WO2008060844A1 - Compositions inhibitrices de polymérisation, leur préparation et leur utilisation - Google Patents

Compositions inhibitrices de polymérisation, leur préparation et leur utilisation Download PDF

Info

Publication number
WO2008060844A1
WO2008060844A1 PCT/US2007/082835 US2007082835W WO2008060844A1 WO 2008060844 A1 WO2008060844 A1 WO 2008060844A1 US 2007082835 W US2007082835 W US 2007082835W WO 2008060844 A1 WO2008060844 A1 WO 2008060844A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
phenylhydroxylamine
nitroso
tris
aluminum salt
Prior art date
Application number
PCT/US2007/082835
Other languages
English (en)
Inventor
Wenfeng Kuang
Original Assignee
Albemarle Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Publication of WO2008060844A1 publication Critical patent/WO2008060844A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation

Definitions

  • This invention relates to novel stable liquid polymerization inhibitor compositions comprised of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt, to methods of forming such compositions, and to use of such compositions in photocurable formulations.
  • Tris(N-nitroso-N-phenylhydroxylamine)aluminum salt is a very effective polymerization inhibitor for use in photocurable formulations (also called radiation curable compositions.)
  • the compound is available from Albemarle Corporation as
  • Tris(N-nitroso-N-phenylhydroxylamine)- aluminum salt is itself in the solid state of aggregation. To enhance its utility as a polymerization inhibitor, it is desirable to provide the compound in a liquid form. [0003] Heretofore, tris(N-nitroso-N-phenylhydroxylamine)aluminum salt has been sold in a liquid polymerization inhibitor blend with the acrylic acid ester of 2-phenoxyethanol. Unfortunately however the blend has a strong unpleasant odor.
  • compositions which possess most if not all of the foregoing attributes.
  • the compositions are highly suitable for use as additives in forming photocurable formulations.
  • these compositions can contain about 10 wt% or more of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt.
  • liquid polymerization inhibitor compositions are formed from ingredients comprised of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt and a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2- methylpropiophenone, ⁇ , ⁇ -diethoxyacetophenone, or 1-benzoylcyclohexanol, or a combination of any two or more of these; or b) benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these; or c) both a) and b), with the proviso that if a) is 1-benzoylcyclohexanol, then at least one ingredient from b) is also present in said composition.
  • the polymerization inhibitor compositions of this invention are liquids.
  • a) is 1-benzoylcyclohexanol
  • an ingredient from b) is also present in the composition in order to make the composition liquid. See in this connection U.S. Pat. No. 4,563,438.
  • This invention also provides a method of producing a liquid polymerization inhibitor composition, which method comprises mixing together tris(N-nitroso-N- phenylhydroxylamine)aluminum salt and a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2- methylpropiophenone, ⁇ , ⁇ -diethoxyacetophenone, or 1-benzoylcyclohexanol, or a combination of any two or more of these; or b) benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these; or c) both a) and b), with the proviso that if a) is 1-benzoylcyclohexanol, then at least one ingredient from b) is also present in said composition, to form a liquid composition. Storing such liquid composition results in
  • the formulation comprises at least one photocurable monomer, oligomer, and/or polymer, in which the improvement is that the polymerization inhibitor in the formulation is a liquid formed from ingredients comprised of tris(N-nitroso- N-phenylhydroxylamine)aluminum salt and a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2- methylpropiophenone, ⁇ , ⁇ -diethoxyacetophenone, or 1-benzoylcyclohexanol, or a combination of any two or more of these; or b) benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these; or c) both a) and b), with the proviso that
  • Benzophenone is called a benzoylphenyl group when it is a substituent moiety. It is to be understood that unless stated otherwise, as used throughout this document, the term "benzoylphenyl” includes both substituted and unsubstituted benzoylphenyl groups. Substituent groups on the benzoylphenyl group can be any substituent that does not prevent formation of a liquid polymerization inhibitor composition when a compound containing a substituted benzoylphenyl group is used in forming the liquid polymerization inhibitor composition.
  • a feature of this invention is that relatively large amounts of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt can be put in liquid form in a polymerization inhibitor composition. Amounts of at least about 0.1%, often about 5% to about 10%, and up to about 12%, based on the total weight of the composition, of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt have been successfully included in liquid polymerization inhibitor compositions of the invention.
  • novel polymerization inhibitor composition is in the form of a liquid formed from ingredients comprised of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt with 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'- (2-hydroxyethoxy)-2-methylpropiophenone, or ⁇ , ⁇ -diethoxyacetophenone, or a combination of any two or more of these.
  • a preferred ingredient for mixing with the tris(N-nitroso-N- phenylhydroxylamine)aluminum salt is 2-hydroxy-2-methylpropiophenone.
  • Another type of novel polymerization inhibitor compositions made available by this invention is in the form of liquids formed from ingredients comprised of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt with benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these.
  • Preferred ingredients for mixing with the tris(N-nitroso-N-phenylhydroxylamine)aluminum salt are benzophenone and at least one ester having a benzoylphenyl group therein; more preferred is benzophenone.
  • Benzoylphenyl esters used to form the compositions of this invention can be represented by the structures
  • R can be, but is not limited to, an alkyl, ether, ester, amino, or amido group.
  • R contains up to about twelve atoms; more preferably, R has about one to about six atoms. It is to be understood that these structural representations are not to be construed to limit the benzoylphenyl-containing esters. More than one ester group may be present, and such ester groups may be on the same ring or on separate rings. Substituents can be present on one or both rings of the benzoylphenyl group.
  • Suitable substituent groups include alkyl (preferably Ci to C 6 ), alkoxy (preferably having up to about twelve carbon atoms), ether, ester, amino, and/or amido groups, and the like.
  • substituents groups for the benzoylphenyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, hydroxy, methoxy, ethoxy, trifluoromethyl, amino, methylamino, diethylamino, dibutylamino, nitro, and fluoro groups.
  • R' can be, but is not limited to, an alkyl, ether, amino, or amido group.
  • R' contains up to about twelve atoms; more preferably, R' has about one to about six atoms.
  • Suitable R groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, trifluoromethyl, amino, methylamino, diethylamino, dibutylamino, fluoro, and the like.
  • Esters having a benzoylphenyl group therein that are suitable for use in this invention include, but are not limited to, methyl ortho-benzoyl benzoate, ethyl meta-benzoyl benzoate, n-propyl para-benzoyl benzoate, isopropyl 2-(3-benzoylphenyl)propionate, n-butyl 2-(p- chlorobenzoyl)phenylpropionate, sec-butyl 3-benzoyl-2-methoxyphenyl)acetate, tert-butyl (2- amino-3-benzoylphenyl)acetate, pentyl 4-benzoyl-alpha-methylbenzeneacetate, cyclopentyl 2-(m-benzoylphenoxy)acetate, hexyl 2-amino-(4'-chlorobenzoyl)phenylacetate, cyclohexyl A- (2-methyl-3-(4-chloro
  • Preferred benzoylphenyl esters have only one ester group; also preferred are benzoylphenyl esters without substituents. More preferred esters are benzoyl benzoates (also known as benzophenone carboxylates), with or without substituents. Still more preferred are benzoyl benzoates without substituents ⁇ i.e., ortho-benzoyl benzoate, meta-benzoyl benzoate, and para-benzoyl benzoate). A highly preferred benzoylphenyl ester is methyl ortho-benzoyl benzoate.
  • Acrylates having a benzoylphenyl group therein that are used to form the compositions of this invention can be represented by the structure
  • R" can be, but is not limited to, hydrogen, an alkyl, ether, ester, amino, or amido group.
  • R" contains up to about twelve atoms; more preferably, R" has about one to about six atoms. It is to be understood that this structural representation is not to be construed to limit the acrylates having a benzoylphenyl group therein. Substituents can be present on one or both rings of the benzoylphenyl group. Suitable substituent groups for the benzoylphenyl group include alkyl (preferably Ci to C 6 ), alkoxy (preferably having up to about twelve carbon atoms), ether, ester, amino, and/or amido groups, and the like.
  • substituent groups on the benzoylphenyl rings include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, hydroxy, methoxy, ethoxy, trifluoromethyl, amino, methylamino, diethylamino, dibutylamino, nitro, and fluoro groups.
  • R" can be, but is not limited to, an alkyl, ether, amino, or amido group.
  • R" contains up to about twelve atoms; more preferably, R" has about one to about six atoms.
  • Suitable R" groups include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, amino, methylamino, diethylamino, dibutylamino, and the like.
  • the acrylates having a benzoylphenyl group therein which can be used as an ingredient in the compositions of the invention.
  • R" when R" is hydrogen, the compound can be called benzoylphenylacrylate or 4-benzoylphenyl 2-propenoate; similarly, when R" is methyl, the compound can be called methyl benzoylphenylacrylate or 4-benzoylphenyl 2-methyl-2- propenoate.
  • Acrylates having a benzoylphenyl group therein that are suitable for use in this invention include ortho-benzoylphenylacrylate, meta-benzoylphenylacrylate, para- benzoylphenylacrylate, 2-methoxy-meta-benzoylphenylacrylate, methyl ortho- benzoylphenylacrylate, ethyl meta-benzoylphenylacrylate, isopropyl para- benzoylphenylacrylate, n-butyl 2-methoxy-meta-benzoylphenylacrylate, 4-benzoyl-3- hydroxyphenyl methacrylate, and the like.
  • Preferred acrylates having a benzoylphenyl group therein are benzoylphenylacrylates without substituents. More preferred acrylates are unsubstituted benzoylphenylacrylates in which R" is hydrogen.
  • a third type of novel polymerization inhibitor compositions of this invention is in the form of solutions formed from ingredients comprised of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt with c), both a) 2-hydroxy-2-methylpropiophenone, 2- hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, ⁇ , ⁇ -diethoxyacetophenone, or 1- benzoylcyclohexanol, or a combination of any two or more of these, and b) benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these.
  • Preferred combinations of ingredients for mixing with the tris(N-nitroso-N- phenylhydroxylamine)aluminum salt include 2-hydroxy-2-methylpropiophenone with benzophenone, 2-hydroxy-2-methylpropiophenone with methyl ortho-benzoyl benzoate, and 1-benzoylcyclohexanol with benzophenone; more preferred is 2-hydroxy-2- methylpropiophenone with benzophenone.
  • Proportions of a) to b) can be any, such as from 0.1 :99.9 to 99.9:0.1, provided that the composition is liquid.
  • the amount of 1-benzoylcyclohexanol is such that the composition is a liquid, and usually is in the range of about 5 to about 80% of the combination; more preferably, the 1-benzoylcyclohexanol is about 30% to about 70% of the combination; even more preferred is about 40% to about 60% 1-benzoylcyclohexanol.
  • the solid ester or acrylate is usually about 80% or less of the combination of a) and b).
  • Preferred proportions of a) to b) are in the range of about 20:80 to about 80:20; more preferred are proportions of a) to b) in the range of about 30:70 to about 70:30. Still more preferred are proportions of a) to b) in the range of about 40:60 to about 60:40.
  • the liquid polymerization inhibitor compositions of this invention have good solubilities in common organic solvents and media, good storage stabilities, and are highly efficient in inhibiting premature polymerization of various photocurable formulations in which they can be used. Moreover the components of these blends can be proportioned so as to provide little if any offensive odor.
  • the polymerization inhibitor compositions of this invention contain at least about 0.1 wt%, typically at least about 1 wt%, preferably at least about 5 wt%, and more preferably at least about 6 wt% of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt based on the total weight of the composition. Amounts up to about 8 wt%, 10 wt%, and 12 wt% tris(N-nitroso- N-phenylhydroxylamine)aluminum salt can be present in the liquid compositions of the invention.
  • the components of the blends are proportioned such that they do not exceed the room temperature (e.g., 23°C) solubility limit of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt in the particular component(s) used in forming the liquid composition.
  • the compositions may even be concentrated cloudy liquids.
  • tris(N-nitroso-N-phenylhydroxylamine)aluminum salt is known in the art and is described for example in U.S. Pat. No. 6,018,078.
  • tris(N-nitroso-N- phenylhydroxylamine)aluminum salt can be prepared by reacting an aluminum salt, such as aluminum sulfate, with N-nitroso-N-phenylhydroxylamine ammonium salt, although other salts, such as halides, phosphates, nitrates, carbonates, and organic acid salts of the metal can also be used.
  • the components thereof are mixed together in any suitable manner using typical mixing apparatus such as a blending tank or vessel equipped with suitable agitation or stirring means.
  • Additional components may be included in the liquid polymerization inhibitor compositions of this invention, provided that such components do not materially detract from the beneficial attributes of compositions in which they are employed.
  • additional components which may be included in the blends of this invention include dyes, acrylate and/or methacrylate monomers acrylate and/or methacrylate oligomers, common organic solvents, oxidation inhibitors, viscosity modifiers, fillers, photoinitiators, and tertiary amines.
  • additional components include acetone, isopropyl alcohol, acetonitrile, waxes, polymer powders, N,N-diethyl-4-aminoazobenzene (DEAB), (2,4,6 trimethyl benzoyl) diphenyl phosphine oxide (TPO, Albemarle Corporation),
  • EDAB ethyl-4(dimethylamino) benzoate
  • ODAB 2-ethylhexyl- 4(dimethylamino)benzoate
  • N-methyl-N,N-diethanolamine N-methyl-N,N-diethanolamine
  • tris-(2,4-di-t-butylphenyl) phosphite ETHAPHOSTM 368, Albemarle Corporation
  • the resultant liquid polymerization inhibitor composition should contain at least about 10 wt% of the combination of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt with a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy- 4'-(2-hydroxyethoxy)-2-methylpropiophenone, ⁇ , ⁇ -diethoxyacetophenone, or 1- benzoylcyclohexanol, or a combination of any two or more of these; or b) benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these; or c) both a) and b), with the proviso that if a) is 1-benzoylcyclohexanol, then at least one ingredient from b) is also present
  • Preferred polymerization inhibitor compositions of this invention are formed from components which — except for traces of impurities that are or may be normally present in the components themselves or traces of impurities resulting from contact with containers, stirring blades and/or shafts, conduits or pipes, or similar equipment encountered in connection with preparation, transportation, and/or storage of the components or the polymerization inhibitor compositions themselves — are composed entirely or substantially entirely (e.g., at least about 10 wt% and preferably at least about 20 wt% of tris(N-nitroso-N- phenylhydroxylamine)aluminum salt with a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy- 4'-(2-hydroxyethoxy)-2-methyl-propiophenone, ⁇ , ⁇ -diethoxyacetophenone, or 1- benzoylcyclohexanol, or a combination of any two or more of these; or b) benzophenone, at least one ester having a benzoylphenyl
  • liquid polymerization inhibitor compositions of this invention can be included as polymerization inhibitors in the preparation of any of a wide variety of photocurable formulations.
  • a photocurable formulation formed using a polymerization inhibitor composition can contain in addition, one or more photocurable monomers, one or more photocurable oligomers or polymers, or one or more photoinitiators (free-radical or cationic).
  • additional components one or more of which can also be in such formulations are, for example, coinitiators (a.k.a. synergists), rheology modifiers, pigments, dyes, light stabilizers, radical scavengers and adhesion promoters.
  • coinitiators a.k.a. synergists
  • rheology modifiers rheology modifiers
  • pigments pigments
  • dyes dyes
  • light stabilizers light stabilizers
  • radical scavengers radical scavengers and adhesion promoters.
  • Photocurable formulations produced by use of liquid polymerization inhibitor compositions of this invention can be formed by mixing a blend of this invention with the ingredients typically used in forming a radiation curable formulation.
  • Mixing apparatus such as a blending tank or vessel equipped with suitable agitation or stirring means can be used in forming the radiation curable formulations of this invention.
  • Photocurable formulations produced by use of polymerization inhibitor compositions of this invention typically contain in the range of about 0.005 to about 10 wt%, and preferably in the range of about 0.1 to about 4 wt%, of a blend of this invention, based on the total weight of the formulation.
  • photocurable monomers, oligomers, and/or polymers that can be used in forming photocurable formulations include monomeric, oligomeric, polymeric, or copolymeric forms of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl acrylate, diethyla
  • Preferred photocurable monomers, oligomers, and/or polymers which may be used in such formulations include monomeric, oligomeric, polymeric, or copolymeric forms of tripropylene glycol diacrylate, trimethylol propane tetraacrylate, ethoxylated trimethylol propane tetraacrylate, propoxylated neopentyl glycol diacrylate, hexanediol diacrylate, and the like, as well as mixtures of any two or more thereof.
  • alpha,beta-ethylenically unsaturated carboxylic acids can be used in conjunction with acrylate and/or methacrylate monomers, oligomers, and/or polymers, typically for the purpose of providing improved adhesion to certain substrates.
  • examples of such acids include methacrylic acid, acrylic acid, itaconic acid, maleic acid, beta- carboxyethyl acrylate, beta-carboxyethyl methacrylate, and the like, as well as mixtures of any two or more thereof.
  • photocurable monomers, oligomers, and/or polymers which may be used in such formulations include monomeric, oligomeric, polymeric, or copolymeric forms of thiols, vinyl ethers, vinyl esters, N-vinyl compounds, unsaturated polyesters, styrene, divinyl benzene, acrylonitrile, polyester acrylates, polyurethane acrylates, epoxy acrylates, polyether acrylates, silicone acrylates, fluoro-acrylates, and amine acrylates.
  • Formulations to be subjected to photocuring typically contain in the range of about 0.5 to about 85 wt% of one or more photocurable monomers, oligomers, or polymers such as those described above.
  • Preferred formulations contain in the range of about 20 to about 75 wt% of one or more of such photocurable substances. Selections within these ranges are typically made for effecting adjustments of viscosity to suit the particular application method to be used.
  • photocurable formulations adapted for use in forming low viscosity web coatings typically contain in the range of about 50 to about 70 wt % of one or more such monomers, oligomers, or polymers based on the weight of the total composition to be subjected to photocuring (radiation curing).
  • Free-radical photoinitiators which can be used in the photocurable formulations that can be formed using the liquid polymerization inhibitor compositions of this invention are of two general types: Type I, those that undergo photocleavage to yield free radicals, and Type II, those that produce initiating radicals through an abstraction process.
  • Type I photoinitiators produce radicals through a unimolecular fragmentation. Examples of these include aromatic carbonyl compounds, such as derivatives of benzoin, benzilketal and acetophenone.
  • Type II (abstraction type) photoinitiators are typically aromatic ketones, such as thioxanthones and benzophenone derivatives.
  • a coinitiator must be present in order to produce an initiating radical.
  • These coinitiators can include amines, alcohols, thiols, or ethers. The process of producing radicals is either through a hydrogen abstraction or an electron transfer mechanism depending on the coinitiator.
  • Non-limiting examples of photoinitiators that can be used in the radiation curable formulations include Type I (unimolecular fragmentation type) initiators, such as alpha- diketone compounds or monoketal derivatives thereof (e.g., diacetyl, benzil, benzyl, or dimethylketal derivatives); acyloins (e.g., benzoin, pivaloin, etc.); acyloin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, etc.), acyl phosphine oxides, and other similar Type I initiators, including mixtures of any two or more such initiators.
  • Type I unimolecular fragmentation type
  • alpha- diketone compounds or monoketal derivatives thereof e.g., diacetyl, benzil, benzyl, or dimethylketal derivatives
  • acyloins e.g.,
  • Type II (abstraction-type) initiators can be used.
  • suitable Type II initiators include xanthone, thioxanthone, 2-chloroxanthone, benzil, benzophenone, 4,4'-bis(N,N'-dimethylamino)benzophenone, polynuclear quinones (e.g., 9,10- anthraquinone, 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and 1,4-naphthoquinone), or the like, as well as mixtures of any two or more thereof.
  • Preferred Type I initiators include ketals such as benzyl dimethyl ketal.
  • Type II initiators include hydrogen quinones such as benzoquinone and 2-ethyl anthraquinone. Mixtures of Type I and Type II initiators can also be used. The initiator or mixture of initiators is typically added in an amount of about 0.01 to about 10 parts by weight, preferably about 0.05 to about 5 parts by weight, per 100 parts by weight of the monomer(s), oligomer(s), or polymer(s) to be photocured. [0038] Of the various coinitiators that can be used in the formulations, tertiary amines are typically favored for use.
  • amine coinitiators which can be used in the formulations include N-[3-(dimethylamino)propyl]-N,N',N'-trimethyl-l,3- propanediamine (Polycat 77; Air Products, Inc.), 2,2'-oxybis[N,N-dimethylethanamine] (DABCO BL- 19; Air Products, Inc.), N,N-dimethyl-4-morpholineethanamine (DABCO XDM; Air Products, Inc.); methyldiethanolamine; acrylate amines; 2-ethylhexyl- 4(dimethylamino)benzoate (ODAB); ethyl-4(dimethylamino) benzoate (EDAB); morpholine derivatives; and one or more trialkylamines each having a total of 10 to about 36 carbon atoms in the molecule and wherein at least one alkyl group has a chain length of at least 8 carbon atoms,
  • Dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethyl- amine, octadecyldimethylamine, didecylmethylamine, and dodecylmethylamine are illustrative of tertiary amines of (A) or (B). Mixtures of two or more tertiary amine coinitiators can be used. Amounts of amines typically are in the range of about 0.5 to about 40 wt% of the total weight of the formulation.
  • Non-limiting examples of rheology modifiers which can be used in forming the formulations include such materials as organic silicone compounds, organic fluoro- compounds, poly ethers, and organic ionic compounds. Typically, rheology modifiers are used in amounts in the range of about 0.01 to about 5 wt% of the formulation.
  • Pigments and dyes can be used, and often are preferably used, in photocurable formulations. Examples of pigments and typical amounts used in the formulation include phthalocyanine blue (about 5 to about 20 wt%), titanium dioxide (about 10 to about 30 wt%), or other organic or inorganic pigments employed in the art.
  • dyes such as nigrosine black or methylene blue may be used to enhance color or tone (e.g., about 1 to about 5 wt%).
  • Light stabilizers are another type of additives which can be used in the photocurable formulation in which a liquid polymerization inhibitor composition of this invention is employed.
  • Non-limiting examples of such light stabilizers include 2-hydroxybenzophenones such as 2,2'-dihydroxy-4,4'-dimethoxylbenzophenone, 2-(2-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxyphenyl)benzotriazole, sterically-hindered amines such as bis(2,2,6,6- tetramethyl-4-piperidyl)sebacate or bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, oxamides such as 4,4'-dioctyloxyanilide, acrylates such as ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate or methyl ⁇ -carbomethoxycinnanamate, and nickel complexes such as the nickel complex of 2,2'- thi
  • Still another type of additive which can be used in forming radiation curable compositions is one or more radical scavengers.
  • suitable radical scavengers for such use include hydroquinone, hydroquinone methyl ether, p-tert- butylcatechol, quinoid compounds such as benzoquinone and alkyl-substituted benzoquinones, as well as other radical scavenger compounds known in the art.
  • these components will be used in amounts in the range of about 100 ppm to about 2 percent by weight of the composition.
  • Adhesion promoters constitute yet another type of additive components which can be used in the formation of photocurable compositions in which a liquid polymerization inhibitor composition of this invention is employed.
  • Such components typically are silane derivatives such as gamma-aminopropyltriethoxysilane (DOW A-I lOO) and equivalent substituted silane products; acid functionally-substituted resins; oligomers or monomers, such as partial esters of phosphoric acid, maleic anhydride, or phthalic anhydride, with or without acrylic or methacrylic unsaturation; and dimers and trimers of acrylic/methacrylic acid.
  • silane derivatives such as gamma-aminopropyltriethoxysilane (DOW A-I lOO) and equivalent substituted silane products
  • acid functionally-substituted resins acid functionally-substituted resins
  • oligomers or monomers such as partial esters of phosphoric acid, maleic anhydr
  • adhesion promoters are used, the preferred types are other than alpha,beta-ethylenically unsaturated carboxylic acids. If and when used, the concentration thereof is determined empirically by adhesion tests. In general, however, amounts are often in the range of about 0.5 to about 20 wt%, and in more preferred cases in the range of about 2 to about 10 wt% of the total weight of the composition. [0044] In effecting photocuring either coherent or non-coherent radiation can be employed.
  • ion gas laser e.g., an argon ion laser, a krypton laser, a helium: cadmium laser, or the like
  • solid state laser e.g., a frequency-doubled Nd: YAG laser
  • arc lamp e.g., a medium pressure mercury lamp, a Xenon lamp, or a carbon arc lamp
  • Exposure sources capable of providing ultraviolet and visible wavelength radiation (with wavelengths typically falling in the range of 200-700 nm) can also be used for conducting the photocuring. Preferred wavelengths are those which correspond to the spectral sensitivity of the initiator being employed.
  • Preferred radiation sources are gas discharge lamps using vapors of mercury, argon, gallium, or iron salts and utilizing magnetic, microwave or electronic ballast; such lamps commonly are medium pressure mercury lamps, or lamps made by Fusion Systems (i.e., D, H, and V lamps).
  • Exposure times can vary depending upon the radiation source, and photoinitiator(s) being used. For high speed applications such as in forming thin coatings on paper webs traveling at high linear speeds, times in the range of about 0.005 to about 0.015 second are desirable. In radiation curing (photopolymerization) operations in which the mixture being polymerized is either stationary or moving slowly as on a conveyor belt, longer exposure times (e.g., in the range of about 0.2 to about 0.4 second) can be used.
  • a photocurable formulation can be photopolymerized as a thin coating on a traveling web.
  • the radiation curable formulation can be photopolymerized or photocured as a coating or laminate on a substrate.
  • the radiation curable formulation is photopolymerized as an article or shape while in a mold.
  • the exposure to radiation for effecting curing or polymerization can be continuous or intermittent.
  • Various radiation cured articles and shapes can be produced by radiation curing of a photopolymerizable composition formed using a polymerization inhibitor of this invention.
  • the radiation cured (photopolymerized) end product can be printed matter on a substrate such as paper, cardboard, or plastic film, etc.; manufactured articles such as handles, knobs, inkstand bases, small trays, rulers, etc.; and coatings or laminates on substrates such as plywood, metal sheeting, polymer composite sheeting, etc.
  • thin coated paper and coated card or thin paperboard stock where the coatings are in the range of about 0.02 to about 10 mils in thickness constitute desirable articles produced from the photocurable compositions.
  • a polymerization inhibitor composition of this invention was formed by preparing a liquid mixture containing 10 wt% of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt
  • a polymerization inhibitor composition of this invention was formed by preparing a liquid mixture containing 8 wt% of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt
  • a polymerization inhibitor composition of this invention was formed by preparing a liquid mixture containing 7.5 wt% of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt
  • a polymerization inhibitor composition of this invention was formed by preparing a liquid mixture containing 7 wt% of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt
  • a polymerization inhibitor composition of this invention was formed by preparing a liquid mixture containing 12 wt% of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition liquide inhibitrice de polymérisation formée à partir d'ingrédients composés d'un sel d'aluminium tris(N-nitroso-N-phenylhydroxylamine) et a) de 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2- methylpropiophenone, α,α-diethoxyacetophenone, ou de 1-benzoylcyclohexanol, ou d'une combinaison de deux composés quelconques ou plus; ou b) d'un benzophénone, d'au moins un ester comprenant un groupe benzoylphényle, ou d'au moins un acrylate comprenant un groupe benzoylphényle, ou d'une combinaison de deux composés quelconques ou plus; ou c) à la fois de a) et de b). Lorsque a) est 1-benzoylcyclohexanol, au moins un ingrédient provenant de b) est également présent dans la composition.
PCT/US2007/082835 2006-11-09 2007-10-29 Compositions inhibitrices de polymérisation, leur préparation et leur utilisation WO2008060844A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86511906P 2006-11-09 2006-11-09
US60/865,119 2006-11-09

Publications (1)

Publication Number Publication Date
WO2008060844A1 true WO2008060844A1 (fr) 2008-05-22

Family

ID=37983548

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/082835 WO2008060844A1 (fr) 2006-11-09 2007-10-29 Compositions inhibitrices de polymérisation, leur préparation et leur utilisation

Country Status (2)

Country Link
TW (1) TW200835700A (fr)
WO (1) WO2008060844A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1209232A (en) * 1967-03-10 1970-10-21 Basf Ag Crosslinkable photosensitive composition for the production of relief-bearing plates, sheets or film
EP0108037A2 (fr) * 1982-10-01 1984-05-09 Ciba-Geigy Ag Dérivés de propiophénone comme photo-initiateurs dans la photo-polymérisation
EP0125206A1 (fr) * 1983-05-06 1984-11-14 Ciba-Geigy Ag Mélange liquide de photo-initiateurs
EP0855376A1 (fr) * 1995-10-02 1998-07-29 Idemitsu Petrochemical Co., Ltd. Procede pour inhiber la polymerisation de composes vinyliques
US6018078A (en) * 1999-06-23 2000-01-25 First Chemical Corporation Stabilized N-nitrosohydroxylamines
JP2003119205A (ja) * 2001-10-12 2003-04-23 Asahi Denka Kogyo Kk 重合禁止剤組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1209232A (en) * 1967-03-10 1970-10-21 Basf Ag Crosslinkable photosensitive composition for the production of relief-bearing plates, sheets or film
EP0108037A2 (fr) * 1982-10-01 1984-05-09 Ciba-Geigy Ag Dérivés de propiophénone comme photo-initiateurs dans la photo-polymérisation
EP0125206A1 (fr) * 1983-05-06 1984-11-14 Ciba-Geigy Ag Mélange liquide de photo-initiateurs
US4563438A (en) * 1983-05-06 1986-01-07 Ciba Geigy Corporation Liquid mixture of photoinitiators
EP0855376A1 (fr) * 1995-10-02 1998-07-29 Idemitsu Petrochemical Co., Ltd. Procede pour inhiber la polymerisation de composes vinyliques
US6018078A (en) * 1999-06-23 2000-01-25 First Chemical Corporation Stabilized N-nitrosohydroxylamines
JP2003119205A (ja) * 2001-10-12 2003-04-23 Asahi Denka Kogyo Kk 重合禁止剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 200422, Derwent World Patents Index; Class A60, AN 2004-229764, XP002432581 *

Also Published As

Publication number Publication date
TW200835700A (en) 2008-09-01

Similar Documents

Publication Publication Date Title
US4054682A (en) Photopolymerizable composition containing a thioether sensitizer
US5358976A (en) Stable thiol-ene compositions
BR112012024198B1 (pt) Composto e processo para a preparação de um aminoacrilato
CN108026197B (zh) 光聚合性组合物
Segurola et al. Photoyellowing and discolouration of UV cured acrylated clear coatings systems: influence of photoinitiator type
JP6833898B2 (ja) 液体光開始化合物とその用途
TW201343609A (zh) 胺基光反應性黏結劑
EP3724171B1 (fr) Photoinitiateurs polymérisables de benzoyl-coumarine
US20070066842A1 (en) Polymerization Inhibitor Compositions, Their Preparation, and Their Use
US9409861B2 (en) Mercapto benzophenone compounds, compositions and preparation method thereof
JP2020507656A (ja) 印刷用調合物において反応性希釈剤として用いられるアクリレート含有モノマー
EP1692088B1 (fr) Photo-initiateur solide blanc se presentant sous forme de poudre et preparation associee
US7297306B2 (en) Class of amine coinitiators in photoinitiated polymerizations
US4251341A (en) Photoinitiators for UV-curable systems
US6441244B1 (en) Benzophenones and the use thereof as photoinitiators
JPH0196145A (ja) 低重合ベンジルケタール及び光開始剤としてのそれらの使用方法
WO2008060844A1 (fr) Compositions inhibitrices de polymérisation, leur préparation et leur utilisation
US20060293404A1 (en) New class of amine coinitiators in photoinitiated polymerizations
EP0434098A2 (fr) Compositions photodurcissables aminées
JPH0625417A (ja) 安定化されたチオール−エン組成物
WO2007044184A1 (fr) Photoinitiateur soluble dans l'eau
US5283160A (en) Polymerizable compositions
EP0037604B1 (fr) Système initiateur pour compositions durcissables par radiations, compositions durcissables par radiation contenant un tel système initiateur, procédé pour durcir les dites compositions et les produits recouverts par celles-ci
US20080103222A1 (en) New Class of Amine Coinitiators in Photoinitiated Polymerizations
US20040122125A1 (en) Lactone compounds as novel photoinitiators

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07844672

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07844672

Country of ref document: EP

Kind code of ref document: A1