JP2006137873A - Functional group-containing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new terminal functional group-containing ethylenic polymer suitable for adhesion of a polyolefin-based resin to a resin having a functional group. <P>SOLUTION: In the olefin polymer having an oxygen-containing group, a sulfur-containing group, a metal-containing group or a halogen-containing group on one terminal, [1] the olefin polymer is produced by treating a vinyl group, a vinylidene group or a vinylidene group of an ethylenic copolymer (P) represented by general formula (1) (R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom or a 1-18C alkyl group; A is a polymer composed of a 2-20C olefin) and having a double bond at one terminal with at least one kind of compound selected from an oxidizing agent, a sulfonating agent, maleic anhydride, a hydroboration agent, a hydroaluminum-forming agent and a halogenating agent and [2] the ethylenic copolymer (P) is a crystalline polymer obtained by polymerizing 2-20C olefins and exhibiting a melting point. An adhesive material composition containing the olefin polymer described above is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a functional group-containing polymer obtained by modifying a polymer having an olefinic double bond at the terminal and introducing a functional group, a method for producing the same, and an adhesive material composition containing the polymer. Is.

  Since the ethylene polymer has a non-polar molecular structure and poor affinity with other substances, it has been attempted to introduce various functional groups into the polymer. Among functional groups, epoxy groups, maleic acid groups, sulfonic acid groups, organometallic-containing groups such as boron and aluminum, and functional groups such as halogen groups can be converted into various derivatives derived from them, which are very useful. is there. By utilizing the reactivity with these functional groups, it is possible to show excellent effects in adhesion between polyolefin and other substances, printability, compatibility in polymer blends, and the like. Therefore, various methods have been reported for producing ethylene / α-olefin copolymers having a double bond at the terminal as a raw material and for modifying the double bond.

  As a report example in which these functional groups have been introduced into an ethylene polymer so far, there is a liquid epoxidized modified ethylene random copolymer of Patent Document 1. However, it does not have a practical mechanical strength as a molded product, and its use area is limited.

  On the other hand, an oxygen-modified product of ethylene polymer having mechanical strength is exemplified in Patent Document 2, but the modification method is limited.

Moreover, in patent document 3, the structural unit derived from (1) ethylene is in the range of 81 to 100 mol%, the structural unit derived from α-olefin is in the range of 0 to 19 mol%, and (2) measured by GPC. The weight average molecular weight (Mw) is 7000 or less, (3) the molecular weight distribution (Mw / Mn) is 1.1 ≦ Mw / Mn ≦ 2.5, and (4) the vinyl or vinylidene group is attached to the end of the polymer main chain. In addition, an oxygen-modified product of an epoxidizing agent of an ethylene polymer, characterized in that the content of these groups measured by ¹ H-NMR is 90% or more of all terminal ends, has been proposed. , A functional group-containing ethylene polymer having a weight average molecular weight (Mw) of 7000 or more is not disclosed.
Japanese Patent Publication No. 7-91338 Japanese Patent Laid-Open No. 2001-2731 JP 2003-73412 A

An object of the present invention is to provide a novel terminal functional group-containing ethylene polymer suitable for adhesion between an adhesive material and a binder between incompatible resins, particularly a polyolefin resin and a resin having a functional group. is there.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above object.

That is, the present invention provides [1] an olefin polymer having an oxygen-containing group, a sulfur-containing group, a metal-containing group or a halogen-containing group at one end,
(i) The following general formula (1)

（１）
（一般式（１）中、Ｒ¹、Ｒ²はそれぞれ独立に水素原子、または炭素数１〜１８のアルキル基を表し、Ａは炭素数２〜２０のオレフィンからなる重合体を表す。）で表される片末端に二重結合を有するエチレン系共重合体（Ｐ）の、ビニル基、ビニレン基またはビニリデン基を、酸化剤、スルホン化剤、無水マレイン酸、ヒドロホウ素化剤、ヒドロアルミニウム化剤及びハロゲン化剤から選ばれる少なくとも1種の化合物で処理することによって製造され、
(ii)前記エチレン系重合体（Ｐ）が、融点を示す結晶性重合体であることを特徴とする、結晶性オレフィン重合体、並びに
［２］ ［１］記載の重合体を含む接着性材料組成物
である。

(1)
(In general formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and A represents a polymer composed of an olefin having 2 to 20 carbon atoms). The vinyl group, vinylene group or vinylidene group of the ethylene-based copolymer (P) having a double bond at one end is represented by oxidizing agent, sulfonating agent, maleic anhydride, hydroborating agent, hydroalumination. Produced by treatment with at least one compound selected from an agent and a halogenating agent,
(ii) A crystalline olefin polymer, wherein the ethylene polymer (P) is a crystalline polymer having a melting point, and an adhesive material comprising the polymer according to [2] [1] It is a composition.

According to the present invention, it is possible to provide uses such as various novel polymers and adhesive materials having polyolefin segments.

  Hereinafter, embodiments of the present invention will be described.

The present invention is an olefin polymer having an oxygen-containing group, a sulfur-containing group, a metal-containing group or a halogen-containing group at one end,
(i) A vinyl group, vinylene group or vinylidene group of an ethylene-based copolymer (P) having a double bond at one end is converted into an oxidizing agent, sulfonating agent, maleic anhydride, hydroborating agent and halogenating agent. Produced by treating with at least one compound selected from
(ii) A crystalline olefin polymer, wherein the ethylene copolymer (P) is a crystalline polymer having a melting point.

  In the olefin polymer of the present invention, one having one end of the polymer chain having an oxygen-containing group means that the following general formula (2)

（２）
（一般式（２）中、Ａ、Ｒ¹、Ｒ²は一般式（１）で定義した通り。）で示されるエポキシ含有重合体、または、下記一般式（３）

(2)
(In the general formula (2), A, R ¹ and R ² are as defined in the general formula (1)), or the following general formula (3)

（３）
（一般式（３）中、Ａ´はＡで表される重合体よりも骨格を形成する炭素数が２少ない炭素数２〜２０のオレフィン系重合体であり、Ｒ¹およびＲ²は一般式（１）で定義した通りであり、Ｒ^３およびＲ^４はどちらか一方がＲ^１であり、もう一方がＲ^２である。）で表される無水マレイン酸基含有重合体等が挙げられる。

(3)
(In the general formula (3), A ′ is an olefin polymer having 2 to 20 carbon atoms having a skeleton that is smaller than the polymer represented by A, and R ¹ and R ² are the general formulas. As defined in (1), one of R ³ and R ⁴ is R ¹ and the other is R ² ).

  Next, in the olefin polymer of the present invention, the olefin polymer having a sulfur-containing group at one end of the polymer chain is represented by the following general formula (4).

（４）
（一般式（４）中、Ａ、Ｒ¹およびＲ²は一般式（１）で定義した通りで、Ｘ^１とＹ^１はどちらか一方が水素原子またはヒドロキシル基でもう一方がスルホキシル基を示す。）で表されるスルホキシル基含有オレフィン重合体などが挙げられる。

(4)
(In the general formula (4), A, R ¹ and R ² are as defined in the general formula (1), and ^one of X ¹ and Y ¹ represents a hydrogen atom or a hydroxyl group and the other represents a sulfoxyl group. And the sulfoxyl group-containing olefin polymer represented by.

  In the olefin polymer of the present invention, the olefin polymer having a halogen group at one end of the polymer chain is represented by the following general formula (5).

（５）
（一般式（５）中、Ａ、Ｒ¹およびＲ²は一般式（１）で定義した通り、Ｘ^２およびＹ^２はどちらか一方が水素原子、もう一方がハロゲン原子、またはどちらもハロゲン原子を表す。）で表されるハロゲン含有オレフィン重合体等が挙げられる。

(5)
(In the general formula (5), A, R ¹ and R ² are as defined in the general formula (1), one of X ² and Y ² is a hydrogen atom, the other is a halogen atom, or both are halogen atoms. The halogen-containing olefin polymer etc. which are represented by these are mentioned.

  In the general formula (1), examples of the olefin of 2 to 20 constituting A include α-olefins such as ethylene, propylene, and 1-butene. Further, it may be copolymerized with other polymerizable unsaturated compounds as long as the characteristics are not impaired. Of these, ethylene, propylene, and 1-butene are particularly preferable.

In the general formulas (1) to (5), R ¹ and R ² are hydrogen or a C 1-18 alkyl group bonded to the double bond of the olefin constituting A, hydrogen, A methyl group, an ethyl group, a propyl group and the like.

  The weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the ethylene copolymer (P) represented by the general formula (1) is 400 to 500,000, preferably 800 to It is 200000, More preferably, it is 1000-100000. Here, Mw is a polystyrene equivalent value.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC of the ethylene copolymer (P) represented by the general formula (1), that is, the molecular weight distribution (Mw / Mn) is 1. It is 1-3.0, Preferably it is 1.1-2.5.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the ethylene copolymer (P) represented by the general formula (1) are, for example, using GPC-150 manufactured by Millipore Corporation under the following conditions: It can be measured.

Separation column: TSK GNH HT (column size: diameter 7.5 mm, length: 300 mm)
Column temperature: 140 ° C
Mobile phase: Orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.)
Antioxidant: Butylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) 0.025% by mass
Movement speed: 1.0 ml / min Sample concentration: 0.1% by mass
Sample injection amount: 500 microliters Detector: As a differential refractometer, it can be measured by measuring the molecular weight of a polyolefin having an unsaturated group at one end, which will be described later, and removing the molecular weight equivalent at the end.

Examples of the method for producing an ethylene polymer (P) having a double bond at one end represented by the general formula (1) of the present invention include the following methods.
(1) A polymerization method using a transition metal compound having a salicylaldoimine ligand as disclosed in Patent Documents 2 to 3 and JP-A 2000-239312 as a polymerization catalyst.
(2) A polymerization method using a titanium catalyst comprising a titanium compound and an organoaluminum compound.
(3) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(4) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

  Among these methods, the method (1) is more preferable in order to satisfy the terminal vinyl group content and terminal unsaturation described later.

<NMR measurement method>
Vinyl, vinylene and vinylidene type double bonds measured by ¹ H-NMR of the ethylene copolymer (P) having a double bond at one end represented by the general formula (1) used in the present invention Among the peaks for 3 protons based on the vinyl group, the peak for 2 protons (H1) is observed near 4.9 to 5.0 ppm, and the remaining 1 proton is observed near 5.7 to 5.9 ppm. The In addition, a peak (H2) for two protons derived from the vinylene group is observed in the vicinity of 5.0 ppm. Furthermore, a peak (H3) for two protons derived from the vinylidene group is observed in the vicinity of 4.7 ppm. The terminal vinyl group content calculated from these integral values and the integral value (Ha) of all protons (L) is defined by the following formula (I).

L (mol%) = (H1 / Ho) × 100 (Ho = H1 + H2 + H3) (I)
The terminal vinyl group content (L) is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more.

Further calculated from these, the integral value (Ha) of the peak of all protons measured by ¹ H-NMR of the ethylene-based copolymer (P) having a double bond at one end, and Mn obtained by GPC. One-terminal unsaturation rate (M) is defined by the following formula (II).

M (mol%) = [{Ho / Ha} / {2 / (Mn / 7)}] × 100
= {(Ho × Mn) / (Ha × 14)} × 100 (II)
(Here, Mn / 7 is the total hydrogen number 2n when the molecular formula of the polymer (P) having a double bond at one end is C _n H _2n and the molecular weight is 12 × n + 1 × 2n = 14n = Mn. is there.)

This one-terminal unsaturation rate (M) is 70 mol% or more, more preferably 75 mol% or more, and still more preferably 80 mol% or more of all one-terminal.
¹ H-NMR was measured at 120 ° C. after completely dissolving the polymer in deuterated 1,1,2,2-tetrachloroethane serving as a lock solvent and a solvent in a measurement sample tube. . The chemical shift was determined by setting the peak of deuterated-1,1,2,2-tetrachloroethane to 5.92 ppm and determining the chemical shift value of other peaks.

<Epoxidation method>
Although the epoxidation method of the double bond of the ethylene-based copolymer (P) having a double bond at one end represented by the general formula (1) is not particularly limited, examples include (1) performic acid, peracetic acid, Oxidation with peracids such as perbenzoic acid,
(2) oxidation with titanosilicate and hydrogen peroxide,
(3) oxidation with a rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide,
(4) oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite,
(5) oxidation with a salen complex such as manganese salen and hydrogen peroxide or hypochlorite,
(6) oxidation with hydrogen peroxide and a TACN complex such as a manganese-triazacyclononane (TACN) complex,
(7) Oxidation with hydrogen peroxide in the presence of a Group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst.

  Among these epoxidation methods, epoxidation by the methods (1) and (7) is preferable in terms of the active surface. In particular, in the epoxidation of a polymer having a high melting point, when the reaction temperature is equal to or higher than the decomposition temperature of the peracid, the decomposition reaction of the peracid by heat may be promoted, so that the method (7) is preferable. Here, the polymer having a high melting point is a polymer having a melting point of 100 ° C. or higher, preferably a polymer having a melting point of 110 ° C. or higher.

Hereinafter, the epoxidation by the methods (1) and (7) will be described.
In the method (1), the organic peroxide is added in an amount of 1 to 10 mol, preferably 1 to 5 mol per mol of the double bond of the ethylene copolymer (P) having a double bond at one end. The range of moles. Moreover, although the temperature of reaction is 0-150 degreeC, Preferably it is 10-100 degreeC, It is necessary to set to below the decomposition temperature of the peracid to be used. Also, depending on the type of peracid, since it exhibits explosive properties, care must be taken when setting the temperature. The time required for the reaction is 0.1 to 10 hours, preferably 0.5 to 5 hours. Furthermore, the polymer concentration is in the range of 5 to 400 g / L, preferably 10 to 300 g / L. The reaction solvent may be any solvent as long as it is not affected by the oxidation reaction, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

  Further, epoxidation may be performed while generating a peracid in the reaction system using a carboxylic acid such as acetic acid and hydrogen peroxide in the presence of an acidic catalyst such as sulfuric acid and a salt such as sodium sulfate.

  Next, the method (7) will be described in detail.

Examples of the group VI transition metal catalyst include tungstic acid, tungstate, or tungsten complex, and examples thereof include tungstic acid, alkali tungstate, ammonium tungstate, phosphotungstic acid, and silicotungstic acid. Particularly preferred tungstates are tungstates with oxidation states II, IV and VI, with the use of Na ₂ WO ₄ or ammonium tungstate being most preferred. Tungstic acids may be used alone or in combination of two or more.

  Examples of the phase transfer catalyst include quaternary ammonium salts, nitrogen ring-containing quaternary ammonium salts, quaternary phosphonium salts, macrocyclic polyethers, etc., but quaternary ammonium salts or nitrogen ring-containing quaternary compounds. Ammonium salts are preferred. Specific examples of the quaternary ammonium salts include trioctylmethylammonium chloride and trioctylethylammonium chloride. These bromides, iodides, sulfites or sulfates may also be used.

  Examples of the nitrogen ring-containing quaternary ammonium salts include quaternary ammonium salts in which the nitrogen ring is a pyridine ring, picoline ring, quinoline ring, imidazoline ring, morpholine ring, or the like. Ammonium compounds are preferred, and specific examples include the following. Alkyl (C8-20 linear or branched alkyl, the same shall apply hereinafter) pyridinium salts (for example, N-laurylpyridinium chloride, N-cetylpyridinium chloride, etc.), alkylpicorium salts (for example, N-laurylpicolinium chloride, etc.) ), Alkyl quinolium chloride, alkyl isoquinolium chloride, alkyl hydroxyethyl imidazoline chloride, alkyl hydroxy morpholine chloride and the like, and may be bromide, iodide or sulfate. The phase transfer catalyst may be used alone or in combination of two or more.

The concentration of hydrogen peroxide used in the method of the present invention is 3% by mass to 90% by mass, preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 50% by mass. The amount of hydrogen peroxide used is 0.5 mol to 10 mol, preferably 0.8 mol to 8 mol, more preferably 1 mol per mol of ethylene copolymer (P) having a double bond at one end of the raw material. 1.0 mol to 5 mol.
In this reaction, a phosphoric acid compound may be added for the purpose of promoting the reaction. Examples of phosphoric acid compounds include phosphoric acid and α-aminomethylphosphonic acids. The amino group of the α-aminomethylphosphonic acid may be substituted with an alkyl group, an aryl group, or the like. Among the α-aminomethylphosphonic acids, α-aminomethylphosphonic acids that leave at least one hydrogen atom on nitrogen are particularly preferred. Useful. Specific examples of the α-aminomethylphosphonic acids include aminomethylphosphonic acid, α-aminoethylphosphonic acid, α-aminopropylphosphonic acid, and the like. These α-aminomethylphosphonic acid and phosphoric acid may be used alone or in combination of two or more.

  In the production method of the present invention, in general, the amounts of tungstic acid, phase transfer catalyst and phosphoric acid used are each set to 0. 0 with respect to the ethylene copolymer (P) having a double bond at one end. 01 to 10 mol%, more preferably 0.1 to 5 mol%, most preferably 0.5 to 2 mol% is used.

  As the reaction solvent, an ethylene-based copolymer (P) having a double bond at one end, a hydrogen peroxide and an inert polymer with respect to the generated terminal epoxy group-containing polymer can be used, such as n-hexane. Aliphatic hydrocarbons, cycloaliphatic alicyclic hydrocarbons, aromatic hydrocarbons such as toluene and xylene, ethyl acetate esters, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, etc. Examples include ketones, halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, and perchloroethane. Industrially, aromatic hydrocarbons such as toluene and xylene are preferred as long as the ethylene-based copolymer (P) containing a single-end double bond as a raw material is not insoluble in the solvent.

  In a general embodiment of the present invention, a tungstic acid, a phase transfer catalyst, phosphoric acid, and an ethylene-based copolymer (P) having a double bond at one end are mixed in a reactor and dissolved uniformly. The temperature rises to After the reaction temperature is reached, hydrogen peroxide is slowly added dropwise. The reaction temperature is preferably a temperature at which the ethylene copolymer (P) having a double bond at one end to be used is melted, but it is 25 ° C to 150 ° C, preferably 50 ° C to 110 ° C, more preferably 80 ° C to 100 ° C. is there. When reacting at 100 ° C. or higher, there is a risk of bumping due to the dropwise addition of hydrogen peroxide, so an appropriate reactor such as an autoclave is selected. The dropping rate of hydrogen peroxide is gradually dropped according to the reaction rate and the removal rate of reaction heat. In the method of the present invention, the reaction may be performed by adjusting the pH of the reaction mixture. The pH is preferably between 1.0 and 4.0, preferably between pH 1.5 and 2.5, particularly preferably about pH 2.0. The pH of the reaction mixture can be adjusted by adding an aqueous solution of an acid such as sulfuric acid or phosphoric acid.

  The reaction time varies depending on the reaction conditions such as the amount of catalyst used, reaction temperature, and reactivity of olefins, but is usually from several minutes to 50 hours. In the production method of the present invention, the production of by-products is small, and after the reaction, the target olefins are removed by simple operations such as crystallization and washing, excluding excess hydrogen peroxide, catalyst, water, and reaction solvent. An epoxy compound can be obtained.

The confirmation of the epoxidation reaction can be confirmed by ¹ H-NMR and IR. For example, in the case of ¹ H-NMR, a peak of an epoxy group modified with a vinyl group is confirmed for a total of 3 protons, one proton each near 2.83 ppm, 2.65 ppm, and 2.38 ppm. In addition, the peak of the epoxy group modified with the vinylene group is observed in the vicinity of 2.95 ppm for two protons, and the peak of the epoxy group modified with vinylidene is observed near 2.5 ppm. When the reaction does not proceed sufficiently, the above-mentioned peak derived from the double bond is observed.

<Maleinization>
The maleic anhydride group-containing polymer represented by the general formula (3) is obtained by reacting the double bond-containing olefin polymer represented by the general formula (1) with maleic anhydride under acidic conditions. A maleic anhydride group-containing olefin polymer can be obtained.

<Sulfonation>
The sulfonic acid group-containing olefin polymer represented by the general formula (4) is reacted with the double bond-containing olefin polymer represented by the general formula (1) using sulfuric acid-acetic anhydride, fuming sulfuric acid or the like as a reactant. Is obtained.

<Boronization and aluminum>
Among the metal-containing group-containing polymers, the boron-containing olefin polymer includes borane, diborane, trimethylborane, and 9-boranebicyclo [3.3.1], in addition to the double bond-containing olefin polymer represented by the general formula (1). It can be obtained by reacting with nonane or the like. The aluminum-containing olefin polymer can be obtained by reacting lithium aluminum hydride, diisobutylaluminum hydride, or the like with the double bond-containing olefin polymer represented by the general formula (1).

<Halogenation>
The halogen-containing olefin polymer represented by the general formula (5) is obtained by reacting the double bond-containing olefin polymer represented by the general formula (1) with hydrogen chloride, hydrogen bromide, hydrogen iodide or the like. Obtainable.

Specific modification conditions (temperature, time, catalyst type, catalyst amount, etc., detailed conditions) with the above-mentioned reactants are the same as those described in, for example, Die Makromolecular Chemie Makromolecular Symposia 48/49, 317-332, 1991. It is possible to comply.

<Adhesive resin composition>
The terminal functional group-containing ethylene polymer of the present invention can be applied to various uses by utilizing the properties of the terminal functional group, for example, various printing inks, paints, adhesive materials with copper and other metals. , Adhesive material with other resins, Adhesive material between incompatible resins, especially used as an adhesive material to improve the interfacial strength between polyolefin resin and resin with functional group having reactivity with terminal functional group it can.

In particular, among the terminal functional group-containing polymers of the present invention, the terminal epoxy group-containing ethylene-based polymer utilizes, for example, the reactivity of the epoxy group, for example, antioxidant properties, ultraviolet absorption properties, antifogging properties, and photosensitivity. It is also possible to use as a resin additive by introducing various compounds having color developability, chelating properties and the like. Furthermore, a material with improved mechanical strength can be provided by the epoxy group-containing ethylene polymer of the present invention.

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

  In addition, the weight average molecular weight Mw and Mw / Mn were measured by the method described in the text using GPC.

  The melting point (Tm) was measured using DSC-60 manufactured by SIMAZU. As the measurement conditions, the peak top temperature obtained by measurement at 25 to 300 ° C. and 10 ° C./min was employed. When multiple peaks were observed, the peak top value with the largest peak area was adopted.

The 5% weight loss temperature was measured with TGA-50 manufactured by SIMAZU. The measurement conditions were 25 to 500 ° C., and the change in sample weight when the temperature was raised at 10 ° C./min was measured.

[Synthesis Example 1]
[Preparation of solid component (A)]
After suspending 30 g of silica (SiO ₂ ) dried at 150 ° C. for 5 hours under nitrogen flow in 466 mL of toluene, 134.3 mL of methylalumoxane in toluene (3.08 mmol / mL in terms of Al atom) was added at 25 ° C. For 30 minutes. After completion of dropping, the temperature was raised to 114 ° C. over 30 minutes, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (A). A part of the obtained solid component (A) was collected and examined for concentration. As a result, the slurry concentration was 0.150 g / mL and the Al concentration was 1.179 mmol / mL.

[Preparation of solid catalyst component (B)]
150 mL of toluene was put into a 300 mL glass flask purged with nitrogen, and the toluene slurry (1.91 g in terms of solid part) of the solid component (A) prepared above was charged with stirring. Next, 50.0 mL of a toluene solution (0.0012 mmol / mL in terms of Zr atom) of the following compound (1) was added dropwise over 15 minutes and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation, washed 3 times with heptane, and 100 mL of heptane was added to prepare a heptane slurry of the solid catalyst component (B). A portion of the resulting heptane slurry of the solid catalyst component (B) was collected to examine the concentration. As a result, the Zr concentration was 0.058 mmol / mL and the Al concentration was 14.8 mmol / mL.

化合物(1)

Compound (1)

450 ml of heptane was charged into a stainless steel autoclave with an internal volume of 1000 ml sufficiently purged with nitrogen, and 100 liter / hr of ethylene was circulated at room temperature for 15 minutes to saturate the liquid phase and the gas phase. Subsequently, 20 NL of propylene was introduced, the temperature was raised to 80 ° C., and then the pressure was increased to 8 kg / cm ² G with ethylene to maintain the temperature. 0.5 ml (0.5 mmol) of a decane solution of triisobutylaluminum (converted to 1.00 mmol / ml of aluminum atoms) was injected, and then the solid catalyst component (B) was injected with 0.0002 mmol converted to Zr atoms. Polymerization was started. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C. for 60 minutes. Then, the polymerization was stopped by press-fitting 5 ml of methanol, and the monomer was depressurized after the temperature was lowered. The obtained polymer slurry was mixed with 2 L of methanol and stirred and then filtered. The obtained product was dried under reduced pressure at 80 ° C. for 10 hours to obtain 65.2 g of a copolymer. The product had Mw = 1890, Mw / Mn = 1.68, melting point 112 ° C., terminal vinylation rate (L) measured by ¹ H-NMR was 83.9 mol% (vinyl group / vinylene group / vinylidene group = 83 9 / 13.4 / 2.8). Unsaturation rate at one end (M) = 78.7 mol%.

[Synthesis Example 2]
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the amount of propylene introduced was 23 NL, and the solid catalyst component (B) was added in an amount of 0.0001 mmol in terms of Zr atoms to obtain 53.2 g of a copolymer. The product had Mw = 1730, Mw / Mn = 1.68, a melting point of 108 ° C., and a terminal vinylation rate (L) measured by ¹ H-NMR of 78.4 mol% (vinyl group / vinylene group / vinylidene group = 78 4 / 17.6 / 3.9). Unsaturation rate at one end (M) = 83.2 mol%.

[Synthesis Example 3]
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the amount of propylene introduced was changed to 28 NL, to obtain 41.4 g of a copolymer. The product had Mw = 1310, Mw / Mn = 1.66, melting point 97.5 ° C., terminal vinylation rate (L) measured by ¹ H-NMR was 70.6 mol% (vinyl group / vinylene group / vinylidene group) = 70.6 / 24.6 / 4.8). Unsaturation rate at one end (M) = 77.2 mol%.

[Synthesis Example 4]
450 ml of heptane was charged into a stainless steel autoclave having an internal volume of 1000 ml sufficiently purged with nitrogen, and 100 liter / hr of propylene was allowed to flow at room temperature for 15 minutes to saturate the liquid phase and the gas phase. Subsequently, the temperature was raised to 80 ° C., and then the pressure of propylene was increased to 4.0 kg / cm ² G to maintain the temperature. Further, ethylene was introduced to 8 kg / cm 2 G to maintain the temperature. 0.25 ml (0.25 mmol) of MMAO (manufactured by Tosoh Finechem) in hexane (1.00 mmol / ml of aluminum atom equivalent) was injected, and then 2.0 ml (0.005 mmol / ml) of a toluene solution of compound 2 (0.0005 mmol / ml). 001 mmol) was injected to initiate the polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C. for 20 minutes, and then the polymerization was stopped by injecting 5 ml of methanol. The product was obtained by distilling off the solvent from the resulting polymer slurry. The copolymer was dried under reduced pressure at 80 ° C. for 10 hours to obtain 39.49 g of a copolymer. The product had Mw = 2940, Mw / Mn = 2.17, and the terminal vinylation rate (L) measured by ¹ H-NMR was 84 mol% (vinyl group / vinylene group / vinylidene group = 84.0 / 14.5 / 1.5). Unsaturation rate at one end (M) = 71.3 mol%.

化合物（２）

Compound (2)

[Example 1]
In a 200 ml separable flask equipped with a thermometer, a nitrogen introduction tube and a condenser, the one-terminal unsaturated ethylene / propylene copolymer obtained in Synthesis Example 1 (Mw 1900, Mn 1130, terminal unsaturation rate (L) = 78.7 mol) %) 20.0 g (13.99 mmol in terms of double bond), toluene 80 g, Na ₂ WO ₄ .2H ₂ O 0.293 g (0.89 mmol), 85% phosphoric acid 44 mg (0.44 mmol), CH ₃ (n-C ₈ H ₁₇ ) ₃ N · HSO ₄ 0.207 g (0.44 mmol) was added, and the mixture was heated to 90 ° C. with stirring to dissolve the polymer. After dissolving the polymer, 6.06 g (53.3 mmol) of 30% hydrogen peroxide water was slowly added dropwise over 1 hour while maintaining the temperature at 90 ° C., and further stirred for 5 hours. After confirming disappearance of the olefin by IR, cooling to 85 ° C., stopping stirring and separating the liquid, removing the aqueous layer, washing with stirring with 30 g of warm water twice, separating and operating, then at 85 ° C. Then, 2.0 g of 20% Na ₂ SO ₃ was added to deactivate the remaining hydrogen peroxide. The reaction solution was cooled to 80 ° C. or lower, and then cooled to room temperature while slowly adding 80 g of acetonitrile for crystallization. The solid collected by filtration from the resulting slurry was dried under reduced pressure (60 ° C., 10 kPa or less) for 8 hours to obtain 19.0 g of an epoxy-modified polymer white solid (olefin conversion rate 100%, yield 94%). Obtained.
¹ H-NMR δ (C ₂ D ₂ Cl ₄ ) 0.80-0.88 (m), 0.9-1.7 (m), 2.37-2.40 (1H, dd, J = 2.64, 5.28 Hz), 2.50 (m), 2.66 ( 1H, dd, J = 3.96, 4.95 Hz) 2.80-2.86 (1H, m), 2.95 (m)
Mw: 2040 Mw / Mn: 1.56 (GPC)
Melting point (Tm) 112.9 ℃ (DSC)
Melt viscosity (140 ° C) 34 (mPa · s)
Softening point 118.0 ℃
5% weight loss temperature 346 ℃ (TGA)

[Example 2]
One-terminal unsaturated ethylene / propylene copolymer was converted into one-terminal unsaturated ethylene / propylene copolymer obtained in Synthesis Example 2 (Mw = 1730, Mn = 994, one-terminal unsaturated ratio (L) = 83.2 mol). %) Was carried out in the same manner as in Example 1 to obtain 23.9 g of an epoxy-modified polymer white solid (olefin conversion rate 100%, yield 94%).
¹ H-NMR δ (C ₂ D ₂ Cl ₄ ) 0.80-0.88 (m), 0.9-1.6 (m), 2.37-2.40 (1H, dd, J = 2.64, 5.28 Hz), 2.50 (m), 2.66 ( 1H, dd, J = 3.96, 5.28 Hz) 2.80-2.86 (1H, m), 2.94 (m)
Mw: 1720 Mw / Mn: 1.58 (GPC)
Melting point (Tm) 99.7 ℃ (DSC)
Hardness 2 (10 ^-1 mm)
Melt viscosity (140 ° C) 32 (mPa · s)
Softening point 114.5 ℃
5% weight loss temperature 334 ℃ (TGA)

[Example 3]
One-terminal unsaturated ethylene / propylene copolymer was converted into one-terminal unsaturated ethylene / propylene copolymer obtained in Synthesis Example 3 (Mw = 1310, Mn = 790, one-terminal unsaturated ratio (L) = 77.2 mol). %) Was performed in the same manner as in Example 1 to obtain 9.53 g of an epoxy-modified polymer white solid (olefin conversion rate 100%, yield 94%).
¹ H-NMR δ (C ₂ D ₂ Cl ₄ ) 0.80-0.88 (m), 0.9-1.6 (m), 2.37-2.40 (1H, dd, J = 2.97, 5.28 Hz), 2.50 (m), 2.66 ( 1H, dd, J = 3.96, 5.28 Hz) 2.80-2.86 (1H, m), 2.95 (m)
Mw: 1470 Mw / Mn: 1.54 (GPC)
Melting point (Tm) 73.6 ℃ (DSC)
Melt viscosity (140 ° C) 19 (mPa · s)
Softening point 101.5 ℃
5% weight loss temperature 322 ℃ (TGA)

[Example 4]
The one-terminal unsaturated ethylene / propylene copolymer was changed to the one-terminal unsaturated ethylene / propylene copolymer obtained in Synthesis Example 4 (Mw 2940, Mn 1350, one-terminal unsaturated ratio (L) = 71.3 mol%). Except for the above, the same operation as in Example 1 was carried out to obtain 2.0 g of an epoxy-modified polymer white solid (olefin conversion rate 100%, yield 100%).
¹ H-NMR δ (C ₂ D ₂ Cl ₄ ) 0.80-0.88 (m), 0.9-1.6 (m), 2.37-2.40 (1H, dd, J = 2.64, 4.95 Hz), 2.50 (m), 2.66 ( 1H, dd, J = 3.96, 5.28 Hz) 2.80-2.86 (1H, m), 2.95 (m)
Melting point (Tm) 120 ℃ (DSC)

  The functional group-containing polymer of the present invention can be used, for example, as a compatibilizer in various inks, paints, adhesive materials for aluminum and other metals, and polymer blends with other resins.

Claims (3)

An olefin polymer having an oxygen-containing group, a sulfur-containing group, a metal-containing group or a halogen-containing group at one end,
(i) The following general formula (1)

(1)
(In general formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and A represents a polymer composed of an olefin having 2 to 20 carbon atoms). The vinyl group, vinylene group or vinylidene group of the ethylene-based copolymer (P) having a double bond at one end is represented by oxidizing agent, sulfonating agent, maleic anhydride, hydroborating agent, hydroalumination. Produced by treatment with at least one compound selected from an agent and a halogenating agent,
(ii) A crystalline olefin polymer, wherein the ethylene polymer (P) is a crystalline polymer having a melting point. (i) The ethylene unit is in the range of 80 to 100 mol%, the α-olefin unit having 3 to 20 carbon atoms is in the range of 0 to 20 mol%,
(ii) shows melting point (Tm) by DSC measurement,
(iii) The molecular weight distribution measured by gel permeation (GPC) is 1.1 ≦ (Mw / Mn) ≦ 3.0, and the molecular weight (Mw) is 400 ≦ Mw ≦ 500000,
^(iv) terminal vinyl group content is calculated by 1 H-NMR (L) and ¹ H-NMR and terminal unsaturation index calculated by GPC (M) is L> 50 mol%
M> 70 mol%
The olefin polymer according to claim 1, wherein An adhesive material composition comprising the polymer according to claim 1.