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WO2025072586A1 - Agents de transfert de chaîne et leurs procédés de préparation - Google Patents

Agents de transfert de chaîne et leurs procédés de préparation Download PDF

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Publication number
WO2025072586A1
WO2025072586A1 PCT/US2024/048751 US2024048751W WO2025072586A1 WO 2025072586 A1 WO2025072586 A1 WO 2025072586A1 US 2024048751 W US2024048751 W US 2024048751W WO 2025072586 A1 WO2025072586 A1 WO 2025072586A1
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Prior art keywords
chain transfer
meth
homocysteine
polymer
water
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Sangwoo Park
Jean-Christophe LEC
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Arkema Inc
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Arkema Inc
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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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • 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
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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

Definitions

  • the invention is related to molecular weight regulation of polymers using thiofunctional chain transfer agents.
  • U.S. Patent No. 5,298,585 discloses polymers having amine sulfide terminal moieties. Amine thiols are used as chain transfer agents.
  • chain transfer agents useful for providing low odor or no odor, low molecular weight water soluble or water swellable polymers, especially homo- and copolymers of (meth)acrylamide and/or derivatives thereof and homo- and co-polymers of (meth)acrylic acid and/or derivatives thereof.
  • chain transfer reagents especially homo- and copolymers of (meth)acrylamide and/or derivatives thereof and homo- and co-polymers of (meth)acrylic acid and/or derivatives thereof.
  • homocysteine and certain derivatives thereof can be excellent chain transfer agents for preparation of low molecular weight homo- and co-polymers of (meth)acrylamide and/or derivatives thereof and homo- and co-polymers of (metli/eth/prop)acrylic acid and/or acidic derivatives thereof.
  • homocysteine and certain of its derivatives can perform significantly better as chain transfer agents than other similar thiol-functional chain transfer agents.
  • cysteine which differs from homocysteine by merely a single methylene is typically not as effective a chain transfer reagent as homocysteine.
  • homocysteine when used as a chain transfer agent, does not impart unpleasant, nor indeed any, odor to the resulting polymer in appropriate quantities.
  • Aqueous (solution/emulsion) polymerization of (meth)acrylamide and derivatives thereof is a well-known procedure to produce low molecular weight poly(meth)acrylamide to date.
  • Chain transfer agents such as sodium hypophosphite have been used to control molecular weight of these polymers.
  • Mercaptans may be useful chain transfer agents that are comparable to sodium hypophosphite for producing low molecular weight polymers, especially polyacrylamide, but the sulfur-containing nature of mercaptan compounds can tend to provide polymer having an unpleasant odor.
  • homocysteine is typically an odor-free component. Therefore, free-radical polymerized polymers with odor sensitive applications may be beneficially produced using homocysteine as a chain transfer agent.
  • homocysteine could be useful when phosphorous and its derivatives are undesirable for the final application of the polymer.
  • L-homocysteine, D-homocysteine or a D/L homocysteine mixture (such as a racemic mixture), or derivatives thereof may be suitable as chain transfer agent(s) for poly((meth/eth/prop)acrylic acid) or acidic derivatives thereof in order to reduce the molecular weight of these polymers.
  • a polymer including a residue of a chain transfer agent and a polymerized monomer is described.
  • the monomer can include: (meth)acrylamide or derivative thereof, (meth/eth/prop)acrylic acid or acidic derivative thereof, or any combination thereof.
  • the chain transfer agent can advantageously be water-compatible (e.g., water soluble or water miscible).
  • the chain transfer agent can include homocysteine or derivatives thereof; C2-C 18 mono- and di- thiols; C3-C 12 ethylene glycol-based mono- and di- thiols; thioglycolic acid or derivative thereof; compounds of Formula (I) (below'); or any combination thereof.
  • At least one polymer terminal end of the polymer can include the residue of the chain transfer agent.
  • a link between the polymer terminal end and the residue of the chain transfer agent can include a sulfur atom (S).
  • a method of preparing a polymer is also provided.
  • the method can include the following steps:
  • Monomer comprising (meth)acrylamide or derivative thereof; (meth/eth/prop)acrylic acid or acidic derivative thereof ; or combination thereof;
  • a water compatible chain transfer agent comprising at least one of homocysteine or derivatives thereof; C2-C18 mono- and di- thiols; C3-C10 ethylene glycol-based mono- and di- thiols; thioglycolic acid or derivative thereof; compounds of Formula (I); and a combination thereof; and
  • the polymer thus formed can include the (meth)acrylamide or derivative thereof; (meth)acrylic acid or derivative thereof; or combination thereof as polymerized monomer, and a residue of the chain transfer agent.
  • At least one polymer terminal end of the polymer can include the residue of the chain transfer agent, wherein a link between the polymer terminal end and the residue of the chain transfer agent can include a sulfur atom (S).
  • Figure 1 shows a reactor set up for polymerization
  • Figure 2 shows an NMR spectrum used for determining monomer conversion in Example 1
  • Figure 3 shows GPC results of polyacrylamide produced without chain transfer agent (Example 1, run 5) compared to polyacrylamide produced with L -homocysteine as chain transfer reagent (Example 1, run 8);
  • Figure 4 shows the plot of the Mayo equation used to determine the chain transfer constant for L-homocysteine
  • Figure 5 shows the GPC chromatograms of polyacrylamides prepared in Example 2.
  • Figure 6 shows the number average molecular weight of polyacrylamide prepared using various levels of L-homocysteine.
  • Figure 7 shows 1 H NMR spectra of L-homocysteine (top) and polyacrylamide at various L-homocysteine loadings
  • Figure 8 shows 1 H NMR spectra of L-homocysteine (top), as reacted polyacrylamide (middle) and purified polyacrylamide (bottom).
  • the present disclosure is directed to the use of certain chain transfer agents to form low molecular weight polymers. It has been found that homocysteine can be used in relatively large amounts as an effective chain transfer agent to provide relatively low molecular weight polymers. Poly(meth)acrylamide and co-polymers thereof can particularly advantageously be formed. The present disclosure is also directed to methods of preparing polymers, especially poly (meth)acrylamide and co-polymers thereof, as well as poly(meth/eth/prop)acrylic acid and acidic derivatives thereof.
  • a polymer comprising a residue of a chain transfer agent and a polymerized monomer is described herein.
  • the monomer to be polymerized can include: (meth)acrylamide or derivative thereof, (meth/eth/prop)acrylic acid or acidic derivatives thereof, or any combination thereof.
  • the chain transfer agent can be water-compatible (e.g. , water soluble or water miscible). Additionally or alternatively, the polymer itself can be water-compatible.
  • water soluble should be understood to mean resulting in no suspended or settled particulates when combined with essentially pure distilled water at room temperature -20-25°C, as determined by human visual observation after stirring for -60 minutes at -500 rpm and after remaining quiescent thereafter for -5 minutes.
  • water miscible should be understood to mean resulting in no settled particulates when combined with (a) essentially pure distilled water, or (b) a single phase of distilled water combined with up to 50 wt% of a cosolvent having a dielectric constant (relative permittivity) of at least 4.0, at room temperature ⁇ 20-25°C, as determined by human visual observation after stirring for -60 minutes at -500 rpm and after remaining quiescent thereafter for -5 minutes.
  • a cosolvent having a dielectric constant (relative permittivity) of at least 4.0, at room temperature ⁇ 20-25°C, as determined by human visual observation after stirring for -60 minutes at -500 rpm and after remaining quiescent thereafter for -5 minutes.
  • water compatible encompasses at least “water soluble” and “water miscible”, potentially as well as other situations in which (i) both initiation and propagation can occur in a medium comprising at least 1 wt% of water, and (ii) chain transfer by functional mercaptan CTAs in such a medium is sufficient/effective to control polymer molecular weight.
  • the chain transfer agent can include homocysteine or derivatives thereof; compounds according to Formula (I) herein; C2-C18 mono- and di- thiols; C3-C12 ethylene glycol-based mono- and di- thiols; thioglycolic acid or derivative thereof; or any combination thereof (in particular, homocysteine, derivatives thereof, and compounds according to Formula (I)).
  • At least one polymer terminal end of the polymer can include the residue of the chain transfer agent.
  • the chain transfer agent can comprise substantially no, or no intentionally added, C2-C18 mono- and di- thiols, C3-C12 ethylene glycol-based mono- and di- thiols, thioglycolic acid or derivative thereof, cysteine, or acetylcysteine.
  • a link between the polymer terminal end and the residue of the chain transfer agent can advantageously include a sulfur atom (S).
  • a method of preparing a (e.g, water-compatible) polymer is also provided.
  • the method includes the steps:
  • a water compatible chain transfer agent comprising at least one of homocysteine or derivative thereof; a compound according to Formula (I); C2-C18 mono- and di- thiols; C3-C 10 ethylene glycol-based mono- and di- thiols; thioglycolic acid or derivative thereof; or a combination thereof (in particular, homocysteine, a derivative thereof, and/or a compound of Formula(I); additionally or alternatively, comprising substantially no, or no intentionally added, C2-C18 mono- and di- thiols, C3-C12 ethylene glycol-based mono- and di- thiols, thioglycolic acid or derivative thereof, cysteine, or acetylcysteine); and
  • An optional carrier preferably comprising water.
  • the next step is reacting the reaction mixture to form the (e.g, water-compatible) polymer.
  • reaction is referred to herein as the “next step,” it is both possible and contemplated for the combination step to overlap the reaction step, instead of serially following completion of the combination step, such as in (semi-)continuous reactors and/or where portions of one or more of initiator, monomer, and/or chain transfer agent (and/or optionally also carrier) may be added after reaction begins (but typically before it is complete).
  • the (e.g. , water-compatible) polymer thus formed can include the (meth)acrylamide or derivative thereof; (meth/eth/prop)acrylic acid or acidic derivative thereof; or combination thereof as polymerized monomer, and a residue of the chain transfer agent.
  • At least one polymer terminal end of the polymer can include the residue of the chain transfer agent, wherein a link between the polymer terminal end and the residue of the chain transfer agent can include a sulfur atom (S).
  • Suitable chain transfer agents can be water-compatible (typically water soluble or water miscible).
  • the chain transfer agent can include at least one of homocysteine or derivatives thereof; C2-C18 mono- and di- thiols; C3-C12 ethylene glycol-based mono- and di- thiols such as 1,8- dimercapto-3,6-dioxaoctane; thioglycolic acid or derivatives thereof; and compounds of Formula
  • R 1 and R 7 are identical or different, and are selected from: a hydrogen atom; or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more heteroatoms (but, when n 1, preferably wherein neither R 1 nor R 7 are acetyl groups or in particular wherein neither R 1 nor R 7 form an amide group with the attached nitrogen);
  • R 2 is selected from: (i) absent when X represents -CN, (ii) a hydrogen atom, (iii) -OR 3 , where: R 3 is a hydrogen atom; or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more
  • Formula (I) is homocysteine.
  • X >C-O
  • n 1
  • Formula (I) is cysteine.
  • the chain transfer agent can advantageously include homocysteine or derivative thereof, specifically L-homocysteine, D-homocysteine, or racemic mixtures of homocysteine.
  • homocysteine or derivative thereof specifically L-homocysteine, D-homocysteine, or racemic mixtures of homocysteine.
  • at least L-homocysteine can be present.
  • Chemical derivatives of homocysteine can be useful as chain transfer agent, according to some embodiments.
  • Non-limiting examples include converting the COOH to NH2 or other functional groups, for example according to Formula I.
  • the chain transfer agent can comprise substantially no, or no intentionally added, C2-C18 mono- and dithiols, C3-C12 ethylene glycol-based mono- and di- thiols, thioglycolic acid or derivative thereof, cysteine, or acetylcysteine.
  • Cysteine, homocysteine, and the other mercaptans of Formula (I) are referred to as functionalized mercaptans, because, in addition to the -SH moiety, they also comprise at least one amine moiety, such as -NR 1 R 7 .
  • n can be from 1 to 3, for example 1 or 2, or 2 or 3. or in particular n can be 2;
  • R 2 can be OR 3 , and R 3 may be a hydrogen atom or a linear or branched, saturated hydrocarbon moiety of 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, optionally comprising one or more heteroatoms, or in particular R 3 may be H: and
  • R 1 and R 7 may individually be a hydrogen atom or a linear or branched, saturated hydrocarbon moiety of 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, optionally comprising one or more heteroatoms (but typically not so as to form an amide group with the attached nitrogen atom and preferably not comprising an acetyl group), or in particular R 1 and R 7 are both H,
  • Formula (I) does not include cysteine or acetylcysteine.
  • mixtures of chain transfer agents in combination with the chain transfer agent homocysteine and/or its derivatives as described above are contemplated.
  • combinations of homocysteine with l,8-dimercapto-3,6-dioxaoctane can be used to achieve acceptable chain transfer activity.
  • other water-soluble chain transfer agents may be used in combination with the homocysteine and/or its derivatives or in combination with one or more compounds according to Formula (I).
  • Non-limiting examples of chain transfer agents that may be blended in this way can include thioglycolic acid, C2-C 18 mono- and di- thiols: C3-C12 ethylene glycol-based mono- and di- thiols such as l,8-dimercapto-3,6- dioxaoctane; optionally sodium hypophosphite; or combinations thereof.
  • the chain transfer agent may include at least 10, 20, 30, 40, 50, 60, 70, 80, or at least 90 % by weight of homocysteine and/or a derivative thereof. According to some embodiments, the chain transfer agent includes at least 10, 20, 30, 40, 50, 60, 70, 80, or at least 90 % by weight of homocysteine. According to some embodiments, the chain transfer agent includes at least 10, 20, 30, 40, 50, 60, 70, 80, or at least 90 % by weight of L- homocysteine and/or a derivative thereof. According to some embodiments, the chain transfer agent includes at least 10, 20, 30, 40, 50, 60, 70, 80, or at least 90 % by weight of L-homocysteine.
  • the chain transfer agent may include at most 100%, 90, 80, 70, 60, 50, 40, 30, or at most 20 % by weight of homocysteine and/or a derivative thereof. According to some embodiments, the chain transfer agent may include at most 100%, 90, 80, 70, 60, 50, 40, 30, or at most 20 % by weight of homocysteine. According to some embodiments, the chain transfer agent may include at most 100%, 90, 80, 70, 60, 50, 40, 30, or at most 20 % by weight of L-homocysteine and/or a derivative thereof. According to some embodiments, the chain transfer agent may include at most 100%, 90, 80, 70, 60, 50, 40, 30, or at most 20 % by weight of L-homocysteine.
  • the chain transfer agent does not include cysteine. Additionally or alternatively, the chain transfer agent can comprise substantially no, or no intentionally added, C2-C18 mono- and di- thiols, C3-C12 ethylene glycol-based mono- and dithiols, thioglycolic acid or derivative thereof, cysteine, or acetylcysteine.
  • the monomer(s) can include at least one of (meth/eth/prop)acrylamide or derivative thereof, (meth/eth/prop)acrylic acid or acidic derivatives thereof, C1-C18 alkyl (meth/eth/prop)acrylates, hydroxy-functional C1 -C18 alkyl (meth/eth/prop)acrylates, and any combination thereof.
  • the monomer(s) can advantageously include (meth)acrylamide, (meth)acrylic acid, Cl -Cl 4 alkyl (meth)acrylates, and/or hydroxy-functional C1-C6 alkyl (meth)aciylates.
  • Nonlimiting examples of suitable derivatives of (meth/eth/prop)acrylamide can include acrylamide, methacrylamide, phosphoalkyl (meth/eth/prop)acrylamides N-(3- dimethylaminopropyl)acrylamide, N-(3-dimethylaminopropyl)-methacrylamide, N- dimethylaminoethylacrylamide, N-diethylaminoethyl-methacry lamide, N- diethylaminoethylacrylamide, N -diethy laminoethy 1-methacry lamide, N-(4 morpho linomethy 1 )acry lamide , N-(4 morpholinomethyl)methacrylamide, N-[3-(l,3- diazacryclohexan)-2-one-propyl]methacrylamide, and combinations thereof.
  • hydroxy-functional Cl- C18 alkyl (meth/eth/prop)acrylates, and combinations thereof may be polymerized itself/copolymerized themselves, or may be copolymerized with one or more other co-monomers, to form a (di-, tri-, multi-) block, alternating, random, gradient, branched, linear, crosslinked, grafted, syndiotactic, isotactic, atactic, and/or other type of copolymer.
  • Non-limiting examples of such other co-monomers can include styrene or derivatives thereof; acrylonitrile or derivatives thereof; other vinylic esters: or combinations thereof.
  • Additional and/or alternative non-limiting examples of suitable co-monomers can include other vinyl monomers, e.g., vinyl cyanide monomers/acrylonitrile, vinyl alcohol, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, n-butylacrylate, n- butylmethacrylate, tert-butylacrylate, tert-butylmethacrylate, n-pentyl acrylate, n-pentyl methacrylate, isopen
  • comonomers can include maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid, 1, 4, 5, 6,7,7- hexachloro-5-norbomene-2,3-dicarboxylic acid, succinic acid, 2,6-naphthalenedicarboxylic acid, glutaric acid, sebacic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- cyclohexanedicarbocylic acid, full and/or partial hydrocarbonaceous (eg., alkyl) esters thereof, and combinations thereof.
  • hydrocarbonaceous eg., alkyl
  • the (e.g., water- compatible) polymer includes at least one terminal end and the at least one terminal end includes a residue of the chain transfer agent, wherein a link between the polymer terminal end and the residue of the chain transfer agent can advantageously include an S (sulfur) atom.
  • the polymer can include a molecular weight distribution containing at least one mode/peak having a number average molecular weight (Mn) of from 500 g/mol to 250,000 g/mol, in particular from 800 g/mol to 100.000 g/mol, from 800 g/mol to 8000 g/mol, or from 1000 g/mol to 5000 g/mol.
  • Mn number average molecular weight
  • the polymer molecular weight distribution can include at least one mode/peak having an Mn of at least 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4500, or 5000 g/mol, and additionally or alternatively can have an Mn of at most 250,000, 200,000, 150,000, 100,000, 75,000, 50.000, 25,000, 20.000, 15,000, 10,000, 8000, or 5000 g/mol.
  • the polymer can have a molecular weight distribution with two modes/peaks (bimodal), typically each of which modes can have an Mn within the range(s) disclosed, but at least one of which two modes can have an Mn within the range(s) disclosed).
  • the polymer can have a molecular weight distribution with more than two modes (polymodal).
  • polymodal at least one or at least two of the modes/peaks (but typically not all of the modes/peaks) can exhibit an Mn within the range(s) disclosed.
  • the polymer can include from 50wt% to 100wt%.
  • the polymer can further include, as polymerized monomer(s), in addition to the (meth)acrylamide, (meth)acrylic acid, alkyl (meth)acrylate, and/or hydroxyl-functional C1 -C18 alkyl (meth)acrylate, at least one of styrene or derivatives thereof; acrylonitrile or derivatives thereof; other vinylic esters; or combinations thereof.
  • polymerization reaction may proceed as shown below, using acrylamide as the exemplary propagating monomer.
  • radical initiator can activate L-homocysteine as shown below.
  • the reaction mixture may include from 500 ppm by weight (wppm) to 500,000 ppm by weight, such as from 10,000 wppm to 100,000 wppm, from 10,000 wppm to 50,000 wppm, or from 15,000 wppm to 30,000 wppm of the chain transfer agent, based on the weight of the monomers.
  • simple feeding of the chain transfer agent which may include homocysteine (such as L -homocysteine) or derivatives thereof, or compounds of Formula (I) as described above, may be used; i.e., the chain transfer agent may be added all at once at the initial polymerization stage.
  • continuous feeding of the chain transfer agent may be advantageous to controlling molecular weight of polymers.
  • any suitable aqueous/water-based polymerization technique may employ the chain transfer agents disclosed herein.
  • Non-limiting examples can include emulsion polymerization of alkyl (meth)acrylates, styrene, their derivatives, and/or mixtures thereof.
  • other polymerization systems e.g. , non- aqueous/solvent-based, as well as including other non- water-soluble monomers and/or forming other non-water-swellable polymer compositions
  • methods e.g, emulsion/suspension/latex polymerizations
  • Various polymerization processes such as batch, semi-batch, semi-continuous, and continuous processes may be suitable for using the chain transfer agents disclosed herein.
  • a range of temperatures may be used to produce the (e.g., water-compatible) polymers mediated by the chain transfer agents disclosed herein and/or including chain ends comprising (sulfur-containing) residues of the chain transfer agents disclosed herein.
  • the chain transfer agent(s) may be used to control the molecular weight of a radical initiated polymerization such as photopolymerization, thermally-activated radical polymerization, redox initiation, or free radical initiated polymerization.
  • various functional mercaptan chain transfer agent loadings may be used for controlling the molecular weight of (e.g., water-compatible) polymers.
  • loadings of ⁇ 3,000 wppm by weight ofthe monomer(s) may produce polymers having an Mn of approximately 100,000 g/mol.
  • Higher loadings of homocysteine or derivative thereof, e.g., ⁇ 10,000 wppm can further reduce molecular weight.
  • Any initiator suitable for radical -based polymerization may be used.
  • suitable initiators can include water-soluble/water-compatible azo initiators, peroxides, redox initiators, UV activated initiators, or combinations, complexes and/or reaction products thereof.
  • free radical initiators can include, but are not necessarily limited to, hydrogen peroxide, organic peroxides such as tert-butyl peroxide, alkali metal persulfates such as potassium peroxydisulfate (a.k.a. potassium persulfate), sodium peroxydisulfate (a.k.a. sodium persulfate), and lithium peroxy disulfate (a. k. a.
  • Nonlimiting examples azo initiators can include V-501 (4,4’-azobis(4-cyanovaleric acid)), VA-086 (2,2’-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]), VA-057 (2,2’-azobis[N-(2- carboxyethyl)-2-methylpropionamidine]tetrahydrate), V-50 (2,2’-azobis(2- methylpropionamidine)dihydrochloride), VA-061 (2,2-’azobis[2-(2-imidazolin-2-yl)propane]), VA-044 (2,2’-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride), or combinations thereof.
  • V-series and VA-series initiators listed herein are commercially available from Fujifilm Wako Chemicals of Richmond, VA (USA).
  • the amount of initiator may be chosen as desired for, among other things, a target polymer molecular weight, for example, from 0.01wt% to 3wt% or from 0.01wt% to lwt%, based on the total weight of monomer.
  • a reducing agent may be used in conjunction with an oxidant.
  • Reducing agents suitable for aqueous/water-based emulsion polymerization can include sulfites (e.g., alkali metal metabisulfite, hydrosulfite, and/or hyposulfite), ascorbic acid derivatives (including ascorbic acid, isoascorbic acid, or an alkali metal (iso)ascorbate salt), or the like, or combinations thereof.
  • the amount of reducing agent may be chosen as desired, for example, from 0.01wt% to 3wt% based on the total amount of monomer. In such redox systems, when desired/present.
  • oxidizing agents can include, for example, water-compatible oxidants such as hydrogen peroxide, alkali metal persulfates, perborates, peracetates, peroxides, and/or percarbonates, other inorganic (such as ammonia) persulfates, perborates, peracetates, peroxides, and/or percarbonates, and combinations thereof, optionally including a water-insoluble/water-immiscible oxidizing agent such as, for example, benzoyl peroxide, lauryl peroxide, t-butyl peroxide, t-butyl hydroperoxide, 2,2'- azobisisobutyronitrile, t-amyl hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, or the like, or a combination thereof.
  • the amount of oxidizing agent(s) may be collectively or individually chosen as desired, for example, from 0.01wt
  • the polymerization temperature can typically be from about 10°C to about 100°C. In the case of persulfate systems, the temperature may be from about 60°C to about 100°C. In redox systems, the temperature may be from about 30°C to about 100°C, such as from about 30°C to about 60°C or from about 30° C to about 45° C.
  • the carrier used in the polymerization may comprise or be water or an aqueous composition that is suitable to dissolve, disperse, or suspend the chain transfer agents.
  • the invention may include, but is not necessarily limited to, the following non-limiting embodiments.
  • Embodiment 1 A water-compatible polymer comprising: a residue of a chain transfer agent and a polymerized monomer comprising at least one of (meth/eth/prop)acrylamide or derivative thereof, (meth/eth/prop)acrylic acid or acidic derivative thereof.
  • R 1 and R 7 are identical or different, and are selected from: a hydrogen atom; or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more heteroatoms but not so as to form an amide group with attached nitrogen;
  • R 2 is selected from:
  • R 3 is a hydrogen atom; or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more heteroatoms, or (iv) NR 4 R 5 , where: R 4 and R 5 are identical or different, and are selected from: a hydrogen atom: or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more heteroatoms; and n is an integer from 1 to 4, provided that, when X is >C(-O), when R 2 is -OH, and when R 1 and R 7 are each hydrogen, n is not equal to 1 or 2.
  • Embodiment 2 The water-compatible polymer of embodiment 1, wherein the chain transfer agent comprises D-homocysteine, L-homocysteine, a derivative thereof, or a compound according to Formula I.
  • Embodiment 3 The water-compatible polymer of embodiment 1 or embodiment 2, wherein the chain transfer agent comprises homocysteine, in particular L-homocysteine.
  • Embodiment 4 The water-compatible polymer of any of embodiments 1-3, wherein the homocysteine comprises at least 90% L-homocysteine.
  • Embodiment 5 The water- compatible polymer of any of embodiments 1-4, wherein the chain transfer agent comprises no intentionally added C2-C 18 mono- and di- thiols, C3-C 12 ethylene glycol-based mono- and di- thiols, thioglycolic acid or derivative thereof, cysteine, or acetylcysteine.
  • Embodiment 6 The w'ater-compatible polymer of any of embodiments 1-5, wherein the polymer exhibits a molecular weight distribution comprising at least one mode having a number average molecular weight (Mn) from 500 g/mol to 250,000 g/mol, from 800 g/mol to 100,000 g/mol, from 800 g/mol to 8000 g/mol, or from 1000 g/mol to 5000 g/mol.
  • Mn number average molecular weight
  • Embodiment 7 The water-compatible polymer of any of embodiments 1-6, wherein the polymer molecular weight distribution is monomodal.
  • Embodiment 8 The water-compatible polymer of any of embodiment 1-7, wherein the polymer comprises from 50wt% to 100wt%, from 75wt% to 100wt%, from 90wt% to 100wt%, or about 100wt% of (meth)acrylamide, (meth)acrylic acid, Cl -Cl 4 alkyl (meth)acrylate, hydroxy-functional C 1-C6 alkyl (meth)acrylate, or a combination thereof, as a polymerized monomer by total weight of the polymer, excluding the terminal end.
  • Embodiment 10 A method of preparing a water-compatible polymer comprising: combining to form a reaction mixture: at least one monomer comprising (meth/eth/prop)acrylamide or derivative thereof; (meth/eth/'prop)acrylic acid or acidic derivative thereof; C1 -C18 alkyl (meth/eth?prop)acrylate; hydroxyl-functional C1 -C18 alkyl (meth/eth/prop)acrylate, or a combination thereof; a free-radical initiator; a water compatible chain transfer agent comprising at least one of homocysteine or derivative thereof; C2-C12 dithiols; C3-C10 ethylene glycol-based dithiols; thioglycolic acid or derivative thereof; a compound of Formula (I); or a combination thereof:
  • R 1 and R 7 are identical or different, and are selected from: a hydrogen atom; or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more heteroatoms but not so as to form an amide group with attached nitrogen;
  • R 2 is selected from:
  • R 3 is a hydrogen atom; or an aromatic or nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety of 1 to 20 carbon atoms optionally comprising one or more heteroatoms, or
  • R 7 are each hydrogen, n is not equal to 1 or 2; and an optional carrier, preferably comprising water; and reacting the reaction mixture to form a water-compatible polymer, wherein the water-compatible polymer comprises the at least one monomer comprising ((meth/eth/prop)acrylamide or derivative thereof: (meth/eth/prop)acrylic acid or acidic derivative thereof; C1 -C18 alkyl (meth/eth/prop)acrylate; hydroxyl -functional C1 -C18 alkyl (meth/eth/prop)acrylate, or a combination thereof, as polymerized monomer, and a residue of the chain transfer agent; and wherein at least one terminal end of the water-compatible polymer comprises the residue of the chain transfer agent, wherein a link between the polymer terminal end and the residue of the chain transfer agent comprises a sulfur atom.
  • the water-compatible polymer comprises the at least one monomer comprising ((meth/eth/prop)acrylamide or derivative thereof: (meth/eth
  • Embodiment 11 The method of embodiment 10, wherein the chain transfer agent comprises D-homocysteine, L-homocysteine, a derivative thereof, or a compound according to Formula I:
  • Embodiment 12 The method of embodiment 10 or embodiment 11, wherein the chain transfer agent comprises homocysteine, in particular L-homocysteine.
  • Embodiment 13 The method of any of embodiments 10-12, wherein the homocysteine comprises at least 90% L-homocysteine.
  • Embodiment 16 The method of any of embodiments 10-15, wherein the polymer molecular weight distribution is monomodal.
  • Embodiment 18 The method of any of embodiments 10-17, wherein the watercompatible polymer further comprises, as polymerized monomers, at least one of styrene or derivatives thereof; acrylonitrile or derivatives thereof; other vinylic esters; or combinations thereof.
  • Embodiment 19 The method of any of embodiments 10-18, wherein the reaction mixture comprises from 500 wppm to 500,000 wppm, from 10,000 wppm to 100.000 wppm. from 10,000 wppm to 50,000 wppm, or from 15,000 wppm weight to 30,000 wppm of the chain transfer agent, by weight of the monomer(s).
  • NMR Nuclear Magnetic Resonance Spectroscopy
  • Solvent Water with -0.2 g/L sodium azide and -0.1 M sodium nitrate.
  • Injection volume -100 pL.
  • Sample Concentration -1 -2 mg/mL of provided sample in water with -0.2 g/L sodium azide and -0.1 M sodium nitrate.
  • Figure 1 illustrates a lab scale setup for polymerization of acrylamide. As shown, a -250 or -500 ml of round bottom flask with 2- or 3-neck reactor was equipped with a magnetic bar stirrer. A nitrogen blanket was applied to create a relatively inert atmosphere in which to run the reaction.
  • Example 1 Comparison of racemic mixture of homocysteine, cysteine, L-homocysteine and no chain transfer agent Table 1 shows the detailed reaction parameters for producing poly (acrylamide) using various chain transfer agents (CTA).
  • the reaction conditions for all the runs in Table 1 were: -20 grams of acrylamide, -45 grams of water, -0.05 gram of potassium peroxydisulfate (potassium persulfate) as initiator (-2,500 ppm weight based on weight of acrylamide), -0.1 gram of chain transfer agent (CTA) (-5,000 ppm weight based on weight of acrylamide).
  • the products were additionally diluted with - 70-100 grams of water.
  • Example 1 The same experimental set up as was used in Example 1 was utilized for these experiments, as shown in Figure 1.
  • the reaction conditions for the runs shown in Table 3 are as follows. -20 grams of acrylamide, -45 grams of water, and -0.05 grams of potassium peroxydisulfate as the initiator. The reactions were carried out at ⁇ 80°C for -4 hours.
  • Table 3 shows the loading of L-homocysteine used for each run in Example 2.
  • the polyacrylamides in each of the runs shown in Table 3 were worked up as follows. After polymerization, each polymer was diluted with about 50 grams of water. Then an excess of methanol (about 350 mL) was slowly added to the aqueous mixture of polymer with vigorous stirring to form a white precipitate. The white precipitate was collected by filtration and dried under vacuum. The samples were re-dissolved in deionized water and the above procedure (diluting with an excess of methanol, etc.) was repeated once more to obtain a purified polymer.
  • NMR analysis was conducted for determining monomer conversion by comparison of peak areas of vinyl (seen at about 5.6-6.4ppm on the spectra) and polymeric backbone (seen at about 1.2-2,4 ppm on the spectra).
  • each sample of purified polyacrylamide was re-dissolved in deuterium oxide and an NMR analysis was conducted.
  • Mw, Mn and poly dispersity (Mw/Mn) were measured by aqueous GPC with polyethylene oxide standards (7 standards having Mw range of -26,000 g/mol to -969.000 g/mol as described above.
  • DP degree of polymerization
  • DP Mn/71.08
  • [CTA] molar concentration of the chain transfer agent
  • [AM] is the mole concentration of the acrylamide monomer.
  • the plot used to determine the chain transfer constant Ct r of -2.33 according to the Mayo equation is shown in Figure 4.
  • the residue of the homocysteine remaining after reaction was completed was determined by liquid chromatography using a mass spectrometer detector.
  • the calibration curve was built using Extracted ion chromatography for -136.04 ([M+H] + ⁇ 136.04) and a representative MS2 (secondary ion fragments) mass spectroscopy spectrum of L-homocysteine was used as validation of identity.
  • Table 4 shows a summary of the polyacrylamides made using various levels of L- homocysteine as the chain transfer agent for Example 2. > > > > > > > >
  • Mw and Mn low molecular weight polyacrylamides
  • the residual chain transfer reagent in the reaction mixtures for four different runs were determined by liquid chromatography with a mass spectrometer detector. Reaction temperature and conversion were varied. No significant differences were observed by reaction temperature (-60 or -80 °C). Similarly, different monomer conversions showed a similar level of L- homocysteine residue (about 300 ppm weight by total weight of polymer and any unreacted monomer). According to GPC and LC-MS results, L-homocysteine seems to exhibit a high Ct r value and effectively reacted to propagating species (growing polymer chain).
  • the residual L-homocysteine was about 300 ppm weight based on the weight of the polyacrylamide. This concentration level was comparable to that of other chain transfer agents left in conventional free radical polymer systems (e.g., n-dodecyl mercaptan used as the chain transfer agent when polymerizing styrene acrylonitrile-grafted polymeric polyol).
  • n-dodecyl mercaptan used as the chain transfer agent when polymerizing styrene acrylonitrile-grafted polymeric polyol.

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Abstract

La présente invention concerne un polymère comprenant un résidu d'un agent de transfert de chaîne et un monomère polymérisé. Le monomère peut comprendre un (méth/éth/prop)acrylamide ou un de ses dérivés; un acide (méth/éth/prop)acrylique ou un de ses dérivés; un (méth/éth/prop)acrylate d'alkyle en C1-C18; un (méth/éth/prop)acrylate d'alkyle en C1-C18 à fonction hydroxyle; ou leur combinaison. L'agent de transfert de chaîne peut être compatible avec l'eau. L'agent de transfert de chaîne peut comprendre de l'homocystéine ou ses dérivés; des monothiols et dithiols en C2-C18; des monothiols et dithiols à base d'éthylène glycol en C3-C12; de l'acide thioglycolique ou un de ses dérivés; ou analogues; ou leur combinaison. Au moins une extrémité terminale polymère du polymère peut comprendre le résidu de l'agent de transfert de chaîne. Une liaison entre l'extrémité terminale polymère et le résidu de l'agent de transfert de chaîne peut comprendre un atome de soufre. L'invention concerne également un procédé de préparation dudit polymère.
PCT/US2024/048751 2023-09-29 2024-09-27 Agents de transfert de chaîne et leurs procédés de préparation Pending WO2025072586A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298585A (en) 1993-03-24 1994-03-29 Rohm And Haas Company Amine-thiol chain transfer agents
US5916985A (en) 1994-09-28 1999-06-29 Lvmh Recherche Functionalised polymers, method for synthesising same and use thereof as surfactants, particularly in cosmetic compositions such as nail varnish
US6433061B1 (en) 2000-10-24 2002-08-13 Noveon Ip Holdings Corp. Rheology modifying copolymer composition
US20120264903A1 (en) * 2010-01-08 2012-10-18 Tesa Se Multimodal copolymers, production of same, and use thereof in bulk contact adhesive
CN109369838A (zh) * 2018-09-18 2019-02-22 佛山市顺德区巴德富实业有限公司 一种用于纤维水泥板的丙烯酸乳液及其制备方法
US20200383896A1 (en) 2017-11-15 2020-12-10 Evonik Operations Gmbh Functionalized polymers
CN115353591A (zh) * 2022-08-31 2022-11-18 科顺防水科技股份有限公司 用于制备js防水涂料用乳液的方法、js防水涂料用乳液、双组份js防水涂料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298585A (en) 1993-03-24 1994-03-29 Rohm And Haas Company Amine-thiol chain transfer agents
US5916985A (en) 1994-09-28 1999-06-29 Lvmh Recherche Functionalised polymers, method for synthesising same and use thereof as surfactants, particularly in cosmetic compositions such as nail varnish
US6433061B1 (en) 2000-10-24 2002-08-13 Noveon Ip Holdings Corp. Rheology modifying copolymer composition
US20120264903A1 (en) * 2010-01-08 2012-10-18 Tesa Se Multimodal copolymers, production of same, and use thereof in bulk contact adhesive
US20200383896A1 (en) 2017-11-15 2020-12-10 Evonik Operations Gmbh Functionalized polymers
CN109369838A (zh) * 2018-09-18 2019-02-22 佛山市顺德区巴德富实业有限公司 一种用于纤维水泥板的丙烯酸乳液及其制备方法
CN115353591A (zh) * 2022-08-31 2022-11-18 科顺防水科技股份有限公司 用于制备js防水涂料用乳液的方法、js防水涂料用乳液、双组份js防水涂料

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BAUDIS STEFAN ET AL: "Photopolymerizable Elastomers for Vascular Tissue Regeneration", vol. 296, no. 1, 1 October 2010 (2010-10-01), DE, pages 121 - 126, XP093140173, ISSN: 1022-1360, Retrieved from the Internet <URL:https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fmasy.201051018> [retrieved on 20240312], DOI: 10.1002/masy.201051018 *
C. HENRIQUEZ ET AL., POLYMER, vol. 44, 2003, pages 5559 - 5561
MAHDAVIAN, ALI-REZA ET AL., JOURNAL OF APPLIED POLYMER SCIENCE, vol. 93, no. 5, 2004, pages 2007 - 2013
MONTENEGRO GERARDO CÁCERES ET AL: "A Safety Strategy for Producing Poly(Acrylic Acid) of Low Molar Mass", vol. 11, no. 3, 19 January 2017 (2017-01-19), Hoboken, USA, XP093140177, ISSN: 1862-832X, Retrieved from the Internet <URL:https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fmren.201600049> [retrieved on 20240312], DOI: 10.1002/mren.201600049 *
ZHANG QIAN ET AL: "Study of the Kinetic Hydrate Inhibitor Performance of Poly( N -vinylcaprolactam) and poly( N -isopropylmethacrylamide) with Varying End Caps", vol. 32, no. 9, 20 September 2018 (2018-09-20), WASHINGTON, DC, US., pages 9211 - 9219, XP055884791, ISSN: 0887-0624, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/acs.energyfuels.8b01985> [retrieved on 20240312], DOI: 10.1021/acs.energyfuels.8b01985 *

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