groups for D1 include -C2H4-, -C3H6-, -C4H8-. Alternatively, D1 may be -C3H6- (e.g., propanediyl).
[0014] In unit formula (I), subscript z represents the number of monofunctional (terminal) units per molecule, and subscript z = 2. Subscripts x and y represent average numbers of each difunctional siloxane unit per molecule. Subscript x may be 1 to 1,000. Alternatively, subscript x may be at least 10, alternatively at least 15, alternatively at least 20, alternatively at least 24; while at the same time, subscript x may be up to 1,000, alternatively up to 950, alternatively up to 900, alternatively up to 750, alternatively up to 500, alternatively up to 250, alternatively up to 100, alternatively up to 90, alternatively up to 85, alternatively up to 39, alternatively up to 38, alternatively up to 37, and alternatively up to 36. Subscript y may be 1 to 100. Alternatively, subscript y may be at least 1 , alternatively at least 2, alternatively at least 2.2, alternatively at least 2.4; while at the same time, subscript y may be up to 10, alternatively up to 8, alternatively up to 6. The Copolymer may have any distribution of the pendant (meth) acrylate - polyether moiety, R2, such as block or random. Alternatively, the Copolymer may have a random distribution of pendant (meth)acrylate - polyether moieties, R2.
[0015] In formula (II), R3 is an endblocker of the poly (meth) acrylate chain in the pendant (meth)acrylate - polyether moiety. R3 may be H. Alternatively, R3 may be another structure resulting from termination of the free radical polymerization to make the Copolymer, as described below.
[0016] In formula (II) above, each D2 is an independently selected alkane-diyl group of 2 to 4 carbon atoms. The alkane-diyl group may be linear or branched and has empirical formula -C3H2s, where subscript s is 2 to 4, alternatively 2 to 3, and alternatively 2. Examples of suitable alkane- diyl groups for D1 include -C2H4-, -C3H6-, -C4H8-. Alternatively, D1 may be -C2H4- or -C3H6-. [0017] In formula (II), each R5 is hydrogen or an alkyl group of 1 to 4 carbon atoms. For example, the alkyl group for R5 may be methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, t-butyl, iso-butyl, and sec-butyl). Alternatively, each R5 may be independently selected from the group consisting of H and methyl. Alternatively, each R5 may be an alkyl group; alternatively methyl.
[0018] In formula (II), subscript w represents the average number of (meth) acrylate - poly(alkylene glycol) units (and, when present, the average number of additional (meth) acrylate monomer units) per group R10. Each subscript w independently has a value > 0, alternatively, each subscript w has a value of at least 1, alternatively 1 to 20, alternatively 1 to 15, alternatively 1 to 10, alternatively 2 to 15. [0019] In formula (II), subscript n represents the average number of alkylene glycol units. In the (meth)acrylate - poly(alkylene glycol) unit, subscript n is 5 to 25. In the additional (meth)acrylate monomer unit, subscript n = 1. In at least one instance of R10, per molecule, subscript n is 5 to 25, alternatively 6 to 20.
[0020] Alternatively, R10 may comprise general formula (III):
Figure imgf000006_0001
are as described above for formula (II), each subscript n’ is independently 5 to 25, alternatively 6 to 20, subscript a represents an average value of additional (meth)acrylate monomer units per group R10, subscript b represents an average value of (meth)acrylate - poly(alkylene glycol) units per group R10, and a quantity (a + b) = w. Alternatively, subscript a may be 0 to 10, and subscript b may be > 0 to 10, alternatively 1 to 10, and alternatively 1 to 5. One skilled in the art would recognize that the additional (meth)acrylate monomer units with subscript a and (meth)acrylate - poly(alkylene glycol) units with subscript b may be in any order and when a > 1 and b > 1 , these units are not necessarily in blocks as shown in general formula (HI) above, e.g., the units may have a random distribution.
Method for Making the Copolymer
[0021] The Copolymer described herein may be prepared by a method comprising:
1) combining, under conditions to effect free radical polymerization reaction, starting materials comprising
A) a mercapto-functional polydiorganosiloxane comprising unit formula (IV): (R12SiO2/2)x(R1R9SiO2/2)y(R13SiOi/2)z, where each R9 is an independently selected mercaptoalkyl group of formula -D'-SH, and subscripts x, y, and z and R1 and D1 are as described and exemplified above for unit formula (I); B) a (meth) acrylate - poly(alkylene glycol) of formula (V):
Figure imgf000007_0001
are each as described and exemplified above for formula (II), and subscript n’ is as described above for formula (III);
Hty optionally C) a (meth)acrylate monomer of formula (VI):
Figure imgf000007_0002
where D2 and R4 are each as described and exemplified above for formula (II);
D) a free radical initiator; and optionally E) a solvent, thereby producing a reaction product comprising the copolymer; and optionally 2) purifying the reaction product, thereby recovering the copolymer. [0022] Step 1) of the method described herein may be performed by any convenient means. The starting materials may be combined in any order in any suitable reactor. For example, starting materials comprising A) the mercapto-functional polydiorganosiloxane and B) the (meth) aery late- poly(alkylene glycol) (and when used C) the (meth)acrylate monomer and E) the solvent) may be combined in a reactor, e.g., with mixing means such as an impeller or baffles. Starting material D), the free radical initiator, may be added to the reactor. One or more of starting materials A), B), C) and D) may optionally be dissolved in E) the solvent before mixing with the other starting materials. The starting materials may be combined under an inert atmosphere, such as nitrogen. Step 1) may further comprise mixing and optionally heating the starting materials. The temperature may depend on various factors such as the selection of solvent, however, step 1) may be performed at a temperature of up to 150 °C, alternatively RT to < 100 °C, and alternatively RT to 65 °C. Reaction time depends on various factors such as the type and amount of free radical initiator selected for starting material D), however, the reaction time may be 30 mins to 24 hours, alternatively 30 mins to 8 hours.
[0023] Step 1) produces a reaction product comprising the Copolymer. The reaction product may further comprise one or more additional components, such as an unreacted starting material, D) the free radical initiator, E) the solvent, if used, and a side product, such as a poly(meth)acrylate polymer, e.g., formed by polymerizing the (meth)acrylate groups of a portion of starting material B) and/or copolymerizing the (meth)acrylate groups of portions of starting materials B) and/or C), when starting material C) is present.
[0024] The method may optionally further comprise step 2): purifying the reaction product, thereby recovering the Copolymer. Purifying may be performed by any convenient means, such as precipitation, filtration, stripping and/or distillation with heating and optionally under reduced pressure. The product of step 2) is the Copolymer having minimized or eliminated content of the one or more additional components of the reaction product, described above. The starting materials used in the method are described in detail, below.
A) Mercapto-Functional Polydiorganosiloxane
[0025] Starting material A) is a reactant used in the method is the mercapto-functional polydiorganosiloxane. The mercapto-functional polydiorganosiloxane comprises unit formula (IV): (R12SiO2/2)x(R1R10SiO2/2)y(R13SiOi/2)z, where subscripts x, y, and z each represent average numbers of each unit in the unit formula, and subscripts x, y, and z have average values as defined above for the Copolymer, each R1 is an independently selected alkyl group of 1 to 10 carbon atoms; and each R10 is an independently selected mercapto-alkyl group of formula -D -SH, where each D1 is an independently selected alkane-diyl group of 1 to 16 carbon atoms, wherein R1 and D1 are as described and exemplified above for the Copolymer.
[0026] The mercapto-functional polydiorganosiloxane may have any distribution of the pendant mercapto-alkyl groups R10, such as block or random. Alternatively, the copolymer may have a random distribution of pendant mercapto-alkyl groups, R10.
[0027] Examples of mercapto-functional polydiorganosiloxanes suitable for use herein include bis-trimethylsiloxy-terminated poly(dimethyl/methyl,mercaptopropyl)siloxanes. Methods for preparing mercapto-functional polydiorganosiloxanes are known as disclosed, for example, in U.S. Patent 5,202,190 and the references cited therein. Pendant mercapto-functional polydiorganosiloxanes are commercially available and are exemplified by poly(dimethyl/methylmercaptoalkyl) siloxanes. For example, GP-367, GP-71-SS, GP-800, and GP- 710 are available from available from Genesee Polymers Corporation of Burton, Michigan, USA; KF-2001 and KF-2004 are available from Shin-Etsu Silicone; SMS-022, SMS-142, and SMS-992 are available from Gelest Inc. of Morrisville, Pennsylvania, USA; and PS848, PS849, and PS850 are available from UCT, Inc. of Bristol, Pennsylvania USA..
B) (Meth)acrylate - Poly/alkylene glycol) [0028] Starting material B) is a reactant used in the method for making the Copolymer is a
(meth)acrylate - poly(alkylene glycol) of formula (
Figure imgf000009_0001
each R5 is independently selected from H and an alkyl group of 1 to 4 carbon atoms, each D2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, each R4 is independently selected from H or methyl, each as described and exemplified above, and subscript n’ is 5 to 25 (alternatively 6 to 20) as described above. For example, the (meth) acrylate - poly(alkylene glycol) may comprise polyethylene glycol) methyl ether (meth)acrylate with average Mn of 300 to 480. (Meth) acrylate - poly(alkylene glycols) are known in the art and are commercially available. For example, polyethylene glycol)methyl ether acrylate and poly(ethylene glycol) methyl ether methacrylate are commercially available from various sources such as Millipore Sigma of St. Eouis, Missouri, USA (Sigma) and TCI America of Portland, Oregon, USA, and poly(ethylene glycol) methyl ether methacrylate compounds with molecular weights of 1,000 to 13,000 are commercially available from Fisher Scientific.
C) Additional (meth )acrylate monomer.
[0029] Starting material C) is a (meth) acrylate monomer, which is an optional additional reactant that may be used to make the Copolymer herein. Starting material C) has formula (VI):
Figure imgf000009_0002
each D2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, and each R4 is independently selected from H or methyl, each as described and exemplified above. Examples of suitable (meth)acrylate monomers include hydroxybutyl (meth)acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth)acrylate, all of which are known in the art and are commercially available, e.g., from BASF SE or Sigma. Alternatively, C) the additional (meth)acrylate monomer may comprise hydroxyethylmethacrylate.
[0030] Starting materials A) and B), and C), when present described above are the reactants used in amounts to provide the Copolymer with the amounts of silicone moieties and pendant (meth)acrylate polyether moieties and the units thereof, described above.
D) Free Radical Initiator [0031] Starting material D) used in the method is a free radical initiator. Free radical initiators are known in the art and are exemplified by peroxides, azo compounds, peracids, and peresters. The peroxide may be an organic peroxide or a hydroperoxide, such as benzoyl peroxide; 4- monochlorobenzoyl peroxide; t-butylperoctoate; t-butyl peroxybenzoate, tert-butylperoxybenzoate, tert-butyl cumyl peroxide, tert-butyloxide 2,5-dimethyl-2,5-di-tert-butylperoxyhexane; 2,4- dichlorobenzoyl peroxide; di-tertbutylperoxy-diisopropyl benzene; l,l-bis(tert-butylperoxy)-3,3,5- trimethylcyclohexane; 2,5-di-tert-butylperoxyhexane-3,2,5-dimethyl-2,5-bis(tert-butylperoxy) hexane; cumyl-tert-butyl peroxide; dicumyl peroxide; di-t-butyl peroxide; t-butyl hydroperoxide; cumene hydroperoxide; di-t-amyl peroxide; and combinations of two or more thereof.
Additionally, di -peroxide radical initiators may be used alone or in combination with other radical initiators. Such di-peroxide radical initiators include, but are not limited to, l,4-bis-(t-butyl peroxycarbo)cyclohexane; 1 ,2-di(t-butyl peroxy)cyclohexane; and 2,5-di(t-butyl peroxy)-3-hexyne. Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma.
[0032] The azo compound may be an aliphatic azo compound such as 1-t-amylazo-l- cyanocyclohexane; azo-bis-isobutyronitrile; and 1-t-butylazo-cy anocyclohexane; 2,2'-azo- bis-(2- methyl)butyronitrile; 2,2’ -azobis(2-methylpropionitrile); 2,2’ -azobis(2-methylpropionamidine) dihydrochloride; 2,2’-azobis(cyanovaleric acid); or a combination of two or more thereof. Azo compounds are known in the art and are commercially available, e.g., under the tradename VAZO™ WSP from The Chemours Company of Wilmington, Delaware, USA. Furthermore, peroxides and azo compounds are disclosed at paragraphs [0057] to [0063] of U.S. Patent Application Publication 2014/0287642. Initiators are also disclosed in U.S. Patent 5,202,190. Alternatively, the initiator used in the method described herein may be an azo compound, such as 2,2'-azobis(2-methylpropionitrile), which is commercially available from Sigma. The amount of free radical initiator depends on various factors including the type of initiator and reaction conditions, such as temperature, selected. Alternatively, the amount of initiator may be 0.1 wt% to 5 wt%, alternatively 0.4 wt% to 2 wt%, based on combined weights of starting materials A), B), and C).
E) Solvent
[0033] Starting material E) is a solvent that may optionally be used in the method described herein to dissolve or disperse one or more of the starting materials before and/or during step 1). For example, D) the free radical initiator may be dissolved in the solvent before or during mixing with the other starting materials, described herein. Suitable solvents may be organic solvents including aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin; hydrocarbon solvents such as industrial gasoline, petroleum benzene, and solvent naphtha; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutylketone, acetonylacetone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2- dimethoxy ethane, and 1,4-dioxane. Alternatively, the solvent may comprise a siloxane solvent such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; and mixtures thereof, which are commercially available from various sources such as Gelest, Inc. of Morrisville, Pennsylvania, USA and from Dow. The amount of solvent is not critical, and may be, for example 1 wt% to 99 wt% based on combined weights of starting materials A), B), C), D) and E).
Method of Use
[0034] The Copolymer described above is useful may find use in a myriad of end use applications and compositions. For example, the Copolymer may be used as a surfactant, wetting agent, formulation aid, and/or dispersant. The Copolymer may be useful as a defoamer for coatings, oil and gas applications and/or pulp and paper applications. Furthermore, the Copolymer may be useful as an additive for adjusting adhesion and/or release force in paper coatings such as pressure sensitive adhesive and/or release coating compositions. The Copolymer may be added to compositions such as coating compositions, pressure sensitive adhesive compositions, and/or release coating compositions by any convenient means such as mixing at RT.
[0035] Alternatively, the Copolymer may be added to a pressure sensitive adhesive composition, such as that disclosed in U.S. Patent Application Publication 2022-0056317, U.S. Patent App Pub 2022-0073800, U.S. Patent Application Publication 2023-0103925 or PCT Publication WO2022/066261, in addition to, or instead of, the silicone - (meth)acrylate copolymer described therein. Alternatively, the Copolymer described herein may be added to a coating composition such as that disclosed in U.S. Patent Application Publication 2023-0086870, U.S. Patent Application Publication 2023-0042417, or PCT Publication W02021/020365 in addition to, or instead of the silicone - (meth) acrylate copolymer described therein. Alternatively, the Copolymer described herein may be used in a personal care composition, such as that described in U.S. Patent 8,258,243 or PCT Publication WO2022/093497 in addition to, or instead of, the silicone - (meth)acrylate copolymer described therein.
EXAMPLES [0036] These examples are provided to illustrate the invention to one skilled in the art and are not to be construed as limiting the scope of the invention set forth in the claims. Starting materials used in the examples are summarized below in Tables 1, 2, and 4.
Table 1 - Starting Materials for Synthesis of Mercapto-Functional Siloxanes
Figure imgf000012_0002
[0037] In Table 1, 3-mercaptopropylmethyldimethoxysilane had formula:
Figure imgf000012_0001
[0038] In this Synthesis Example 1, a mercapto-functional siloxane was prepared as follows:
Figure imgf000013_0001
367.0 g of silanol-terminated PDMS, 40.1 g of hexamethyldisiloxane (HMDS), 73.0 g of 3- mercaptopropylmethyldimethoxysilane (MPMDMS), 16.6 g of deionized (DI) water, and 95.8 g of heptane were charged into a 1000 mL 4-neck flask equipped with a mechanical stirrer, a thermocouple, a Dean-Stark trap equipped with a condenser and N2 outlet to a bubbler. The flask was purged with N2 for 3 minutes (at a flow rate of 2 L per min), after which time a heating block was used to heat the reaction mixture. When the reaction mixture reached 60 °C, 0.6 mL of trifluoromethane sulfonic acid was added. A liquid began to collect in the Dean-Stark trap when the reaction mixture reached approximately 78 °C. After 45 minutes at ~78 °C 12.0 g of liquid had been collected. At this time, 20.0 g of DI water was added to the reactor. The temperature of the reaction mixture rose as additional liquid was observed to collect in the Dean-Stark trap. After approximately 4 hours, the pot temperature had risen to approximately 122 °C, and no additional liquid was observed collecting in the Dean-Stark trap. The heating block was removed and 24.0 g of CaCCL was added to the reactor at the point when the reaction mixture reached 70 °C. The mixture was then stirred overnight at RT °C. After cooling to room temperature, the reaction mixture was filtered through a 0.45 pm nylon membrane. Volatile species were evacuated under reduced pressure using a rotary evaporator with a heating bath set to 100 °C and a pressure of ~1 torr for 1.5 hour. 376.4 g of clear liquid was obtained. The resulting mercapto-functional PDMS was used in copolymer synthesis, described below.
Table 2 - Starting Materials for Copolymer Synthesis.
Figure imgf000014_0003
[0039] In Table 2, above, HEMA has formula
Figure imgf000014_0001
480 has formula
Figure imgf000014_0002
sufficient to provide PEGA-480
Figure imgf000015_0001
sufficient to provide PEGMA-300 with Mn = 300 Da. Each Mercapto-functional PDMS in Table 2 has the
Figure imgf000015_0002
x and y are as shown above in Table 2, and where the difunctional units with subscripts x and y are not necessarily in blocks, but may be randomly or semi-randomly distributed in the polydiorganosiloxane.
[0040] In this Synthesis Example 2, Copolymers were prepared. The following is a representative example for the synthesis of sample “4- A”. Mercapto-functional PDMS GP-367 (15.0 g), PEG- acrylate (12.0 g), HEMA (3.0 g), and EtOAc (75.0 g) were added to a glass reactor outfitted with a thermocouple, N2 inlet, condenser, and stainless steel impeller. The reactor contents were stirred at 150 RPM. The reactor contents were sparged with N2 for 15 mins at room temperature while stirring at 150 RPM. AIBN (0.80 g) was added to the reactor. The reactor contents were then placed under a N2 blanket, and heated from 25 °C to 65 °C over 30 mins, while stirring at 250 RPM. The reactor contents were then stirred for 6 hrs at 65 °C. After cooling to RT, the reactor contents were evacuated under reduced pressure on a rotary evaporator, and then transferred to a pear-shaped flask equipped with a stir bar and placed in a water bath at 50 °C. The contents of the flask were stirred vigorously, and placed under high vacuum (~50 milliTorr, 6.67 Pa) for ~4 hr. The contents of the flask were then left overnight under high vacuum at RT and collected for use. Additional samples were made using modifications to this procedure, by varying the relative composition of starting materials, as listed in Table 3.
Table 3 - Silicone, polyether, (meth)acrylate copolymers prepared according to the procedure of Synthesis Example 2.
Figure imgf000016_0001
[0041] In Table 3, above, % Silicone refers to the weight % of Mercapto-functional PDMS used based on combined weights of Mercapto-functional PDMS, PEG(M)A, and HEMA used to prepare the copolymer. %PEG(M)A refers to the weight % of polyethylene glycol (meth) acrylate based on combined weights of Mercapto-functional PDMS, PEG(M)A, and HEMA used to prepare the copolymer.
Industrial Applicability [0042] The method for manufacturing the Copolymer described herein provides the benefit of being capable of producing Copolymer species with varying amounts of silicone and pendant (meth)acrylate - polyether moieties, as well as varying amounts of (meth)acrylate - poly(alkylene glycol) and additional (meth) acrylate monomer units in the pendant (meth) acrylate - poly ether moiety. Furthermore, the method for manufacturing the Copolymer described herein may minimize or avoid the generation of aldehyde by-products, such as formaldehyde, resulting in improved foam formulations over foam formulations containing SPEs with formaldehyde impurities.
Definitions and Usage of Terms
[0043] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated. The SUMMARY and ABSTRACT are hereby incorporated by reference. The transitional phrases “comprising”, “consisting essentially of’, and “consisting of’ are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., II., and III. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. The abbreviations used herein have the definitions in
Table 9.
Table 9 - Abbreviations
Figure imgf000017_0001

Claims

Claims:
1. A silicone - (meth) acrylate - poly ether copolymer comprising a linear backbone comprising a silicone moiety having a mercapto- alkyl linker and a pendant (meth)acrylate - polyether moiety, where the mercapto-alkyl linker comprises a sulfur atom covalently bonded to an alkyl group, where the alkyl group in the linker is covalently bonded to a silicon atom in the silicone moiety, and where the sulfur atom in the linker is covalently bonded to a (meth)acrylate group of the pendant (meth)acrylate - polyether moiety.
2. The copolymer of claim 1 , where the copolymer comprises 20 wt % to 90 wt % of the silicone moiety, and 10 wt % to 80 wt % of the pendant (meth) acrylate - polyether moiety, each based on combined weights of reactants used to make the copolymer.
3. The copolymer of claim 1 or claim 2, where the pendant (meth) acrylate - polyether moiety comprises a (meth)acrylate poly(alkylene glycol) unit and a (meth)acrylate monomer unit.
4. The copolymer of claim 3, where the pendant (meth)acrylate - polyether moiety comprises 70 wt% to < 100 wt% of the (meth)acrylate poly(alkylene glycol) unit and > 0 to 30 wt% of the (meth)acrylate monomer unit.
5. A silicone - (meth) acrylate - poly ether copolymer comprising unit formula: (R12SiO2/2)x(R1R2SiO2/2)y(R13SiOi/2)z, where subscripts x, y, and z each represent average numbers of each unit in the unit formula, and subscripts x, y, and z have average values such that z = 2, x = 1 to 1,000, and y = 1 to 100, each R1 is an independently selected alkyl group of 1 to 10 carbon atoms; each R2 is an independently selected group of formula:
-D'-S-R10, where each D1 is an independently selected alkane-diyl group of 1 to 16 carbon atoms, and
R10 has formula
Figure imgf000019_0001
each R3 is an endblocker for a poly(meth)acrylate chain, each R4 is independently selected from H or methyl, each D2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, each subscript n is independently 1 to 25, each R5 is independently selected from H and an alkyl group of 1 to 4 carbon atoms, each subscript w is independently > 0 to 20, and with the provisos that in at least one instance of R10, per molecule, subscript n is 5 to 25.
6. The copolymer of claim 5, where R2 comprises formula:
Figure imgf000019_0002
D1, R3, R4, D2, and R5 are as described above, subscripts a and b represent average values of each unit in the formula, subscript a is 0 to 10, subscript b is > 0 to 10, and a quantity 0 < (a + b) < 20 , and with the proviso that units with subscripts a and b may have a random distribution; and each subscript n’ is independently 5 to 25.
7. The copolymer of claim 6, where R1 is methyl, D1 has empirical formula -C3H6-, R5 is hydrogen or methyl, D2 has empirical formula -C2H4-, and subscript n’ is 6 to 20.
8. The copolymer of any one of claims 5 to 7, where subscript x is 20 to 90; subscript y is 2 to 8.
9. The copolymer of any one of claims 1 to 8, wherein the copolymer has a random distribution of pendant groups.
10. A method of making the copolymer of any one of claims 1 to 9, wherein the method comprises: 1) combining, under conditions to effect free radical polymerization reaction, starting materials comprising
20 wt % to 90 wt%, based on combined weights of starting materials A), B), and C), of A) a mercapto-functional siloxane comprising unit formula: (R1 2SiO2/2)x(R1R9SiO2/2)y(R13SiOi/2)z, where subscripts x, y, and z each represent average numbers of each unit in the unit formula, and subscripts x, y, and z have average values such that z = 2, x = 1 to 1,000, and y = 1 to 100, each R1 is an independently selected alkyl group of 1 to 10 carbon atoms; and each R9 is an independently selected mercapto-alkyl group of formula -D'SH, where each D1 is an independently selected alkane-diyl group of 1 to 16 carbon atoms;
10 wt% to 80 wt%, based on combined weights of starting materials A), B), and C), of B) a
(meth) acrylate - poly(alkylene glycol) of formula
Figure imgf000020_0001
where each R5 is independently selected from H and an alkyl group of 1 to 4 carbon atoms, each D2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, each R4 is independently selected from H or methyl, and subscript n’ is 5 to 25;
0 to 30 wt%, based on combined weights of starting materials A), B), and C), of C) a
(meth) acrylate monomer of formula
Figure imgf000021_0001
each D2 is independently selected alkane-diyl group of 2 to 4 carbon atoms, and each R4 is independently selected from H or methyl;
D) a free radical initiator; and optionally E) a solvent.
11. The method of claim 10, where B) the (meth) acrylate - poly(alkylene glycol) comprises polyethylene glycol) methyl ether (meth)acrylate with average Mn of 300 to 480.
12. The method of claim 10 or claim 13, where C) the additional (meth)acrylate monomer is present in an amount > 0 wt% to 10 wt%, based on combined weights of starting materials A), B), and C).
13. Use of the copolymer of any one of claims 1 to 9 in a personal care composition.
14. Use of the copolymer of any one of claims 1 to 9 as a film forming agent.
15. Use of the copolymer of any one of claims 1 to 9 in a pressure sensitive adhesive composition or a release coating composition.
PCT/US2024/021023 2023-05-23 2024-03-22 Silicone - (meth)acrylate - polyether copolymer and synthesis method WO2024242750A1 (en)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5202190A (en) 1989-08-14 1993-04-13 Minnesota Mining And Manufacturing Company Method of making vinyl-silicone copolymers using mercapto functional silicone chain-transfer agents and release coatings made therewith
US20110230619A1 (en) * 2010-02-22 2011-09-22 Evonik Goldschmidt Gmbh Nitrogen-Containing Organosilicon Graft Copolymers
US8258243B2 (en) 2007-04-27 2012-09-04 3M Innovative Properties Company Grafted silicone polymer and products made therewith
US20140287642A1 (en) 2010-12-29 2014-09-25 3M Innovative Properties Company Low adhesion backsize for silicone adhesive articles and methods
US20150011671A1 (en) * 2012-03-22 2015-01-08 Anubhav Saxena Organo-modified silicone polymers and hydrogels comprising the same
WO2021020365A1 (en) 2019-07-29 2021-02-04 京セラ株式会社 Coated tool, and cutting tool comprising same
CN113402681A (en) * 2021-06-24 2021-09-17 中科院广州化学有限公司 Mercapto-containing organic silicon modified styrene-acrylic emulsion and preparation method and application thereof
US20220056317A1 (en) 2019-03-14 2022-02-24 Dow Silicones Corporation Polyorganosiloxane having poly(meth)acrylate groups and methods for the preparation and use thereof
WO2022066261A1 (en) 2020-09-22 2022-03-31 Dow Silicones Corporation Curable silicone-(meth)acrylate composition and methods for its preparation and use
WO2022093497A1 (en) 2020-10-28 2022-05-05 Dow Silicones Corporation Silicon -(meth)acrylate copolymer and methods for its preparation and use in personal care compositions
US20230042417A1 (en) 2019-12-31 2023-02-09 Dow Silicones Corporation Method of preparing silicone-acrylate hybrid composition and hybrid composition formed thereby
US20230086870A1 (en) 2020-01-22 2023-03-23 Dow Silicones Corporation Silicone-acrylate polymers, copolymers, and related methods and compositions
US20230103925A1 (en) 2020-04-20 2023-04-06 Dow Silicones Corporation Polyorganosiloxane hybrid pressure sensitive adhesive and methods for the preparation and use thereof

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5202190A (en) 1989-08-14 1993-04-13 Minnesota Mining And Manufacturing Company Method of making vinyl-silicone copolymers using mercapto functional silicone chain-transfer agents and release coatings made therewith
US8258243B2 (en) 2007-04-27 2012-09-04 3M Innovative Properties Company Grafted silicone polymer and products made therewith
US20110230619A1 (en) * 2010-02-22 2011-09-22 Evonik Goldschmidt Gmbh Nitrogen-Containing Organosilicon Graft Copolymers
US20140287642A1 (en) 2010-12-29 2014-09-25 3M Innovative Properties Company Low adhesion backsize for silicone adhesive articles and methods
US20150011671A1 (en) * 2012-03-22 2015-01-08 Anubhav Saxena Organo-modified silicone polymers and hydrogels comprising the same
US20220056317A1 (en) 2019-03-14 2022-02-24 Dow Silicones Corporation Polyorganosiloxane having poly(meth)acrylate groups and methods for the preparation and use thereof
US20220073800A1 (en) 2019-03-14 2022-03-10 Dow Silicones Corporation Polyorganosiloxane hybrid pressure sensitive adhesive and methods for the preparation and use thereof
EP3938426B1 (en) * 2019-03-14 2023-01-11 Dow Silicones Corporation Polyorganosiloxane hybrid pressure sensitive adhesive and methods for the preparation and use thereof
WO2021020365A1 (en) 2019-07-29 2021-02-04 京セラ株式会社 Coated tool, and cutting tool comprising same
US20230042417A1 (en) 2019-12-31 2023-02-09 Dow Silicones Corporation Method of preparing silicone-acrylate hybrid composition and hybrid composition formed thereby
US20230086870A1 (en) 2020-01-22 2023-03-23 Dow Silicones Corporation Silicone-acrylate polymers, copolymers, and related methods and compositions
US20230103925A1 (en) 2020-04-20 2023-04-06 Dow Silicones Corporation Polyorganosiloxane hybrid pressure sensitive adhesive and methods for the preparation and use thereof
WO2022066261A1 (en) 2020-09-22 2022-03-31 Dow Silicones Corporation Curable silicone-(meth)acrylate composition and methods for its preparation and use
WO2022093497A1 (en) 2020-10-28 2022-05-05 Dow Silicones Corporation Silicon -(meth)acrylate copolymer and methods for its preparation and use in personal care compositions
CN113402681A (en) * 2021-06-24 2021-09-17 中科院广州化学有限公司 Mercapto-containing organic silicon modified styrene-acrylic emulsion and preparation method and application thereof

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