JP2009102598A - Manufacturing method of olefinic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an olefinic polymer which can be freely material-designed, and is excellent in chemical stability without adversely affecting mechanical properties and the like. <P>SOLUTION: The manufacturing method of an olefinic polymer comprises processing an olefin polymer (PO-X) having as a main constitutional unit a repeat unit originated from at least one kind of the olefins selected from the olefins containing a halogen atom and having 2 to 20 carbon atoms, and an olefin polymer (PO'-M) having as a main constitutional unit a repeat unit originated from at least one kind of the olefins selected from the olefins containing a dissociable metal atom and having 2 to 20 carbon atoms. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an olefin polymer.

  Polyolefins have excellent processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc. for various applications. It is used.

  In recent years, physical property requirements for polyolefins have been diversified and compounded. For example, in Japanese Patent Application Laid-Open No. 2004-131620, development of an olefin-based polymer material having segments having different properties is in progress. Further, for example, as described in JP-A No. 2004-204058, different properties such as blending a crystalline polyolefin excellent in heat resistance and an amorphous polyolefin excellent in impact resistance having a soft feel. It is also necessary to blend and use polyolefins. When polyolefins having different properties are blended as described above, usually, a sea-island structure in which the dispersed phase is dispersed in the matrix phase is obtained. Generally, the smaller the diameter of the dispersed phase, the better the advantages of the polyolefins having different properties. Has been. However, in a blend of polyolefins having different properties, it is difficult to make the dispersed phase fine because of the problem of poor compatibility, and it is difficult to exhibit the performance expected by the blend. For this reason, attempts have been made to reduce the diameter of the dispersed phase by blending polyolefins having different properties together with a compatibilizing agent such as an elastomer. It was difficult to make the diameter as fine as 1 μm or less.

  Further, the long-chain branched polymer having a specific structure is generally disclosed in, for example, JP 2002-308933 A as a polymer having a structure excellent in both moldability and mechanical strength, but has a limited structure. Only polymer materials are known.

  In order to solve these problems, for example, in WO2002 / 022713, a block type olefin polymer having a specific structure has been developed, but it has a chemically reversible binding site, and the chemistry of the binding site. There is a problem with mechanical stability. Therefore, it is industrially valuable if a more chemically stable material can be developed.

  In terms of chemical stability, a block-type olefin polymer having a relatively stable crosslinked structure, such as a silicon-carbon bond or silicon-oxygen bond, is reported in, for example, JP-A-9-59317. However, the polymer tends to have a gelled structure, the structure is difficult to control, and the processability of the polymer is also problematic.

Therefore, it has been desired to develop a block-type olefin polymer that can be freely designed and manufactured and has excellent chemical stability.

JP 2004-131620 A JP 2004-204058 A JP 2002-308933 A WO2002 / 022713 JP-A-9-59317

  The present invention is intended to solve such a problem, and is a method for producing an olefin polymer having excellent chemical stability without adversely affecting mechanical properties, etc. I will provide a.

As a result of intensive studies to solve the above problems, the present inventors have obtained an olefin polymer containing a halogen atom (PO-X) and an olefin polymer containing a dissociative metal atom (PO'-M). A method for producing an olefin polymer to be treated has been found.
That is, the method for producing an olefin-based polymer of the present invention comprises a olefin weight mainly comprising a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms and containing a halogen atom. Olefin polymer (PO) containing as a main constituent unit a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, comprising a polymer (PO-X) and a dissociative metal atom. It is a method for producing an olefin polymer characterized in that it is produced by treating '-M).

  The method for producing an olefin polymer in the present invention is a method of treating an olefin polymer containing a halogen atom (PO-X) and an olefin polymer containing a dissociative metal atom (PO'-M). The present invention is extremely useful industrially because it is possible to freely design materials and to produce an olefin polymer having excellent chemical stability without adversely affecting mechanical properties.

  Hereafter, the manufacturing method of the olefin polymer of this invention is explained in full detail.

[PO-X]
PO-X in the present invention is an olefin polymer containing, as a main structural unit, a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms and containing a halogen atom.

  Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, conjugated dienes, and nonconjugated polyenes.

  Examples of the linear α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, -C2-C20 linear alpha olefins, such as eicosene. Among these, linear α-olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene are preferable.

  Examples of the branched α-olefin include 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like having 5 to 20, preferably 5 to 10 carbon atoms Examples include α-olefins.

  Examples of the cyclic olefin include cyclic olefins having 3 to 20 carbon atoms, preferably 5 to 15 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.

  Conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene, Examples thereof include conjugated dienes having 4 to 20, preferably 4 to 10, carbon atoms such as 1,3-octadiene.

  Non-conjugated polyenes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2- Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1, 4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2 -Norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-dii Propylidene-5-norbornene, 5-2-ethylidene-3-isopropylidene-norbornene, such as a non-conjugated polyene having 5 to 20 carbon atoms, such as 2-propenyl-2,2-norbornadiene and the like. Among these, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl- 1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, cyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2 Non-conjugated polyenes having 5 to 10 carbon atoms such as -norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 2-propenyl-2,2-norbornadiene are preferred.

  PO-X in the present invention may contain a small amount of an aromatic vinyl compound or a functionalized vinyl compound as a monomer constituting PO.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethyl. Examples thereof include alkyl styrene such as styrene.

  Examples of the functionalized vinyl compound include a hydroxyl group-containing olefin, a halogenated olefin, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, an unsaturated carboxylic acid halide, an unsaturated amine, and an unsaturated epoxy compound.

  Examples of the unsaturated carboxylic acid include acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid. Can be mentioned.

  Examples of the unsaturated carboxylic acid anhydride include (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride, and anhydride of the unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid halide include compounds in which the carboxyl group of the unsaturated carboxylic acid is replaced with a carboxy halide group.

  Examples of the unsaturated amine include allylamine, 5-hexeneamine, and 6-hepteneamine.

  Examples of the unsaturated epoxy compound include 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9- Epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene and the like can be mentioned.

  The hydroxyl group-containing olefin is not particularly limited as long as it is a hydroxyl group-containing olefin compound, and examples thereof include terminal hydroxylated olefin compounds.

  Examples of the terminal hydroxylated olefin compound include a terminal hydroxylated linear α-olefin and a terminal hydroxylated branched α-olefin.

  As the terminal hydroxylated linear α-olefin, vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 7-octen-1-ol, 2-20 carbon atoms, such as 9-decene-1-ol, 11 dodecene-1-ol, 13 tetradecene-1-ol, 15 hexadecene-1-ol, 17 octadecene-1-ol, 19 eicosen-1-ol And terminal aquatic linear α-olefins. Among these compounds, vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 7-octen-1-ol, 9-decene-1-ol A terminal aquatic linear α-olefin having 2 to 10 carbon atoms such as is preferred.

  Examples of the terminal hydroxylated branched α-olefin include 2-methyl-3-buten-2-ol, 2-methyl-4-penten-2-ol, 3-methyl-4-penten-1-ol, and 3-ethyl. -4-penten-1-ol, 2,4-dimethyl-4-penten-2-ol, 2-methyl-5-hexen-2-ol 2,2-dimethyl-5-hexen-3-ol, 3- Examples thereof include terminal hydroxylated branched α-olefins having 5 to 20, preferably 5 to 10, carbon atoms such as ethyl-5-hexen-3-ol.

  Examples of the halogenated olefin include a halogenated linear α-olefin having a group 17 atom of the periodic table of chlorine, bromine, iodine, and a halogenated branched α-olefin.

  Examples of the halogenated linear α-olefin include vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, and halogenated-1-decene. Halogenated linear α having 2 to 20 carbon atoms, such as halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1-eicocene -Olefin and the like. Among these compounds, the number of carbon atoms is 2 to 2, such as vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, and halogenated-1-decene. Ten halogenated linear α-olefins are preferred.

  Examples of the halogenated branched α-olefin include halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogenated-3-methyl-1-pentene, and halogenated-3-ethyl. -1-pentene, halogenated-4,4-dimethyl-1-pentene, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1 Examples thereof include halogenated branched α-olefins having 5 to 20, preferably 5 to 10, carbon atoms such as hexene and halogenated-3-ethyl-1-hexene.

  The total content of aromatic vinyl compound and functionalized vinyl compound in PO is 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less. .

  PO-X is an olefin polymer containing, as a main constituent unit, a repeating unit derived from at least one olefin selected from these olefins containing a halogen atom, and the content of halogen atoms in PO-X Is 0.0001 to 30 wt%, preferably 0.001 to 20 wt%, more preferably 0.005 to 15 wt%, still more preferably 0.01 to 10 wt%, and most preferably 0.05 to 5 wt%. If the halogen atom content is low, it is disadvantageous for the production of the olefin polymer, and if it is too high, the mechanical properties of the olefin polymer are lowered.

  PO-X is an ethylene polymer, a propylene polymer, a copolymer of at least one olefin selected from ethylene and an olefin having 3 to 20 carbon atoms, and propylene from the viewpoint of strength such as mechanical properties. And a copolymer obtained from at least one olefin selected from olefins having 4 to 20 carbon atoms.

  When the molecular weight of the PO-X is small, it is disadvantageous for the expression of desired physical properties, and when the molecular weight is too large, the viscosity becomes high during the production of the olefin polymer. The molecular weight of the PO-X is in the range of 0.05 to 15 dl / g, preferably in the range of 0.1 to 12 dl / g, in the intrinsic viscosity ([η]) measurement measured in decalin. More preferably, it exists in the range of 0.15-10 dl / g.

  Next, a method for producing PO-X according to the present invention will be described. PO-X can be produced by producing an olefin polymer by polymerizing the above-mentioned olefin constituting PO using an olefin polymerization catalyst, and then performing a halogenation treatment. PO-X can also be produced as an olefin polymer having as a structural unit a repeating unit derived from at least one olefin selected from the above olefins containing a halogenated olefin.

  First, the olefin polymerization catalyst used for the production of the polyolefin will be described. Examples of the olefin polymerization catalyst used for the production of polyolefin include magnesium-supported titanium catalysts, metallocene catalysts, and other conventionally known catalysts. For example, the catalysts described in International Patent Publications WO01 / 53369 or WO01 / 27124 are preferred. Used.

  For example, when a solid titanium catalyst component (a) or a prepolymerized catalyst thereof, an organometallic compound catalyst component (b), and a magnesium-supported titanium catalyst system containing an electron donor (ED) as constituent components are used, the solid The titanium catalyst component (a) or its prepolymerized catalyst is usually used in an amount of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, in terms of titanium atom per liter of polymerization volume, The organometallic compound catalyst component (b) is usually 1 to 2000 mol, preferably 1 to 2000 mol of metal atoms in the catalyst component (b) with respect to 1 mol of titanium atoms in the solid titanium catalyst component (a) in the polymerization system. Is used in an amount of 2 to 1000 mol, and the electron donor (ED) is usually 0.001 mol to 10 mol, preferably 0, relative to 1 mol of the metal atom of the organometallic compound catalyst component (b). 01 mol to 5 used in an amount of mol.

  In the case of polymerization using the magnesium-supported titanium catalyst system, the hydrogen concentration is usually 0 to 0.01 mol, preferably 0 to 0.005 mol, more preferably 0 to 0.005 mol per mol of the monomer. The amount is 001 mol.

  In the case of polymerization using the magnesium-supported titanium catalyst system, the polymerization temperature is usually 70 ° C. or higher, preferably 80 to 150 ° C., more preferably 85 to 140 ° C., particularly preferably 90 to 130 ° C. The polymerization pressure is usually set to normal pressure to 10 MPa, preferably normal pressure to 5 MPa.

  For example, when a metallocene catalyst containing a metallocene compound (c) and an organoaluminum oxy compound (d) as constituent components is used, the concentration of the metallocene compound (c) is usually 0.00005 per liter of polymerization volume. The organoaluminum oxy compound (d) is used in an amount of ˜0.1 mmol, preferably 0.0001 to 0.05 mmol, and the organoaluminum oxycompound (d) is used as a transition metal atom (M) in the metallocene compound (c). The molar ratio (Al / M) is usually 5 to 1000, preferably 10 to 400. Further, when the organoaluminum compound (e) is used, it is usually about 1 to 300 mol, preferably about 2 to 200 mol, per 1 mol of the transition metal atom in the metallocene compound (c). Used in quantity.

  The metallocene catalyst may be used as a solution in a solvent in which the catalyst is soluble, or may be supported on an inorganic compound, a resin composition, or the like and used as a supported catalyst.

  When the metallocene catalyst is used, the polymerization temperature is usually in the range of −20 to 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and the polymerization pressure exceeds 0 to 8 MPa. , Preferably in the range of more than 0 and 5 MPa.

  The polyolefin part can be produced by either liquid phase polymerization such as solution polymerization or suspension polymerization, or gas phase polymerization. The polyolefin part can be produced by any of batch, semi-continuous and continuous systems.

Further, the polymerization can be carried out in two or more stages. When carrying out by dividing into two or more steps, the reaction conditions may be the same or different. In the above polymerization, the above-mentioned olefin homopolymer may be produced, or a random copolymer or block copolymer may be produced from two or more kinds of olefins selected from the above-mentioned olefins.
PO-X can be produced by a known halogenation method using the olefin polymer described above. Known halogenation methods can be used without exception, but specifically, bromination methods using brominating agents such as bromine and N-bromosuccinimide, iodination methods using iodine, and chlorine. The chlorination method used is mentioned. These methods can be carried out in a solution state or a suspension state using an appropriate solvent, and can be directly halogenated without a solvent. As a suitable solvent, a saturated hydrocarbon solvent such as hexane or decane, a halogenated aromatic solvent such as chlorobenzene, or the like can be preferably used. Moreover, after producing a hydroxyl group-containing olefin polymer, PO-X can be produced by treating with a halogenated alkyl acid halide such as bromo-butyryl bromide. The treatment method can be carried out by employing a known organic synthesis method.

  The halogen atom in PO-X may be of any kind, but bromine is preferably used from the viewpoint of environmental load.

[PO'-M]
PO′-M in the present invention is an olefin polymer comprising a dissociative metal atom and having as a main structural unit a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms. is there.

  Examples of the olefin having 2 to 20 carbon atoms include olefins used for the PO-X described above and ionic olefin compounds.

  Examples of the ionic olefin compound include olefin sulfonates such as sodium tetradecenesulfonate and olefin carboxylates such as potassium undecylenate.

  The dissociative metal atom is not particularly limited as long as it is a metal atom constituting a carboxylate salt, but is preferably one or more metal species selected from Groups 1 to 3 of the periodic table, More preferably, lithium, sodium and potassium are suitably used.

  PO′-M is an olefin polymer comprising a dissociative metal atom and having as a main structural unit a repeating unit derived from at least one olefin selected from these olefins. The content of the dissociable metal atom is 0.0001 to 30 wt%, preferably 0.001 to 20 wt%, more preferably 0.005 to 15 wt%, still more preferably 0.01 to 10 wt%, and most preferably 0.00. It is 05-5 wt%. If the content of the dissociative metal atom is small, it is disadvantageous for the production of the olefin polymer, and if it is too much, the mechanical properties of the olefin polymer are deteriorated.

  PO′-M is an ethylene polymer, a propylene polymer, a copolymer of at least one olefin selected from ethylene and an olefin having 3 to 20 carbon atoms, from the viewpoint of strength such as mechanical properties, and A copolymer obtained from at least one olefin selected from propylene and olefins having 4 to 20 carbon atoms is preferred.

  If the molecular weight of the PO′-M is small, it is disadvantageous for the expression of desired physical properties. If the molecular weight is too large, the viscosity is high during production of the olefin polymer, which is not preferable. The molecular weight of the PO′-M is in the range of 0.05 to 15 dl / g, preferably in the range of 0.1 to 12 dl / g in the measurement of intrinsic viscosity ([η]) measured in decalin. More preferably, it is in the range of 0.15 to 10 dl / g.

  Next, a method for producing PO′-M according to the present invention will be described. PO'-M can be produced by polymerizing the olefin as described above for the production of PO-X to produce an olefin polymer, followed by a dissociative metal atom introduction treatment. PO'-M can also be produced as an olefin polymer having as a structural unit a repeating unit derived from at least one olefin selected from the above olefins containing an ionic olefin.

  For the dissociative metal atom introduction treatment, a known method can be used without exception, but specifically, an acid and / or an acid anhydride treatment of the olefin polymer produced as necessary is performed, and the acid and This is carried out by neutralizing an olefin polymer containing an acid anhydride with a dissociable metal atom-containing compound.

  Examples of the dissociative metal atom-containing compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide and other hydroxides, and hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. And carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, and magnesium carbonate.

  The treatment method using the dissociable metal atom-containing compound can be carried out in a solution state or a suspension state using an appropriate solvent, and the dissociative metal atom can be introduced without a solvent. Suitable solvents include water, ketones such as acetone and methyl ethyl ketone, saturated hydrocarbon solvents such as hexane and decane, aromatic solvents such as toluene and xylene, and the like.

  The treatment temperature is usually in the range of −20 to 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and the treatment pressure is more than 0 to 8 MPa, preferably more than 0 to 5 MPa. is there.

[Production of olefin polymers]
Next, the manufacturing method of the olefin polymer which concerns on this invention is demonstrated.

  The olefin polymer according to the present invention is a block-type olefin polymer in which a PO group and a PO ′ group are bonded to each other, and can be produced by treating the above PO-X and PO′-M.

  Examples of the production method include a solution method, a suspension method, a melt kneading method, and other known methods. Among the above methods, the solution method and the suspension method are preferable from the viewpoint of controlling the structure of the polymer to be produced.

  Although it can use without a restriction | limiting in particular as a solvent, Aromatic hydrocarbon solvents, such as aliphatic hydrocarbon solvents, such as hexane, heptane, a decane, toluene, xylene, etc. are used suitably. The above production is usually performed in a temperature range of 0 ° C to 400 ° C, preferably 20 ° C to 250 ° C, more preferably 50 ° C to 220 ° C.

  The treatment time of PO-X and PO′-M is usually 1 minute to 40 hours, preferably 5 minutes to 20 hours. In order to promote the reaction, a known catalyst may be used.

  The melt-kneading method is performed using a lab plast mill, a single-screw kneader, a multi-screw kneader having two or more screws, a kneading extruder, a stirrer, or the like. The kneading temperature is not particularly limited and may be room temperature, but is usually in the range of about 50 ° C to 400 ° C, preferably in the range of about 100 ° C to 350 ° C. The kneading time is usually in the range of about 0.1 second to 5 hours, preferably in the range of about 1 second to 1 hour. At the time of melt kneading, a known catalyst may be added to promote the reaction. Moreover, you may add organic solvents, such as toluene and xylene, for viscosity adjustment and reaction efficiency improvement at the time of melt-kneading.

  The molecular weight of the olefin polymer produced by the present invention is such that the value of [η] (dl / g) observed by polar viscosity measurement in decalin is in the range of 0.2 to 15.0 dl / g. If the molecular weight is small, it is disadvantageous for expression of desired physical properties, and if the molecular weight is too large, the viscosity becomes high during production of the olefin polymer, which is not preferable. The value of [η] (dl / g) is preferably in the range of 0.25 to 13 dl / g, more preferably in the range of 0.3 to 12 dl / g, still more preferably 0.5 to 10 dl / g. It is in the range of g.

  The gel fraction of the olefin polymer produced by the present invention is 20% by weight or less. A large gel fraction is not preferable when the olefin polymer is used for molding. The gel fraction is preferably 15% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, and most preferably 2% by weight or less.

  In the olefin polymer produced according to the present invention, the melting point derived from at least one group selected from PO and PO ′ is preferably observed at 60 ° C. or higher by differential scanning calorimetry. Differential scanning calorimetry is performed by melting the polymer once, then lowering the temperature to 10 ° C./min to room temperature, and then raising the temperature at 10 ° C./min. In the olefin polymer produced according to the present invention, it is preferable that at least one group selected from PO and PO ′ has heat resistance in order to exhibit mechanical properties such as strength. The melting point observed by differential scanning calorimetry is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 120 ° C. or higher.

  The properties and structure of the produced olefin polymer can usually be analyzed by generally known analysis methods. For example, specific parts can be identified by nuclear magnetic resonance analysis, infrared spectroscopic analysis, ultraviolet / visible spectroscopic analysis, X-ray scattering, Raman spectroscopy, etc., and temperature elution fractionation, gel permeation chromatography, intrinsic viscosity, etc. The molecular weight can be measured by measurement, and the thermal characteristics can be confirmed by thermal analysis. Morphology can also be confirmed by morphological observation using a transmission electron microscope, a scanning electron microscope, an atomic force microscope, or the like.

    The olefin polymer produced according to the present invention can be suitably produced by the above-described methods, but when produced by these methods, depending on the production conditions, as a mixture containing unreacted PO-X and PO′-M. In some cases. A mixture of these polymers can be separated into each polymer by a column or the like, but in the present invention, the obtained olefin polymer may be used as it is depending on its use.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

〔Evaluation of the physical properties〕
In the examples, physical properties were measured under the following conditions.
(IR analysis)
Measuring device: JEOL FT-IR 410 spectrometer (FT mode)
Sample processing: A press sheet of the sample was prepared by heat pressing at 200 ° C., and used as an analysis sample.
(Measurement of bromine content by ion chromatography analysis)
Measuring device (ion chromatograph): DX-500 (Dionex)
(Column): IonPacAS14 (Dionex)
Data processing: The sample was decomposed by an oxygen flask combustion method, and the bromine content was quantified by an ion chromatography method.
(Intrinsic viscosity)
Measurements were made at 135 ° C. in decalin.
(Maleic anhydride group content)
It was calculated from the peak attributed to maleic anhydride by 1H-NMR analysis.
(Melting point measurement by DSC)
The melting point (Tm) of the polymer was determined by differential scanning calorimetry (DSC), after the polymer sample held at 200 ° C. for 5 minutes was cooled to 20 ° C. and held for 5 minutes, the temperature was raised at 10 ° C./min. It was calculated from the crystal melting peak at that time.
(Gel fraction)
It calculated from the residue after extracting with boiling xylene for 3 hours using a 325 mesh SUS filter.

(Production example of PO-X)
[Production Example 1]
150 parts by weight of an ethylene / butene copolymer (80% ethylene content, [η] = 1.61 dl / g) manufactured by Mitsui Chemicals Co., Ltd. was dissolved at 110 ° C. in 2000 parts by weight of chlorobenzene, and 3 parts by weight of N-butylsuccinimide was dissolved. In addition, the mixture was stirred at 110 ° C. for 2 hours. This was added to 3000 parts by weight of acetone, and the resulting polymer was washed three times with 3000 parts by weight of methanol, then washed with 3000 parts by weight of acetone, and dried at 120 ° C. for 10 hours under reduced pressure. 151 parts by weight of a polymer (PO-X (1)) was obtained.
From the ion chromatography analysis, it was confirmed that the bromine content in the obtained PO-X (1) was 0.43% by weight. The intrinsic viscosity ([η]) was 1.51 dl / g.

[Production Example 2]
The same operation as in Production Example 1 was carried out except that 150 parts by weight of Mitsui Chemicals ethylene / butene copolymer (ethylene content 80%, [η] = 2.13 dl / g) was used, and the bromine content was 0.34. 150 parts by weight of a polymer (PO-X (2)) having a weight percent of intrinsic viscosity ([η]) of 2.00 dl / g was obtained.

(Production example of PO'-M)
[Production Example 3]
Propylene polymer having an intrinsic viscosity ([η]) of 7.2 dl / g, 3.5 parts by weight of maleic anhydride and organic peroxide (2,5-dimethyl-2,5-di- (tert-butylperoxide) Oxy) hexyne-3) 0.1 part by weight was added and charged into a single screw extruder (thermo 20 mmφ) and melt kneaded at a resin temperature of 250 ° C. to obtain a maleic anhydride graft-modified propylene polymer (A).
The intrinsic viscosity ([η]) of the resulting modified propylene polymer was 0.45 dl / g. From the IR measurement, it was confirmed that the maleic anhydride group content in the modified propylene polymer was 3.0 parts by weight.

  50 parts by weight of the maleic anhydride graft-modified propylene polymer (A) was suspended in 100 mL of acetone, 150 mL of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 4 hours. The reaction product obtained by filtration was recovered, washed three times with 500 parts by weight of water, then once with 500 parts by weight of methanol, and dried under reduced pressure at 80 ° C. to give 50 parts by weight of PO′-M. (1) was obtained. [Η] of PO′-M (1) was 0.47 dl / g. From the sodium metal analysis, it was observed that 5000 ppm of sodium metal was present in the polymer. From the DSC measurement, a melting point was observed at 155.1 ° C.

[Production Example 4]
In the same manner as in Production Example 3, the intrinsic viscosity ([η]) is 0.89 dl / g, and the maleic anhydride graft-modified propylene polymer has a maleic anhydride group content of 0.5 parts by weight in the modified propylene polymer. (B) was obtained.

  50 parts by weight of the maleic anhydride graft-modified propylene polymer (B) was suspended in 100 mL of acetone, 150 mL of 1N aqueous potassium hydroxide solution was added, and the mixture was stirred at room temperature for 4 hours. The reaction product obtained by filtration was recovered, washed three times with 500 parts by weight of water, then once with 500 parts by weight of methanol, and dried under reduced pressure at 80 ° C. to give 50 parts by weight of PO′-M. (2) was obtained. [Η] of PO′-M (2) was 0.89 dl / g. From the potassium metal analysis, it was observed that 300 ppm of potassium metal was present in the polymer. From the DSC measurement, a melting point was observed at 165.8 ° C.

  (Examples and comparative examples of olefin polymers)

70 parts by weight of PO-X (1) obtained in Production Example 1 and 30 parts by weight of PO′-M (1) obtained in Production Example 3 are dissolved in 1500 parts by weight of xylene, and are heated at 130 ° C. for 4 hours. Stir processing was performed. This was added to 3000 parts by weight of methanol, and the resulting polymer was washed three times with 3000 parts by weight of methanol and then dried at 120 ° C. under reduced pressure for 10 hours to obtain 99 parts by weight of an olefin polymer.
The intrinsic viscosity ([η]) of the obtained polymer was 1.54 dl / g, and the gel fraction was 1.8% by weight. From the DSC measurement, a melting point was observed at 154.8 ° C.

70 parts by weight of PO-X (1) obtained in Production Example 2 and 30 parts by weight of PO′-M (1) obtained in Production Example 4 are dissolved in 1500 parts by weight of xylene, and are heated at 130 ° C. for 4 hours. Stir processing was performed. This was added to 3000 parts by weight of methanol, and the resulting polymer was washed 3 times with 3000 parts by weight of methanol and then dried at 120 ° C. under reduced pressure for 10 hours to obtain 98 parts by weight of an olefin polymer.
The intrinsic viscosity ([η]) of the obtained polymer was 2.05 dl / g, and the gel fraction was 1.4% by weight. From the DSC measurement, a melting point was observed at 165.5 ° C.

[Comparative Example 1]
Maleic anhydride-modified ethylene / butene copolymer ([η] = 2.05 dl / g, maleic anhydride group content: 0.5% by weight) prepared by referring to Examples disclosed in JP-A-2005-047986 Parts by weight, 30 parts by weight of a hydroxyl group-containing polypropylene prepared with reference to JP-A-2002-145944, and 0.1 parts by weight of p-toluenesulfonic acid are dissolved in 1500 parts by weight of xylene, and heated at 130 ° C. for 4 hours. Stir processing was performed. This was added to 3000 parts by weight of methanol, and the resulting polymer was washed three times with 3000 parts by weight of methanol and then dried at 120 ° C. under reduced pressure for 10 hours to obtain 99 parts by weight of an olefin polymer.
The intrinsic viscosity ([η]) of the obtained polymer was 1.99 dl / g, and the gel fraction was 22% by weight. From the DSC measurement, the melting point was observed at 163.5 ° C.

Claims (5)

An olefin polymer (PO-X) containing a halogen atom, a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms, and a dissociative metal atom Characterized in that it is produced by treating an olefin polymer (PO′-M) containing as a main constituent unit a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms. A method for producing an olefin polymer.   2. The olefin polymer according to claim 1, wherein at least one group selected from PO-X and PO′-M is a group whose melting point is observed at 60 ° C. or higher by differential scanning calorimetry. Production method   3. The method for producing an olefin polymer according to claim 1, wherein the dissociative metal atom in PO'-M is a metal atom constituting a carboxylate.   The method for producing an olefin polymer according to claim 3, wherein the metal atom constituting the carboxylate is one or more metal species selected from Groups 1 to 3 of the periodic table.   The value of the intrinsic viscosity [η] observed by polar viscosity measurement in decalin of the produced olefin polymer is in the range of 0.2 to 15.0 dl / g, and the gel fraction is 20% by weight. The method for producing an olefin polymer according to claim 1, wherein: