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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups

Definitions

• the present invention relates to a macropolymerization initiator and a method for producing a macropolymerization initiator.
• the polyolefin adhesive resin has adhesive properties to the polyolefin base material.
• the polar adhesive resin has adhesive properties to polar resin materials.
• the polyolefin adhesive resin includes a maleic anhydride-modified propylene/1-butene copolymer.
• the polyolefin adhesive resin described in Patent Document 1 may have insufficient adhesion to a polyolefin base material.
• the present invention provides a macropolymerization initiator that can easily produce a block polymer that can improve adhesion to a polyolefin substrate, and a method for producing the macropolymerization initiator.
• the present invention [1] includes a macropolymerization initiator represented by the following general formula (1).
• P1 represents a polyolefin.
• R1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group.
• R2 represents carbonyloxy group, alkylene group, and phenylene group. Two R 1 's may be the same or different from each other.
• n is an integer of 1 or more.
• the present invention [2] includes the macropolymerization initiator of the above [1], wherein in the general formula (1), R 1 is a methyl group and R 2 is a carbonyloxy group.
• the present invention [3] is a method for producing a macropolymerization initiator according to the above [1] or [2], which includes a preparation step of preparing a polyolefin, and a terminal structure represented by the following general formula (2) in the polyolefin. and an introduction step of introducing a macropolymerization initiator.
• R 1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. Two R 1s may be the same, They may be different from each other.
• a hydroxy polyolefin which is a polyolefin having a hydroxy group, is prepared, and in the introduction step, the hydroxy polyolefin is reacted with a compound represented by the following general formula (3). It includes the method for producing a macropolymerization initiator as described in [3] above.
• R 1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. Two R 1s may be the same, (They may be different from each other.
• R 3 represents any one of a hydroxy group, an alkoxy group, and a halogen atom.
• Claim [5] provides the macropolymerization method according to [4] above, wherein the hydroxy polyolefin is obtained by hydroborating and oxidizing the ethylenically unsaturated group of a polyolefin having an ethylenically unsaturated group in the preparation step. Includes a method for producing an initiator.
• the macropolymerization initiator has a portion made of polyolefin.
• the obtained block polymer has blocks made of polyolefin, it is possible to improve the adhesion to the polyolefin base material.
• a macropolymerization initiator can be easily produced by introducing the terminal structure represented by the above general formula (2) into a polyolefin.
• FIG. 1 is a graph showing changes in the GPC peak of a block polymer with the passage of polymerization time in the production of the block polymer.
• Macropolymerization initiators can be used in living radical polymerization.
• the macropolymerization initiator has a main chain made of polyolefin and has an iodine atom as a protecting group at the end.
• the macropolymerization initiator may have an iodine atom in the side chain of the polyolefin.
• the macropolymerization initiator is represented by the following general formula (1).
• the macropolymerization initiator generates radicals by cleavage of the bond between an iodine atom and a carbon atom.
• P1 represents polyolefin.
• polyolefins examples include polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, ⁇ -olefin copolymers, ethylene-propylene-diene copolymers, cyclic olefin copolymers, conjugated diene copolymers, and modifications thereof.
• One example is the body.
• Examples of the ⁇ -olefin copolymer include ethylene/propylene copolymer, ethylene/propylene/1-butene copolymer, and propylene/1-butene copolymer.
• modified products include graft modified products.
• graft modified products include maleic anhydride modified products.
• polystyrene resin examples include polybutadiene and ⁇ -olefin copolymers, and more preferably hydrogenated polybutadiene and propylene/1-butene copolymers.
• R 1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group.
• Examples of the aliphatic group include a straight-chain alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms.
• Examples of straight chain alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Examples include n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.
• Examples of the branched alkyl group having 3 to 12 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, and 2-ethylhexyl group.
• the aliphatic group may be substituted. Aliphatic groups are preferably unsubstituted.
• the number of substituents is not limited.
• the aliphatic group may have one substituent or multiple substituents.
• a substituent for example, a halogen atom, a straight chain or branched alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a non-aromatic heterocyclic group, a straight chain or branched alkoxy group having 1 to 12 carbon atoms. , a cyano group, and a nitro group.
• the alkyl group, aromatic hydrocarbon group, and non-aromatic heterocyclic group as a substituent may also be substituted.
• aromatic group examples include an aromatic hydrocarbon group or an aromatic heterocyclic group.
• aromatic hydrocarbon group examples include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, binaphthyryl group, azulenyl group, anthracenyl group, and phenanthrenyl group.
• aromatic heterocyclic groups include furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, isoxazolyl group, thiazolyl group, thiadiazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, benzofuryl group, indolyl group , quinolyl group, isoquinolyl group, quinazolinyl group, quinoxalinyl group, cinnolinyl group, benzothiazolyl group, carbazolyl group, phenanthridinyl group, phenazinyl group, phenoxazinyl group, and phenothiazinyl group.
• R 1 's may be the same or different from each other.
• both R 1 are unsubstituted methyl groups.
• R 2 represents any one of a carbonyloxy group, an alkylene group, and a phenylene group.
• alkylene group examples include a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 2 to 12 carbon atoms, or a cycloalkylene group having 3 to 12 carbon atoms.
• linear alkylene groups having 1 to 12 carbon atoms include methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, and 1,6-hexylene group. 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, and 1,12-dodecylene group.
• Examples of branched alkylene groups having 2 to 12 carbon atoms include 1,1-ethylene group, 1,1-propylene group, 1,2-propylene group, 2,2-propylene group, 1,1-butylene group, 1 , 2-butylene group, 1,3-butylene group, 2,2-butylene group, and 2,3-butylene group.
• Examples of the cycloalkylene group having 4 to 12 carbon atoms include 1,1-cyclopropyl group, 1,2-cyclopropyl group, 1,1-cyclobutyl group, 1,2-cyclobutyl group, and 1,3-cyclobutyl group. , 1,1-cyclopentyl group, 1,2-cyclopentyl group, and 1,3-cyclopentyl group.
• R 2 is a carbonyloxy group.
• n is an integer of 1 or more. n is, for example, 10 or less, preferably 2 or less.
• the macropolymerization initiator represented by general formula (1) has a portion made of polyolefin.
• the method for producing a macropolymerization initiator includes a preparation step and an introduction step.
• hydroxypolyolefin is prepared.
• Hydroxy polyolefin is a polyolefin having a hydroxy group.
• the preparation process includes a first preparation process, a second preparation process, and a third preparation process.
• a commercially available hydroxy polyolefin may be purchased.
• polyolefin is prepared.
• commercially available polyolefins may be purchased or polyolefins may be synthesized.
• the polyolefin prepared in the first preparation step does not have a polar group or a polar bond, and examples of the polar group include a hydroxy group, a carboxy group, and an alkoxy group.
• Polar bonds include ether bonds and ester bonds.
• olefin monomers are polymerized in the presence of a known metallocene catalyst.
• metallocene catalyst examples include a combination of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride as the metallocene and methylaluminoxane and triisobutylaluminum as cocatalysts.
• olefin monomers examples include ⁇ -olefins, cyclic olefins, and conjugated dienes.
• Examples of the ⁇ -olefin include linear or branched ⁇ -olefins having 2 to 20 carbon atoms.
• Examples of linear or branched ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl- Examples include 1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
• Examples of the cyclic olefin include cyclic olefins having 4 to 20 carbon atoms.
• Examples of the cyclic olefin having 4 to 20 carbon atoms include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.
• Examples of the conjugated diene include aliphatic conjugated dienes having 4 to 20 carbon atoms.
• Examples of aliphatic conjugated dienes having 4 to 20 carbon atoms include 1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3 -hexadiene and 1,3-octadiene.
• Examples of methods for introducing an ethylenically unsaturated group include a thermal decomposition method, a high pressure method, and a method of polymerizing a compound having an ethylenically unsaturated group using a Ziegler catalyst or a metallocene catalyst.
• examples of the Ziegler catalyst include JP-A-57-63310, JP-A-58-83006, JP-A-3-706, Japanese Patent No. 3476793, JP-A-4-218508, and JP-A-4-218508.
• Examples include the magnesium-supported titanium catalyst described in Publication No. 2003-105022.
• metallocene catalysts examples include those described in WO 01/53369 pamphlet, WO 01/27124 pamphlet, WO 2004/087775 pamphlet, JP-A-3-193796 and JP-A-02-41303. Examples include metallocene catalysts.
• an ethylenically unsaturated group is introduced into the polyolefin by a thermal decomposition method.
• polyolefin is heated in a pyrolysis device to thermally decompose it.
• a vinylidene group which is an example of an ethylenically unsaturated group, can be introduced into the polyolefin.
• the heating temperature in the pyrolysis apparatus is, for example, 300°C or higher, preferably 350°C or higher, and, for example, 500°C or lower, preferably 450°C or lower.
• the heating time in the pyrolysis apparatus is, for example, 1 hour or more, preferably 3 hours or more, and, for example, 8 hours or less, preferably 5 hours or less.
• the functional group equivalent of the vinylidene group can be adjusted.
• the ethylenically unsaturated group introduced into the polyolefin with a hydroxy group, for example, the ethylenically unsaturated group is hydroborated and oxidized.
• boron is introduced into the polyolefin by reacting an ethylenically unsaturated group with an alkylborane.
• alkylborane examples include 9-borabicyclo[3.3.1]nonane, dicyamylborane, thexylborane, dicyclohexylborane, catecholborane, pinacolborane, and diisopinocampheylborane.
• the polyolefin into which boron has been introduced is reacted with hydrogen peroxide in the presence of a base, and the boron introduced into the polyolefin is substituted with a hydroxy group.
• a hydroxy polyolefin is obtained.
• the base include sodium hydroxide.
• a polyolefin into which an ethylenically unsaturated group has been introduced is dissolved in a solvent, an alkylborane is added to the resulting solution, and the mixture is heated for, for example, 30 minutes or more, preferably for 1 hour or more, and for example, for 5 hours or less. , preferably for up to 3 hours.
• the alkylborane reacts with the ethylenically unsaturated group of the polyolefin, and boron is introduced into the polyolefin.
• a base and hydrogen peroxide are added to the solution and stirred for, for example, 12 hours or more, preferably 20 hours or more, but for example, 48 hours or less, preferably 30 hours or less.
• the boron introduced into the polyolefin is substituted with a hydroxy group.
• the obtained hydroxypolyolefin may be modified (for example, modified with maleic anhydride).
• introduction step a terminal structure represented by the following general formula (2) is introduced into the polyolefin.
• R 1 is the same as R 1 in general formula (1) above. That is, in the general formula (2), R 1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. Two R 1 's may be the same or different from each other.
• the hydroxypolyolefin obtained in the preparation step is reacted with a compound represented by the following general formula (3).
• R 1 is the same as R 1 in general formula (1) above. That is, in the general formula (3), R 1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. Two R 1 's may be the same or different from each other.
• R 3 represents any one of a hydroxy group, an alkoxy group, and a halogen atom.
• reaction formula (A) hydroxypolyolefin (P1-OH) is dissolved or suspended in a solvent, and ⁇ -iodocarboxylic acid (I-CR 1 2 -COOH) and undergo a condensation reaction.
• R 1 is the same as R 1 in general formula (1) above.
• hydroxypolyolefin is first dissolved or suspended in a solvent.
• ⁇ -iodocarboxylic acid and a condensing agent are added to the resulting solution or suspension.
• a nucleophilic compound may be added to the solution or suspension.
• the amount of ⁇ -iodocarboxylic acid added is, for example, 1 equivalent or more, for example, 10 equivalents or less, and preferably 3 equivalents or less, based on the hydroxy group of the hydroxy polyolefin.
• the amount of the condensing agent added is, for example, 1 equivalent or more, for example, 10 equivalents or less, and preferably 3 equivalents or less, based on the hydroxy group of the hydroxy polyolefin.
• the amount of the nucleophilic compound added is, for example, 0.01 equivalent or more, preferably 0.05 equivalent or more, for example, 5 equivalent or less, based on the hydroxy group of the hydroxy polyolefin. Preferably, it is 2 equivalents or less.
• the solution or suspension is heated for example at -40°C or higher, preferably at -20°C or higher, for example at 150°C or lower, preferably at 100°C or lower, for example at least 5 minutes, preferably at least 15 minutes.
• the mixture is stirred for, for example, 48 hours or less, preferably 24 hours or less.
• condensing agent examples include carbodiimide, carbodiimidazole, phosgene derivatives, phosphonium, uronium, and triflate reagents.
• carbodiimide examples include N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.
• carbodiimidazole examples include carbonyldiimidazole and 1,1'-carbonyldi(1,2,4-triazole).
• phosgene derivatives include triphosgene, thiophosgene, and di(N-succinimidyl) carbonate.
• Examples of phosphonium include BOP and BroP.
• Examples of uronium include HATU and TATU.
• triflate reagents examples include 4-nitrophenyl trifluoromethanesulfonate and trifluoromethanesulfonate chloride.
• examples of the condensing agent include chloroformate, p-toluenesulfonic acid chloride, 2,4,6-trichlorobenzoic acid chloride, and 2-chloro-1-methylpyridinium iodide.
• nucleophilic compounds include pyridine compounds, imidazole compounds, amine compounds, N-hydroxysuccinimide, and 1-hydroxybenzotriazole.
• examples of the pyridine compound include pyridine, N,N-dimethyl-4-aminopyridine, and 4-pyrrolidinopyridine.
• examples of the imidazole compound include imidazole and 1-methylimidazole.
• An example of the amine compound is triethylamine.
• the solvent is not limited as long as it can be used in the condensation reaction.
• the solvent include halogen solvents, ether solvents, hydrocarbon solvents, and aprotic polar solvents.
• halogen solvent include dichloromethane and chloroform.
• ether solvents include tetrahydrofuran and diethyl ether.
• hydrocarbon solvents include toluene and benzene.
• aprotic polar solvents include acetonitrile and dimethylformamide.
• hydroxy polyolefin (P1-OH) and ⁇ -halogenated carboxylic acid (X-CR 1 2 -COOH) are subjected to a condensation reaction to perform macropolymerization.
• An initiator precursor (X-CR 1 2 -COO-P1) is synthesized, and the halogen atom (X) of the obtained macropolymerization initiator precursor is replaced with an iodine atom by a halogen exchange reaction such as Finkelstein reaction.
• a macropolymerization initiator can also be obtained by doing so.
• R 1 is the same as R 1 in the above general formula (1).
• X is a halogen atom other than iodine. Examples of the halogen atom include chlorine and bromine.
• macropolymerization can also be initiated by the transesterification reaction between hydroxy polyolefin (P1-OH) and ⁇ -iodoester (I-CR 1 2 -COOR 4 ). agent can be obtained.
• R 1 is the same as R 1 in general formula (1) above.
• R 4 is an alkyl group.
• macropolymerization is initiated by a transesterification reaction between hydroxy polyolefin (P1-OH) and ⁇ -halogenated ester (X-CR 1 2 -COOR 4 ), as shown in reaction formula (D) below.
• a precursor of the macropolymerization initiator (X-CR 1 2 -COO-P1) is synthesized, and the halogen atom (X) of the obtained precursor of the macropolymerization initiator is replaced with an iodine atom by a halogen exchange reaction to perform macropolymerization.
• Initiators can also be obtained.
• reaction formula (D) R 1 is the same as R 1 in the above general formula (1).
• X is the same as X in the above reaction formula (B).
• R 4 is the same as R 4 in the above reaction formula (C).
• reaction formula (E) hydroxy polyolefin (P1-OH) and ⁇ -iodocarboxylic acid halide (I-CR 1 2 -CO-X') are reacted. , a macropolymerization initiator can also be obtained. In this case no condensing agent is required.
• R 1 is the same as R 1 in general formula (1) above.
• X' is a halogen atom. Examples of the halogen atom include chlorine and bromine.
• reaction formula (F) hydroxy polyolefin (P1-OH) and ⁇ -halogenated carboxylic acid halide (X-CR 1 2 -CO-X') are reacted. Then, a macropolymerization initiator precursor (X-CR 1 2 -COO-P1) was synthesized, and the halogen atom (X) of the obtained macropolymerization initiator precursor was replaced with an iodine atom by a halogen exchange reaction. A macropolymerization initiator can also be obtained by doing so. In this case too, no condensing agent is necessary.
• reaction formula (F) R 1 is the same as R 1 in the above general formula (1).
• X is the same as X in the above reaction formula (B).
• X' is the same as X' in the above reaction formula (E).
• a macropolymerization initiator in which R 2 in general formula (1) is an alkylene group can be used, for example, by converting the ethylenically unsaturated group of the polyolefin obtained in the second preparation step into hydrogen iodide. It can be produced by reacting with and iodinating.
• a macropolymerization initiator in which R 2 in general formula (1) is a phenylene group is obtained by first searching for a macropolymerization initiator in which R 2 in general formula (1) is an alkylene group and 4-methylphenylmagnesium bromide. Make a nuclear substitution reaction.
• Block Polymer Next, a block polymer produced using the above macropolymerization initiator will be explained.
• the block polymer has a first block (the block represented by P1 in the following general formula (4)) and a second block (the block represented by P2 in the following general formula (4)).
• the first block consists of the polyolefin described above.
• the second block consists of a polymer of radically polymerizable monomers. Block polymers have iodine atoms. The block polymer may have an iodine atom at the end of the second block.
• the block polymer is represented by the following general formula (4).
• P1, R 1 , R 2 and n are the same as P1, R 1 , R 2 and n in general formula (1) above.
• P2 consists of a polymer of a radically polymerizable monomer.
• a radically polymerizable monomer is a monomer that can be radically polymerized.
• examples of radically polymerizable monomers include ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, ethylenically unsaturated carboxylic acid esters, aromatic vinyls, and conjugated dienes.
• Examples of ethylenically unsaturated carboxylic acids include monocarboxylic acids and dicarboxylic acids.
• Examples of monocarboxylic acids include acrylic acid and methacrylic acid.
• Examples of dicarboxylic acids include fumaric acid, maleic acid, and itaconic acid.
• anhydrides of ethylenically unsaturated carboxylic acids include maleic anhydride and itaconic anhydride.
• ethylenically unsaturated carboxylic esters examples include acrylic esters and methacrylic esters.
• acrylic esters include alkyl acrylic esters.
• acrylic acid alkyl ester examples include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.
• methacrylic esters examples include methacrylic acid alkyl esters.
• examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate.
• aromatic vinyl examples include styrene.
• conjugated diene examples include the above-mentioned conjugated dienes.
• the radically polymerizable monomer preferably has an acrylic group or a methacrylic group.
• Preferable examples of the radically polymerizable monomer include acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester.
• the weight average molecular weight (Mw) of the block polymer is, for example, 1,000 or more, preferably 2,000 or more.
• the weight average molecular weight (Mw) of the block polymer is, for example, 2,000,000 or less, preferably 200,000 or less.
• the number average molecular weight (Mn) of the block polymer is, for example, 1,000 or more, preferably 2,000 or more.
• the number average molecular weight (Mn) of the block polymer is, for example, 1,000,000 or less, preferably 100,000 or less.
• the weight average molecular weight and number average molecular weight are polystyrene equivalent values (PS equivalent values) measured by GPC (gel permeation chromatography) under the conditions described in the examples below and determined by a general-purpose calibration method. .
• the degree of dispersion (Mw/Mn) of the block polymer is, for example, 1 or more, preferably 1.05 or more.
• the degree of dispersion (Mw/Mn) of the block polymer is, for example, 5 or less, preferably 2 or less.
• the block polymer represented by general formula (4) has a first block made of polyolefin.
• the second block made of a polymer of radically polymerizable monomers can improve adhesion even to a substrate having a polarity different from that of the polyolefin substrate.
• a radically polymerizable monomer is polymerized using the above-mentioned macropolymerization initiator in the presence of iodine (I 2 ) and a catalyst.
• the proportion of iodine is, for example, 0.01 mol or more, preferably 0.02 mol or more, and, for example, 0.05 mol or less, preferably 0.03 mol or less, per 1 mol of macropolymerization initiator. It is.
• the catalyst does not contain transition metals.
• Examples of the catalyst include tributylmethylphosphonium iodide, tetrabutylammonium iodide, and tetraoctylammonium iodide.
• a macropolymerization initiator a radically polymerizable monomer, a catalyst, iodine, and a reaction solvent are placed in a reaction vessel purged with nitrogen, and heated while stirring. .
• iodine may be removed by a known method as a post-treatment after the reaction is completed.
• the radically polymerizable monomer is polymerized with the macropolymerization initiator (living radical polymerization), and the block polymer shown in the above general formula (4) is obtained.
• P2 (second block) of the above general formula (4) grows again by a chain reaction of the radically polymerizable monomer with the generated carbon radical. Thereby, a block polymer shown in the above general formula (4) is obtained.
• the heating temperature is, for example, 50°C or higher, preferably 60°C or higher, and, for example, 100°C or lower, preferably 90°C or lower.
• the polymerization time is, for example, 8 hours or more, preferably 20 hours or more, and, for example, 48 hours or less, preferably 30 hours or less.
• macropolymerization is carried out by polymerizing radically polymerizable monomers in the presence of iodine using a macropolymerization initiator represented by general formula (1).
• the radically polymerizable monomer can be reliably reacted with the initiator.
• the block polymer represented by the general formula (4) can be stably produced while suppressing the unreacted macropolymerization initiator from remaining.
• the block polymer represented by the general formula (4) is, for example, blended into a coating agent that covers a polyolefin base material.
• the coating agent may be an adhesive layer that adheres the polyolefin substrate and a substrate having a different polarity from the polyolefin substrate.
• the coating agent can be used as an adhesive layer for decorative films.
• the coating agent contains a block polymer represented by general formula (4) as an essential component.
• the block polymer is blended into the coating agent in an amount of, for example, 5% by mass or more, preferably 7% by mass or more, and, for example, 20% by mass or less, preferably 15% by mass or less, in terms of solid content.
• the dosage form of the coating agent is not limited.
• the coating agent may be, for example, a coating liquid or a film such as a hot melt adhesive film (heat seal film).
• the coating agent when the coating agent is a coating liquid, the coating agent may contain, as necessary, a solvent, a surfactant, a polar resin, a curing agent, a curing catalyst, a leveling agent, an antifoaming agent, an antioxidant, to the extent that the effect is not impaired.
• ком ⁇ онент agents heat stabilizers, light stabilizers (UV absorbers, etc.), plasticizers, pigments (rutile titanium oxide, zinc oxide, carbon black, etc.), thixotropic agents, thickeners, tackifiers (rosin resins, terpenes, etc.) resin, etc.), a surface conditioner, an antisettling agent, a weathering agent, a pigment dispersant, an antistatic agent, a filler, an organic or inorganic fine particle, an antifungal agent, and a silane coupling agent.
• the coating agent when the coating agent is a film, the coating agent can be obtained, for example, by a method of printing/coating a varnish containing a block polymer and drying it, or a method of forming a block polymer into a film.
• the varnish may be the coating liquid described above.
• Production of macropolymerization initiator (1) Preparation process (1-1) Production of polyolefin (first preparation process) A 2000 ml polymerization apparatus purged with nitrogen was charged with 900 ml of dry hexane (solvent), 30 g of 1-butene, and 1.0 mmol of triisobutylaluminum at room temperature.
• the internal temperature of the polymerization apparatus was raised to 70° C., and propylene gas was introduced into the polymerization apparatus so that the internal pressure of the polymerization apparatus became 0.7 MPa.
• the obtained polymerization solution was mixed with 2 L of methanol to precipitate a propylene/1-butene copolymer from the polymerization solution.
• the precipitated propylene/1-butene copolymer was dried under vacuum at 130°C for 12 hours.
• the internal temperature of the pyrolysis apparatus was raised to 380°C while nitrogen was being introduced, and the propylene/1-butene copolymer was melted.
• stirring is started, and after the temperature of the propylene/1-butene copolymer in the pyrolysis device reaches a predetermined temperature, heating is performed for 4.5 hours to thermally decompose the propylene/1-butene copolymer. Ta.
• a propylene/1-butene copolymer having a vinylidene group at the end was uniformly dissolved in methylcyclohexane, and then cooled to room temperature.
• the solution in the eggplant flask was cooled to 0°C, and 15 mL (62 mmol, 4.0 mol/L) of a methanol/water (1/4) mixed solution of NaOH and 5.0 mL (52 mmol) of an aqueous H 2 O 2 solution were added. , 35%) was added to an eggplant-shaped flask, and after 10 minutes, the temperature was raised to room temperature.
• reaction product was washed. Specifically, 100 mL of methylcyclohexane and 100 mL of distilled water were added to a solution containing the reaction product, and extracted and washed using a separating funnel. Furthermore, 50 mL of 10% hydrochloric acid was added to the solution containing the reaction product for extraction and washing, and 50 mL of distilled water was added for washing. Further, 50 mL of a saturated aqueous sodium bicarbonate solution was added to the solution containing the reaction product for extraction and washing, and further, 50 mL of distilled water was added for washing. Furthermore, 50 mL of saturated brine was added for washing, and the resulting organic layer was dried by adding magnesium sulfate, and then reprecipitated in methanol.
• hydroxy polyolefin (XKP-001, number average molecular weight (Mn): 10260, degree of dispersion (Mw/Mn): 1.95, hydroxy group weight: 3.3 pieces/1000C) was suspended in chlorobenzene, 140 mL of suspension was obtained. Note that the amount of hydroxyl groups was measured by the method described in Reference Examples described later.
• the synthesized condensate is a macropolymerization initiator in which P1 in the above general formula (1) is a propylene/1-butene copolymer, both R 1 are methyl groups, and R 2 is a carbonyloxy group. It is.
• the obtained macropolymerization initiator was pretreated using an oxygen flask combustion method, and the iodine ratio (iodine content) in the macropolymerization initiator was measured using ion chromatography.
• the iodine content was 2.4% by mass.
• the introduction rate (introduction amount/1000C) of the iodine initiator group (terminal structure represented by the above general formula (2)) of the macropolymerization initiator was 2.2 as determined by 1 H-NMR measurement using a nuclear magnetic resonance apparatus. It was calculated using the ratio of the integrated intensity of -2.0 ppm and the integrated intensity of 2.0-0.5 ppm. The calculated "introduction amount/1000C" is shown in Table 1.
• the 1 H-NMR spectrum of the macropolymerization initiator has a peak at 2.1 ppm corresponding to the iodine initiating group, and the intensity of the peak corresponds to the amount of the iodine initiating group introduced. Further, the signal intensity up to 2.0-0.5 ppm corresponds to the main skeleton of the macropolymerization initiator (the portion corresponding to P1 in the above general formula (1)).
• compositional formula of acyclic saturated aliphatic compounds can be described as C n H 2n+1 , so if n is sufficiently large, the number of carbon atoms in the polymer will be half the number of hydrogen atoms. Therefore, "amount introduced/1000C" in Table 1 is calculated from the following formula.
• Production example 1-8 A macropolymerization initiator was produced by the following steps using a Schlenk tube purged with argon gas.
• Production example 1-9 A macropolymerization initiator was obtained in the same manner as Production Example 1-8 except that chlorobenzene was changed to mesitylene. Table 1 shows the "introduced amount/1000C" of the obtained macropolymerization initiator.
• the temperature of the obtained slurry solution was raised to 50° C. while stirring to dissolve the hydroxypolyolefin in tetrahydrofuran, and the hydroxypolyolefin and acetic anhydride were reacted for 2.5 hours. As a result, the hydrogen atoms of the hydroxy groups in the hydroxy polyolefin are replaced with acetyl groups.
• the amount of acetyl groups introduced can be considered to be the same amount as the hydroxy groups in the hydroxy polyolefin (XKP-001). . Therefore, the amount of acetyl groups introduced corresponds to the amount of hydroxy groups in the hydroxy polyolefin (XKP-001).
• DIC N,N'-diisopropylcarbodiimide
• DMAP N,N-dimethyl-4-aminopyridine
• TsCl p-toluenesulfonic acid chloride
• NMI 1-methylimidazole Ac 2 O: acetic anhydride Production Example 2-1
• a macropolymerization initiator was produced by the following steps using a 300 mL four-necked glass flask purged with argon gas.
• the obtained macropolymerization initiator was pretreated by an oxygen flask combustion method, and the iodine content of the macropolymerization initiator was measured from ion chromatography of the combustion gas absorption liquid.
• the iodine content was 9.7% by mass.
• Production example 2-2 As the hydroxy polyolefin, 36 g of hydrogenated polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., product name: NISSO PB GI-2000, Mn: 2394, Mw/Mn: 1.92, hydroxyl value (KOHmg/g): 40-55) was used. 35 g of a pale yellow to yellow viscous liquid macropolymerization initiator was obtained in the same manner as in Production Example 2-1 except that The iodine content of the obtained macropolymerization initiator was 8.0% by mass.
• Production example 2-3 As the hydroxy polyolefin, 60 g of hydrogenated polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., product name: NISSO PB GI-3000, Mn: 4573, Mw/Mn: 1.32, hydroxyl value (KOHmg/g): 25-35) was used. 58 g of a pale yellow to yellow viscous liquid macropolymerization initiator was obtained in the same manner as in Production Example 2-1 except that The iodine content of the obtained macropolymerization initiator was 5.1% by mass.
• methyl methacrylate is polymerized at the end of the macropolymerization initiator, producing a block polymer of propylene/1-butene copolymer and polymethyl methacrylate.
• the reaction solution in the test tube was mixed with 200 g of methanol to precipitate the block polymer.
• the obtained precipitate was collected by filtration and dried under reduced pressure. As a result, a dried block polymer was obtained.
• Example 2 A block polymer was obtained in the same manner as in Example 1, except that the amount of methyl methacrylate was changed to 1.0 g (10 mmol).
• Example 3 A block polymer was obtained in the same manner as in Example 1, except that the amount of methyl methacrylate was changed to 0.40 g (4.0 mmol).
• Each of the obtained coating agents was coated with bar coater No. No. 14 was used to coat each of a polypropylene plate and a TSOP (Toyota Super Olefin Polymer (registered trademark): thermoplastic resin containing PP (polypropylene) and EPDM (ethylene-propylene-diene rubber)) plate.
• TSOP Toyota Super Olefin Polymer (registered trademark): thermoplastic resin containing PP (polypropylene) and EPDM (ethylene-propylene-diene rubber)
• the obtained coating film was left to stand at room temperature for 20 minutes, and further left to stand at 120°C for 20 minutes.
• the dried coating film of the above test piece was cross-cut (100 squares) into a 1 ⁇ 1 mm checkerboard shape using a cutter knife.
• the adhesive tape was peeled off in 0.5 seconds at an angle of 60° to the coating film, and adhesion was evaluated based on the number of remaining squares. Table 2 shows the number of remaining squares.
• the applied UV-curable acrylic top coat agent was irradiated with ultraviolet rays using an ultraviolet irradiation device equipped with a high-pressure mercury lamp of 80 mW/cm 2 at an irradiation distance of 8.5 cm and a line speed of 1.2 m/min.
• the UV-curable acrylic top coat agent was cured. Thereby, an acrylic resin layer was formed on the dried coating film of the coating agent.
• the block polymer of each example has excellent adhesion to the polyolefin substrate even when an acrylic resin layer is formed on the dry coating film of the coating agent. There is.
• the macropolymerization initiator of the present invention can be used for producing block polymers.
• the method for producing a macropolymerization initiator of the present invention can produce a macropolymerization initiator that can be used for producing a block polymer.

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