JP2004099694A - Olefinic block copolymer and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a specific block copolymer comprising a polyolefin segment and a functional segment, and to provide a method for producing the same. <P>SOLUTION: This olefinic block copolymer (A-1) comprising the polyolefin segment and the poly(meth)acrylate segment and obtained by reacting a polyolefin having hydroxy groups at the terminals of the main chain and the terminals of the side chains or only at the terminals of the side chains with an organic lithium compound or organic phosphorous compound to produce the lithium- or phosphorus-containing group-having polyolefin represented by the general formula (I): PO<SP>1</SP>-O-LP (I) (PO<SP>1</SP>is the polyolefin segment having a weight-average mol. wt. of 1,000 to 10,000,000; LP is the lithium- or phosphorus-containing group), and then anionically polymerizing a (meth)acrylate in the presence of the lithium- or phosphorus-containing group-having polyolefin. <P>COPYRIGHT: (C)2004,JPO

Description

上記式において、Ｒ^３およびＲ^４は、互いに同一でも異なっていてもよく、水素原子または炭素原子数が１〜３のアルキル基を示し、具体的には、メチル基、エチル基、プロピル基およびイソプロピル基を挙げることができる。また、Ｒ^５は炭素原子数１〜３の炭化水素基またはハロゲン原子を示し、具体的には、メチル基、エチル基、プロピル基およびイソプロピル基並びに塩素原子、臭素原子およびヨウ素原子などを挙げることができる。また、ｎは通常は０〜５、好ましくは１〜５の整数を表す。
【００２４】
上記式で表される芳香族ビニル化合物の具体的な例としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｍ−メチルスチレン、ｐ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロメチルスチレンなどが挙げられる。
ヘテロ環式化合物残基含有ビニル化合物の具体的な例としては、４−ビニルピリジン、２−ビニルピリジン、５−エチル−２−ビニルピリジン、２−メチル−５−ビニルピリジン、２−イソプロペニルピリジン、２−ビニルキノリン、３−ビニルイソキノリン、Ｎ−ビニルカルバゾール、Ｎ−ビニルピロリドンなどが挙げられる。
これらの中で、２種以上の芳香族系ビニル化合物を共重合してポリ芳香族系ビニル化合物セグメントを製造することもできる。
【００２５】
本発明に係るアニオン重合では、（メタ）アクリル酸エステルと芳香族系ビニル化合物を併用して共重合体セグメントを製造することもできる。
【００２６】
次にオレフィン系ブロック共重合体の製造方法について説明する。
本発明に係る第一のオレフィン系ブロック共重合体（Ａ−１）の製造方法では、主鎖末端および側鎖末端、あるいは側鎖末端のみに水酸基を有するポリオレフィンと、有機リチウム化合物または有機リン化合物とを反応させて末端にリチウムまたはリン含有基を有するポリオレフィンとし、次いで該末端にリチウムまたはリン含有基を有するポリオレフィンの存在下に（メタ）アクリル酸エステルを重合させて、ポリオレフィンセグメントとポリ（メタ）アクリル酸エステルセグメントからなるブロック共重合体（Ａ−１）を製造している。
【００２７】
また本発明に係る第二のオレフィン系ブロック共重合体（Ａ−２）の製造方法では、主鎖末端および／または側鎖末端に水酸基を有するポリオレフィンと、有機リチウム化合物または有機リン化合物とを反応させて末端にリチウムまたはリン含有基を有するポリオレフィンとし、次いで該末端にリチウムまたはリン含有基を有するポリオレフィンの存在下に芳香族系ビニル化合物を重合させて、ポリオレフィンセグメントとポリ芳香族系ビニル化合物セグメントとからなるブロック共重合体（Ａ−２）を製造している。
【００２８】
また本発明に係る第三のオレフィン系ブロック共重合体（Ａ−３）の製造方法では、アルキル金属化合物存在下に（メタ）アクリル酸エステルをアニオン重合させ、主鎖末端および／または側鎖末端にハロゲン原子を有するポリオレフィンと接触させることで反応を停止することによって、ポリオレフィンセグメントとポリ（メタ）アクリル酸エステルセグメントとからなるオレフィン系ブロック共重合体（Ａ−３）を製造している。
【００２９】
また本発明に係る第四のオレフィン系ブロック共重合体（Ａ−４）の製造方法では、アルキル金属化合物存在下に芳香族系ビニル化合物をアニオン重合させ、主鎖末端および／または側鎖末端にハロゲン原子を有するポリオレフィンと接触させることで反応を停止することによって、ポリオレフィンセグメントとポリ芳香族系ビニル化合物セグメントとからなるオレフィン系ブロック共重合体（Ａ−４）を製造している。
【００３０】
主鎖末端および側鎖末端、あるいは側鎖末端のみに水酸基を有するポリオレフィンは、例えばオレフィン重合触媒の存在下に、主鎖末端および側鎖末端、あるいは側鎖末端のみが修飾されたポリオレフィンを製造し、次いで該末端修飾ポリオレフィンの末端基と官能基構造を有する化合物との置換反応を行った後加溶媒分解するか、または、該末端修飾ポリオレフィンの末端基を加溶媒分解により官能基を形成する構造を有する化合物との置換反応を行った後加溶媒分解することにより製造することができる。
主鎖末端および／または側鎖末端に水酸基を有するポリオレフィンは、例えばオレフィン重合触媒の存在下に、主鎖末端および／または側鎖末端が修飾されたポリオレフィンを製造し、次いで該末端修飾ポリオレフィンの末端基と官能基構造を有する化合物との置換反応を行った後加溶媒分解するか、または、該末端修飾ポリオレフィンの末端基を加溶媒分解により官能基を形成する構造を有する化合物との置換反応を行った後加溶媒分解することにより製造することができる。主鎖末端および／または側鎖末端にハロゲン原子を有するポリオレフィンは、例えばオレフィン重合触媒の存在下に、炭素数２〜２０のオレフィンとハロゲン化オレフィンを共重合させ、主鎖末端および／または側鎖末端が修飾されたポリオレフィンを製造することができる。あるいはオレフィン重合触媒の存在下に、炭素数２〜２０のオレフィンと非共役ポリエンを共重合させ、得られた共重合体の末端ビニル基をハロゲン原子含有基に変性することにより製造することができる。
【００３１】
まず、上記末端修飾ポリオレフィンの製造に用いられるオレフィン重合触媒について説明する。
末端修飾ポリオレフィンの製造に用いられるオレフィン重合触媒は、従来公知のいずれの触媒であってもよい。従来公知の触媒としては、例えばマグネシウム担持型チタン触媒、メタロセン触媒などが挙げられ、例えば国際公開特許ＷＯ０１／５３３６９あるいはＷＯ０１／２７１２４中に記載の触媒が好適に用いられる。
【００３２】
有機アルミニウム化合物存在下で上記重合触媒により、炭素数２〜２０のオレフィンとの共重合体、および／または、２種類以上の炭素数２〜２０のオレフィンを含んでなる共重合体、あるいは水酸基含有オレフィンとの共重合体を製造する場合、下記一般式（ＩＶ）あるいは（Ｖ）で表される末端修飾ポリオレフィンが製造される。
ＰＯ^１−ＡｌＲ^１Ｒ^２　　　…（ＩＶ）
ＰＯ^２−ＡｌＲ^１Ｒ^２　　　…（Ｖ）
Ｒ^１およびＲ^２は、互いに同一でも異なっていてもよく炭素原子数１〜１０の炭化水素基、水素原子またはハロゲン原子から選ばれる基または原子である。
炭素原子数１〜１０の炭化水素基としては、メチル、エチル、プロピル、ブチル、ペンチル、オクチル、デシルなどが挙げられる。
【００３３】
次に、得られた該末端修飾ポリオレフィンの−ＡｌＲ^１Ｒ^２基を加溶媒分解により官能基を形成する構造を与える化合物との置換反応を行い、次いで加溶媒分解することにより下記一般式（ＶＩ）あるいは（ＶＩＩ）で表されるポリオレフィンを製造する。
ＰＯ^１−ＯＨ　　　…（ＶＩ）
ＰＯ^２−ＯＨ　　　…（ＶＩＩ）
式中、ＰＯ^１、ＰＯ^２は前記と同様である。
また、加溶媒分解により官能基を形成する構造を与える化合物としては、酸素、オゾンなどが挙げられる。
【００３４】
上記のようにして得られた該末端修飾ポリオレフィンの−ＡｌＲ^１Ｒ^２基と、官能基構造を有する化合物または加溶媒分解により官能基を形成する構造を与える化合物との置換反応は、通常０〜３００℃、好ましくは１０〜２００℃の温度で、０〜１００時間、好ましくは０．５〜５０時間行われる。
置換反応を行った後、加溶媒分解する際の温度は、通常０〜１００℃、好ましくは１０〜８０℃の温度であり、加溶媒分解時間は、０〜１００時間、好ましくは０．５〜５０時間である。加溶媒分解に用いられる溶媒としては、メタノール、エタノール、プロパノール、ブタノール、水などが挙げられる。
【００３５】
また、末端ビニル基を有するポリオレフィンを変性することによって得られる末端水酸基含有ポリオレフィンは、末端が不飽和結合であるポリオレフィンと、１３族元素を含む化合物、例えば有機アルミニウム化合物または有機ホウ素化合物とを反応させて、上記一般式（ＩＶ）あるいは（Ｖ）で表される末端修飾ポリオレフィンとし、次いで上記のようにして末端を水酸基に変換することによっても製造することができる。末端が不飽和結合であるポリオレフィン（末端不飽和ポリオレフィン）は、例えば有機アルミニウム化合物を用いずに、上記のようなオレフィン重合触媒を用いて製造することができる。
【００３６】
また、末端ハロゲン基を有するポリオレフィンを変性して得られる末端水酸基を有するポリオレフィンは、末端がハロゲンであるポリオレフィンと、水あるいは水酸基含有化号物との反応によって末端を水酸基に変換し製造することができる。末端がハロゲンであるポリオレフィンは、上記のようなオレフィン重合触媒を用いて製造することができる。
【００３７】
上記の末端修飾ポリオレフィンの重合は、溶媒懸濁重合法、液体状オレフィンを溶媒とする懸濁重合法などによって行われる。
溶媒懸濁重合を実施する際には、重合溶媒として、重合不活性な炭化水素を用いることができる。この際用いられる不活性炭化水素媒体として具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油などの脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタンなどの脂環族炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；エチレンクロリド、クロルベンゼンなどのハロゲン化炭化水素、またはこれらの組み合わせが挙げられる。これらのうち、特に脂肪族炭化水素を用いることが好ましい。
【００３８】
マグネシウム担持型チタン触媒系を用いる場合、重合系内においては、固体状チタン触媒成分（ａ）またはその予備重合触媒は、重合容積１リットル当りチタン原子に換算して、通常は約０．０００１〜５０ミリモル、好ましくは約０．００１〜１０ミリモルの量で用いられる。有機金属化合物触媒成分（ｂ）は、該触媒成分（ｂ）中の金属原子が、重合系中の固体状チタン触媒成分（ａ）中のチタン原子１モルに対し、通常１〜２０００モル、好ましくは２〜１０００モルの量で用いられる。電子供与体（ＥＤ）は、有機金属化合物触媒成分（ｂ）の金属原子１モルに対し、通常０．００１モル〜１０モル、好ましくは０．０１モル〜５モルの量で用いられる。
重合工程における、水素濃度はモノマー１モルに対して０〜０．０１モル、好ましくは０〜０．００５モル、より好ましくは０〜０．００１モルの量であることが好ましい。
【００３９】
オレフィン重合は、溶液重合、懸濁重合などの液相重合法または気相重合法のいずれにおいても実施することができる。懸濁重合の反応溶媒としては、前述の不活性溶媒を用いることもできるし、反応温度において液状のオレフィンを用いることもできる。重合温度は、通常、７０℃以上、好ましくは８０〜１５０℃、より好ましくは８５〜１４０℃、特に好ましくは９０〜１３０℃の範囲であり、圧力は、通常、常圧〜１０ＭＰａ、好ましくは常圧〜５ＭＰａに設定される。重合は回分式、半連続式、連続式のいずれの方法においても行うことができ、２段以上に分けて行う場合は、反応条件は同じであっても異なっていてもよい。
【００４０】
オレフィン重合は、溶液重合、懸濁重合などの液相重合法または気相重合法のいずれにおいても実施することができる。重合形態としては、懸濁重合の反応形態を採ることが好ましく、この時の反応溶媒としては、不活性炭化水素溶媒を用いることもできるし、反応温度において液状のオレフィンを用いることもできる。
この際用いられる不活性炭化水素媒体としては、具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油などの脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタンなどの脂環族炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；エチレンクロリド、クロルベンゼンなどのハロゲン化炭化水素、またはこれらの組み合わせが挙げられる。これらのうち、特に脂肪族炭化水素を用いることが好ましい。
【００４１】
触媒としてマグネシウム担持型チタン触媒系を用いて末端不飽和ポリオレフィンを製造する場合には、固体状チタン触媒成分（ａ）またはその予備重合触媒は、重合容積１リットル当りチタン原子に換算して、通常は約０．００１〜１００ミリモル、好ましくは約０．００５〜２０ミリモルの量で用いられる。有機金属化合物触媒成分（ｂ）は、該触媒成分（ｂ）中の金属原子が、重合系中の固体状チタン触媒成分（ａ）中のチタン原子１モルに対し、通常約１〜２０００モル、好ましくは約２〜５００モルとなるような量で用いられる。電子供与体（ＥＤ）は、有機金属化合物触媒成分（ｂ）の金属原子１モルに対し、通常０モル〜１０モル、好ましくは０モル〜５モルの量で用いられる。
【００４２】
重合工程における、水素濃度は通常モノマー１モルに対して０〜０．２５モル、好ましくは０〜０．２０モル、より好ましくは０〜０．１５の量である。
マグネシウム担持型チタン触媒系を用いた場合の重合温度は、通常約２０〜３００℃、好ましくは約５０〜１５０℃の範囲であり、重合圧力は、０．０１〜１０ＭＰａ、好ましくは０．０５〜５ＭＰａの範囲である。
【００４３】
触媒としてメタロセン系触媒を用いて末端不飽和ポリオレフィンを製造する場合には、重合系内のメタロセン化合物（ｃ）の濃度は、重合容積１リットル当り、通常０．００００５〜０．１ミリモル、好ましくは０．０００１〜０．０５ミリモルの量で用いられる。有機アルミニウムオキシ化合物（ｄ）は、メタロセン化合物（ｃ）中の遷移金属原子（Ｍ）に対するアルミニウム原子（Ａｌ）のモル比（Ａｌ／Ｍ）で、５〜１０００、好ましくは１０〜４００となるような量で用いられる。また有機アルミニウム化合物（ｂ−２）が用いられる場合には、メタロセン化合物（ｃ）中の遷移金属原子１モルに対して、通常約１〜３００モル、好ましくは約２〜２００モルとなるような量で用いられる。
メタロセン系触媒を用いた場合の重合温度は、通常温度が−２０〜１５０℃、好ましくは０〜１２０℃、さらに好ましくは０〜１００℃の範囲であり、重合圧力は０を超えて８ＭＰａ、好ましくは０を超えて５ＭＰａの範囲である。
【００４４】
オレフィン重合は、バッチ式、半連続式、連続式のいずれの方法においても行うことができる。さらに重合を、反応条件を変えて２段以上に分けて行うこともできる。オレフィン重合では、オレフィンの単独重合体を製造してもよく、また２種以上のオレフィンからランダム共重合体を製造してもよい。
【００４５】
このようにして得られた末端不飽和ポリオレフィンと１３族元素を含む化合物を反応させて１３族元素が結合した末端に変換する。
反応に用いられる１３族元素を含む化合物は、前述の有機化合物触媒成分として例示した化合物の中から選ばれ、有機アルミニウム化合物または有機ホウ素化合物として例示した化合物が好ましく用いられる。中でも、トリアルキルアルミニウム、ジアルキルアルミニウムハイドライドまたは１つ以上の水素−ホウ素結合を有するホウ素化合物であることがより好ましく、有機アルミニウムとしてはジアルキルアルミニウムハイドライドが特に好ましく、有機ホウ素化合物としては９−ボラビシクロ［３，３，１］ノナンが特に好ましい。
【００４６】
末端が不飽和結合末端であるポリオレフィンと、１３族元素を含む化合物との反応は、例えば以下のようにして行われる。
▲１▼末端がビニリデン基であるポリプロピレン０．１〜５０ｇと、ジイソブチルアルミニウムハイドライドの０．０１〜５モル／リットル−オクタン溶液を５〜１０００ｍｌとを混合し、０．５〜６時間還流させる。
▲２▼末端がビニリデン基であるポリプロピレン０．１〜５０ｇと、５〜１０００ミリリットルの無水テトラヒドロフランと、０．１〜５０ミリリットルの９−ボラビシクロ［３．３．１］ノナンの０．０５〜１０モル／リットル−テトラヒドロフラン溶液とを混合し、２０〜６５℃で０．５〜２４時間攪拌する。
【００４７】
（末端にリチウムまたはリン含有基を有するポリオレフィンの調製）
末端にリチウムまたはリン含有基を有するポリオレフィンの調製方法について、末端にリチウムを有するポリオレフィンの調製方法を例に説明する。
末端にリチウムを有するポリオレフィンは、上記末端に水酸基を有するポリオレフィンと、有機リチウム化合物とを反応させることにより得られる。末端に水酸基を有するポリオレフィンと、有機リチウム化合物との反応は、通常溶媒中で行われる。
有機リチウム化合物としては、ブチルリチウム、プロピルリチウム、エチルリチウム、メチルリチウムなどのアルキルリチウム；ブトキシリチウム、プロポキシリチウム、エトキシリチウム、メトキシリチウムなどのアルコキシリチウムなどが挙げられる。本発明においては、アルキルリチウムがより好ましく用いられる。
【００４８】
反応に用いる溶媒としては、不活性炭化水素媒体として例示した炭化水素と同様のものが挙げられる。
末端に水酸基を有するポリオレフィンと、有機リチウム化合物とを反応させるに際し、有機リチウム化合物は、ポリオレフィン末端の水酸基１モルに対し、０．１〜１００モル、好ましくは０．２〜１０モルの範囲で用いられる。反応温度は、通常−１００〜１００℃、好ましくは０〜８０℃であり、反応時間は通常０．１〜４８時間、好ましくは０．５〜１２時間である。
【００４９】
上記末端に水酸基を有するポリオレフィンとの反応に用いられる有機リン化合物としては、トリス（ジメチルアミノ）｛トリス（ジメチルアミノ）ホスホラニリデンアミノ｝ホスホニウム、トリス（ジエチルアミノ）｛トリス（ジエチルアミノ）ホスホラニリデンアミノ｝ホスホニウム、ビス（ジメチルアミノ）ビス｛トリス（ジメチルアミノ）ホスホラニリデンアミノ｝ホスホニウム、ジメチルアミノトリス｛トリス（ジメチルアミノ）ホスホラニリデンアミノ｝ホスホニウム、テトラキス｛トリス（ジメチルアミノ）ホスホラニリデンアミノ｝ホスホニウム、テトラキス｛トリス（モルホリノ）ホスホラニリデンアミノ｝ホスホニウム、テトラキス｛トリス（ピペリジノ）ホスホラニリデンアミノ｝ホスホニウムなどのハロゲン化物であることが好ましく、塩化物であることがより好ましい。
有機リン化合物としては、カチオンの発生が容易であるものが好ましく、ホスホラニリデンアミノホスホニウムカチオンの発生が容易であるものがより好ましい。
なお末端のリン含有基は、前述の開環重合活性種としても好ましい。
本発明においてＲ^８の立体規則性を制御する場合は、末端にリチウムを有するポリオレフィンを使用することが好ましい。
【００５０】
このようにして下記一般式（Ｉ）あるいは（ＩＩ）で表される、末端にリチウムまたはリン含有基を有するポリオレフィンを製造する。
ＰＯ^１−Ｏ−ＬＰ　　　…（Ｉ）
ＰＯ^２−Ｏ−ＬＰ　　　…（ＩＩ）
式中、ＰＯ^１、ＰＯ^２はポリオレフィンセグメントを示し、ＬＰはリチウムまたはリン含有基を示す。
【００５１】
（ブロック共重合体の製造）
本発明では、上記末端にリチウムまたはリン含有基を有するポリオレフィンの存在下に（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物をアニオン重合させて、ポリオレフィンセグメントと（メタ）アクリル酸エステルセグメントあるいはポリ芳香族系ビニル化合物とからなるポリオレフィン系ブロック共重合体を得る。
重合は溶媒と末端リチウムまたはリン含有基ポリオレフィンと（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物とを混合するか、または末端にリチウムまたはリン含有基ポリオレフィンと液状の（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物とを混合することにより行われる。末端にリチウムまたはリン含有基ポリオレフィンと溶媒と（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物とを混合することによってアニオン重合活性種を形成させることができる。
溶媒としては、例えばヘキサン、ヘプタンなどの脂肪族炭化水素；シクロペンタン、シクロヘキサンなどの脂環式炭化水素；ベンゼン、トルエンなどの芳香族炭化水素；ジエチルエーテル、ジオキサン、テトラヒドロフラン（ＴＨＦ）、モノグリム、ジグリムなどのエーテル系溶媒などが用いられる。これらの溶媒は、１種単独または２種以上組み合わせて用いることができる。中でも、芳香族炭化水素とエーテル系溶媒が好ましく用いられる。
【００５２】
また、重合に際してトリフェニルフォスフィン、α，α’−ジピリジル、ヘキサメチルホスホロアミド（ＨＭＰＡ）、四塩化チタン、アルキルリチウム、アルコキシリチウムなどのアニオン重合活性種の形成に有用な化合物を添加してもよい。
重合は、通常−１００℃〜１００℃、好ましくは−８０℃〜８０℃、より好ましくは−７０℃〜７０℃の重合温度で、１分間〜５００時間、好ましくは１０分間〜３００時間、より好ましくは１５分間〜１５０時間かけて実施される。この重合においては、末端Ｌｉポリオレフィンは、０．００１〜１００モル／リットル、好ましくは０．００５〜５０モル／リットル、より好ましくは０．０１〜１０モル／リットル、さらに好ましくは０．１〜５モル／リットルの濃度で使用される。また（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物は、通常０．００１〜５００モル／リットル、好ましくは０．００５〜３００モル／リットル、より好ましくは０．０１〜１５０モル／リットルの濃度で使用される。
【００５３】
また本発明は、アルキル金属化合物存在下に（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物をアニオン重合させ、主鎖末端および／または側鎖末端にハロゲン原子を有するポリオレフィンと接触させることで反応を停止することによって、ポリオレフィンセグメントとポリ（メタ）アクリル酸エステルセグメントあるいはポリ芳香族系ビニル化合物セグメントとからなるオレフィン系ブロック共重合体に関する。
（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物のアニオン重合は、溶媒とアルキル金属化合物と（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物とを混合するか、または末端にリチウムまたはリン含有基ポリオレフィンと液状の（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物とを混合することにより行われる。
【００５４】
用いるアルキル金属化合物としては通常のアニオン重合に用いられるものであれば特に制限は無いが、具体的に、例えば、リチウム、ナトリウム、カリウム等の周期表第１族金属類、メチルリチウム、エチルリチウム、ブチルリチウム、ヘキシルリチウム、メチルナトリウム、エチルナトリウム、ブチルナトリウム、ヘキシルナトリウム、メチルカリウム、エチルカリウム、ブチルカリウム、ヘキシルカリウム等のアルキルアルカリ類、メチルマグネシウムクロリド、エチルマグネシウムクロリド、ブチルマグネシウムクロリド、ヘキシルマグネシウムクロリド、メチルマグネシウムブロミド、エチルマグネシウムブロミド、ブチルマグネシウムブロミド、ヘキシルマグネシウムブロミド等のグリニャール試薬が挙げられる。
【００５５】
溶媒としては、例えばヘキサン、ヘプタンなどの脂肪族炭化水素；シクロペンタン、シクロヘキサンなどの脂環式炭化水素；ベンゼン、トルエンなどの芳香族炭化水素；ジエチルエーテル、ジオキサン、テトラヒドロフラン（ＴＨＦ）、モノグリム、ジグリムなどのエーテル系溶媒などが用いられる。これらの溶媒は、１種単独または２種以上組み合わせて用いることができる。中でも、芳香族炭化水素とエーテル系溶媒が好ましく用いられる。
主鎖末端および／または側鎖末端にハロゲン原子を有するポリオレフィンとの接触は、溶媒中でアルキル金属化合物存在下に（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物をアニオン重合させたところに、直接ポリオレフィンを加えてもよく、または上記例示された溶媒中に溶解あるいは懸濁させた後、加えて実施してもよい。
【００５６】
重合は、通常−１００℃〜１００℃、好ましくは−８０℃〜８０℃、より好ましくは−７０℃〜７０℃の重合温度で、１分間〜５００時間、好ましくは１０分間〜３００時間、より好ましくは１５分間〜１５０時間かけて実施される。また（メタ）アクリル酸エステルあるいは芳香族系ビニル化合物は、通常０．００１〜５００モル／リットル、好ましくは０．００５〜３００モル／リットル、より好ましくは０．０１〜１５０モル／リットルの濃度で使用される。
この主鎖末端および／または側鎖末端にハロゲン原子を有するポリオレフィンとの接触においては、末端ハロゲン化ポリオレフィンは、０．００１〜１００モル／リットル、好ましくは０．００５〜５０モル／リットル、より好ましくは０．０１〜１０モル／リットル、さらに好ましくは０．１〜５モル／リットルの濃度で使用される。
【００５７】
前記オレフィン系ブロック共重合体中のポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物セグメントは、重量平均分子量が通常５００以上、好ましくは５００〜１，０００，０００、より好ましくは５，０００〜８００，０００、特に好ましくは１０，０００〜５００，０００の範囲にあることが望ましい。
前記オレフィン系ブロック共重合体中のポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物セグメントは、オレフィン系ブロック共重合体に対して、好ましくは０．０１〜９９．９９重量％、好ましくは１〜９９重量％、より好ましくは１〜９５重量％、特に好ましくは１〜９０重量％の量で含まれる。
【００５８】
以上のようにして、ポリオレフィンセグメント（ＰＯ^１あるいはＰＯ^２）とポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物セグメントとが化学的に結合したブロック共重合体を含むポリマーを製造できるが、このポリマーが上記セグメントＰＯ^１あるいはＰＯ^２と、ポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物セグメントとが化学的に結合したポリマーを含んでいるかどうかは、例えば得られたポリマーの分子量、有機溶媒への溶解度、または、分光学的解析によって判断することができる。すなわち、本発明の方法で得られるポリマーの分子量が上記末端にリチウムまたはリン含有基を有するポリオレフィンのセグメントＰＯ^１あるいはＰＯ^２の分子量に対して高い値を示すこと、本発明の方法で得られるオレフィン系ブロック共重合体ポリマーのセグメントＰＯ^１あるいはＰＯ^２に相当するポリマーと該ポリマーのアニオン重合によって製造されるポリマーのセグメントに相当するポリマーとの混合物が示す有機溶媒への溶解挙動が、本発明の方法で得られるオレフィン系ブロック共重合体の有機溶媒への溶解挙動とは異なっていること、または、本発明の方法で得られるオレフィン系ブロック共重合体の末端構造を^１３Ｃ−ＮＭＲで解析してセグメントＰＯ^１あるいはＰＯ^２とアニオン重合によって製造されるポリマーのポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物との化学的結合に由来するピークを検出することによって目的とするブロック共重合体が製造できたものと判断することができる。
【００５９】
（用途）
本発明に係るオレフィン系ブロック共重合体は、主鎖を構成するポリオレフィンセグメントと側鎖を構成するポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物セグメントとが化学的に結合したブロック共重合体であり、両セグメントの物性、特性を兼ね備えた重合体である。
本発明におけるオレフィン系ブロック共重合体は、必要に応じて本発明の目的を損なわない範囲において、各種の添加剤、例えば軟化剤、安定剤、充填剤、酸化防止剤、結晶核剤などを配合することができる。
【００６０】
本発明に係る接着用樹脂は、粘着性、耐熱クリープ性、流動性に優れた特徴を有する、前記した本発明に係るオレフィン系ブロック共重合体を含んでなるホットメルト接着剤のような接着剤として、好適に用いられる。
本発明に係るホットメルト接着剤組成物は、前記オレフィン系ブロック共重合体と、粘着性付与樹脂（Ｂ）とを含有している。粘着性付与剤（Ｂ）は、ベースポリマーであるオレフィン系ブロック共重合体の溶融時の粘度を調整し、ホットタック性やヌレ性を向上させるために配合されるものである。この粘着性付与剤（Ｂ）は、オレフィン系ブロック共重合体に配合して、加熱時に、オレフィン系ブロック共重合体のホットタックやヌレをよくすることができるものであれば、特に限定されない。
粘着性付与剤として具体的には、脂環族系水添タッキファイヤー、ロジン、変性ロジンまたはこれらのエステル化物、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、脂肪族成分と芳香族成分の共重合石油樹脂、低分子量スチレン系樹脂、イソプレン系樹脂、アルキル、フェノール樹脂、テルペン樹脂、クマロン・インデン樹脂などが好適な粘着性付与剤として例示される。本発明では、これらの粘着性付与剤は、１種単独でまたは２種以上組み合わせて用いることができる。
【００６１】
本発明に係るホットメルト接着剤組成物は、上記オレフィン系ブロック共重合体と粘着性付与樹脂（Ｂ）とを含み、オレフィン系ブロック共重合体と粘着性付与樹脂（Ｂ）との合計量１００重量部に対して、オレフィン系ブロック共重合体を１０〜９０重量部、好ましくは２０〜８５重量部、より好ましくは３０〜８０重量部、粘着性付与樹脂（Ｂ）を９０〜１０重量部、好ましくは８０〜１５重量部、より好ましくは７０〜２０重量部の量で含んでいる。
本発明のホットメルト接着剤組成物は、上記オレフィン系ブロック共重合体と粘着性付与樹脂（Ｂ）、および必要に応じて、前記各種の添加剤を、所定の配合割合でブラベンダーなどの混合機に供給し、加熱して溶融混合して、これを所望の形状、例えば粒状、フレーク状、棒状などに成形することによって調製することができる。
【００６２】
本発明に係る成形体は、強度や透明性などの物性バランスが優れる前記した本発明に係るオレフィン系ブロック共重合体と、本発明以外の熱可塑性樹脂とを含んでなる重合体組成物として、建材・土木用成形体、自動車用内外装材またはガソリンタンク、電気電子部品、医療用成形体、雑貨成形体などの成形体として、好適に用いられる。
これらのオレフィン系ブロック共重合体は通常単独で用いてもよいし、水酸化マグネシウムなどの無機充填材またはビニルトリメトキシシランなどの架橋剤と併用して用いることができる。本発明においては、水酸化マグネシウムなどの無機充填材、ビニルトリメトキシシランなどの架橋剤と併用して用いることもできる。
また前記のようなオレフィン系ブロック共重合体と磁性粉を混練することにより、優れた磁気記録用素材を得ることができる。この場合、オレフィン系ブロック共重合体と磁性粉との配合比率（オレフィン系ブロック共重合体／磁性粉：重量比）は、９９／１〜１０／９０であることが好ましい。また、これらはプラスチックマグネットとして文房具などに好ましく用いることができる。
【００６３】
本発明に係る医療・衛生用成形体は、使用する用途に応じて、例えば上記オレフィン系ブロック共重合体などの製造方法と同様にしてカレンダー成形、押出成形、射出成形、ブロー成形、プレス成形、スタンピング成形などによって製造することができる。このようにして得られる医療・衛生用成形体は、シート、フィルム、中空成形体などである。また、得られるシート、フィルムなどを用いて、さらに不織布積層体などの成形体を得ることもできる。
フィラメントは、例えば溶融した組成物を、紡糸口金を通して押出すことにより製造することができる。
本発明では必要に応じて、無機フィラーを添加して使用することもできる。これらの添加量は、接着性樹脂１００重量部に対して、前記オレフィン系ブロック共重合体は通常５〜５０重量部、好ましくは５〜２０重量部であり、無機フィラーは通常１０〜６０重量部、好ましくは２０〜４０重量部であることが望ましい。
【００６４】
本発明に係るフィルムまたはシートは、組成の異なる２層以上の層から成る多層構造のフィルムまたはシートであって、これらの層のうち少なくとも１層が前記した本発明に係るオレフィン系ブロック共重合体から成る層であり、外観、機械強度特性に優れたフィルムまたはシートとして好適に用いられる。オレフィン系ブロック共重合体を用いて得られるフィルムまたはシートは、特に透明性、耐熱性、防雲性に優れるため、農業用、ラップ用として好ましい。
本発明のフィルムおよびシートを成形する方法としては、具体的には、押出成形、射出成形、インフレーション成形、ブロー成形、押出ブロー成形、射出ブロー成形、プレス成形、真空成形、カレンダー成形、発泡成形などが挙げられる。
【００６５】
本発明に係る改質剤は、前記した本発明に係るオレフィン系ブロック共重合体を含んで成る改質剤であり、樹脂用、ゴム用、ワックス用、潤滑用、セメント用またはインキ・塗料用の改質剤として、好適に用いられる。
本発明に係る各種改質剤用の改質剤は、上記オレフィン系ブロック共重合体と、樹脂、ゴム、潤滑油用基材、ワックス、セメントまたはインキ・塗料とを含むオレフィン系重合体組成物であってもよい。
【００６６】
本発明に係る分散体は、前記した本発明に係るオレフィン系ブロック共重合体と本発明以外の熱可塑性樹脂とを含んでなる分散体として、水性樹脂分散体、油性樹脂分散体として、好適に用いられる。
熱可塑性樹脂の配合量は特に限定されないが、熱可塑性樹脂１００重量部に対し、上記オレフィン系ブロック共重合体を、通常０．０１〜１５０重量部、必要に応じて充填剤を０．０１〜３００重量部、好ましくはオレフィン系ブロック共重合体を０．１〜２０重量部、充填剤を０．１〜４０重量部、さらに好ましくはオレフィン系ブロック共重合体を０．５〜１０重量部、充填剤を０．５〜２０重量部の量で用いることが好ましい。
【００６７】
【実施例】
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【００６８】
〔実施例１〕
［触媒溶液の調製］
窒素置換を十分行ったガラス容器に、ビス（１，３−ジメチルシクロペンタジエニル）ジルコニウムジクロリド１０．０ｍｇを秤量し、これにメチルアルミノキサンのトルエン溶液をアルミニウム原子が１７．２ｍｍｏｌとなるように加え、２３℃で１５分間超音波照射を行った。次いで適当量のトルエンを添加して全体を５０ｍｌとし、これを触媒溶液とした。
【００６９】
［エチレン／１０−ウンデセン−１−オール共重合］
十分に窒素置換した内容積１リットルのステンレス製オートクレーブに、室温、窒素雰囲気下で１０−ウンデセン−１−オールを２１ｇ含むシクロヘキサン溶液６００ｍｌを装入した。次いで、トリイソブチルアルミニウム１５０ｍｍｏｌを添加し、系内をエチレンで置換した。エチレンで加圧、さらに昇温し、系内の温度が５０℃、全圧が０．７ＭＰａとした。そこで上記のように調製した触媒溶液１２．８ｍｌを反応器内へ加圧窒素を用いて圧入し、重合を開始した。その後はエチレンのみを供給し、全圧０．７ＭＰａ、５０℃で３０分間重合を行った。重合開始から３０分後、イソプロパノール（ＩＰＡ）５０ｍｌを加圧窒素を用いて反応器内へ圧入して、重合反応を停止させた。
脱圧後ポリマー溶液を取り出し、水１リットルに対し濃塩酸５０ｍｌを添加した水溶液と該ポリマー溶液とを、１：１の割合でホモミキサーを用いて強撹拌下で接触させ、触媒残渣を水相へ移行させた。この接触混合液を静置した後水相を分離除去し、さらに水洗を２回行って重合液相を精製分離した。
次いで精製分離した重合液を３倍量のメタノールと強撹拌下で接触させ、共重合体を析出させた後、固体部（共重合体）をろ過により採取し、メタノールで十分洗浄した。固体部をろ過により採取し、窒素流通下、８０℃、１６０ｍｍＨｇで１０時間減圧乾燥した。
このようにして得られたエチレン／１０−ウンデセン−１−オール共重合体（Ｃ２／Ｕｎ−ＯＨ）の収量は２５．７ｇであった。したがって触媒活性は４１．８ｋｇ／ｍｍｏｌ−Ｚｒ・ｈｒであった。ＮＭＲ分析の結果、１０−ウンデセン−１−オールの含量は２．５モル％であった。また、ＧＰＣ測定の結果、Ｍｗ（重量平均分子量）は８０，０００であった。ＧＰＣ測定とＮＭＲ分析から、得られたポリオレフィンの主鎖末端および側鎖末端、あるいは側鎖末端のみに水酸基が存在していることを確認した。
【００７０】
［末端リチウム化］
前記の水酸基含有ポリエチレン２．５ｇにトルエン３０ｍｌを加え、１．６Ｍのｎ−ブチルリチウムのヘキサン溶液を１ｍｌ加えて、室温で２４時間攪拌した。反応後のスラリーを−２０℃まで冷却し、濾別したポリエチレンを−２０℃に冷却しながらトルエンで数回洗浄した。得られたポリエチレンの末端がリチウム化されていることは^１Ｈ−ＮＭＲによって確認した。
【００７１】
［アニオン重合］
前記のようにして得られた末端Ｌｉポリエチレン２．０ｇにベンゼン３０ｍｌとメタクリル酸メチル（ＭＭＡ）３０ｍｌとを加え、２０℃で１００時間、マグネチックスターラーで攪拌して反応させた。反応はメタノールを添加することによって停止させ、ポリマーをヘキサンで充分に洗浄した後、４５℃で減圧乾燥した。
ＭＭＡの転化率は１０．５％であり、得られたブロック共重合体のポリＭＭＡセグメントのトライアッドタクティシティは７７％であった。得られたブロック共重合体が、ポリエチレンとポリＭＭＡとがエーテル酸素を介して結合したブロック共重合体であることは^１３Ｃ−ＮＭＲで確認した。
【００７２】
〔実施例２〕
［スチレン重合］
密閉したフラスコに実施例１にて調製した末端Ｌｉポリエチレンの１０ｇを入れ、乾燥スチレン（Ｓｔ）５．０ｇ、ＴＨＦ５０ｍｌを加えて反応を開始した。室温で１３５時間撹拌した後、１０ｍｌのメタノールを加えて反応を停止させた。析出したポリマーはソックスレー抽出器により窒素雰囲気下、２４時間かけてアセトン、ヘプタンで抽出分取し、不溶成分としてポリエチレン／ポリスチレンブロック共重合体を得た。
下記式により算出したポリスチレン（ＰＳｔ）部の重量平均分子量（Ｍｗ_２）は５，０００であった。
Ｍｗ_２＝Ｍｗ_１・（Ｗ_２−Ｗ_１）／Ｗ_１
上記式において
Ｍｗ_１：水酸基含有ポリエチレン部のＭｗ
Ｍｗ_２：ＰＳｔ部のＭｗ
Ｗ_１：スチレン重合に使用したの末端Ｌｉポリエチレン重量
Ｗ_２：ジブロック共重合体の収量
をそれぞれ示す。
このようにして調製したジブロック共重合体は、ＭＦＲ（２３０℃）が１４ｇ／１０分であり、Ｍｗ／Ｍｎが２．５であった。
【００７３】
〔実施例３〕
［触媒溶液の調製］
窒素置換を十分行ったガラス容器に、エチレンビス（インデニル）ジルコニウムジクロリド８．０ｍｇを秤量し、これにメチルアルミノキサンのトルエン溶液をアルミニウム原子が２０ｍｍｏｌとなるように加え、２３℃で１５分間超音波照射を行った。次いで適当量のトルエンを添加して全体を２０ｍｌとし、これを触媒溶液とした。
［プロピレン／ブロモウンデセン共重合］
十分に窒素置換した内容積１リットルのガラス性重合器に、室温、窒素雰囲気下でブロモウンデセン８．０ｇ含むトルエン溶液５００ｍｌを装入した。系内をプロピレンで置換した後、昇温し、系内の温度を５０℃とした。そこで上記のように調製した触媒溶液を反応器内へ導入し、重合を開始した。プロピレンを１００Ｌ／時の割合で重合系内に供給し、常圧下、５０℃で３０分間重合を行った。重合開始から３０分後、イソプロパノール（ＩＰＡ）１０ｍｌを導入して、重合反応を停止させた。
重合液を、少量の塩酸を含んだ３倍量のメタノールと強撹拌下で接触させ、共重合体を析出させた後、固体部（共重合体）をろ過により採取し、メタノールで十分洗浄した。固体部をろ過により採取し、窒素流通下、８０℃、１６０ｍｍＨｇで１０時間減圧乾燥した。
このようにして得られたプロピレン／ブロモウンデセン（Ｃ３／Ｕｎ−Ｂｒ）の収量は７．７ｇであった。
ＮＭＲ分析の結果、ブロモウンデセンの含量は１．５モル％であった。また、ＧＰＣ測定の結果、Ｍｗ（重量平均分子量）は３０，０００であった。ＧＰＣ測定とＮＭＲ分析から、得られたポリオレフィンの主鎖末端および側鎖末端にブロモ原子が存在していることを確認した。
【００７４】
［スチレン重合］
密閉したフラスコにｎ−ブチルリチウムヘキサン溶液（１．６Ｍ）を１．６ｍｌ入れ、乾燥スチレン（Ｓｔ）５．０ｇ、シクロヘキサン５０ｍｌを加えて反応を開始した。５０℃で１時間撹拌した後、１ｍｌの重合液を１０ｍｌのメタノール中に加えて反応を停止させた。析出したポリマーはＧＰＣ測定の結果、Ｍｗ＝８６００、Ｍｗ／Ｍｎ＝１．１の重合体であった。
【００７５】
［カップリング反応］
上記調製したプロピレン／ブロモウンデセン共重合体２．２４ｇをシクロヘキサン１００ｍｌ中に懸濁させ、残りの重合液を加えて、室温で７２時間攪拌した。１０ｍｌのメタノールを加えて反応を停止させた。析出したポリマーはソックスレー抽出器により窒素雰囲気下、２４時間かけてアセトン、ヘプタンで抽出分取し、不溶成分としてポリプロピレン／ポリスチレンブロック共重合体を得た。
【００７６】
〔実施例４〕
［ＭＭＡ重合］
密閉したフラスコにｎ−ブチルリチウムヘキサン溶液（１．６Ｍ）を１．６ｍｌ入れ、乾燥ＭＭＡ３．０ｇ、シクロヘキサン５０ｍｌを加えて反応を開始した。５０℃で１時間撹拌した後、１ｍｌの重合液を１０ｍｌのメタノール中に加えて反応を停止させた。析出したポリマーはＧＰＣ測定の結果、Ｍｗ＝５２００、Ｍｗ／Ｍｎ＝１．１の重合体であった。
【００７７】
［カップリング反応］
上記調製したプロピレン／ブロモウンデセン共重合体２．２４ｇをシクロヘキサン１００ｍｌ中に懸濁させ、残りの重合液を加えて、室温で１２０時間攪拌した。１０ｍｌのメタノールを加えて反応を停止させた。析出したポリマーはソックスレー抽出器により窒素雰囲気下、２４時間かけてアセトン、ヘプタンで抽出分取し、不溶成分としてポリプロピレン／ポリメタクリル酸メチルブロック共重合体を得た。
【００７８】
〔実施例５〕
実施例１で得られたジブロック共重合体を２００℃でプレス成形およびチューブ成形し、試験片を得た。この試験片を用いて各物性を下記のように測定した。結果を表１に示す。
ＪＩＳ　Ａ硬度（Ａ）
ＪＩＳ　Ｋ７２１５に準拠した。
引張強度
ＪＩＳ　Ｋ６２５１に準拠して、ＪＩＳ　３号ダンベルを用い、スパン間：２０ｍｍ、引張速度：５００ｍｍ／分で２３℃にて測定した。
接着性試験
ＪＩＳ　Ｋ６２５６に準拠して試験した。
ＴＭＡ（針入温度：耐熱性）
１．８ｍｍφの圧子を用い２ｋｇ／ｃｍ^２、昇温速度５℃／分の条件で針入温度を求めた。
表面硬度（ショアーＡ硬度）
ＡＳＴＭ　Ｄ６７６に準拠して測定した。
耐傷つき性（マルテンス硬度）
マルテンス硬度：ダイアモンド針に２０ｇの荷重をかけこれでプレス試験片に傷を付け、この傷の幅を読みとりこの値の逆数をマルテンス硬度とした。
繰り返しインパルス
１ｍｍの単線導体に内部導電層を形成し、その周囲に試験を行う共重合体の絶縁層（厚さ１．５ｍｍ）を形成した。このケーブルの雷インパルス試験１００ｋＶを５分間隔で印加）を行った。
破壊電圧
ＡＳＴＭ　Ｄ−１４９に準拠して１ｍｍのプレスシートを用い、２５℃で測定した。
【００７９】
〔比較例１〕
エチレン・ブテン共重合体（エチレン含量：８８モル％、密度：８８５ｋｇ／ｍ^３、Ｍｗ：１５５，０００、Ｍｗ／Ｍｎ：１．８７）を用いこと以外は実施例５と同様に各物性を測定した。結果を表１に示す。
【００８０】
【表１】

耐熱性、柔軟性、耐傷つき性、繰り返しインパルス、絶縁破壊電圧で実施例５が優れている。
【００８１】
【発明の効果】
本発明に係るオレフィン系ブロック共重合体は、主鎖を構成するポリオレフィンセグメントと側鎖を構成するポリ（メタ）アクリル酸エステルセグメントあるいは芳香族系ビニル化合物セグメントとが化学的に結合したブロック共重合体であり、両セグメントの物性、特性を兼ね備えた重合体ゆえに、耐熱性、柔軟性、電気特性などに優れる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an olefin-based block copolymer, a method for producing the olefin-based block copolymer, and its use, and more specifically, an olefin-based block copolymer having a specific structure including a polyolefin segment and a functional segment, a method for producing the olefin-based block copolymer, and a use thereof About.
[0002]
[Prior art]
Polyolefins are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extruded products, injection molded products, hollow molded products, films, sheets, etc., and used for various applications. I have. However, since polyolefin is a so-called non-polar resin having no polar group in the molecule, it has poor affinity for various polar substances such as metals, and it is difficult to adhere to the polar substance or blend with the polar resin. Was. Also, the surface of the molded article made of polyolefin is hydrophobic, and in applications where anti-fogging properties and antistatic properties are required, it is necessary to incorporate a low molecular weight surfactant, etc. Problems such as dirt sometimes occurred.
[0003]
In recent years, the demand for physical properties of polyolefins has been diversified. For example, polyolefins having various properties such as polyolefins having excellent heat resistance and polyolefins having a soft feel such as soft polyvinyl chloride have been desired.
Methods for improving the physical properties of polyolefins include methods for adjusting the type of monomers, molar ratio, etc., methods for changing monomer arrangements such as random and block, and methods for graft copolymerizing polar monomers to polyolefins. Methods have been tried.
[0004]
When a polar monomer (polar olefin) is graft-copolymerized to a polyolefin, a method of reacting a polyolefin with a radical polymerizable monomer in the presence of a radical initiator is generally performed. The graft copolymer often contains a homopolymer of a radically polymerizable monomer or an unreacted polyolefin, and has a non-uniform graft structure. Furthermore, since the cross-linking reaction and the decomposition reaction of the polymer chain are accompanied with the graft polymerization, the physical properties of the polyolefin often change greatly. WO 98/02472 discloses a method for synthesizing a block polymer of a polyolefin and a polar polymer without the above-described crosslinking / decomposition reaction, after adding a boron compound to a polyolefin having an unsaturated bond at a terminal. A method is described in which radical polymerization active species are formed by oxidation with oxygen, and then radical polymerization is performed.
[0005]
As a method for producing a block (co) polymer comprising two different polymer segments, JP-A-60-252614, JP-A-60-252623, JP-A-5-503546, JP-A-8-92338 and JP-A-9-87343 disclose methods utilizing living polymerization. Japanese Patent Application Laid-Open No. 60-252614 discloses a method of producing a block copolymer comprising a polyolefin segment and a polymethacrylate segment by living polymerization. However, in this method using living polymerization, only one polymer can be obtained from one catalytically active point, and the number of polymers obtained from one catalytically active point is preferably as large as possible from the viewpoint of cost.
[0006]
[Problems to be solved by the invention]
The present inventors have studied based on such conventional techniques, and as a result, have found that a specific block copolymer containing a polyolefin segment and a functional segment can solve the above-described problems. A block copolymer and a method for producing the same have been found.
[0007]
[Means for Solving the Problems]
The first olefin-based block copolymer of the present invention is obtained by reacting a polyolefin having a hydroxyl group only at a main chain terminal and a side chain terminal or only at a side chain terminal with an organic lithium compound or an organic phosphorus compound to obtain a compound represented by the following general formula ( A polyolefin having a lithium or phosphorus-containing group at the terminal represented by I),
PO¹-O-LP ... (I)
(Where PO¹Represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and LP represents a lithium or phosphorus-containing group. )
Next, it comprises a polyolefin segment and a poly (meth) acrylate segment obtained by anionically polymerizing a (meth) acrylate ester in the presence of a polyolefin having a lithium or phosphorus-containing group at the terminal. .
[0008]
In addition, the second olefin block copolymer of the present invention is obtained by reacting a polyolefin having a hydroxyl group at a main chain terminal and / or a side chain terminal with an organic lithium compound or an organic phosphorus compound to obtain a compound represented by the following general formula (II): A polyolefin having a lithium or phosphorus-containing group at the terminal represented by
PO²-O-LP (II)
(Where PO²Represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and LP represents a lithium or phosphorus-containing group. )
Next, it is characterized by comprising a polyolefin segment and a polyaromatic vinyl compound segment obtained by anionic polymerization of an aromatic vinyl compound in the presence of a polyolefin having a lithium or phosphorus-containing group at the terminal.
[0009]
Further, the third olefin block copolymer of the present invention is obtained by anionic polymerization of a (meth) acrylic ester in the presence of an alkyl metal compound to form a main chain terminal and / or side chain represented by the following formula (III). It is characterized by comprising a polyolefin segment and a poly (meth) acrylate segment obtained by terminating the reaction by contacting with a polyolefin having a halogen atom at the chain end.
PO³-X ... (III)
(Where PO³Represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and X represents a halogen atom. )
[0010]
Further, the fourth olefin block copolymer of the present invention is obtained by subjecting an aromatic vinyl compound to anionic polymerization in the presence of an alkyl metal compound to form a main chain terminal and / or side chain represented by the following general formula (III). It is characterized by comprising a polyolefin segment and a polyaromatic ring-containing vinyl compound segment obtained by terminating the reaction by contacting with a polyolefin having a halogen atom at a terminal.
PO³-X ... (III)
(Where PO³Represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and X represents a halogen atom. )
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the olefin block copolymer according to the present invention will be specifically described.
The polyolefin represented by the general formula (I) that forms the olefin-based block copolymer according to the present invention is a copolymer of a hydroxyl group-containing olefin and an olefin having 2 to 20 carbon atoms, and / or two types. It is a copolymer comprising the above olefin having 2 to 20 carbon atoms. Alternatively, the polyolefin represented by the general formula (I) includes a copolymer of a non-conjugated polyene and an olefin having 2 to 20 carbon atoms and / or two or more olefins having 2 to 20 carbon atoms. Is a polymer obtained by modifying a terminal vinyl group of the copolymer represented by the formula into a hydroxyl group. Alternatively, the polyolefin represented by the general formula (I) includes a copolymer of a halogenated olefin and an olefin having 2 to 20 carbon atoms and / or two or more olefins having 2 to 20 carbon atoms. Is a polymer obtained by modifying a terminal halogen atom of the copolymer represented by the formula into a hydroxyl group.
[0012]
The polyolefin represented by the general formula (II) that forms the olefin-based block copolymer according to the present invention is a copolymer with an olefin having 2 to 20 carbon atoms and / or two or more carbon atoms having 2 carbon atoms. It is a copolymer containing up to 20 olefins. Alternatively, it is a copolymer of a hydroxyl group-containing olefin and an olefin having 2 to 20 carbon atoms, and / or a copolymer containing two or more olefins having 2 to 20 carbon atoms. Alternatively, the polyolefin represented by the general formula (II) includes a copolymer of a non-conjugated polyene and an olefin having 2 to 20 carbon atoms and / or two or more olefins having 2 to 20 carbon atoms. Is a polymer obtained by modifying a terminal vinyl group of the copolymer represented by the formula into a hydroxyl group. Alternatively, the polyolefin represented by the general formula (II) includes a copolymer of a halogenated olefin and an olefin having 2 to 20 carbon atoms and / or two or more olefins having 2 to 20 carbon atoms. Is a polymer obtained by modifying a terminal halogen atom of the copolymer represented by the formula into a hydroxyl group.
[0013]
The polyolefin represented by the general formula (III) that forms the olefin-based block copolymer according to the present invention is a copolymer of a halogenated olefin and an olefin having 2 to 20 carbon atoms, and / or two types. It is a copolymer comprising the above olefin having 2 to 20 carbon atoms. Alternatively, the polyolefin represented by the general formula (III) contains a copolymer of a non-conjugated polyene and an olefin having 2 to 20 carbon atoms and / or two or more olefins having 2 to 20 carbon atoms. Is a polymer obtained by modifying the terminal vinyl group of the copolymer represented by the formula (1) to a halogen atom-containing group.
[0014]
When these polyolefin segments have stereoregularity, they may be either isotactic polyolefins or syndiotactic polyolefins.
Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and non-conjugated polyenes.
[0015]
Specific examples of the linear or branched α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, A linear α-olefin having 2 to 20, preferably 2 to 10 carbon atoms, such as hexadecene, 1-octadecene and 1-eicosene; for example, 3-methyl-1-butene, 4-methyl-1-pentene; 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1- Preferably, 5 to 20, more preferably 5 to 10 branched α-olefins such as hexene and 3-ethyl-1-hexene are exemplified.
[0016]
Examples of the cyclic olefin include those having 3 to 20, preferably 5 to 15 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-methylstyrene. Mono- or polyalkylstyrenes such as ethylstyrene are mentioned.
Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, and 1,3-hexadiene. , 1,3-octadiene and the like having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.
[0017]
Examples of the non-conjugated polyene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, -Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1 , 4,8-Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropen-2-norbornene, 2, -Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms. .
[0018]
Examples of the hydroxyl group-containing olefin include a terminal hydroxylated olefin compound.
Specific examples of the terminal hydroxylated olefin compound include vinyl alcohol, hydroxyl-1-butene, hydroxyl-1-pentene, hydroxyl-1-hexene, hydroxyl-1-octene, hydroxyl-1-decene, C2-C20 such as hydroxyl-1-undecene, hydroxyl-1-dodecene, hydroxyl-1-tetradecene, hydroxyl-1-hexadecene, hydroxyl-1-octadecene and hydroxyl-1-eicosene; Preferably 2 to 10 linear hydroxylated α-olefins; for example, 3-methyl-1-butene hydroxide, 4-methyl-1-pentene hydroxide, 3-methyl-1-pentene hydroxide; 3-ethyl-1-pentene hydroxide, 4,4-dimethyl-1-pentene hydroxide, 4-methyl-1-hexene hydroxide, 4,4-dimethyl-1-hexene hydroxide, hydroxide -4-eth 1-hexene, preferably such as hydroxide-3-ethyl-1-hexene 5-20, or more preferably branched hydroxide α- olefins 5-10.
[0019]
Specific examples of the halogenated olefin include vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, and halogenated-1-hexene having a Group 17 atom such as chlorine, bromine, and iodine. -1-octene, halogenated-1-decene, hydroxyl-1-undecene, halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated- Linear halogenated α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as 1-eicosene; for example, halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene , Halogenated-3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4,4-dimethyl-1-pentene Preferred such as phenyl, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene and 3-ethyl-1-hexene halides. Is 5 to 20, more preferably 5 to 10 branched halogenated α-olefins.
[0020]
Each of the polyolefins represented by the above general formulas (I) to (III) has a weight average molecular weight (Mw) of 1,000 to 10,000,000, as determined by gel permeation chromatography (GPC). More preferably, it is 1,500 to 5,000,000. The molecular weight distribution (Mw / Mn) represented by the ratio to the number average molecular weight (Mn) is preferably 1.5 or more, more preferably 1.7 or more.
[0021]
The (meth) acrylate used in the anionic polymerization according to the present invention includes, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate , Vinyl acrylate, 2-methoxyethyl methacrylate, 2- (N, N-diethylamino) ethyl methacrylate, and the like. These (meth) acrylic acid esters can be used alone or in combination of two or more. As the combination of the (meth) acrylic ester, two or more selected from acrylic esters, two or more selected from methacrylic esters, one or more selected from acrylic esters, and one or more selected from methacrylic esters And a combination with Of these, it is preferable to produce a poly (meth) acrylate segment by copolymerizing two or more (meth) acrylates.
[0022]
Examples of the aromatic vinyl compound used for anionic polymerization according to the present invention include compounds represented by the following formula.
[0023]
Embedded image

In the above formula, R³And R⁴May be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Also, R⁵Represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specific examples include a methyl group, an ethyl group, a propyl group and an isopropyl group, and a chlorine atom, a bromine atom and an iodine atom. N represents an integer of usually 0 to 5, preferably 1 to 5.
[0024]
Specific examples of the aromatic vinyl compound represented by the above formula include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene and the like.
Specific examples of the vinyl compound containing a heterocyclic compound residue include 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, and 2-isopropenylpyridine. , 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, N-vinylpyrrolidone and the like.
Among these, a polyaromatic vinyl compound segment can be produced by copolymerizing two or more aromatic vinyl compounds.
[0025]
In the anionic polymerization according to the present invention, a copolymer segment can be produced by using a (meth) acrylate and an aromatic vinyl compound in combination.
[0026]
Next, a method for producing the olefin-based block copolymer will be described.
In the method for producing the first olefin-based block copolymer (A-1) according to the present invention, a polyolefin having a hydroxyl group only at a main chain terminal and a side chain terminal, or only at a side chain terminal, and an organic lithium compound or an organic phosphorus compound To give a polyolefin having a lithium or phosphorus-containing group at the terminal, and then polymerizing a (meth) acrylate in the presence of the polyolefin having a lithium or phosphorus-containing group at the terminal to obtain a polyolefin segment and a poly (meth) ) A block copolymer (A-1) comprising an acrylate segment is produced.
[0027]
In the second method for producing an olefin-based block copolymer (A-2) according to the present invention, a polyolefin having a hydroxyl group at a main chain terminal and / or a side chain terminal is reacted with an organic lithium compound or an organic phosphorus compound. To give a polyolefin having a lithium or phosphorus-containing group at the terminal, and then polymerizing an aromatic vinyl compound in the presence of a polyolefin having a lithium or phosphorus-containing group at the terminal to obtain a polyolefin segment and a polyaromatic vinyl compound segment. And a block copolymer (A-2) comprising:
[0028]
In the third method for producing an olefin-based block copolymer (A-3) according to the present invention, (meth) acrylic acid ester is anionically polymerized in the presence of an alkyl metal compound to form a main chain terminal and / or a side chain terminal. The olefin block copolymer (A-3) comprising a polyolefin segment and a poly (meth) acrylate segment is produced by contacting a polyolefin having a halogen atom with the polyolefin to stop the reaction.
[0029]
Further, in the fourth method for producing an olefin block copolymer (A-4) according to the present invention, an aromatic vinyl compound is anionically polymerized in the presence of an alkyl metal compound to form a polymer at the main chain terminal and / or the side chain terminal. An olefin block copolymer (A-4) composed of a polyolefin segment and a polyaromatic vinyl compound segment is produced by stopping the reaction by contacting with a polyolefin having a halogen atom.
[0030]
Polyolefins having hydroxyl groups only at the main chain terminals and side chain terminals, or only at the side chain terminals, can be produced, for example, in the presence of an olefin polymerization catalyst to produce a polyolefin in which only the main chain terminals and the side chain terminals, or only the side chain terminals are modified. Then, after performing a substitution reaction between the terminal group of the terminal-modified polyolefin and a compound having a functional group structure, and performing solvolysis, or forming a functional group by solvolysis of the terminal group of the terminal-modified polyolefin. By performing a substitution reaction with a compound having the following formula, followed by solvolysis.
The polyolefin having a hydroxyl group at a main chain terminal and / or a side chain terminal is produced by, for example, producing a polyolefin having a main chain terminal and / or a side chain terminal modified in the presence of an olefin polymerization catalyst, and then preparing a terminal of the terminal-modified polyolefin. After performing a substitution reaction between the group and a compound having a functional group structure, solvolysis is performed, or the substitution reaction with a compound having a structure that forms a functional group by solvolysis of the terminal group of the terminal-modified polyolefin is performed. It can be produced by solvolysis after the reaction. The polyolefin having a halogen atom at a main chain terminal and / or a side chain terminal is obtained by, for example, copolymerizing an olefin having 2 to 20 carbon atoms with a halogenated olefin in the presence of an olefin polymerization catalyst to obtain a main chain terminal and / or a side chain. A terminal-modified polyolefin can be produced. Alternatively, it can be produced by copolymerizing an olefin having 2 to 20 carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst, and modifying the terminal vinyl group of the obtained copolymer to a halogen atom-containing group. .
[0031]
First, the olefin polymerization catalyst used for producing the terminal-modified polyolefin will be described.
The olefin polymerization catalyst used for producing the terminal-modified polyolefin may be any conventionally known catalyst. Examples of conventionally known catalysts include, for example, a magnesium-supported titanium catalyst and a metallocene catalyst. For example, the catalysts described in International Patent Publication Nos. WO 01/53369 or WO 01/27124 are suitably used.
[0032]
A copolymer with an olefin having 2 to 20 carbon atoms, and / or a copolymer containing two or more olefins having 2 to 20 carbon atoms, or a hydroxyl group-containing copolymer, in the presence of an organoaluminum compound, by the polymerization catalyst When producing a copolymer with an olefin, a terminal-modified polyolefin represented by the following general formula (IV) or (V) is produced.
PO¹-AlR¹R²… (IV)
PO²-AlR¹R²… (V)
R¹And R²Are the same or different and may be a group or atom selected from a hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom and a halogen atom.
Examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, octyl, and decyl.
[0033]
Next, -AlR of the obtained terminal-modified polyolefin¹R²The group is subjected to a substitution reaction with a compound giving a structure that forms a functional group by solvolysis, and then subjected to solvolysis to produce a polyolefin represented by the following general formula (VI) or (VII).
PO¹-OH (VI)
PO²-OH (VII)
Where PO¹, PO²Is the same as above.
Examples of the compound that provides a structure that forms a functional group by solvolysis include oxygen and ozone.
[0034]
-AlR of the terminal-modified polyolefin obtained as described above¹R²The substitution reaction between the group and a compound having a functional group structure or a compound that provides a structure that forms a functional group by solvolysis is performed at a temperature of usually 0 to 300 ° C, preferably 10 to 200 ° C, for 0 to 100 hours. It is preferably performed for 0.5 to 50 hours.
After performing the substitution reaction, the temperature for solvolysis is usually 0 to 100 ° C, preferably 10 to 80 ° C, and the solvolysis time is 0 to 100 hours, preferably 0.5 to 100 ° C. 50 hours. Solvents used for solvolysis include methanol, ethanol, propanol, butanol, water and the like.
[0035]
Further, a terminal hydroxyl group-containing polyolefin obtained by modifying a polyolefin having a terminal vinyl group is obtained by reacting a polyolefin having an unsaturated bond at a terminal with a compound containing a Group 13 element, for example, an organic aluminum compound or an organic boron compound. Then, it can also be produced by converting into a terminal-modified polyolefin represented by the general formula (IV) or (V), and then converting the terminal to a hydroxyl group as described above. The polyolefin having a terminal unsaturated bond (terminal unsaturated polyolefin) can be produced, for example, using an olefin polymerization catalyst as described above without using an organoaluminum compound.
[0036]
Further, a polyolefin having a terminal hydroxyl group obtained by modifying a polyolefin having a terminal halogen group can be produced by converting a terminal into a hydroxyl group by reacting a polyolefin having a terminal halogen with water or a hydroxyl-containing compound. it can. The polyolefin having a terminal halogen can be produced using the olefin polymerization catalyst as described above.
[0037]
The above-mentioned terminal-modified polyolefin is polymerized by a solvent suspension polymerization method, a suspension polymerization method using a liquid olefin as a solvent, or the like.
When performing solvent suspension polymerization, a polymerization-inactive hydrocarbon can be used as a polymerization solvent. Specific examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; oils such as cyclopentane, cyclohexane, and methylcyclopentane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or combinations thereof. Among these, it is particularly preferable to use an aliphatic hydrocarbon.
[0038]
When a magnesium-supported titanium catalyst system is used, in the polymerization system, the solid titanium catalyst component (a) or its prepolymerized catalyst is usually used in an amount of about 0.0001 to 1 in terms of titanium atoms per liter of polymerization volume. It is used in an amount of 50 mmol, preferably about 0.001 to 10 mmol. In the organometallic compound catalyst component (b), the metal atom in the catalyst component (b) is usually 1 to 2000 mol, preferably 1 to 2000 mol, per 1 mol of the titanium atom in the solid titanium catalyst component (a) in the polymerization system. Is used in an amount of 2 to 1000 mol. The electron donor (ED) is used in an amount of usually 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, per 1 mol of the metal atom of the organometallic compound catalyst component (b).
In the polymerization step, the hydrogen concentration is preferably 0 to 0.01 mol, preferably 0 to 0.005 mol, more preferably 0 to 0.001 mol per 1 mol of the monomer.
[0039]
The olefin polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. As the reaction solvent for suspension polymerization, the above-mentioned inert solvent can be used, or an olefin that is liquid at the reaction temperature can be used. The polymerization temperature is usually 70 ° C. or higher, preferably 80 to 150 ° C., more preferably 85 to 140 ° C., and particularly preferably 90 to 130 ° C., and the pressure is usually normal pressure to 10 MPa, preferably normal pressure. The pressure is set to ５5 MPa. The polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system. When the polymerization is carried out in two or more stages, the reaction conditions may be the same or different.
[0040]
The olefin polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. As the polymerization mode, a reaction mode of suspension polymerization is preferably employed. As a reaction solvent at this time, an inert hydrocarbon solvent can be used, or an olefin liquid at the reaction temperature can be used.
Specific examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and combinations thereof. Among these, it is particularly preferable to use an aliphatic hydrocarbon.
[0041]
In the case of producing a terminally unsaturated polyolefin using a magnesium-supported titanium catalyst system as a catalyst, the solid titanium catalyst component (a) or its prepolymerized catalyst is usually converted into titanium atoms per liter of polymerization volume. Is used in an amount of about 0.001 to 100 mmol, preferably about 0.005 to 20 mmol. The organometallic compound catalyst component (b) has a metal atom in the catalyst component (b) in an amount of usually about 1 to 2000 mol per 1 mol of the titanium atom in the solid titanium catalyst component (a) in the polymerization system. It is preferably used in an amount of about 2 to 500 mol. The electron donor (ED) is used in an amount of usually 0 mol to 10 mol, preferably 0 mol to 5 mol, per 1 mol of the metal atom of the organometallic compound catalyst component (b).
[0042]
In the polymerization step, the hydrogen concentration is usually 0 to 0.25 mol, preferably 0 to 0.20 mol, more preferably 0 to 0.15 per 1 mol of the monomer.
The polymerization temperature when using a magnesium-supported titanium catalyst system is usually in the range of about 20 to 300 ° C, preferably about 50 to 150 ° C, and the polymerization pressure is 0.01 to 10 MPa, preferably 0.05 to 10 MPa. The range is 5 MPa.
[0043]
When a terminally unsaturated polyolefin is produced using a metallocene-based catalyst as a catalyst, the concentration of the metallocene compound (c) in the polymerization system is usually 0.00005 to 0.1 mmol, preferably, 0.001 to 0.1 mmol per liter of polymerization volume. It is used in an amount of 0.0001 to 0.05 mmol. The organoaluminum oxy compound (d) has a molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (c) of 5 to 1000, preferably 10 to 400. Used in appropriate amounts. When the organoaluminum compound (b-2) is used, the amount is usually about 1 to 300 mol, preferably about 2 to 200 mol, per 1 mol of the transition metal atom in the metallocene compound (c). Used in quantity.
The polymerization temperature when using a metallocene-based catalyst is usually -20 to 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C, and the polymerization pressure is more than 0 to 8 MPa, preferably Is in the range of more than 0 to 5 MPa.
[0044]
The olefin polymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions. In the olefin polymerization, a homopolymer of olefin may be produced, or a random copolymer may be produced from two or more olefins.
[0045]
The thus-obtained terminally unsaturated polyolefin is reacted with a compound containing a Group 13 element to convert it into a terminal having a Group 13 element bonded thereto.
The compound containing a Group 13 element used in the reaction is selected from the compounds exemplified as the organic compound catalyst component, and the compounds exemplified as the organic aluminum compound or the organic boron compound are preferably used. Among them, a trialkylaluminum, a dialkylaluminum hydride or a boron compound having at least one hydrogen-boron bond is more preferable. As the organic aluminum, a dialkylaluminum hydride is particularly preferable, and as the organic boron compound, 9-borabicyclo [3 [3,1] nonane is particularly preferred.
[0046]
The reaction between the polyolefin whose terminal is an unsaturated bond terminal and the compound containing a Group 13 element is performed, for example, as follows.
{Circle around (1)} 0.1 to 50 g of polypropylene having a vinylidene group at the end and 5-1000 ml of a 0.01 to 5 mol / l-octane solution of diisobutylaluminum hydride are mixed and refluxed for 0.5 to 6 hours.
{Circle around (2)} 0.1 to 50 g of polypropylene having a vinylidene group at its end, 5 to 1000 ml of anhydrous tetrahydrofuran, and 0.05 to 10 of 0.1 to 50 ml of 9-borabicyclo [3.3.1] nonane. Mol / l-tetrahydrofuran solution and stir at 20-65 ° C for 0.5-24 hours.
[0047]
(Preparation of polyolefin having a terminal group containing lithium or phosphorus)
A method for preparing a polyolefin having a lithium or phosphorus-containing group at a terminal will be described with reference to a method for preparing a polyolefin having a lithium terminal.
The polyolefin having a terminal lithium can be obtained by reacting the polyolefin having a hydroxyl group at the terminal with an organic lithium compound. The reaction between the polyolefin having a hydroxyl group at the terminal and the organolithium compound is usually performed in a solvent.
Examples of the organic lithium compound include alkyl lithium such as butyl lithium, propyl lithium, ethyl lithium, and methyl lithium; and alkoxy lithium such as butoxy lithium, propoxy lithium, ethoxy lithium, and methoxy lithium. In the present invention, alkyl lithium is more preferably used.
[0048]
Examples of the solvent used for the reaction include the same hydrocarbons as those exemplified as the inert hydrocarbon medium.
When reacting a polyolefin having a hydroxyl group at the terminal with an organic lithium compound, the organic lithium compound is used in an amount of 0.1 to 100 mol, preferably 0.2 to 10 mol, per 1 mol of the hydroxyl group at the polyolefin terminal. Can be The reaction temperature is generally -100 to 100C, preferably 0 to 80C, and the reaction time is generally 0.1 to 48 hours, preferably 0.5 to 12 hours.
[0049]
Examples of the organic phosphorus compound used for the reaction with the polyolefin having a hydroxyl group at the terminal include tris (dimethylamino) ア ミ ノ tris (dimethylamino) phosphoranylideneamino｝ phosphonium, tris (diethylamino) ｛tris (diethylamino) phosphoranylideneamino {Phosphonium, bis (dimethylamino) bis} tris (dimethylamino) phosphoranylideneamino} phosphonium, dimethylaminotris [tris (dimethylamino) phosphoranylideneamino] phosphonium, tetrakis [tris (dimethylamino) phosphoranylideneamino] Halides such as phosphonium, tetrakistris (morpholino) phosphoranylideneamino｝ phosphonium and tetrakistris (piperidino) phosphoranylideneamino｝ phosphonium It is preferred, more preferably chloride.
As the organic phosphorus compound, a compound that can easily generate a cation is preferable, and a compound that can easily generate a phosphoranylideneaminophosphonium cation is more preferable.
The terminal phosphorus-containing group is also preferable as the above-described ring-opening polymerization active species.
In the present invention, R⁸When the stereoregularity of is controlled, it is preferable to use a polyolefin having a lithium terminal.
[0050]
In this way, a polyolefin having a terminal group containing lithium or phosphorus represented by the following general formula (I) or (II) is produced.
PO¹-O-LP ... (I)
PO²-O-LP (II)
Where PO¹, PO²Represents a polyolefin segment, and LP represents a lithium or phosphorus-containing group.
[0051]
(Production of block copolymer)
In the present invention, the (meth) acrylic ester or the aromatic vinyl compound is anionically polymerized in the presence of the polyolefin having a lithium or phosphorus-containing group at the terminal to form a polyolefin segment and a (meth) acrylic ester segment or a polyaromatic segment. A polyolefin block copolymer comprising an aromatic vinyl compound is obtained.
The polymerization is carried out by mixing a solvent with a terminal lithium- or phosphorus-containing group polyolefin and a (meth) acrylate or an aromatic vinyl compound, or by mixing a terminal lithium- or phosphorus-containing polyolefin with a liquid (meth) acrylate or aroma. It is performed by mixing with a group-based vinyl compound. Anionic polymerization active species can be formed by mixing a lithium or phosphorus-containing group polyolefin at the terminal with a solvent and a (meth) acrylate or an aromatic vinyl compound.
Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran (THF), monoglyme, and diglyme. And the like. These solvents can be used alone or in combination of two or more. Among them, aromatic hydrocarbons and ether solvents are preferably used.
[0052]
In addition, compounds useful for the formation of anionic polymerization active species such as triphenylphosphine, α, α'-dipyridyl, hexamethylphosphoramide (HMPA), titanium tetrachloride, alkyllithium, and alkoxylithium are added during polymerization. Is also good.
The polymerization is usually carried out at a polymerization temperature of -100C to 100C, preferably -80C to 80C, more preferably -70C to 70C, for 1 minute to 500 hours, preferably 10 minutes to 300 hours, more preferably Is carried out for 15 minutes to 150 hours. In this polymerization, the terminal Li polyolefin is 0.001 to 100 mol / L, preferably 0.005 to 50 mol / L, more preferably 0.01 to 10 mol / L, and still more preferably 0.1 to 5 mol / L. Used at a concentration of mol / l. The (meth) acrylic acid ester or the aromatic vinyl compound is usually used at a concentration of 0.001 to 500 mol / L, preferably 0.005 to 300 mol / L, more preferably 0.01 to 150 mol / L. used.
[0053]
In the present invention, the (meth) acrylic acid ester or the aromatic vinyl compound is anionically polymerized in the presence of an alkyl metal compound, and the reaction is brought into contact with a polyolefin having a halogen atom at a main chain terminal and / or a side chain terminal. By terminating, the present invention relates to an olefin block copolymer composed of a polyolefin segment and a poly (meth) acrylate segment or a polyaromatic vinyl compound segment.
The anionic polymerization of the (meth) acrylate or the aromatic vinyl compound is carried out by mixing the solvent with the alkyl metal compound and the (meth) acrylate or the aromatic vinyl compound, or by adding a lithium or phosphorus-containing polyolefin to the terminal. And a liquid (meth) acrylate or an aromatic vinyl compound.
[0054]
The alkyl metal compound to be used is not particularly limited as long as it is used for ordinary anionic polymerization. Specifically, for example, lithium, sodium, potassium and other Group 1 metals of the periodic table, methyllithium, ethyllithium, Butyl lithium, hexyl lithium, methyl sodium, ethyl sodium, butyl sodium, alkyl alkalis such as hexyl sodium, methyl potassium, ethyl potassium, butyl potassium, hexyl potassium, methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride And Grignard reagents such as methylmagnesium bromide, ethylmagnesium bromide, butylmagnesium bromide and hexylmagnesium bromide.
[0055]
Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran (THF), monoglyme, and diglyme. And the like. These solvents can be used alone or in combination of two or more. Among them, aromatic hydrocarbons and ether solvents are preferably used.
The contact with the polyolefin having a halogen atom at the terminal of the main chain and / or the side chain is carried out directly by anionic polymerization of the (meth) acrylate or the aromatic vinyl compound in the presence of the alkyl metal compound in a solvent. Polyolefin may be added, or it may be added and dissolved or suspended in the solvent exemplified above.
[0056]
The polymerization is usually carried out at a polymerization temperature of -100C to 100C, preferably -80C to 80C, more preferably -70C to 70C, for 1 minute to 500 hours, preferably 10 minutes to 300 hours, more preferably Is carried out for 15 minutes to 150 hours. The (meth) acrylic acid ester or the aromatic vinyl compound is usually used at a concentration of 0.001 to 500 mol / L, preferably 0.005 to 300 mol / L, more preferably 0.01 to 150 mol / L. used.
In the contact with the polyolefin having a halogen atom at the main chain terminal and / or the side chain terminal, the terminal halogenated polyolefin is 0.001 to 100 mol / L, preferably 0.005 to 50 mol / L, more preferably Is used at a concentration of 0.01 to 10 mol / l, more preferably 0.1 to 5 mol / l.
[0057]
The poly (meth) acrylate segment or the aromatic vinyl compound segment in the olefin block copolymer has a weight average molecular weight of usually 500 or more, preferably 500 to 1,000,000, more preferably 5,000. To 800,000, particularly preferably 10,000 to 500,000.
The poly (meth) acrylate segment or the aromatic vinyl compound segment in the olefin-based block copolymer is preferably 0.01 to 99.99% by weight, preferably, of the olefin-based block copolymer. It is present in an amount of from 1 to 99% by weight, more preferably from 1 to 95% by weight, particularly preferably from 1 to 90% by weight.
[0058]
As described above, the polyolefin segment (PO¹Or PO²) And a polymer containing a block copolymer in which a poly (meth) acrylate segment or an aromatic vinyl compound segment is chemically bonded.¹Or PO²Whether the polymer contains a polymer in which a poly (meth) acrylate segment or an aromatic vinyl compound segment is chemically bonded is determined by, for example, the molecular weight of the obtained polymer, the solubility in an organic solvent, or spectroscopy. Can be determined by statistical analysis. That is, the molecular weight of the polymer obtained by the method of the present invention has a segment PO of a polyolefin having a lithium or phosphorus-containing group at the terminal.¹Or PO²Having a high value with respect to the molecular weight of the olefin-based block copolymer obtained by the method of the present invention.¹Or PO²The solubility behavior of the mixture of the polymer corresponding to the above and the polymer corresponding to the segment of the polymer produced by the anionic polymerization of the polymer in the organic solvent shown in the mixture of the olefinic block copolymer obtained by the method of the present invention, To the dissolution behavior of the olefin-based block copolymer obtained by the method of the present invention.^ThirteenAnalyzed by C-NMR, segment PO¹Or PO²And those in which a target block copolymer can be produced by detecting a peak derived from a chemical bond with a poly (meth) acrylate segment or an aromatic vinyl compound of a polymer produced by anionic polymerization. You can judge.
[0059]
(Application)
The olefin block copolymer according to the present invention is a block copolymer in which a polyolefin segment constituting a main chain and a poly (meth) acrylate segment or an aromatic vinyl compound segment constituting a side chain are chemically bonded. It is a polymer that is combined and has both physical properties and characteristics of both segments.
The olefin-based block copolymer of the present invention contains various additives such as a softening agent, a stabilizer, a filler, an antioxidant, and a crystal nucleating agent, if necessary, within a range not to impair the purpose of the present invention. can do.
[0060]
The adhesive resin according to the present invention is characterized by having excellent tackiness, heat creep resistance, and fluidity, and an adhesive such as a hot melt adhesive containing the olefin block copolymer according to the present invention described above. Are preferably used.
The hot melt adhesive composition according to the present invention contains the olefin-based block copolymer and a tackifying resin (B). The tackifier (B) is compounded to adjust the viscosity of the olefin-based block copolymer as a base polymer at the time of melting and to improve hot tack property and wettability. The tackifier (B) is not particularly limited as long as it can be blended with the olefin block copolymer and can improve the hot tack and wetting of the olefin block copolymer during heating.
Specific examples of the tackifier include an alicyclic hydrogenated tackifier, rosin, modified rosin or an ester thereof, an aliphatic petroleum resin, an alicyclic petroleum resin, an aromatic petroleum resin, and an aliphatic petroleum resin. Examples of suitable tackifiers include copolymerized petroleum resins of component and aromatic components, low molecular weight styrene resins, isoprene resins, alkyls, phenol resins, terpene resins, and cumarone / indene resins. In the present invention, these tackifiers can be used alone or in combination of two or more.
[0061]
The hot melt adhesive composition according to the present invention contains the olefin block copolymer and the tackifier resin (B), and has a total amount of 100 of the olefin block copolymer and the tackifier resin (B). 10 to 90 parts by weight, preferably 20 to 85 parts by weight, more preferably 30 to 80 parts by weight, and 90 to 10 parts by weight of the tackifier resin (B), based on parts by weight. Preferably, it is contained in an amount of 80 to 15 parts by weight, more preferably 70 to 20 parts by weight.
The hot melt adhesive composition of the present invention comprises a mixture of the olefin-based block copolymer and the tackifying resin (B), and if necessary, the above-mentioned various additives in a predetermined mixing ratio such as Brabender. It can be prepared by feeding into a machine, heating and melt-mixing, and shaping this into a desired shape, for example, granule, flake, rod, and the like.
[0062]
The molded article according to the present invention is, as the polymer composition containing the olefin block copolymer according to the present invention, which has an excellent balance of properties such as strength and transparency, and a thermoplastic resin other than the present invention, It is suitably used as a molded article such as a molded article for building materials and civil engineering, an interior / exterior material for automobiles or a gasoline tank, an electric / electronic component, a molded article for medical use, and a molded article for miscellaneous goods.
These olefin block copolymers may be used alone or in combination with an inorganic filler such as magnesium hydroxide or a crosslinking agent such as vinyltrimethoxysilane. In the present invention, it can be used in combination with an inorganic filler such as magnesium hydroxide and a crosslinking agent such as vinyltrimethoxysilane.
By kneading the above-mentioned olefin block copolymer and magnetic powder, an excellent magnetic recording material can be obtained. In this case, the compounding ratio of the olefin block copolymer and the magnetic powder (olefin block copolymer / magnetic powder: weight ratio) is preferably from 99/1 to 10/90. Further, these can be preferably used as stationery and the like as a plastic magnet.
[0063]
The molded article for medical and sanitary use according to the present invention is, depending on the intended use, for example, calender molding, extrusion molding, injection molding, blow molding, press molding, and the like in the same manner as in the method for producing the olefin-based block copolymer and the like. It can be manufactured by stamping molding or the like. The medical / sanitary molded article thus obtained is a sheet, a film, a hollow molded article, or the like. Further, a molded article such as a nonwoven fabric laminate can be obtained by using the obtained sheet, film and the like.
Filaments can be made, for example, by extruding a molten composition through a spinneret.
In the present invention, an inorganic filler can be added and used as necessary. The addition amount of the olefin block copolymer is usually 5 to 50 parts by weight, preferably 5 to 20 parts by weight, and the inorganic filler is usually 10 to 60 parts by weight based on 100 parts by weight of the adhesive resin. And preferably 20 to 40 parts by weight.
[0064]
The film or sheet according to the present invention is a film or sheet having a multilayer structure composed of two or more layers having different compositions, wherein at least one of these layers is the olefin-based block copolymer according to the present invention described above. And is suitably used as a film or sheet having excellent appearance and mechanical strength characteristics. A film or sheet obtained using an olefin-based block copolymer is particularly excellent in transparency, heat resistance, and cloud-proofing properties, and thus is preferable for agricultural use and wrapping.
As a method of forming the film and sheet of the present invention, specifically, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calender molding, foam molding and the like Is mentioned.
[0065]
The modifier according to the present invention is a modifier comprising the olefin-based block copolymer according to the present invention described above, and is used for resin, rubber, wax, lubrication, cement or ink / paint. It is suitably used as a modifier for
The modifier for various modifiers according to the present invention is an olefin polymer composition containing the olefin block copolymer, a resin, a rubber, a base material for a lubricating oil, a wax, a cement or an ink or paint. It may be.
[0066]
The dispersion according to the present invention is preferably a dispersion containing the olefin-based block copolymer according to the present invention and a thermoplastic resin other than the present invention, an aqueous resin dispersion, and an oil-based resin dispersion. Used.
The blending amount of the thermoplastic resin is not particularly limited, but based on 100 parts by weight of the thermoplastic resin, the olefin-based block copolymer is usually 0.01 to 150 parts by weight, and if necessary, the filler is 0.01 to 150 parts by weight. 300 parts by weight, preferably 0.1 to 20 parts by weight of the olefin-based block copolymer, 0.1 to 40 parts by weight of the filler, more preferably 0.5 to 10 parts by weight of the olefin-based block copolymer, Preferably, the filler is used in an amount of 0.5 to 20 parts by weight.
[0067]
【Example】
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
[0068]
[Example 1]
[Preparation of catalyst solution]
In a glass container sufficiently purged with nitrogen, 10.0 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was weighed, and a toluene solution of methylaluminoxane was added thereto so that aluminum atoms became 17.2 mmol. At 23 ° C. for 15 minutes. Then, an appropriate amount of toluene was added to make the whole 50 ml, which was used as a catalyst solution.
[0069]
[Ethylene / 10-undecene-1-ol copolymerization]
A 1-liter stainless steel autoclave sufficiently purged with nitrogen was charged with 600 ml of a cyclohexane solution containing 21 g of 10-undecene-1-ol at room temperature under a nitrogen atmosphere. Next, 150 mmol of triisobutylaluminum was added, and the inside of the system was replaced with ethylene. The system was pressurized with ethylene, and the temperature was further increased, so that the temperature in the system was 50 ° C. and the total pressure was 0.7 MPa. Then, 12.8 ml of the catalyst solution prepared as described above was injected into the reactor using pressurized nitrogen to initiate polymerization. Thereafter, only ethylene was supplied, and polymerization was performed at a total pressure of 0.7 MPa and 50 ° C. for 30 minutes. Thirty minutes after the start of the polymerization, 50 ml of isopropanol (IPA) was pressed into the reactor using pressurized nitrogen to stop the polymerization reaction.
After depressurization, the polymer solution was taken out, and an aqueous solution obtained by adding 50 ml of concentrated hydrochloric acid to 1 liter of water was brought into contact with the polymer solution at a ratio of 1: 1 using a homomixer under vigorous stirring. Moved to After the contact mixture was allowed to stand, the aqueous phase was separated and removed, and further washed twice with water to purify and separate the polymerization liquid phase.
Then, the polymer solution purified and separated was brought into contact with a three-fold amount of methanol under vigorous stirring to precipitate a copolymer, and then a solid part (copolymer) was collected by filtration and sufficiently washed with methanol. The solid portion was collected by filtration, and dried under reduced pressure at 160 ° C and 160 mmHg for 10 hours under nitrogen flow.
The yield of the ethylene / 10-undecene-1-ol copolymer (C2 / Un-OH) thus obtained was 25.7 g. Therefore, the catalyst activity was 41.8 kg / mmol-Zr · hr. As a result of NMR analysis, the content of 10-undecene-1-ol was 2.5 mol%. As a result of GPC measurement, Mw (weight average molecular weight) was 80,000. From GPC measurement and NMR analysis, it was confirmed that a hydroxyl group was present only in the main chain terminal and the side chain terminal, or only in the side chain terminal of the obtained polyolefin.
[0070]
[Terminal lithium]
To 2.5 g of the hydroxyl group-containing polyethylene, 30 ml of toluene was added, and 1 ml of a 1.6 M hexane solution of n-butyllithium was added, followed by stirring at room temperature for 24 hours. The slurry after the reaction was cooled to −20 ° C., and the filtered polyethylene was washed several times with toluene while cooling to −20 ° C. The end of the obtained polyethylene is lithiated¹Confirmed by 1 H-NMR.
[0071]
[Anionic polymerization]
30 ml of benzene and 30 ml of methyl methacrylate (MMA) were added to 2.0 g of the terminal Li polyethylene obtained as described above, and the mixture was reacted by stirring with a magnetic stirrer at 20 ° C. for 100 hours. The reaction was stopped by adding methanol, the polymer was thoroughly washed with hexane, and then dried at 45 ° C. under reduced pressure.
The conversion of MMA was 10.5%, and the triad tacticity of the polyMMA segment of the obtained block copolymer was 77%. The obtained block copolymer is a block copolymer in which polyethylene and polyMMA are bonded via ether oxygen.^ThirteenConfirmed by C-NMR.
[0072]
[Example 2]
[Styrene polymerization]
10 g of the terminal Li polyethylene prepared in Example 1 was placed in a sealed flask, and 5.0 g of dry styrene (St) and 50 ml of THF were added to start the reaction. After stirring at room temperature for 135 hours, the reaction was stopped by adding 10 ml of methanol. The precipitated polymer was extracted and fractionated with acetone and heptane over 24 hours using a Soxhlet extractor under a nitrogen atmosphere to obtain a polyethylene / polystyrene block copolymer as an insoluble component.
The weight average molecular weight (Mw) of the polystyrene (PSt) part calculated by the following equation₂) Was 5,000.
Mw₂= Mw₁・ (W₂-W₁) / W₁
In the above formula
Mw₁: Mw of hydroxyl-containing polyethylene part
Mw₂: Mw of PSt part
W₁: Weight of terminal Li polyethylene used for styrene polymerization
W₂: Yield of diblock copolymer
Are respectively shown.
The diblock copolymer thus prepared had an MFR (230 ° C.) of 14 g / 10 minutes and an Mw / Mn of 2.5.
[0073]
[Example 3]
[Preparation of catalyst solution]
8.0 mg of ethylenebis (indenyl) zirconium dichloride was weighed and placed in a glass container sufficiently purged with nitrogen, and a toluene solution of methylaluminoxane was added thereto so that aluminum atoms became 20 mmol, and ultrasonic irradiation was performed at 23 ° C. for 15 minutes. Was done. Then, an appropriate amount of toluene was added to make a total of 20 ml, which was used as a catalyst solution.
[Propylene / bromoundecene copolymerization]
500 ml of a toluene solution containing 8.0 g of bromoundecene was charged at room temperature under a nitrogen atmosphere into a 1-liter glass polymerization vessel sufficiently purged with nitrogen. After replacing the inside of the system with propylene, the temperature was raised to 50 ° C. in the system. Then, the catalyst solution prepared as described above was introduced into the reactor, and polymerization was started. Propylene was fed into the polymerization system at a rate of 100 L / hour, and polymerization was performed at 50 ° C. for 30 minutes under normal pressure. Thirty minutes after the start of the polymerization, 10 ml of isopropanol (IPA) was introduced to stop the polymerization reaction.
The polymer solution was brought into contact with a three-fold amount of methanol containing a small amount of hydrochloric acid under vigorous stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and washed sufficiently with methanol. . The solid portion was collected by filtration, and dried under reduced pressure at 160 ° C and 160 mmHg for 10 hours under nitrogen flow.
The yield of propylene / bromoundecene (C3 / Un-Br) thus obtained was 7.7 g.
As a result of NMR analysis, the content of bromoundecene was 1.5 mol%. As a result of GPC measurement, Mw (weight average molecular weight) was 30,000. GPC measurement and NMR analysis confirmed that bromo atoms were present at the main chain terminals and side chain terminals of the obtained polyolefin.
[0074]
[Styrene polymerization]
1.6 ml of an n-butyllithium hexane solution (1.6 M) was placed in a sealed flask, and 5.0 g of dry styrene (St) and 50 ml of cyclohexane were added to initiate a reaction. After stirring at 50 ° C. for 1 hour, 1 ml of the polymerization solution was added to 10 ml of methanol to stop the reaction. As a result of GPC measurement, the precipitated polymer was a polymer having Mw = 8600 and Mw / Mn = 1.1.
[0075]
[Coupling reaction]
2.24 g of the propylene / bromoundecene copolymer prepared above was suspended in 100 ml of cyclohexane, the remaining polymerization liquid was added, and the mixture was stirred at room temperature for 72 hours. The reaction was stopped by adding 10 ml of methanol. The precipitated polymer was extracted and fractionated with acetone and heptane over 24 hours by a Soxhlet extractor under a nitrogen atmosphere to obtain a polypropylene / polystyrene block copolymer as an insoluble component.
[0076]
[Example 4]
[MMA polymerization]
1.6 ml of an n-butyllithium hexane solution (1.6 M) was placed in a sealed flask, and 3.0 g of dry MMA and 50 ml of cyclohexane were added to initiate the reaction. After stirring at 50 ° C. for 1 hour, 1 ml of the polymerization solution was added to 10 ml of methanol to stop the reaction. As a result of GPC measurement, the precipitated polymer was a polymer having Mw = 5200 and Mw / Mn = 1.1.
[0077]
[Coupling reaction]
2.24 g of the propylene / bromoundecene copolymer prepared above was suspended in 100 ml of cyclohexane, and the remaining polymerization liquid was added, followed by stirring at room temperature for 120 hours. The reaction was stopped by adding 10 ml of methanol. The precipitated polymer was extracted and fractionated with acetone and heptane over 24 hours using a Soxhlet extractor under a nitrogen atmosphere to obtain a polypropylene / poly (methyl methacrylate) block copolymer as an insoluble component.
[0078]
[Example 5]
The diblock copolymer obtained in Example 1 was subjected to press molding and tube molding at 200 ° C. to obtain test pieces. Each physical property was measured as follows using this test piece. Table 1 shows the results.
JIS A hardness (A)
It conformed to JIS K7215.
Tensile strength
In accordance with JIS K6251, a JIS No. 3 dumbbell was used and measured at 23 ° C. at a span interval of 20 mm and a tensile speed of 500 mm / min.
Adhesion test
The test was performed in accordance with JIS K6256.
TMA (penetration temperature: heat resistance)
2kg / cm using 1.8mmφ indenter²The penetration temperature was determined under the conditions of a heating rate of 5 ° C./min.
Surface hardness (Shore A hardness)
It was measured according to ASTM D676.
Scratch resistance (Martens hardness)
Martens hardness: A load of 20 g was applied to the diamond needle, thereby damaging the pressed test piece. The width of the scratch was read, and the reciprocal of this value was defined as the Martens hardness.
Repetitive impulse
An inner conductive layer was formed on a 1 mm single-wire conductor, and an insulating layer (thickness: 1.5 mm) of the copolymer to be tested was formed around the inner conductive layer. The cable was subjected to a lightning impulse test of 100 kV at 5 minute intervals).
Breakdown voltage
It measured at 25 degreeC using the press sheet of 1 mm according to ASTM @ D-149.
[0079]
[Comparative Example 1]
Ethylene-butene copolymer (ethylene content: 88 mol%, density: 885 kg / m³, Mw: 155,000, Mw / Mn: 1.87), except that the physical properties were measured in the same manner as in Example 5. Table 1 shows the results.
[0080]
[Table 1]

Example 5 is excellent in heat resistance, flexibility, scratch resistance, repeated impulse, and dielectric breakdown voltage.
[0081]
【The invention's effect】
The olefin-based block copolymer according to the present invention is a block copolymer in which a polyolefin segment constituting a main chain and a poly (meth) acrylate segment or an aromatic vinyl compound segment constituting a side chain are chemically bonded. Since it is a polymer having both physical properties and characteristics of both segments, it is excellent in heat resistance, flexibility, electric properties and the like.

Claims (9)

By reacting a polyolefin having a hydroxyl group only at the main chain terminal and the side chain terminal or only at the side chain terminal with an organic lithium compound or an organic phosphorus compound, a lithium or phosphorus-containing group is added to the terminal represented by the following general formula (I). Having polyolefin,
PO ¹ -O-LP (I)
(Wherein PO ¹ represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and LP represents a lithium or phosphorus-containing group.)
Next, an olefin block copolymer comprising a polyolefin segment and a poly (meth) acrylate segment obtained by anionic polymerization of a (meth) acrylate in the presence of a polyolefin having a lithium or phosphorus-containing group at the terminal. Combination (A-1). Reacting a polyolefin having a hydroxyl group at a main chain terminal and / or a side chain terminal with an organic lithium compound or an organic phosphorus compound to obtain a polyolefin having a lithium or phosphorus-containing group at a terminal represented by the following general formula (II);
^{PO 2 -O-LP ... (II} )
(Wherein PO ² represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and LP represents a lithium or phosphorus-containing group.)
Next, an olefin block copolymer comprising a polyolefin segment and a polyaromatic ring-containing vinyl compound segment obtained by anionically polymerizing an aromatic ring-containing vinyl compound in the presence of a polyolefin having a lithium or phosphorus-containing group at the terminal. Combination (A-2). The reaction is carried out by anionically polymerizing the (meth) acrylic ester in the presence of an alkyl metal compound and then contacting it with a polyolefin having a halogen atom at a main chain terminal and / or a side chain terminal represented by the following general formula (III). An olefin block copolymer (A-3) comprising a polyolefin segment and a poly (meth) acrylate segment, which is obtained by stopping.
PO ³ -X (III)
(In the formula, PO ³ represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and X represents a halogen atom.) The reaction is carried out by subjecting an aromatic ring-containing vinyl compound to anionic polymerization in the presence of an alkyl metal compound and then contacting with a polyolefin having a halogen atom at a main chain terminal and / or a side chain terminal represented by the following general formula (III). An olefin-based block copolymer (A-4) comprising a polyolefin segment and a polyaromatic ring-containing vinyl compound segment, obtained by stopping.
PO ³ -X (III)
(In the formula, PO ³ represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, and X represents a halogen atom.) An adhesive resin comprising the olefin-based block copolymer according to claim 1. A molded article comprising the olefin-based block copolymer according to claim 1. A film or sheet comprising the olefin block copolymer according to claim 1. A modifier comprising the olefin block copolymer according to claim 1. A dispersion comprising the olefin block copolymer according to claim 1.