JP2007002232A - Supported catalyst composition for polymerization of vinyl ester-based monomer and use of the same vinyl ester-based monomer to polymerization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simply carry out isotactic polymerization of a vinyl ester-based monomer such as vinyl acetate under milder conditions. <P>SOLUTION: In the supported catalyst composition for isotactic polymerization of the vinyl ester-based monomer, isotacticity of a polymer is ≥50% based on meso diad (m). The supported catalyst composition for isotactic polymerization comprises a catalyst obtained by supporting a metal compound (component A) selected from halides, alkylated materials, arylated materials, allylated materials, hydrogenated materials, oxygen-containing organized materials and nitrogen-containing organized materials of metals of group 4 to group 9 of the periodic table on an inorganic support or an organic support and a compound (component B) having at least one 1-20C aliphatic hydrocarbon group or 6-40C aromatic hydrocarbon group which may have a substituent and selected from compounds having ≥3 atomic numbers and belonging to elements of groups 1, 2, 12 and 13 and perchlorate. The supported catalyst composition is used for polymerization of the vinyl ester-based monomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a supported catalyst composition for vinyl ester monomer polymerization containing a metal compound of Group 4 to Group 9 of the Periodic Table, and isotactic polymerization of vinyl ester monomers using the same.

  In general, a polymer of a vinyl ester monomer such as vinyl acetate is converted into polyvinyl alcohol (PVA) by saponification and used in various fields such as fibers, films, and adhesives. It is known that the physical properties of PVA vary greatly depending on the stereoregularity of the hydroxyl group that is the side chain of the polymer. For example, PVA rich in isotacticity or syndiotacticity is superior in terms of strength, heat resistance and the like as compared to an atactic polymer.

  As an addition polymerization method for vinyl ester monomers, radical polymerization is known. However, the radical polymerization method has limitations in stereoregularity control, and requires complicated solvents such as the necessity of using a special solvent and the necessity of polymerization at extremely low temperatures. It is difficult to control regularity. The isotacticity of PVA obtained from radical polymerization of vinyl acetate, which is usually used industrially, shows 50% or less in meso diads (m), and does not exceed 50% even when the polymerization solvent and polymerization temperature are changed. .

  On the other hand, coordination polymerization represented by polymerization using a Ziegler-Natta catalyst or a metallocene catalyst is known to be relatively easy to control stereoregularity. For this reason, several attempts have been made to stereoregularly polymerize vinyl ester monomers using transition metal catalysts. For example, Non-Patent Documents 1 to 3 have been reported. These reports only mention that the polymer can be obtained in a yield of 5 to 10%, and none of them reveals the stereoregularity of the produced polymer. From the expression mechanism of isospecific polymerization, it is presumed that polyvinyl acetate having a high isotacticity has not been obtained.

  Patent Document 1 reports a method for producing an ethylene-vinyl acetate copolymer using a rhodium compound as a catalyst. Although it is described that the vinyl acetate content in the ethylene-vinyl acetate copolymer obtained by this method can be controlled to 0.001 to 50%, homopolymerization of vinyl acetate and ethylene-vinyl acetate copolymer The length of the vinyl acetate chain in the coalescence and its stereoregularity are unknown.

JP-A-3-296505 Industrial Chemical Journal, 65, 74, 1962 Z. Anorg. Allorg. Chem. 629, 781, 2003 Polym. Prepr. Jpn. 46, 1311, 1997

  Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, and to produce a PVA having a high isotacticity from vinyl ester monomers under a milder condition and having good quality and physical properties. An object of the present invention is to provide a supported catalyst composition for polymerization and a method for producing a polymer having high isotacticity.

That is, the present invention
A supported catalyst composition for isotactic polymerization of a vinyl ester monomer having a polymer isotacticity of 50% or more in meso diads (m), and at least one metal compound selected from the following component A The present invention relates to a supported catalyst composition for isotactic polymerization, comprising a catalyst in which is supported on an inorganic carrier or an organic carrier and at least one compound selected from the following component B.
Component A: Halides, alkylates, arylates, allylates, hydrides, oxygenated organic compounds, nitrogenous organic compounds of Group 4 to Group 9 metals of the Periodic Table.
Component B: having at least one aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, A compound having an atomic number of 3 or more and a Group 1, 2, 12 or 13 element of the periodic table, or a perchlorate.

  Furthermore, the present invention relates to the use of the above-mentioned supported catalyst composition for polymerization for isotactic polymerization of vinyl ester monomers.

  According to the polymerization catalyst composition of the present invention, a vinyl ester polymer that can polymerize a vinyl ester monomer under milder conditions, has high isotacticity, and has good quality and physical properties is produced. can do. The obtained polyvinyl alcohol is useful for high-strength and high-modulus materials, heat-resistant materials, and the like.

The supported catalyst composition for isotactic polymerization of the present invention comprises a combination of a catalyst in which a metal compound of component A is supported on an inorganic carrier or an organic carrier and a compound of component B.
Component A to be contained in the polymerization-supported catalyst composition for polymerization of the present invention is a halide, alkylated product, arylated product, allylated product, hydride, oxygenated organic compound of group 4 to group 9 metal in the periodic table. And at least one metal compound selected from the group consisting of nitrogen-containing organic compounds. The metal of the metal compound is titanium, zirconium, hafnium of Group 4 of the periodic table, vanadium, niobium, tantalum of Group 5 of the periodic table, chromium, molybdenum, tungsten of Group 6 of the periodic table, Periodic Table 7 Group manganese, rhenium, periodic table group 8 iron, ruthenium, osmium, periodic table group 9 cobalt, rhodium, iridium, especially titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, cobalt Rhodium is preferred.

  Examples of the metal halides of Group 4 to Group 9 of the periodic table include fluoride, chloride, bromide, iodide, perchlorate and the like. Specific examples of the group 4 to 9 metal halides of the periodic table include titanium (III) fluoride, titanium (IV) fluoride, zirconium (IV) fluoride, hafnium (IV) fluoride, Vanadium fluoride (IV), vanadium oxyfluoride (V), niobium fluoride (V), tantalum fluoride (V), chromium fluoride (II), chromium fluoride (III), molybdenum fluoride (VI), Tungsten fluoride (VI), manganese fluoride (III), iron fluoride (II), cobalt fluoride (II), cobalt fluoride (III), titanium chloride (IV), titanium chloride (III), titanium chloride ( II), dichlorobis (cyclopentadienyl) titanium (IV), trichloro (cyclopentadienyl) titanium (IV), trichloro (pentamethylcyclopentadienyl) titanium (IV), dichloro (Cyclopentadienyl) titanium (III), chlorobis (cyclopentadienyl) titanium (III), dichlorobis (pentamethylcyclopentadienyl) titanium (IV), trichloro (pentamethylcyclopentadienyl) zirconium (IV) , Dichlorobis (cyclopentadienyl) zirconium (IV), oxobis [chlorobis (cyclopentadienyl) zirconium (IV)], dichloro [ethylenebis (indenyl)] zirconium (IV), dichloro [ethylenebis (tetrahydroindenyl) ] Zirconium (IV), dichlorobis (pentamethylcyclopentadienyl) zirconium (IV), zirconium chloride (IV), trichloro (cyclopentadienyl) hafnium (IV), trichloro (pentamethylcyclopentadienyl) huff Um (IV), dichlorobis (cyclopentadienyl) hafnium (IV), oxobis [chlorobis (cyclopentadienyl) hafnium (IV)], dichlorobis (pentamethylcyclopentadienyl) hafnium (IV), hafnium chloride (IV) ), Chlorobis (cyclopentadienyl) vanadium, dichlorobis (cyclopentadienyl) vanadium, chloro (cyclopentadienyl) (tetrahydrofuran) vanadium, trichloro (pentamethylcyclopentadienyl) vanadium, dichloro (cyclopentadienyl) Oxovanadium, vanadium chloride (II), vanadium chloride (III), vanadium chloride (IV), chlorotris (triphenylphosphine) cobalt (I), cobalt chloride (II), cobalt perchlorate (II), chromyl chloride, Loro (cyclopentadienyl) dicarbonyl acid iron (II), chloro (cyclopentadienyl) [1,2-bis (diphenylphosphino) ethane] iron (II), dichlorobis [1,2-bis (diethylphos Fino) ethane] iron (II), chlorohydridobis [bis (1,2-diphenylphosphino) ethane] iron (II), dichlorobis (triphenylphosphine) iron (II), iron chloride (II), iron chloride ( III), iron (II) perchlorate, iron (III) perchlorate, hafnium oxychloride, chloropentacarbonylmanganese (I), chlorodicarbonyl (hexamethylbenzene) manganese (I), manganese chloride (II), Manganese (II) perchlorate, zirconyl chloride, zirconyl perchlorate, chromium (II) chloride, chromium (III) chloride, iridium (III) chloride, iridium chloride IV), ruthenium (III) nitrosilkyl chloride, trichloronitrosylbis (triphenylphosphine) ruthenium (III), chlorodinitrosylbis (triphenylphosphine) tetrafluoroborate ruthenium (II), dichlorobis (acetonitrile) bis (triphenylphosphine) ) Ruthenium (II), dichlorotetrakis (t-butyl isocyanate) ruthenium (II), dichloro (pentamethylcyclopentadienyl) ruthenium (III), chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium (II) ), Chloro (cyclopentadienyl) bis (trimethylphosphine) ruthenium (II), chlorodicarbonyl (cyclopentadienyl) ruthenium (II), chlorodicarbonyl (pentamethylcyclopentadienyl) l Tenium (II), chloro (cyclopentadienyl) (1,5-cyclooctadiene) ruthenium (II), chloro (pentamethylcyclopentadienyl) (1,5-cyclooctadiene) ruthenium (II), chloro (Pentamethylcyclopentadienyl) bis (methyldiphenylphosphine) ruthenium (II), dichloro (pentamethylcyclopentadienyl) (triphenylphosphine) ruthenium (III), trichloro (pentamethylcyclopentadienyl) ruthenium (IV ), Dichloro (allyl) (cyclopentadienyl) ruthenium (IV), dichloro (allyl) (pentamethylcyclopentadienyl) ruthenium (IV), tetrachlorobis (benzene) diruthenium (II), tetrachlorobis ( Hexamethylbenzene) diruthenium (II), b Palladium (V) oxychloride, rhenium (III) chloride, dichlorotetracarbonyl dirhodium (I), chlorotris (triphenylphosphine) rhodium (I), dichlorotetrakis (allyl) dirhodium (III), rhodium chloride (III), Dichlorobis (chlorotricarbonyl) ruthenium (II), dichlorotris (triphenylphosphine) ruthenium (II), carbonylchlorohydridotris (triphenylphosphine) ruthenium (II), ruthenium (III) chloride, tetrachloro (cyclopentadienyl) ) Niobium (V), Tetrachloro (pentamethylcyclopentadienyl) niobium (V), Dichlorobis (cyclopentadienyl) niobium (V), Dichlorobis (pentamethylcyclopentadienyl) niobium (V), Trichloro (diphenyl) Acetile Niobium, niobium chloride (V), rhenium chloride (V), tetrachloro (cyclopentadienyl) tantalum (V), tetrachloro (pentamethylcyclopentadienyl) tantalum (V), dichlorobis (pentamethylcyclopenta) Dienyl) tantalum (V), cyclopentadienyl) (ethene) tantalum, dichlorocyclopentadienyldicarbonyltantalum, trichloro (2,2-dimethylpropylidene) bis (trimethylphosphine) tantalum, tantalum chloride (V), Cobalt bromide (II), iron bromide (II), bromopentacarbonylmanganese, manganese bromide (II), bromopentacarbonylrhenium (I), bromotricarbonyl (allyl) iron (II), bromo (cyclopentadi) Enyl) carbonyl (trimethylphosphine) iron (II), iron (III) bromide, bromide Iridium (III), rhodium (III) bromide, bromo (cyclopentadienyl) bis (triphenylphosphine) ruthenium (II), bromo (cyclopentadienyl) bis (trimethylphosphine) ruthenium (II), bromo (cyclo Pentadienyl) (1,5-cyclooctadiene) ruthenium (II), ruthenium (III) bromide, vanadium (III) bromide, hafnium bromide (IV), titanium bromide (IV), dibromobis (cyclopenta) Dienyl) titanium (IV), tribromo (cyclopentadienyl) titanium (IV), tribromo (cyclopentadienyl) zirconium tetraallyl zirconium (IV), zirconium bromide (IV), niobium bromide (V), odor Tantalum (V), chromium (II) bromide, chromium (III) bromide, carbonyl (cyclopentadienyl) di Iodocobalt (III), (cyclopentadienyl) (triphenylphosphine) diiodocobalt (III), carbonyldiiodo (pentamethylcyclopentadienyl) cobalt (III), diiodobis [pentamethylcyclopentadienyl] iodo Cobalt (III)], cobalt iodide (II), iron iodide (II), hafnium iodide (IV), manganese iodide (II), rhodium iodide (III), iododicarbonyl (pentamethylcyclopentadi Enyl) ruthenium (II), ruthenium (III) iodide, vanadium (III) iodide, titanium (IV) iodide, zirconium (IV) iodide, niobium iodide (V), tantalum iodide (V), iodine Chromium (II) iodide, chromium (III) iodide, chromium (III) perchlorate, molybdenum (III) chloride, molybdenum chloride (V), molybdenum bromide (III), molybdenum dichloride dioxide (VI) molybdenum oxychloride (VI), molybdocene dichloride (IV), chlorotricarbonyl (cyclopentadienyl) molybdenum (II), tungsten chloride (IV), tungsten chloride (VI) , Tungsten bromide (V), tungsten dichloride dioxide (VI), tungsten oxychloride (VI), diacetonitrile (allyl) (dicarbonyl) (chloro) tungsten (II), bromotricarbonyl (cyclopentadienyl) tungsten (II), dichlorobis (cyclopentadienyl) tungsten (IV), dichlorobis (cyclopentadienyl) oxotungsten (VI), and the like.

  As an alkylated product of Group 4 to Group 9 metal represented by Component A, at least one aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is coordinated The metal compound which has as a child is shown. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Linear, branched or cyclic aliphatic hydrocarbons such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl Groups. Examples of the substituent for these groups include the above-described aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, tert. -Functional groups such as alkoxy groups such as butoxy group, allyloxy groups such as phenoxy group, halogen (F, Cl, Br, I), acetoxy group, nitro group, sulfonic acid group, carbonyl group, amino group, and the like. These substituents may further have a substituent. Specific examples of group 4-9 metal alkylates in the periodic table include trichloromethyltitanium (IV), tribromomethyltitanium (IV), dimethylbis (cyclopentadienyl) titanium (IV), chloro (Methyl) bis (cyclopentadienyl) titanium (IV), dimethylbis (pentamethylcyclopentadienyl) titanium (IV), trimethyl (cyclopentadienyl) titanium (IV), methyltriisopropoxytitanium (IV) , Tris (dimethylamino) methyltitanium (IV), 1,4-tetramethylenebis (cyclopentadienyl) titanium (IV), bis (cyclopentadienyl) (2,3-isopropylidene) titanacyclobutane (IV ), Bis (cyclopentadienyl) dimethylzirconium (IV), iodomethylbi Sus (cyclopentadienyl) zirconium (IV), bis (cyclopentadienyl) dimethylhafnium (IV), methylbis (pentamethylcyclopentadienyl) vanadium, tetrachloromethyl niobium (V), dichlorotrimethylniobium (V) , Ethylbis (cyclopentadienyl) (propyne) niobium, tetrachloromethyltantalum (V), dichlorotrimethyltantalum (V), trimethylbis (cyclopentadienyl) tantalum (V), methyl (methylidene) bis (cyclopentadiene) Enyl) tantalum, tetramethylchromium (IV), tetrakis (trimethylsilylmethyl) chromium (IV), tricarbonyl (cyclopentadienyl) methylmolybdenum (II), tricarbonyl (cyclopentadienyl) ethylmolybdenum (II), tri Carbonyl (Siku Pentadienyl) isopropylmolybdenum (II), tricarbonyl (cyclopentadienyl) chloromethylmolybdenum (II), tricarbonyl (cyclopentadienyl) iodomethylmolybdenum (II), tricarbonyl (cyclopentadienyl) bromopropylmolybdenum ( II), tricarbonyl (cyclopentadienyl) bromobutylmolybdenum (II), dimethyl (benzene) bis (trimethylphosphine) molybdenum (II), hexamethyltungsten (VI), hexakis (trimethylsilylmethyl) ditungsten (III), Pentacarbonylmethylmanganese (I), pentacarbonylmethylrhenium (I), carbonylnitrosylmethyl (pentamethylcyclopentadienyl) rhenium (I), methyl (trioxo) rhenium (VII), (Si Lopentadienyl) methylcarbonyliron (II), (cyclopentadienyl) methylcarbonyl (trimethylphosphine) iron (II), chloromethyl (cyclopentadienyl) carbonyl (triphenylphosphine) iron (II), tetrakis (triphenylphosphine) ) Methyl cobalt (I) and the like.

  As an arylation product of a metal of Group 4 to Group 9 of the periodic table, a metal compound having at least one aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent as a ligand Indicates. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, indenyl group, fluorenyl group, azulenyl group, benzyl group, phenethyl group, styryl group, and cinnamyl group. Benzhydryl group, tolyl group, xylyl group, cumenyl group, mesityl group and the like. In addition, the substituents of these groups include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, tert-butoxy groups. And functional groups such as alkoxy groups such as groups, allyloxy groups such as phenoxy groups, halogens (F, Cl, Br, I), acetoxy groups, nitro groups, sulfonic acid groups, carbonyl groups, amino groups, and the like. These substituents may further have a substituent. Specific examples of arylates of metals from Groups 4 to 9 of the Periodic Table include tetrabenzyltitanium (IV), bis (cyclopentadienyl) diphenyltitanium (IV), triphenyltris (tetrahydrofuran) chromium (III And the like.

  As an allylated product of Group 4 to Group 9 metal in the periodic table, a metal compound having at least one π-bonded ligand as a ligand is shown. Examples of the π-bonding ligand include an allyl group, a cyclopentadienyl group, an indenyl group, a fluorenyl group and the like which may have a substituent. In addition, the substituents of these groups include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, tert-butoxy groups. And functional groups such as alkoxy groups such as groups, allyloxy groups such as phenoxy groups, halogens (F, Cl, Br, I), acetoxy groups, nitro groups, sulfonic acid groups, carbonyl groups, amino groups, and the like. These substituents may further have a substituent. Specific examples of the allylic compounds of Group 4 to Group 9 metals in the periodic table include dicyclopentadienylbis (cyclopentadienyl) titanium (IV), tetraallylzirconium (IV), tetraallylhafnium (IV ), Bis (cyclopentadienyl) vanadium, bis (pentamethylcyclopentadienyl) vanadium, tris (allyl) chromium (III), tetrakis (allyl) dichrome (II), hexacarbonylbis (cyclopentadienyl) Dichromium (I), chromocene (II), bis (cyclopentadienyl) ethylenemolybdenum (II), bis (cyclopentadienyl) (1,2-diphenylethyne) molybdenum (II), (allyl) bis (cyclo Pentadienyl) molybdenum (IV) tosylate, tricarbonyl (cyclopentadienyl) (ethylene) Nungsten (II) hexafluorophosphate, hexacarbonylbis (cyclopentadienyl) ditungsten (I), potassium tricarbonyl (cyclopentadienyl) tungsten (0) potassium, bis (cyclopentadienyl) tungsten ( II), allyl bis (cyclopentadienyl) tungsten (IV) hexafluorophosphate, bis (pentamethylcyclopentadienyl) manganese (II), ferrocene, ruthenocene, cobaltcene and the like.

  The metal hydride of Group 4 to Group 9 of the Periodic Table represents a metal compound having at least one hydrogen atom as a ligand. Specific examples of Group 4 to Group 9 metal hydrides in the periodic table include dihydridobis (pentamethylcyclopentadienyl) titanium (IV), dihydridobis [bis (cyclopentadienyl) titanium (III)], Poly [hydridobis (cyclopentadienyl)] titanium (III), bis (cyclopentadienyl) dihydridozirconium (IV), chlorobis (cyclopentadienyl) hydridozirconium (IV), bis (pentamethylcyclopentadienyl) ) Dihydridozirconium (IV), chlorobis (cyclopentadienyl) hydridohafnium (IV), dihydridobis (pentamethylcyclopentadienyl) hafnium (IV), trihydridobis (cyclopentadienyl) niobium (V), hydridobis (Cyclopentadienyl) ethylenenio (III), hydridobis (cyclopentadienyl) (3,3-dimethylbutyne) niobium, trihydridobis (cyclopentadienyl) tantalum (V), tricarbonylhydrido (cyclopentadienyl) chromium (II), Bis (cyclopentadienyl) dihydridomolybdenum (IV), tricarbonyl (cyclopentadienyl) hydridomolybdenum (II), tricarbonylhydrido (pentamethylcyclopentadienyl) molybdenum (II), dihydrido (benzene) bis ( Triphenylphosphine) molybdenum (II), tetrahydridobis {1,2-bis (diphenylphosphino) ethane} molybdenum (IV), dihydridopentakis (trimethylphosphine) molybdenum (II), formatohydridobis {1, 2-bis (diphenylphosphino) ethane} Ribden (II), tricarbonyl (cyclopentadienyl) (hydrido) tungsten (II), bis (cyclopentadienyl) dihydride tungsten (II), bis (cyclopentadienyl) (ethylene) (hydrido) tungsten ( II) Hexafluorophosphate, hydridopentacarbonylmanganese (I), tris (hydridotetracarbonylmanganese) (I), hydridopentacarbonylrhenium (I), (hydrido) (propenyl) (octacarbonyl) direnium, dicarbonyl Dihydrido (cyclopentadienyl) rhenium (III), trihydridobis [1,2-bis (diphenylphosphino) ethane] rhenium (III), tricarbonylhydrido (triphenylphosphine) iron (0) tetraethylammonium, (Cyclopentadie ) Hydridodicarbonyliron (II), dihydridobis [1,2-bis (diphenylphosphino) ethane] iron (II), hydridobis [1,2-bis (diphenylphosphino) ethane] iron (I), dihydride ( Dinitrogen) tris (ethyldiphenylphosphine) iron (II), dihydridotetrakis (triphenylphosphine) ruthenium (II), tetrahydridotris (triphenylphosphine) ruthenium (II), dihydrido (trifluorophosphine) tris (phenylphosphine) ) Ruthenium (II), Acetatohydridotris (triphenylphosphine) ruthenium (II), Hydridonitrosyltris (triphenylphosphine) ruthenium (II), Hydrido (cyclopentadienyl) bis (triphenylphosphine) ruthenium (II) , Hydride ( Cyclopentadienyl) (1,5-cyclooctadiene) ruthenium (II), trihydride (pentamethylcyclopentadienyl) (triphenylphosphine) ruthenium (IV), hydridotetracarbonylcobalt (I), hydride (dinitrogen) ) Tris (triphenylphosphine) cobalt (I), hydridotetracarbonylrhodium (I), hydridocarbonyltris (triphenylphosphine) rhodium (I), hydridotris (triisopropylphosphine) rhodium (I) hydridotetrakis (triphenylphosphine) ) Rhodium (I), [dihydridobis (triphenylphosphine) bis (acetonitrile) rhodium (I)] perchlorate, dihydridobis (triethylsilyl) pentamethylcyclopentadienyl rhodium (V) It is shown.

  Examples of the oxygenated organic compounds of Group 4 to Group 9 metals in the periodic table include alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, and tert-butoxy group, which may have a substituent, At least one oxygen-containing organic ligand such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group or other noncarboxyl group such as phenoxy group, acetylacetonate group, acetoxy group or amide group One represents a metal compound as a ligand. Specific examples of oxygenated organic compounds of Group 4 to Group 9 metals in the periodic table include acetylchlorobis (cyclopentadienyl) titanium (IV), triisopropoxytitanium chloride (IV), tris (2, 6-diisopropylphenoxy) (2,2-dimethylpropylidene) tantalum, tetrachloro (2,6-diisopropylphenoxy) tantalum (V), chromium (III) acetate, benzoylacetonate chromium (III), hexafluoroacetylacetonate Chromium (III), chromium naphthenate (III), molybdenum acetate (II), molybdenum 2-ethylhexanoate, bis (acetylacetonato) molybdenum oxide (IV), bis (2,2,6,6-tetramethyl) -3,5-Heptanedionate) Molybdenum oxide (VI), tungsten (VI) ethoxide, acetylacetate Natochrome (III), tris (salicylaldehyde) chromium (III), bis (acetylacetonato) dioxomolybdenum (VI), pentacarbonylacetylrhenium (I), diacetatodicarbonylbis (triphenylphosphine) ruthenium ( II), dicarbonyl (hydroxymethyl) (pentamethylcyclopentadienyl) ruthenium (II), 2,4-pentanedionate bis (ethylene) rhodium (I), bis (acetylacetonato) dichlorotitanium (IV), Trichloro (acetylacetonate) dichlorotitanium (IV), acetylacetonate zirconium (IV), acetylacetonate vanadium (IV), acetylacetonate manganese (III), acetylacetonate manganese (II), acetylacetonate iron (III) ), Acetyl Examples include ruacetonate iron (II), acetylacetonate toruthenium (III), acetylacetonate cobalt (III), acetylacetonate cobalt (II), acetylacetonatotrodium (III) and the like.

  As the nitrogen-containing organic compounds of Group 4 to Group 9 metals in the periodic table, at least nitrogen-containing organic ligands such as amino groups, amide groups, imino groups, and nitrile groups which may have a substituent are included. One shows the metal compound which has as a ligand. Specific examples of nitrogen-containing organic compounds of Group 4 to Group 9 metals in the periodic table include tris (dimethylamino) titanium (IV) bromide, chromium (III) tetraphenylporphine chloride, tris (2-aminoethanolato) Examples include chromium (III), tris (glycinato) chromium (III), (trimethylenediaminetetraacetato) sodium chromium (III), and the like.

  When the component A is supported on an inorganic carrier or an organic carrier, it is useful for isotactic polymerization of vinyl ester monomers. Examples of the inorganic carrier include inorganic substances, metal oxides and halides. For example, activated carbon, alumina, silica, alumina-silica, zeolite, magnesium chloride, magnesium oxide, calcium chloride, copper chloride and the like are exemplified. Furthermore, what can become an inorganic support | carrier by reaction can also be used. For example, a reaction product of metallic magnesium and alcohol can be used.

  Examples of the organic carrier include a polymer compound insoluble in an organic solvent and an ion exchange resin. For example, polystyrene beads, cyclodextrin, Amberlyst, Nafion, Dowex, Sephadex, silica gel and the like can be mentioned.

  As a method of supporting the component A on an inorganic carrier or an organic carrier, a method usually used in the technical field of catalyst production can be used. For example, a method in which the component A and an inorganic carrier are co-ground in an inert gas atmosphere in a ball mill or a vibration mill, a method in which an inorganic carrier or an organic carrier is immersed in a solution of the component A, and then dried and supported. Examples thereof include a method in which the ligand of A is chemically bonded to an organic carrier. The amount of the component A supported on the inorganic carrier or the organic carrier is not particularly limited, but is preferably about 0.001 to 30 wt%.

  Component B to be contained in the polymerization-supported catalyst composition for polymerization of the present invention may have an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted carbon number. A compound having an atomic number of 3 or more and a Group 1, 2, 12 or 13 element in the periodic table, or a perchlorate having at least one 6 to 40 aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group. , Indenyl group, fluorenyl group, azulenyl group and the like. Examples of the substituent for these groups include the above-described aliphatic hydrocarbon group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 20 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, tert. -Functional groups such as alkoxy groups such as butoxy group, allyloxy groups such as phenoxy group, halogen (F, Cl, Br, I), acetoxy group, nitro group, sulfonic acid group, carbonyl group, amino group and the like. These substituents may have further substituents.

  Examples of the compound contained in Component B include alkyl lithium, alkyl sodium, alkyl magnesium, alkyl zinc, alkyl aluminum, organoboron compound, perchlorate and the like. Specific examples include methyl lithium, butyl lithium, phenyl lithium, butyl sodium, butyl ethyl magnesium, methyl magnesium bromide, ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium bromide, methyl magnesium chloride, ethyl magnesium chloride, chloride. Butyl magnesium, phenyl magnesium chloride, diethyl zinc, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diisobutyl aluminum methoxide, diisobutyl aluminum ethoxide Diisobutylaluminum isopropoxy , Diethylaluminum ethoxide, dibutylaluminum butoxide, ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, diisopropylaluminum hydride, methylaluminum bis (2,6-ditert-butylphenoxide), methylaluminum bis (2,6- Ditert-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-ditert-butylphenoxide), isobutylaluminum bis (2,6-ditert-butyl-4-methylphenoxide), methylaluminum bis {2 -(N-phenylimino) phenoxide}, isobutylaluminum bis {2- (N-phenylimino) phenoxide}, diethylaluminum {2- (N-phenylimino) phenoxide}, dimethyl Aluminum (N, N`-diisopropylacetamidinate), dimethylaluminum (N, N`-dicyclohexylacetamidinate), dimethylgallium (N, N`-diisopropylacetamidinate), dimethylgallium (N, N `-Dicyclohexylacetamidinate), an aluminoxane compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom. Of these, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloridealuminoxane compound and the like are preferable.

  In addition to organic boron compounds in a narrow sense, organic boron compounds include organic boric acid compounds. Specific examples include trispentafluorophenyl boron, tris (trifluoromethyl) boron, and tetrakispentafluorophenyl borate triphenyl. Examples include methyl, tetrakis [3,5-di (trifluoromethyl) phenyl] triphenylmethylborate, sodium tetrakis [3,5-di (trifluoromethyl) phenyl] borate, and the like. The perchlorate includes a metal salt of perchloric acid or a salt of perchloric acid and an organic cation, and specific examples include silver perchlorate and triphenylmethyl perchlorate. Component B can be used by mixing one or more of these compounds.

  As the vinyl ester monomer used in the present invention, vinyl acetate is typically shown, but in the present invention, a vinyl ester monomer having 3 to 20 carbon atoms may be used in addition to vinyl acetate. . Examples of such monomers include vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl 2-ethylhexanoate, vinyl benzoate, and the like. Moreover, these may be individual or may combine 2 or more types. A monomer that can be copolymerized with a vinyl ester monomer during polymerization of the vinyl ester monomer using the supported catalyst composition for polymerization of the present invention, for example, an α-olefin such as ethylene, propylene, and isobutene; acrylic acid Unsaturated acids such as methacrylic acid, crotonic acid, maleic acid, itaconic acid, maleic anhydride, salts or mono- or dialkyl esters thereof; acrylonitrile, methacrylonitriles; acrylamide, methacrylamides; vinyl ethers; A small amount of vinylidene chloride; styrene, α-methylstyrene; butadiene, isoprene, 1,5-hexadiene, cyclopentadiene, vinyl norbornene, norbornadiene; vinyl sulfonic acid or its salt;

  The polymerization conditions are not particularly limited, but it is preferable to use a mixed solution of a vinyl ester monomer and an inert solvent. As the inert solvent, any solvent can be used as long as it does not inhibit the polymerization. In particular, an aliphatic hydrocarbon having 4 to 20 carbon atoms such as isobutane, pentane, hexane, heptane, cyclohexane, etc .; aromatic Hydrocarbons such as toluene, xylene, etc .; halogenated aliphatic hydrocarbons having 1 to 20 carbon atoms such as chloroform, methylene chloride, carbon tetrachloride, dibromoethane, tetrachloroethane, etc .; halogenated aromatic hydrocarbons such as chlorobenzene, di Chlorobenzene and the like; aliphatic esters having 3 to 20 carbon atoms such as methyl acetate, ethyl acetate, 2-ethylhexyl acetate, phenyl acetate and ethyl hexanoate; or aromatic esters such as methyl benzoate and ethyl benzoate; Is appropriate.

  In the practice of the present invention, component A is an amount corresponding to 0.001 to 2.5 moles of metal atoms of Group 4 to Group 9 of the periodic table per liter of a mixed solution containing a vinyl ester monomer and an inert solvent. It is preferable to use it, and it can be used at a higher concentration depending on the conditions.

  Component B can be appropriately changed in concentration depending on the type of component A, etc., but is usually a metal from Group 1, 2, 11, 12 or 13 of the periodic table per liter of a mixed solution containing a vinyl ester monomer and an inert solvent. It is preferably used at a concentration of 0.02 to 50 mol of atoms. The molar ratio of component B / component A of the catalyst composition is not particularly limited, but is usually 10,000 or less, preferably 5000 or less, and more preferably 0.1 to 1000.

  The polymerization operation in the main polymerization can be performed not only in a single-stage polymerization performed under normal single polymerization conditions but also in a multi-stage polymerization performed under a plurality of polymerization conditions.

  Although the polymerization conditions in this invention are not specifically limited, Usually, it is -100 degreeC-200 degreeC, Preferably it is -20 degreeC-100 degreeC.

  From the vinyl ester polymer obtained by polymerizing a vinyl ester monomer using the supported catalyst composition of the present invention, PVA can be produced by saponification. There is no limitation, and an alcohol solution of a vinyl ester polymer can be saponified by a known method using an alkali such as sodium hydroxide or potassium hydroxide as a catalyst. The supported catalyst composition of the present invention is for polymerizing a vinyl ester monomer to obtain a vinyl ester polymer having an isotacticity of 50% or more by meso diad (m). . In the present invention, the isotacticity of the vinyl ester polymer means that the vinyl ester polymer is alkali saponified and converted to PVA, and a value obtained by a nuclear magnetic resonance apparatus according to the method described in Examples below. Shall point to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the measuring method used for the Example and the comparative example is as follows.

(Isotacticity (Duplicate))
Polyvinyl acetate was saponified with alkali according to a conventional method and converted to PVA, proton NMR was measured with a nuclear magnetic resonance apparatus (JNM-LAMBDA-400, manufactured by JEOL Ltd.), and triplet (mm / mr / rr) The ratio (%) was determined, and isotacticity (duplex) (m) (%) was calculated from the following formula.
Isotacticity (doublet) (m) = mm + (mr / 2)

(Molecular weight of polymer)
Vinyl ester in a tetrahydrofuran solvent at 40 ° C. using a gel permeation chromatograph (manufactured by Tosoh Corporation) equipped with a column (Tosoh Corporation, TSKgelGMHHR-M and TSKgelG2000HHR) and a differential refractometer (Tosoh Corporation, RI-8020). The weight average molecular weight (Mw) and molecular weight dispersity (MWD) [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer were determined in terms of polystyrene.

Synthesis example 1
[Preparation of supported catalyst]
Acetylacetonatochrome (III) was supported on magnesium chloride as an inorganic carrier. That is, 0.1 g of acetylacetonatochromium (III), 5.0 g of magnesium chloride and 0.015 L of toluene were charged in a glass Schlenk tube having an internal volume of 0.2 L in an argon atmosphere and stirred for 24 hours. Thereafter, toluene was distilled off under reduced pressure to support lower acetylacetonatochrome (III) on the carrier. The chromium content in the obtained magnesium chloride-supported acetylacetonate chromium (III) catalyst was 0.056 mmol / g.

Example 1
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) and diethylaluminum chloride (11 mmol) in Synthesis Example 1 Further, vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 1. The catalytic activity per 1 mol of chromium was 7.44 kg / mol-Cr.

Example 2
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) and diethylaluminum chloride (11 mmol) in Synthesis Example 1 Was added. The reaction solution was stirred at room temperature for 10 minutes, the liquid layer was removed, and an equivalent amount of toluene was added. Vinyl acetate (0.01 L) was then added to this solution and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 1.

Example 3
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) and methylaluminoxane (converted to aluminum atoms) in Synthesis Example 1 2 mmol) was added and vinyl acetate (0.01 L) was added to the solution and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 1.

Example 4
Polymerization of vinyl acetate A 0.1 L Schlenk flask substituted with argon was charged with n-heptane (0.01 L), and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) of Synthesis Example 1 and diethylaluminum chloride ( 11 mmol), vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 1.

Example 5
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) and diethylaluminum chloride (11 mmol) in Synthesis Example 1 Then, vinyl acetate (0.01 L) was further added and stirred at room temperature for 6 hours. After 6 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 1.

Example 6
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) and diethylaluminum chloride (11 mmol) in Synthesis Example 1 Further, vinyl acetate (0.01 L) was added and stirred at 40 ° C. for 6 hours. After 6 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 1.

Example 7
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an ethylene-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate chromium (III) (1.0 g) and diethylaluminum chloride (11 mmol) in Synthesis Example 1 were used. Then, vinyl acetate (0.01 L) was further added and stirred at room temperature for 6 hours. After 6 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 2.

Example 8
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an ethylene-substituted 0.1 L Schlenk flask, and magnesium chloride-supporting acetylacetonate chromium (III) (1.0 g) of Synthesis Example 1 and ethyl benzoate (3 mmol) And diethylaluminum chloride (11 mmol) were added, and vinyl acetate (0.01 L) was further added, followed by stirring at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 2.

Example 9
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported trifluoroacetylacetonate chromium (III) (1.0 g) prepared in the same manner as in Synthesis Example 1. ) And diethylaluminum chloride (11 mmol), vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 2.

Example 10
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported benzoylacetylacetonate chromium (III) (1.0 g) prepared in the same manner as in Synthesis Example 1. And diethylaluminum chloride (11 mmol) were added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 2.

Example 11
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported bis (acetylacetonato) molybdenum oxide (IV) (1) prepared in the same manner as in Synthesis Example 1 0.0 g) and diethylaluminum chloride (11 mmol) were added, and vinyl acetate (0.01 L) was further added, followed by stirring at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 2.

Example 12
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported bis (acetylacetonato) dichlorotitanium (IV) (1) prepared in the same manner as in Synthesis Example 1 (1) 0.0 g) and diethylaluminum chloride (11 mmol) were added, and vinyl acetate (0.01 L) was further added, followed by stirring at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 3.

Example 13
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate zirconium (IV) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 3.

Example 14
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonate vanadium (IV) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at 0 ° C. for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 3.

Example 15
Polymerization of vinyl acetate Magnesium chloride-supported acetylacetonate vanadium (III) (1.0 g) and diethylaluminum chloride (10 mmol) prepared by the method according to Synthesis Example 1 were added to an argon-substituted 0.1 L Schlenk flask, and acetic acid was further added. Vinyl (0.01 L) was added and stirred at 0 ° C. for 6 hours. After 6 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 3.

Synthesis example 2
[Synthesis of 2-methyl-1,3-butanedioate vanadium (III)]
1) Synthesis of 2-methyl-1,3-butanionate ligand: Powdered CH ₃ ONa (0.24 mol), HCOOCH ₃ (0.53 mol) and THF (300 ml) were added to a 500 ml Schlenk tube equipped with a dropping funnel. Introduced. Next, after cooling the reaction vessel to 0 ° C., methyl ethyl ketone (0.26 mol) was slowly added dropwise over 30 minutes while stirring. Thereafter, the mixture was stirred at 0 ° C. for 4 hours and at room temperature for 20 hours. The reaction solution was allowed to stand for 2 days to separate into a solution part and a solid part, and only the solution part was removed. The solid part (light yellow) of the target product was dried under reduced pressure (yield: about 90%).
2) Synthesis of complex: 2-methyl-1,3-butanionate (57 mmol) synthesized by the above method was placed in a 300 ml Schlenk tube and dissolved in 50 ml of distilled water. To this solution was added an aqueous VCl ₃ solution (3.0 g / 50 ml) and stirred for 1 hour. Next, this solution was allowed to stand for several hours, and then the supernatant was removed. Thus, the target complex was purified by washing about 10 times with distilled water. Finally, a brown complex was obtained by drying under reduced pressure (yield about 50%) [see Makromol. Chem., Rapid Commun., 8, 285 (1987)].

Example 16
Polymerization of vinyl acetate 2-methyl-1,3-butanedioate vanadium (III) obtained in Synthesis Example 2 was supported on magnesium chloride by a method according to Synthesis Example 1. Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported 2-methyl-1,3-butanedioate vanadium (III) (1.0 g) and diethylaluminum chloride (10 mmol). Further, vinyl acetate (0.01 L) was added and stirred at 0 ° C. for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 3.

Example 17
Polymerization of vinyl acetate 2-methyl-1,3-butanedioate vanadium (III) obtained in Synthesis Example 2 was supported on magnesium chloride by a method according to Synthesis Example 1. To a 0.1 L Schlenk flask substituted with argon, magnesium chloride-supported 2-methyl-1,3-butanedioate vanadium (III) (1.0 g) and diethylaluminum chloride (10 mmol) were added, and further vinyl acetate (0.01 L) was added. And stirred at 0 ° C. for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 3.

Example 18
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonate manganese (III) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 4.

Example 19
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonate manganese (II) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 4.

Example 20
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonate iron (III) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 5.

Example 21
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonate iron (II) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 5.

Example 22
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonate ruthenium (III) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 5.

Example 23
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supporting acetylacetonate cobalt (III) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 6.

Example 24
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supporting acetylacetonate cobalt (II) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 6.

Example 25
Polymerization of vinyl acetate Heptane (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supporting acetylacetonate cobalt (III) (1.0 g) prepared by the method according to Synthesis Example 1 Diethylaluminum chloride (10 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 6 hours. After 6 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 6.

Example 26
Polymerization of vinyl acetate To a 0.1 L Schlenk flask substituted with argon was added magnesium chloride-supporting acetylacetonate cobalt (III) (1.0 g) and diethylaluminum chloride (5 mmol) prepared by the method according to Synthesis Example 1, and acetic acid was further added. Vinyl (0.01 L) was added and stirred at room temperature for 6 hours. After 6 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 6.

Example 27
Polymerization of vinyl acetate Toluene (0.02 L) was charged into an argon-substituted 0.1 L Schlenk flask, and magnesium chloride-supported acetylacetonate cobalt (III) (1.0 g) prepared by the method according to Synthesis Example 1 and Diethylaluminum chloride (10 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at 60 ° C. for 3 hr. After 3 hours, the reaction vessel was poured into 0.1 L of a 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 6.

Example 28
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported acetylacetonato rhodium (III) (1.0 g) prepared in the same manner as in Synthesis Example 1 Diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 7.

Example 29
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported trichloro (cyclopentadienyl) titanium (IV) (1) prepared in the same manner as in Synthesis Example 1 (1) 0.0 g) and methylaluminoxane (2 mmol in terms of aluminum atom) were added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at 0 ° C. for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 7.

Example 30
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and magnesium chloride-supported rac-ethylenebis (indenyl) dichlorozirconium (IV) (IV) prepared in the same manner as in Synthesis Example 1 ( 1.0 g) and methylaluminoxane (2 mmol in terms of aluminum atom) were added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The results are shown in Table 7.

Comparative Example 1
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, azoisobutyronitrile (10 mg) was added, and vinyl acetate (0.01 L) was further added at 60 ° C. for 24 hours. Stir for hours. After 24 hours, the reaction solution was concentrated to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. The said conditions correspond to the comparative example as normal radical polymerization. The results are shown in Table 8.

Comparative Example 2
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, acetylacetonatochromium (III) (17.5 mg) and diethylaluminum chloride (11 mmol) were added, and vinyl acetate ( 0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 8.

Comparative Example 3
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, acetylacetonatochromium (III) (175 mg) and diethylaluminum chloride (11 mmol) were added, and vinyl acetate (0. 01L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 8.

Comparative Example 4
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, diethylaluminum chloride (11 mmol) was added, vinyl acetate (0.01 L) was further added, and the mixture was stirred at room temperature for 24 hours. . After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not used. The results are shown in Table 8.

Comparative Example 5
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask purged with argon, magnesium chloride (1.0 g) and azoisobutyronitrile (10 mg) were added, and vinyl acetate (0.01 L) was added. ) And stirred at 60 ° C. for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example as normal radical polymerization in the presence of a carrier. The results are shown in Table 8.

Comparative Example 6
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, trifluoroacetylacetonatochrome (III) (25.6 mg) and diethylaluminum chloride (1.1 mmol) were added, Further, vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 9.

Comparative Example 7
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and benzoylacetylacetonatochrome (III) (26.8 mg) and diethylaluminum chloride (1.1 mmol) were added. Vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 9.

Comparative Example 8
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, and bis (acetylacetonato) molybdenum oxide (IV) (16.3 mg) and diethylaluminum chloride (1.1 mmol) were added. In addition, vinyl acetate (0.01 L) was further added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 9.

Comparative Example 9
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, magnesium chloride (1.0 g) and diethylaluminum chloride (11 mmol) were added, and vinyl acetate (0.01 L) was further added. In addition, the mixture was stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not used. The results are shown in Table 9.

Comparative Example 10
Polymerization of vinyl acetate Toluene (0.01 L) was charged into an argon-substituted 0.1 L Schlenk flask, methylaluminoxane (2 mmol in terms of aluminum atom) was added, and vinyl acetate (0.01 L) was further added at room temperature. Stir for hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not used. The results are shown in Table 9.

Comparative Example 11
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, acetylacetonatochrome (III) (17.5 mg) and methylaluminoxane (2 mmol in terms of aluminum atom) were added, and further Vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 10.

Comparative Example 12
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and trifluoroacetylacetonate chromium (III) (25.6 mg) and methylaluminoxane (2 mmol in terms of aluminum atom) were added. Further, vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 10.

Comparative Example 13
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, benzoylacetylacetonatochrome (III) (26.8 mg) and methylaluminoxane (2 mmol in terms of aluminum atom) were added, Further, vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 10.

Comparative Example 14
Polymerization of vinyl acetate Toluene (0.01 L) was charged into a 0.1 L Schlenk flask substituted with argon, and bis (acetylacetonato) molybdenum oxide (IV) (16.3 mg) and methylaluminoxane (2 mmol in terms of aluminum atom). Further, vinyl acetate (0.01 L) was added and stirred at room temperature for 24 hours. After 24 hours, the reaction vessel was put into 0.1 L of 0.1 M hydrochloric acid aqueous solution, and the product was extracted with chloroform to obtain polyvinyl acetate. The obtained polyvinyl acetate was converted to PVA by alkali saponification according to a conventional method. This condition corresponds to a comparative example in which component A is not supported on a carrier. The results are shown in Table 10.

As is clear from the comparison between Examples 1-30 and Comparative Examples 1-14, it can be seen that a polymer having high isotacticity can be produced under mild conditions by using the supported catalyst composition for polymerization of the present invention. .

Claims (7)

A supported catalyst composition for isotactic polymerization of a vinyl ester monomer having a polymer isotacticity of 50% or more in meso diads (m), and at least one metal compound selected from the following component A A supported catalyst composition for isotactic polymerization, comprising a catalyst in which is supported on an inorganic carrier or an organic carrier and at least one compound selected from the following Component B.
Component A: Halides, alkylates, arylates, allylates, hydrides, oxygenated organic compounds, nitrogenous organic compounds of Group 4 to Group 9 metals of the Periodic Table.
Component B: having at least one aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, A compound having an atomic number of 3 or more and a Group 1, 2, 12 or 13 element of the periodic table, or a perchlorate.   The supported catalyst composition for polymerization according to claim 1, wherein Component A is a metal compound having at least one acetylacetonate group which may have a substituent as a ligand.   The supported catalyst composition for polymerization according to claim 1 or 2, wherein the carrier on which component A is supported is a metal halide of Group 1 or Group 2 of the Periodic Table.   The supported catalyst composition for polymerization according to any one of claims 1 to 3, wherein Component B is an organolithium compound, an organomagnesium compound, an organoboron compound, an organoaluminum compound, or a perchlorate.   Use of the supported catalyst composition for polymerization according to any one of claims 1 to 4 for isotactic polymerization of a vinyl ester monomer.   6. Use of vinyl ester monomer for isotactic polymerization according to claim 5, wherein the vinyl ester monomer has 3 to 20 carbon atoms. The use of the vinyl ester monomer for isotactic polymerization according to claim 6, wherein the vinyl ester monomer is vinyl acetate.