JP4524275B2 - A vinyl group- and polar group-containing propylene copolymer and a method for producing a polymer using the same. - Google Patents

Description

  The present invention relates to a vinyl group- and polar group-containing propylene copolymer and a method for producing a polymer using the same.

  Polypropylene is used in many fields as one of the most important plastic materials because of its excellent mechanical properties, moldability, chemical stability, and excellent cost performance. However, while being chemically stable, there are problems such as poor adhesion and dyeability due to nonpolarity and poor miscibility with other plastic materials. In order to solve this problem, many attempts have been made to produce a propylene-based copolymer into which a polar group has been introduced.

  First, in JP-A-55-98209, JP-A-3-177403, JP-A-6-172447, JP-A-8-53516, etc., polar group-containing monomers are used as Zieglar-Natta catalysts. It was proposed to polymerize directly in the presence. However, Zieglar-Natta catalyst has a very high affinity with Lewis bases such as oxygen and reacts with them to deactivate them. Therefore, the polar group is protected with a Lewis acid such as organoaluminum for polymerization. Used. However, this method also has problems such as requiring an extremely large amount of Lewis acid and extremely reducing the polymerization activity.

  Next, JP-A-55-165907, Kim, I. et al. Shin, Y .; S; Lee, J .; K. J. et al. Polym. Sci. Part A: Polym. Chem. 2000, 38, 1590 etc. have proposed a method for copolymerizing non-conjugated dienes. In this method, addition polymerization is performed on one olefin portion, and the other olefin portion remaining in the side chain is post-modified. This method has a problem in that both olefin portions of the diene undergo polymerization within the molecule or between the molecules, causing gelation due to cyclization or crosslinking, resulting in failure to obtain a desired propylene copolymer.

  Further, in JP-A-4-1210, JP-A-4-93305, JP-A-4-218514, etc., a copolymer in which alkenylborane and alkenylsilane are copolymerized, and then oxidatively decomposed to introduce hydroxyl groups. The method of obtaining is proposed. However, in the case of borane, the reagent for obtaining alkenylborane is expensive, and an aprotic polar solvent such as tetrahydrofuran is required as a reaction solvent. There is a problem that requires. Even in the case of silane, there are problems such as requiring severe reaction conditions in the oxidative decomposition reaction.

By the way, in recent years, an attempt has been made to directly polymerize a polar monomer without a protective group by using a late transition metal complex having a low oxygen affinity. For example, Brookhart et al. Have obtained a copolymer of an olefin and an alkyl acrylate with a palladium complex (Brookhart, MJ Chem. Soc. 1996, 118, 267-268). Have also developed nickel chelate complexes (Grubbs, R. Science 2000, 287, 460-462). However, these are copolymers with ethylene, and in the α-olefin system including propylene, direct copolymerization of polar monomers is extremely difficult from the viewpoint of copolymerization performance and stereoregularity.
Therefore, a method for easily and inexpensively producing a stereoregular propylene copolymer containing a polar group has been demanded.
On the other hand, a stereoregular propylene polymer having a double bond at the terminal has been demanded for its production technique as a macromer for introducing a long chain branch into polypropylene. In Macromolecules 28, 2, 437 (1995), a polypropylene having an octenyl group at its terminal is produced by TiCl ₃ , octenyl zinc and diethylaluminum chloride. However, octenyl zinc is complicated in its own production method, and a technique that can be easily produced industrially has been demanded.

  An object of the present invention is to provide a polar group-containing propylene-based copolymer capable of solving the above problems and technical problems.

  As a result of studying in view of such a situation, the present inventors copolymerized a trialkenyl aluminum compound with propylene to obtain a propylene-trialkenyl aluminum copolymer having an alkenyl group at the terminal. In addition, the role of a macromer during the polymerization was also shown, and the way of producing a propylene copolymer having a long-chain branched polypropylene was shown. Furthermore, it has been found that a propylene-based copolymer having a vinyl group at a terminal and containing a polar group can be easily produced by subjecting this to a post-reaction such as oxidative decomposition. Furthermore, it has been found that the propylene-based copolymer containing a polar group produced by this method can obtain a copolymer having a novel comonomer structure by adjusting the post reaction. The present invention has been completed based on these findings.

（式中、ｎは１〜２０の整数を示す。）
一般式（Ｄ）：

（式中、ｎは１〜２０の整数、Ｘは−ＯＨ、−ＣＯＯＨ、−ＳＯＯＨ又は−ＳＯＯＯＨ基を示す。）
一般式（Ｅ）：
ＣＨ_２＝ＣＨ−（ＣＨ_２）_ｎ−
（式中、ｎは１〜２０の整数）
本発明におけるビニル基および極性基含有プロピレン系共重合体を単に極性基含有プロピレン系共重合体ともいう。 That is, according to the first invention of the present invention, the propylene unit is 50 to 99.9 mol%, the unit represented by the following general formula (C) is 0 to 49.9 mol%, and the following general formula (D) 0.1 to 50 mol% of the unit represented by the formula, the terminal has a structure represented by the following general formula (E), and the weight average molecular weight is 1,000 to 1,000,000. A vinyl group and polar group-containing propylene-based copolymer is provided.
Formula (C):

(In the formula, n represents an integer of 1 to 20.)
Formula (D):

(In the formula, n represents an integer of 1 to 20, and X represents an —OH, —COOH, —SOOH or —SOOOH group.)
Formula (E):
_{CH 2 = CH- (CH 2)} n -
(Where n is an integer from 1 to 20)
The vinyl group and polar group-containing propylene copolymer in the present invention is also simply referred to as a polar group-containing propylene copolymer.

Further, according to the second aspect of the present invention, the copolymer according to the first invention and the macromer, this manufacturing method of a polymer polymerized or copolymerized is provided.

  The present invention provides a polar group-containing propylene-based copolymer obtained by further converting a propylene-alkenylaluminum copolymer having a terminal vinyl group having a novel comonomer structure, which includes expensive reagents and harsh reactions. It can manufacture without using conditions. As the polar group, a hydroxyl group, a carboxyl group, a sulfinyl group, or the like is applicable.

  The polar group-containing propylene-based copolymer of the present invention can be produced by copolymerizing a trialkenyl aluminum compound and propylene in the presence of a catalyst and reacting the obtained copolymer with a decomposing agent.

1. Trialkenyl aluminum compound The trialkenyl aluminum compound is preferably represented by the following general formula (A).
Formula (A):
_{[CH 2 = CH- (CH 2} ) n] 3 -Al

In general formula (A), n is an integer of 1-20, Preferably it is an integer of 2-12, More preferably, it is 3, 4, 6, 8, or 10. The three alkenyl groups may be the same or different as long as n satisfies 2 to 20.
Specific compounds of the general formula (A) include, for example, tripropenyl aluminum, tributenyl aluminum, tripentenyl aluminum, pentenyl dibutenyl aluminum, trihexenyl aluminum, hexenyl dipropenyl aluminum, trioctenyl aluminum, dioctenyl propenyl aluminum And tridecenyl aluminum, decenyl dibutenyl aluminum, dodecenyl dibutenyl aluminum, undecenyl dioctenyl aluminum, and the like. Among these, tripropenyl aluminum, tributenyl aluminum, trihexenyl aluminum, trioctenyl aluminum, dioctenyl butenyl aluminum, octenyl dihexenyl aluminum, and tridecenyl aluminum are preferable.

  Methods for producing the above trialkenyl aluminum compounds are known, and many known methods such as hydroalumination reactions of non-conjugated dienes, cross-coupling reactions of alkenyl halides with organoaluminum compounds, organic compounds such as alkenyl lithium and alkenyl magnesium. There is a transmetalation reaction between a metal compound and an organoaluminum compound. Among these, a preferred method is a hydroalumination reaction of a nonconjugated diene, and a trialkenylaluminum compound can be produced by reacting a nonconjugated diene and a trialkylaluminum under high temperature conditions.

2. Copolymerization of Propylene and Trialkenyl Aluminum Compound (1) Catalyst The catalyst used for obtaining a copolymer of propylene and a trialkenyl aluminum compound is not particularly limited, but is usually a coordination anion type catalyst used for polymerization of propylene. Among them, in order to introduce a vinyl group at the terminal, it is possible to use a catalyst for coordination polymerization of a type that involves an alkenylation reaction with organoaluminum in the chain transfer or activation mechanism to organoaluminum.
For example, a solid catalyst component essentially containing magnesium, titanium, or halogen, or a metallocene catalyst can be used. Among these, it is preferable to use a metallocene catalyst from the viewpoint of copolymerization of a trialkenyl aluminum compound and production of a so-called long chain branched propylene copolymer in which the obtained vinyl group-containing copolymer is further polymerized as a macromer. From the viewpoint of obtaining a copolymer having a vinyl group at one end, usually at one end, with good yield, it is important that chain transfer to organoaluminum occurs preferentially, and from that viewpoint, magnesium, titanium It is preferable to polymerize at a relatively high temperature under hydrogen-free conditions using a catalyst comprising a solid catalyst component containing halogen as an essential component.

Here, the metallocene catalyst is composed of the following component (a) and component (b) and, if necessary, component (c).
Component (a): Group 4-6 transition metal compound having at least one conjugated five-membered ring ligand Component (b): An activator for activating component (a), -1) to (b-4).
(B-1) Aluminum oxy compound (b-2) Ionic compound capable of reacting with component (a) to convert component (a) into a cation (b-3) Lewis acid (b-4) Ion exchange layered Silicate Component (c): Organoaluminum Hereinafter, the component (a), the component (b), and the component (c) will be described.

Component (a): Group 4-6 transition metal compound having at least one conjugated five-membered ring ligand Component (a) is a metallocene transition metal compound represented by the following general formula (1). .
^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b) MeXY ... formula (1)
[In the formula (1), Q represents a bonding group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, X and Y represent a hydrogen atom, a halogen atom, An atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, R ¹ and R ² are hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, A silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group is shown. ]

In the metallocene transition metal compound represented by the general formula (1), Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, such as a divalent hydrocarbon group or a silylene group. Examples thereof include an oligosilylene group, a silylene or oligosilylene group having a hydrocarbon group as a substituent, or a germylene group having a hydrocarbon group as a substituent. Among these, a divalent hydrocarbon group and a silylene group having a hydrocarbon group as a substituent are preferable.
X and Y may be independent of each other, that is, the same or different, and indicate the following. Hydrogen, halogen, hydrocarbon group, or hydrocarbon group containing oxygen, nitrogen, or silicon, and preferable examples include hydrogen, chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide group, etc. can do.

R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Represents. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition, as halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group, methoxy group, ethoxy group, phenoxy group Typical examples include trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group, dimethoxyboron group, and the like. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable. By the way, adjacent R ¹ and R ² may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.

  Me is a metal selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

  Among the above components (a), preferred for the production of the propylene polymer of the present invention are a substituted cyclopentadienyl group, substituted indenyl group crosslinked with a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. Group, a substituted fluorenyl group, a transition metal compound comprising a ligand having a substituted azulene group, particularly preferably a silylene group having a hydrocarbon substituent or a 2,4-position substituted indenyl group crosslinked with a germylene group, It is a transition metal compound composed of a ligand having a 2,4-substituted azulene group.

  Component (b): (b-1) an aluminum oxy compound, (b-2) an ionic compound capable of reacting with component (a) to convert component (a) into a cation (excluding Lewis acid), It is one or more components selected from (b-3) Lewis acid and (b-4) ion-exchangeable layered silicate. For specific methods for producing the compounds for (b-1), (b-2), (b-3), and (b-4), JP-A-6-239914, JP-A-8-208733, Examples include compounds and production methods exemplified in each publication of Japanese Utility Model Laid-Open No. 10-226712.

  As a specific compound, for example, as component (b-1), methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, two types of trialkyls Examples thereof include methyl ethyl alumoxane, methyl butyl alumoxane, and methyl isobutyl alumoxane obtained from aluminum and water. A reaction product of trialkylaluminum and alkylboronic acid can also be used. Examples of the alkyl boronic acid include alkyl boronic acids such as methyl boronic acid, ethyl boronic acid, butyl boronic acid, and isobutyl boronic acid.

  Examples of the component (b-2) include triphenylcarbonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Examples of (b-3) include triphenylcarbonium tetrakis (pentafluorophenyl) borate. Examples thereof include phenylborane, tris (3,5-difluorophenyl) borane, and tris (pentafluorophenyl) borane.

  Examples of the component (b-4) include smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, vermiculite group, and mica group. These may form a mixed layer, and are preferably subjected to chemical treatment such as acid treatment, alkali treatment, salt treatment, and organic matter treatment.

Component (c): Organoaluminum compound Component (c) is an organoaluminum compound and is used as necessary.
An example of the organoaluminum compound is a compound represented by the following general formula (2).
AlR _a P _3-a Formula (2)
(In the formula (2), R is a hydrocarbon group having 1 to 20 carbon atoms, P is hydrogen, halogen, alkoxy group, and a is a number of 0 <a ≦ 3.)
Specific examples of the organoaluminum compound represented by the general formula (2) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, or halogen such as diethylaluminum monochloride and diethylaluminum monomethoxide. Alternatively, alkoxy-containing alkyl aluminum can be mentioned. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

Furthermore, the metallocene catalyst that is suitably used is preferably one that expresses the desired isotactic specificity and syndiotactic specificity.
Moreover, since a trialkenyl aluminum compound is used as a comonomer, a polymerization method in which no other organic aluminum is used except for the (b-1) aluminum oxy compound used as an activator is also possible. That is, the trialkenyl aluminum compound acts both as a conomomer and as an organoaluminum component (c).

On the other hand, solid catalyst components that contain magnesium, titanium, and halogen as essential components are known, and known catalyst components can be used.
Examples of the magnesium compound that is a magnesium source of the solid catalyst component include magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like. Can be mentioned. Magnesium dihalides Among them, dialkoxy ^Mg _{(OR 3),} such as magnesium _{2-p X p} (where, ^{R 3} is a hydrocarbon group, preferably of about 10 carbon atoms, X is a halogen And p is 0 ≦ p ≦ 2).

As the titanium compound serving as a titanium source, the general formula _{^{Ti (OR 4) 4-q}} X q ( where, ^{R 4} is a hydrocarbon group, preferably of 1 to 10 carbon atoms, X is a halogen And q is 0 ≦ q ≦ 4)). Specific examples include, for example, TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-i- _{C 3 H 7) Cl 3,} Ti (O-n-C 4 H 9) Cl 3, Ti (O-n-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Br 3, Ti (OC _{2 H 5) (O-n} -C 4 H 9) 2 Cl, Ti (O-n-C 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-i-C 4 H _{9) 2 Cl 2, Ti (} OC 5 H 11) Cl 3, Ti (OC 6 H 13) Cl 3, Ti (OC 2 H 5) 4, Ti (O-n-C 3 H 7) 4, Ti ( _{O-n-C 4 H 9} ) 4, Ti (O-i-C 4 H 9) 4, Ti (O-n-C 6 H 13) 4, T _{(O-n-C 8 H} 17) 4, Ti (OCH 2 CH (C 2 H 5) C 4 H 9) 4 , and the like.
Further, a molecular compound obtained by reacting an electron donor described later with TiX ₄ (where X is a halogen) can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH ₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O and the like can be mentioned.
In addition, TiCl ₃ (including TiCl ₄ reduced with hydrogen, aluminum metal reduced or organometallic compound reduced), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , It is also possible to use titanium compounds such as dicyclopentadienyl titanium dichloride and cyclopentadienyl titanium trichloride. Among these titanium compounds, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are preferable.

The halogen is usually supplied from the aforementioned magnesium and / or titanium halogen compounds, but other halogen sources, for example, aluminum halides such as AlCl ₃ , boron halides such as BCl ₃ , SiCl It can also be supplied from known halogenating agents such as silicon halides such as ₄ ; phosphorus halides such as PCl ₃ and PCl ₅ ; tungsten halides such as WCl ₆ ; and molybdenum halides such as MoCl ₅ . The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

  In order to improve stereoregularity, it is possible to use an electron donor together. Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Examples thereof include oxygen electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, sulfur-containing electron donors such as sulfonate esters, and the like.

  More specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, ) Phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 ketones such as benzophenone, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolu Aldehydes having 2 to 15 carbon atoms such as aldehyde and naphthaldehyde, (e) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, Ethyl herbate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolol Organic acid monoesters such as kuton, α-valerolactone, coumarin, phthalide, or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl tartrate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate Carbon number of organic acid polyvalent ester such as ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane-1,2-dicarboxylic acid-n-hexyl, diethyl 1,1-cyclobutanedicarboxylate 20 organic acid esters, (f) inorganic acid esters such as ethyl silicate, butyl silicate and the like, (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, 2 carbon atoms such as phthaloyl chloride 15 acid halides, (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1 , 3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2 , 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane, 2,2′-dimethoxybiphenyl, 2 , 2′-dimethoxybinaphthyl and the like, ethers having 2 to 30 carbon atoms, (li) acetic acid amide, benzoic acid amide, toluic acid amide, urea, and other acid amides, (nu) methylamine, ethylamine, diethylamine, tri Amines such as butylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, nitriles such as (l) acetonitrile, benzonitrile, tolunitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-Butoxymethyl) -ethyl benzoate, 3-ethoxy Alkoxy ester compounds such as ethyl 2-phenylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, ethyl 3-ethoxy-2-t-butylpropionate; -Ketoester compounds such as ethyl benzoylbenzoate, ethyl 2- (4'-methylbenzoyl) benzoate, ethyl 2-benzoyl-4,5-dimethylbenzoate, (f) methyl benzenesulfonate, ethyl benzenesulfonate, Examples include sulfonic acid esters such as ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate. Two or more kinds of these electron donors can be used. Among these, organic acid ester compounds, acid halide compounds and diether compounds are preferred, and phthalic acid diester compounds, phthalic dihalide compounds, substituted succinic acid esters and 1,3-diether compounds are particularly preferred.

In the polymerization, organoaluminum and an electron donating compound added during the polymerization can be used as necessary.
As organoaluminum, R ⁵ _3-r AlX _r (where R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, X is a halogen, hydride, or alkoxy group, and r is 0 ≦ r <3.)
Specifically, (i) trialkylaluminum such as (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, (b) diethylaluminum monochrome Aldehyde, diisobutylaluminum monochloride, alkylaluminum halide such as ethylaluminum sesquichloride, ethylaluminum dichloride, (c) alkylaluminum hydride such as diethylaluminum hydride, diisobutylaluminum hydride, (d) diethylaluminum ethoxide, diethylaluminum phenoxide Examples include alkyl aluminum alkoxide.
A plurality of these can be used in combination. For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum monochloride And the combination use with.
Further, a trialkenyl aluminum compound used as a comonomer of this patent can be used as an organoaluminum compound for polymerization without using such an organic aluminum. However, in order to effectively produce the terminal vinyl group-containing propylene copolymer of the purpose of this patent, it is preferable not to use an organic aluminum other than the trialkenyl aluminum compound.

Moreover, as an electron donating compound used in order to improve stereoregularity, an alkoxy silicon compound and a diether compound are common. As the alkoxy silicon compound, a general formula R ⁶ _m Si (OR ⁷ ) _4-m (where R ⁶ and R ⁷ are hydrocarbon groups having 1 or more carbon atoms, preferably hydrocarbon groups having 1 to 10 carbon atoms). And m is 0 ≦ m <4.) (B) (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH _{3) 3 CSi (n-C} 3 H 7) (OCH 3) 2, (CH 3) 3 CSi (n-C 6 H 13) (OCH 3) 2, (C 2 H 5) 3 CSi (CH 3) _{(OCH 3) 2, (CH} 3) (C 2 H 5) CHSi (CH 3) (OC _{3) 2, ((CH 3} ) 2 CHCH 2) 2 Si (OCH 3) 2, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OCH 3) 2, (C 2 H 5) ( CH ₃ ) ₂ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (OCH ₃ ) ₃ , (CH ₃ ) ₃ CSi (OC ₂ H ₅ ) ₃ , (CH ₃ ) (C ₂ H ₅ ) CHSi (OCH ₃ ) ₃ , (CH ₃ ) ₂ CH (CH ₃ ) ₂ CSi (CH ₃ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₃ C) ₂ Si (OCH ₃ ) ₂ , (C _{2 H 5) (CH 3)} 2 CSi (OCH 3) 3, (C 2 H 5) (CH 3) 2 CSi (OC 2 H 5) 3, (CH 3) 3 CSi (OC (CH 3) 3) (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CH) ₂ Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CH) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₅ H ₉ ) ₂ Si (OCH ₃ ) ₂ , (C ₅ H ₉ ) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₅ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ , (C ₅ H ₉ ) ((CH ₃ ) ₂ CHCH ₂ ) Si (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ((CH ₃ ) ₂ CHCH ₂ ) Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH _{2) ((C 2 H 5} ) (CH 3) CH) Si (OCH 3) 2, ((CH 3) 2 CHCH 2) ((CH 3) 2 CH) Si (OC 5 H 11) 2, HC ( _{CH 3) 2 C (CH 3} ) 2 Si (CH 3) (OCH 3) 2, HC ( _{H 3) 2 C (CH 3} ) 2 Si (CH 3) (OC 2 H 5) 2, HC (CH 3) 2 C (CH 3) 2 Si (OCH 3) 3, (CH 3) 3 CSi (OCH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) _{2 and} other alkylalkoxysilicon compounds, (ro) bis (pyrrolidino) dimethoxysilane, bis ( 2-methyl-pyrrolidino) dimethoxysilane, bis (3-methyl-pyrrolidino) dimethoxysilane, bis (piperidino) dimethoxysilane, bis (2-methyl-piperidino) dimethoxysilane, bis (3-methyl-piperidino) dimethoxysilane, bis (4-Methyl-piperidino) dimethoxysilane, bis (2,2,6,6-tetramethyl-piperidino) dimethoxysilane Bis (2,6-dimethyl - piperidino) dimethoxysilane, bis (deca hydroxy Norino) dimethoxysilane, bis silicon compounds containing (perhydroisoquinolino) amino group such as silane, (iii) (n-C ₃ H _{7 O) 2 Si (OCH 3} ) 2, (i-C 3 H 7 O) 2 Si (OCH 3) 2, (t-C 4 H 9 O) 2 Si (OCH 3) 2, (sec-C 4 _{H 9 O) 2 Si (OCH} 3) 2, (n-C 4 H 9 O) 2 Si (OCH 3) 2, (i-C 4 H 9 O) 2 Si (OCH 3) 2, (n-C _{3 H 7 O) (n-} C 4 H 9 O) Si (OCH 3) 2, (i-C 3 H 7 O) (n-C 4 H 9 O) Si (OCH 3) 2, (n-C _{3 H 7 O) (t-} C 4 H 9 O) Si (OCH 3) 2, (t-C _{4 H 9 O) (n-} C 4 H 9 O) Si (OCH 3) 2, (sec-C 4 H 9 O) (i-C 4 H 9 O) Si ( tetra alkoxycarbonyl such as _{OCH 3) 2} A silicon compound is mentioned.
Among these, (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi _{(CH 3) (OC 2 H} 5) 2, (CH 3) 3 CSi (C 2 H 5) (OCH 3) 2, (CH 3) 3 CSi (n-C 3 H 7) (OCH 3) 2, _{(CH 3) 3 CSi (n} -C 6 H 13) (OCH 3) 2, (C 5 H 9) 2 Si (OCH 3) 2, (C 5 H 9) 2 Si (OC 2 H 5) 2, _{(C 6 H 11) Si (} CH 3) (OCH 3) 2, include ₂ or the like _{(C 6 H 11) 2 Si} (OCH 3).

  Examples of diether compounds include 1,3-diether, 1,2-dimethoxycyclohexane, 2,2'-dimethylbisnaphthyl ether, and the like. Specifically, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2- Isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl-2 -Isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane, 2,2′- Methoxy-biphenyl, 2,2'-dimethoxy-binaphthyl and the like.

(2) Polymerization method During copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change the mixing ratio over time. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.
The purpose of the copolymerization is to introduce a unit represented by the general formula (B) described later, that is, a trialkenyl aluminum compound unit at a maximum of 50 mol%. Here, the raw material charging ratio for obtaining a copolymer containing a large amount of such a trialkenyl aluminum compound unit will be described. This charging ratio varies depending on the copolymerizability of the catalyst used in the polymerization reaction and the chain length (carbon number) of the trialkenyl aluminum compound. In general, as the chain length increases, the copolymerizability to propylene tends to decrease. The molar ratio of propylene to the trialkenyl aluminum compound for introducing a maximum of 50 mol% of the trialkenyl aluminum compound unit is 1: 0.001 to 1:10, preferably 1: 0.001 to 1: 5. More preferably, it is 1: 0.001-1: 2.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a slurry method using propylene as a solvent without substantially using an inert solvent, a slurry method using a trialkenyl aluminum compound as a solvent, a solution polymerization method, or a substantially liquid. A vapor phase method without using a solvent can be employed. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used alone or as a mixture as a polymerization solvent. The polymerization temperature is 0 to 200 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 50 kg / cm ² G.

3. Propylene-trialkenylaluminum copolymer The propylene-trialkenylaluminum copolymer obtained by the above copolymerization is a structure derived from a trialkenylaluminum compound represented by the following general formula (B) in a structural unit derived from propylene. The unit is randomly distributed and has a terminal vinyl group-containing structure represented by the following general formula (E) at the terminal.

General formula (B)

（式中、ｎは１〜２０の整数を示す。）

(In the formula, n represents an integer of 1 to 20.)

Formula (E):
_{CH 2 = CH- (CH 2)} n -
(Where n is an integer from 1 to 20)

  In the structure of the propylene-trialkenylaluminum copolymer, the propylene unit is 50 to 99.9 mol%, preferably 60 to 99.9 mol%, more preferably 65 to 99.9 mol%. ) Is 0.1 to 50 mol%, preferably 0.1 to 40 mol%, more preferably 0.1 to 35 mol%. When the structural unit derived from trialkenylaluminum is less than 0.1 mol%, it is difficult to obtain the effects (improvement of dyeability, adhesion, etc.) when the dialkenylaluminum group is converted to a polar group. Moreover, when it exceeds 50 mol%, there exists a problem that the original performance of a polypropylene cannot be taken out. Further, the terminal vinyl group-containing structure is usually only on one side.

  By the way, depending on the use of the final polar group-containing propylene-based copolymer, the preferred range of the amount of structural units derived from trialkenyl aluminum may differ. For applications that require rigidity and heat resistance, such as automotive materials and industrial parts, the content of the unit represented by the general formula (B) is preferably not too large, more preferably 0.1 to 5 mol%. Preferably, it is 0.1-3 mol%. This is because if it exceeds 5 mol%, the crystallinity is lowered and the rigidity and heat resistance are adversely affected. However, when used as a soft material or a resin additive, it is preferable that the content of the unit represented by the general formula (B) is large, and the content of the unit represented by the general formula (B) is It is 20-50 mol%, Preferably it is 20-40 mol%, More preferably, it is 20-35 mol%.

The propylene-trialkenyl aluminum copolymer preferably has stereoregularity such as isotactic and syndiotactic. Particularly preferably, the peak intensity observed in the vicinity of 20.9 ppm of the peak attributed to the methyl group of the propylene unit in the absorption spectrum of ¹³ C-NMR is 0. 0 of the peak intensity of all methyl groups attributed to the propylene unit. Among the peaks attributed to the methyl group of the propylene unit in the absorption spectrum of ¹³ C-NMR having an isotactic structure showing 5 or more, the intensity of the peak observed in the vicinity of 20.2 ppm belongs to the propylene unit. It has a syndiotactic structure showing 0.5 or more of the peak intensity of the methyl group. When this ratio is less than 0.5, stickiness of the product occurs and becomes a problem.

The content of the trialkenyl aluminum compound-derived unit and the determination of stereoregularity are determined using ¹³ C-NMR. The measurement conditions are as follows.
NMR apparatus: JEOL-La-500 manufactured by JEOL Ltd., measurement temperature: 120 ° C., solvent: 1,1,2,2-tetrachloroethane-d ₂ , pulse angle: 45 °, number of scans: 1000, pulse interval 7 seconds. Regarding the determination of the chemical shift of each absorption spectrum, 1,1,2,2-tetrachloroethane is determined as an internal standard. The chemical shift of 1,1,2,2-tetrachloroethane is 74.47 ppm.

  Propylene-trialkenylaluminum copolymer is very unstable and easily decomposes with moisture or oxygen in the air. Therefore, the polymerization product is reacted with methanol under a nitrogen atmosphere to convert the carbon-aluminum bond to a carbon-hydrogen bond, so that a methyl group derived from propylene (around 16 to 23 ppm) and a methyl derived from alkenyldialkylaluminum. The copolymerization amount of the trialkenyl aluminum unit is identified from the area ratio of the absorption spectrum of the group (around 12 to 15 ppm).

The molecular weight of the propylene-trialkenylaluminum copolymer is 1,000 to 1,000,000, preferably 3,000 to 800,000, and more preferably 5,000 to 600,000 in terms of weight average molecular weight. The ratio of the weight average molecular weight to the number average molecular weight is not particularly limited, and a wide range can be produced depending on the polymerization conditions, but is generally about 2 to 8.
In addition, a weight average molecular weight and a number average molecular weight are measured as follows. That is, measurement is performed by a gel permeation chromatography method using Waters 150C. The conditions are: measurement temperature: 140 ° C., solvent: orthodichlorobenzene, column: Shodex 80M / S, 2 and calculation of molecular weight is determined from standard polystyrene.

The melting point of the propylene-trialkenylaluminum copolymer is not particularly limited, but is generally 70 to 165 ° C., and the heat of fusion is 10 to 120 (J / g).
The melting point and the heat of fusion were measured using a differential scanning calorimeter (DSC-220, manufactured by Seiko Instruments Inc.), and 5 mg of a sample piece made into a sheet was packed in an aluminum pan, and the temperature was raised from room temperature to 220 ° C. once. After holding for 10 minutes, the temperature was lowered to −40 ° C. at 10 ° C./min for crystallization, and then the melting maximum peak temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min was taken as the melting point. Is the heat of fusion (J / g).

4). Polar group-containing propylene copolymer The polar group-containing propylene copolymer of the present invention will be specifically described. The polar group-containing propylene copolymer can be produced by reacting the propylene-trialkenylaluminum copolymer obtained above with various decomposing agents. That is, it can be obtained by converting a dialkenylaluminum group (carbon-aluminum bond) in the copolymer into a carbon-polar group bond.
The reaction with the decomposing agent can be carried out according to a known method relating to the reaction between the low molecular weight organoaluminum compound and the inorganic compound. Examples of the decomposing agent include sulfur oxides such as oxygen, peroxide, carbon dioxide, sulfur dioxide, or sulfur trioxide.

  Specifically, dialkenylaluminum can be converted to a hydroxyl group by contacting with oxygen or peroxide and then hydrolyzing, and a hydroxyl group-containing propylene-based copolymer can be obtained. For conversion to a hydroxyl group, see R.A. Rienacker and G. Ohloff, Angew. chem. 1961, 73, 240, p. Tesseire and M.M. Plattier, Recherches, 1963, 13, 34 [Chem. abstr. , 1964, 60, 15915] can be referred to if necessary. Moreover, it is possible to convert a dialkenyl aluminum group into a carboxyl group by contacting with carbon dioxide and then hydrolyzing, and a carboxyl group-containing propylene copolymer is obtained. For conversion to a carboxyl group, see K. et al. Zieglar, F.A. Krupp, K.M. Weyer and W.W. Larbig, Liebugs Ann. Chem. , 1960, 629, 251 and the like can be referred to if necessary. Furthermore, it is possible to convert dialkenylaluminum groups into sulfinyl (SOOH) groups and sulfonyl (SOOOOH) groups by bringing them into contact with sulfur dioxide and sulfur trioxide, followed by hydrolysis. A propylene-based copolymer containing can be obtained. Again, K.K. Zieglar, F.A. Krupp, K.K. Weyer and W.W. Larbig, Liebugs Ann. Chem. , 1960, 629, 251; J. et al. Kunchin, L.M. I. Akhmetov, V.M. P. Yur'ev and G. A. Tolstikov, J.A. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 420; J. et al. Rutkowski and A.R. F. Turbak, US Pat. 3121737 [Chem. abstr. , 1964, 60, 10550] can be referred to if necessary.

  In the polar group-containing propylene copolymer of the present invention obtained as described above, the structural units represented by the general formula (C) and the general formula (D) are randomly distributed in the structural units derived from propylene. In addition, it has an alkenyl structure having a terminal vinyl group represented by the general formula (E) at the terminal, usually at one terminal.

Formula (C):

（式中、ｎは１〜２０の整数を示す。）

(In the formula, n represents an integer of 1 to 20.)

Formula (D):

（式中、ｎは１〜２０の整数、Ｘは−ＯＨ、−ＣＯＯＨ、−ＳＯＯＨ又は−ＳＯＯＯＨ基を示す。）

(In the formula, n represents an integer of 1 to 20, and X represents an —OH, —COOH, —SOOH or —SOOOH group.)

Formula (E):
_{CH 2 = CH- (CH 2)} n -
(Where n is an integer from 1 to 20)

  By the way, in the above decomposition reaction, the ratio of converting the dialkenyl aluminum group to the polar group is not necessarily 100%. If necessary, a component having a structure of the general formula (C) in which a carbon-aluminum bond is simply hydrolyzed (converted to a carbon-hydrogen bond) can be contained.

  As a method for such partial decomposition, when oxygen or carbon dioxide and a propylene-trialkenylaluminum copolymer are brought into contact with each other, alcohol or water is mixed, and oxygen or carbon dioxide is mixed with trialkenylaluminum. It can be achieved by bringing the content into contact with the content or less (equivalent or less), or changing the temperature or time during the reaction.

  In the polar group-containing propylene-based copolymer of the present invention, the propylene unit is 50 to 99.9 mol%, preferably 60 to 99.9 mol%, more preferably 65 to 99.9 mol%, and the general formula (C). 0 to 49.9 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%, 0.1 to 50 mol% of the unit represented by the general formula (D), Preferably it is 0.1-40 mol%, More preferably, it contains 0.1-35 mol%. When the structural unit represented by the general formula (D) is less than 0.1 mol%, polar group effects such as dyeability and adhesiveness cannot be obtained. Moreover, when it exceeds 50 mol%, there exists a problem that the original performance of a polypropylene cannot be taken out. In the general formula (D), preferable n is 2 to 6, and X is a hydroxyl group OH.

  By the way, the content of the structural unit represented by the general formula (C) greatly affects the crystallinity of the copolymer. For this reason, as for content of the structural unit represented by general formula (C), a preferable range changes with uses. For applications that require rigidity and heat resistance, such as automotive materials and industrial parts, the content of the unit represented by the general formula (C) is preferably not too large, preferably 20 mol mol% or less, more preferably 10 mol. % Or less. If it exceeds 20 mol%, the crystallinity is lowered and the rigidity and heat resistance are adversely affected. However, when used as a soft material or a resin additive, it is preferable that the content of the unit represented by the general formula (C) is large, and the content of the unit represented by the general formula (C) is It is 20-50 mol%, Preferably it is 20-40 mol%.

Content of the structural unit represented by general formula (C) and general formula (D) is the same as the above-mentioned measurement conditions of ¹³ C-NMR, and a propylene-derived methyl group (16 to 23 ppm), general formula ( C) a methyl group derived from a structural unit represented by C) (around 12 ppm), a methyl group derived from a structural unit represented by the general formula (D) (40 ppm or more), provided that in the case of a carboxyl group, carbon of the carboxyl group, The content of each unit is identified from the area ratio of the absorption spectrum.

  Furthermore, the molecular weight of the polar group-containing propylene-based copolymer of the present invention preferably has a molecular weight, melting point and heat of fusion within the ranges described for the propylene-trialkenylaluminum copolymer.

  The propylene-trialkenylaluminum copolymer and the polar group-containing propylene-based copolymer of the present invention are used as macromers, which are further polymerized or copolymerized to obtain copolymers having various characteristics. Can be manufactured.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, the measurement of physical properties and reaction raw materials / auxiliaries in the following examples are as follows. All the reactions in this example were performed under a purified nitrogen atmosphere.

1. Measurement Method of Physical Properties (1) Measurement of Melting Point and Measurement of Heat of Melting Using DSC-220 manufactured by Seiko Instruments Inc., 5 mg of a sheet sample was packed in an aluminum pan, heated from room temperature to 220 ° C. and heated to 5 ° C. After holding for 10 minutes, the temperature was lowered to −40 ° C. at 10 ° C./min for crystallization, and then the melting maximum peak temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min was taken as the melting point. The amount of heat was the heat of fusion.
(2) Measurement of molecular weight and molecular weight distribution Using 150C manufactured by Waters, the molecular weight and molecular weight distribution were measured by gel permeation chromatography. The conditions were measurement temperature: 140 ° C., solvent: orthodichlorobenzene, column: 2 Shodex 80M / S, and calculation of molecular weight was determined from standard polystyrene.
(3) Reaction product, trialkenyl aluminum, structure of general formula (B), (C), (D)
Measurement by ¹ H-NMR: JEOL-La-300 manufactured by JEOL Ltd. was used and the pulse Fourier transform method was performed at room temperature.
Measurement by ¹³ C-NMR: JEOL-La-500 manufactured by JEOL, measurement temperature: 120 ° C., solvent: 1,1,2,2-tetrachloroethane-d ₂ , pulse angle: 45 °, number of scans: 1000, pulse The test was carried out at an interval of 7 seconds.
Measurement by gas chromatography: GC-353 manufactured by GL Science Co., Ltd., injection sample: 1 μml, injection temperature: 250 ° C., detector: FID, detector temperature, column temperature: 40 ° C. Identification of the composition of the reaction mixture was calculated from the comparison with the retention time of the authentic sample and the peak area of the chromatogram.

2. Raw material, auxiliary agent (1) Propylene: Propylene manufactured by Tonen Chemical Co., Ltd. was purified at 60 ° C. through a packed column of manganese oxide and molecular sieve 4A.
(2) 1,7-octadiene: Tokyo Kasei Co., Ltd. was dehydrated using calcium hydride and further distilled.
(3) Toluene: dehydrated using calcium hydride and further distilled.
(4) Nitrogen, argon: Trace amounts of oxygen and moisture were removed through a packed tower of manganese oxide and molecular sieve 4A.
(5) Diisbutyl aluminum hydride: Tosoh Finechem Corporation was used as it was.
(6) Metallocene complex:
(I) Metallocene-1: rac-dimethylsilylbis (2-methylindenyl) zirconium dichloride; rac-Me ₂ Si [2-Me (Ind) ₂ ] ZrCl ₂ used as it is manufactured by Boulder Scientific Company did.
(Ii) Metallocene-2: Diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride; Ph ₂ C [(Cp) (9-Flu)] ZrCl ₂ is manufactured by Boulder Scientific Company. used.
(7) Triphenylcarbenium tetrakis (pentafluorophenyl) borate; [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]: Asahi Glass Co., Ltd. was used as it was.

(8) Magnesium, titanium, halogen-containing solid catalyst component: Prepared and used as follows.
In a 0.5 L glass reactor with stirring, 17.2 g (0.18 mol) of magnesium chloride and 43 ml (0.31 mol) of titanium tetrachloride were mixed and reacted at 100 ° C. for 2 hours. After completion of the reaction, the supernatant was extracted, washed several times with 250 ml of hexane to remove excess titanium tetrachloride, and dried under reduced pressure at room temperature to obtain the target magnesium, titanium and halogen-containing solid catalyst component. This solid catalyst component contained 0.9% by weight of titanium.

(9) Trioctenylaluminum (TOTNA): Prepared and used as follows.
1,7-octadiene (14 ml: 0.11 mol) and triisobutylaluminum (7.5 ml: 0.0168 mol) were added to a 50 ml glass reactor equipped with a stirrer and reacted at 120 ° C. for 6 hours. Thereafter, the remaining 1,7-octadiene was removed under reduced pressure to obtain a reaction product. This reaction product was analyzed by gas chromatography and NMR. 0.5 ml of the reaction product was diluted with 2 ml of meta-xylene (internal standard), then decomposed by adding distilled water and hydrochloric acid and used for analysis.
As a result, since all were (100%) alkenyl-derived 1-octene, it was confirmed that trioctenylaluminum was quantitatively produced.

Production Example 1
To a 200 ml glass reactor equipped with a stirrer, 0.0005 mol of toluene and trioctenylaluminum (TOTNA) was added. Here, the amount of toluene added was adjusted so that the volume of trioctenylaluminum and toluene was 100 ml. added. The inside of the reactor was set to 40 ° C. Here, propylene was circulated, and propylene was dissolved so that the internal pressure became 1 atm. Here, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] is added as a toluene solution so as to be 12 μmol, and rac-Me ₂ Si [2-Me (Ind) ₂ ] ZrCl ₂ is added to a concentration of 12 μmol. The polymerization was carried out at a temperature of 30 ° C. for 30 minutes. During the polymerization, the pressure of propylene was maintained at 1 atm with a gas flow meter. After 30 minutes, a small amount of methanol / hydrochloric acid was directly added to terminate the polymerization reaction. The reaction product was filtered off and dried under reduced pressure at 60 ° C. for 6 hours to obtain 2.2 g of a copolymer. The number average molecular weight (Mn) of this copolymer was 11.3 × 10 ⁴ , the molecular weight distribution (Mw / Mn) was 2.2, the melting point (Tm) was 132 ° C., and the vinyl group content was 0.1 mol%. . The vinyl group of the polymer obtained in Production Example 1 is shown in FIG.

Production Examples 2-3
The same operation as in Production Example 1 was carried out except that the addition amount of trioctenyl aluminum (TOTNA) to be added was changed as shown in Table 1. The yield of the obtained copolymer and the physical properties of the polymer are shown in Table 1.
Further, the ¹³ C-NMR absorption spectrum and attribution of the polymer of Production Example 2 are shown in FIG. This copolymer has an isotactic structure, and the peak intensity observed in the vicinity of 20.9 ppm among the peaks attributed to the methyl group of the propylene unit in the absorption spectrum of ¹³ C-NMR is propylene. The peak intensity of all methyl groups belonging to the unit was 0.94.
Furthermore, the vinyl group of the polymer obtained in Production Example 3 is shown in FIG.

Production Examples 4-6
Rac-Me ₂ Si [2-Me (Ind) ₂ ] ZrCl ₂ used in Production Example 1 was changed to Ph ₂ C [(Cp) (9-Flu)] ZrCl ₂ , and trioctenylaluminum (TOTNA) The same operation as in Production Example 1 was carried out except that the addition amount was changed as shown in Table 1. The yield of the obtained copolymer and the physical properties of the polymer are shown in Table 1. Moreover, the absorption spectrum of ¹³ C-NMR and the analysis result of the polymer obtained in Production Example 6 are shown in FIG.
This copolymer has a syndiotactic structure, and the peak intensity observed in the vicinity of 20.2 ppm of the peaks attributed to the methyl group of the propylene unit in the absorption spectrum of ¹³ C-NMR is propylene. The peak intensity of all methyl groups belonging to the unit was 0.84.

Production Examples 7-8
Instead of using the metallocene catalyst, polymerization was conducted according to Production Example 1 except that a solid catalyst component composed of magnesium, titanium, and halogen was used.
That is, toluene and trioctenyl aluminum (TOTNA) 0.00018 mol and 0.00054 mol were added to a 200 ml glass reactor equipped with a stirrer. Here, the amount of toluene added was adjusted so that the volume of trioctenylaluminum and toluene was 100 ml. The inside of the reactor was set to 40 ° C. Next, 48 mg of solid catalyst component consisting of magnesium, titanium and halogen (8.9 μmol as Ti in the solid catalyst) was introduced, and polymerization was carried out at a temperature of 40 ° C. for 30 minutes. During the polymerization, the pressure of propylene was maintained at 1 atm with a gas flow meter. After 30 minutes, a small amount of methanol / hydrochloric acid was directly added to terminate the polymerization reaction. The reaction product was filtered off and dried under reduced pressure at 60 ° C. for 6 hours to obtain a copolymer. The weight and physical properties of this copolymer are shown in Table 1.
This polymer having an isotactic structure and an atactic structure was separated by the following method. That is, 1 g of the polymer obtained by polymerization was placed in a 200 ml flask, dissolved in 100 ml of xylene, and heated to 120 ° C. under nitrogen. After heating and dissolving, the temperature was slowly returned to room temperature, and the solid portion was filtered with a filter, washed several times with hexane, completely dehydrated with xylene, and dried to obtain an isotactic polymer. On the other hand, the room temperature xylene soluble portion was precipitated and recovered in excess methanol. Each obtained solid was dried under reduced pressure at 60 ° C. for 6 hours and used for various subsequent analyses. The results are shown in Table 1. The heat of fusion, vinyl group content, and the content of the unit represented by the general formula (B) were measured separately for the isotactic structure polymer (IP) and the atactic structure polymer (AP), and the values are shown in the table. 1 is shown as (IP value / AP value).

Example 1
After copolymerization of propylene and trioctenyl aluminum for 30 minutes under the same polymerization conditions as in Production Example 1, 200 ml / min of dry oxygen was introduced at room temperature for 1.5 hours before decomposition with methanol / hydrochloric acid. . Thereafter, the organoaluminum bond was decomposed with hydrochloric acid / methanol, and the reaction product was filtered off and dried under reduced pressure at 60 ° C. for 6 hours. As a result, a hydroxyl group-containing propylene copolymer was obtained. Since the copolymer had a hydroxyl group content of 0.3 mol%, it was estimated that almost all branches with organoaluminum were converted to terminal hydroxyl groups.

Examples 2-8
In the same manner as in Example 1, polymerization was performed under the same conditions as in Production Examples 2 to 8, and after dry oxygen treatment, the hydroxyl groups of each polymer were measured. The results are shown in Table 2.
The analysis results and the absorption spectrum of ¹³ C-NMR of the polymer of example 2 in FIG. 2 (b), the analysis results and the absorption spectrum of ¹³ C-NMR of the polymer of example 6 shown in FIG. 3 (b).
Moreover, the absorption spectrum of ¹³ C-NMR of the polymer of Example 7 and an analysis result are shown in FIG. 4 (FIG. 4 (a) is an atactic polymer, (b) is an isotactic polymer).
In Table 2, the amount of the general formula (D) unit indicates that obtained by subjecting the octenylaluminum branched chain to oxygen decomposition + hydrochloric acid / methanol decomposition, and the amount of the general formula (C) unit is This indicates that oxygen was not inserted when the tenenylaluminum branched chain was subjected to oxygen decomposition, and the terminal was changed to CH ₃ by the subsequent hydrochloric acid / methanol treatment, the amount of propylene unit represents the propane terminal derived from propylene, and OH The conversion ratio indicates the ratio of octenyl aluminum molecular chains converted to hydroxyl groups.
Moreover, the terminal other than vinyl visible in the metallocene system is generated due to a difference in chain transfer. In this case, some cases of vinylidene due to beta hydrogen abstraction were observed. Tri-substituted olefins are associated with metallocene specific hydrogen evolution and are presumed to be less relevant to the polymer ends.

Reference examples 1 and 2
In Production Examples 1 and 4, triisobutylaluminum (0.0017 mol) was added instead of trioctenylaluminum, and the other operations were performed in the same manner as Production Examples 1 and 4 to obtain 8.0 g of a propylene homopolymer. . Table 1 shows the physical properties of this polymer. There was no terminal vinyl group (see FIG. 1 (a)).

Reference examples 3 and 4
In Examples 2 and 5, triisobutylaluminum (0.0017 mol) was added instead of trioctenylaluminum, and the same operations as in Examples 2 and 5 were performed. Table 2 shows the physical properties of this polymer. Only propylene units were detected in this polymer.

Reference examples 5 and 6
Polymerization using a solid catalyst component containing magnesium, titanium and halogen was carried out in the same manner as in Production Example 8 and Example 8 except that 0.02 mol of triisobutylaluminum was used instead of trioctenylaluminum. The results are shown in Tables 1 and 2.

2 shows ¹ H-NMR spectra and analysis results of the copolymers of Production Examples 1 and 3 and the propylene homopolymer of Reference Example 1. It is a ¹³ C-NMR spectrum and analysis result of the copolymer of Production Example 2 and the propylene-based copolymer of Example 2. It is a ¹³ C-NMR spectrum and analysis result of the copolymer of Production Example 6 and the propylene-based copolymer of Example 6. It is a ¹³ C-NMR spectrum and analysis result of the propylene-based copolymer of Example 7.

Claims (2)

50 to 99.9 mol% of propylene units, 0 to 49.9 mol% of units represented by the following general formula (C), and 0.1 to 50 mol% of units represented by the following general formula (D) Containing a vinyl group and a polar group-containing propylene copolymer having a terminal structure represented by the following general formula (E) and a weight average molecular weight of 1,000 to 1,000,000 Coalescence.
Formula (C):

(In the formula, n represents an integer of 1 to 20.)
Formula (D):

(In the formula, n represents an integer of 1 to 20, and X represents an —OH, —COOH, —SOOH or —SOOOH group.)
Formula (E):
_{CH 2 = CH- (CH 2)} n -
(Where n is an integer from 1 to 20)   A method for producing a polymer, wherein the copolymer according to claim 1 is used as a macromer and polymerized or copolymerized.

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