JP2004244595A - Modified halogen-containing polyolefin-based resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified halogen-containing polyolefin-based resin obtained by the modification of introducing a suitable side chain in the halogen-containing polyolefin-based resin or a double bond in the main chain, having a practical degree of polymerization and being used by forming a polymer alloy with another resin or as a compatibilizing agent. <P>SOLUTION: This modified halogen-containing polyolefin-based resin has a structure expressed by general formula (1) [wherein, X is a halogen; and (m), (n) are each an integer] and ≥100 average degree of polymerization. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００８】
式（１）中、Ｘはハロゲン基を表し、ｍ、ｎは整数を表す。
【０００９】
本発明２は、下記一般式（２）で表される構造を有し、平均重合度が１００以上である改質ハロゲン含有ポリオレフィン系樹脂である。
【００１０】
【化８】

【００１１】
式（２）中、ｐ、ｑ、ｒは整数を表し、Ｘはハロゲン基を表し、ＹはＸとは異なるハロゲン基、水酸基、又は、ビニル基、アクリロイル基、メタアクリロイル基、チオール基、グリシジル基、シラノール基又は脂環式エポキシ基を有する化合物に由来する基を表す。
以下に本発明を詳述する。
【００１２】
本発明１の改質ハロゲン含有ポリオレフィン系樹脂は、上記一般式（１）で表される構造を有する。
本発明１の改質ハロゲン含有ポリオレフィン系樹脂は、ポリハロゲン化ビニルから脱ハロゲン化水素により主鎖の一部に二重結合を導入したような構造を有するものであり、ハロゲン基及び二重結合の含有量を調整することによりハロゲン基に由来する優れた性質を維持したまま、他の樹脂との相溶性等の諸性質をコントロールすることができる。
【００１３】
本発明１の改質ハロゲン含有ポリオレフィン系樹脂中のハロゲン基と二重結合との含有量としては特に限定されず、用途により調整することができるが、二重結合の含有量が多くなると分子全体としての極性が高くなり、極性の高い樹脂との相溶性が向上する。
【００１４】
本発明１の改質ハロゲン含有ポリオレフィン系樹脂の重合度は１００以上である。１００未満であると，他の樹脂と混練したときにポリマーブレンド表面に析出（ブリードアウト）してしまうことがある。好ましくは３００以上である。重合度の上限は特にないが，原料としてポリハロゲン化ビニルを用いるときは２万程度が上限となる。
【００１５】
本発明１の改質ハロゲン含有ポリオレフィン系樹脂を製造する方法としては特に限定されないが、例えば、ポリハロゲン化ビニルを超臨界流体中又は亜臨界流体中で脱離反応させる方法が好適である。この方法によれば、入手が容易なポリハロゲン化ビニルを原料として、複雑な工程を経ることなく、しかも原料ポリハロゲン化ビニルの重合度に近い重合度の改質ハロゲン含有ポリオレフィン系樹脂を得ることができる。また、反応条件を調整することにより、得られる改質ハロゲン含有ポリオレフィン系樹脂中のハロゲン基と二重結合の含有量を調整することができる。更に、触媒として、特別な酸、アルカリ又は遷移金属系触媒を用いることなく反応を行うことができることから、洗浄等の煩雑な工程を要することなく不純物のないの極めて高純度な改質ハロゲン含有ポリオレフィン系樹脂を得ることができる。
【００１６】
本明細書において、超臨界流体とは、臨界圧力（以下、Ｐｃともいう）以上、かつ臨界温度（以下、Ｔｃともいう）以上の条件の流体を意味する。また、亜臨界流体とは、超臨界状態以外の状態であって、反応時の圧力、温度をそれぞれＰ、Ｔとしたときに、０．５＜Ｐ／Ｐｃ＜１．０かつ０．５＜Ｔ／Ｔｃ、又は、０．５＜Ｐ／Ｐｃかつ０．５＜Ｔ／Ｔｃ＜１．０の条件の流体を意味する。上記亜臨界流体の好ましい圧力、温度の範囲は、０．６＜Ｐ／Ｐｃ＜１．０かつ０．６＜Ｔ／Ｔｃ、又は、０．６＜Ｐ／Ｐｃかつ０．６＜Ｔ／Ｔｃ＜１．０である。ただし、流体が水である場合には、亜臨界流体となる温度、圧力の範囲は、０．５＜Ｐ／Ｐｃ＜１．０かつ０．５＜Ｔ／Ｔｃ、又は、０．５＜Ｐ／Ｐｃかつ０．５＜Ｔ／Ｔｃ＜１．０である。
【００１７】
上記超臨界流体又は亜臨界流体は、水又は常温常圧で液体の有機溶媒であることが好ましい。これらは単独で用いられても良いし、混合流体として用いられても良い。水は使いやすい流体であるうえ、安価であるので経済的であり、環境に与える影響の点でも好ましい。また、有機溶媒の中でもアルコールは、同様の理由により好ましい。
上記超臨界流体又は亜臨界流体として水のみを用いる場合には、原料ポリハロゲン化ビニルの溶解性が小さいために充分に反応が進行しない可能性がある。しかし、水に有機溶媒を混合し、混合流体とすることにより、ポリハロゲン化ビニルの溶解度を向上させ、反応を良好に行わせることができる。
【００１８】
上記有機溶媒としては、例えば、メタノール、エタノール、イソプロパノール等のアルコールや、アセトン、メチルエチルケトン、メチルフェニルケトン等のケトン等が挙げられる。また、ジメチルスルホキシド等のスルホキシド類、ジメチルホルムアミド等のアミン類、ジエチルエーテル、ジメチルエーテル等のエーテル類、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、シクロヘキサン等の脂肪族炭化水素類が挙げられる。
【００１９】
また、上記超臨界流体又は亜臨界流体は、二酸化炭素であることも好ましい。
二酸化炭素を用いた場合も、上記有機溶媒の場合と同様に、原料ポリハロゲン化ビニルの溶解度を向上させて反応を良好に行わせることができる。また、二酸化炭素は臨界温度が低いことから、原料ポリハロゲン化ビニルが熱安定性に欠ける場合であっても安定して反応を行うことができる。
また、超臨界流体又は亜臨界流体として二酸化炭素を用いる場合には、常温常圧で液体の場合と同じく、メチルアルコール、エチルアルコール、イソプロパノール等を少量添加し、モディファイヤー（改質剤）として用いてもよい。モディファイヤーを用いることで原料ポリハロゲン化ビニルの超臨界流体又は亜臨界流体に対する溶解度が向上する。
【００２０】
上記超臨界流体又は亜臨界流体の使用量としては、原料ポリハロゲン化ビニルに対して過剰量を用いることが好ましい。上記超臨界流体又は亜臨界流体の量の過剰の程度は、目的とする本発明１の改質ハロゲン含有ポリオレフィン系樹脂を得るために理論的に必要な超臨界流体、亜臨界流体等の最少量に対して、少なくとも等倍以上であることが好ましく、より好ましい上限は１０００倍である。使用量が理論的に必要な最少量より少ないと、反応が充分に進行しないことがあり、使用量が理論的に必要な最少量の１０００倍を超えると、生成する改質ハロゲン含有ポリオレフィン系樹脂の濃度が非常に薄くなるため、反応の効率が低下して経済的でない。更に好ましい上限は２００倍である。
【００２１】
このようなポリハロゲン化ビニルから改質ハロゲン含有ポリオレフィン系樹脂を製造する方法は、例えば、図１に示したような簡単な装置を用いて行うことができる。図１の製造装置は、ヒーター３を備え固定ネジ２を用いて密封できる構造を有する反応容器１に、攪拌羽５及びポンプ７及びストップバルブ８を介して流体貯蔵槽６が取り付けられている。反応容器１の温度は熱電対４で、圧力は圧力計９で制御される。なお、図１の製造装置では加熱手段としてヒーター３を用いたが、その他にも、例えば、バーナー、燃焼ガス、蒸気、熱媒、サンドバス、溶融金属槽等の加熱手段を用いることができる。
【００２２】
ポリフッ化ビニルから本発明１の改質フッ素含有ポリオレフィン系樹脂を製造する場合を例として挙げ、図１の装置を用いた変性反応について説明する。
まず、ポリフッ化ビニルを反応容器１に投入し、固定ねじ２により充分にシールし、流体貯蔵槽６に貯蔵した流体を反応容器１に導入した後、ヒーター３により所定温度に加熱し、流体の温度及び圧力を所定の超臨界域又は亜臨界領域にして脱離反応を開始させる。攪拌羽５により攪拌しながら所定の時間反応させた後、素早く冷却し、充分に冷却した後、反応容器１内の生成物を取り出し、水を加えて改質フッ素含有ポリオレフィン系樹脂を沈殿させた後、ろ過により分離、乾燥を行う。
【００２３】
ポリハロゲン化ビニルから本発明１の改質ハロゲン含有ポリオレフィン系樹脂を製造する製造装置としては、図１に示したような簡便なものも用いることもできるが、図２に示したような、調整槽又は重合反応容器１１と、反応容器１２と、調整された原料液液又は重合反応液を反応容器１２に供給するための供給手段１３と、超臨界流体又は亜臨界流体となり得る流体を反応容器１２に連続的に供給するための供給手段１４ａと、反応容器１２を加熱して流体を超臨界状態又は亜臨界状態にするための加熱手段１５と、改質ハロゲン含有ポリオレフィン系樹脂を含有する流体を冷却するための熱交換器１６と、冷却された改質ハロゲン含有ポリオレフィン系樹脂を含有する流体から改質ハロゲン含有ポリオレフィン系樹脂を分離回収するための分離器１７とからなる製造装置が好適に用いられる。なお、１４ｃ及び１４ｄは流体用の容器である。混合流体を使用する場合には、混合させる流体を反応容器１２に連続的に供給するための供給手段１４ｂと、上記流体を加熱するための加熱手段１８を有する。
【００２４】
上記反応容器１２は、超臨界域又は超臨界域近傍になる過酷な反応条件下でも反応を行うため、この条件に耐えられる材質及び肉厚の容器が使用される。
上記反応容器１２の材質としては、例えば、炭素鋼、Ｎｉ、Ｃｒ、Ｖ 、Ｍｏ等の特殊鋼、オーステナイト系ステンレス鋼、ハステロイ、チタン又はこれらにガラス、セラミック、カーバイト等をライニング処理した鋼材、他の金属をクラッドした鋼材等が挙げられる。
【００２５】
上記反応容器１２の形状としては特に限定されず、例えば、槽型、管型の他、特殊な形状のものでも使用できる。しかし耐熱、耐圧性能が必要であるので槽型又は管型が好ましい。バッチ式の場合は、オートクレ−ブや管型反応管が好ましい。なお、管型としては直線状の管でもよいが、コイル状に巻いていたり、Ｕ字型に折り曲げられたりした構造の管でもよい。
【００２６】
上記反応容器１２内には金属やセラミック等からなる硬質ボールや所定形状の障害物を置き、乱流を生じさせることが好ましい。反応容器１２内に硬質ボール等が備えられていると振とうにより乱流が発生するので攪拌効率が高められ反応効率を上げることができる。更に、反応容器１２が硬質ボール等で充填されていると容器を振とうするだけで攪拌効率が高くなり好ましい。
また、上記硬質ポールの充填率は２０〜８０％であることが好ましい。この範囲外であると、攪拌効率が悪くなる。なお、直径の異なる２種以上の硬質ボールを用いることが好ましい。充填率を向上させることができ、攪拌効率を上げることができる。
【００２７】
また、上記反応容器１２内にはオリフィスがあいている板が備えられていることが好ましい。反応容器１２内にオリフィスがあいている板が備えられていると振とうにより乱流が発生するので攪拌効率が高められ反応効率を上げることができる。
【００２８】
本発明１の改質ハロゲン含有ポリオレフィン系樹脂の原料となるポリハロゲン化ビニルは、単量体を重合する手段を組み合わせて直前に重合したものを供給してもよいし、既に合成されたものを入手して用いてもよい。
原料ポリハロゲン化ビニルとして、単量体を重合する装置を組み合わせて直前に重合したものを供給する場合には、上記製造装置は、更に、重合反応器１１と、重合反応液を反応容器１２に供給するための供給手段とを有することが好ましい。重合反応容器１１中に単量体を供給すると同時に重合反応を行い、得られた重合反応液を連続的に反応容器１２に供給することにより、更に効率的に変性反応生成物を得ることができる。
【００２９】
原料ポリハロゲン化ビニルとして、既に合成されたものを用いる場合には、上記製造装置は、更に、高分子化合物を溶融、溶解、分散又は膨潤する調整槽１１と、調整された原料液を反応容器１２に供給するための供給手段とを有することが好ましい。
なお、上記調整槽又は重合反応容器１１としては、通常の槽型、管型重合反応器を用いることができる。
【００３０】
図２に示した製造装置を用いて、本発明１の改質ハロゲン含有ポリオレフィン系樹脂は以下のように製造される。
原料ポリハロゲン化ビニルを調整槽又は重合反応容器１１中で溶融、溶解、分散、膨潤又は重合し、次いで調整された原料液又は重合反応液を反応容器１２に、例えば高圧ポンプのような供給手段１３で供給し、別ラインから脱離反応を行わせるための超臨界流体又は亜臨界流体になりうる流体を例えば高圧ポンプのような供給手段１４ａを用いて供給する。次に、例えばヒーターのような加熱手段１８により所定の温度、圧力に保持された超臨界流体又は亜臨界流体を、反応容器１２に連続的に供給してポリハロゲン化ビニルの脱離反応を行い、得られた改質ハロゲン含有ポリオレフィン系樹脂を含有する液体を熱交換器１６に供給して室温まで冷却し、冷却された改質ハロゲン含有ポリオレフィン系樹脂を含有する液体を、例えば液体サイクロンのような分離器１７に供給し、改質ハロゲン含有ポリオレフィン系樹脂を得る。また、反応容器１２を、例えばヒーターのような加熱装置１５で反応温度に保持することにより、目的の反応を所定時間内に行わせることができる。このようにして、本発明１の改質ハロゲン含有ポリオレフィン系樹脂を連続で合成することができる。更に使用流体が混合流体の場合には別ラインから混合させる超臨界流体又は亜臨界流体を例えば高圧ポンプのような供給手段１４ｂを用いて供給する。
【００３１】
原料ポリハロゲン化ビニルが熱安定性に劣る場合には、図２に示す製造装置を用いることが好ましい。即ち、反応容器１２に投入される各原料のうち、超臨界流体又は亜臨界流体となりうる流体のみ変性反応容器内で必要な温度以上に加熱しておくことが好ましい。流体が高温であれば混合される他の原料の温度が低くとも反応容器１２内を目的温度に調整できる。また、図２において、反応容器１２は、ヒーターにより加熱され、流体が超臨界状態又は亜臨界状態に達するようにされている。従って、反応容器１２内の温度管理は難しく、反応容器１２内の一部が過熱され、熱安定性に劣る化合物がある場合は、分解してしまうおそれがあった。しかしながら、このような熱に敏感な化合物がある場合であっても、流体のみ高温に加熱しておき、反応容器１２を加熱しないか、流体の温度が下がらないようわずかに加熱して保温しておけば反応容器１２内を過熱することなく反応を進行させることができる。
【００３２】
更に、上記製造装置では、反応容器１２から排出される改質ハロゲン含有ポリオレフィン系樹脂を含有する液体と、上記反応容器１２に供給する前の流体との間で熱交換されることが好ましい。この好ましい製造装置は、流体が液体であるときに用いられる。例えば図２に示した装置では、分離器１７から回収される液体を蒸留するための蒸留塔１９が設けられている。蒸留塔１９から回収された流体は熱交換器１６に導かれて、反応容器１２から排出される改質ハロゲン含有ポリオレフィン系樹脂の溶液又は分散液との間で熱交換する。この製造装置では、分離器１７により液体を改質ハロゲン含有ポリオレフィン系樹脂から分離した後、回収された液体を、圧力調整弁２０を通じて排出し、蒸留塔１９に供給する。そして、蒸留塔１９により、混合流体をそれぞれの流体に分離し回収する。回収した流体を、熱交換器１６に導き、反応容器１２から熱交換器１６に排出されてくる高温の改質ハロゲン含有ポリオレフィン系樹脂を含有する液体とで熱交換させ、熱交換によって高温にされた流体を反応容器１２に戻して脱離反応に用いる。このようにすると、超臨界流体又は亜臨界流体を形成するための流体と高温で排出されてくる改質ハロゲン含有ポリオレフィン系樹脂を含有する液体とが熱交換するので、エネルギーを効率よく利用できる。なお、この方法により本発明１の改質ハロゲン含有ポリオレフィン系樹脂を製造する場合には、通常は必要とする触媒（例えば、塩酸や硝酸）が必要ないか又は少量であるため、蒸留等の回収プロセスがかなり簡略化できる。従って、残留イオンが非常に少ないか、又は、イオンフリーの純度の高い改質ハロゲン含有ポリオレフィン系樹脂を得ることができる。
【００３３】
図２に示した製造装置は、原料となるポリハロゲン化ビニルと超臨界流体又は亜臨界流体となり得る流体とを連続的に供給して反応を行う流通方式であることから、生産効率が極めて優れることに加え、反応速度が速いため反応速度の遅い副生成物が生じる前に反応を完結させることができる。従って、副生成物の発生や熱分解性生成物の発生を抑えることができる。
【００３４】
本発明２の改質ハロゲン含有ポリオレフィン系樹脂は、上記一般式（２）で表される構造を有する。
本発明２の改質ハロゲン含有ポリオレフィン系樹脂は、ポリハロゲン化ビニルのハロゲン基Ｘの一部を他の官能基Ｙで置換し、更に必要に応じて主鎖の一部に二重結合を導入したような構造を有するものであり、ハロゲン基Ｘ、他の官能基Ｙ及び二重結合の含有量を調整することによりハロゲン基Ｘに由来する優れた性質を維持したまま、更に他の官能基Ｙに由来する性質を付与したり、他の樹脂との相溶性等の諸性質をコントロールしたりすることができる。
【００３５】
上記導入する他の官能基Ｙは、Ｘとは異なるハロゲン基、水酸基、又は、ビニル基、アクリロイル基、メタアクリロイル基、チオール基、グリシジル基、シラノール基又は脂還式エポキシ基を有する化合物に由来する基である。
【００３６】
上記官能基Ｙとしては、炭素−炭素二重結合に対して反応することにより導入できるものであれば特に限定されない。即ち、官能基Ｙは、水、官能基Ｘとは異なるハロゲン、ハロゲン化水素等の直接炭素−炭素二重結合に付加できる化合物を反応させることにより導入したもの、又は、炭素−炭素二重結合と反応し得る官能基を有する化合物を炭素−炭素二重結合に反応させることにより導入したものである。また、官能基Ｙは、１種類の化合物に由来するものであってもよく、複数種類の化合物に由来するものであってもよい。
【００３７】
上記炭素−炭素二重結合と反応し得る官能基としては、二重結合を有する官能基と二重結合を有さない官能基とに大別される。
上記炭素−炭素二重結合と反応し得る二重結合を有する官能基としては特に限定されないが、例えば、ビニル基、アクリロイル基、メタアクリロイル基等が好適である。このような炭素−炭素二重結合と反応し得る二重結合を有する官能基を有する化合物としては特に限定されず、上記官能基以外の部分を選択することにより、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂に種々の特性を付与することができる。例えば、アクリル酸、メタアクリル酸、アクリル酸エステル、メタアクリル酸エステル、無水マレイン酸、スチレン等の芳香族系モノマー；プロピレン、ブテン等の直鎖オレフィン系モノマー等が挙げられる。これらのモノマーの二重結合部分以外の部分は、用途により変性されていてもよく、例えば、ハロゲン化されていたり、アミノ基やグリシジル基など他の官能基が導入されていたりしてもよい。また、上記炭素−炭素二重結合と反応し得る二重結合を有する官能基を有する化合物としては、炭素−炭素二重結合と反応し得る二重結合を有する官能基を有するマクロモノマーも好適である。このようなマクロモノマーのポリマー部分としては、例えば、スチレン系；アクリル酸及びアクリル酸エステルを含むアクリル系；メタクリル酸及びメタクリル酸エステルを含むポリメタアクリル系；ジメチルシロキサン系を含むシロキサン系；アクリル系、メタクリル系、スチレン系、シロキサン系からなる群より選択される少なくとも２種類からなる共重合体系等が挙げられる。
【００３８】
上記炭素−炭素二重結合と反応し得る二重結合を有さない官能基としては特には限定されないが、例えば、チオール基、グリシジル基、シラノール基、脂環式エポキシ基等が挙げられる。
このような炭素−炭素二重結合と反応し得る二重結合を有さない官能基を有する分子としては、特には限定されず、上記官能基以外の部分を選択することにより、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂に種々の特性を付与することができる。
例えば、上記チオール基を有する化合物として、チオール基以外の部分が直鎖、分岐、環状アルキル基であるものを用いた場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂のガラス転移温度を上昇させるたり、疎水化させたりすることが出来る。また、上記チオール基以外のアルキル部分の水素原子の少なくとも一つがフッ素に置換された化合物を用いた場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂の表面電気特性、摺動性、耐候性を向上させたり、撥水性や離型性等の性能を付与させたりすることができる。また、上記チオール基以外の部分がポリジメチルシロキサンなどのシラン系化合物である化合物を用いた場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂の離型性や耐候性の向上を図ることができる。更に、チオール基を有するマクロモノマーを用いた場合にも、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂のガラス転移温度を調整したり、極性を付与したりすることができ、このことから接着性の向上や極性樹脂への相溶性を向上させることができる。
上記グリシジル基、脂環式エポキシ基を有する化合物として、グリシジル基、脂環式エポキシ基以外の部分が直鎖、分岐、環状アルキル基であるものを用いた場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂のガラス転移温度を上昇させたり、疎水化したりすることができる。上記グリシジル基、脂環式エポキシ基以外のアルキル部分の水素原子の少なくとも一つがフッ素に置換された化合物を用いた場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂の表面電気特性、摺動性、耐候性を向上させたり、撥水性や離型性等の性能を付与させたりすることができる。また、上記グリシジル基、脂環式エポキシ基以外の部分がポリジメチルシロキサンなどのシラン系化合物である化合物を用いた場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂の離型性や耐候性の向上を図ることができる。更に、グリシジル基、脂環式エポキシ基を有するマクロモノマーを用いた場合にも、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂のガラス転移温度を調整したり、極性を付与したりすることができ、このことから接着性の向上や極性樹脂への相溶性を向上させることができる。
【００３９】
上記官能基Ｙは、本発明２の改質ハロゲン含有ポリオレフィン系樹脂の用途に応じて選択され、種々の特性を本発明２の改質ハロゲン含有ポリオレフィン系樹脂に付与することができる。
例えば、官能基Ｙとして、スチレン、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、無水マレイン酸、アクリル系マクロモノマー、スチレン系マクロモノマー、アクリルスチレン系マクロモノマーに由来する基を選択する場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂は、他樹脂のガラス転移温度を上昇させるための改質剤や、他樹脂に接着性を付与するための改質剤として好適に用いることができる。
例えば、官能基Ｙとして、シロキサン系マクロモノマーに由来する基を選択する場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂は、他樹脂の離型性、撥水性、耐光性を向上させるための改質剤として好適に用いることができる。この場合、他の樹脂に、官能基Ｙとしてシロキサン系マクロモノマーがグラフトされた本発明２の改質ハロゲン含有ポリオレフィン系樹脂を混練、成形し、その後、ガラス転移温度付近の温度で熱養生を加えることで本発明２の改質ハロゲン含有ポリオレフィン系樹脂のシロキサン部分を成形体の表面に析出させることができ、表面性の改善度を向上させることができる。
例えば、官能基Ｙとして、フッ素又はフッ素化不飽和オレフィンに由来する基を選択する場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂は、他樹脂の離型性，撥水性，耐光性，表面電気特性，摺動性を改善するための改質剤として好適に用いることができる。この場合、他の樹脂に、官能基Ｙとしてフッ素等がグラフトされた本発明２の改質ハロゲン含有ポリオレフィン系樹脂を混練、成形し、その後、ガラス転移温度付近の温度で熱養生を加えることで本発明２の改質ハロゲン含有ポリオレフィン系樹脂のフッ素化部分を成形体の表面に偏在させることができ、表面性の改善度を向上させることができる。
例えば、官能基Ｙとして、水酸基を選択する場合には、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂に親水性を付与することができ、疎水性の樹脂を両親媒性にすることができる。
【００４０】
本発明２の改質ハロゲン含有ポリオレフィン系樹脂中のハロゲン基Ｘ、他の官能基Ｙ及び二重結合との含有量としては特に限定されず、用途により調整することができる。
【００４１】
本発明２の改質ハロゲン含有ポリオレフィン系樹脂の重合度は１００以上である。１００未満であると，他の樹脂と混練したときにポリマーブレンド表面に析出（ブリードアウト）してしまうことがある。好ましくは３００以上である。重合度の上限は特にないが，原料としてポリハロゲン化ビニルを用いるときは２万程度が上限となる。
【００４２】
本発明２の改質ハロゲン含有ポリオレフィン系樹脂を製造する方法としては特に限定されないが、例えば、ハロゲン化ビニルと上述の水、官能基Ｘとは異なるハロゲン、ハロゲン化水素等の直接炭素−炭素二重結合に付加できる化合物や炭素−炭素二重結合と反応し得る官能基を有する化合物とを超臨界流体中又は亜臨界流体中で反応させる方法；本発明１の改質ハロゲン含有ポリオレフィン系樹脂と上述の水、官能基Ｘとは異なるハロゲン、ハロゲン化水素等の直接炭素−炭素二重結合に付加できる化合物や炭素−炭素二重結合と反応し得る官能基を有する化合物とを超臨界流体中又は亜臨界流体中で反応させる方法等が好適である。この方法によれば、入手が容易なポリハロゲン化ビニル、又は、ポリハロゲン化ビニルから製造した本発明１の改質ハロゲン含有ポリオレフィン系樹脂を原料として、複雑な工程を経ることなく、しかも原料ポリハロゲン化ビニルの重合度に近い重合度の改質ハロゲン含有ポリオレフィン系樹脂を得ることができる。また、反応条件を調整することにより、得られる本発明２の改質ハロゲン含有ポリオレフィン系樹脂中のハロゲン基Ｘ、他の官能基Ｙ及び二重結合の含有量を調整することができる。更に、触媒として、特別な酸、アルカリ又は遷移金属系触媒を用いることなく反応を行うことができることから、洗浄等の煩雑な工程を要することなく不純物のないの極めて高純度な改質ハロゲン含有ポリオレフィン系樹脂を得ることができる。
【００４３】
超臨界流体中又は亜臨界流体中で反応させる方法としては、上述の本発明１の改質ハロゲン含有ポリオレフィン系樹脂の製造方法と略同様の方法を用いることができる。
例えば、図１の製造装置を用いてポリフッ化ビニルからＹとしてポリメタクリル酸系マクロモノマーが導入された本発明２の改質フッ素含有ポリオレフィン系樹脂を製造する場合について説明する。
まず、ポリフッ化ビニルとポリメタクリル酸系マクロモノマーとを反応容器１に投入し、固定ねじ２により充分にシールし、流体貯蔵槽６に貯蔵した流体を反応容器１に導入した後、ヒーター３により所定温度に加熱し、流体の温度及び圧力を所定の超臨界域又は亜臨界領域にして脱離反応を開始させる。攪拌羽５により攪拌しながら所定の時間反応させた後、素早く冷却し、充分に冷却した後、反応容器１内の生成物を取り出し、水を加えて改質フッ素含有ポリオレフィン系樹脂を沈殿させた後、ろ過により分離、乾燥を行う。
この例ではポリフッ化ビニルを原料として直接本発明２の改質フッ素含有ポリオレフィン系樹脂の製造を行ったが、いったんポリフッ化ビニルから本発明１の改質フッ素含有ポリオレフィン系樹脂を製造した後、これを原料として同様の方法によりポリアクリル酸が導入された本発明２の改質フッ素含有ポリオレフィン系樹脂を製造してもよい。
【００４４】
また、図２に示した製造装置を用いて、本発明２の改質ハロゲン含有ポリオレフィン系樹脂は以下のように製造される。
原料ポリハロゲン化ビニルとこれと反応させるポリアクリル酸等を調整槽又は重合反応容器１１中で溶融、溶解、分散、膨潤又は重合し、次いで調整された原料液又は重合反応液を反応容器１２に、例えば高圧ポンプのような供給手段１３で供給し、別ラインから反応を行わせるための超臨界流体又は亜臨界流体になりうる流体を例えば高圧ポンプのような供給手段１４ａを用いて供給する。次に、例えばヒーターのような加熱手段１８により所定の温度、圧力に保持された超臨界流体又は亜臨界流体を、反応容器１２に連続的に供給してポリハロゲン化ビニルとポリアクリル酸等との反応を行い、得られた改質ハロゲン含有ポリオレフィン系樹脂を含有する液体を熱交換器１６に供給して室温まで冷却し、冷却された改質ハロゲン含有ポリオレフィン系樹脂を含有する液体を、例えば液体サイクロンのような分離器１７に供給し、改質ハロゲン含有ポリオレフィン系樹脂を得る。また、反応容器１２を、例えばヒーターのような加熱装置１５で反応温度に保持することにより、目的の反応を所定時間内に行わせることができる。このようにして、本発明２の改質ハロゲン含有ポリオレフィン系樹脂を連続で合成することができる。更に使用流体が混合流体の場合には別ラインから混合させる超臨界流体又は亜臨界流体を例えば高圧ポンプのような供給手段１４ｂを用いて供給する。
【００４５】
本発明１の改質ハロゲン含有ポリオレフィン系樹脂は、ポリハロゲン化ビニルから脱ハロゲン化水素により主鎖の一部に二重結合を導入したような構造を有するものであり、ハロゲン基及び二重結合の含有量を調整することによりハロゲン基に由来する優れた性質を維持したまま、他の樹脂との相溶性等の諸性質をコントロールすることができ、他の樹脂と混合してポリマーアロイを形成させたり、相溶化剤として用いたりすることができる。また、本発明２の改質ハロゲン含有ポリオレフィン系樹脂を製造するための中間体としても有用である。
本発明２の改質ハロゲン含有ポリオレフィン系樹脂は、ポリハロゲン化ビニルのハロゲン基の一部を他の官能基で置換し、更に必要に応じて主鎖の一部に二重結合を導入したような構造を有するものであり、ハロゲン基、他の官能基及び二重結合の含有量を調整することによりハロゲン基に由来する優れた性質を維持したまま、他の官能基に由来する性質を付与したり、他の樹脂との相溶性等の諸性質をコントロールすることができ、他の樹脂と混合してポリマーアロイを形成させたり、相溶化剤として用いたりすることができる。
【００４６】
【実施例】
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。
【００４７】
（実施例１）
重合度５００のポリビニルアルコール（けん化度９９％、クラレ社製、ＰＶＡ１０５）１０ｇを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いで、ストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた水を反応容器１に導入し、反応容器内の圧力を３０ＭＰａまで上昇させ、５分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後氷冷した。氷冷後、得られた液体をイソプロパノールに沈殿し、黄白色の固体を得た。黄白色固体を水への溶解とイソプロパノールへの沈殿を３回繰り返し、充分洗浄した後、最終的に真空乾燥を行い、黄白色の固体を得た。得られた黄白色の固体を水に溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ及び３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。
更に、得られた黄白色の固体についてゲルパーミエーションクロマトグラフィーで重合度を測定したところ約５００であった。
【００４８】
（実施例２）
重合度５００のポリビニルアルコール１０ｇを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を１５０℃に加熱した。次いで、ストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、３０分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後氷冷した。氷冷後、得られた固体を水への溶解とイソプロパノールへの沈殿を３回繰り返し、充分洗浄した後、最終的に真空乾燥を行い、黄白色の固体を得た。
得られた黄白色の固体を水に溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ、３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。
更に、得られた黄白色の固体についてゲルパーミエーションクロマトグラフィーで重合度を測定したところ約５００であった。
【００４９】
（実施例３）
実施例１で得られた黄白色の固体１０ｇと分子量１０００のメタクリロキシ基を有するメタクリル系シロキサンマクロモノマー（チッソ社製、サイラプレーンＦＭ０７１１）１０ｇを図１に示した回分式の反応容器（耐圧硝子社製、樽型容器、内容量１００ｍＬ）に投入し、固定ねじ２を用いて充分にシールした後、反応容器１を１５０℃に加熱した。次いで、ストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器１内の圧力を８ＭＰａまで上昇させ、３０分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後、氷冷した。氷冷後、得られた固体をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、固体を充分に洗浄後、最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体をジメチルスルホキシドに溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、炭素−炭素二重結合に起因するピークを検出した。同時に水酸基に起因する吸収も検出した。
更に、得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、シロキサンに起因するケイ素を検出した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、原料として用いた実施例１で得られた黄白色の固体（ポリビニルアルコール−ポリエン化合物）の重合度と比較して高分子量側にシフトした。
【００５０】
（実施例４）
実施例１で得られた黄白色の固体１０ｇと分子量１０００のメタクリロキシ基を有するメタクリル系シロキサンマクロモノマー（チッソ社製、サイラプレーンＦＭ０７１１）１０ｇを図１に示した回分式の反応容器（耐圧硝子社製、樽型容器、内容量１００ｍＬ）に投入し、固定ねじ２を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器１内の圧力を３０ＭＰａまで上昇させ、５分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後、氷冷した。氷冷後、得られた固体をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、固体を充分に洗浄後、最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体をジメチルスルホキシドに溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ、３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。
更に、得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、シロキサンに起因するケイ素を検出した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、原料として用いた実施例１で得られた黄白色の固体（ポリビニルアルコール−ポリエン化合物）の重合度と比較して高分子量側にシフトした。
【００５１】
（実施例５）
実施例１で得られた黄白色の固体１０ｇとフッ化水素０．５ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ２を用いて充分にシールした後、反応容器１を１５０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、３０分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後、氷冷した。氷冷後、白色の固体を得た。白色の固体をジメチルスルホキシドへの溶解とイソプロパノールへの沈殿を３回繰り返し、固体を充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体をジメチルスルホキシドに溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ、３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。
更に、得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、フッ素原子の存在を確認できた。また、得られた白色固体についてゲルパーミエーションクロマトグラフィーで分子量を測定したところ、原料として用いた実施例１で得られた黄白色の固体（ポリビニルアルコール−ポリエン化合物）の重合度と比較して高分子量側にシフトした。
【００５２】
（実施例６）
実施例１で得られた黄白色の固体１０ｇとフッ化水素０．５ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ２を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた水を反応容器１に導入し、反応容器内の圧力を３００ＭＰａまで上昇させ、５分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後、氷冷した。氷冷後、白色の固体を得た。白色の固体をジメチルスルホキシドへの溶解とイソプロパノールへの沈殿を３回繰り返し、固体を充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体をジメチルスルホキシドに溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ、３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。
更に、得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、フッ素原子の存在を確認できた。また、得られた白色固体についてゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いた実施例１で得られた黄白色の固体（ポリビニルアルコール−ポリエン化合物）と比較して高分子量側にシフトした。
【００５３】
（実施例７）
重合度５００のポリビニルアルコール（けん化度９９％、クラレ社製、ＰＶＡ１０５）と分子量１０００のメタクリロキシ基を有するメタクリル系シロキサンマクロモノマー（チッソ社製、サイラプレーンＦＭ０７１１）１０ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた水を反応容器１に導入し、反応容器内の圧力を３０ＭＰａまで上昇させ、１０分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、シロキサンに起因するケイ素を検出した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いたポリビニルアルコールと比べて高分子両側にシフトした。
【００５４】
（実施例８）
重合度５００のポリビニルアルコール（けん化度９９％、クラレ社製、ＰＶＡ１０５）と分子量１０００のメタクリロキシ基を有するメタクリル系シロキサンマクロモノマー（チッソ社性、サイラプレーンＦＭ０７１１）１０ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を８０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、１時間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、シロキサンに起因するケイ素を検出した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いたポリビニルアルコールと比べて高分子両側にシフトした。
【００５５】
（実施例９）
重合度５００のポリビニルアルコール（けん化度９９％、クラレ社製、ＰＶＡ１０５）とフッ化水素０．５ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を８０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、１時間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して蛍光Ｘ線測定を行ったところ、フッ素を検出した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いたポリビニルアルコールと比べて高分子両側にシフトした。
【００５６】
（実施例１０）
実施例１で得られた黄白色の固体１０ｇとブチルグリシジルエーテル（坂本薬品工業性、ＢＧＥ−Ｒ）１ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を８０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、１時間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して赤外吸収スペクトルを測定したところ、グリシジル基の付加に起因するエーテル基の存在を確認した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いた実施例１で得られた黄白色の固体（ポリビニルアルコール−ポリエン化合物）と比較して高分子量側にシフトした。
【００５７】
（実施例１１）
実施例１で得られた黄白色の固体１０ｇとブチルグリシジルエーテル（坂本薬品工業性、ＢＧＥ−Ｒ）１ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を８０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、１時間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して赤外吸収スペクトルを測定したところ、グリシジル基の付加に起因するエーテル基の存在を確認した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いた実施例１で得られた黄白色の固体（ポリビニルアルコール−ポリエン化合物）と比較して高分子量側にシフトした。
【００５８】
（実施例１２）
重合度５００のポリビニルアルコール（けん化度９９％、クラレ社製、ＰＶＡ１０５）とブチルグリシジルエーテル（坂本薬品工業性、ＢＧＥ−Ｒ）１ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を８０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、１時間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して赤外吸収スペクトルを測定したところ、グリシジル基の付加に起因するエーテル基の存在を確認した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いたポリビニルアルコールと比べて高分子両側にシフトした。
【００５９】
（実施例１３）
重合度５００のポリビニルアルコール（けん化度９９％、クラレ社製、ＰＶＡ１０５）と１−ブタンチオール１ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を８０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた二酸化炭素を反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、１時間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体に対して蛍光Ｘ線測定を行ったところチオールに起因する硫黄の存在を確認した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いたポリビニルアルコールと比べて高分子両側にシフトした。
【００６０】
（実施例１４）
重合度５００のポリ塩化ビニル１０ｇを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いで、ストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していた水を反応容器１に導入し、反応容器内の圧力を３０ＭＰａまで上昇させ、５分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後氷冷した。氷冷後、得られた液体をイソプロパノールに沈殿し、黄白色の固体を得た。黄白色固体を水への溶解とイソプロパノールへの沈殿を３回繰り返し、充分洗浄した後、最終的に真空乾燥を行い、黄白色の固体を得た。
得られた黄白色の固体を水に溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ及び３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。
また、得られた黄白色の固体に対して蛍光Ｘ線測定を行ったところ、塩素原子の存在を確認できた。更に、得られた黄白色の固体についてゲルパーミエーションクロマトグラフィーで重合度を測定したところ約５００であった。
【００６１】
（実施例１５）
実施例１４で得られた黄白色の固体１０ｇと水１ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していたイソプロパノールを反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、５分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体をジメチルスルホキシドに溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ、３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。更に、得られた白色の固体に対して蛍光Ｘ線測定を行ったところ塩素の存在を確認した。また、ゲルパーミエーションクロマトグラフィーで分子量を測定したところ、ピークが原料として用いた実施例１４で得られた黄白色の固体（ポリ塩化ビニル−ポリエン化合物）と比較して高分子量側にシフトした。
【００６２】
（実施例１６）
重合度１５００のポリ塩化ビニル１０ｇと水１ｇとを図１に示した回分式の反応容器１（耐圧硝子社製、樽型容器、内容積１００ｍＬ）に投入し、固定ねじ１を用いて充分にシールした後、反応容器１を２５０℃に加熱した。次いでストップバルブ８を開き、ポンプ７により流体貯蔵槽６に貯蔵していたイソプロパノールを反応容器１に導入し、反応容器内の圧力を８ＭＰａまで上昇させ、５分間保持した。反応後、反応容器１を冷却浴により急速に冷却し、その後表冷した。得られた白色沈殿をジメチルスルホキシドへの溶解とアセトンへの沈殿を３回繰り返し、充分に洗浄した。最終的に真空乾燥を行い、白色の固体を得た。
得られた白色の固体をジメチルスルホキシドに溶解後、分光光度計でＵＶ吸収スペクトルを測定したところ、２３０ｎｍ、２８０ｎｍ、３３０ｎｍに炭素−炭素二重結合に起因するピークが検出された。また、同時に水酸基のピークも検出された。更に、得られた白色の固体に対して蛍光Ｘ線測定を行ったところ塩素の存在を確認した。
【００６３】
【発明の効果】
本発明によれば、実用的な重合度を有し、他の樹脂とポリマーアロイを形成したり、相溶化剤として用いたりすることができる改質ハロゲン含有ポリオレフィン系樹脂を提供することができる。
【図面の簡単な説明】
【図１】本発明の改質ハロゲン含有ポリオレフィン系樹脂を製造するための製造装置の１実施態様を示す模式図である。
【図２】本発明の改質ハロゲン含有ポリオレフィン系樹脂を製造するための製造装置の１実施態様を示す模式図である。
【符号の説明】
１ 反応容器
２ 固定ネジ
３ ヒーター
４ 熱電対
５ 攪拌羽
６ 流体貯蔵槽
７ ポンプ
８ ストップバルブ
９ 圧力計
１１ 調整槽又は重合反応容器
１２ 反応容器
１３ 供給手段
１４ａ 供給手段
１４ｂ 供給手段
１４ｃ 流体用の容器
１４ｄ 流体用の容器
１５ 加熱手段
１６ 熱交換器
１７ 分離器
１８ 加熱手段
１９ 蒸留塔
２０ 圧力調節弁[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel modified halogen-containing polyolefin-based resin.
[0002]
[Prior art]
BACKGROUND ART Halogen-containing polyolefin resins such as polyvinyl chloride and polyvinyl fluoride have been applied in a wide range because of their high versatility. For example, those containing fluorine have excellent characteristics such as high chemical resistance, water repellency, and low surface friction resistance.
Such a halogen-containing polyolefin-based resin is extremely useful even when used alone, and is used by forming a polymer alloy with a resin having another property, for example, a polyolefin-based resin such as polyethylene or polypropylene. There is also a possibility that infinite properties can be given according to. It is also expected to play a role as a compatibilizer that promotes the mixing of the polyolefin resin with another resin.
[0003]
However, when a halogen-containing polyolefin-based resin is mixed with another resin to form a polymer alloy, or when used as a compatibilizing agent, usually, resins having different properties are inferior in compatibility and easily uniform. There was a problem that mixing was not possible.
[0004]
On the other hand, by introducing an appropriate side chain into the halogen-containing polyolefin-based resin or by introducing a double bond into the main chain, it is possible to improve the compatibility with other resins. I thought it could be done. However, it is extremely difficult to introduce an appropriate side chain into the halogen-containing polyolefin-based resin or to introduce a double bond into the main chain, and even if it can be produced, the main chain is cleaved during the process. Conventionally, there has been no such modified halogen-containing polyolefin-based resin that can be used industrially because the reaction proceeds and only a polymer having a low degree of polymerization is obtained.
[0005]
[Problems to be solved by the invention]
In view of the above circumstances, the present invention provides a modified halogen-containing polyolefin-based resin having a practical degree of polymerization and capable of forming a polymer alloy with other resins or being used as a compatibilizer. With the goal.
[0006]
[Means for Solving the Problems]
The present invention 1 is a modified halogen-containing polyolefin-based resin having a structure represented by the following general formula (1) and having an average degree of polymerization of 100 or more.
[0007]
Embedded image

[0008]
In the formula (1), X represents a halogen group, and m and n represent integers.
[0009]
The present invention 2 is a modified halogen-containing polyolefin-based resin having a structure represented by the following general formula (2) and having an average degree of polymerization of 100 or more.
[0010]
Embedded image

[0011]
In the formula (2), p, q, and r represent integers, X represents a halogen group, and Y represents a halogen group different from X, a hydroxyl group, or a vinyl group, an acryloyl group, a methacryloyl group, a thiol group, and glycidyl. Represents a group derived from a compound having a group, a silanol group or an alicyclic epoxy group.
Hereinafter, the present invention will be described in detail.
[0012]
The modified halogen-containing polyolefin resin of the first aspect of the present invention has a structure represented by the general formula (1).
The modified halogen-containing polyolefin resin of the present invention 1 has a structure in which a double bond is introduced into a part of the main chain from polyvinyl halide by dehydrohalogenation, and the halogen group and the double bond By adjusting the content of, various properties such as compatibility with other resins can be controlled while maintaining excellent properties derived from halogen groups.
[0013]
The content of the halogen group and the double bond in the modified halogen-containing polyolefin-based resin of the present invention 1 is not particularly limited, and can be adjusted according to the application. And the compatibility with a resin having a high polarity is improved.
[0014]
The polymerization degree of the modified halogen-containing polyolefin resin of the first invention is 100 or more. If it is less than 100, it may precipitate (bleed out) on the surface of the polymer blend when kneaded with another resin. Preferably it is 300 or more. There is no particular upper limit for the degree of polymerization, but when polyvinyl halide is used as a raw material, the upper limit is about 20,000.
[0015]
The method for producing the modified halogen-containing polyolefin-based resin of the present invention 1 is not particularly limited. For example, a method in which a polyvinyl halide is desorbed in a supercritical fluid or a subcritical fluid is preferable. According to this method, it is possible to obtain a modified halogen-containing polyolefin-based resin having a degree of polymerization close to the degree of polymerization of the raw material polyvinyl halide, without going through complicated steps, using the easily obtainable polyvinyl halide as a raw material. Can be. Further, by adjusting the reaction conditions, the content of the halogen group and the double bond in the resulting modified halogen-containing polyolefin-based resin can be adjusted. Furthermore, since the reaction can be carried out without using a special acid, alkali or transition metal catalyst as a catalyst, an extremely high-purity modified halogen-containing polyolefin containing no impurities without requiring complicated steps such as washing. A system resin can be obtained.
[0016]
In the present specification, the supercritical fluid means a fluid under a condition of not less than a critical pressure (hereinafter, also referred to as Pc) and not less than a critical temperature (hereinafter, also referred to as Tc). The subcritical fluid is a state other than the supercritical state, and when the pressure and temperature during the reaction are P and T, respectively, 0.5 <P / Pc <1.0 and 0.5 < It means T / Tc or a fluid satisfying the condition of 0.5 <P / Pc and 0.5 <T / Tc <1.0. The preferred pressure and temperature ranges of the subcritical fluid are 0.6 <P / Pc <1.0 and 0.6 <T / Tc, or 0.6 <P / Pc and 0.6 <T / Tc. <1.0. However, when the fluid is water, the range of temperature and pressure at which the fluid becomes a subcritical fluid is 0.5 <P / Pc <1.0 and 0.5 <T / Tc, or 0.5 <P / Pc. / Pc and 0.5 <T / Tc <1.0.
[0017]
The supercritical fluid or subcritical fluid is preferably water or an organic solvent that is liquid at normal temperature and normal pressure. These may be used alone or as a mixed fluid. Water is an easy-to-use fluid, is economical because it is inexpensive, and is preferable in terms of its effect on the environment. Further, among organic solvents, alcohol is preferable for the same reason.
When only water is used as the supercritical fluid or subcritical fluid, the reaction may not proceed sufficiently because the solubility of the raw material polyvinyl halide is low. However, by mixing an organic solvent with water to form a mixed fluid, the solubility of polyvinyl halide can be improved, and the reaction can be favorably performed.
[0018]
Examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol, and ketones such as acetone, methyl ethyl ketone and methyl phenyl ketone. In addition, sulfoxides such as dimethyl sulfoxide, amines such as dimethylformamide, ethers such as diethyl ether and dimethyl ether, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as hexane and cyclohexane are exemplified.
[0019]
Further, the supercritical fluid or the subcritical fluid is also preferably carbon dioxide.
Also in the case of using carbon dioxide, the reaction can be favorably performed by improving the solubility of the raw material polyvinyl halide as in the case of the organic solvent. In addition, since carbon dioxide has a low critical temperature, the reaction can be stably performed even when the raw material polyvinyl halide lacks thermal stability.
When carbon dioxide is used as a supercritical fluid or subcritical fluid, a small amount of methyl alcohol, ethyl alcohol, isopropanol, etc. is added as in the case of a liquid at normal temperature and normal pressure, and used as a modifier (modifier). You may. By using the modifier, the solubility of the raw material polyvinyl halide in the supercritical fluid or the subcritical fluid is improved.
[0020]
It is preferable to use an excess amount of the supercritical fluid or the subcritical fluid with respect to the raw material polyvinyl halide. The degree of excess of the supercritical fluid or subcritical fluid is determined by the minimum amount of supercritical fluid, subcritical fluid, etc. theoretically necessary to obtain the intended modified halogen-containing polyolefin-based resin of the present invention 1. Is preferably at least equal to or more, and the more preferable upper limit is 1000 times. If the amount used is less than the theoretically necessary minimum amount, the reaction may not proceed sufficiently. If the amount used exceeds 1000 times the theoretically necessary minimum amount, the modified halogen-containing polyolefin-based resin produced Is very low, so that the efficiency of the reaction is low and it is not economical. A more preferred upper limit is 200 times.
[0021]
Such a method for producing a modified halogen-containing polyolefin-based resin from polyvinyl halide can be carried out, for example, using a simple apparatus as shown in FIG. In the manufacturing apparatus shown in FIG. 1, a fluid storage tank 6 is attached via a stirring blade 5, a pump 7 and a stop valve 8 to a reaction container 1 having a heater 3 and having a structure that can be sealed using a fixing screw 2. The temperature of the reaction vessel 1 is controlled by a thermocouple 4 and the pressure is controlled by a pressure gauge 9. Although the heater 3 is used as the heating means in the manufacturing apparatus shown in FIG. 1, other heating means such as a burner, a combustion gas, steam, a heat medium, a sand bath, a molten metal tank, and the like can be used.
[0022]
An example in which the modified fluorine-containing polyolefin-based resin of the present invention 1 is produced from polyvinyl fluoride will be described by way of example.
First, polyvinyl fluoride is charged into the reaction vessel 1, sealed sufficiently with the fixing screw 2, the fluid stored in the fluid storage tank 6 is introduced into the reaction vessel 1, and then heated to a predetermined temperature by the heater 3, and the The desorption reaction is started by setting the temperature and pressure to a predetermined supercritical region or subcritical region. After reacting for a predetermined time while stirring with the stirring blades 5, the reaction was cooled quickly, and after sufficiently cooling, the product in the reaction vessel 1 was taken out, and water was added to precipitate the modified fluorine-containing polyolefin-based resin. Thereafter, separation and drying are performed by filtration.
[0023]
As a production apparatus for producing the modified halogen-containing polyolefin-based resin of the present invention 1 from polyvinyl halide, a simple apparatus as shown in FIG. 1 can be used. A tank or polymerization reaction vessel 11, a reaction vessel 12, a supply means 13 for supplying the adjusted raw material liquid or polymerization reaction liquid to the reaction vessel 12, and a fluid that can be a supercritical fluid or a subcritical fluid. A heating means 15 for heating the reaction vessel 12 to bring the fluid into a supercritical state or a subcritical state, and a fluid containing a modified halogen-containing polyolefin-based resin. And a separator for recovering the modified halogen-containing polyolefin-based resin from the cooled fluid containing the modified halogen-containing polyolefin-based resin. Of consisting separator 17. manufacturing apparatus is preferably used. In addition, 14c and 14d are containers for fluid. When a mixed fluid is used, a supply unit 14b for continuously supplying a fluid to be mixed to the reaction vessel 12 and a heating unit 18 for heating the fluid are provided.
[0024]
Since the reaction vessel 12 performs a reaction under severe reaction conditions at or near the supercritical region, a container having a material and a wall thickness that can withstand these conditions is used.
Examples of the material of the reaction vessel 12 include carbon steel, special steels such as Ni, Cr, V, and Mo, austenitic stainless steel, Hastelloy, titanium, and steel materials obtained by lining glass, ceramic, and carbide with these, A steel material clad with another metal may be used.
[0025]
The shape of the reaction vessel 12 is not particularly limited. For example, a tank type, a tube type, or a special shape can be used. However, a tank type or a tube type is preferable because heat resistance and pressure resistance are required. In the case of a batch type, an autoclave or a tubular reaction tube is preferable. The tube may be a straight tube, but may be a tube wound in a coil or bent into a U-shape.
[0026]
It is preferable to place a hard ball made of metal, ceramic, or the like or an obstacle having a predetermined shape in the reaction vessel 12 to generate turbulence. If a hard ball or the like is provided in the reaction vessel 12, turbulence is generated by shaking, so that the stirring efficiency is increased and the reaction efficiency can be increased. Further, it is preferable that the reaction vessel 12 is filled with a hard ball or the like because the stirring efficiency is increased only by shaking the vessel.
The filling ratio of the hard pole is preferably 20 to 80%. If it is outside this range, the stirring efficiency will be poor. It is preferable to use two or more types of hard balls having different diameters. The filling rate can be improved, and the stirring efficiency can be increased.
[0027]
Further, it is preferable that a plate having an orifice is provided in the reaction vessel 12. When a plate having an orifice is provided in the reaction vessel 12, turbulence is generated by shaking, so that the stirring efficiency is increased and the reaction efficiency can be increased.
[0028]
Polyvinyl halide as a raw material of the modified halogen-containing polyolefin-based resin of the present invention 1 may be supplied immediately before polymerization by combining means for polymerizing monomers, or may be synthesized already. It may be obtained and used.
In the case where a raw material polyvinyl halide is supplied in combination with a device for polymerizing a monomer and polymerized immediately before, the production apparatus further includes a polymerization reactor 11 and a polymerization reaction solution in a reaction vessel 12. It is preferable to have supply means for supplying. The polymerization reaction is performed simultaneously with the supply of the monomer into the polymerization reaction vessel 11, and the resulting polymerization reaction liquid is continuously supplied to the reaction vessel 12, whereby the modification reaction product can be obtained more efficiently. .
[0029]
In the case of using a synthesized polyvinyl halide as the raw material, the production apparatus further includes an adjustment tank 11 for melting, dissolving, dispersing or swelling the polymer compound, and a reaction vessel for the adjusted raw material liquid. It is preferable to have a supply means for supplying the water to the fuel supply 12.
In addition, as the adjustment tank or the polymerization reaction vessel 11, a normal tank-type or tube-type polymerization reactor can be used.
[0030]
Using the production apparatus shown in FIG. 2, the modified halogen-containing polyolefin-based resin of the present invention 1 is produced as follows.
The raw material polyvinyl halide is melted, dissolved, dispersed, swelled or polymerized in an adjusting tank or polymerization reaction vessel 11, and then the prepared raw material liquid or polymerization reaction liquid is supplied to the reaction vessel 12 by, for example, a supply means such as a high-pressure pump. 13 and a fluid that can be a supercritical fluid or a subcritical fluid for performing a desorption reaction from another line is supplied using a supply means 14a such as a high-pressure pump. Next, a supercritical fluid or subcritical fluid maintained at a predetermined temperature and pressure by a heating means 18 such as a heater is continuously supplied to the reaction vessel 12 to perform a desorption reaction of the polyvinyl halide. Then, the obtained liquid containing the modified halogen-containing polyolefin-based resin is supplied to the heat exchanger 16 and cooled to room temperature, and the cooled liquid containing the modified halogen-containing polyolefin-based resin is converted into a liquid such as a liquid cyclone. To obtain a modified halogen-containing polyolefin-based resin. In addition, by holding the reaction vessel 12 at a reaction temperature by a heating device 15 such as a heater, a target reaction can be performed within a predetermined time. Thus, the modified halogen-containing polyolefin-based resin of the present invention 1 can be continuously synthesized. Further, when the working fluid is a mixed fluid, a supercritical fluid or a subcritical fluid to be mixed from another line is supplied by using a supply means 14b such as a high-pressure pump.
[0031]
When the raw material polyvinyl halide is inferior in thermal stability, it is preferable to use the production apparatus shown in FIG. That is, it is preferable that only the fluid that can be a supercritical fluid or a subcritical fluid among the raw materials charged into the reaction vessel 12 is heated to a required temperature or higher in the modification reaction vessel. If the temperature of the fluid is high, the inside of the reaction vessel 12 can be adjusted to the target temperature even if the temperature of the other raw materials to be mixed is low. In FIG. 2, the reaction vessel 12 is heated by a heater so that the fluid reaches a supercritical state or a subcritical state. Therefore, it is difficult to control the temperature inside the reaction vessel 12, and when a part of the inside of the reaction vessel 12 is overheated and there is a compound having poor thermal stability, it may be decomposed. However, even when there is such a compound sensitive to heat, only the fluid is heated to a high temperature, and the reaction vessel 12 is not heated, or the fluid is slightly heated so as not to lower the temperature and kept warm. This allows the reaction to proceed without overheating the inside of the reaction vessel 12.
[0032]
Further, in the manufacturing apparatus, it is preferable that heat is exchanged between the liquid containing the modified halogen-containing polyolefin-based resin discharged from the reaction vessel 12 and the fluid before being supplied to the reaction vessel 12. This preferred manufacturing apparatus is used when the fluid is a liquid. For example, in the apparatus shown in FIG. 2, a distillation column 19 for distilling the liquid recovered from the separator 17 is provided. The fluid recovered from the distillation column 19 is guided to the heat exchanger 16 and exchanges heat with the solution or dispersion of the modified halogen-containing polyolefin resin discharged from the reaction vessel 12. In this manufacturing apparatus, after the liquid is separated from the modified halogen-containing polyolefin resin by the separator 17, the recovered liquid is discharged through the pressure regulating valve 20 and supplied to the distillation column 19. Then, the mixed fluid is separated into respective fluids by the distillation column 19 and collected. The recovered fluid is led to the heat exchanger 16 and heat-exchanged with a high-temperature liquid containing the modified halogen-containing polyolefin-based resin discharged from the reaction vessel 12 to the heat exchanger 16, and is heated to a high temperature by heat exchange. The recovered fluid is returned to the reaction vessel 12 and used for the desorption reaction. By doing so, heat exchange occurs between the fluid for forming the supercritical fluid or the subcritical fluid and the liquid containing the modified halogen-containing polyolefin-based resin discharged at a high temperature, so that energy can be used efficiently. When the modified halogen-containing polyolefin-based resin of the present invention 1 is produced by this method, the required catalyst (for example, hydrochloric acid or nitric acid) is usually unnecessary or small, so that the recovery by distillation or the like is required. The process can be considerably simplified. Therefore, it is possible to obtain a modified halogen-containing polyolefin-based resin having a very small amount of residual ions or a high ion-free purity.
[0033]
The production system shown in FIG. 2 is a flow system in which the reaction is carried out by continuously supplying the raw material polyvinyl halide and the fluid that can be a supercritical fluid or a subcritical fluid, so that the production efficiency is extremely excellent. In addition, since the reaction rate is high, the reaction can be completed before by-products having a low reaction rate are generated. Therefore, generation of by-products and generation of thermally decomposable products can be suppressed.
[0034]
The modified halogen-containing polyolefin resin of the second aspect of the present invention has a structure represented by the general formula (2).
The modified halogen-containing polyolefin-based resin of the present invention 2 is obtained by substituting a part of the halogen group X of the polyvinyl halide with another functional group Y and further introducing a double bond into a part of the main chain as necessary. Having a structure as described above, while maintaining the excellent properties derived from the halogen group X by adjusting the content of the halogen group X, the other functional group Y and the double bond, and further maintaining the other functional groups. Properties derived from Y can be imparted, and various properties such as compatibility with other resins can be controlled.
[0035]
The other functional group Y to be introduced is derived from a compound having a halogen group different from X, a hydroxyl group, or a vinyl group, an acryloyl group, a methacryloyl group, a thiol group, a glycidyl group, a silanol group, or a redox epoxy group. It is a group to do.
[0036]
The functional group Y is not particularly limited as long as it can be introduced by reacting with a carbon-carbon double bond. That is, the functional group Y is introduced by reacting a compound that can be directly added to a carbon-carbon double bond, such as water, a halogen different from the functional group X, or a hydrogen halide, or a carbon-carbon double bond. Is introduced by reacting a compound having a functional group capable of reacting with a carbon-carbon double bond. Further, the functional group Y may be derived from one kind of compound, or may be derived from plural kinds of compounds.
[0037]
The functional group capable of reacting with the carbon-carbon double bond is roughly classified into a functional group having a double bond and a functional group having no double bond.
The functional group having a double bond capable of reacting with the carbon-carbon double bond is not particularly limited. For example, a vinyl group, an acryloyl group, a methacryloyl group, and the like are preferable. The compound having a functional group having a double bond capable of reacting with such a carbon-carbon double bond is not particularly limited, and the modified product of the present invention 2 obtained by selecting a portion other than the above functional group can be obtained. Various properties can be imparted to the halogen-containing polyolefin-based resin. For example, aromatic monomers such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, maleic anhydride, and styrene; and linear olefin monomers such as propylene and butene are exemplified. Portions other than the double bond portion of these monomers may be modified depending on the use, for example, they may be halogenated, or may have other functional groups such as amino groups or glycidyl groups introduced. Further, as the compound having a functional group having a double bond capable of reacting with the carbon-carbon double bond, a macromonomer having a functional group having a double bond capable of reacting with a carbon-carbon double bond is also preferable. is there. Examples of the polymer portion of such a macromonomer include styrene-based; acrylic-based including acrylic acid and acrylate; polymethacryl-based including methacrylic acid and methacrylic-ester; siloxane-based including dimethylsiloxane-based; acrylic-based And methacrylic, styrenic, and siloxane-based copolymers.
[0038]
The functional group having no double bond capable of reacting with the carbon-carbon double bond is not particularly limited, and examples thereof include a thiol group, a glycidyl group, a silanol group, and an alicyclic epoxy group.
Such a molecule having a functional group having no double bond capable of reacting with a carbon-carbon double bond is not particularly limited, and the present invention can be obtained by selecting a portion other than the above functional group. Various properties can be imparted to the modified halogen-containing polyolefin-based resin (2).
For example, when a compound having a portion other than a thiol group is a linear, branched or cyclic alkyl group as the compound having a thiol group, the glass transition of the resulting modified halogen-containing polyolefin-based resin of the present invention 2 is obtained. The temperature can be raised or made hydrophobic. When a compound in which at least one hydrogen atom of the alkyl moiety other than the thiol group is substituted with fluorine is used, the resulting modified halogen-containing polyolefin-based resin of the present invention 2 has a surface electric property and a slidability. In addition, it is possible to improve the weather resistance and to impart properties such as water repellency and releasability. When a compound other than the thiol group is a silane-based compound such as polydimethylsiloxane, the release property and weather resistance of the resulting modified halogen-containing polyolefin-based resin of the present invention 2 are improved. Can be planned. Furthermore, even when a macromonomer having a thiol group is used, the glass transition temperature of the modified halogen-containing polyolefin-based resin of the present invention 2 to be obtained can be adjusted or polarity can be imparted. Adhesion and compatibility with polar resins can be improved.
When the compound having a glycidyl group and an alicyclic epoxy group as the compound having a portion other than the glycidyl group and the alicyclic epoxy group is a linear, branched, or cyclic alkyl group, the compound of the present invention 2 is obtained. The glass transition temperature of the modified halogen-containing polyolefin-based resin can be increased or made hydrophobic. When a compound in which at least one of the hydrogen atoms of the alkyl portion other than the glycidyl group and the alicyclic epoxy group is substituted with fluorine is used, the surface electric properties of the modified halogen-containing polyolefin resin of the present invention 2 obtained are obtained. Slidability, weather resistance, and performance such as water repellency and mold releasability. When a compound other than the glycidyl group and the alicyclic epoxy group is a silane compound such as polydimethylsiloxane, the releasability of the resulting modified halogen-containing polyolefin resin of the present invention 2 is obtained. And improved weather resistance. Furthermore, even when a macromonomer having a glycidyl group or an alicyclic epoxy group is used, the glass transition temperature of the resulting modified halogen-containing polyolefin-based resin of the present invention 2 is adjusted or polarity is imparted. This can improve the adhesiveness and the compatibility with the polar resin.
[0039]
The functional group Y is selected according to the use of the modified halogen-containing polyolefin resin of the second invention, and various properties can be imparted to the modified halogen-containing polyolefin resin of the second invention.
For example, when a group derived from styrene, acrylic acid, methacrylic acid, acrylate, methacrylate, maleic anhydride, acrylic macromonomer, styrene macromonomer, acrylstyrene macromonomer is selected as the functional group Y. The resulting modified halogen-containing polyolefin-based resin of the present invention 2 is preferably used as a modifier for increasing the glass transition temperature of another resin or a modifier for imparting adhesion to another resin. Can be used.
For example, when a group derived from a siloxane-based macromonomer is selected as the functional group Y, the resulting modified halogen-containing polyolefin-based resin of the present invention 2 has the releasability, water repellency, and light resistance of another resin. It can be suitably used as a modifier for improving. In this case, the modified halogen-containing polyolefin-based resin of the present invention 2 in which a siloxane-based macromonomer is grafted as a functional group Y is kneaded and molded into another resin, and then heat-cured at a temperature near the glass transition temperature. As a result, the siloxane portion of the modified halogen-containing polyolefin-based resin of the second aspect of the present invention can be precipitated on the surface of the molded body, and the degree of improvement in surface properties can be improved.
For example, when a group derived from fluorine or a fluorinated unsaturated olefin is selected as the functional group Y, the resulting modified halogen-containing polyolefin-based resin of the present invention 2 has a releasability, water repellency, It can be suitably used as a modifier for improving light resistance, surface electric characteristics, and slidability. In this case, the modified halogen-containing polyolefin-based resin of the present invention 2 in which fluorine or the like is grafted as the functional group Y is kneaded and molded into another resin, and then heat curing is performed at a temperature near the glass transition temperature. The fluorinated portion of the modified halogen-containing polyolefin-based resin of the second aspect of the present invention can be unevenly distributed on the surface of the molded article, and the degree of improvement in surface properties can be improved.
For example, when a hydroxyl group is selected as the functional group Y, it is possible to impart hydrophilicity to the resulting modified halogen-containing polyolefin-based resin of the present invention 2 and make the hydrophobic resin amphiphilic. it can.
[0040]
The content of the halogen group X, the other functional group Y, and the double bond in the modified halogen-containing polyolefin resin of the second invention is not particularly limited, and can be adjusted depending on the application.
[0041]
The polymerization degree of the modified halogen-containing polyolefin resin of the second invention is 100 or more. If it is less than 100, it may precipitate (bleed out) on the surface of the polymer blend when kneaded with another resin. Preferably it is 300 or more. There is no particular upper limit for the degree of polymerization, but when polyvinyl halide is used as a raw material, the upper limit is about 20,000.
[0042]
The method for producing the modified halogen-containing polyolefin-based resin of the present invention 2 is not particularly limited. For example, vinyl halide and water, a halogen different from the functional group X, a direct carbon-carbon A method in which a compound capable of being added to a heavy bond or a compound having a functional group capable of reacting with a carbon-carbon double bond is reacted in a supercritical fluid or a subcritical fluid; In a supercritical fluid, a compound which can be directly added to a carbon-carbon double bond, such as water or a halogen or a hydrogen halide different from the functional group X, or which has a functional group capable of reacting with the carbon-carbon double bond, is used in a supercritical fluid. Alternatively, a method in which the reaction is performed in a subcritical fluid is suitable. According to this method, the polyhalogenated polyvinyl halide or the modified halogen-containing polyolefin-based resin of the present invention 1 produced from the polyhalogenated vinyl is used as a raw material without going through a complicated process, and the raw material polystyrene is used. A modified halogen-containing polyolefin-based resin having a degree of polymerization close to the degree of polymerization of vinyl halide can be obtained. Further, by adjusting the reaction conditions, the content of the halogen group X, other functional groups Y and double bonds in the resulting modified halogen-containing polyolefin-based resin of the present invention 2 can be adjusted. Furthermore, since the reaction can be carried out without using a special acid, alkali or transition metal catalyst as a catalyst, an extremely high-purity modified halogen-containing polyolefin containing no impurities without requiring complicated steps such as washing. A system resin can be obtained.
[0043]
As a method for reacting in a supercritical fluid or a subcritical fluid, a method substantially similar to the above-described method for producing the modified halogen-containing polyolefin-based resin of the present invention 1 can be used.
For example, a case where the modified fluorine-containing polyolefin-based resin of the present invention 2 in which a polymethacrylic acid-based macromonomer is introduced as Y from polyvinyl fluoride using the manufacturing apparatus of FIG. 1 will be described.
First, polyvinyl fluoride and polymethacrylic acid-based macromonomer are charged into the reaction vessel 1, sufficiently sealed with the fixing screw 2, the fluid stored in the fluid storage tank 6 is introduced into the reaction vessel 1, and then the heater 3 is used. By heating to a predetermined temperature, the temperature and pressure of the fluid are set to a predetermined supercritical region or subcritical region to start a desorption reaction. After reacting for a predetermined time while stirring with the stirring blades 5, the reaction was cooled quickly, and after sufficiently cooling, the product in the reaction vessel 1 was taken out, and water was added to precipitate the modified fluorine-containing polyolefin-based resin. Thereafter, separation and drying are performed by filtration.
In this example, the modified fluorine-containing polyolefin-based resin of the present invention 2 was produced directly from polyvinyl fluoride as a raw material, but once the modified fluorine-containing polyolefin-based resin of the present invention 1 was produced from polyvinyl fluoride, May be used as a raw material to produce a modified fluorine-containing polyolefin-based resin of the present invention 2 in which polyacrylic acid is introduced by the same method.
[0044]
The modified halogen-containing polyolefin-based resin of the present invention 2 is produced as follows using the production apparatus shown in FIG.
The raw material polyvinyl halide and the polyacrylic acid and the like to be reacted therewith are melted, dissolved, dispersed, swelled or polymerized in the adjusting vessel or the polymerization reaction vessel 11, and then the prepared raw material liquid or polymerization reaction liquid is supplied to the reaction vessel 12. For example, a supply means 13 such as a high-pressure pump supplies a fluid that can be a supercritical fluid or a subcritical fluid for performing a reaction from another line using a supply means 14a such as a high-pressure pump. Next, for example, a supercritical fluid or a subcritical fluid maintained at a predetermined temperature and pressure by a heating means 18 such as a heater is continuously supplied to the reaction vessel 12 so that the polyvinyl halide and the polyacrylic acid are added. The resulting liquid containing the modified halogen-containing polyolefin-based resin is supplied to the heat exchanger 16 and cooled to room temperature, and the cooled liquid containing the modified halogen-containing polyolefin-based resin is subjected to, for example, The modified halogen-containing polyolefin-based resin is supplied to a separator 17 such as a liquid cyclone. In addition, by holding the reaction vessel 12 at a reaction temperature by a heating device 15 such as a heater, a target reaction can be performed within a predetermined time. Thus, the modified halogen-containing polyolefin-based resin of the present invention 2 can be continuously synthesized. Further, when the working fluid is a mixed fluid, a supercritical fluid or a subcritical fluid to be mixed from another line is supplied by using a supply means 14b such as a high-pressure pump.
[0045]
The modified halogen-containing polyolefin resin of the present invention 1 has a structure in which a double bond is introduced into a part of the main chain from polyvinyl halide by dehydrohalogenation, and the halogen group and the double bond By adjusting the content of, it is possible to control various properties such as compatibility with other resins while maintaining excellent properties derived from halogen groups, and to form a polymer alloy by mixing with other resins Or used as a compatibilizer. It is also useful as an intermediate for producing the modified halogen-containing polyolefin-based resin of the present invention 2.
The modified halogen-containing polyolefin resin of the present invention 2 has a structure in which a part of the halogen group of the polyvinyl halide is substituted with another functional group, and further, a double bond is introduced into a part of the main chain, if necessary. By adjusting the content of halogen groups, other functional groups and double bonds, the properties derived from other functional groups are imparted while maintaining the excellent properties derived from halogen groups. Properties, such as compatibility with other resins, can be controlled, and can be mixed with other resins to form a polymer alloy or used as a compatibilizer.
[0046]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0047]
(Example 1)
10 g of polyvinyl alcohol (polymerization degree: 99%, saponification degree: 99%, PVA105, manufactured by Kuraray Co., Ltd.) is charged into the batch-type reaction vessel 1 (pressure-resistant glass, barrel-shaped vessel, inner volume: 100 mL) shown in FIG. 1 and fixed. After sufficiently sealing with the screw 1, the reaction vessel 1 was heated to 250 ° C. Next, the stop valve 8 was opened, the water stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, the pressure in the reaction vessel was increased to 30 MPa, and the pressure was maintained for 5 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling with ice, the obtained liquid was precipitated in isopropanol to obtain a yellow-white solid. Dissolution of the yellow-white solid in water and precipitation in isopropanol was repeated three times, and after sufficient washing, vacuum drying was finally performed to obtain a yellow-white solid. After the obtained yellow-white solid was dissolved in water, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to carbon-carbon double bonds were detected. At the same time, a hydroxyl group peak was detected.
Further, the degree of polymerization of the obtained yellow-white solid was measured by gel permeation chromatography and found to be about 500.
[0048]
(Example 2)
10 g of polyvinyl alcohol having a polymerization degree of 500 was charged into a batch-type reaction vessel 1 (manufactured by Pressure-Resistant Glass Co., Ltd., barrel-shaped vessel, internal volume of 100 mL) shown in FIG. Vessel 1 was heated to 150 ° C. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, the pressure in the reaction vessel was increased to 8 MPa, and the pressure was maintained for 30 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling on ice, the obtained solid was repeatedly dissolved in water and precipitated in isopropanol three times, and after sufficiently washing, finally vacuum dried to obtain a yellow-white solid.
After dissolving the obtained yellow-white solid in water, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to a carbon-carbon double bond were detected. At the same time, a hydroxyl group peak was detected.
Further, the degree of polymerization of the obtained yellow-white solid was measured by gel permeation chromatography and found to be about 500.
[0049]
(Example 3)
The batch-type reaction vessel (pressure-resistant glass company) shown in FIG. 1 was prepared by using 10 g of the yellow-white solid obtained in Example 1 and 10 g of a methacryl-based siloxane macromonomer having a molecular weight of 1000 and having a methacryloxy group (manufactured by Chisso Corporation, Silaprene FM0711). After the reaction container 1 was heated to 150 ° C. after being sufficiently sealed with a fixing screw 2. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, the pressure in the reaction vessel 1 was increased to 8 MPa, and the pressure was maintained for 30 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling with ice, the obtained solid was repeatedly dissolved in dimethylsulfoxide and precipitated in acetone three times, and after sufficiently washing the solid, vacuum drying was performed to obtain a white solid.
After dissolving the obtained white solid in dimethyl sulfoxide, a UV absorption spectrum was measured with a spectrophotometer, and a peak due to a carbon-carbon double bond was detected. At the same time, absorption due to hydroxyl groups was detected.
Furthermore, when fluorescent X-ray measurement was performed on the obtained white solid, silicon due to siloxane was detected. When the molecular weight was measured by gel permeation chromatography, the molecular weight was shifted to a higher molecular weight side as compared with the degree of polymerization of the yellowish white solid (polyvinyl alcohol-polyene compound) obtained in Example 1 used as a raw material.
[0050]
(Example 4)
The batch-type reaction vessel (pressure-resistant glass company) shown in FIG. 1 was prepared by using 10 g of the yellow-white solid obtained in Example 1 and 10 g of a methacryl-based siloxane macromonomer having a molecular weight of 1000 and having a methacryloxy group (manufactured by Chisso Corporation, Silaprene FM0711). After the reaction vessel 1 was heated to 250 ° C., the vessel was sufficiently sealed with a fixing screw 2. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel 1 was increased to 30 MPa and maintained for 5 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling with ice, the obtained solid was repeatedly dissolved in dimethylsulfoxide and precipitated in acetone three times, and after sufficiently washing the solid, vacuum drying was performed to obtain a white solid.
After the obtained white solid was dissolved in dimethyl sulfoxide, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to a carbon-carbon double bond were detected. At the same time, a hydroxyl group peak was detected.
Furthermore, when fluorescent X-ray measurement was performed on the obtained white solid, silicon due to siloxane was detected. When the molecular weight was measured by gel permeation chromatography, the molecular weight was shifted to a higher molecular weight side as compared with the degree of polymerization of the yellowish white solid (polyvinyl alcohol-polyene compound) obtained in Example 1 used as a raw material.
[0051]
(Example 5)
10 g of the yellow-white solid obtained in Example 1 and 0.5 g of hydrogen fluoride were charged into a batch-type reaction vessel 1 (pressure-resistant glass, barrel-shaped vessel, internal volume 100 mL) shown in FIG. After sufficiently sealing with the fixing screw 2, the reaction vessel 1 was heated to 150 ° C. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 30 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling on ice, a white solid was obtained. Dissolution of the white solid in dimethyl sulfoxide and precipitation in isopropanol was repeated three times, and the solid was sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
After the obtained white solid was dissolved in dimethyl sulfoxide, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to a carbon-carbon double bond were detected. At the same time, a hydroxyl group peak was detected.
Furthermore, when the obtained white solid was subjected to fluorescent X-ray measurement, the presence of a fluorine atom could be confirmed. When the molecular weight of the obtained white solid was measured by gel permeation chromatography, it was higher than the degree of polymerization of the yellowish white solid (polyvinyl alcohol-polyene compound) obtained in Example 1 used as a raw material. It shifted to the molecular weight side.
[0052]
(Example 6)
10 g of the yellow-white solid obtained in Example 1 and 0.5 g of hydrogen fluoride were charged into a batch-type reaction vessel 1 (pressure-resistant glass, barrel-shaped vessel, internal volume 100 mL) shown in FIG. After sufficiently sealing with the fixing screw 2, the reaction vessel 1 was heated to 250 ° C. Next, the stop valve 8 was opened, and the water stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 300 MPa and maintained for 5 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling on ice, a white solid was obtained. Dissolution of the white solid in dimethyl sulfoxide and precipitation in isopropanol was repeated three times, and the solid was sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
After the obtained white solid was dissolved in dimethyl sulfoxide, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to a carbon-carbon double bond were detected. At the same time, a hydroxyl group peak was detected.
Furthermore, when the obtained white solid was subjected to fluorescent X-ray measurement, the presence of a fluorine atom could be confirmed. When the molecular weight of the obtained white solid was measured by gel permeation chromatography, the peak was higher than that of the yellowish white solid (polyvinyl alcohol-polyene compound) obtained in Example 1 in which the peak was used as a raw material. Shifted to the side.
[0053]
(Example 7)
The batch method shown in FIG. 1 was composed of 10 g of polyvinyl alcohol having a degree of polymerization of 500 (99% saponification degree, manufactured by Kuraray Co., Ltd., PVA105) and a methacryl-based siloxane macromonomer having a molecular weight of 1,000 and having a methacryloxy group (manufactured by Chisso Corporation, Cylaprene FM0711). Was placed in a reaction container 1 (manufactured by Pressure Glass Co., Ltd., barrel-shaped container, internal volume: 100 mL), sufficiently sealed with a fixing screw 1, and then heated to 250 ° C. Next, the stop valve 8 was opened, the water stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, the pressure in the reaction vessel was increased to 30 MPa, and the pressure was maintained for 10 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When fluorescent X-ray measurement was performed on the obtained white solid, silicon caused by siloxane was detected. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to both sides of the polymer as compared with the polyvinyl alcohol used as the raw material.
[0054]
(Example 8)
The batch method shown in FIG. 1 was composed of polyvinyl alcohol having a polymerization degree of 500 (99% saponification degree, manufactured by Kuraray Co., Ltd., PVA105) and 10 g of a methacryl-based siloxane macromonomer having a molecular weight of 1000 and having a methacryloxy group (manufactured by Chisso Co., Silaplane FM0711). Was placed in a reaction vessel 1 (manufactured by Pressure-Resistant Glass Co., Ltd., barrel-shaped vessel, internal volume: 100 mL), sufficiently sealed with a fixing screw 1, and then heated to 80 ° C. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 1 hour. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When fluorescent X-ray measurement was performed on the obtained white solid, silicon caused by siloxane was detected. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to both sides of the polymer as compared with the polyvinyl alcohol used as the raw material.
[0055]
(Example 9)
Batch reaction vessel 1 shown in FIG. 1 containing polyvinyl alcohol having a polymerization degree of 500 (99% saponification degree, PVA105 manufactured by Kuraray Co., Ltd.) and 0.5 g of hydrogen fluoride. 100 mL), and after sufficiently sealing with the fixing screw 1, the reaction vessel 1 was heated to 80 ° C. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 1 hour. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When fluorescent X-ray measurement was performed on the obtained white solid, fluorine was detected. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to both sides of the polymer as compared with the polyvinyl alcohol used as the raw material.
[0056]
(Example 10)
10 g of the yellowish white solid obtained in Example 1 and 1 g of butyl glycidyl ether (Sakamoto Pharmaceutical Industrial Co., Ltd., BGE-R) shown in FIG. Then, the reaction vessel 1 was heated to 80 ° C. after being sufficiently sealed with the fixing screw 1. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 1 hour. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When an infrared absorption spectrum of the obtained white solid was measured, it was confirmed that an ether group was present due to the addition of a glycidyl group. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to the high molecular weight side as compared with the yellowish white solid (polyvinyl alcohol-polyene compound) obtained in Example 1 used as a raw material.
[0057]
(Example 11)
10 g of the yellowish white solid obtained in Example 1 and 1 g of butyl glycidyl ether (Sakamoto Pharmaceutical Industrial Co., Ltd., BGE-R) shown in FIG. Then, the reaction vessel 1 was heated to 80 ° C. after being sufficiently sealed with the fixing screw 1. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 1 hour. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When an infrared absorption spectrum of the obtained white solid was measured, it was confirmed that an ether group was present due to the addition of a glycidyl group. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to the high molecular weight side as compared with the yellowish white solid (polyvinyl alcohol-polyene compound) obtained in Example 1 used as a raw material.
[0058]
(Example 12)
Batch reaction vessel 1 (pressure-resistant glass company) shown in FIG. 1 containing polyvinyl alcohol having a polymerization degree of 500 (99% saponification degree, manufactured by Kuraray Co., PVA105) and 1 g of butyl glycidyl ether (Sakamoto Pharmaceutical Industrial, BGE-R). After the reaction vessel 1 was heated to 80 ° C. after being sufficiently sealed with the fixing screw 1. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 1 hour. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When an infrared absorption spectrum of the obtained white solid was measured, it was confirmed that an ether group was present due to the addition of a glycidyl group. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to both sides of the polymer as compared with the polyvinyl alcohol used as the raw material.
[0059]
(Example 13)
Batch-type reaction vessel 1 (manufactured by Pressure Glass Co., Ltd., barrel-shaped vessel, internal volume 100 mL) shown in FIG. ) And sufficiently sealed with the fixing screw 1, and then the reaction vessel 1 was heated to 80 ° C. Next, the stop valve 8 was opened, the carbon dioxide stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 1 hour. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
When the obtained white solid was subjected to fluorescent X-ray measurement, the presence of sulfur derived from thiol was confirmed. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to both sides of the polymer as compared with the polyvinyl alcohol used as the raw material.
[0060]
(Example 14)
After charging 10 g of polyvinyl chloride having a polymerization degree of 500 into the batch-type reaction vessel 1 (manufactured by Pressure Glass Co., Ltd., barrel-shaped vessel, internal volume of 100 mL) shown in FIG. 1 and sufficiently sealing with the fixing screw 1, Reaction vessel 1 was heated to 250 ° C. Next, the stop valve 8 was opened, the water stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, the pressure in the reaction vessel was increased to 30 MPa, and the pressure was maintained for 5 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled with ice. After cooling with ice, the obtained liquid was precipitated in isopropanol to obtain a yellow-white solid. Dissolution of the yellow-white solid in water and precipitation in isopropanol was repeated three times, and after sufficient washing, vacuum drying was finally performed to obtain a yellow-white solid.
After the obtained yellow-white solid was dissolved in water, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to carbon-carbon double bonds were detected.
Further, when the obtained yellow-white solid was subjected to fluorescent X-ray measurement, the presence of chlorine atoms was confirmed. Further, the degree of polymerization of the obtained yellow-white solid was measured by gel permeation chromatography and found to be about 500.
[0061]
(Example 15)
10 g of the yellowish-white solid obtained in Example 14 and 1 g of water were put into the batch-type reaction vessel 1 (pressure-resistant glass, barrel-shaped vessel, internal volume 100 mL) shown in FIG. After sufficiently sealing using, the reaction vessel 1 was heated to 250 ° C. Next, the stop valve 8 was opened, and the isopropanol stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 5 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
After the obtained white solid was dissolved in dimethyl sulfoxide, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to a carbon-carbon double bond were detected. At the same time, a hydroxyl group peak was detected. Further, when the obtained white solid was subjected to fluorescent X-ray measurement, the presence of chlorine was confirmed. When the molecular weight was measured by gel permeation chromatography, the peak was shifted to the high molecular weight side as compared with the yellowish white solid (polyvinyl chloride-polyene compound) obtained in Example 14 used as a raw material.
[0062]
(Example 16)
10 g of polyvinyl chloride having a polymerization degree of 1500 and 1 g of water are put into a batch-type reaction vessel 1 (manufactured by Pressure Glass Co., Ltd., barrel-shaped vessel, internal volume of 100 mL) shown in FIG. After sealing, the reaction vessel 1 was heated to 250 ° C. Next, the stop valve 8 was opened, and the isopropanol stored in the fluid storage tank 6 was introduced into the reaction vessel 1 by the pump 7, and the pressure in the reaction vessel was increased to 8 MPa and maintained for 5 minutes. After the reaction, the reaction vessel 1 was rapidly cooled by a cooling bath, and then cooled down. Dissolution of the resulting white precipitate in dimethylsulfoxide and precipitation in acetone was repeated three times, and sufficiently washed. Finally, vacuum drying was performed to obtain a white solid.
After the obtained white solid was dissolved in dimethyl sulfoxide, the UV absorption spectrum was measured with a spectrophotometer. As a result, peaks at 230 nm, 280 nm, and 330 nm due to a carbon-carbon double bond were detected. At the same time, a hydroxyl group peak was detected. Further, when the obtained white solid was subjected to fluorescent X-ray measurement, the presence of chlorine was confirmed.
[0063]
【The invention's effect】
According to the present invention, it is possible to provide a modified halogen-containing polyolefin-based resin having a practical degree of polymerization and capable of forming a polymer alloy with another resin or being used as a compatibilizer.
[Brief description of the drawings]
FIG. 1 is a schematic view showing one embodiment of a production apparatus for producing a modified halogen-containing polyolefin-based resin of the present invention.
FIG. 2 is a schematic view showing one embodiment of a production apparatus for producing the modified halogen-containing polyolefin-based resin of the present invention.
[Explanation of symbols]
1 reaction vessel
2 Fixing screw
3 heater
4 Thermocouple
5 stirring wings
6. Fluid storage tank
7 pump
8 Stop valve
9 Pressure gauge
11 Conditioning tank or polymerization reaction vessel
12 reaction vessels
13 Supply means
14a Supply means
14b supply means
14c Container for fluid
14d fluid container
15 heating means
16 heat exchanger
17 Separator
18 heating means
19 Distillation tower
20 Pressure control valve

Claims (8)

A modified halogen-containing polyolefin resin having a structure represented by the following general formula (1) and having an average degree of polymerization of 100 or more.

In the formula (1), X represents a halogen group, and m and n represent integers. A modified halogen-containing polyolefin resin having a structure represented by the following general formula (2) and having an average degree of polymerization of 100 or more.

In the formula (2), p, q, and r represent integers, X represents a halogen group, and Y represents a halogen group different from X, a hydroxyl group, or a vinyl group, an acryloyl group, a methacryloyl group, a thiol group, and glycidyl. Represents a group derived from a compound having a group, a silanol group or an alicyclic epoxy group. A modified halogen-containing polyolefin resin having a structure represented by the following general formula (2) and having an average degree of polymerization of 100 or more.

In the formula (2), p, q, and r represent integers, X represents a halogen group, and Y represents styrene, acrylic acid, methacrylic acid, acrylate, methacrylate, maleic anhydride, an acrylic macromonomer, It represents a group derived from a styrene-based macromonomer or an acryl-styrene-based macromonomer. A modified halogen-containing polyolefin resin having a structure represented by the following general formula (2) and having an average degree of polymerization of 100 or more.

In the formula (2), p, q, and r represent integers, X represents a halogen group, and Y represents a group derived from a siloxane-based macromonomer. A modified halogen-containing polyolefin resin having a structure represented by the following general formula (2) and having an average degree of polymerization of 100 or more.

In the formula (2), p, q, and r represent integers, X represents a halogen group, and Y represents a hydroxyl group. A modified halogen-containing polyolefin resin having a structure represented by the following general formula (2) and having an average degree of polymerization of 100 or more.

In the formula (2), p, q, and r represent integers, X represents a halogen group other than fluorine, and Y represents a group derived from fluorine or a fluorinated unsaturated olefin. 6. The modified halogen-containing polyolefin-based resin according to claim 1, wherein X is a fluorine group. 7. The modified halogen-containing polyolefin resin according to claim 1, wherein X is a chlorine group.

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