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
  • 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
• • 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
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal

Definitions

• transparent methacrylic resins can be produced by dissolving zinc diacrylate and/or zinc dimethacrylate (hereinafter also referred to as zinc di(meth)acrylate) in methyl methacrylate and copolymerizing them.
• zinc di(meth)acrylate has low solubility in methyl methacrylate, and in order to produce a methacrylic resin while maintaining properties such as transparency, it is necessary to keep the amount of zinc di(meth)acrylate used extremely small, which creates the problem that the resulting methacrylic resin cannot fully exhibit the properties derived from zinc di(meth)acrylate, such as heat resistance and mechanical strength.
• Patent Document 1 proposes a resin composition by copolymerization that has improved heat resistance without impairing the inherent transparency and mechanical properties of methacrylic resins.
• Zinc di(meth)acrylate is also known to be blended into rubber compositions to improve vulcanization properties, and to be used as a modifier for synthetic resins (Patent Documents 2 to 5).
• JP 6-145255 A Japanese Patent Application Laid-Open No. 52-154436 Japanese Patent Publication No. 53-83834 Japanese Patent Publication No. 60-94434 JP 2-218639 A
• zinc di(meth)acrylate is usually limited to those mentioned above. They discovered that the reason behind this is that zinc di(meth)acrylate can only be dissolved in limited solvents such as water. Therefore, they thought that if zinc di(meth)acrylate could be dissolved in various solvents and monomers other than water, the versatility of zinc di(meth)acrylate would be significantly improved.
• the objective of the present invention is to provide a technology that increases the solubility of zinc compounds having an alkenyloxycarbonyl group, such as zinc di(meth)acrylate or its derivatives, in various solvents and monomers.
• One aspect of the present invention is a compound represented by the following general formula (I):
• each L is independently a ligand that is a nitrogen-containing organic compound
• each R is independently an alkenyl group having 2 to 10 carbon atoms that may be substituted with a methyl group at the ⁇ -position of the double bond. This is a zinc complex.
• One aspect of the present invention is a compound represented by the following general formula (II): Zn(OCOR a ) 2 ... (II) wherein R a each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group at the ⁇ -position of the double bond; and a nitrogen-containing organic compound in an amount of 2 or more molar equivalents relative to the zinc atom of the zinc carboxylate.
• FIG. 1 shows the results of single crystal X-ray structure analysis.
• the range “X to Y” means “X or more and Y or less.”
• the disclosure of each numerical value as the upper limit, the disclosure of each numerical value as the lower limit, and the combination of the upper and lower limits are all disclosed (i.e., the basis for the correction is lawful).
• corrections to X1 or more, corrections to Y2 or less, corrections to X1 or less, corrections to Y2 or more, corrections between X1 and X2, corrections between X1 and Y2, etc. must all be considered lawful.
• operations and measurements of physical properties are performed at room temperature (20 to 25°C) and a relative humidity of 50 ⁇ 5% RH.
• each L is independently a ligand which is a nitrogen-containing organic compound
• each R is independently an alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group at the ⁇ -position of the double bond.
• This complex is soluble in various organic solvents and monomers other than water.
• the organic solvent and/or (other) monomer may also be referred to as a solvent.
• a technology can be provided for increasing the solubility of zinc compounds having an alkenyloxycarbonyl group, such as zinc di(meth)acrylate or a derivative thereof, in various solvents and monomers.
• the alkenyl group having 2 to 10 carbon atoms in which the ⁇ -position of the double bond may be substituted with a methyl group in R may have a substituent.
• R is an alkenyl group having 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, or 2 to 4 carbon atoms in which the ⁇ -position of the double bond may be substituted with a methyl group.
• the alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group at the ⁇ -position of the double bond, is a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), an isopropenyl group, a 1-butenyl group, a 1-methyl-1-butenyl group, a 2-butenyl group, a 2-methyl-2-butenyl group, a 3-butenyl group, a 3-methyl-3-butenyl group, a 1-pentenyl group, a 1-methyl-1-pentenyl group, a 2-pentenyl group, a 2-methyl-2-pentenyl group, a 3-pentenyl group, a 3-methyl-3-pentenyl group, a 4-pentenyl group, a 5-pentenyl group, a 6-pentenyl group, a 7-pentenyl group, a 8-pentenyl group,
• the nitrogen-containing organic compound may be an organic compound containing one or more nitrogen atoms in the molecule.
• the nitrogen-containing organic compound may be a tertiary amine or a nitrogen-containing heterocyclic compound.
• the nitrogen-containing organic compound includes those that do not have a polymerizable group, such as an ethylenically unsaturated group.
• the tertiary amine may be represented by N(R 1 )(R 2 )(R 3 ), where R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, which may be substituted with a substituent.
• alkyl group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a c-propyl group, an n-butyl group, an i-butyl group, a s-butyl group, a t-butyl group, a c-butyl group, an n-pentyl group, a c-pentyl group, an n-hexyl group, a c-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
• R 1 , R 2 and R 3 may each independently be an alkyl group having 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 1 or 2 carbon atoms, which may be substituted with a substituent.
• the substituents substituted on the alkyl group having 1 to 10 carbon atoms in R 1 , R 2 and R 3 may each independently be -OCOR b (wherein each R b is independently an alkenyl group having 2 to 10 carbon atoms and which may be substituted with a methyl group at the ⁇ -position of the double bond).
• the alkenyl group having 2 to 10 carbon atoms and which may be substituted with a methyl group at the ⁇ -position of the double bond in R b is an alkenyl group having 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, or 2 to 4 carbon atoms and which may be substituted with a methyl group at the ⁇ -position of the double bond.
• R The alkenyl group in b which may be substituted with a methyl group at the ⁇ -position of the double bond having 2 to 10 carbon atoms, is a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), an isopropenyl group, a 1-butenyl group, a 1-methyl-1-butenyl group, a 2-butenyl group, a 2-methyl-2-butenyl group, a 3-butenyl group, a 3-methyl-3-butenyl group, a 1-pentenyl group, a 1-methyl-1-pentenyl group, a 2-pentenyl group, a 2-methyl-2-pentenyl group, a 3-pentenyl group, a 3-methyl-3-pentenyl group, a 4-pentenyl group, a 4- Examples include a methyl-4-pentenyl group, a 1-hexenyl group, a 1-methyl-1-
• the number of substituents on R 1 , R 2 and R 3 is 1, 2 or 3, respectively.
• R 1 , R 2 and R 3 are an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms substituted with -OCOR b , respectively.
• R 1 , R 2 and R 3 are each independently an unsubstituted alkyl group having 1 to 10 carbon atoms.
• the heterocycle in the nitrogen-containing heterocyclic compound may be a five-membered ring or may be a six-membered ring.
• the heteroatom other than the nitrogen atom in the nitrogen-containing heterocyclic compound may be at least one of an oxygen atom and a sulfur atom.
• the nitrogen-containing heterocyclic compound may have at least one of an aromatic ring and an alicyclic ring.
• the nitrogen-containing heterocyclic compound may be a single ring or a condensed ring.
• the nitrogen-containing heterocyclic compound may have one, two or three heteroatoms.
• nitrogen-containing heterocyclic compound examples include pyridine, N-methylpyrrolidone, quinoline, piperazine, piperidine, morpholine, carbazole, triazine, etc.
• pyridine as the nitrogen-containing heterocyclic compound can improve the stability of the zinc complex as a crystal.
• the nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
• the zinc complex represented by general formula (I) is represented by the following general formula (II): Zn(OCOR a ) 2 ... (II) wherein R a are each independently an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group, and a nitrogen-containing organic compound in an amount of 2 or more molar equivalents relative to the zinc atom of the zinc carboxylate. If the molar equivalent of the nitrogen-containing organic compound relative to the zinc atom of the zinc carboxylate is less than 2 molar equivalents, it is difficult to obtain a dicoordinated complex.
• one embodiment of the present invention is a compound represented by the following general formula (II): Zn(OCOR a ) 2 ... (II) wherein R a's are each independently an alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group at the ⁇ -position of the double bond; and a nitrogen-containing organic compound in an amount of 2 or more molar equivalents relative to the zinc atom of the zinc carboxylate.
• the alkenyl group having 2 to 10 carbon atoms and optionally substituted with a methyl group at the ⁇ -position of the double bond in R a may have a substituent.
• the alkenyl group having 2 to 10 carbon atoms and optionally substituted with a methyl group at the ⁇ -position of the double bond in R a is an alkenyl group having 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, or 2 to 4 carbon atoms and optionally substituted with a methyl group at the ⁇ -position of the double bond.
• R The alkenyl group in a which may be substituted with a methyl group at the ⁇ -position of the double bond having 2 to 10 carbon atoms, is a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), an isopropenyl group, a 1-butenyl group, a 1-methyl-1-butenyl group, a 2-butenyl group, a 2-methyl-2-butenyl group, a 3-butenyl group, a 3-methyl-3-butenyl group, a 1-pentenyl group, a 1-methyl-1-pentenyl group, a 2-pentenyl group, a 2-methyl-2-pentenyl group, a 3-pentenyl group, a 3-methyl-3-pentenyl group, a 4-pentenyl group, a 4- Examples include a methyl-4-pentenyl group, a 1-hexenyl group, a 1-methyl-1-
• the nitrogen-containing organic compound mixed with the zinc carboxylate can be the same as described above for (nitrogen-containing heterocyclic compound).
• the molar equivalent of the nitrogen-containing organic compound relative to the zinc atom of the zinc carboxylate is 30 molar equivalents or less, 25 molar equivalents or less, 10 molar equivalents or less, 8 molar equivalents or less, 6 molar equivalents or less, 4.5 molar equivalents or less, 4 molar equivalents or less, 3.5 molar equivalents or less, 3 molar equivalents or less, or 2.5 molar equivalents or less.
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group (e.g., zinc diacrylate) is generally poorly soluble in water and organic solvents/monomers other than methanol (or alcohol). Therefore, it is difficult to use it in liquid phase polymerization, and it has been mostly used as a rubber modifier in solid phase polymerization.
• a nitrogen-containing organic compound is used, and the solubility of the zinc carboxylate (e.g., zinc diacrylate) in an organic solvent/monomer can be dramatically improved. This is thought to be because the nitrogen-containing organic compound is coordinated/complexed to the zinc carboxylate (e.g., zinc diacrylate) (e.g., 2 to 4 molecules), which results in improved solubility.
• the zinc carboxylate e.g., zinc diacrylate
• the zinc complex may have a tetrahedral structure.
• the zinc complex is soluble in various organic solvents and monomers and is polymerizable.
• the method of mixing the zinc carboxylate with the nitrogen-containing organic compound is not particularly limited.
• the nitrogen-containing organic compound may be added to the zinc carboxylate, or the zinc carboxylate may be added to the nitrogen-containing organic compound.
• the zinc carboxylate with the nitrogen-containing organic compound may be mixed together with various solvents and/or various monomers, and there is no particular limit to the order of addition.
• the zinc complex according to one embodiment of the present invention has excellent solubility in various monomers and organic solvents.
• the indicator of solubility is transmittance. This transmittance can be calculated by the measurement method described in the Examples. More specifically, it can mean the transmittance at a wavelength of 660 nm using a spectrophotometer of a monomer/organic solvent (composition temperature: 25° C.) containing a zinc complex (zinc carboxylate) at a concentration of 2.5 mass % calculated as zinc salt.
• the compound is represented by the following general formula (I):
• L is independently a ligand which is a nitrogen-containing organic compound
• R is independently an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group.
• the zinc complex contains a zinc salt at a concentration of 2.5 mass % and has a transmittance of 90% or more in at least one of another monomer having an ethylenically unsaturated bond group and an organic solvent. Note that the phrase "another monomer having an ethylenically unsaturated bond" is used to distinguish it from R, which also has an ethylenically unsaturated bond.
• the zinc complex obtained by mixing the zinc complex contains the zinc complex at a concentration of 2.5% by mass calculated as the zinc salt, and has a transmittance of 90% or more in at least one of another monomer having an ethylenically unsaturated bond group and an organic solvent.
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group.
• the zinc carboxylate shown has excellent solubility in methanol even when not complexed. In that sense, the organic solvent does not need to be methanol. In one embodiment of the present invention, the organic solvent does not contain alcohol. In one embodiment of the present invention, the organic solvent does not contain methanol.
• the transmittance may be, for example, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, or 98% or more.
• the other monomer having an ethylenically unsaturated bond group is a zinc complex and/or a monomer represented by the following general formula (II): Zn(OCOR a ) 2 ... (II)
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group.
• (meth)acrylic acid ester compounds ((meth)acrylic acid alkyl) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate; olefinic hydrocarbons such as ethylene, propylene, and vinyl chloride, or halogen-substituted derivatives thereof; aromatic vinyl compounds such as styrene and methylstyrene; vinyl compounds of monovalent carboxylic acids such as vinyl acetate and vinyl propionate.
• (meth)acrylic acid alkyl) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, but
• Suitable monomers include ester compounds, unsaturated alcohol compounds such as (meth)allyl alcohol and crotonic alcohol, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid compounds such as (meth)acrylic acid, crotonic acid and cinnamic acid, unsaturated dibasic carboxylic acids such as maleic acid, fumaric acid and itaconic acid, monoester compounds of monohydric alcohols and unsaturated dibasic carboxylic acids such as maleic acid monomethyl ester and maleic acid monoallyl ester, and polyvinyl compounds such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and diallyl maleate.
• unsaturated alcohol compounds such as (meth)allyl alcohol and crotonic alcohol
• ⁇ , ⁇ -ethylenically unsaturated carboxylic acid compounds such as (meth)acrylic
• the number of carbon atoms of the alkyl in the (meth)acrylate is 1 to 18, 1 to 15, 1 to 10, 1 to 7, or 1 to 4.
• the alkyl in the (meth)acrylate may be substituted with a hydroxyl group.
• the alkyl in the (meth)acrylate may be substituted with an alkoxy group.
• the alkoxy group may have 1 to 5 carbon atoms, or alternatively 1 to 3 carbon atoms.
• the alkyl (meth)acrylate may be substituted with an alkenyloxy group.
• the alkyl (meth)acrylate may have an alkenyloxy group and an ether bond.
• the alkenyloxy group may have 1 to 3 carbon atoms.
• the other monomer may be an oligomer.
• oligomer means one having two or more repeating units, which may also be recognized as a polymer.
• the other monomer when it is an oligomer (polymer), it may be less than 5% by mass, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0% by mass of the total mass of the monomer.
• the organic solvent may be an organic compound that is liquid at room temperature and normal pressure (25° C., 1 atm). When the organic solvent also corresponds to a nitrogen-containing organic compound, it is classified as a nitrogen-containing organic compound. Thus, the organic solvent in this specification is not a nitrogen-containing organic compound.
• the organic solvent includes an organic solvent that does not have a polymerizable group such as an ethylenically unsaturated group. This embodiment can more effectively impart properties derived from zinc di(meth)acrylate, such as heat resistance.
• the organic solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, propanol, butanol, methoxybutanol, glycol ethers (e.g., glycol ethers such as ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate), and polyfunctional alcohols (e.g., ethylene glycol, propylene glycol, and trimethylolpropane); esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methyl lactate, and butyl lactate; hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; and ethers (diethyl ether, diphenyl ether, ethylene glycol diethyl ether, and t
• glycol ethers
• a composition comprising the zinc complex and a solvent, the solvent being substantially composed of another monomer having an ethylenically unsaturated bond group and/or an organic solvent.
• a composition which comprises a zinc carboxylate, wherein R a is independently an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group, a nitrogen-containing organic compound, and a solvent, wherein the solvent consists essentially of other monomers having an ethylenically unsaturated bond group and/or an organic solvent.
• the solvent does not contain any medium other than the monomer having an ethylenically unsaturated bond group and the organic solvent, or if it does contain any medium, the amount of such medium in the solvent is, for example, 5% by mass or less, 1% by mass or less, 0.1% by mass or less, 0.05% by mass or less, 0.01% by mass or less, 0.005% by mass or less, or 0.001% by mass or less.
• the solvent does not substantially contain water.
• substantially free of water not only encompasses cases in which the solvent does not contain any water at all, but also conceptually encompasses cases in which the solvent unavoidably contains moisture from the air, or cases in which the solvent contains a very small amount of water, for example, 5% by mass or less, 1% by mass or less, 0.1% by mass or less, 0.05% by mass or less, 0.01% by mass or less, 0.005% by mass or less, or 0.001% by mass or less.
• the explanation given in ⁇ Solubility of zinc complex> can be applied to the explanation of the other monomer having an ethylenically unsaturated bond group and the type of organic solvent.
• zinc carboxylate has excellent solubility in methanol even if it is not complexed. In that sense, the organic solvent does not have to be methanol.
• Zinc carboxylate may have excellent solubility in alcohol. Therefore, in one embodiment of the present invention, the organic solvent does not have to be alcohol. In one embodiment of the present invention, the organic solvent does not include alcohol. In one embodiment of the present invention, the organic solvent does not include methanol.
• the proportion of other monomers having ethylenically unsaturated bond groups in the composition may be 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. In one embodiment of the present invention, the proportion of other monomers having ethylenically unsaturated bond groups in the composition may be 99.5% by weight or less, 97.5% by weight or less, 96% by weight or less, 94% by weight or less, 92% by weight or less, 90% by weight or less, 88% by weight or less, 86% by weight or less, or 84% by weight or less.
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a methyl group at the ⁇ -position of the double bond
• the proportion of the zinc carboxylate may be 0.01 parts by mass to 40 parts by mass, 0.01 to 30 parts by mass, 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass.
• the proportion of organic solvent in the composition may be 60% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. In one embodiment of the present invention, the proportion of organic solvent in the composition may be 97.5% by weight or less, 96% by weight or less, 94% by weight or less, 92% by weight or less, 90% by weight or less, 88% by weight or less, 86% by weight or less, 84% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, or 65% by weight or less.
• the proportion of the zinc complex in the composition may be 0.5% by weight or more, 0.7% by weight or more, 1% by weight or more, 1.2% by weight or more, 1.5% by weight or more, 1.7% by weight or more, 2% by weight or more, 2.2% by weight or more, 2.4% by weight or more, 2.6% by weight or more, 2.8% by weight or more, 3% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6% by weight or more, 6.5% by weight or more, 7% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, or 30% by weight or more. In one embodiment of the present invention, the proportion of the zinc complex in the composition may be 55% by weight or less, 50% by weight or less, or 45% by weight or less.
• the proportion of zinc carboxylate in the composition may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.7% by weight or more, 1% by weight or more, 1.2% by weight or more, 1.5% by weight or more, 1.7% by weight or more, 2% by weight or more, 2.2% by weight or more, 2.4% by weight or more, 2.6% by weight or more, 2.8% by weight or more, 3% by weight or more, 4% by weight or more, 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, or 9% by weight or more.
• the proportion of zinc carboxylate in the composition may be 40% by weight or less, 30% by weight or less, or 25% by weight or less.
• the molar ratio of the nitrogen-containing organic compound to the zinc atom of the zinc carboxylate is 2 moles or more.
• the molar equivalent of the nitrogen-containing organic compound to the zinc atom of the zinc carboxylate is 30 molar equivalents or less, 20 molar equivalents or less, 10 molar equivalents or less, 8 molar equivalents or less, 6 molar equivalents or less, 4.5 molar equivalents or less, 4 molar equivalents or less, 3.5 molar equivalents or less, 3 molar equivalents or less, or 2.5 molar equivalents or less.
• the composition containing the zinc complex and a solvent may further contain a polymerization initiator.
• a polymerization initiator Zn(OCOR a ) 2 ... (II) wherein R a is each independently an alkenyl group having 2 to 10 carbon atoms which may be substituted at the ⁇ -position of the double bond with a methyl group, a nitrogen-containing organic compound, and a solvent, the composition may further contain a polymerization initiator.
• the polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
• the photopolymerization initiator is not particularly limited, and may be benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; alkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthr
• benzophenone 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone and the like benzophenones; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(0-acetyloxime) and the like oxime esters; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and the
• the proportion of the photopolymerization initiator in the composition may be 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, or 0.4% by weight or more. In one embodiment of the present invention, the proportion of the photopolymerization initiator in the composition may be 20% by weight or less, 10% by weight or less, or 5% by weight or less.
• the composition containing the zinc complex and the solvent may further contain known additives such as plasticizers, inorganic fillers, colorants, reinforcing agents, modifiers, stabilizers, extenders, release agents, and dispersants. These may be used alone or in combination of two or more.
• the composition may further contain a compound represented by the following general formula (II): Zn(OCOR a ) 2 ...
• composition containing a zinc carboxylate, a nitrogen-containing organic compound, and a solvent represented by the formula: wherein R a is each independently an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group, may further contain known additives such as a plasticizer, an inorganic filler, a colorant, a reinforcing agent, a modifier, a stabilizer, an extender, a release agent, a dispersant, etc. These may be used alone or in combination of two or more kinds.
• the method of mixing the zinc complex with the solvent is not particularly limited.
• the solvent may be added to the zinc complex, or the zinc complex may be added to the solvent.
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of which may be substituted with a methyl group
• the method of mixing the zinc carboxylate, the nitrogen-containing organic compound, and the solvent is also not particularly limited. They may be added in any order.
• the method of mixing these is similarly not particularly limited. They may be added in any order.
• the polymerization of the composition may be thermal polymerization or photopolymerization.
• the light source used for exposure to light in the photopolymerization in one embodiment of the present invention is not particularly limited, but may be a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an ultraviolet LED, or the like.
• the exposure dose (ultraviolet illuminance) in the photopolymerization in one embodiment of the present invention is not particularly limited, but may be, for example, 0.1 to 600 mW/cm 2 , 1 to 400 mW/cm 2 , or 5 to 200 mW/cm 2 for 0.1 seconds to 60 minutes, 1 second to 45 minutes, or 5 seconds to 30 minutes.
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms in which the ⁇ -position of the double bond may be substituted with a methyl group, and an ionomer including a structural unit derived from a zinc carboxylate and a monomer having an ethylenically unsaturated bond group other than the structural unit derived from the zinc carboxylate can be provided.
• nitrogen-containing organic compounds such as triethylamine can be removed by drying under reduced pressure.
• liquid phase polymerization which was previously difficult, is now possible, and it is expected to be used in a wide range of applications.
• the present invention may include the following aspects and configurations:
• each L is independently a ligand that is a nitrogen-containing organic compound
• each R is independently an alkenyl group having 2 to 10 carbon atoms and in which the ⁇ -position of the double bond may be substituted with a methyl group, forming a zinc complex.
• each R a is independently an alkenyl group having 2 to 4 carbon atoms and optionally substituted with a methyl group at the ⁇ -position of the double bond.
• a composition comprising the zinc complex according to any one of 1. to 9. above and a solvent, wherein the solvent essentially consists of other monomers having an ethylenically unsaturated bond group and/or an organic solvent.
• composition according to 11 wherein the proportion of the zinc carboxylate in the composition is 0.1 mass% or more, and the molar ratio of the nitrogen-containing organic compound to the zinc atoms of the zinc carboxylate is 2 moles or more.
• a method for producing an ionomer containing zinc atoms comprising polymerizing a composition described in any one of 10. to 12.
• R a each independently represents an alkenyl group having 2 to 10 carbon atoms, the ⁇ -position of the double bond of which may be substituted with a methyl group, and an ionomer comprising: a structural unit derived from a zinc carboxylate; and a structural unit derived from a monomer having an ethylenically unsaturated bond group other than the structural unit derived from the zinc carboxylate.
• zinc diacrylate can be dissolved in toluene that contains various dissolution aids, but zinc diacrylate cannot be dissolved in toluene that does not contain any dissolution aids.
• Thermogravimetric measurement The thermal mass of the powder was measured using a Hitachi STA7200 TG/DTA. Specifically, the mass loss rate at the time of constant weight when held at 100° C. under a nitrogen flow was regarded as the amount of free ligands and compared with the theoretical value. The results are shown in the table below.
• bromine number measurement The bromine number of the powder was measured according to JIS K 2605:1996 and compared with the theoretical value. The results are shown in the table below.
• solubility Measurement the solubility of zinc diacrylate in various solvents and various monomers was evaluated by the following method. That is, in the comparative example (without triethylamine (TEA)), 1 g of zinc diacrylate was prepared in a sealed container. Various solvents and various monomers (25°C) were gradually added thereto while stirring, and it was visually confirmed that the solution was completely dissolved, and the solubility (mass%) was calculated from the mass of the solution (25°C) at that time.
• TAA triethylamine
• Transmittance Measurement As an index showing the effect of the solubilizing agent, the transmittance was measured in various solvents and various monomers when the solubilizing agent (TEA) was 2.5% by mass as is.
• samples 25°C were prepared with the following mass ratios, and the transmittance (%) at a wavelength of 660 nm was measured using a spectrophotometer (model number V-650, manufactured by JASCO Corporation).
• the ratio of various solvents and various monomers to zinc diacrylate was 97.5:2.5.
• the ratio of various solvents/various monomers: zinc diacrylate: triethylamine was 92.5:2.5:5.0.
• the use of a dissolution aid dramatically improved the solubility of zinc diacrylate in various solvents and monomers.
• the presence or absence of a dissolution aid resulted in a significant difference in the transmittance in various solvents and monomers.
• the indicator of "solubility" is a transmittance of 90% or more.
• a structure was prepared by sandwiching a double-sided tape as a spacer between two transparent glass plates to provide a gap of about 2 mm thickness, and each mixture (2 g) was poured into the gap, and UV irradiation was performed for 30 minutes at a UV intensity of 170 mW/ cm2 using HLR100T-2 manufactured by Sen Special Light Sources Co., Ltd. Thereafter, the mixture was peeled off from the glass plate to obtain a polymer. The glass transition temperature of each obtained polymer was measured by differential thermal analysis (DTA).
• DTA differential thermal analysis
• the glass transition temperature of the polymer obtained by polymerizing methyl methacrylate and butyl acrylate in the presence of a dissolution aid and zinc diacrylate is higher than the glass transition temperature of the polymer of methyl methacrylate and butyl acrylate in Comparative Example 1. This shows that the addition of a dissolution aid and zinc diacrylate has the effect of improving heat resistance.

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