JP4216691B2 - Method for producing terminal hydroxylated olefin polymer - Google Patents

Description

  The present invention relates to a method for producing a terminal hydroxylated olefin polymer, and more specifically, a terminal hydroxylated olefin polymer obtained by treating an olefin polymer having an unsaturated bond with an organometallic compound and then treating with a halogenated epoxy compound. The present invention relates to a method for manufacturing coalescence.

  Polyolefins are excellent in 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., and used in various applications. Yes. However, since polyolefin is a so-called nonpolar resin that does not have a polar group in the molecule, it has poor affinity with various polar substances including metals, and adhesion with polar substances or blending with polar resins is difficult. It was. In addition, the surface of the molded body made of polyolefin is hydrophobic, and in applications that require anti-fogging properties and antistatic properties, it is necessary to add a low molecular weight surfactant, etc. In some cases, problems such as contamination occurred.

In order to solve these problems, introduction of polar groups into polyolefin has been performed. When a polar compound (polar olefin) is introduced, a method of reacting a polyolefin and a polar olefin in the presence of a radical initiator is generally performed. A polar group-containing olefin polymer obtained by such a method is used. In many cases, a radically polymerizable polar olefin homopolymer or unreacted polyolefin is contained, and the introduction position is also non-uniform. Furthermore, since the polymer chain is accompanied by a crosslinking reaction or a decomposition reaction, the physical properties of the polyolefin often change greatly. Regarding the method for introducing a polar group into a polyolefin without crosslinking and decomposing reaction as described above, Polymer Journal (Vol. 31, 332, 1999) describes an aluminum compound in a polyolefin having an unsaturated bond at the terminal. A method is described in which a hydroxyl group is introduced to the end of a polyolefin by oxidation with oxygen after addition. In JP 2002-155109 A, JP 2002-145944 A, etc., a hydroxyl group-containing olefin polymer is obtained by using an aluminum-modified monomer obtained by treating a hydroxyl group-containing olefin compound with an organoaluminum compound for the production of an olefin polymer. A method is disclosed. However, these methods have problems such as poor conversion efficiency to the hydroxyl group at the end of the polyolefin and low productivity per unit catalyst, and development of a method capable of efficiently producing a terminal hydroxylated olefin polymer is desired. Yes.
JP 2002-155109 A Japanese Patent Laid-Open No. 2002-145944 Polymer Journal, Vol. 31, 332, 1999)

  As a result of investigations based on such conventional techniques, the present inventors have processed an unsaturated olefin polymer with an organometallic compound and then treated with a halogenated epoxy compound to make the terminal hydroxylated olefin polymer efficient. We found a method that can be manufactured well.

The present invention provides a method for producing a terminal hydroxylated olefin polymer by treating an olefin polymer having an unsaturated bond with an organometallic compound and then treating with an halogenated epoxy compound.

A terminal hydroxylated olefin polymer can be produced efficiently.

  Hereinafter, the method for producing a terminal hydroxylated olefin polymer according to the present invention will be described in detail. The method for producing a terminal hydroxylated olefin polymer according to the present invention comprises an olefin weight having an unsaturated bond at the terminal position, obtained by polymerizing at least one olefin selected from olefins having 2 to 20 carbon atoms. The coalescence is treated with an organometallic compound and then treated with a halogenated epoxy compound.

  Hereinafter, the manufacturing method of the terminal hydroxylated olefin polymer of this invention is explained in full detail.

  The olefin polymer having an unsaturated bond at the terminal used in the present invention is unsaturated at the terminal having a repeating unit derived from at least one olefin selected from olefins having 2 to 20 carbon atoms as a main constituent unit. It is an olefin polymer having a group.

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

  Specific examples of the linear or branched α-olefin include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 A linear α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as hexadecene, 1-octadecene, 1-eicosene, etc .; for example, 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- Preferably branched α-olefins such as hexene and 3-ethyl-1-hexene are preferably 5 to 20, more preferably 5 to 10.

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

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Mono or polyalkyl styrenes such as ethyl styrene are mentioned.

  Examples of 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. , 1,3-octadiene and the like having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.

  Non-conjugated polyenes include, for example, 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, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -5 carbon atoms such as norbornadiene 20, preferably include the 5 to 10.

  The olefin polymer used in the present invention is a polymer comprising these olefins, but preferably at least one olefin selected from ethylene or a homopolymer of propylene, ethylene and an olefin having 3 to 20 carbon atoms. A copolymer obtained from at least one olefin selected from propylene and ethylene and / or an olefin having 4 to 20 carbon atoms.

  Next, the manufacturing method of the olefin polymer which has a terminal unsaturated bond used for this invention is demonstrated. First, an olefin polymerization catalyst used for production of an olefin polymer will be described. The olefin polymerization catalyst used for the production of the olefin polymer may be any conventionally known catalyst. Conventionally known catalysts include, for example, magnesium-supported titanium catalysts and metallocene catalysts. For example, the catalysts described in International Patent Publications WO01 / 53369 or WO01 / 27124 can be used. .

  The production of the olefin polymer can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. As the polymerization form, it is preferable to adopt a suspension polymerization reaction form. As the reaction solvent at this time, an inert hydrocarbon solvent can be used, or a liquid olefin can be used at the reaction temperature.

  Specific examples of the inert hydrocarbon medium used here include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or combinations thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

  When a magnesium-supported titanium catalyst system is used, in the polymerization system, the solid titanium catalyst component (a) or its prepolymerized catalyst is usually about 0.0001 to about 0.0001 to 1 in terms of titanium atoms per liter of polymerization volume. It is used in an amount of 50 mmol, preferably about 0.001 to 10 mmol. In the organometallic compound catalyst component (b), the metal atom in the catalyst component (b) is usually 1 to 2000 mol, preferably 1 mol to 1 mol of titanium atom in the solid titanium catalyst component (a) in the polymerization system. Is used in an amount of 2 to 1000 mol. The electron donor (ED) is generally used in an amount of 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, relative to 1 mol of the metal atom of the organometallic compound catalyst component (b).

  In the polymerization step, the hydrogen concentration is preferably 0 to 0.01 mol, preferably 0 to 0.005 mol, more preferably 0 to 0.001 mol with respect to 1 mol of the monomer.

  The polymerization temperature is usually in the range of 70 ° C. or higher, preferably 80 to 150 ° C., more preferably 85 to 140 ° C., particularly preferably 90 to 130 ° C., and the pressure is usually normal pressure to 10 MPa, preferably normal. The pressure is set to 5 MPa. The polymerization can be carried out by any of batch, semi-continuous and continuous methods. When the polymerization is carried out in two or more stages, the reaction conditions may be the same or different.

  When an olefin polymer is produced using a metallocene catalyst as a catalyst, the concentration of the metallocene compound (c) in the polymerization system is usually from 0.000005 to 0.1 mmol, preferably 0, per liter of polymerization volume. Used in an amount of .0001 to 0.05 mmol. The organoaluminum oxy compound (d) has a molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (c) and is 5-1000, preferably 10-400. Used in various amounts. When the organoaluminum compound (e) is used, the amount 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.

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

  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 Is in the range of more than 0 and 5 MPa.

  The production of the olefin polymer can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. In olefin polymerization, an olefin homopolymer may be produced, or a random copolymer may be produced from two or more olefins.

  An olefin polymer having an unsaturated bond at the terminal position is produced by chain transfer of the polymer generated during olefin polymerization. It is also produced by decomposition of an olefin polymer.

  The decomposition of the olefin polymer is preferably carried out by thermal decomposition. The decomposition temperature of the olefin polymer is 150 to 600 ° C., preferably 250 to 500 ° C., and the reaction time is set to 0.1 minutes to 10 hours. Is desirable. The atmosphere in the reaction system may be any atmosphere as long as it does not interfere with this reaction. For example, the decomposition can be performed in a nitrogen atmosphere. In addition, a solid acid catalyst may be used as necessary at the time of thermal decomposition. As the solid acid catalyst, crystalline silica / alumina, amorphous silica / alumina, aluminum oxide (alumina), silicon oxide (silica), silica magnesia , Zinc oxide, bauxite, natural soil (acid clay, activated clay, Kanuma pumice, Imaichi pumice, seven cherry blossoms, Akadama, volcanic ash, Moka pumice, Kashiwagi pumice), iron oxide, copper oxide, nickel oxide, oxidation A heavy metal oxide such as molybdenum can be given. When a solid acid catalyst is used, the amount used is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on the olefin polymer. The olefin polymer may be thermally decomposed while supplying water to the reaction system.

  The reaction apparatus used for the thermal decomposition of the olefin polymer may be any of a batch type, a continuous type and a semi-continuous type, and may be any type such as a tank type, a screw type and a pipe type. Specific examples of the cracking reaction apparatus include a plastmill, a tube-type cracking furnace equipped with a conveying screw and a steam supply means in a tube, and the olefin polymer is heated to 150 to 600 ° C, preferably 250 to 500 ° C. And a device having a mechanism for performing the above-described operation. Since this type of decomposition reaction apparatus has a continuous decomposition capability, it is suitable for a processing facility in which a large amount of plastic is constantly (continuously) accumulated.

  The organometallic compound used for the treatment with the olefin polymer having an unsaturated bond at the terminal position can be used without exception as long as it is an organometallic compound that reacts with the unsaturated bond site. Specifically, a compound containing a metal selected from Group 1 of the periodic table such as an organic lithium compound or an organic sodium compound, a compound containing a metal selected from Group 2 of the periodic table such as an organic magnesium compound, an organic zinc compound, an organic Compounds containing transition metals such as copper compounds and organic iron compounds, compounds containing metals selected from Group 13 of the periodic table such as organoboron compounds and organoaluminum compounds, selected from Group 14 of the periodic table such as organosilicon compounds A compound containing a metal selected from Group 15 of the periodic table, such as a compound containing a metal and an organic phosphorus compound, can be used.

  As the organometallic compound, those containing a metal selected from Group 13 of the periodic table are particularly preferable. Among them, an organoaluminum compound, an organoboron compound, a complex alkyl compound of a group 1 element and aluminum or boron can be preferably exemplified. . As an organoaluminum compound, the organoaluminum compound shown by a following formula can be illustrated, for example.

R ^a _n AlX _3-n
(In the formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3).
R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. Pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

  Specific examples of such organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; trialkenylaluminums such as triisoprenylaluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum Alkylaluminum sesquihalides such as kibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum dihydride Can be mentioned.

  Moreover, the compound shown by a following formula can also be used as an organoaluminum compound.

R ^a _n AlY _3-n
In the above formula, R ^a is the same as above, and Y is —OR ^b group, —OSiR ^c ₃ group, —OA1R ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group or —N (R ^g ). AlR ^h ₂ group, n is 1-2.

R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., and R ^e is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, etc. A group, a trimethylsilyl group, and the like, and R ^f and R ^g are a methyl group, an ethyl group, and the like.

Specific examples of such an organoaluminum compound include the following compounds.
_{^{(I) R a n Al (}} OR b) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide,
_{^{(Ii) R a n Al (}} OSiR c) a compound represented by _3-n, e.g., _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), (iso-Bu) 2 Al (OSiEt ₃ ) etc.
_{^{(Iii) R a n Al (}} OAlR d 2) a compound represented by _3-n, e.g., Et ₂ AlOAlEt _2, such as _{(iso-Bu) 2 AlOAl (} iso-Bu) 2,
_{^{(Iv) R a n Al (}} NR e 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt, Et 2 AlN (Me 3 Si) 2, (iso-Bu) ₂ AlN (Me ₃ Si) ₂ etc.
_{^{(V) R a n Al (}} SiR f 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} ,
(Vi) R ^a _n Al [N (R ^g) -AlR ^h _2] A compound represented by _{3-n, e.g., Et 2 AlN (Me) -AlEt} 2,
(iso-Bu) ₂ AlN (Et) Al (iso-Bu) ₂ etc.

In addition, similar compounds, for example, an organoaluminum compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom can be given. More _{specifically, (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 4 H 9) 2 AlOAl (C 4 H 9) 2, (C 2 H 5) 2 AlN (C 2 H ₅ ) Al (C ₂ H ₅ ) ₂ and aluminoxanes (organoaluminum oxy compounds) such as methylaluminoxane.

  Moreover, the organoaluminum compound of a following formula can also be used.

R ^a AlXY (R ^a , X and Y are the same as above)
Organic boron compounds include triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, texylborane, dicyclohexylborane, dicyamilborane, diisopinocanphenylborane, 9-borabicyclo [3.3.1] nonane, catechol Examples thereof include borane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, and borane-methyl sulfide complex.

  Moreover, you may use an ionic compound as an organoboron compound. Such compounds include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) Ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, N, N-dimethylanilinium tetra ( Phenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, bis [ And tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and the like.

  Examples of complex alkylated products of Group 1 elements and aluminum include compounds represented by the following general formula.

M ¹ AlR ^j ₄
(M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms.)
Specific examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the organoboron compound and the complex alkylated product of group 1 element and boron include the above-described organoaluminum compound and a compound having a structure in which aluminum in the complex alkylated product of group 1 element and aluminum is substituted with boron.

  The treatment of the olefin polymer having an unsaturated bond at the terminal and the organometallic compound can be carried out either in solution, in suspension or in the gas phase. The treatment form is preferably in solution or suspension, and an inert hydrocarbon solvent can be used as the solvent at this time. The treatment temperature may be carried out in a liquid olefin polymer without using a solvent.

  Specific examples of the inert hydrocarbon medium used here include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or combinations thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

  The amount of the organometallic compound used for the treatment with the olefin polymer having an unsaturated bond at the terminal is the ratio [M] / [U] of the molar amount [M] of the organometallic compound to the unsaturated group molar amount [U]. However, it is preferable that it exists in the range of 0.1-100, More preferably, it is the range of 1-50.

  The treatment temperature is usually 0 ° C. or higher, preferably 10 to 200 ° C., more preferably 20 to 100 ° C., and the treatment time is usually 1 minute to 24 hours, preferably 10 minutes to 10 hours, and more. Preferably, the processing pressure is usually set to normal pressure to 3 MPa, preferably normal pressure to 1 MPa for 15 minutes to 8 hours. The reaction can be carried out by any of batch, semi-continuous and continuous methods.

  Next, the manufacturing method of the terminal hydroxylated olefin polymer of this invention is explained in full detail.

  In the present invention, the method for producing a terminal hydroxylated olefin polymer may utilize an olefin polymer having a metal atom at a terminal, obtained by treating an olefin polymer having an unsaturated bond at a terminal with an organometallic compound. Importantly, a terminal hydroxylated olefin polymer is produced by treating the resulting olefin polymer having a metal atom at the terminal with a halogenated epoxy compound.

  As the halogenated epoxy compound used in the present invention, any epoxy compound having one reactive halogen atom in one compound can be used without any particular limitation. Specifically, epichlorohydrin, 2-chloromethyl-2 -Methyloxirane, 2-chloromethyl-2-ethyloxirane, 1-chloro-2,3-epoxybutane, 2-chloroethyloxirane, 2-chloroethyl-2-methyloxirane, 2-chloroethyl-2-ethyloxirane, 1 -Chloro-2,3-epoxypentane, 1-chloro-3,4-epoxypentane, 2-chloropropyloxirane, 2-chloropropyl-2-methyloxirane, 2-chloropropyl-2-ethyloxirane, 1-chloro -2,3-epoxyhexane, 1-chloro-4,5-epoxyhexa 2-chlorobutyloxirane, 2-chlorobutyl-2-methyloxirane, 2-chlorobutyl-2-ethyloxirane, 1-chloro-2,3-epoxyheptane, 1-chloro-5,6-epoxyheptane, 2-fluoro Methyloxirane, 2-fluoromethyl-2-methyloxirane, 2-fluoromethyl-2-ethyloxirane, 1-fluoro-2,3-epoxybutane, 2-fluoroethyloxirane, 2-fluoroethyl-2-methyloxirane, 2-fluoroethyl-2-ethyloxirane, 1-fluoro-2,3-epoxypentane, 1-fluoro-3,4-epoxypentane, 2-fluoropropyloxirane, 2-fluoropropyl-2-methyloxirane, 2- Fluoropropyl-2-ethyloxirane, 1-fluoro 2,3-epoxyhexane, 1-fluoro-4,5-epoxyhexane, 2-fluorobutyloxirane, 2-fluorobutyl-2-methyloxirane, 2-fluorobutyl-2-ethyloxirane, 1-fluoro-2, 3-epoxyheptane, 1-fluoro-5,6-epoxyheptane, 2-bromomethyloxirane, 2-bromomethyl-2-methyloxirane, 2-bromomethyl-2-ethyloxirane, 1-bromo-2,3-epoxybutane 2-bromoethyloxirane, 2-bromoethyl-2-methyloxirane, 2-bromoethyl-2-ethyloxirane, 1-bromo-2,3-epoxypentane, 1-bromo-3,4-epoxypentane, 2-bromo Propyloxirane, 2-bromopropyl-2-methyloxirane, 2-butyl Lomopropyl-2-ethyloxirane, 1-bromo-2,3-epoxyhexane, 1-bromo-4,5-epoxyhexane, 2-bromobutyloxirane, 2-bromobutyl-2-methyloxirane, 2-bromobutyl-2- Examples thereof include 2-halogenated alkyl epoxy compounds such as ethyl oxirane, 1-bromo-2,3-epoxyheptane, 1-bromo-5,6-epoxyheptane, among which epichlorohydrin is preferably used.

  The treatment of the olefin polymer having a metal atom at the terminal and the halogenated epoxy compound can be carried out either in solution, in suspension or in the gas phase. The treatment form is preferably in solution or suspension, and an inert hydrocarbon solvent can be used as the solvent at this time. The treatment temperature may be carried out in a liquid olefin polymer without using a solvent.

  Specific examples of the inert hydrocarbon medium used here include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or combinations thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

  The amount of the halogenated epoxy compound used in the treatment is the ratio of the molar amount [E] of the halogenated epoxy compound to the molar amount [M] of the organometallic compound used in the treatment with the olefin polymer having an unsaturated bond at the terminal [ E] / [M] is preferably in the range of 0.01 to 200, more preferably in the range of 0.1 to 100.

  The treatment temperature is usually 0 ° C. or higher, preferably 10 to 200 ° C., more preferably 20 to 100 ° C., and the treatment time is usually 1 minute to 24 hours, preferably 10 minutes to 10 hours, and more. Preferably, the processing pressure is usually set to normal pressure to 3 MPa, preferably normal pressure to 1 MPa for 15 minutes to 8 hours. The reaction can be carried out by any of batch, semi-continuous and continuous methods.

  The amount of hydroxyl group introduced into the terminal hydroxylated olefin polymer can be controlled by the amount of the organometallic compound and / or halogenated epoxy compound used and the processing conditions, and has an unsaturated bond at the terminal. 0.01 mol% to 100% of hydroxyl groups can be introduced into the olefin polymer with respect to the unsaturated groups in the olefin polymer.

  The terminal hydroxylated olefin polymer can be recovered by a known method, and may be recovered by any method such as decantation treatment, flash treatment, and degassing treatment. The obtained terminal hydroxylated olefin polymer has the same appearance as that of the usually obtained olefin polymer.

(Use)
The obtained terminal hydrogenated olefin polymer is excellent in paintability, adhesiveness, printability and the like, and is used for automobile exterior materials, bonding with resin films, surface printing resins, and the like. Moreover, it is used also as resin which provided high barrier property as film resin for metal vapor deposition, such as aluminum. Further, it is also suitably used as a compatibilizer for polymer alloys with other resins.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Reference Example 1]
(Production of olefin polymer having an unsaturated bond at the terminal position 1)
Polypropylene ([η] = 7.6) manufactured by Mitsui Chemicals was treated at 360 ° C. for 2 hours under a nitrogen atmosphere using a plastomill. The number average molecular weight (Mn) of the polymer obtained by the treatment was 26500 g / mol based on the molecular weight measurement by gel permeation chromatography (GPC). From the results of IR analysis, it was confirmed that 0.74 vinylidene groups were present per polymer chain.

[Reference Example 2]
(Production of olefin polymer having an unsaturated bond at the terminal position 2)
In a glass reactor with an internal volume of 500 ml equipped with a stirrer sufficiently purged with nitrogen, 400 ml of toluene was added and the temperature was raised to 50 ° C., and then propylene gas was blown into the decane at a rate of 100 NL / hr. Propylene saturated. Next, ethylene bus indenyl zirconium (0.005 mmol) and a toluene solution of methylalumoxane (5 mmol [Al]) were added to the reactor, and polymerization was carried out at 50 ° C. for 15 minutes while supplying propylene. The reaction solution was poured into a methanol (1.5 L) / acetone (1.5 L) mixed solution containing 30 ml of 1N hydrochloric acid. After stirring at room temperature for 30 minutes, the solid component was recovered by filtration. It was dried at 80 ° C. for 10 hours under reduced pressure to obtain 11.5 g of a white polymer.

  From the molecular weight measurement by gel permeation chromatography (GPC), the number average molecular weight (Mn) of the obtained polymer was 9900 g / mol. As a result of NMR analysis, an unsaturated bond was present at the polymer terminal, and 94% of the polymer one terminal was a vinylidene group.

(Production of terminal hydroxylated olefin polymer 1)
Into a glass reactor having an internal volume of 1000 ml with a stirrer sufficiently purged with nitrogen, 800 ml of decane and an olefin polymer having an unsaturated bond at the terminal position obtained in Reference Example 1 (25.0 g) were added at 140 ° C. Then, the olefin polymer was dissolved, and diisobutylaluminum hydride (9 mmol) was added, followed by treatment at 140 ° C. for 6 hours in a nitrogen atmosphere. The solution temperature was cooled to 100 ° C. and epichlorohydrin (4.5 ml) was added into the vessel and contacted at 100 ° C. for 1 hour. The reaction solution was poured into a methanol (1.5 L) / acetone (1.5 L) mixed solution containing 30 ml of 1N hydrochloric acid. After stirring at room temperature for 30 minutes, the solid component was recovered by filtration. It was dried at 80 ° C. for 10 hours under reduced pressure to obtain 24.8 g of a white polymer.

  From the results of nuclear magnetic resonance (NMR) analysis, signals derived from unsaturated bonds were not detected, and it was confirmed that a hydroxyl group was present at the polymer terminal. 67% of the polymer one end was a hydroxyl group.

(Production of terminal propylene hydroxide 2)
Into a glass reactor having an internal volume of 500 ml with a stirrer sufficiently purged with nitrogen, 400 ml of decane and an olefin polymer having an unsaturated bond at the terminal position obtained in Reference Example 2 (10.0 g) were added at 140 ° C. Then, the olefin polymer was dissolved, and diisobutylaluminum hydride (9 mmol) was added, followed by treatment at 140 ° C. for 6 hours in a nitrogen atmosphere. The solution temperature was cooled to 100 ° C. and epichlorohydrin (4.5 ml) was added into the vessel and contacted at 100 ° C. for 1 hour. The reaction solution was poured into a methanol (1.5 L) / acetone (1.5 L) mixed solution containing 30 ml of 1N hydrochloric acid. After stirring at room temperature for 30 minutes, the solid component was recovered by filtration. It was dried at 80 ° C. under reduced pressure for 10 hours to obtain 9.9 g of a white polymer.

  From the results of nuclear magnetic resonance (NMR) analysis, signals derived from unsaturated bonds were not detected, and it was confirmed that a hydroxyl group was present at the polymer terminal. 66% of the polymer terminals were hydroxyl groups.

[Comparative Example 1]
25.0 g of the terminal vinylidene group-containing polypropylene obtained in Reference Example 1 was placed in a 1000 ml glass reactor sufficiently purged with nitrogen, 800 ml of decane and 6 mmol of diisobutylaluminum hydride were added, and the mixture was heated and stirred at 140 ° C. for 6 hours. While keeping the decane solution at 140 ° C. and continuously supplying dry air at a flow rate of 200 liters / h for 6 hours, 10 ml of isobutyl alcohol was added at a solution temperature of 100 ° C. The reaction solution was added to a methanol (1.5 L) / acetone (1.5 L) mixed solution containing 50 ml of 1N hydrochloric acid to precipitate a polymer, and the polymer recovered by filtration was dried at 80 ° C. under reduced pressure for 10 hours. As a result, 24.8 g of a polymer was obtained. As a result of NMR analysis, a hydroxyl group was present at the polymer end, and 40% of the polymer one end was a hydroxyl group.

Claims (3)

An olefin polymer having an unsaturated bond at the terminal position obtained by polymerizing at least one olefin selected from olefins having 2 to 20 carbon atoms is treated with an organometallic compound, and then a halogenated epoxy. A method for producing a terminal hydroxylated olefin polymer, characterized by treating with a compound. The method for producing a terminal hydroxylated olefin polymer according to claim 1, wherein the organometallic compound is an organoaluminum compound and / or an organoboron compound. 3. The method for producing a terminal hydroxylated olefin polymer according to claim 1, wherein the halogenated epoxy compound is epichlorohydrin.