JP2004256719A - Polyester polymerization catalyst and manufacturing process of polyester using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization catalyst which gives a polyester scarcely containing foreign matters and having good color tone, and a manufacturing process of the polyester using it. <P>SOLUTION: The catalyst for polymerizing the polyester is a compound in which the number of titanium atoms in one molecule is 4-8, the composition ratio of titanium atoms to phosphorus atoms is 0.7-2, and which has at least one Ti-O-Ti bond. The manufacturing process of the polyester uses it. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００２１】
（式１〜式６中、Ｒ_１〜Ｒ_３はそれぞれ独立に水素、炭素数１〜３０の炭化水素基、アルコキシ基または水酸基またはカルボニル基またはアセチル基またはカルボキシル基またはエステル基またはアミノ基を有する炭素数１〜３０の炭化水素基を表す。）
本発明の式１としては、エトキシド、プロポキシド、イソプロポキシド、ブトキシド、２−エチルヘキソキシド等のアルコキシ基、乳酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシ多価カルボン酸系化合物からなる官能基が挙げられる。
【００２２】
また、式２としては、アセチルアセトン等のβ−ジケトン系化合物、アセト酢酸メチル、アセト酢酸エチル等のケトエステル系化合物からなる官能基が挙げられる。
【００２３】
また、式３としては、フェノキシ、クレシレイト、サリチル酸等からなる官能基が挙げられる。
【００２４】
また、式４としては、ラクテート、ステアレート等のアシレート基、フタル酸、トリメリット酸、トリメシン酸、ヘミメリット酸、ピロメリット酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、シクロヘキサンジカルボン酸またはそれらの無水物等の多価カルボン酸系化合物、エチレンジアミン四酢酸、ニトリロ三プロピオン酸、カルボキシイミノ二酢酸、カルボキシメチルイミノ二プロピオン酸、ジエチレントリアミノ五酢酸、トリエチレンテトラミノ六酢酸、イミノ二酢酸、イミノ二プロピオン酸、ヒドロキシエチルイミノ二酢酸、ヒドロキシエチルイミノ二プロピオン酸、メトキシエチルイミノ二酢酸等の含窒素多価カルボン酸からなる官能基が挙げられる。
【００２５】
また、式５としては、アニリン、フェニルアミン、ジフェニルアミン等からなる官能基が挙げられる。
中でも式１及び／または式４が含まれていることがポリマーの熱安定性及び色調の観点から好ましい。
【００２６】
本発明のポリエステル重合用触媒は、末端の置換基を有するチタン原子１つあたりの末端基の数Ｔ／Ｕが、下記式（２）に示す範囲内にあることが好ましい。
１≦Ｔ／Ｕ＜１．５ （２）
（式中、Ｔはチタン原子の置換基のうち末端の数、Ｕは末端の置換基を有するチタン原子の数）
この値が過大の場合には実用に耐える色調が得られない恐れがあり、過小の場合には十分な活性が得られない恐れがある。より好ましくは、１．１０以上１．３５未満である。
【００２７】
本発明のポリエステル重合用触媒の合成方法は、例えば（１）チタン化合物を溶媒に混合してその一部または全部を溶媒中に溶解し、この混合溶液にリン化合物と微量の水を溶媒に溶解または希釈させ滴下する。（２）ヒドロキシカルボン酸系化合物や多価カルボン酸系化合物等のチタン化合物の配位子を用いる場合は、チタン化合物または配位子化合物を溶媒に混合してその一部または全部を溶媒中に溶解し、この混合溶液に配位子化合物またはチタン化合物を原液または溶媒に溶解希釈させ滴下し、その後、この混合溶液にさらにリン化合物を加えることにより得られる。特にこの際、リン化合物と微量の水を溶媒に溶解希釈させ滴下することが、異物形成抑制および色調改善の観点から好ましい。上記の反応条件は０〜２００℃の温度で１分以上、さらには２０〜１００℃の温度で２〜１００分間加熱することによって行うことが好ましい。この際の反応圧力に特に制限はなく、常圧でも良い。また、ここで用いる溶媒は、チタン化合物、リン化合物及びチタン原子に結合する化合物の一部または全部を溶解し得るものから選択することができるが、具体的には、メタノール、エタノール、１−プロパノール、２−プロパノール、エチレングリコール、プロパンジオール、ブタンジオール、ジエチルエーテル、アセトン、酢酸エチル、ジメチルスルホキシド、ジメチルホルムアミド、テトラヒドロフラン、ジクロロメタン、１，２−ジクロロエタン等が挙げられる。
【００２８】
なお、本発明のポリエステル重合用触媒の合成において使用する原料チタン化合物としては、前記置換基を有するもの、もしくはそれらと容易に交換可能な置換基を有するものであれば、特に限定されない。具体的には、チタンテトライソプロポキシド、チタンテトラブトキシド、チタンジイソプロポキシビスアセチルアセトナート、チタントリエタノールアミネートイソプロポキシドなどが挙げられる。 また、出発原料のリン化合物としては、リン酸系、亜リン酸系、ホスホン酸系、ホスフィン酸系、ホスフィンオキサイド系、亜ホスホン酸系、亜ホスフィン酸系、ホスフィン系から選ばれる少なくとも１種であることが好ましく、いずれか１種または２種であることがより好ましい。具体的には、例えば、リン酸、リン酸トリメチル、リン酸トリエチル、リン酸トリフェニル等のリン酸系、亜リン酸、亜リン酸トリメチル、亜リン酸トリエチル、亜リン酸トリフェニル等の亜リン酸系、メチルホスホン酸、エチルホスホン酸、プロピルホスホン酸、イソプロピルホスホン酸、ブチルホスホン酸、フェニルホスホン酸、ベンジルホスホン酸、トリルホスホン酸、キシリルホスホン酸、ビフェニルホスホン酸、ナフチルホスホン酸、アントリルホスホン酸、２−カルボキシフェニルホスホン酸、３−カルボキシフェニルホスホン酸、４−カルボキシフェニルホスホン酸、２，３−ジカルボキシフェニルホスホン酸、２，４−ジカルボキシフェニルホスホン酸、２，５−ジカルボキシフェニルホスホン酸、２，６−ジカルボキシフェニルホスホン酸、３，４−ジカルボキシフェニルホスホン酸、３，５−ジカルボキシフェニルホスホン酸、２，３，４−トリカルボキシフェニルホスホン酸、２，３，５−トリカルボキシフェニルホスホン酸、２，３，６−トリカルボキシフェニルホスホン酸、２，４，５−トリカルボキシフェニルホスホン酸、２，４，６−トリカルボキシフェニルホスホン酸、メチルホスホン酸ジメチルエステル、メチルホスホン酸ジエチルエステル、エチルホスホン酸ジメチルエステル、エチルホスホン酸ジエチルエステル、フェニルホスホン酸ジメチルエステル、フェニルホスホン酸ジエチルエステル、フェニルホスホン酸ジフェニルエステル、ベンジルホスホン酸ジメチルエステル、ベンジルホスホン酸ジエチルエステル、ベンジルホスホン酸ジフェニルエステル、リチウム（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、ナトリウム（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、マグネシウムビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、カルシウムビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、ジエチルホスホノ酢酸、ジエチルホスホノ酢酸メチル、ジエチルホスホノ酢酸エチル等のホスホン酸系化合物、次亜リン酸、次亜リン酸ナトリウム、メチルホスフィン酸、エチルホスフィン酸、プロピルホスフィン酸、イソプロピルホスフィン酸、ブチルホスフィン酸、フェニルホスフィン酸、トリルホスフィン酸、キシリルホスフィン酸、ビフェニリルホスフィン酸、ジフェニルホスフィン酸、ジメチルホスフィン酸、ジエチルホスフィン酸、ジプロピルホスフィン酸、ジイソプロピルホスフィン酸、ジブチルホスフィン酸、ジトリルホスフィン酸、ジキシリルホスフィン酸、ジビフェニリルホスフィン酸、ナフチルホスフィン酸、アントリルホスフィン酸、２−カルボキシフェニルホスフィン酸、３−カルボキシフェニルホスフィン酸、４−カルボキシフェニルホスフィン酸、２，３−ジカルボキシフェニルホスフィン酸、２，４−ジカルボキシフェニルホスフィン酸、２，５−ジカルボキシフェニルホスフィン酸、２，６−ジカルボキシフェニルホスフィン酸、３，４−ジカルボキシフェニルホスフィン酸、３，５−ジカルボキシフェニルホスフィン酸、２，３，４−トリカルボキシフェニルホスフィン酸、２，３，５−トリカルボキシフェニルホスフィン酸、２，３，６−トリカルボキフェニルホスフィン酸、２，４，５−トリカルボキシフェニルホスフィン酸、２，４，６−トリカルボキシフェニルホスフィン酸、ビス（２−カルボキシフェニル）ホスフィン酸、ビス（３−カルボキシフェニル）ホスフィン酸、ビス（４−カルボキシフェニル）ホスフィン酸、ビス（２，３−ジカルボキルシフェニル）ホスフィン酸、ビス（２，４−ジカルボキシフェニル）ホスフィン酸、ビス（２，５−ジカルボキシフェニル）ホスフィン酸、ビス（２，６−ジカルボキシフェニル）ホスフィン酸、ビス（３，４−ジカルボキシフェニル）ホスフィン酸、ビス（３，５−ジカルボキシフェニル）ホスフィン酸、ビス（２，３，４−トリカルボキシフェニル）ホスフィン酸、ビス（２，３，５−トリカルボキシフェニル）ホスフィン酸、ビス（２，３，６−トリカルボキシフェニル）ホスフィン酸、ビス（２，４，５−トリカルボキシフェニル）ホスフィン酸、およびビス（２，４，６−トリカルボキシフェニル）ホスフィン酸、メチルホスフィン酸メチルエステル、ジメチルホスフィン酸メチルエステル、メチルホスフィン酸エチルエステル、ジメチルホスフィン酸エチルエステル、エチルホスフィン酸メチルエステル、ジエチルホスフィン酸メチルエステル、エチルホスフィン酸エチルエステル、ジエチルホスフィン酸エチルエステル、フェニルホスフィン酸メチルエステル、フェニルホスフィン酸エチルエステル、フェニルホスフィン酸フェニルエステル、ジフェニルホスフィン酸メチルエステル、ジフェニルホスフィン酸エチルエステル、ジフェニルホスフィン酸フェニルエステル、ベンジルホスフィン酸メチルエステル、ベンジルホスフィン酸エチルエステル、ベンジルホスフィン酸フェニルエステル、ビスベンジルホスフィン酸メチルエステル、ビスベンジルホスフィン酸エチルエステル、ビスベンジルホスフィン酸フェニルエステル等のホスフィン酸系、トリメチルホスフィンオキサイド、トリエチルホスフィンオキサイド、トリプロピルホスフィンオキサイド、トリイソプロピルホスフィンオキサイド、トリブチルホスフィンオキサイド、トリフェニルホスフィンオキサイド等のホスフィンオキサイド系、メチル亜ホスホン酸、エチル亜ホスホン酸、プロピル亜ホスホン酸、イソプロピル亜ホスホン酸、ブチル亜ホスホン酸、フェニル亜ホスホン酸等の亜ホスホン酸系、メチル亜ホスフィン酸、エチル亜ホスフィン酸、プロピル亜ホスフィン酸、イソプロピル亜ホスフィン酸、ブチル亜ホスフィン酸、フェニル亜ホスフィン酸、ジメチル亜ホスフィン酸、ジエチル亜ホスフィン酸、ジプロピル亜ホスフィン酸、ジイソプロピル亜ホスフィン酸、ジブチル亜ホスフィン酸、ジフェニル亜ホスフィン酸等の亜ホスフィン酸系等が挙げられ、これらの少なくとも１種、もしくは、いずれか１種または２種であることが好ましい。特に異物抑制および色調改善の観点から、リン酸系および／またはホスホン酸系であることが好ましく、中でも、リン酸系リン化合物が、リン酸および／またはリン酸エステル化合物、ホスホン酸系リン化合物が、ホスホン酸および／またはホスホン酸エステル化合物であることが好ましい
なお、本発明の触媒とは、ジカルボン酸またはそのエステル形成性誘導体およびジオールまたはそのエステル形成性誘導体から合成されるポリマーにおいて、実質的にエステル反応またはエステル交換反応が終了し、得られたポリエチレンテレフタレート低重合体を脱ジオール反応にて高重合度化せしめる重縮合反応全てまたは一部の素反応の反応促進に実質的に寄与する化合物を指す。
【００２９】
従って、繊維の艶消し剤等に無機粒子として一般的に用いられている二酸化チタン粒子は上記の反応に対して実質的に触媒作用を有しておらず、本発明の触媒として用いることができるチタンとリンの化合物とは異なる。
【００３０】
本発明におけるチタンとリンの化合物（二酸化チタン粒子を除く）は得られるポリマーに対してチタン原子換算で０．５〜１５０ｐｐｍ含有されていることが好ましい。１〜１００ｐｐｍであるとポリマーの熱安定性や色調がより良好となり好ましく、更に好ましくは３〜５０ｐｐｍである。
【００３１】
本発明で用いるチタンとリンの化合物は、ポリエステルの反応系にそのまま添加してもよいが、予めエチレングリコールやプロピレングリコール等のポリエステルを形成するジオール成分を含む溶媒と混合し、溶液またはスラリーとし、必要に応じて該化合物合成時に用いたアルコール等の低沸点成分を除去した後、反応系に添加すると、ポリマー中での異物生成がより抑制されるため好ましい。添加時期は、実質的に重縮合反応開始前であればよく、エステル化反応やエステル交換反応の前、あるいは反応終了後、重縮合反応触媒が開始される前に添加してもよい。さらに、色調改善および熱安定性の観点から、リン化合物を別途添加してもよい。この場合、チタンとリンの化合物を含む本発明のポリエステル重合用触媒とリン化合物が接触することによる触媒の失活を抑制するために、異なる反応槽に添加する方法や、同一の反応槽において本発明のポリエステル重合用触媒とリン化合物の添加間隔を１〜１５分とする方法や添加位置を離す方法を用いてもよい。
【００３２】
本発明のポリエステルの製造方法において任意の時点でコバルト化合物またはマンガン化合物を添加すると得られるポリマーの色調が良好となり好ましい。この場合に用いるコバルト化合物としては特に限定はないが、具体的には、例えば、塩化コバルト、硝酸コバルト、炭酸コバルト、コバルトアセチルアセトネート、ナフテン酸コバルト、酢酸コバルト四水塩等が挙げられる。また、マンガン化合物についても特に限定はないが、具体的には、例えば、塩化マンガン、臭化マンガン、硝酸マンガン、炭酸マンガン、マンガンアセチルアセトネート、酢酸マンガン四水塩、酢酸マンガン二水塩等が挙げられる。
【００３３】
また、得られるポリマーの色調やポリマーの熱安定性を向上させる目的で、アルカリ金属化合物、アルカリ土類金属化合物、アルミニウム化合物、亜鉛化合物、スズ化合物等を添加してもよい。
【００３４】
さらに、二酸化チタン、酸化ケイ素、炭酸カルシウム、チッ化ケイ素、クレー、タルク、カオリン、カーボンブラック等の粒子のほか、着色防止剤、安定剤、抗酸化剤等を添加しても差支えない。
【００３５】
本発明のポリエステルの製造方法を説明する。具体例としてポリエチレンテレフタレートの例を記載するがこれに限定されるものではない。
【００３６】
ポリエチレンテレフタレートは通常、次のいずれかのプロセスで製造される。すなわち、（１）テレフタル酸とエチレングリコールを原料とし、直接エステル化反応によって低重合体を得、さらにその後の重縮合反応によって高分子量ポリマーを得るプロセス、（２）ジメチルテレフタレートとエチレングリコールを原料とし、エステル交換反応によって低重合体を得、さらにその後の重縮合反応によって高分子量ポリマーを得るプロセスである。また、エステル交換反応においては、マンガン、カルシウム、マグネシウム、亜鉛、リチウム等の化合物を用いて進行させ、またエステル交換反応が実質的に完結した後に、該反応に用いた触媒を不活性化する目的で、リン化合物を添加することが行われる。
【００３７】
本発明の製造方法は、（１）または（２）の一連の反応の任意の段階、好ましくは（１）または（２）の一連の反応の前半で得られた低重合体に、艶消し剤として二酸化チタン粒子や、コバルト化合物、マンガン化合物等の添加物を添加した後、重縮合触媒として前述のチタンとリンの化合物を添加し重縮合反応を行い、高分子量のポリエチレンテレフタレートを得るというものである。
【００３８】
また、上記の反応は回分式、半回分式あるいは連続式等の形式に適応し得る。
【００３９】
【実施例】
以下実施例により本発明をさらに詳細に説明する。なお、実施例中の物性値は以下に述べる方法で測定した。
（１）ポリマーの固有粘度ＩＶ
オルソクロロフェノールを溶媒として２５℃で測定した。
（２）ポリマーの色調
得られたポリマーを溶融状態から急冷し、チップ状に成形してから、石英ガラス製の容器に充填した状態でハンター型色差計（スガ試験機（株）製ＳＭカラーコンピュータ型式ＳＭ−３）を用いて測定し、ハンターのＬ、ｂ値を得た。
【００４０】
ポリマー色調としてはｂ値が４以下であることが好ましく、より好ましくは３以下、特に好ましくは１．５以下である。
（３）溶液ヘイズ
測定する試料２．０ｇをオルソクロロフェノール２０ｍＬに溶解させ、ヘイズメーター（スガ試験機社製，ＨＧＭ−２ＤＰ型）を用い、積分球式光電光度法にて分析を行った。ポリマー中の異物量としては、ヘイズ値が２．０以下であることが好ましく、より好ましくは、１．５以下である。
（４）ポリエステル中のチタン元素、リン元素の含有量
蛍光Ｘ線元素分析装置（堀場製作所社製、ＭＥＳＡ−５００Ｗ型）により求めた。なお、ポリエステルに二酸化チタン粒子が含有されている際には、次の前処理をした上で蛍光Ｘ線分析を行った。すなわち、ポリエステルをオルソクロロフェノールに溶解（溶媒１００ｇに対してポリマー５ｇ）し、このポリマー溶液と同量のジクロロメタンを加えて溶液の粘性を調製した後、遠心分離器（回転数１８０００ｒｐｍ、１時間）で粒子を沈降させる。その後、傾斜法で上澄み液のみを回収し、上澄み液と同量のアセトンを添加することによりポリマーを再析出させ、そのあと３Ｇ３のガラスフィルター（ＩＷＡＫＩ社製）で濾過し、濾上物をさらにアセトンで洗浄した後、室温で１２時間真空乾燥してアセトンを除去した。以上の前処理を施して得られたポリマーについてチタン元素、リン元素、アンチモン元素及びマンガン元素の分析を行った。
【００４１】
一方、二酸化チタン粒子が含有されていない場合は、前処理を行う必要がないので、ポリマーをそのまま分析すればよい。
（５）Ｔｉ−Ｏ−Ｔｉの有無、単酸素原子数Ｐ、リン原子に結合する酸素全原子数Ｒ、そのうちＴｉと結合している数
触媒調製にて得られた固体状の触媒化合物のＸ線結晶構造解析を行い（リガク電機製単結晶自動Ｘ線構造解析装置ＲＡＳＡ−７）、原子間距離が各イオン半径の和よりも小さい場合に各原子間に相互作用があると判定した。チタン原子と酸素原子のイオン半径の和は２．８７Å、リン原子と酸素原子のイオン半径距離の和は１．７３Å。
【００４２】
実施例１
Ａ．触媒の調製
撹拌機および温度計を備えた１Ｌのフラスコ中でジメチルスルホキシド（５００ｍｌ）にテトライソプロポキシド（３５６ｇ、１．２５モル）を溶解させた。この撹拌されている溶液に、滴下漏斗からフェニルホスホン酸（１００ｇ、０．６３モル）と水（３．７８ｇ、０．２１モル）のジメチルスルホキシド溶液（１５０ｍｌ）をゆっくり加えた。この混合物を２５℃、常圧下、２時間撹拌した後、２日間放置すると、白色固体が生成する。この固体を濾別し、ジエチルエーテル（３００ｍｌ）を用いて洗浄した後、減圧乾燥させた（収量１０２ｇ）。この固体１０ｇを秤量し、エチレングリコール（４００ｍｌ）に分散させた。一方、この固体の構造解析を行い、１分子中にチタン原子数が４（Ｑ＝４）、リン原子数が３（Ｓ＝３），Ｔｉ_３−（μ_３ーＯ）のフラグメントを１つ有し（Ｐ＝１）、リン原子に結合する９つの酸素原子（Ｒ＝９）全てがチタン原子と結合しており、チタン原子の末端置換基数が５（Ｔ＝５）、その置換基をもつチタン原子数が４（Ｕ＝４）であることを確認した。
Ｂ．ポリエチレンテレフタレートの製造方法
高純度テレフタル酸（三井化学社製）１００ｋｇとエチレングリコール（日本触媒社製）４５ｋｇのスラリーを予めビス（ヒドロキシエチル）テレフタレート約１２３ｋｇが仕込まれ、温度２５０℃、圧力１．２×１０^５Ｐａに保持されたエステル化反応槽に４時間かけて供給し、供給終了後もさらに１時間かけてエステル化反応を完結させた。次に、このエステル化反応生成物の１２３ｋｇを重縮合槽に移送した。
【００４３】
引き続いて、エステル化反応生成物が移送された前記重縮合反応槽に、酸化チタン粒子のエチレングリコールスラリーを得られるポリマーに対して０．３重量％添加した。５分間撹拌した後、酢酸コバルトおよび酢酸マンガンのエチレングリコール溶液を得られるポリマーに対してコバルト原子換算で３０ｐｐｍ、マンガン原子換算で１５ｐｐｍとなるように加えた。更に５分間撹拌した後、上記触媒溶液を、得られるポリマーに対してチタン原子換算で１０ｐｐｍとなるように添加し、その後、低重合体を３０ｒｐｍで攪拌しながら、反応系を２５０℃から２８５℃まで徐々に昇温するとともに、圧力を４０Ｐａまで下げた。最終温度、最終圧力到達までの時間はともに６０分とした。所定の攪拌トルクとなった時点で反応系を窒素パージし常圧に戻し重縮合反応を停止し、冷水にストランド状に吐出、直ちにカッティングしてポリマーのペレットを得た。なお、減圧開始から所定の撹拌トルク到達までの時間は３時間であった。
【００４４】
表１に示すように、得られたポリマーのＩＶは０．６７、溶液ヘイズは０．５％と、異物が少なく、色調Ｌ値７４、ｂ値１．０と、色調が良好であった。
【００４５】
【表１】

【００４６】
比較例１、２
触媒化合物を構成するチタン原子の数およびリン原子の数が異なること以外は実施例１と同様に触媒調製および重合を行った。表２に示すように、ポリマーの色調が不良であり、比較例２については異物が多かった。
【００４７】
比較例３、４
触媒化合物を構成するチタン原子の数とリン原子の数の比が異なること以外は実施例１と同様にして触媒調製および重合を行った。共に色調が非常に悪化し、比較例３では触媒が失活しているためか、重合の進行が非常に遅かった。
【００４８】
比較例５
触媒化合物中にＴｉ−Ｏ−Ｔｉの結合がないこと以外は実施例１と同様に重合を行った。表２に示すように、色調は良好であったものの、異物が非常に多かった。
【００４９】
【表２】

【００５０】
実施例２、３
触媒化合物を構成するチタン原子の数およびリン原子の数が異なること以外は実施例１と同様に触媒調製および重合を行った。表１に示すように、いずれも異物が少なく、良好な色調のポリマーを与えた。
【００５１】
実施例４、５
触媒化合物を構成するチタン原子の数とリン原子の数の比が異なること以外は実施例１と同様に触媒調製および重合を行った。表１に示すように、いずれも異物が少なく、良好な色調のポリマーを与えた。
【００５２】
実施例６
触媒化合物中のリン原子に結合する酸素原子の一部がチタン原子と結合していないこと以外は実施例１と同様に触媒調製および重合を行った。異物が少なく、良好な色調のポリマーを与えた。
【００５３】
実施例７、８
触媒化合物に含まれるＴｉ−Ｏ−Ｔｉの結合の単酸素原子の数が異なること以外は実施例１と同様に触媒調製および重合を行った。異物が少なく、良好な色調のポリマーを与えた。
【００５４】
実施例９
触媒の調製以外は実施例１と同様に重合を行い、表３に示すように、異物が少なく、良好な色調のポリマーを得た。
【００５５】
なお、以下に触媒の調製方法を記す。
【００５６】
撹拌機、凝縮器および温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）に乳酸（２７０ｇ、３．００モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトラブトキシド（３４０ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりブタノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、真空下で加熱してブタノール／水を除去し、曇った淡黄色の生成物を得た。
【００５７】
この生成物を撹拌機および温度計を備えた１Ｌのフラスコ中でジメチルスルホキシド（５００ｍｌ）に溶解させた。この撹拌されている溶液に、滴下漏斗からフェニルホスホン酸（１００ｇ、０．６３モル）と水（３．７８ｇ、０．２１モル）のジメチルスルホキシド溶液（１５０ｍｌ）をゆっくり加えた。この混合物を２５℃、常圧下、２時間撹拌した後、２日間放置すると、白色固体が生成する。この固体を濾別し、ジエチルエーテル（３００ｍｌ）を用いて洗浄した後、減圧乾燥させた（収量９８ｇ）。この固体１０ｇを秤量し、エチレングリコール（４００ｍｌ）に分散させた。
【００５８】
【表３】

【００５９】
実施例１０
触媒の調製以外は実施例１と同様に重合を行い、表３に示すように、異物が少なく、良好な色調のポリマーを得た。
【００６０】
なお、以下に触媒の調製方法を記す。
【００６１】
撹拌機、凝縮器および温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）にマレイン酸（３４８ｇ、３．００モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトラブトキシド（３４０ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりブタノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、真空下で加熱してブタノール／水を除去し、わずかに曇った淡黄色の生成物を得た。
【００６２】
この生成物を撹拌機および温度計を備えた１Ｌのフラスコ中でジメチルスルホキシド（５００ｍｌ）に溶解させた。この撹拌されている溶液に、滴下漏斗からフェニルホスホン酸（１００ｇ、０．６３モル）と水（３．７８ｇ、０．２１モル）のジメチルスルホキシド溶液（１５０ｍｌ）をゆっくり加えた。この混合物を２５℃、常圧下、２時間撹拌した後、２日間放置すると、白色固体が生成する。この固体を濾別し、ジエチルエーテル（３００ｍｌ）を用いて洗浄した後、減圧乾燥させた（収量１２５ｇ）。この固体１０ｇを秤量し、エチレングリコール（４００ｍｌ）に分散させた。
【００６３】
実施例１１
触媒の調製以外は実施例１と同様に重合を行い、表３に示すように、異物が少なく、良好な色調のポリマーを得た。
【００６４】
なお、以下に触媒の調製方法を記す。
【００６５】
撹拌機、凝縮器および温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）にフェノール（２８２ｇ、３．００モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトラブトキシド（３４０ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりブタノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、真空下で加熱してブタノール／水を除去し、淡黄色の生成物を得た。
【００６６】
この生成物を撹拌機および温度計を備えた１Ｌのフラスコ中でジメチルスルホキシド（５００ｍｌ）に溶解させた。この撹拌されている溶液に、滴下漏斗からフェニルホスホン酸（１００ｇ、０．６３モル）と水（３．７８ｇ、０．２１モル）のジメチルスルホキシド溶液（１５０ｍｌ）をゆっくり加えた。この混合物を２５℃、常圧下、２時間撹拌した後、２日間放置すると、白色固体が生成する。この固体を濾別し、ジエチルエーテル（３００ｍｌ）を用いて洗浄した後、減圧乾燥させた（収量１３７ｇ）。この固体１０ｇを秤量し、エチレングリコール（４００ｍｌ）に分散させた。
【００６７】
実施例１２
触媒の調製以外は実施例１と同様に重合を行い、表６に示すように、異物が少なく、良好な色調のポリマーを得た。
【００６８】
なお、以下に触媒の調製方法を記す。
【００６９】
撹拌機、凝縮器および温度計を備えた３Ｌのフラスコ中に２−プロパノール（３７１ｇ）にアニリン（２７９ｇ、３．００モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトラブトキシド（３４０ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりブタノール／２−プロパノール混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、真空下で加熱してブタノール／２−プロパノール／水を除去し、淡黄色の生成物を得た。
【００７０】
この生成物を撹拌機および温度計を備えた１Ｌのフラスコ中でジメチルスルホキシド（５００ｍｌ）に溶解させた。この撹拌されている溶液に、滴下漏斗からフェニルホスホン酸（１００ｇ、０．６３モル）と水（３．７８ｇ、０．２１モル）のジメチルスルホキシド溶液（１５０ｍｌ）をゆっくり加えた。この混合物を２５℃、常圧下、２時間撹拌した後、２日間放置すると、白色固体が生成する。この固体を濾別し、ジエチルエーテル（３００ｍｌ）を用いて洗浄した後、減圧乾燥させた（収量１４２ｇ）。この固体１０ｇを秤量し、エチレングリコール（４００ｍｌ）に分散させた。
【００７１】
実施例１３〜１６
末端の置換基を有するチタン原子１つあたりの末端基の数Ｔ／Ｕが異なること以外は実施例１と同様に触媒調製および重合を行った。異物が少なく、良好な色調のポリマーを与えた。
【００７２】
【発明の効果】
本発明のポリエステル重合用触媒およびそれを用いたポリエステルの製造方法によれば、異物が少なく、色調の良好なポリエステルを得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyester polymerization catalyst capable of obtaining a polyester having a small amount of foreign matter and a good color tone, and a method for producing a polyester.
[0002]
[Prior art]
Polyester is used for many purposes because of its usefulness, for example, for clothing, materials, and medical use. Among them, polyethylene terephthalate is excellent in versatility and practicality, and is preferably used.
[0003]
Generally, polyethylene terephthalate is produced from terephthalic acid or its ester-forming derivative and ethylene glycol, but in commercial processes for producing high molecular weight polymers, antimony compounds are widely used as polycondensation catalysts. However, polymers containing antimony compounds have some undesirable properties, as described below.
[0004]
For example, when a polymer obtained by using an antimony catalyst is melt-spun into fibers, it is known that residues of the antimony catalyst accumulate around the die hole. If the deposition proceeds, it causes a defect in the filament. It is believed that the deposition of the antimony catalyst residue occurs because the antimony compound in the polymer is denatured in the vicinity of the die, a part of which evaporates and dissipates, and then a component mainly composed of antimony remains in the die.
[0005]
Also, the antimony catalyst residue in the polymer tends to be relatively large particles, and becomes a foreign substance, which causes an increase in the filter pressure of the filter during molding, breakage of the yarn during spinning, or breakage of the film during film formation. It has unfavorable characteristics, and is one of the causes of lowering operability.
[0006]
In view of the above background, polyesters having a low or no antimony content have been demanded. Therefore, when a role of the polycondensation catalyst is required for a compound other than the antimony compound, a germanium compound is known, but the germanium compound is very expensive and is difficult to be used for general purposes.
[0007]
On the other hand, it has been proposed to use a titanium complex comprising a titanium compound and a phosphorus compound as a polymerization catalyst as a polyester polymerization catalyst (see Patent Documents 1 to 3). According to this method, foreign matter due to the catalyst can be reduced, but it is not sufficient, and the color tone of the obtained polymer is not sufficient. Therefore, further improvement of titanium compounds is required.
[0008]
In view of the above, in the present invention, the above problems have been improved, and as a result of diligent studies on polyesters with less thread breakage, it has been found that the object of the present invention can be achieved by using a compound of titanium and phosphorus having a specific structure as a polymerization catalyst. Obtained knowledge.
[0009]
[Patent Document 1]
JP 2001-524536 A (page 1)
[0010]
[Patent Document 2]
JP-T-2002-512267 (page 1)
[0011]
[Patent Document 3]
JP-A-2002-293909 (page 1)
[0012]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned conventional problems, and to provide a polyester having a good thread-forming property and a good film-forming property, and having a small amount of foreign substances as compared with conventional products, and capable of obtaining a polyester excellent in polyester color tone. An object of the present invention is to provide a catalyst and a method for producing a polyester using the catalyst.
[0013]
[Means for Solving the Problems]
The above problem is that the number of titanium atoms in one molecule is 4 to 8, the composition ratio of titanium atoms to phosphorus atoms is 0.7 to 2, and at least one or more Ti—O—Ti bond is formed. This can be achieved by a polyester polymerization catalyst characterized by being a compound having the same and a method for producing polyester using the same.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The polyester of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Those which can be used as molded articles such as fibers, films, bottles and the like are preferable.
[0015]
Specific examples of such a polyester include, for example, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyethylene-1,2-. Bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate and the like can be mentioned. The present invention is particularly suitable for the most widely used polyethylene terephthalate or polyester copolymer containing mainly ethylene terephthalate units.
[0016]
These polyesters also include dicarboxylic acids such as adipic acid, isophthalic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, cyclohexanedicarboxylic acid, and the like, in addition to diethylene glycol. Formable derivatives, dioxy compounds such as polyethylene glycol, hexamethylene glycol, neopentyl glycol, polypropylene glycol, and cyclohexane dimethanol; oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid; It may be polymerized.
[0017]
The catalyst for polyester polymerization of the present invention has a titanium atom number in one molecule of 4 to 8, a titanium atom to phosphorus atom composition ratio of 0.7 to 2, and at least one or more Ti—O—Ti bond. It is important that the compound has a compound from the viewpoints of color tone improvement and foreign matter suppression. The composition ratio between titanium atoms and phosphorus atoms is preferably 0.8 to 1.7, and more preferably 1.1 to 1.4.
[0018]
Further, the number of Ti—O—Ti bonds is preferably within the range of the following expression (1).
1 ≦ P ≦ (3.5Q- (RS)) / 2 (1)
(In the formula, Q is the total number of titanium atoms in one molecule, R is the number of oxygen atoms bonded to phosphorus atoms, and S is the number of phosphorus atoms.)
In the polyester polymerization catalyst of the present invention, it is preferable from the viewpoint of suppressing foreign substances that all of the oxygen atoms bonded to the phosphorus atom are bonded to the titanium atom. Further, when there is an oxygen atom which is not bonded, the number is preferably 4 or less.
[0019]
In the catalyst for polyester polymerization of the present invention, the substituent of the titanium atom is preferably at least one selected from the group consisting of functional groups represented by the following formulas 1 to 6.
[0020]
Embedded image

[0021]
(In Formulas 1 to 6, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. Represents a hydrocarbon group having 1 to 30 carbon atoms.)
Formula 1 of the present invention includes an alkoxy group such as ethoxide, propoxide, isopropoxide, butoxide, and 2-ethylhexoxide, and a hydroxy polycarboxylic acid compound such as lactic acid, malic acid, tartaric acid, and citric acid. Functional groups.
[0022]
Formula 2 includes a functional group composed of a β-diketone compound such as acetylacetone and a ketoester compound such as methyl acetoacetate and ethyl acetoacetate.
[0023]
Formula 3 includes a functional group composed of phenoxy, cresylate, salicylic acid, and the like.
[0024]
Formula 4 includes an acylate group such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemi-mellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacine. Polycarboxylic acid compounds such as acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or anhydride thereof, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid And a functional group comprising a nitrogen-containing polycarboxylic acid such as triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid.
[0025]
Formula 5 includes a functional group composed of aniline, phenylamine, diphenylamine, and the like.
Above all, it is preferable to include Formula 1 and / or Formula 4 from the viewpoint of the thermal stability and color tone of the polymer.
[0026]
In the catalyst for polyester polymerization of the present invention, the number T / U of terminal groups per one titanium atom having a terminal substituent is preferably within the range shown by the following formula (2).
1 ≦ T / U <1.5 (2)
(Wherein, T is the number of terminals among the substituents of the titanium atom, and U is the number of titanium atoms having the terminal substituent)
If the value is excessively large, there is a possibility that a color tone that can be used practically may not be obtained, and if the value is excessively small, sufficient activity may not be obtained. More preferably, it is not less than 1.10 and less than 1.35.
[0027]
In the method for synthesizing the polyester polymerization catalyst of the present invention, for example, (1) a titanium compound is mixed in a solvent, a part or all of the compound is dissolved in the solvent, and a phosphorus compound and a trace amount of water are dissolved in the solvent in the mixed solution. Or it is diluted and added dropwise. (2) When using a ligand of a titanium compound such as a hydroxycarboxylic acid-based compound or a polycarboxylic acid-based compound, the titanium compound or the ligand compound is mixed with a solvent, and a part or all of the mixture is placed in the solvent. It is obtained by dissolving, dissolving and diluting a ligand compound or a titanium compound in a stock solution or a solvent and dropping the solution in the mixed solution, and then further adding a phosphorus compound to the mixed solution. Particularly, at this time, it is preferable to dissolve and dilute the phosphorus compound and a small amount of water in a solvent and then add the solution dropwise from the viewpoints of suppressing foreign matter formation and improving color tone. The above reaction conditions are preferably carried out by heating at a temperature of 0 to 200 ° C for 1 minute or more, and more preferably at a temperature of 20 to 100 ° C for 2 to 100 minutes. The reaction pressure at this time is not particularly limited, and may be normal pressure. The solvent used here can be selected from those capable of dissolving part or all of a titanium compound, a phosphorus compound and a compound binding to a titanium atom. Specifically, methanol, ethanol, 1-propanol , 2-propanol, ethylene glycol, propanediol, butanediol, diethyl ether, acetone, ethyl acetate, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dichloromethane, 1,2-dichloroethane and the like.
[0028]
The raw material titanium compound used in the synthesis of the catalyst for polyester polymerization of the present invention is not particularly limited as long as it has the above-mentioned substituent or has a substituent which can be easily exchanged for them. Specific examples include titanium tetraisopropoxide, titanium tetrabutoxide, titanium diisopropoxy bisacetylacetonate, and titanium triethanolaminate isopropoxide. The phosphorus compound as a starting material is at least one selected from phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinous acid, and phosphine. It is preferable that any one or two types be used. Specifically, for example, phosphoric acids, such as phosphoric acid, trimethyl phosphate, triethyl phosphate, and triphenyl phosphate, and phosphorous acids, such as phosphorous acid, trimethyl phosphite, triethyl phosphite, and triphenyl phosphite. Phosphoric acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthryl Phosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5-dicarboxy Phenylphosphonic acid, 2,6-dicarboxy Nylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2,3,5-tricarboxyphenylphosphonic acid, 2,3 2,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethyl Phosphonic acid diethyl ester, Phenylphosphonic acid dimethyl ester, Phenylphosphonic acid diethyl ester, Phenylphosphonic acid diphenyl ester, Benzylphosphonic acid dimethyl ester, Benzylphosphonic acid diethyl ester, Benzylphosphonic acid diester Phenyl ester, lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), magnesium bis (3, Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), diethylphosphonoacetic acid, methyl diethylphosphonoacetate, Phosphonic acid compounds such as ethyl diethylphosphonoacetate, hypophosphorous acid, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid , Xylylphosphinic acid, Biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid, dixylylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, Anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid, 2,4-dicarboxyphenylphosphinic acid, 2,5- Dicarboxyphenylphosphinic acid, 2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-dicarboxyphenylphosphinic acid, 2,3,4-trica Boxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2,4,6-tricarboxy Phenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-dicarboxylphenyl) phosphinic acid, bis ( 2,4-dicarboxyphenyl) phosphinic acid, bis (2,5-dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, Bis (3,5-dicarboxyphenyl) phosphinic acid, bis (2,3 4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphinic acid, bis (2,4,5-tricarboxyphenyl) ) Phosphinic acid, and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methyl phosphinic acid methyl ester, dimethyl phosphinic acid methyl ester, methyl phosphinic acid ethyl ester, dimethyl phosphinic acid ethyl ester, ethyl phosphinic acid methyl ester, Methyl diethylphosphinic acid ester, ethyl phosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenyl Phenyl phosphinic acid methyl ester, diphenyl phosphinic acid ethyl ester, diphenyl phosphinic acid phenyl ester, benzyl phosphinic acid methyl ester, benzyl phosphinic acid ethyl ester, benzyl phosphinic acid phenyl ester, bisbenzyl phosphinic acid methyl ester, bisbenzyl phosphinic acid ethyl ester, Phosphinic acids such as bisbenzylphosphinic acid phenyl ester, phosphine oxides such as trimethyl phosphine oxide, triethyl phosphine oxide, tripropyl phosphine oxide, triisopropyl phosphine oxide, tributyl phosphine oxide, triphenyl phosphine oxide, methyl phosphonous acid, ethyl Phosphonous acid, propyl phosphonous acid, isopropyl acid Phosphonic acid such as sulfonic acid, butylphosphonous acid, phenylphosphonous acid, methyl phosphinous acid, ethyl phosphinous acid, propyl phosphinous acid, isopropyl phosphinous acid, butyl phosphinous acid, phenyl phosphinous acid, dimethyl Examples include phosphinous acids such as phosphinous acid, diethyl phosphinous acid, dipropyl phosphinous acid, diisopropyl phosphinous acid, dibutyl phosphinous acid, and diphenyl phosphinous acid, and at least one of these, or any one of them. Preferably, it is a species or two. In particular, from the viewpoint of suppressing foreign substances and improving color tone, phosphoric acid and / or phosphonic acid compounds are preferable. Among them, phosphoric acid-based phosphorus compounds are preferably phosphoric acid and / or phosphate ester compounds, and phosphonic acid-based phosphorus compounds. , A phosphonic acid and / or a phosphonate ester compound, wherein the catalyst of the present invention is substantially a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. The ester reaction or transesterification reaction is completed, and the compound which substantially contributes to the acceleration of all or some elementary reactions of the polycondensation reaction to increase the degree of polymerization of the obtained polyethylene terephthalate low polymer by the diol removal reaction Point.
[0029]
Therefore, titanium dioxide particles generally used as inorganic particles in a matting agent for fibers have substantially no catalytic action on the above reaction, and can be used as the catalyst of the present invention. Different from titanium and phosphorus compounds.
[0030]
In the present invention, the compound of titanium and phosphorus (excluding titanium dioxide particles) is preferably contained in an amount of 0.5 to 150 ppm in terms of titanium atoms with respect to the obtained polymer. When the content is 1 to 100 ppm, the thermal stability and color tone of the polymer become better, and the content is more preferably 3 to 50 ppm.
[0031]
The compound of titanium and phosphorus used in the present invention may be added as it is to the polyester reaction system, but is previously mixed with a solvent containing a diol component forming a polyester such as ethylene glycol or propylene glycol to form a solution or slurry, It is preferable to remove the low-boiling components such as alcohol used in the synthesis of the compound as necessary, and then add the resultant to the reaction system, since the generation of foreign substances in the polymer is further suppressed. The timing of addition may be substantially before the start of the polycondensation reaction, and may be added before the esterification reaction or the transesterification reaction, or after the end of the reaction and before the start of the polycondensation reaction catalyst. Further, from the viewpoint of color tone improvement and thermal stability, a phosphorus compound may be separately added. In this case, in order to suppress the deactivation of the catalyst caused by the contact of the phosphorus compound with the catalyst for polyester polymerization of the present invention containing a compound of titanium and phosphorus, a method of adding the catalyst to a different reaction tank or the method of adding the catalyst to the same reaction tank may be used. A method in which the addition interval between the catalyst for polyester polymerization of the present invention and the phosphorus compound is set to 1 to 15 minutes or a method in which the addition positions are separated may be used.
[0032]
It is preferable to add a cobalt compound or a manganese compound at any time in the method for producing the polyester of the present invention because the color tone of the obtained polymer becomes good. The cobalt compound used in this case is not particularly limited, but specific examples thereof include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate. Although there is no particular limitation on the manganese compound, specifically, for example, manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, manganese acetate tetrahydrate, manganese acetate dihydrate and the like. No.
[0033]
Further, an alkali metal compound, an alkaline earth metal compound, an aluminum compound, a zinc compound, a tin compound, or the like may be added for the purpose of improving the color tone of the obtained polymer or the thermal stability of the polymer.
[0034]
Further, in addition to particles such as titanium dioxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, and carbon black, coloring inhibitors, stabilizers, antioxidants and the like may be added.
[0035]
The method for producing the polyester of the present invention will be described. An example of polyethylene terephthalate will be described as a specific example, but the present invention is not limited to this.
[0036]
Polyethylene terephthalate is usually produced by one of the following processes. That is, (1) a process of obtaining a low polymer by a direct esterification reaction using terephthalic acid and ethylene glycol as raw materials and further obtaining a high molecular weight polymer by a subsequent polycondensation reaction, and (2) a process of using dimethyl terephthalate and ethylene glycol as raw materials. In this process, a low polymer is obtained by a transesterification reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction. Further, in the transesterification reaction, the reaction is carried out by using a compound such as manganese, calcium, magnesium, zinc, lithium, and the like, and after the transesterification reaction is substantially completed, the purpose is to inactivate the catalyst used in the reaction. Then, a phosphorus compound is added.
[0037]
The production method of the present invention comprises the step of adding a matting agent to the low polymer obtained at any stage of the series of reactions (1) or (2), preferably in the first half of the series of reactions (1) or (2). After adding additives such as titanium dioxide particles, a cobalt compound, and a manganese compound, the above-mentioned compound of titanium and phosphorus is added as a polycondensation catalyst and a polycondensation reaction is performed to obtain a high-molecular-weight polyethylene terephthalate. is there.
[0038]
The above reaction can be applied to a batch system, a semi-batch system or a continuous system.
[0039]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. The physical properties in the examples were measured by the methods described below.
(1) Intrinsic viscosity IV of polymer
The measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(2) Color tone of polymer The obtained polymer is rapidly cooled from a molten state, formed into chips, filled in a quartz glass container, and then charged with a hunter type color difference meter (SM color computer manufactured by Suga Test Instruments Co., Ltd.). It was measured using the model SM-3), and the L and b values of the hunter were obtained.
[0040]
The b value of the polymer color tone is preferably 4 or less, more preferably 3 or less, and particularly preferably 1.5 or less.
(3) 2.0 g of a sample to be measured for solution haze was dissolved in 20 mL of orthochlorophenol, and the solution was analyzed by a haze meter (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP type) by an integrating sphere photoelectricity method. As the amount of foreign matter in the polymer, the haze value is preferably 2.0 or less, more preferably 1.5 or less.
(4) Content of Titanium Element and Phosphorus Element in Polyester Determined by a fluorescent X-ray elemental analyzer (MESA-500W type, manufactured by Horiba, Ltd.). In addition, when titanium dioxide particles were contained in the polyester, the following pretreatment was performed and then the fluorescent X-ray analysis was performed. That is, the polyester is dissolved in orthochlorophenol (5 g of the polymer with respect to 100 g of the solvent), and the same amount of dichloromethane as the polymer solution is added to adjust the viscosity of the solution. Then, the centrifuge (18,000 rpm, 1 hour) To settle the particles. Thereafter, only the supernatant was recovered by a gradient method, and the same amount of acetone as that of the supernatant was added to reprecipitate the polymer. Thereafter, the polymer was filtered through a 3G3 glass filter (manufactured by IWAKI), and the filtered material was further filtered. After washing with acetone, acetone was removed by vacuum drying at room temperature for 12 hours. The polymer obtained by performing the above pretreatment was analyzed for titanium element, phosphorus element, antimony element and manganese element.
[0041]
On the other hand, when the titanium dioxide particles are not contained, it is not necessary to perform the pretreatment, and the polymer may be analyzed as it is.
(5) The presence or absence of Ti—O—Ti, the number of single oxygen atoms P, the total number of oxygen atoms bonded to phosphorus atoms R, and the number of oxygen atoms bonded to Ti, X of the solid catalyst compound obtained by preparing the catalyst A line crystal structure analysis was performed (single crystal automatic X-ray structure analyzer RASA-7 manufactured by Rigaku Denki), and it was determined that there was an interaction between the atoms when the interatomic distance was smaller than the sum of the ionic radii. The sum of the ionic radii of the titanium atom and the oxygen atom is 2.87 °, and the sum of the ionic radii of the phosphorus atom and the oxygen atom is 1.73 °.
[0042]
Example 1
A. Preparation of Catalyst Tetraisopropoxide (356 g, 1.25 mol) was dissolved in dimethyl sulfoxide (500 ml) in a 1 L flask equipped with a stirrer and a thermometer. To this stirred solution was slowly added a solution of phenylphosphonic acid (100 g, 0.63 mol) and water (3.78 g, 0.21 mol) in dimethyl sulfoxide (150 ml) from a dropping funnel. The mixture is stirred at 25 ° C. and normal pressure for 2 hours, and then left for 2 days to produce a white solid. This solid was separated by filtration, washed with diethyl ether (300 ml), and dried under reduced pressure (yield 102 g). 10 g of this solid was weighed and dispersed in ethylene glycol (400 ml). On the other hand, a structural analysis of this solid was performed, and one fragment having 4 titanium atoms (Q = 4), 3 phosphorus atoms (S = 3), and Ti ₃ − (μ ₃ -O) in one molecule was obtained. All (P = 1), all nine oxygen atoms (R = 9) bonded to the phosphorus atom are bonded to the titanium atom, and the number of terminal substituents of the titanium atom is 5 (T = 5). It was confirmed that the number of titanium atoms contained was 4 (U = 4).
B. Method for Producing Polyethylene Terephthalate A slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) is charged in advance with about 123 kg of bis (hydroxyethyl) terephthalate at a temperature of 250 ° C. and a pressure of 1.2. The mixture was supplied to the esterification reaction tank maintained at × 10 ⁵ Pa over 4 hours, and the esterification reaction was completed over 1 hour after the supply was completed. Next, 123 kg of the esterification reaction product was transferred to a polycondensation tank.
[0043]
Subsequently, 0.3% by weight based on the polymer from which an ethylene glycol slurry of titanium oxide particles was obtained was added to the polycondensation reaction tank in which the esterification reaction product was transferred. After stirring for 5 minutes, an ethylene glycol solution of cobalt acetate and manganese acetate was added so as to be 30 ppm in terms of cobalt atoms and 15 ppm in terms of manganese atoms with respect to the obtained polymer. After further stirring for 5 minutes, the above-mentioned catalyst solution was added to the obtained polymer so as to be 10 ppm in terms of titanium atoms, and then the reaction system was heated from 250 ° C. to 285 ° C. while stirring the low polymer at 30 rpm. And gradually reduced the pressure to 40 Pa. The time required to reach the final temperature and the final pressure was 60 minutes. When the stirring torque reached a predetermined value, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged into cold water in a strand form, and immediately cut to obtain polymer pellets. The time from the start of the pressure reduction to the arrival of the predetermined stirring torque was 3 hours.
[0044]
As shown in Table 1, the obtained polymer had an IV of 0.67, a solution haze of 0.5%, and few foreign substances. The color tone L value was 74 and the b value was 1.0, and the color tone was good.
[0045]
[Table 1]

[0046]
Comparative Examples 1 and 2
Catalyst preparation and polymerization were carried out in the same manner as in Example 1 except that the number of titanium atoms and the number of phosphorus atoms constituting the catalyst compound were different. As shown in Table 2, the color tone of the polymer was poor, and Comparative Example 2 had many foreign substances.
[0047]
Comparative Examples 3 and 4
Catalyst preparation and polymerization were carried out in the same manner as in Example 1 except that the ratio of the number of titanium atoms to the number of phosphorus atoms constituting the catalyst compound was different. In both cases, the color tone was extremely deteriorated, and in Comparative Example 3, the progress of polymerization was very slow, probably because the catalyst was deactivated.
[0048]
Comparative Example 5
Polymerization was carried out in the same manner as in Example 1 except that there was no Ti—O—Ti bond in the catalyst compound. As shown in Table 2, the color tone was good, but the amount of foreign matters was very large.
[0049]
[Table 2]

[0050]
Examples 2 and 3
Catalyst preparation and polymerization were carried out in the same manner as in Example 1 except that the number of titanium atoms and the number of phosphorus atoms constituting the catalyst compound were different. As shown in Table 1, all of the polymers contained little foreign matter and had good color tone.
[0051]
Examples 4 and 5
Catalyst preparation and polymerization were carried out in the same manner as in Example 1, except that the ratio of the number of titanium atoms to the number of phosphorus atoms constituting the catalyst compound was different. As shown in Table 1, all of the polymers contained little foreign matter and had good color tone.
[0052]
Example 6
Catalyst preparation and polymerization were carried out in the same manner as in Example 1, except that part of the oxygen atoms bonded to the phosphorus atoms in the catalyst compound were not bonded to titanium atoms. A polymer having a good color tone with little foreign matter was given.
[0053]
Examples 7 and 8
Catalyst preparation and polymerization were carried out in the same manner as in Example 1 except that the number of single oxygen atoms in the Ti—O—Ti bond contained in the catalyst compound was different. A polymer having a good color tone with little foreign matter was given.
[0054]
Example 9
Polymerization was carried out in the same manner as in Example 1 except for the preparation of the catalyst. As shown in Table 3, a polymer having a small amount of foreign matter and a good color tone was obtained.
[0055]
The method for preparing the catalyst is described below.
[0056]
Lactic acid (270 g, 3.00 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetrabutoxide (340 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated and refluxed for 1 hour to form a cloudy solution from which the butanol / water mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The resulting product was filtered and heated under vacuum to remove butanol / water to give a cloudy pale yellow product.
[0057]
This product was dissolved in dimethyl sulfoxide (500 ml) in a 1 L flask equipped with a stirrer and thermometer. To this stirred solution was slowly added a solution of phenylphosphonic acid (100 g, 0.63 mol) and water (3.78 g, 0.21 mol) in dimethyl sulfoxide (150 ml) from a dropping funnel. The mixture is stirred at 25 ° C. and normal pressure for 2 hours, and then left for 2 days to produce a white solid. This solid was separated by filtration, washed with diethyl ether (300 ml), and dried under reduced pressure (yield 98 g). 10 g of this solid was weighed and dispersed in ethylene glycol (400 ml).
[0058]
[Table 3]

[0059]
Example 10
Polymerization was carried out in the same manner as in Example 1 except for the preparation of the catalyst. As shown in Table 3, a polymer having a small amount of foreign matter and a good color tone was obtained.
[0060]
The method for preparing the catalyst is described below.
[0061]
Maleic acid (348 g, 3.00 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetrabutoxide (340 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated and refluxed for 1 hour to form a cloudy solution from which the butanol / water mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The resulting product was filtered and heated under vacuum to remove butanol / water to give a slightly cloudy pale yellow product.
[0062]
This product was dissolved in dimethyl sulfoxide (500 ml) in a 1 L flask equipped with a stirrer and thermometer. To this stirred solution was slowly added a solution of phenylphosphonic acid (100 g, 0.63 mol) and water (3.78 g, 0.21 mol) in dimethyl sulfoxide (150 ml) from a dropping funnel. The mixture is stirred at 25 ° C. and normal pressure for 2 hours, and then left for 2 days to produce a white solid. This solid was separated by filtration, washed with diethyl ether (300 ml), and dried under reduced pressure (yield 125 g). 10 g of this solid was weighed and dispersed in ethylene glycol (400 ml).
[0063]
Example 11
Polymerization was carried out in the same manner as in Example 1 except for the preparation of the catalyst. As shown in Table 3, a polymer having a small amount of foreign matter and a good color tone was obtained.
[0064]
The method for preparing the catalyst is described below.
[0065]
Phenol (282 g, 3.00 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetrabutoxide (340 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated and refluxed for 1 hour to form a cloudy solution from which the butanol / water mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The resulting product was filtered and heated under vacuum to remove butanol / water to give a pale yellow product.
[0066]
This product was dissolved in dimethyl sulfoxide (500 ml) in a 1 L flask equipped with a stirrer and thermometer. To this stirred solution was slowly added a solution of phenylphosphonic acid (100 g, 0.63 mol) and water (3.78 g, 0.21 mol) in dimethyl sulfoxide (150 ml) from a dropping funnel. The mixture is stirred at 25 ° C. and normal pressure for 2 hours, and then left for 2 days to produce a white solid. This solid was separated by filtration, washed with diethyl ether (300 ml), and dried under reduced pressure (yield: 137 g). 10 g of this solid was weighed and dispersed in ethylene glycol (400 ml).
[0067]
Example 12
Polymerization was carried out in the same manner as in Example 1 except for the preparation of the catalyst. As shown in Table 6, a polymer having a small amount of foreign matter and a good color tone was obtained.
[0068]
The method for preparing the catalyst is described below.
[0069]
Aniline (279 g, 3.00 mol) was dissolved in 2-propanol (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetrabutoxide (340 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated at reflux for 1 hour to form a cloudy solution from which the butanol / 2-propanol mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The resulting product was filtered and heated under vacuum to remove butanol / 2-propanol / water to give a pale yellow product.
[0070]
This product was dissolved in dimethyl sulfoxide (500 ml) in a 1 L flask equipped with a stirrer and thermometer. To this stirred solution was slowly added a solution of phenylphosphonic acid (100 g, 0.63 mol) and water (3.78 g, 0.21 mol) in dimethyl sulfoxide (150 ml) from a dropping funnel. The mixture is stirred at 25 ° C. and normal pressure for 2 hours, and then left for 2 days to produce a white solid. This solid was separated by filtration, washed with diethyl ether (300 ml), and dried under reduced pressure (yield 142 g). 10 g of this solid was weighed and dispersed in ethylene glycol (400 ml).
[0071]
Examples 13 to 16
Catalyst preparation and polymerization were carried out in the same manner as in Example 1 except that the number T / U of terminal groups per titanium atom having a terminal substituent was different. A polymer having a good color tone with little foreign matter was given.
[0072]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the polyester polymerization catalyst of this invention and the manufacturing method of the polyester using the same, a foreign material is few and a polyester with favorable color tone can be obtained.

Claims (6)

The number of titanium atoms in one molecule is 4 to 8, the composition ratio of titanium atoms to phosphorus atoms is 0.7 to 2, and the compound has at least one or more Ti—O—Ti bond. A polyester polymerization catalyst characterized by the above-mentioned. The polyester polymerization catalyst according to claim 1, wherein all of the oxygen atoms bonded to the phosphorus atom are bonded to the titanium atom. The catalyst for polyester polymerization according to claim 1 or 2, wherein the number P of the single oxygen atoms bridging the titanium atoms satisfies the following formula (1).
1 ≦ P ≦ (3.5Q- (RS)) / 2 (1)
(Where Q is the total number of titanium atoms in one molecule, R is the number of oxygen atoms bonded to the phosphorus atom, and S is the number of phosphorus atoms) The polyester polymerization according to any one of claims 1 to 3, wherein the substituent bonded to the titanium atom is at least one selected from the group consisting of functional groups represented by the following formulas (1) to (6). Catalyst.

(In Formulas 1 to 6, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. Represents a hydrocarbon group having 1 to 30 carbon atoms.) The polyester polymerization catalyst according to any one of claims 1 to 4, wherein the number T / U of terminal groups per titanium atom having a terminal substituent satisfies the following formula (2).
1 ≦ T / U <1.5 (2)
(Wherein T is the number of terminals among the substituents of the titanium atom, U is the number of titanium atoms having the terminal substituent) A method for producing a polyester, comprising using the polymerization catalyst according to claim 1.