WO2018013330A1 - Polymeric material and methods of making using controlled radical initiators - Google Patents

Polymeric material and methods of making using controlled radical initiators Download PDF

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WO2018013330A1
WO2018013330A1 PCT/US2017/039368 US2017039368W WO2018013330A1 WO 2018013330 A1 WO2018013330 A1 WO 2018013330A1 US 2017039368 W US2017039368 W US 2017039368W WO 2018013330 A1 WO2018013330 A1 WO 2018013330A1
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formula
monomer
alkyl
polymeric
polymeric material
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French (fr)
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George W. Griesgraber
Stephen B. Roscoe
Hae-Seung Lee
Serkan YURT
Joon Chatterjee
Duane D. Fansler
Stefan H. Gryska
Babu N. Gaddam
Kevin M. Lewandowski
John L. Battiste
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to US16/314,760 priority Critical patent/US10400055B2/en
Priority to JP2019500836A priority patent/JP6949099B2/ja
Priority to EP17740824.2A priority patent/EP3481872B1/en
Priority to CN201780042617.1A priority patent/CN109476774B/zh
Publication of WO2018013330A1 publication Critical patent/WO2018013330A1/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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
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    • C08F2/00—Processes of polymerisation
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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/023—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type using a coupling agent
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • Controlled radical initiators compositions containing the controlled radical initiators, and polymeric materials formed using the controlled radical initiators are provided.
  • the performance characteristics of polymers are determined not only by their composition but also by their molecular architecture.
  • various properties such as melt viscosity, glass transition temperature, and modulus are often a function of the distribution of the different monomelic units along the polymeric chain.
  • Conventional radical polymerization methods have limited utility in synthesizing polymers with precise architectural and structural characteristics.
  • Living controlled radical polymerization methods have been developed that allow the preparation of polymers with well-defined molecular weight, polydispersity, topology, composition, and microstructure. These methods are based on the use of special polymerization mediators, which temporarily and reversibly transform propagating radicals into dormant and/or stable species. The reversible transformations are typically either accomplished by reversible deactivation or by reversible chain transfer. Some of the methods that involve living controlled radical polymerization through reversible transformations include iniferter methods, nitroxide mediated polymerization (NMP) methods, atom transfer polymerization (ATRP) methods, and reversible addition-fragmentation (RAFT) methods.
  • NMP nitroxide mediated polymerization
  • ATRP atom transfer polymerization
  • RAFT reversible addition-fragmentation
  • iniferter and "photoiniferters” refer to molecules that can act as an initiator, transfer agent, and terminator. Various iniferters were discussed in Otsu et al., Makromol. Chem., Rapid
  • XDC p-xylene bis(N,N-diethyldithiocarbamate)
  • Controlled radical initiators reaction mixtures containing the controlled radical initiators plus various ethylenically unsaturated monomers, and polymeric materials formed from the reaction mixtures are provided.
  • the controlled radical initiators are bis-dithiocarbamate or bis-dithiocarbonate compounds with a single carbon atom between the two dithiocarbamate or dithiocarbonate groups.
  • Polymeric materials such as homopolymers, random copolymers, and block copolymers can be prepared using the controlled radical initiators.
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where group R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Ri)2.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • the group R3 is equal to
  • Ri, R4, X, P, y, and z are the same as in Formula (I). In many embodiments z is equal to y. Typically, the polymeric material is not crosslinked.
  • the group X is equal to -NR 2 - and the polymeric material is of Formula (1-6).
  • Ri, R2, R3, P, y, and z are the same as in Formula (I). In many embodiments z is equal to y. Typically, the polymeric material is not crosslinked.
  • the group Ri is equal to 5 and the polymeric material is of Formula (1-7).
  • R3, P, X, y, and z are the same as in Formula (I).
  • Group R5 is a fluorinated alkyl.
  • y is equal to z.
  • the polymeric material is not crosslinked.
  • the polymeric material is of
  • variables Ri, R3, X, and P are the same as in Formula (I).
  • the variable y2 is an integer equal to at least 2 (e.g., in a range of 2 to 10 or in a range of 2 to 5) and the variable z2 is an integer in a range of 0 to y2 (e.g., in a range of 0 to 10, in a range of 2 to 10, or in a range of 2 to 5).
  • (P) y 2 means that there are y2 polymer blocks and
  • P) Z 2 means that there are z2 polymeric blocks.
  • a first reaction mixture in a second aspect, includes a) a photoinitiator and b) a first monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • the initiator is of Formula (V)
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Ri)2.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • the photoinitator of Formula (V) is of Formula (V-2) where X is equal to -NR 2 -.
  • group Ri in the initiator of Formula (V) is equal to R5 and the initiator is of Formula (V-9).
  • groups R3 and X are the same as in Formula (V).
  • Group R5 is a fluorinated alkyl.
  • a second reaction mixture in a third aspect, includes a) a polymeric material of Formula (II)
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR 2 - where R 2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(R
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Pi is the first polymeric block, the first polymeric block being a polymerized product of the first monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • group R3 in the polymeric material of Formula (II) is equal to -N(R4)2. That is, the polymeric material is of Formula (II- 1).
  • a third reaction mixture includes a) ; polymeric material of Formula (III)
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Ri)2.
  • Each Ri is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Pi is a first polymeric block, the first polymeric block being a polymerized product of a first monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • Each P2 is a second polymeric block different from the first polymeric block Pi, the second polymeric block P2 being a polymerized product of a second monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • a first method of making a polymeric material includes providing an initiator of Formula (V).
  • Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Ri)2.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • the first method further includes preparing a first reaction mixture containing the initiator of Formula (V) and a first monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • the first method still further includes forming a first polymeric material of Formula (II) from the first reaction mixture.
  • group X in the initiator is equal to -NR2-. That is, the initiator is of Formula (V-2)
  • a second method of making a polymeric material includes providing a polym
  • a compoun ded In a seventh aspect, a compoun ded.
  • FIG. 1 shows the aromatic region of the l NMR spectrum for Comparative Example G after 93 percent conversion (i.e., polymerization) of the monomer.
  • Controlled radical initiators reaction mixtures containing the controlled radical initiators plus various ethylenically unsaturated monomers, and polymeric materials formed from the reaction mixtures are provided.
  • the controlled radical initiators are bis-dithiocarbamate or bis-dithiocarbonate compounds with a single carbon atom between the two dithiocarbamate or dithiocarbonate groups.
  • the controlled radical initiator compounds can be referred to as iniferters because they can function as a controlled radical initiator, transfer agent, and terminator.
  • the controlled radical initiators can be referred to as photoinitiators or photoiniferters because the controlled radical polymerization reaction typically is photolytically induced.
  • Polymeric materials such as homopolymers, random copolymers, and block copolymers having well controlled architectures can be formed using these photoinitiator compounds.
  • fluorinated alkyl refers to an alkyl group substituted with at least one fluorine atom (i.e., at least one hydrogen atom is replaced with a fluorine atom). If all of the hydrogen atoms are replaced with fluorine atoms, the fluorinated alkyl is a "perfluoroalkyl".
  • aralkyl refers to an alkyl group substituted with at least one aryl group.
  • the aralkyl group contains 6 to 40 carbon atoms.
  • the aralkyl group often contains an alkyl group having 1 to 20 carbon atoms and an aryl group having 5 to 20 carbon atoms.
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl.
  • Group X is oxy or -NR2- where R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl.
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(R() 2 .
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Suitable aralkyl and substituted aryl groups often have 6 to 40 carbon atoms, 7 to 20 carbon atoms, or 7 to 10 carbon atoms.
  • Some example substituted aryl groups are phenyl substituted with an alkyl, an alkoxy, or both with each alkyl or alkoxy group having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • Some example aralkyl group have an alkyl group with 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms that is substituted with phenyl.
  • Ri is an alkyl or fluorinated alkyl.
  • Suitable alkyl and fluorinated alkyl groups typically have at least 1 carbon atom, at least 2 carbon atoms, at least 3 carbon atoms, or at least 4 carbon atoms and can have up to 20 carbon atoms, up to 18 carbon atoms, up to 16 carbon atoms, up to 12 carbon atoms, or up to 10 carbon atoms.
  • Some example alkyl and fluorinated alkyl groups have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 2 to 10 carbon atoms, 1 to 6 carbon atoms, 2 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • the fluorinated alkyl groups can have one to all of the hydrogen atoms replaced with fluorine atoms.
  • the heterocyclic ring typically has a first ring structure with 5 to 7 ring members or 5 to 6 ring members and with 1 to 3 heteroatoms or 1 to 2 heteroatoms in the ring. If there is one heteroatom in the first ring structure, the heteroatom is nitrogen. If there are two or three heteroatoms in the first ring structure, one heteroatom is nitrogen and any additional heteroatom is selected from nitrogen, oxygen, and sulfur.
  • the first ring structure optionally can be fused to additional ring structures.
  • the additional ring structures can be heterocyclic or carbocyclic.
  • the first ring structure or any additional ring structures can be saturated or unsaturated (e.g., partially or fully unsaturated).
  • Suitable monomers with a single (meth)acryloyl group include, but are not limited to, alkyl (meth)acrylates, fluorinated alkyl (meth)acrylates, aryl (meth)acrylates, aralkyl (meth)acrylates, substituted aryl (meth)acrylates, (meth)acrylic acid, (meth)acrylamide, N-alkyl (meth)acrylamide, N,N- dialkyl (meth)acrylamide, N-alkylaminoalkyl (meth)acrylate, ⁇ , ⁇ -dialkylaminoalkyl (meth)acrylate, N- alkylaminoalkyl (meth)acrylamide, N,N-dialkylaminoalkyl (meth)acrylamide, hydroxy-substituted alkyl (meth)acrylates, hydroxy-substituted alkyl (meth)acrylamides, alkoxylated alkyl (meth)acrylate, acid- substituted al
  • Suitable monomers with a single ethylenically unsaturated group that is not a (meth)acryloyl group include, but are not limited to, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, vinyl methyl ether, styrene, isoprene, butadiene, vinyl dimethylazlactone (VDM), isopropenyl
  • first monomer there can be a single first monomer or a plurality of first monomers.
  • second monomer there can be a single second monomer or a plurality of second monomers.
  • the monomer composition typically does not contain monomers having more than one ethylenically unsaturated group.
  • (P) y means that there are y polymer blocks and (P) z means that there are z polymeric blocks.
  • the variable y is an integer equal to at least 1 (e.g., in a range of 1 to 10, in a range of 1 to 5, in a range of 1 to 3, or in a range of 1 to 2) and the variable z is an integer in a range of 0 to y. If the variable y is equal to 1, the variable z is equal to 0 or 1. If z is equal to 0, then the resulting polymeric material has a mono-directional polymeric chain. That is, there is a polymeric chain only on one side of the divalent group -C[(CO)-XRi]H- in Formula (I).
  • the resulting polymeric material has a bi-directional polymeric chain. That is, there is a polymeric chain on both sides of the divalent group -C[(CO)-XRi]H- in Formula (I).
  • the polymeric material formed in the early stages of polymerization of the monomer composition results in the formation of a polymeric chain growing on one but not on both sides of the divalent group -C[(CO)-XRi]H- in Formula (I). That is, the reaction product is
  • the reaction product includes a mixture of a first polymeric material having y equal to 1 and z equal to 0 (i.e., this first polymeric material can be referred to as a "mono-directional polymeric material") and a second polymeric material having y equal to 1 and z equal to 1 (i.e., this second polymeric material can be referred to as a "bi-directional polymeric material").
  • this first polymeric material can be referred to as a "mono-directional polymeric material”
  • a second polymeric material having y equal to 1 and z equal to 1 i.e., this second polymeric material can be referred to as a "bi-directional polymeric material”
  • the percentage of the polymeric material that is bi-directional typically increases.
  • the amount of bi-directional polymeric material is often at least 80 weight percent, at least 90 weight percent, or at least 95 weight percent based on the total weight of polymeric material (i.e., the mono-directional plus bi-directional polymeric material).
  • the group R3 is equal to -N(R()2 and the polymeric materi
  • R 1; R4, X, P, y, and z are the same as in Formula (I). In many embodiments, z is equal to y.
  • Ri, R2, R3, P, y, and z are the same as in Formula (I). In many of these embodiments, y is equal to z.
  • the group Ri is equal to 5 and the polymeric material is of Formula (1-7).
  • X, R3, P, y, and z are the same as in Formula (I).
  • Group Re is a fluorinated alkyl. In many of these embodiments, y is equal to z.
  • variable y is equal to at least 2 and the polymeric material
  • variables y2 is an integer equal to at least 2 (e.g., in a range of 2 to 10 or in a range of 2 to 5) and the variable z2 is an integer in a range of 0 to y2 (e.g., in a range of 0 to 10, in a range of 2 to 10, or in a range of 2 to 5). In many embodiments of Formula (1-4), y2 is equal to z2.
  • (P)i means that there is one polymeric block (y is equal to 1 in Formula (I)) and (P)o means that there are 0 to 1 polymeric blocks (z is 0 to 1 in Formula (I)).
  • both y and z in Formula (I) are equal to 1 and the polymeric material of Formula (II).
  • Pi refers to a first polymeric block.
  • the first polymeric block Pi is a polymerized product of a first monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • Pi can be a homopolymer or a copolymer. If Pi is a copolymer, it is typically a random copolymer.
  • Groups Ri, R3, and X are the same as defined for Formula (I).
  • the polymeric material of Formula (II) can be considered as having a single polymeric block Pi and the polymeric block has a pendant group -(CO)-XRi. That is, there is a divalent group of formula -C[(CO)-XRi]H- between two monomelic units within polymeric block Pi.
  • the polymeric material of Formula (II) is of Formula (II- 1).
  • Ri, Rt, and X are defined as in Formula (I) and Pi is defined as in Formula (II).
  • the polymeric material is of Formula ( ⁇ -2). (II-2)
  • R 1; R2, and R3 are defined as in Formula (I) and Pi is defined as in Formula (II).
  • the polymeric material is of Formula ( ⁇ -3).
  • R3, and X are defined as in Formula (I)
  • Pi is defined as in Formula (II)
  • Re is a fluorinated alkyl.
  • y is equal to 2 and z is an integer in a range of 0 to 2.
  • the resulting polymeric material is of Formula (1-2).
  • Pi is a first polymeric block that is a polymerized product of a first monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • P2 is a second polymeric block that is a polymerized product of a second monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • the composition of the second polymeric block P2 is different than the composition of the first polymeric block Pi. That is, first monomer composition is different than second monomer composition.
  • Groups Ri, R3, and X are the same as defined for Formula (I).
  • Each block Pi and P 2 can be a homopolymer or a copolymer. If either block is a copolymer, it is typically a random copolymer.
  • the polymeric material of Formula (III) can be referred to as a triblock with two P 2 blocks separated by a Pi block having a pendant group
  • R3 is equal to -N(Ri)2 and the polymeric material is of Formula (III-l).
  • Ri is equal to R5, which is a fluorinated alkyl, and the polymeric material is of Formula ( ⁇ -3).
  • Groups X and R3 are as defined in Formula (I) and groups Pi and P2 are defined as in Formula (III).
  • y is equal to 3 and z is an integer in a range of 0 to 3.
  • the resulting polymeric material is of Formula (1-3).
  • (P)3 means that there are three polymeric blocks (y is equal to 3 in Formula (I)) and (P)o-3 means that there are 0, 1, 2 or 3 polymeric blocks (z is an integer in a range of 0 to 3 in Formula (I)). In many embodiments of Formula (1-3), both y and z in Formula (I) are equal to 3 and the polymeric material of Formula (IV).
  • Pi is a first polymeric block that is a polymerized product of a first monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • P 2 is a second polymeric block that is a polymerized product of a second monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • P3 is a third polymeric block that is a polymerized product of a third monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • the composition of the second polymeric block P2 is different than the composition of the first polymeric block Pi and different than the composition of the third polymeric block P3.
  • second monomer composition is different than both first monomer composition and third monomer composition; first monomer composition can be the same as or different than third monomer composition.
  • the composition of the first polymeric block Pi can be the same or different than the composition of the third polymeric block P3.
  • Groups Ri, R3, and X are the same as defined for Formula (I).
  • Each block Pi, P 2 , and P3 can be a homopolymer or a copolymer. If any block is a copolymer, it is typically a random copolymer.
  • the polymeric material of Formula (IV) can be referred to as a pentablock with two P3 blocks plus two P2 blocks separated by a Pi block having a pendant group -(CO)-XRi. That is, there is a divalent group of formula -C[(CO)-XRi]H- between two monomelic units within polymeric block Pi.
  • Each polymeric block (e.g., P, Pi, P2, or P3) can have any desired molecular weight.
  • the molecular weight of each block (even if given the same designation such as Pi, P 2 , or P3) can be the same or different than any other polymeric block.
  • the weight average molecular weight of any polymeric block is at least 1,000 Daltons, at least 2,000 Daltons, at least 5,000 Daltons, at least 10,000 Daltons, at least 20,000 Daltons, at least 50,000 Daltons, or at least 100,000 Daltons.
  • the weight average molecular weight of any polymeric block can be up to 1 million Daltons or even higher, up to 750,000 Daltons, up to 500,000 Daltons, up to 200,000 Daltons, or up to 100,000 Daltons.
  • the group R3 in some embodiments of the photoinitiators of Formula (V) is of formula -N(Ri)2 where Rt is the same as defined above for Formula (I).
  • These photoinitiators are of Formula (V-3) and are bis-dithiocarbamate compounds having a single carbon atom between the two dithiocarbamate groups.
  • the groups R3 in some embodiments of the photoinitiators of Formulas (V) are alkoxy or fluorinated alkoxy groups of formula -OR5. That is, the photoinitiators are of Formula (V-6) where R5 is an alkyl or fluorinated alkyl.
  • These photoinitiators are bis-dithiocarbonate compounds having a single carbon atom between the two dithiocarbonate groups.
  • group -OR5 is an alkoxy and Ri is an alkyl, or fluorinated alkyl.
  • Specific examples of compounds of Formula (V-3) include, but are not limited to, methyl 2,2-bis(isopropoxycarbothioylsulfanyl)acetate, ethyl 2,2- bis(isopropoxycarbothioylsulfanyl)acetate, tert-butyl 2,2-bis(isopropoxycarbothioylsulfanyl)acetate, 2- ethylhexyl 2,2-bis(isopropoxycarbothioylsulfanyl)acetate, and 2,2,3, 3,4,4,4-heptafluorobutyl 2,2- bis(isopropoxycarbothioylsulfanyl)acetate.
  • group -OR5 is alkoxy
  • Ri is an alkyl or fluorinated alkyl
  • R2 is hydrogen, alkyl, or fluorinated alkyl.
  • group -OR5 is alkoxy
  • Ri is alkyl
  • R2 is hydrogen, or alkyl.
  • Specific examples of compounds of Formula (V-8) include, but are not limited to, N,N-dibutyl-2,2- bis(isopropoxycarbothioylsulfanyl)acetamide.
  • Group R5 in Formula (V-9) is a fluorinated alkyl that typically contains 1 to 20 carbon atoms.
  • the fluorinated alkyl can have at least 1 carbon atom, at least 2 carbon atoms, at least 3 carbon atoms, or at least 4 carbon atoms and can have up to 20 carbon atoms, up to 18 carbon atoms, up to 16 carbon atoms, up to 12 carbon atoms, or up to 10 carbon atoms.
  • Some example alkyl and fluorinated alkyl groups have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 2 to 10 carbon atoms, 1 to 6 carbon atoms, 2 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • the fluorinated alkyl groups can have 1 to all of the hydrogen atoms replaced with fluorine atoms.
  • all of the hydrogen atoms are replaced with fluorine or all of the hydrogen atoms except those on the carbon atom immediately adjacent to the X group are replaced with fluorine.
  • the photoinitiator of Formula (V) (including those of Formula (V-l) to (V-9)) is mixed with a monomer composition to form a reaction mixture that is used to form the polymeric materials of Formula (I) (more specifically, the polymeric material is of Formula (II)). While not wishing to be bound by theory, it is believed that polymerization occurs as shown in Reaction Scheme B.
  • Reaction III the photoinitator of Formula (V), which is shown as compound (8), undergoes photolysis of one of the C-S bonds when exposed to actinic radiation (e.g., ultraviolet radiation) (Reaction IV).
  • actinic radiation e.g., ultraviolet radiation
  • Two different radicals, the radical (9) and the radical (10), are formed in Reaction IV.
  • radical (9) reacts with ethylenically unsaturated monomers (compound ( 11)).
  • the monomers polymerize and radical (12) is formed.
  • the radical (12) can combine with a radical (10) and the polymerization reaction is terminated.
  • the resulting polymeric material of Reaction VI is compound (13).
  • radical (12) combines with another molecule of compound (13) to generate radical (17).
  • radical (17) undergoes homolysis of a carbon-sulfur bond to regenerate radical (12) and compound (13).
  • Reaction (XII) radical (17) undergoes homolysis on the opposite side of the dithiocarbamate or dithiocarbonate group to generate compound (13) and radical (14), a net transfer of the dithiocarbamate or dithiocarbonate group.
  • Group R b is hydrogen or methyl and group R9 is the remainder, for example, of any monomer described herein having a (meth)acryloyl group.
  • Polymeric materials having one or more polymeric blocks of Formula (I) can be formed by mixing a photoinitiator of Formula (V) with a first monomer composition and exposing the resulting first reaction mixture to actinic radiation (e.g., ultraviolet light).
  • actinic radiation e.g., ultraviolet light
  • the actinic radiation exposure causes the photolysis of the photoinitiator and permits controlled radical polymerization of the first monomer composition to form a first polymeric block Pi that includes the carbon atom in the photoinitiator having a pendant -(CO)-X-Ri group.
  • the product of the first polymerization is a polymeric material of Formula (I-l).
  • the polymeric material of Formula (I-l) is of Formula (II).
  • the length of the polymeric chains Pi on either size of the pendant -(CO)-X-Ri group in Formula (II) can be the same or different.
  • 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate 2,2,3, 3,4,4,5, 5,5-nonafluoropentyl (meth)acrylate, 2,2,3,3,4,4,5,5, 6,6,6-undecafluorohexyl (meth)acrylate, 2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl (meth)acrylate, 2,2,3,3,4,4,5, 5,6,6,7,7,8, 8, 8-pentadecafluoro octyl (meth)acrylate,
  • Rf-Q-0-(CO)-CR b CH2 where R b is hydrogen or methyl, Q is a divalent linking group, and Rf is C3F70(CF(CF3)CF20) a CF(CF3)- where a is in a range of 1 to 50, in a range of 1 to 30, in a range of 1 to 10, or in a range of 1 to 5. Examples include, but are not limited to,
  • Example aryl (meth)acrylates, aralkyl (meth)acrylates, and substituted aryl (meth)acrylates include, but are not limited to, phenyl (meth)acrylate, 2-biphenylhexyl (meth)acrylate, and benzyl (meth)acrylate.
  • Example N-alkyl (meth)acrylamides and ⁇ , ⁇ -dialkyl (meth)acrylamides include, but are not limited to, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N- tert-octyl (meth)acrylamide, N-octyl (meth)acrylamide, ⁇ , ⁇ -dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, ⁇ , ⁇ -dipropyl (meth)acrylamide, and ⁇ , ⁇ -dibutyl (meth)acrylamide.
  • N-alkylaminoalkyl (meth)acrylates and ⁇ , ⁇ -dialkylaminoalkyl (meth)acrylates include, but are not limited to, N-methyl aminoethyl (meth)acrylate, ⁇ , ⁇ -dimethyl aminoethyl (meth)acrylate, N-methylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N- diethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-ethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, and N-morpholino (meth)acrylate.
  • Example N-alkylaminoalkyl (meth)acrylamides and N,N-dialkylaminoalkyl (meth)acrylamide include, but are not limited to, N-methylaminoethyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N-methylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl
  • (meth)acrylamide N-ethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N- ethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide.
  • Example hydroxy-substituted alkyl (meth)acrylates and hydroxy-substituted alkyl (meth)acrylamides include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylamide, and 3-hydroxypropyl (meth)acrylamide.
  • Example alkoxylated alkyl (meth)acrylates include, but are not limited to, ethoxyethoxyethyl
  • poly(alkylene oxide) (meth)acrylates such as poly(ethylene oxide) (meth)acrylates and poly(propylene oxide) (meth)acrylates.
  • the poly(alkylene oxide) acrylates are often referred to as poly(alkylene glycol) (meth)acrylates.
  • These monomers can have any suitable end group such as a hydroxyl group or an alkoxy group. For example, when the end group is a methoxy group, the monomer can be referred to as methoxy poly (ethylene glycol) (meth)acrylate.
  • Example acid-substituted alkyl (meth)acrylates, and acid-substituted alkyl (meth)acrylamides include, but are not limited to, ⁇ -carboxyethyl acrylate, 2-(meth)acrylamidoethanesulfonic acid, and 2- (meth)acrylamido-2-methylpropane sulfonic acid.
  • Example glycidyl -containing (meth)acrylates include, but are not limited to, glycidyl
  • Example aminosulfonyl-containing (meth)acrylates include, but are not limited to, and N- methyl-perfluorobutyl)sulfonylaminoethyl (meth)acrylate.
  • the reaction mixture includes a monomer composition containing a monomer having a single ethylenically unsaturated group that is not a (meth)acryloyl group.
  • Suitable such monomers include, but are not limited to, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, vinyl methyl ether, vinyl-2-ethylhexanoate, vinyl neodecanoate, styrene, isoprene, butadiene, vinyl dimethylazlactone (VDM), isopropenyl dimethylazlactone (IDM), and vinyl oxazole, and the like.
  • VDM vinyl dimethylazlactone
  • IDM isopropenyl dimethylazlactone
  • the reaction mixture usually does not include a monomer with more than one ethylenically unsaturated group (i.e., the reaction mixture is free of monomers having two or more ethylenically unsaturated groups). That is, the polymeric materials formed are linear polymers and are not crosslinked. If a monomer having more than one ethylenically unsaturated group is added, the amount added is typically sufficiently low so that the polymeric material can flow for coating onto a substrate. This amount of monomer having more than one ethylenically unsaturated group tends to result in branching rather than crosslinking.
  • the polymeric material that is formed can have one or more polymeric blocks and each block can be a homopolymer or a random copolymer.
  • Each polymeric block is formed from a reaction mixture that includes a monomer composition and a photoinitiator of Formula (V).
  • Some example monomer compositions include 50 to 100 weight percent of the first monomer with a single (meth)acryloyl group and 0 to 50 weight percent of the second monomer with a single ethylenically unsaturated group that is not a (meth)acryloyl group.
  • the monomer composition used to form any of the blocks in the polymeric material of Formulas (I) can contain at least 55 weight percent, at least 60 weight percent, at least 70 weight percent, at least 75 weight percent, at least 80 weight percent, at least 85 weight percent, at least 90 weight percent, at least 95 weight percent, at least 98 weight percent, at least 99 weight percent, or 100 weight percent of the first monomer.
  • Any remaining monomer typically is a second monomer having the ethylenically unsaturated group that is not a (meth)acryloyl group.
  • the monomer composition contains at least 80 weight percent of the first monomer, the monomer composition contains 80 to 100 weight percent of the first monomer and 0 to 20 weight percent of the second monomer.
  • the weight percent values are based on the total weight of monomers in the monomer composition for any block.
  • the amount of the photoinitiator impacts the weight average molecular weight of the resulting polymeric block. That is, the weight average molecular weight can be controlled based on the amount of photoinitiator added to the reaction mixture.
  • the amount of photoinitiator is typically in a range of 0.001 to 15 weight percent based on the weight of the monomers in the reaction mixture.
  • the photoinitiator is at least 0.001 weight percent, at least 0.005 weight percent, at least 0.01 weight percent, at least 0.02 weight percent, at least 0.03 weight percent, or at least 0.5 weight percent and can be up to 15 weight percent, up to 12 weight percent, up to 10 weight percent, up to 8 weight percent, up to 6 weight percent, up to 5 weight percent, up to 3 weight percent, up to 2 weight percent, or up to 1 weight percent.
  • This amount of photoinitiator often results in the formation of polymeric blocks having a weight average molecular weight in a range of 1,000 to 3 million Daltons or in the range of 1,000 to 1 million Daltons.
  • the reaction mixtures typically do not include a transfer agent. Transfer agents are not needed to control the molecular weight of the resulting polymeric material. Rather, the molecular weight can be varied and controlled through selection of the desired amount of the photoinitiator of Formula (V) and of the desired reaction temperature.
  • reaction mixtures typically do not include any other initiator other than the photoinitiator of Formula (V). That is, there is no thermal initiator such as an azo initiator, peroxide initiator, redox initiator, or persulfate initiator. No other photoinitiator other than those of Formula (V) are included in the reaction mixtures.
  • a first monomer composition is mixed with a photoinitiator of Formula (V) to form a first reaction mixture.
  • the first reaction mixture can be neat (i.e., no solvent is present) or can be mixed with a solvent that dissolves both the first monomer composition and the photoinitiator of Formula (V).
  • the solvent can be added, for example, to lower the viscosity of the first reaction mixture. Any solvent that is added is usually selected so that the growing polymeric material is also soluble.
  • the percent solids in the first reaction mixture is at least 10 weight percent, at least 20 weight percent, at least 30 weight percent, or at least 40 weight percent and up to 100 weight percent, up to 80 weight percent, or up to 60 weight percent.
  • the amount of solvent added is often selected based on the desired viscosity, particularly the viscosity of the final polymerized material.
  • the desired viscosity is usually sufficiently low so that the final polymeric material can be readily removed from the reactor and/or applied to a substrate.
  • the solvent is often an ester (e.g., ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether acetate), an ether (e.g., dimethyl ether, diethyl ether, ethyl propyl ether, dipropyl ether, methyl t-butyl ether, di-t-butyl ether, dimethoxy ethane, 2-methoxyethanol, diethylene glycol dimethyl ether, dioxane, and tetrahydrofuran), acetonitrile, methylene chloride, an aromatic hydrocarbon (e.g., benzene, xylene, and toluene), or a ketone (e.g., acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone).
  • ester e.g., ethyl acetate, butyl acetate, and ethylene
  • Polymerization of the first monomer composition can start at room temperature (e.g., about 20°C to 25°C) but can also start, if desired at higher or lower temperatures.
  • the first reaction mixture is exposed to actinic radiation (e.g., ultraviolet radiation) to activate the photoinitator of Formula (V) and commence controlled radical polymerization of the first monomer composition.
  • actinic radiation e.g., ultraviolet radiation
  • the resulting block Pi can be a homopolymer or a random copolymer having a pendant group -(CO)-XRi in the polymeric material of Formula (II).
  • the group -(CO)-XRi is attached to the single carbon in the photoinitiator of Formula (V) that was used to prepare the polymeric material.
  • the polymerization reaction is usually allowed to proceed until at least 80 weight percent, at least 85 weight percent, at least 90 weight percent, at least 95 weight percent, at least 98 weight percent, or at least 99 weight percent of the monomers in the first monomer composition have undergone controlled radical polymerization.
  • Group P i and the first monomer composition can be selected so that the presence of the pendant -(CO)-XRi group is not discernible in the resulting polymeric material of Formula (II).
  • the groups R b , X, and Ri are the same as defined above.
  • Formula (III) is equal to Formula (I) where both z and y are equal to 2.
  • actinic radiation e.g., ultraviolet radiation
  • a second reaction mixture is formed by adding a second monomer composition to the reaction product of the first reaction mixture.
  • the second reaction mixture includes a first polymeric material of Formula (II) plus a second monomer composition having at least one monomer with a single ethylenically unsaturated group. It is typically not necessary to add further photoinitiator of Formula (V) to the second reaction mixture.
  • any optional solvent that is included in the second reaction mixture is usually selected so that it solubilizes the first polymeric material of Formula (II), the photoinitiator of Formula (V), and the second monomer composition. That is, the second reaction mixture is typically a single phase.
  • the percent solids in the second reaction mixture is selected to have percent solids equal to at least 10 weight percent, at least 20 weight percent, at least 30 weight percent, or at least 40 weight percent and up to 100 weight percent (i.e., no solvent is added), up to 80 weight percent, or up to 60 weight percent.
  • Suitable solvents are the same as those discussed above for the first reaction mixture.
  • the amount of solvent added is selected based on the desired viscosity, particularly the viscosity of the final polymerized material. The desired viscosity is usually sufficiently low so that the final polymeric material can be readily removed from the reactor and/or applied to a substrate.
  • the second reaction mixture is exposed to actinic radiation (e.g., ultraviolet radiation) to commence controlled radical polymerization of the second monomer composition.
  • actinic radiation e.g., ultraviolet radiation
  • Each of the two resulting P 2 blocks can be a homopolymer or a random copolymer.
  • the two P 2 blocks are separated by a Pi block having a pendant group -(CO)-XRi in the polymeric material of Formula (III).
  • the polymerization reaction is usually allowed to proceed until at least 80 weight percent, at least 85 weight percent, at least 90 weight percent, at least 95 weight percent, at least 98 weight percent, or at least 99 weight percent of the monomers in the second monomer composition have undergone controlled radical polymerization.
  • Polymerization of the second monomer composition can occur at room temperature (e.g., about 20°C to 25°C) but can also occur, if desired at higher or lower temperatures.
  • the composition of polymeric block P2 is typically different than the composition of polymeric block Pi.
  • the polymeric blocks Pi and P2 have different glass transition temperatures as measured by Differential Scanning Calorimetry.
  • the difference in the glass transition temperature of polymeric blocks Pi and P2 is at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, or at least 100°C. It is preferable, however, that the polymeric material of Formula (II) is soluble in the second reaction mixture containing the second monomer composition used to form the polymeric material of Formula (III).
  • the transition between two polymeric blocks can be controlled by the percent conversion of the first reaction mixture to the first polymeric block. If the percent conversion is relatively low (e.g., less than 90 percent), then the second reaction mixture will include a mixture of the second monomer composition plus remaining unreacted first monomer composition. That is, some of the monomers from the first monomer composition will be in the second polymeric block P 2 . To minimize the presence of the first monomer composition in the second polymeric block P 2 , the percent conversion of the first monomer composition should be maximized. A higher percent conversion must be balanced, however, against a longer reaction time.
  • Formula (IV) is equal to Formula (I) where both z and y are equal to 3.
  • the polymerization reaction is stopped by terminating exposure to actinic radiation (e.g., ultraviolet radiation).
  • actinic radiation e.g., ultraviolet radiation.
  • a third reaction mixture is formed by adding a third monomer composition to the reaction product of the second reaction mixture.
  • the third reaction mixture includes a second polymeric material of Formula (III) plus a third monomer composition having at least one monomer with a single ethylenically unsaturated group.
  • any optional solvent that is included in the third reaction mixture is usually selected so that it solubilizes the polymeric material of Formula (III), the photoinitator of Formula (V), and the third monomer composition. That is, the third reaction mixture is typically a single phase.
  • the percent solids in the third reaction mixture is selected to have percent solids equal to at least 10 weight percent, at least 20 weight percent, at least 30 weight percent, or at least 40 weight percent and up to 100 weight percent (i.e., no solvent is added), up to 80 weight percent, or up to 60 weight percent.
  • Suitable solvents are the same as those discussed above for the first reaction mixture.
  • the amount of solvent added is selected based on the desired viscosity, particularly the viscosity of the final polymerized material. The desired viscosity is usually sufficiently low so that the final polymeric material can be readily removed from the reactor and/or applied to a substrate.
  • the third reaction mixture is exposed to actinic radiation (e.g., ultraviolet radiation) to commence controlled radical polymerization of the third monomer composition.
  • actinic radiation e.g., ultraviolet radiation
  • Each of the two resulting P3 blocks can be a homopolymer or a random copolymer.
  • the two P3 blocks are separated by two P2 blocks and a Pi block having a pendant group -(CO)-XRi in the polymeric material of Formula (IV).
  • the polymerization reaction is usually allowed to proceed until at least 80 weight percent, at least 85 weight percent, at least 90 weight percent, at least 95 weight percent, at least 98 weight percent, or at least 99 weight percent of the monomers in the second monomer composition have undergone controlled radical polymerization.
  • Polymerization of the third monomer composition can occur at room temperature (e.g., about 20°C to 25°C) but can also occur, if desired at higher or lower temperatures.
  • composition of polymeric block P 3 is typically different than the composition of polymeric block P 2
  • composition of polymeric block P 2 is typically different than the composition of polymeric block Pi
  • the composition of polymeric block P 3 can be the same or different than the composition of polymeric block Pi.
  • the polymeric blocks P3 and P 2 have different glass transition temperatures and the polymeric blocks P2 and Pi have different glass transition temperatures as measured by Differential Scanning Calorimetry.
  • the difference in the glass transition temperature between the polymeric blocks is at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, or at least 100°C.
  • Additional polymeric blocks can be added to the polymeric material of Formula (IV) to form polymeric materials of Formula (I) where the number of blocks (y) is greater than 3.
  • Each precursor polymeric material having (y - 2) polymeric blocks is added to a monomer composition to form a reaction mixture.
  • the reaction mixture is exposed to actinic radiation to form the polymeric material with two additional polymeric blocks as described above.
  • Adjacent polymeric blocks typically have different compositions, different glass transition temperatures, and different solubility parameters. Because of these differences, a phase separated morphology may result. This phase separation leads to physical crosslinking within the block copolymer and can, for example, increase the cohesive strength of the polymeric material even in the absence of chemical crosslinks.
  • the resulting polymeric materials of Formula (I) have dithiocarbamate or dithiocarbonate terminal groups. That is, the terminal group is typically Pv3-(CS)-S-. If desired, this terminal group can be replaced after the polymeric material has formed using known methods such as those described, for example, in (a) Taton et al., Handbook of RAFT Polymerization. Barner-Kowollik, ed., Wiley-VCH:
  • Suitable methods include, for example, converting the dithiocarbamate or dithiocarbonate functionality into a thiol end group through reaction with nucleophiles.
  • the polymeric material with the thiol end group can undergo various radical reactions (e.g., radical catalyzed thiol-ene reactions and radical catalyzed thiol-yne reactions), nucleophilic reactions (e.g., thiol-ene Michael addition reactions, thiol-epoxy reactions, thiol-halide reactions, thiol-isocyanate reactions), or sulfur exchange reactions (e.g., thiol-alkanethiosulfonate reactions and thiol-pyridyl disulfide reactions).
  • radical reactions e.g., radical catalyzed thiol-ene reactions and radical catalyzed thiol-yne reactions
  • nucleophilic reactions e.g., thiol-ene Michael
  • the polymeric materials of Formula (I) can be melt processed. That is, the polymeric materials are usually thermoplastic and can flow upon application of heat (e.g., application of heat below a temperature that would result in the degradation of the polymeric material). The polymeric materials can be heated in an extruder and coated onto a substrate.
  • (V) can be used to form polymeric blocks with a high acid content. That is, greater than 10 weight percent, greater than 20 weight percent, greater than 30 weight percent, greater than 40 weight percent, greater than 50 weight percent, greater than 60 weight percent, greater than 70 weight percent, greater than 80 weight percent, greater than 90 weight percent, or even 100 weight percent of the monomers in any reaction mixture used to form a polymer block can be an acidic monomer.
  • polymeric blocks can be prepared using (meth)acrylic acid as the only or major component of the monomer composition.
  • the photoinitiators of Formula (V) undergo photolysis upon exposure to actinic radiation, particularly actinic radiation in the ultraviolet region of the electromagnetic spectrum (e.g., light having wavelengths in a range of 250 to 450 nanometers, in a range of 250 to 405 nanometers, or in a range of 300 to 405 nanometers.
  • actinic radiation particularly actinic radiation in the ultraviolet region of the electromagnetic spectrum
  • Any light source that provides ultraviolet light can be used.
  • the light source is a light emitting diode having a narrow wavelength distribution around 365 nanometers.
  • the polymeric material can be used for any desired purpose.
  • the polymeric material is applied to a substrate and can function as a coating layer or as an adhesive layer depending on the composition of the various polymeric blocks.
  • the polymeric material can be combined with other known components that can be included in adhesive layers and coating layers.
  • Various embodiments are provided that are polymeric materials, reaction mixtures, methods of making the polymeric materials, or photoinitiators.
  • Embodiment 1 A is a po
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with an alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where group R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl.
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(R()2.
  • Embodiment 2A is the polymeric material of embodiment 1A, wherein the polymeric material is of Formula (I) is of Formula (1-4)
  • variable y2 is an integer equal to at least 2 (e.g., in a range of 2 to 10 or in a range of 2 to 5) and the variable z2 is an integer in a range of 0 to y2 (e.g., in a range of 0 to 10, in a range of 2 to 10, or in a range of 2 to 5).
  • z2 is equal to y2.
  • Groups X, Ri, R3, and P are defined as in Formula (I).
  • Embodiment 4A is the polymeric material of embodiment 1A, wherein the polymeric material of Formula (I) is of Formula (1-6).
  • Embodiment 7A is the polymeric material of embodiment 6A, wherein the polymeric material of Formula (1-1) is of Formula (II).
  • Group Pi is defined as in Formula (II).
  • Groups X and R3 are defined as in Formula (I) and group R5 is a fluorinated alkyl.
  • Embodiment 25 A is the polymeric material of embodiment 23 A, wherein two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Embodiment 26A is the polymeric material of any one of embodiments lA to 25 A, wherein each polymeric block comprises a polymerized product of a monomer composition comprising 50 to 100 weight percent of a first monomer with a single (meth)acrylolyl group and 0 to 50 weight percent of a second monomer having a single ethylenically unsaturated group that is not a (meth)acryloyl group. The weight percent is based on the total weight of monomers in the monomer composition.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Embodiment 4B is the first reaction mixture of embodiment IB, wherein the photoinitiator of Formula (V) is of Formula (V-3).
  • Embodiment 6B is the first reaction mixture of embodiment 4B, wherein the initiator of Formula (V-3) is of Formula (V-5).
  • Embodiment 8B is the first reaction mixture of embodiment 7B, wherein the initiator of Formula (V-6) is of Formula (V-7).
  • Embodiment 12B is the first reaction mixture of embodiment 1 IB, wherein the first monomer composition comprises 80 to 100 weight percent of the first monomer and 0 to 20 weight percent of the second monomer.
  • Embodiment 13B is the first reaction mixture of any one of embodiments IB to 12B, wherein the first reaction mixture is free of a monomer having more than one ethylenically unsaturated groups.
  • Embodiment 1C is a second reaction mixture.
  • the second reaction mixture includes a) a polymeric material of Formula (II)
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR 2 - where R 2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Ri)2.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Pi is the first polymeric block, the first polymeric block being a polymerized product of the first monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • Embodiment 2C is the second reaction mixture of embodiment 1C, wherein the polymeric material of Formula (II) is of Formula (II- 1).
  • Embodiment 3C is the second reaction mixture of embodiment IC, wherein the polymeric material of Formula (II) is of Formula ( ⁇ -2).
  • Embodiment 4C is the second reaction mixture of embodiment IC, wherein the polymeric material of Formula (II) is of Formula ( ⁇ -3).
  • Embodiment 5C is the second reaction mixture of embodiment IC, 2C, or 4C, wherein X is oxy.
  • Embodiment 6C is the second reaction mixture of embodiments IC, 2C, or 4C, wherein X is
  • Embodiment 7C is the second reaction mixture of embodiment 3C or 4C, wherein R 2 is hydrogen, alkyl, or fluorinated alkyl.
  • Embodiment 8C is the second reaction mixture of any one of embodiments IC, 3C, or 4C, wherein R3 is alkoxy or fluorinated alkoxy.
  • Embodiment 9C is the second reaction mixture of any one of embodiments IC, 3C, or 4C, wherein R3 is -N(Ri)2.
  • Embodiment IOC is the second reaction mixture of embodiment 9C, wherein R 4 is alkyl or fluorinated alkyl.
  • Embodiment 11C is the second reaction mixture of embodiment 9C wherein two adjacent R 4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Embodiment 12C is the second reaction mixture of any one of embodiments IC to 11C, wherein the second monomer composition comprises 50 to 100 weight percent of a first monomer with a single (meth)acryloyl group and 0 to 50 weight percent of a second monomer having a single ethylenically unsaturated group that is not a (meth)acryloyl group. The weight percent is based on the total weight of monomers in the second monomer composition.
  • Embodiment 13C is the second reaction mixture of embodiment 12C, wherein the second monomer composition comprises 80 to 100 weight percent of the first monomer and 0 to 20 weight percent of the second monomer.
  • Embodiment 14C is the second reaction mixture of any one of embodiments 1C to 13C, wherein the second reaction mixture is free of a monomer having more than one ethylenically unsaturated groups.
  • Embodiment ID is a third reaction mixture.
  • the third reaction mixture includes a) a polymeric material of Formula (III)
  • group Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with at least one alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Ri)2.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Pi is a first polymeric block, the first polymeric block being a polymerized product of the first monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • Each P 2 is a second polymeric block different from the first polymeric block, the second polymeric block being a polymerized product of a second monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • Embodiment 2D is the third reaction mixture of embodiment ID, wherein the polymeric material of Formula (III) is of Formul -l).
  • Embodiment 3D is the third reaction mixture of embodiment ID, wherein the polymeric material of Formula (III) is of Formula (III -2).
  • Embodiment 4D is the third reaction mixture of embodiment ID, wherein the polymeric material of Formula (III) is of Formula ( ⁇ -3).
  • Embodiment 5D is the third reaction mixture of any one of embodiments ID, 2D, or 4D, wherein X is oxy.
  • Embodiment 6D is the third reaction mixture of any one of embodiments ID, 2D, or 4D, wherein X is -NR 2 -.
  • Embodiment 7D is the third reaction mixture of embodiment 3D, wherein R 2 is hydrogen, alkyl, or fluorinated alkyl.
  • Embodiment 8D is the third reaction mixture of any one of embodiments ID, 3D, or 4D, wherein R3 is alkoxy or fluorinated alkoxy.
  • Embodiment 9D is the third reaction mixture of embodiment 3D or 4D, wherein R3 is -N(Ri)2.
  • Embodiment 10D is the third reaction mixture of embodiment 9D, wherein R4 is alkyl or fluorinated alkyl.
  • Embodiment 11D is the third reaction mixture of embodiment 9D wherein two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • Embodiment 12D is the third reaction mixture of any one of embodiments ID to 1 ID, wherein the third monomer composition comprises 50 to 100 weight percent of a first monomer with a single (meth)acryloyl group and 0 to 50 weight percent of a second monomer having a single ethylenically unsaturated group that is not a (meth)acryloyl group. The weight percent is based on the total weight of monomers in the third monomer composition.
  • Embodiment 13D is the third reaction mixture of embodiment 12D, wherein the third monomer composition comprises 80 to 100 weight percent of the first monomer and 0 to 20 weight percent of the second monomer.
  • Embodiment 14D is the third reaction mixture of any one of embodiments ID to 13D, wherein the third reaction mixture is free of a monomer having more than one ethylenically unsaturated groups.
  • Embodiments IE is a method of making a polymeric material. The method includes providing an initiator of Formula (V).
  • Ri is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, substituted aryl (e.g., an aryl substituted with an alkyl and/or alkoxy).
  • Group X is oxy or -NR2- where R2 is hydrogen, alkyl, fluorinated alkyl, aryl, aralkyl, or substituted aryl (e.g., an aryl substituted with an alkyl and/or alkoxy).
  • Group R3 is an alkoxy, fluorinated alkoxy, or -N(Rt)2.
  • Each R4 is an alkyl or fluorinated alkyl, or two adjacent R4 groups are combined together with the nitrogen to which they are both attached to form a first heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, the first heterocyclic ring being saturated or unsaturated and optionally fused to one or more second rings that are carbocyclic or heterocyclic.
  • the method further includes preparing a first reaction mixture containing the initiator of Formula (V) and a first monomer composition containing at least one monomer having a single ethylenically unsaturated group.
  • the method still further includes forming a first polymeric material of Formula (II) from the first reaction mixture.
  • Pi is a first polymeric block, the first polymeric block being a polymerized product of the first monomer composition.
  • R 1; R 2 , R3, and X are the same as in Formula (V).
  • Embodiment 2E is the method of embodiment IE, wherein the initiator of Formula (V) is of Formula (V-3)
  • Embodiment 3E is the method of embodiment IE, wherein the initiator of Formula (V) is of Formula (V-2)
  • Embodiment 4E is the method of embodiment IE, wherein the initiator of Formula (V) is of Formula (V-9)
  • Embodiment 5E is the method of embodiment IE, further comprising preparing a second reaction mixture comprising the first polymeric material of Formula (II) and a second monomer composition different than the first monomer composition, the second monomer composition comprising at least one monomer having a single ethylenically unsaturated group.
  • the method further comprises forming a second polymeric
  • Embodiment 6E is the method of embodiment 5E, wherein the first polymeric material is of Formula (II- 1)
  • Embodiment 7E is the method of embodiment 5E, wherein the first polymeric material is of Formula ( ⁇ -2)
  • Embodiment 8E is the method of embodiment 5E, wherein the first polymeric material is of Formula ( ⁇ -3)
  • Embodiment 10E is the method of embodiment 9E, wherein the second polymeric material of Formula (III) is of Formula (III-l)
  • Embodiment 15E is the method of any one of embodiments IE to 2E, 4E to 6E, 8E to 10E and
  • Embodiment 16E is the method of any one of embodiments 3E, 7E, HE, and 15E, wherein R2 is hydrogen, alkyl, or fluorinated alkyl.
  • Embodiment 18E is the method of any one of embodiments IE, 3E to 5E, 7E to 9E, and HE to 12E, wherein R3 is -N(Rt)2.
  • Embodiment 19E is the method of any one of embodiments 2E, 6E, 10E, and 18E, wherein R4 is alkyl or fluorinated alkyl.
  • Embodiment 22E is the method of embodiment 2 IE, wherein the first monomer composition comprises 80 to 100 weight percent of the first monomer and 0 to 20 weight percent of the first monomer.
  • Embodiment 23E is the method of embodiment 5E or 8E, wherein the second monomer composition comprises 50 to 100 weight percent of a first monomer with a single (meth)acryloyl group and 0 to 50 weight percent of a second monomer having a single ethylenically unsaturated group that is not a (meth)acryloyl group. The weight percent is based on the total weight of monomers in the second monomer composition.
  • Embodiment 4F is the compound of embodiment 3F, wherein R 2 is hydrogen, alkyl, or fluorinated alkyl.
  • Embodiment 6F is the compound of any one of embodiments IF to 4F, wherein R3 is -N(R4)2.
  • Photoinitiator Example 1 Methyl 2,2-bis(diethylcarbamothioylsulfanyl)acetate
  • Photoinitiator Example 7 tert-Butyl -bis(isopropoxycarbothioylsulfanyl)acetate
  • Photoinitiator Comparative Example B 2-(2-Ethoxycarbothioylsulfanylacetyl)oxyethyl 2- ethoxycarbothioylsulfanylacetate
  • the probe of a ReactIR 15 in-situ infrared spectrometer (Mettler-Toledo Autochem, Redmond, VA) was inserted into one neck of the flask and the tip of the IR probe was maintained below the surface of the reaction solution.
  • the lamp was turned on and an infrared spectrum recorded every minute for the first hour, every 5 minutes for the next three hours, and 15 minutes thereafter.
  • the weight percent monomer conversion was calculated as:
  • the probe of a ReactIR 15 in-situ infrared spectrometer was inserted into one neck of the flask and the tip of the IR probe was maintained below the surface of the reaction solution.
  • the flask was immersed in a water bath maintained at 10- 12 °C.
  • the lamp was turned on and an infrared spectrum recorded every 30 seconds.
  • the weight percent monomer conversion was calculated as:
  • a 10.0 gram portion of the polymerization product mixture from Example 8 i.e. polymer product recovered before the reported purification procedure
  • isobornyl acrylate 5.0 grams, available from Sartomer, Exton, PA
  • ethyl acetate 15.0 grams
  • a plastic cap which was equipped with two needles to provide an inlet and an outlet, was attached to the vial. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes. The needles were then removed and the holes in the cap were plugged.
  • the vial was placed on a roller mixer and irradiated for 15 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial. The light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • the molecular weight (M w ) of the resulting block copolymer (A-B-A) was determined with test method 1. The molecular weight and polydispersity values are reported in Table 12.
  • a 10.0 gram portion of the polymerization product mixture from Example 11 i.e. polymer product recovered before the reported purification procedure
  • acrylic acid 0.05 grams, available from Thermo Fisher Scientific
  • 2-ethylhexyl acrylate 4.96 grams
  • ethyl acetate 15.0 grams
  • a plastic cap which was equipped with two needles to provide an inlet and an outlet, was attached to the vial. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes. The needles were then removed and the holes in the cap were plugged.
  • the vial was placed on a roller mixer and irradiated for 15 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial.
  • the light intensity measured at a distance of 10 cm was 1.25 mW.
  • the molecular weight (M w ) of the resulting block copolymer (A-B-A) was determined with test method 1.
  • the molecular weight and polydispersity values are reported in Table 14.
  • a 9.0 gram portion of the polymerization product mixture from Example 12 i.e. polymer product recovered before the reported purification procedure
  • acrylic acid 0.045 grams, available from Thermo Fisher Scientific
  • 2-ethylhexyl acrylate 4.46 grams
  • ethyl acetate 13.5 grams
  • the vial was placed on a roller mixer and irradiated for 15 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial.
  • the light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • the molecular weight (M w ) of the resulting block copolymer (A-B-A) was determined with test method 1.
  • the molecular weight and polydispersity values are reported in Table 14.
  • 2-ethylhexyl acrylate (25.0 grams, available from BASF Corporation), ethyl acetate (25 grams) and 2-ethylhexyl 2,2-bis(isopropoxycarbothioylsulfanyl)acetate (0.126 grams, Photoinitiator Example 4) were added to a glass vial.
  • a plastic cap which was equipped with two needles to provide an inlet and an outlet, was attached to the vial. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes. The needles were then removed and the holes in the cap were plugged.
  • the vial was placed on a roller mixer and irradiated for 40 minutes using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial.
  • the light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • the molecular weight (M w ) of the resulting polymer was determined with test method 1. The molecular weight and polydispersity values are reported in Table 15.
  • the molecular weight (M w ) of the resulting block copolymer (A-B-A) was determined with test method 1.
  • the molecular weight and polydispersity values are reported in Table 15.
  • a 4.80 gram portion of the polymerization product mixture from Example 26 and isobornyl acrylate (2.51 grams) were added to a glass vial.
  • a plastic cap which was equipped with two needles to provide an inlet and an outlet, was attached to the vial. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes. The needles were then removed and the holes in the cap were plugged.
  • the vial was placed on a roller mixer and irradiated for 2 hours using a UV lamp
  • the molecular weight (M w ) of the resulting block copolymer (C-A-B-A-C) was determined with test method 1. The molecular weight and polydispersity values are reported in Table 15.
  • the bottle was placed on a roller mixer and irradiated for 24 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial.
  • the light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • a 40 gram portion of the polymerization product mixture from Example 29, methyl methacrylate (3 grams, available from Sigma-Aldrich Corporation), and ethyl acetate (3 grams) were added to a 100 mL glass bottle.
  • a plastic cap with an inlet and an outlet port was attached to the vial.
  • a plastic needle was inserted through the inlet port and into the mixture. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes.
  • the cap and needle assembly was then removed and replaced with a solid cap that sealed the bottle.
  • the bottle was placed on a roller mixer and irradiated for 14 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial. The light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • Polymer Example 36 (Polymer EX 36) A 40 gram portion of the polymerization product mixture from Example 30, methyl methacrylate (6 grams), and ethyl acetate (6 grams) were added to a 100 mL glass bottle. A plastic cap with an inlet and an outlet port was attached to the vial. A plastic needle was inserted through the inlet port and into the mixture. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes. The cap and needle assembly was then removed and replaced with a solid cap that sealed the bottle. The bottle was placed on a roller mixer and irradiated for 14 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial. The light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • a UV lamp Sylvania F40/350BL black light
  • a 40 gram portion of the polymerization product mixture from Example 31, methyl methacrylate (9 grams), and ethyl acetate (9 grams) were added to a 100 mL glass bottle.
  • a plastic cap with an inlet and an outlet port was attached to the vial.
  • a plastic needle was inserted through the inlet port and into the mixture. Nitrogen gas was added through the needle and bubbled through the mixture for 15 minutes.
  • the cap and needle assembly was then removed and replaced with a solid cap that sealed the bottle.
  • the bottle was placed on a roller mixer and irradiated for 14 hours using a UV lamp (Sylvania F40/350BL black light) placed 10 cm above the vial. The light intensity measured at a distance of 10 cm was 1.25 mW/cm2.
  • the probe of a ReactIR 15 in-situ infrared spectrometer was inserted into one neck of the flask and the tip of the IR probe was maintained below the surface of the reaction solution.
  • the flask was immersed in a water bath maintained at 10-12 °C.
  • the lamp was turned on and an infrared spectrum recorded every 15 seconds.
  • the weight percent monomer conversion was calculated as:
  • FIG. 1 shows the aromatic region of the l NMR spectrum for 93 percent conversion (i.e., polymerization) of the monomers.
  • the peak assignments were confirmed from a 2D gHMBC experiment.
  • the mono-directional polymeric chain has two aromatic resonances (7.28 and 7.10 ppm) that correlate to methylenes at 41.9 and 33.0 ppm in 13 C, corresponding to the Ctt attached to sulfur or the first polymer chain unit, respectively.
  • the term "mono- directional" refers to polymeric chains where a single radical group of formula R3-(CS)-S* (which in this comparative example is the carbamate group (C 2 H5) 2 N-(CS)-S*) has been cleaved to initiate polymeric chain growth in a single direction.
  • the aromatic resonance at 7.03 ppm is a symmetric resonance for all four protons of the "bi-directional" phenyl group that has a methylene attached to polymer chain on both sides. This resonance also has a gHMBC correlation to 33.0 ppm, consistent with attachment to the polymer chain.
  • bi-directional refers to polymeric chains where two radical groups of formula R3-(CS)-S* (which in this comparative example are both the carbamate groups (C2H5)2 -(CS)-S*) have been cleaved to initiate polymeric chain growth in two directions and the resulting initiator fragment *-CH2-Ph-CH2-* is left in the middle of the polymer chain.
  • the moles of polymer chain is the mono-directional resonance at 7.10 ppm divided by 2 plus the bi-directional resonance at 7.03 ppm divided by 4.
  • the M n is calculated as DP* 128.17 (the molecular weight of a BA repeat unit).
  • the mole fraction of free initiator remaining was calculated from the moles of free initiator (phenyl integral at 7.33 ppm divided by 4) divided by the moles of total initiator species (moles free initiator plus moles mono-directional phenyl (7.10 ppm integral divided by 2) and bi-directional phenyl (7.03 ppm integral divided by 4)).
  • the mole fraction of mono-directional polymeric chains was calculated by dividing the integral of mono-directional polymeric chains by the total polymeric chains (mono-directional and bi-directional).
  • XDC has poor efficiency of initiation with half of the initiator unreacted at 92% conversion.
  • the second cleavage event to produce bi-directional polymeric chains is also inefficient with the majority of polymeric chains still mono-directional at 92% conversion.
  • the M n profile is non-ideal for living radical behavior with non-linear growth and high initial values of M n that decreases with percent conversion.
  • CEX H Compared to CEX G, CEX H has slightly improved reaction kinetics, but still overall non- optimum characteristics of high unreacted initiator and a significant percentage of mono-directional polymer chains at high conversion.
  • the l NMR spectrum is shown in FIG. 2.
  • Two different types of polymeric chains were observed in NMR spectra as indicated by the changes in methyl ester chemical shift.
  • the methyl ester of the free initiator is a sharp singlet at 3.82 ppm.
  • the singlet at 3.73 ppm was assigned to mono-directional polymer chain via gHMBC correlations to a carbonyl at 171 ppm that a S-CH methine also has correlations with.
  • the multiple resonances are believed to be from sequence effects of low molecular weight oligomers.
  • the resonance shifts to a single peak at 3.66 ppm at higher molecular weight.
  • Quantitative results were determined in a similar manner to CEX G with the following integrals calculations used: free initiator (3.82 ppm divided by 3), mono-directional polymer chain (3.73 ppm divided by 3), and bi-directional polymer chain (3.66-3.71 ppm divided by 3).

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