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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
  • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
• • 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
  • C08F120/10—Esters
  • C08F120/12—Esters of monohydric alcohols or phenols
  • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
  • C08F2/46—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/28—Treatment by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
  • C08J2375/08—Polyurethanes from polyethers

Definitions

• - monomer (B) comprises at least two functional groups W 3 and W 4 , said W 3 and W 4 being independently selected from -OH, -CH 2 OH, -NH 2 , -NHR 11 , -SH, -Si(OR n ) 2 -H,
• Polymeric photoinitiators being copolymers of monomer (A) of formula (I) provides the means for efficient curing of polymeric materials, such as for example coatings on, or materials in, medical devices, paints, or lacquers.
• the photoinitiator monomers of the present invention by their two functional groups, allow for incorporation by covalent bonds into polymeric materials, hereby limiting or even preventing the migration of the photoinitiator itself, or its by products, to the surface of the final product encompassing the polymeric material.
• photoinitiator monomers and polymeric photoinitiators of the present invention are useful in connection with a wide variety of polymers, such as for example polyurethanes, polyureas, polythiourethanes, polythioureas, polydithiourethanes, polyesters, polycarbonates, polyphosphonites, polyphosphonates and polyphosphates.
• Polyureas are typically formed by the reaction between one monomer having at least two isocyanate functional groups (-NCO) or macromonomer having two terminal -NCO groups, and another monomer or macromonomer having at least two amine (-NH 2 ) groups.
• polyureas can be formed by the reaction between one monomer having at least two amine (-NH 2 ) groups, and phosgene (COCI 2 ) or diphosgene (Cl- CO-OCC ).
• a polyurea according to the present invention may in this manner also be a polymer having such urea moieties in the chain in between macromonomer moieties of e.g. polyether, polyester or polycarbonate.
• This may for example be the case when a polyurea comprises A, B and C monomers, where A has two amine groups, B has two isocyanate groups, and C is a polyamine macromonomer having two free terminal amine groups (giving e.g.
• polythioureas are typically formed by the reaction between one monomer having at least two isothiocyanate functional groups (-NCS), and another monomer having at least two amine (-NH 2 ) groups.
• a polythiourea according to the present invention may in this manner also be a polymer having such thiourea moieties in the chain in between macromonomer moieties of e.g.
• -Xi-Wi and -X 2 -W 2 are each independently attached to Y at either the N-atom or the -Z-, -Za-, -Zb-, or -Zc- linker, one or both of the -Xi-Wi and -X 2 -W 2 may be attached to the same linker moiety wherever it is chemically feasible (the dotted lines represent a point of attachment on N-atom or linkers, and the wavy line represent the attachment point of Pi); with the proviso that when the linker is either Z or -Za-Zb-, at least one of -Xi-Wi and -X 2 -W 2 is attached to an atom other than the N-atom; when one of -Xt-VJt or -X 2 -W 2 is attached to the N-atom, said N-atom is also substituted with R 5 ; when neither of -Xi-Wi or -X 2 -W 2 are attached to the N-atom, it is substituted
• Pi of general formula (I) is a non-cleavable photoinitiator, more preferably a Norrish type II photoinitiator. This due to the goal of the present invention to provide photoinitiator monomers of formula (I) where the migration of by-products from the final polymer product is avoided or at least considerably decreased.
• Photoinitiator moieties (Pi) in Formula (I) may be selected from, but not exclusively restricted to, the group consisting of benzoin ethers, phenyl hydroxyalkyl ketones, phenyl aminoalkyl ketones, benzophenones, thioxanthones, xanthones, acridones, anthraquinones, fluorenones, dibenzosuberones, benzils, benzil ketals, -dialkoxy-acetophenones, -hydroxy-alkyl- phenones, ⁇ -amino-alkyl-phenones, acyl-phosphine oxides, phenyl ketocoumarins, camphorquinones, silane and derivatives thereof, and maleimides.
• cycloalkyl as used herein, unless otherwise indicated, includes non-aromatic saturated cyclic alkylene moieties, where alkylene is as defined above, or cyclic alkyl moieties, where alkyl is as defined above.
• Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.
• Cycloalkyl is preferably C 3 -C 8 cycloalkyl, i.e. cycloalkyl groups containing from 3 to 8 carbon atoms, and more preferably C 3 -C 6 cycloalkyl.
• aryl is used to define moieties derived from arenes in which two H atoms have been removed to form a diradical species (i.e. arylene). Examples include 1,2-phenylene, 1,3-phenylene and 1,4- phenylene.
• photoinitiator monomers of formula (I) comprise only two end groups Wi and W 2 capable of taking part in a particular polymerisation reaction
• the monomer of formula (I) will be incorporated in the polymer backbone with the photoinitiator as a pendant group via the linkers Z, ZaZb and Zc, branching of the polymer is additionally avoided. It is therefore to be avoided that other functional groups being capable of participating in the desired polymer reaction are present in the photoinitiator monomers of the present invention. This therefore also applies to any optional substituents being present on photoinitiators of formula (I).
• Z may be selected from optionally substituted Ci-C 6 alkylene and optionally substituted -0-(Ci-C 6 alkylene)-.
• the -(C 1 -C 12 alkylene)- -(C 2 -Ci 2 alkenylene)-, C 3 -C 8 cycloalkyl, - heterocyclyl-, and -aryl- groups may be substituted or unsubstituted.
• Xi and X 2 may be linked to one another or to linker Zc to form one or more ring structures;
• R 3 is H or optionally substituted Ci-Ci 2 alkyl
• R 4 is optionally substituted C 1 -C 12 alkyl
• R 1 may alternatively be optionally substituted Ci-C 6 alkyl, such as e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl.
• R 2 may be optionally substituted Ci-C 6 alkyl, such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl.
• Ci-C 6 alkyl such as e.g. methyl, ethyl, propyl, butyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl.
• R 3 may be H.
• R 3 may alternatively be optionally substituted Ci-C 6 alkyl, such as e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl.
• R 4 may be optionally substituted Ci-C 6 alkyl, such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl.
• Ci-C 6 alkyl such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or isopentyl.
• the N-atom of Y is always to be a tertiary amine.
• R 5 when there herein is written "when one of -Xt-VJt or -X 2 -W 2 is attached to the N-atom, said N-atom is substituted with R 5 ; when neither of -Xi-Wi or -X 2 -W 2 are attached to the N-atom, said N-atom is substituted with both R 5 and R 6 " it is meant to described that the N-atom of the tertiary amine always will be "substituted" with three "moieties", one of which always is a linker (Z, Za, Zb or Zc), the other two being selected from: -Xi-Wi, -X 2 -W 2 , R 5 and R 6 .
• Xi and X 2 may independently be selected from optionally substituted Ci-Ci 2 alkylene, when Wi and W 2 are -OH.
• Xi and X 2 may preferably be independently selected from a single bond or optionally substituted Ci-Ci 2 alkylene, when Wi and W 2 are -CH 2 OH.
• monomer (B) is a polyisocyanate, preferably a diisocyanate.
• Suitable polyisocya nates have an average of about two or more isocyanate groups, preferably an average of about two to about four isocyanate groups and include aliphatic, cycloaliphatic, aralkyl and aromatic polyisocya nates, used alone or in mixtures of two or more. Diisocyanates are preferred, this is for example the case where the polymeric photoinitiator is a polyurethane.
• the polymeric photoinitiator is a polyurethane photoinitiator.
• Wi and W 2 are selected to be alcohol functional groups
• W 3 and W 4 are selected as isocyanate groups to provide urethane moieties when monomer (A) reacts with monomer (B).
• the polymeric photoinitiator of the invention When the polymeric photoinitiator of the invention is mixed with acrylate monomers (Ac), these reactive radicals undergo chain propagation with the acrylate monomers (Ac), and rapid curing of such monomers can occur. As growth is initiated from the polymeric photoinitiator, the polymeric photoinitiator will itself be incorporated by means of covalent bonds into the growing polyacrylate.
• acrylate monomers Ac
• M n is number average molecular weight value. It is defined as arithmetic mean of the molecular weights of the individual
• pentaerythritol triacrylate pentaerythritol propoxylate triacrylate, glycerol propoxylate triacrylate, triallylcyanurate, pentaerythritol tetraacrylate, pentaerythritol tetra methacrylate, di(trimethylolpropane) tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
• the polyacrylate of the invention may comprise two or more different acrylate monomers (Ac). Different acrylate monomers (Ac) can be mixed in various ratios, depending on the desired properties of the resulting polyacrylate.
• the polyacrylate of the invention may comprise additional monomers.
• a copolymer of the acrylate monomer(s) (Ac) with other monomers may be obtained.
• the polymeric photoinitiator of the invention may be used to initiate the
• the reactions can be conveniently carried out in aromatic solvents such as toluene at temperatures ranging from 0 °C to 80 °C in the presence of tertiary amines.
• a general scheme for the formation of polyurethanes of Formula (III) using photoinitiator monomers of Formula (I) is shown in Scheme 1 below :
• a photoinitiator of Formula (I) is :
• Za and Zb together form a linker in which Za is selected from optionally substituted -[0-(Ci-Ci 2 alkylene)] n -, optionally substituted -[NR 2 -(Ci-Ci 2 alkylene)] n , and optionally substituted -[S-(Ci-Ci 2 alkylene)] n -, wherein Za is joined to Pi via the O, N or S atom in Za, and Zb is a linker moiety;
• Wi and W 2 are each independently selected from -OH, -CH 2 OH, -NH 2 , -NHR 8 , -SH,
• R 3 is H or optionally substituted Ci-Ci 2 alkyl
• Pi is a photoinitiator moiety
• R 4 is optionally substituted C1-C12 alkyl
• Zb is selected from a single bond, optionally substituted Ci-Ci 2 alkylene, optionally substituted C 2 - C12 alkenylene, -0-, -S-, -NR 2 -, -[0-(Ci-Ci 2 alkylene)] n -, and combinations thereof, wherein R 2 is optionally substituted C1-C12 alkyl and n is an integer from 1-20 .
• Y is selected from :
• R 8 is Ci-C 6 alkyl.
• Pi is a photoinitiator moiety selected from benzophenones, thioxanthones, benzilketals and phenyl hydroxyalkyl ketones, such as 2-hydroxy-2-methyl-l-phenylpropan-l-ones.
• Q is selected from the group consisting of optionally substituted aryl and optionally substituted biaryl.
• HDI isophorone diisocyanate
• IPDI isophorone diisocyanate
• HMDI bis(4- isocyanatocyclohexyl)methane
• TMHDI 2,2,5-trimethylhexane diisocyanate
• CHDI 1,4-cyclohexane diisocyanate
• HXDI l,3-bis(isocyanato-methyl)cyclohexane
• T is selected from the group consisting of -[0-(Ci-Ci 2 alkylene)] m -, -[S-(Ci-Ci 2 alkylene)] m -, where m is an integer from 1-1000.
• W 5 and W 6 are independently selected from -OH, -CH 2 OH, -NH 2 , -NHR 13 , and -SH, preferably -OH or -CH 2 OH.

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• Polyurethanes Or Polyureas (AREA)

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