JP3965025B2 - Method for producing polyester macromonomer - Google Patents

Description

【００１１】
ここで、ｎは１〜５０の整数であり、Ｘは重合可能な官能基または水素（但し、両末端に同時に水素が付加される場合を除く）であり、Ｒはグリコール残基である。
【００１２】
本発明では前記官能基はビニルフェニレン基、アリル基、アクリロイル基またはメタクリロイル基であることが好ましい。ここでアクリロイル基はアクリレートを、メタアクリロイル基はメタアクリレートを含む用語である。さらに本発明は、また飽和ポリエステル樹脂をグリコールで分解し、その分解生成物を原料として、ビニルフェニレン基、アリル基、アクリロイル基またはメタクリロイル基を分子鎖の片末端または両末端に有するポリエステルマクロモノマーの製造方法である。ここで前記飽和ポリエステル樹脂は、その廃棄物が使用できる。
【００１３】
ポリエステルマクロモノマーの製造法において、飽和ポリエステル樹脂をグリコールで分解し、この分解物に、無水フタル酸、無水コハク酸または無水マレイン酸を反応させ、その後、クロロメチルスチレンまたは臭化アリルを反応させて、ビニルフェニレン基末端またはアリル基末端を有するポリエステルマクロモノマーを製造することができる。
【００１４】
また他のポリエステルマクロモノマーの製造法においては、飽和ポリエステル樹脂をグリコールで分解し、この分解生成物にメタクリル酸またはアクリル酸を反応させ、メタクリロイル基末端またはアクリロイル基末端を有するポリエステルマクロモノマーを製造することができる。
【００１５】
ここでポリエステルマクロモノマーの製造法においては、飽和ポリエステル樹脂にポリエチレンテレフタレートが好適に使用される。
【００１６】
【発明の実施の形態】
本発明者は、飽和ポリエステル樹脂、またはその廃棄物を破砕した後、１００〜３００℃程度でグリコールにより分解し、この分解生成物を原料として用い、ポリエステルマクロモノマーを製造することにより、飽和ポリエステル樹脂廃棄物の再利用を可能にする。
【００１７】
ポリエステルマクロモノマーを製造するには次の方法で行なう。まず粉砕された飽和ポリエステル樹脂、またはその廃棄物をグリコールに混入し、触媒を用いて、あるいは無触媒で飽和ポリエステル樹脂廃棄物の分解生成物を得る。そしてその分解生成物の少なくとも片末端に重合可能な官能基を有する化合物を縮合反応させて、ポリエステルマクロモノマーを製造する。
【００１８】
本発明では前記飽和ポリエステル樹脂として好適にはポリエチレンテレフタレートが使用される。そして、飽和ポリエステル樹脂はボトル、フィルム、成型品に用いられるポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレート（ＰＥＮ）等、あるいはこれらの廃棄物を使用できる。
【００１９】
本発明において飽和ポリエステル樹脂は破砕、必要ならば洗浄、ふるい掛け等の前処理を行なう。破砕は衝撃式破砕機（ハンマー式、チェーン式）、せん断式破砕機、切断式破砕機、圧縮式破砕機（ロール式、コンベア式、スクリュ式）、スタンプミル、ボールミル、ロッドミル粉砕機等により行なう。破砕物は小さい方が好ましいが、目の開き２０ｍｍのふるいを通る物が好適である。好ましくは１０ｍｍ、更に好ましくは５ｍｍのふるいを通る破砕物が使用される。
【００２０】
飽和ポリエステル樹脂（Ｅ）と、該飽和ポリエステル樹脂を分解するのに用いるグリコール（Ｇ）の重量比（Ｅ／Ｇ）は１／０．２〜１／５、好ましくは１／０．５〜１／２の範囲である。この重量比を変えることにより、分解生成物の分子量を調整できる。グリコールの混合量が少ないと分解生成物の分子量が大きくなり、グリコールの混合量が多いと、分解生成物の分子量は小さくなる。
【００２１】
そして、上記分解生成物に更にに新しい飽和ポリエステル樹脂を加えて、飽和ポリエステル樹脂を分解することもできる。また分解生成物より過剰のグリコールを分離することにより、飽和ポリエステル樹脂を効率良くリサイクルできる。
【００２２】
本発明では飽和ポリエステル樹脂を分解するグリコールとして、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ポリエチレングリコール、トリプロピレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、水素化ビスフェノールＡ、ビスフェノールＡプロピレンオキシド付加物、ビスフェノールＡエチレンオキシド付加物、トリシクロデカンジメタノールエチレンオキシド付加物、ジブロムネオペンチルグリコールなどを使用できる。
【００２３】
本発明では飽和ポリエステル樹脂の分解は、無触媒下で行なうことができるが、触媒を用いることが好ましい。ここで触媒として、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、酢酸亜鉛、酢酸マグネシウム、酢酸カルシウム、酢酸リチウム、酢酸ナトリウムなどの酢酸金属塩、酸化アンチモン、トリブチル錫メトキシド、チタンアルコキシドなど及びこれらの混合物がある。触媒の使用量は通常０．１〜１．０％の範囲である。
【００２４】
飽和ポリエステル樹脂を分解する温度は通常１００℃〜３００℃の範囲、好ましくは１５０℃〜２５０℃の範囲である。この分解温度範囲で、飽和ポリエステル樹脂の分解速度が速く、効率的にポリエステルマクロモノマーが製造できる。そして分解反応は窒素雰囲気下で、酸化防止剤存在下で行なうことにより、酸化反応による着色等が防止できる。本発明では大気圧下あるいは加圧下で分解反応を行なうこともできる。なお分解反応に低沸点のグリコールを用いて、グリコールの沸点以上の温度で分解反応を行なう場合は、加圧下で行なう。
【００２５】
グリコールによる飽和ポリエステル樹脂の分解反応は速い。グリコールによる分解生成物は通常両末端にＯＨ基を有する。該分解生成物のＯＨ基と重合可能な官能基を有する化合物、例えばアクリル酸またはメタクリル酸をエステル化反応させて、メタクリレート（メタクリロイル基）、アクリレート（アクリロイル基）を末端に有するポリエステルマクロモノマーが製造される。このエステル化反応には、ｐ−トルエンスルホン酸のような酸触媒を用いることができる。
【００２６】
次に、式（３）の構造を有するスチレン（ビニルフェニレン基）または式（４）の構造を有するアリル基を、分子鎖末端に有するポリエステルマクロモノマーは次の方法で製造される。まずグリコールによる飽和ポリエステル樹脂の分解生成物に、無水フタル酸のような二塩基酸を反応させて、分解生成物の分子鎖末端にカルボン酸を導入する。そしてこのカルボン酸にクロロメチルスチレンまたはアリルブロマイドを反応させ脱ハロゲン化水素反応により式（３）、式（４）の構造の、重合可能な官能基を分子鎖末端に有するポリエステルマクロモノマーを製造する。なお脱ハロゲン化水素反応には、塩基触媒あるいは相間移動触媒を用いることができる。
【００２７】
【化３】

【００２８】
式（３）、式（４）において、Ｚは次の式（５）、式（６）及び式（７）を表わす。
【００２９】
【化４】

【００３０】
本発明のポリエステルマクロモノマーは、重合開始剤の存在下、必要ならば所定量の多官能モノマーを添加して重合させる。ポリエステルマクロモノマーは、通常分子量が３００〜２０，０００の範囲であり、均一系で、通常の重合モノマーに近い反応性を有する。
【００３１】
本発明のポリエステルマクロモノマーは、不飽和ポリエステルの架橋剤としても使用できる。不飽和ポリエステルの重合性の炭素−炭素二重結合は通常トランス体に異性化するためフマレート基を有する。このフマレート基のエステル部分は長鎖であるが、その重合性はジイソプロピルフマレートとほぼ同じと考えられる。ここでビニルモノマー（Ｍ１）とジイソプロピルフマレート（Ｍ２）のラジカル共重合におけるモノマー反応性比を示す。
【００３２】
【表１】

【００３３】
T.Otsu,A.Matsumoto,K.Shiraishi,N.Amaya,Y.Koinuma,J.Polym.Sci.:PartA:Polym.Chem.,30(8),1559(1992)
表１から、メチルアクリレート及びメチルメタクリレート等のビニルモノマー（Ｍ１）とジイソプロピルフマレート（Ｍ２）のラジカル共重合モノマー反応性比（ｒ₁，ｒ₂）が大きく相違することが判る。したがって、メタクリレートを末端に有するポリエステルマクロモノマーを不飽和ポリエステルの架橋に用いる場合は、スチレンあるいはスチレンを末端に有するポリエステルマクロモノマーと併用することが好ましい。そしてアクリレートを末端に有するポリエステルマクロモノマーの場合は、単独でも使用可能であるが、スチレンあるいはスチレンを末端に有するポリエステルマクロモノマーと併用するほうがよい。スチレンを末端に有するポリエステルマクロモノマーは単独で用いることができる。
【００３４】
次に、フマレート（Ｍ１）とジアリルフタレート（Ｍ２）のラジカル共重合のモノマー反応性比を示す。
【００３５】
【表２】

【００３６】
この表２より、フマレート（Ｍ１）とジアリルフタレート（Ｍ２）のラジカル共重合モノマー反応性比の積（ｒ₁×ｒ₂）が０に近いので共重合性が悪く、アリル基を末端に有するポリエステルマクロモノマーも不飽和ポリエステルの架橋に使用できる。
【００３７】
これらのポリエステルマクロモノマーはコーティング剤、ＵＶ硬化インキ、光ディスク用コーティング剤、接着剤、塗料、フォトレジスト、プリント基板用レジスト、感光性樹脂凸版、光重合歯科材料などとして使用される。
【００３８】
【作用】
本発明によるポリエステルマクロモノマーは硬い塗膜を形成する。飽和ポリエステル樹脂のグリコール分解により分解物を得て、これを原料として反応させ、高付加価値のポリエステルマクロモノマーを製造することができる。
【００３９】
【実施例】
以下に実施例をあげ本発明を具体的に説明する。
【００４０】
以下の実施例では、ポリエステル樹脂からなる飲料水ボトルを、鋏で切断後、ロータリーカッターミル、（株）ホーライ製Granulaters U-140によって粒径５ｍｍに、破砕した試料を用いた。
【００４１】
実施例１
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにプロピレングリコール１５．２２ｋｇ（モル比１：２）を加え、２４０℃で２時間分解した。ＰＥＴは１００％分解し、分解物の酸価＝１９．９３ｍｇＫＯＨ／ｇ、ＯＨ価（試料１ｋｇ当たりのＯＨ基のモル数）＝９．０ｍｏｌ／ｋｇ、数平均分子量＝３３２、重量平均分子量＝４１８であった。
【００４２】
得られた分解物１０ｇに無水フタル酸１３．１２ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１２．６ｇ得られ、酸価＝４．９ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝３９０、重量平均分子量＝４３８であった。
【００４３】
フタル酸付加物１０ｇに，クロロメチルスチレン２２．００ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液２．６ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物８．３０ｇが得られ、酸価＝０．４ｍｏｌ／ｋｇ、数平均分子量＝４１６、重量平均分子量＝７８６であった。
【００４４】
生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃溶媒）で測定し、そのＮＭＲ測定結果を表４に示す。
【００４５】
実施例２
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにプロピレングリコール１１．４１ｋｇ（モル比１：１．５）を加え、２４０℃で２時間分解した。１００％分解し、分解物の酸価＝１８．８３ｍｇＫＯＨ／ｇ、ＯＨ価（ＯＨ基のモル数）＝８．２ｍｏｌ／ｋｇ、数平均分子量＝３６３、重量平均分子量＝４８９であった。
【００４６】
得られた分解物１０ｇに無水フタル酸１２．００ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１４．３ｇ得られ、酸価＝４．６ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝４１９、重量平均分子量＝５２６であった。
【００４７】
フタル酸付加物１０ｇに，クロロメチルスチレン２０．６５ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液２．４ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物７．２８ｇが得られ、酸価＝０．２ｍｏｌ／ｋｇ、数平均分子量＝５３０、重量平均分子量＝６６７であった。
【００４８】
生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃溶媒）を測定し、そのＮＭＲ測定結果を表４に示す。
【００４９】
実施例３
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにジエチレングリコール１５．９２ｋｇ（モル比１：１．５）を加え、２４０℃で１時間分解した。１００％分解し、分解物の酸価＝１０．６０ｍｇＫＯＨ／ｇ、ＯＨ価（ＯＨ基のモル数）＝７．５ｍｏｌ／ｋｇ、数平均分子量＝３９６、重量平均分子量＝５３８であった。
【００５０】
得られた分解物１０ｇに無水フタル酸１１．０６ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１３．８ｇ得られ、酸価＝４．５ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝４３８、重量平均分子量＝５４９であった。
【００５１】
フタル酸付加物１０ｇに，クロロメチルスチレン２０．２０ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液２．４ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物７．６２ｇが得られ、酸価＝０．５ｍｏｌ／ｋｇ、数平均分子量＝６０１、重量平均分子量＝７１１であった。
【００５２】
生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＤＭＳＯーｄ₆溶媒）を測定し、そのＮＭＲ測定結果を表４に示す。
【００５３】
実施例４
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにジプロピレングリコール２０．１３ｋｇ（モル比１：１．５）を加え、２４０℃で２時間分解した。１００％分解し、分解物の酸価＝９．１６ｍｇＫＯＨ／ｇ、ＯＨ価（ＯＨ基のモル数）＝６．６ｍｏｌ／ｋｇ、数平均分子量＝５３９、重量平均分子量＝７４４であった。
【００５４】
得られた分解物１０ｇに無水フタル酸９．７６ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１４．０ｇ得られ、酸価＝３．９ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝５４７、重量平均分子量＝７２０であった。
【００５５】
フタル酸付加物１０ｇに，クロロメチルスチレン１７．５１ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液２．０ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物９．２３ｇが得られ、酸価＝０．２ｍｏｌ／ｋｇ、数平均分子量＝７９９、重量平均分子量＝９７８であった。
【００５６】
生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃溶媒）を測定し、そのＮＭＲ測定結果を表４に示す。
【００５７】
実施例５
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにトリプロピレングリコール２８．８４ｋｇ（モル比１：１．５）を加え、２４０℃で２時間分解した。１００％分解し、分解物の酸価＝７．７９ｍｇＫＯＨ／ｇ、ＯＨ価（ＯＨ基のモル数）＝５．７ｍｏｌ／ｋｇ、数平均分子量＝６９８、重量平均分子量＝８９８であった。
【００５８】
得られた分解物１０ｇに無水フタル酸８．３７ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１０．８ｇ得られ、酸価＝３．４ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝６３０、重量平均分子量＝８３９であった。
【００５９】
フタル酸付加物１０ｇに，クロロメチルスチレン１５．２６ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液１．７ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物７．０８ｇが得られ、酸価＝０．９ｍｏｌ／ｋｇ、数平均分子量＝９００、重量平均分子量＝１１８８であった。生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃溶媒）を測定し、そのＮＭＲ測定結果を表４に示す。
【００６０】
実施例６
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにジプロピレングリコール２０．１３ｋｇ（モル比１：１．５）を加え、２４０℃で２時間分解した。１００％分解し、分解物の酸価＝９．１６ｍｇＫＯＨ／ｇ、ＯＨ価（ＯＨ基のモル数）＝６．６ｍｏｌ／ｋｇ、数平均分子量＝５３９、重量平均分子量＝７４４であった。
【００６１】
得られた分解物１０ｇに無水フタル酸９．７６ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１４．０ｇ得られ、酸価＝３．９ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝５４７、重量平均分子量＝７２０であった。
【００６２】
フタル酸付加物１０ｇに，クロロメチルスチレン８．７６ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液０．８５ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物６．６５ｇが得られ、酸価＝１．４ｍｏｌ／ｋｇ、数平均分子量＝６８２、重量平均分子量＝８１８であった。
【００６３】
生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃溶媒）を測定し、そのＮＭＲ測定結果を表４に示す。
【００６４】
実施例７
廃ＰＥＴボトルを粉砕後、ＰＥＴ１９．２２ｋｇにジプロピレングリコール２０．１３ｋｇ（モル比１：１．５）を加え、２４０℃で２時間分解した。１００％分解し、分解物の酸価＝９．１６ｍｇＫＯＨ／ｇ、ＯＨ価（ＯＨ基のモル数）＝６．６ｍｏｌ／ｋｇ、数平均分子量＝５３９、重量平均分子量＝７４４であった。
【００６５】
得られた分解物１０ｇに無水フタル酸９．７６ｇ、ピリジン５０ｍｌを加え、６０℃で１時間反応させた。生成物をＴＨＦに溶解し、ヘキサンに沈殿させ、２回精製した。フタル酸付加物は１４．０ｇ得られ、酸価＝３．９ｍｏｌ／ｋｇ（カルボキシル基のモル数）、ＯＨ価は検出されず、生成物の数平均分子量＝５４７、重量平均分子量＝７２０であった。
【００６６】
フタル酸付加物１０ｇに，アリルブロマイド１１．８５ｇ、ＤＭＦ５０ｍｌ、５０％ＮａＯＨ水溶液１．７ｍｌを加え、室温、窒素下で、２４時間攪拌、反応させた。反応終了後ＤＭＦの２倍量のｏ−ジクロロベンゼン、ヒドロキノン０．１％を加え、減圧下、ＤＭＦを留去した。生成物のｏ−ジクロロベンゼン溶液を多量のヘキサンに投入し、沈殿を得た。この沈殿をＴＨＦに溶解し、ヘキサンに投入し、２回精製し、減圧乾燥した。生成物８．２０ｇが得られ、酸価＝１．１ｍｏｌ／ｋｇ、数平均分子量＝８９０、重量平均分子量＝１０３８であった。
【００６７】
生成物の¹Ｈ−ＮＭＲ（４００ＭＨｚ、ＤＭＳＯ−ｄ₆溶媒）を測定し、そのＮＭＲ測定結果を表４に示す。
【００６８】
実施例８
ＰＥＴ廃棄物粉砕物１１３．６ｇをビスフェノールＡ酸化エチレン４モル付加物２８７．０ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）、０．２ｇＮａＯＨに加え、窒素下で、２４０℃、２時間分解した。その後、希硫酸で中和した。分解物のＯＨ価＝３．４２モル／ｋｇ、ＯＨ当量＝２９２．１ｇ／ｍｏｌ、酸価＝１．９ｍｇＫＯＨ／ｇ、ＧＰＣによる数平均分子量＝９５３、重量平均分子量＝１５０２であった。
【００６９】
分解物２０３．１ｇ（０．６９ ＯＨグラム当量）にメタクリル酸６１．９ｇ（０．７２モル、モル比１：１．０４）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．４ｇを加え、攪拌しながら、加熱、還流、脱水し、５時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８８．９％、酸価＝４．０ｍｇＫＯＨ／ｇ、屈折率（ｎ_D ²⁵）＝１．５４７、粘度（ｍＰａ・ｓ／２５℃）＝２７０００、ＧＰＣによる数平均分子量＝９３６、重量平均分子量＝１５４６であった。
【００７０】
得られたポリエステルマクロモノマーのＦＴ−ＩＲを測定し、そのＦＴ−ＩＲ測定結果を表５に示す。
【００７１】
得られたマクロモノマーについて、ＵＶ開始剤Irgacure907（チバガイギー社製）を用いてＵＶ硬化特性を試験した。その結果を表３に示す。
【００７２】
【表３】

【００７３】
表３より、合成したメタクリレート末端を有するポリエステルマクロモノマーはＵＶ硬化速度は比較的遅く、特に空気中では表面の硬化が遅く、べたつきがあるが、５回照射で完全に硬化した。そして多官能ウレタンアクリレートＵ−１５ＨＡ（新中村化学工業（株）製）を配合すると、硬化速度は速くなった。
【００７４】
実施例９
ＰＥＴ廃棄物粉砕物１８７．４ｇをトリプロピレングリコール２２４．９ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）に加え、窒素下で、２４０℃、２時間分解した。分解物のＯＨ価＝５．３７モル／ｋｇ、ＯＨ当量＝１８６．１ｇ／ｍｏｌ、酸価＝２．７ｍｇＫＯＨ／ｇ、ＧＰＣによる数平均分子量＝６６２、量平均分子量＝１００６であった。
【００７５】
分解物１７６．１ｇ（０．９４６ ＯＨグラム当量）にメタクリル酸８６．０ｇ（１．００モル、モル比１：１．０６）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．５ｇを加え、攪拌しながら、加熱、還流、脱水し、８時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８１．５％、酸価＝３．４ｍｇＫＯＨ／ｇ、ＧＰＣによる数平均分子量＝６５５、重量平均分子量＝１０２２であった。
【００７６】
得られたポリエステルマクロモノマーのＦＴ−ＩＲを測定し、そのＦＴ−ＩＲ測定結果を表５に示す。
【００７７】
実施例１０
ＰＥＴ廃棄物粉砕物１８２．０ｇをテトラエチレングリコール２２０．７ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）に加え、窒素下で、２４０℃、２時間分解した。分解物のＯＨ価＝５．３５モル／ｋｇ、ＯＨ当量＝１８６．７ｇ／ｍｏｌ、酸価＝２．０ｍｇＫＯＨ／ｇ、ＧＰＣによる数平均分子量＝６４０、重量平均分子量＝１０６０であった。
【００７８】
分解物１７７．１ｇ（０．９４７ ＯＨグラム当量）にメタクリル酸８６．０ｇ（１．００モル、モル比１：１．０６）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．５ｇを加え、攪拌しながら、加熱、還流、脱水し、６時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８６．４％、酸価＝３．２ｍｇＫＯＨ／ｇ、屈折率（ｎ_D ²⁵）＝１．５０３、粘度（ｍＰａ・ｓ／２５℃）＝３５０、ＧＰＣによる数平均分子量＝６３８、重量平均分子量＝１０８０であった。
【００７９】
得られたポリエステルマクロモノマーのＦＴ−ＩＲを測定し、そのＦＴ−ＩＲ測定結果を表５に示す。
【００８０】
実施例１１
ＰＥＴ廃棄物粉砕物１１４．２ｇをポリエチレングリコール＃４００ ２８５．６ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）に加え、窒素下で、２４０℃、２時間分解した。分解物のＯＨ価＝３．４１モル／ｋｇ、ＯＨ当量＝２９３．３ｇ／ｍｏｌ、酸価＝１．９ｍｇＫＯＨ／ｇ、ＧＰＣによる数平均分子量＝１０３６、重量平均分子量＝１６５６であった。
【００８１】
分解物１９６．１ｇ（０．６６９ ＯＨグラム当量）にメタクリル酸６０．２ｇ（０．６９９モル、モル比１：１．０４）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．５ｇを加え、攪拌しながら、加熱、還流、脱水し、７時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８６．５％、酸価＝１．２ｍｇＫＯＨ／ｇ、屈折率（ｎ_D ²⁵）＝１．４９５、粘度（ｍＰａ・ｓ／２５℃）＝４７０、ＧＰＣによる数平均分子量＝１１１７、重量平均分子量＝１６７５であった。
【００８２】
得られたポリエステルマクロモノマーのＦＴ−ＩＲを測定し、そのＦＴ−ＩＲ測定結果を表５に示す。
【００８３】
実施例１２
ＰＥＴ廃棄物粉砕物１２１．２ｇをトリシクロデカンジメタノール酸化エチレン４モル付加物２８２．３ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）に加え、窒素下で、２４０℃、２時間分解した。分解物のＯＨ価＝３．６１モル／ｋｇ、ＯＨ当量＝２７４．０ｇ／ｍｏｌ、酸価＝１．８ｍｇＫＯＨ／ｇ、ＧＰＣによる重量平均分子量＝１０３９であった。
【００８４】
分解物２００．０ｇ（０．７２２ ＯＨグラム当量）にメタクリル酸６４．５ｇ（０．７４９モル、モル比１：１．０４）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．５ｇを加え、攪拌しながら、加熱、還流、脱水し、６時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８９．２％、酸価＝１．０ｍｇＫＯＨ／ｇ、屈折率（ｎ_D ²⁵）＝１．５１５、粘度（ｍＰａ・ｓ／２５℃）＝３７００、ＧＰＣによる重量平均分子量＝１０７９であった。
【００８５】
得られたポリエステルマクロモノマーのＦＴ−ＩＲを測定し、そのＦＴ−ＩＲ測定結果を表５に示す。
【００８６】
実施例１３
ＰＥＴ廃棄物粉砕物１２１．２ｇをトリシクロデカンジメタノール酸化エチレン４モル付加物２８２．３ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）に加え、窒素下で、２４０℃、２時間分解した。分解物のＯＨ価＝３．６１モル／ｋｇ、ＯＨ当量＝２７４．０ｇ／ｍｏｌ、酸価＝１．８ｍｇＫＯＨ／ｇ、ＧＰＣによる重量平均分子量＝１０３９であった。
【００８７】
分解物２００．０ｇ（０．７２２ ＯＨグラム当量）にアクリル酸５４．０ｇ（０．７４９モル、モル比１：１．０４）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．５ｇを加え、攪拌しながら、加熱、還流、脱水し、６時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８５．０％、酸価＝１．５ｍｇＫＯＨ／ｇ、屈折率（ｎ_D ²⁵）＝１．５００、粘度（ｍＰａ・ｓ／２５℃）＝３６００、ＧＰＣによる重量平均分子量＝１０２０であった。
【００８８】
実施例１４
ＰＥＴ廃棄物粉砕物１２１．２ｇをトリシクロデカンジメタノール酸化エチレン４モル付加物２８２．３ｇ（ＰＥＴのエステル基：グリコールのモル比＝１：１．２）に加え、窒素下で、２４０℃、２時間分解した。分解物のＯＨ価＝３．６１モル／ｋｇ、ＯＨ当量＝２７４．０ｇ／ｍｏｌ、酸価＝１．８ｍｇＫＯＨ／ｇ、ＧＰＣによる重量平均分子量＝１０３９であった。
【００８９】
分解物２００．０ｇ（０．７２２ ＯＨグラム当量）にアクリル酸２７．０ｇ（０．３７５モル、モル比１：０．５２）、トルエン８００ｍｌ、ｐ−トルエンスルホン酸２０ｇ、ヒドロキノン０．５ｇを加え、攪拌しながら、加熱、還流、脱水し、６時間、エステル化反応を行なった。反応終了後、１０％ＮａＯＨ水溶液で洗浄し、触媒、ヒドロキノンを除去し、中性になるまで水洗した。そして硫酸ナトリウムを入れ、一夜乾燥し、トルエンを減圧下で留去した。収率は８４．０％、酸価＝１．４ｍｇＫＯＨ／ｇ、屈折率（ｎ_D ²⁵）＝１．５００、粘度（ｍＰａ・ｓ／２５℃）＝３６５０、ＧＰＣによる重量平均分子量＝１０１５であった。
【００９０】
【表４】

【００９１】
【表５】

【００９２】
実施例の生成物の構成成分をＮＭＲの測定によって求めた結果を、表４及び図１〜図３にまとめて示している。図１に実施例１、２、４、５及び６に基づく生成物の構成成分の成分量を示す。また図２に実施例７に基く生成物の構成成分の成分量を示す。図３に実施例３に基く生成物の構成成分の成分量を示す。
【００９３】
今回開示された実施の形態及び実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。
【００９４】
【発明の効果】
本発明によるとポリエステルマクロモノマーが容易に製造でき、飽和ポリエステル樹脂、またはその廃棄物から、工業的に有用な原料を得ることができる。そして、廃棄物のグリコール分解物から合成されるポリエステルマクロモノマーは高付加価値なモノマーとして利用できる。
【図面の簡単な説明】
【図１】 実施例１、２、４、５及び６に基づく生成物の構成成分の成分量を示す図である。
【図２】 実施例７に基く生成物の構成成分の成分量を示す図である。
【図３】 実施例３に基く生成物の構成成分の成分量を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester macromonomer and a method for producing the same. Furthermore, the present invention provides a method for obtaining a valuable raw material that enables recycling of polyester resin waste, and in particular, can chemically treat polyester resin waste to be industrially reused.
[0002]
[Prior art]
The polyester macromonomer is an oligomer or polymer having an ester structure in the molecular main chain, a molecular weight of several hundred to several tens of thousands, and having a polymerizable functional group at its terminal. Here, the polymerizable functional group is a vinyl group, a vinylidene group, a vinylene group, a cyclic olefin or the like, and a graft copolymer can be obtained by the functional group.
[0003]
Polyester macromonomers that have been produced in the past are polyester condensates of phthalic acid and glycol, aliphatic dibasic acids such as adipic acid and glycol, or caprolactone ring-opening polymerization polymers. It was.
[0004]
In general, in the production of an aromatic polyester, the reactivity with glycol is greatest for phthalic acid, and decreases in the order of isophthalic acid and then terephthalic acid. Therefore, since the polyester of terephthalic acid is most difficult to produce, it is also most difficult to produce a polyester macromonomer having terephthalic acid in the molecular main chain.
[0005]
Conventionally, the recycling of PET bottles and films has been carried out mainly by material recycling that melts and remolds by heat (edited by RJ Ehring, translated by Plastic Recycling Study Group, "Plastic recycling-from recovery to recycling", p.71, Industrial Research Committee (1993)). In addition, as a method for recycling PET bottles and films, a technique has been developed in which monomers are recovered by hydrolysis, methanol decomposition, and glycol decomposition and re-synthesized into PET (“Waste Plastic Thermal & Chemical Recycling”, p. 201, Chemical Industry Daily (1994)).
[0006]
[Problems to be solved by the invention]
The conventional polyester macromonomer is a polyester macromonomer having a polyester structure of terephthalic acid, in which the polyester part is produced from a condensate of phthalic acid and glycol, a condensate of adipic acid and glycol, or a caprolactone ring-opening polymer Was difficult. The regeneration of the saturated polyester resin waste is performed by the material recycling method in which re-molding is performed after melting, which is generally adopted for thermoplastic resins. However, in the case of colored resin or soiled resin, this recycling method is not carried out because it has no commercial value. In this method, hydrolysis is caused by moisture at the time of re-molding, resulting in a decrease in molecular weight and a decrease in product properties.
[0007]
In addition, techniques for recovering monomers by hydrolysis, methanol decomposition, or glycol decomposition for regenerating PET bottles and films and re-synthesizing them into PET have been developed. However, most of the oligomers are produced and it is difficult to purify the monomers.
[0008]
In view of this, the present invention is a method of chemically decomposing polyethylene terephthalate resin, particularly its waste, with glycol in a relatively short period of time to easily produce a raw material for polyester macromonomer industrially without purification. It is intended to be illustrated. That is, this invention provides the polyester macromonomer obtained from the decomposition product of a polyester resin waste, and its manufacturing method.
[0009]
[Means for Solving the Problems]
The present invention is a polyester macromonomer having a structure represented by the following chemical formula (1) or (2).
[0010]
[Chemical 2]

[0011]
Here, n is an integer of 1 to 50, X is a polymerizable functional group or hydrogen (except when hydrogen is simultaneously added to both ends), and R is a glycol residue.
[0012]
In the present invention, the functional group is preferably a vinylphenylene group, an allyl group, an acryloyl group, or a methacryloyl group. Here, the acryloyl group is a term including acrylate, and the methacryloyl group is a term including methacrylate. Furthermore, the present invention also provides a polyester macromonomer having a vinyl phenylene group, an allyl group, an acryloyl group, or a methacryloyl group at one end or both ends of a molecular chain, using a decomposition product as a raw material after decomposing a saturated polyester resin with glycol. It is a manufacturing method. Here, the waste of the saturated polyester resin can be used.
[0013]
In a method for producing a polyester macromonomer, a saturated polyester resin is decomposed with glycol, and this decomposition product is reacted with phthalic anhydride, succinic anhydride or maleic anhydride, and then reacted with chloromethylstyrene or allyl bromide. A polyester macromonomer having a vinylphenylene group end or an allyl group end can be produced.
[0014]
In another polyester macromonomer production method, a saturated polyester resin is decomposed with glycol, and this decomposition product is reacted with methacrylic acid or acrylic acid to produce a polyester macromonomer having a methacryloyl group end or an acryloyl group end. be able to.
[0015]
Here, in the production method of the polyester macromonomer, polyethylene terephthalate is suitably used for the saturated polyester resin.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The present inventor, after crushing a saturated polyester resin or waste thereof, decomposes with glycol at about 100 to 300 ° C., and uses this decomposition product as a raw material to produce a polyester macromonomer. Enables reuse of waste.
[0017]
A polyester macromonomer is produced by the following method. First, the pulverized saturated polyester resin or its waste is mixed in glycol, and a decomposition product of the saturated polyester resin waste is obtained using a catalyst or without a catalyst. Then, a polyester macromonomer is produced by subjecting a compound having a polymerizable functional group to at least one terminal of the decomposition product to a condensation reaction.
[0018]
In the present invention, polyethylene terephthalate is preferably used as the saturated polyester resin. As the saturated polyester resin, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), etc. used in bottles, films and molded products, or wastes thereof can be used.
[0019]
In the present invention, the saturated polyester resin is subjected to pretreatment such as crushing, washing, sieving, etc. if necessary. Crushing is performed by impact type crusher (hammer type, chain type), shear type crusher, cutting type crusher, compression type crusher (roll type, conveyor type, screw type), stamp mill, ball mill, rod mill crusher, etc. . The crushed material is preferably small, but is preferably a material that passes through a 20-mm sieve. A crushed material is preferably used which passes through a 10 mm, more preferably 5 mm sieve.
[0020]
The weight ratio (E / G) of the saturated polyester resin (E) and the glycol (G) used to decompose the saturated polyester resin is 1 / 0.2 to 1/5, preferably 1 / 0.5 to 1. The range is / 2. By changing this weight ratio, the molecular weight of the decomposition product can be adjusted. When the mixing amount of glycol is small, the molecular weight of the decomposition product increases, and when the mixing amount of glycol is large, the molecular weight of the decomposition product decreases.
[0021]
And a saturated polyester resin can also be decomposed | disassembled by adding a new saturated polyester resin to the said decomposition product further. Further, the saturated polyester resin can be efficiently recycled by separating the excess glycol from the decomposition product.
[0022]
In the present invention, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, tricyclodecane dimethanol ethylene oxide adduct, dibromoneopentyl glycol, and the like can be used.
[0023]
In the present invention, the saturated polyester resin can be decomposed without a catalyst, but a catalyst is preferably used. Here, as a catalyst, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, zinc acetate, magnesium acetate, calcium acetate, lithium acetate, sodium acetate and other acetic acid metal salts, antimony oxide, tributyltin methoxide, titanium alkoxide And mixtures thereof. The amount of catalyst used is usually in the range of 0.1 to 1.0%.
[0024]
The temperature for decomposing the saturated polyester resin is usually in the range of 100 ° C to 300 ° C, preferably in the range of 150 ° C to 250 ° C. In this decomposition temperature range, the polyester polyester monomer can be produced efficiently because the decomposition rate of the saturated polyester resin is fast. The decomposition reaction is performed in a nitrogen atmosphere and in the presence of an antioxidant, whereby coloring due to the oxidation reaction can be prevented. In the present invention, the decomposition reaction can be carried out under atmospheric pressure or under pressure. In the case where a low-boiling glycol is used for the decomposition reaction and the decomposition reaction is performed at a temperature equal to or higher than the boiling point of the glycol, the decomposition is performed under pressure.
[0025]
Degradation reaction of saturated polyester resin with glycol is fast. The decomposition product by glycol usually has OH groups at both ends. A polyester macromonomer having a terminal of methacrylate (methacryloyl group) or acrylate (acryloyl group) is produced by esterification of a compound having a polymerizable functional group with OH group of the decomposition product, for example, acrylic acid or methacrylic acid. Is done. An acid catalyst such as p-toluenesulfonic acid can be used for this esterification reaction.
[0026]
Next, a polyester macromonomer having a styrene (vinylphenylene group) having the structure of the formula (3) or an allyl group having the structure of the formula (4) at the molecular chain terminal is produced by the following method. First, a dibasic acid such as phthalic anhydride is reacted with a decomposition product of a saturated polyester resin by glycol to introduce a carboxylic acid at the molecular chain terminal of the decomposition product. Then, this carboxylic acid is reacted with chloromethylstyrene or allyl bromide to produce a polyester macromonomer having a polymerizable functional group at the molecular chain terminal having a structure of formula (3) or formula (4) by dehydrohalogenation reaction. . In the dehydrohalogenation reaction, a base catalyst or a phase transfer catalyst can be used.
[0027]
[Chemical 3]

[0028]
In Formula (3) and Formula (4), Z represents the following Formula (5), Formula (6), and Formula (7).
[0029]
[Formula 4]

[0030]
The polyester macromonomer of the present invention is polymerized by adding a predetermined amount of a polyfunctional monomer if necessary in the presence of a polymerization initiator. The polyester macromonomer usually has a molecular weight in the range of 300 to 20,000, is homogeneous, and has a reactivity close to that of a normal polymerization monomer.
[0031]
The polyester macromonomer of the present invention can also be used as a crosslinking agent for unsaturated polyester. The polymerizable carbon-carbon double bond of an unsaturated polyester usually has a fumarate group for isomerization to a trans form. The ester portion of this fumarate group is a long chain, but its polymerizability is considered to be almost the same as diisopropyl fumarate. Here, the monomer reactivity ratio in radical copolymerization of vinyl monomer (M1) and diisopropyl fumarate (M2) is shown.
[0032]
[Table 1]

[0033]
T.Otsu, A.Matsumoto, K.Shiraishi, N.Amaya, Y.Koinuma, J.Polym.Sci.: PartA: Polym.Chem., 30 (8), 1559 (1992)
From Table 1, the radical copolymerization monomer reactivity ratio (r) of vinyl monomer (M1) such as methyl acrylate and methyl methacrylate and diisopropyl fumarate (M2)₁, R₂) Is significantly different. Therefore, when a polyester macromonomer having a methacrylate terminal is used for crosslinking an unsaturated polyester, it is preferable to use styrene or a polyester macromonomer having a styrene terminal in combination. In the case of a polyester macromonomer having an acrylate terminal, it can be used alone, but it is better to use it together with styrene or a polyester macromonomer having a styrene terminal. The polyester macromonomer having styrene at the terminal can be used alone.
[0034]
Next, the monomer reactivity ratio of radical copolymerization of fumarate (M1) and diallyl phthalate (M2) is shown.
[0035]
[Table 2]

[0036]
From Table 2, the product of the radical copolymerization monomer reactivity ratio of fumarate (M1) and diallyl phthalate (M2) (r₁Xr₂) Is close to 0, the copolymerizability is poor, and a polyester macromonomer having an allyl group at the end can also be used for crosslinking of the unsaturated polyester.
[0037]
These polyester macromonomers are used as coating agents, UV curable inks, optical disk coating agents, adhesives, paints, photoresists, printed circuit board resists, photosensitive resin relief plates, photopolymerized dental materials, and the like.
[0038]
[Action]
The polyester macromonomer according to the invention forms a hard coating. A degradation product is obtained by glycol decomposition of a saturated polyester resin, and this is reacted as a raw material to produce a high-value-added polyester macromonomer.
[0039]
【Example】
The present invention will be specifically described with reference to the following examples.
[0040]
In the following examples, a drinking water bottle made of a polyester resin was cut with a scissors, and then a sample crushed to a particle size of 5 mm by a rotary cutter mill and Granulaters U-140 manufactured by Horai Co., Ltd. was used.
[0041]
Example 1
After crushing the waste PET bottle, 15.22 kg of propylene glycol (molar ratio 1: 2) was added to 19.22 kg of PET and decomposed at 240 ° C. for 2 hours. PET decomposes 100%, acid value of decomposed product = 19.93 mg KOH / g, OH value (number of moles of OH group per kg of sample) = 9.0 mol / kg, number average molecular weight = 332, weight average molecular weight = 418 Met.
[0042]
To 10 g of the resulting decomposition product, 13.12 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 12.6 g of phthalic acid adduct was obtained, acid value = 4.9 mol / kg (number of moles of carboxyl group), OH value was not detected, number average molecular weight of product = 390, weight average molecular weight = 438.
[0043]
To 10 g of phthalic acid adduct, 22.00 g of chloromethylstyrene, 50 ml of DMF, and 2.6 ml of 50% NaOH aqueous solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. 8.30 g of product was obtained, acid value = 0.4 mol / kg, number average molecular weight = 416, weight average molecular weight = 786.
[0044]
Product¹H-NMR (400 MHz, CDCl_ThreeSolvent) and the NMR measurement results are shown in Table 4.
[0045]
Example 2
After pulverizing the waste PET bottle, 11.41 kg of propylene glycol (molar ratio 1: 1.5) was added to 19.22 kg of PET, and decomposed at 240 ° C. for 2 hours. The decomposition value was 100%, and the acid value of the decomposition product was 18.83 mg KOH / g, the OH value (number of moles of OH groups) was 8.2 mol / kg, the number average molecular weight was 363, and the weight average molecular weight was 489.
[0046]
To 10 g of the resulting decomposition product, 12.00 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.3 g of phthalic acid adduct was obtained, acid value = 4.6 mol / kg (number of moles of carboxyl group), OH value was not detected, number average molecular weight of product = 419, weight average molecular weight = 526.
[0047]
To 10 g of the phthalic acid adduct, 20.65 g of chloromethylstyrene, 50 ml of DMF, and 2.4 ml of 50% NaOH aqueous solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. 7.28 g of product was obtained, acid value = 0.2 mol / kg, number average molecular weight = 530, weight average molecular weight = 667.
[0048]
Product¹H-NMR (400 MHz, CDCl_ThreeSolvent) was measured, and the NMR measurement results are shown in Table 4.
[0049]
Example 3
After crushing the waste PET bottle, 15.92 kg of diethylene glycol (molar ratio 1: 1.5) was added to 19.22 kg of PET and decomposed at 240 ° C. for 1 hour. The acid value of the decomposed product was 10.60 mg KOH / g, the OH value (number of moles of OH groups) was 7.5 mol / kg, the number average molecular weight was 396, and the weight average molecular weight was 538.
[0050]
To 10 g of the resulting decomposition product, 11.06 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 13.8 g of phthalic acid adduct was obtained, acid value = 4.5 mol / kg (number of moles of carboxyl group), no OH value was detected, and the product had a number average molecular weight = 438 and a weight average molecular weight = 549.
[0051]
To 10 g of phthalic acid adduct, 20.20 g of chloromethylstyrene, 50 ml of DMF, and 2.4 ml of 50% NaOH aqueous solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. 7.62 g of the product was obtained, and the acid value was 0.5 mol / kg, the number average molecular weight was 601 and the weight average molecular weight was 711.
[0052]
Product¹H-NMR (400 MHz, DMSO-d₆Solvent) was measured, and the NMR measurement results are shown in Table 4.
[0053]
Example 4
After pulverizing the waste PET bottle, 20.13 kg of dipropylene glycol (molar ratio 1: 1.5) was added to 19.22 kg of PET and decomposed at 240 ° C. for 2 hours. Decomposition was 100%, and the acid value of the decomposition product was 9.16 mg KOH / g, the OH value (number of moles of OH group) was 6.6 mol / kg, the number average molecular weight was 539, and the weight average molecular weight was 744.
[0054]
To 10 g of the resulting decomposition product, 9.76 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.0 g of phthalic acid adduct was obtained, acid value = 3.9 mol / kg (number of moles of carboxyl group), OH value was not detected, and the product had a number average molecular weight = 547 and a weight average molecular weight = 720.
[0055]
To 10 g of the phthalic acid adduct, 17.51 g of chloromethylstyrene, 50 ml of DMF, and 2.0 ml of 50% NaOH aqueous solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. 9.23 g of the product was obtained, and the acid value was 0.2 mol / kg, the number average molecular weight was 799, and the weight average molecular weight was 978.
[0056]
Product¹H-NMR (400 MHz, CDCl_ThreeSolvent) was measured, and the NMR measurement results are shown in Table 4.
[0057]
Example 5
After the waste PET bottle was pulverized, 28.84 kg of tripropylene glycol (molar ratio 1: 1.5) was added to 19.22 kg of PET and decomposed at 240 ° C. for 2 hours. The decomposition product had an acid value of 7.79 mg KOH / g, an OH value (number of moles of OH groups) of 5.7 mol / kg, a number average molecular weight of 698, and a weight average molecular weight of 898.
[0058]
To 10 g of the resulting decomposition product, 8.37 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 10.8 g of phthalic acid adduct was obtained, acid value = 3.4 mol / kg (number of moles of carboxyl group), no OH value was detected, and the product had a number average molecular weight = 630 and a weight average molecular weight = 839.
[0059]
To 10 g of the phthalic acid adduct, 15.26 g of chloromethylstyrene, 50 ml of DMF, and 1.7 ml of 50% NaOH aqueous solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. 7.08 g of product was obtained, acid value = 0.9 mol / kg, number average molecular weight = 900, weight average molecular weight = 1188. Product¹H-NMR (400 MHz, CDCl_ThreeSolvent) was measured, and the NMR measurement results are shown in Table 4.
[0060]
Example 6
After pulverizing the waste PET bottle, 20.13 kg of dipropylene glycol (molar ratio 1: 1.5) was added to 19.22 kg of PET and decomposed at 240 ° C. for 2 hours. Decomposition was 100%, and the acid value of the decomposition product was 9.16 mg KOH / g, the OH value (number of moles of OH group) was 6.6 mol / kg, the number average molecular weight was 539, and the weight average molecular weight was 744.
[0061]
To 10 g of the resulting decomposition product, 9.76 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.0 g of phthalic acid adduct was obtained, acid value = 3.9 mol / kg (number of moles of carboxyl group), OH value was not detected, and the product had a number average molecular weight = 547 and a weight average molecular weight = 720.
[0062]
To 10 g of the phthalic acid adduct, 8.76 g of chloromethylstyrene, 50 ml of DMF, and 0.85 ml of 50% aqueous NaOH solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. 6.65 g of product was obtained, acid value = 1.4 mol / kg, number average molecular weight = 682, weight average molecular weight = 818.
[0063]
Product¹H-NMR (400 MHz, CDCl_ThreeSolvent) was measured, and the NMR measurement results are shown in Table 4.
[0064]
Example 7
After pulverizing the waste PET bottle, 20.13 kg of dipropylene glycol (molar ratio 1: 1.5) was added to 19.22 kg of PET and decomposed at 240 ° C. for 2 hours. Decomposition was 100%, and the acid value of the decomposition product was 9.16 mg KOH / g, the OH value (number of moles of OH group) was 6.6 mol / kg, the number average molecular weight was 539, and the weight average molecular weight was 744.
[0065]
To 10 g of the resulting decomposition product, 9.76 g of phthalic anhydride and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.0 g of phthalic acid adduct was obtained, acid value = 3.9 mol / kg (number of moles of carboxyl group), OH value was not detected, and the product had a number average molecular weight = 547 and a weight average molecular weight = 720.
[0066]
To 10 g of the phthalic acid adduct was added 11.85 g of allyl bromide, 50 ml of DMF, and 1.7 ml of 50% NaOH aqueous solution, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, 2-fold amount of o-dichlorobenzene and hydroquinone 0.1% were added, and DMF was distilled off under reduced pressure. The product o-dichlorobenzene solution was poured into a large amount of hexane to obtain a precipitate. This precipitate was dissolved in THF, poured into hexane, purified twice, and dried under reduced pressure. As a result, 8.20 g of the product was obtained, and the acid value was 1.1 mol / kg, the number average molecular weight was 890, and the weight average molecular weight was 1038.
[0067]
Product¹H-NMR (400 MHz, DMSO-d₆Solvent) was measured, and the NMR measurement results are shown in Table 4.
[0068]
Example 8
PET waste pulverized product 113.6 g was added to bisphenol A ethylene oxide 4 mol adduct 287.0 g (Mole ratio of PET ester group: glycol = 1: 1.2), 0.2 g NaOH, and 240 ° C. under nitrogen. Decomposed for 2 hours. Then, it neutralized with dilute sulfuric acid. The decomposition product had an OH value of 3.42 mol / kg, an OH equivalent of 292.1 g / mol, an acid value of 1.9 mg KOH / g, a number average molecular weight by GPC of 953, and a weight average molecular weight of 1502.
[0069]
Add 61.9 g (0.72 mol, molar ratio 1: 1.04) of methacrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.4 g of hydroquinone to 203.1 g (0.69 OH gram equivalent) of the decomposition product. While stirring, the mixture was heated, refluxed, dehydrated and subjected to esterification for 5 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. Yield is 88.9%, acid value = 4.0 mgKOH / g, refractive index (n_D ^{twenty five}) = 1.547, viscosity (mPa · s / 25 ° C.) = 27000, number average molecular weight by GPC = 936, weight average molecular weight = 1546.
[0070]
FT-IR of the obtained polyester macromonomer was measured, and the FT-IR measurement results are shown in Table 5.
[0071]
About the obtained macromonomer, UV curing property was tested using UV initiator Irgacure907 (made by Ciba Geigy). The results are shown in Table 3.
[0072]
[Table 3]

[0073]
From Table 3, the synthesized polyester macromonomer having a methacrylate terminal has a relatively slow UV curing rate, and in particular, the curing of the surface is slow and sticky in the air, but it is completely cured by five irradiations. And when polyfunctional urethane acrylate U-15HA (made by Shin-Nakamura Chemical Co., Ltd.) was mix | blended, the cure rate became quick.
[0074]
Example 9
187.4 g of the PET waste pulverized product was added to 224.9 g of tripropylene glycol (PET ester group: glycol molar ratio = 1: 1.2) and decomposed at 240 ° C. for 2 hours under nitrogen. The decomposition product had an OH number of 5.37 mol / kg, an OH equivalent of 186.1 g / mol, an acid value of 2.7 mg KOH / g, a number average molecular weight by GPC of 662 and a weight average molecular weight of 1006.
[0075]
To 176.1 g (0.946 OH gram equivalent) of the decomposed product, 86.0 g (1.00 mol, molar ratio 1: 1.06) of methacrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone were added. While stirring, the mixture was heated, refluxed, dehydrated and subjected to esterification for 8 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. The yield was 81.5%, the acid value was 3.4 mg KOH / g, the number average molecular weight by GPC was 655, and the weight average molecular weight was 1022.
[0076]
FT-IR of the obtained polyester macromonomer was measured, and the FT-IR measurement results are shown in Table 5.
[0077]
Example 10
182.0 g of the ground PET waste was added to 220.7 g of tetraethylene glycol (Mole ratio of PET ester group: glycol = 1: 1.2), and decomposed under nitrogen at 240 ° C. for 2 hours. The decomposition product had an OH value of 5.35 mol / kg, an OH equivalent of 186.7 g / mol, an acid value of 2.0 mg KOH / g, a number average molecular weight by GPC of 640, and a weight average molecular weight of 1060.
[0078]
To 177.1 g (0.947 OH gram equivalent) of the decomposed product, 86.0 g (1.00 mol, molar ratio 1: 1.06) of methacrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone were added. While stirring, the mixture was heated, refluxed, dehydrated and subjected to esterification for 6 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. Yield is 86.4%, acid value = 3.2 mgKOH / g, refractive index (n_D ^{twenty five}) = 1.503, viscosity (mPa · s / 25 ° C.) = 350, number average molecular weight by GPC = 638, weight average molecular weight = 1080.
[0079]
FT-IR of the obtained polyester macromonomer was measured, and the FT-IR measurement results are shown in Table 5.
[0080]
Example 11
114.2 g of the PET waste pulverized product was added to 285.6 g of polyethylene glycol # 400 (PET ester group: glycol molar ratio = 1: 1.2) and decomposed under nitrogen at 240 ° C. for 2 hours. The decomposition product had an OH value of 3.41 mol / kg, an OH equivalent of 293.3 g / mol, an acid value of 1.9 mg KOH / g, a number average molecular weight by GPC of 1036, and a weight average molecular weight of 1656.
[0081]
To 196.1 g (0.669 OH gram equivalent) of the decomposition product, 60.2 g (0.699 mol, molar ratio 1: 1.04) of methacrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone were added. While stirring, the mixture was heated, refluxed, dehydrated, and subjected to esterification for 7 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. Yield is 86.5%, acid value = 1.2 mgKOH / g, refractive index (n_D ^{twenty five}) = 1.495, viscosity (mPa · s / 25 ° C.) = 470, number average molecular weight by GPC = 1117, weight average molecular weight = 1675.
[0082]
FT-IR of the obtained polyester macromonomer was measured, and the FT-IR measurement results are shown in Table 5.
[0083]
Example 12
121.2 g of the PET waste pulverized product was added to 282.3 g of tricyclodecane dimethanol ethylene oxide 4 mol adduct (Mole ratio of ester group of glycol: glycol = 1: 1.2), 240 ° C. under nitrogen, Decomposed for 2 hours. The decomposition product had an OH value of 3.61 mol / kg, an OH equivalent of 274.0 g / mol, an acid value of 1.8 mg KOH / g, and a weight average molecular weight by GPC of 1039.
[0084]
To 200.0 g (0.722 OH gram equivalent) of the decomposed product, 64.5 g (0.749 mol, molar ratio 1: 1.04) of methacrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone were added. While stirring, the mixture was heated, refluxed, dehydrated and subjected to esterification for 6 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. Yield is 89.2%, acid value = 1.0 mgKOH / g, refractive index (n_D ^{twenty five}) = 1.515, viscosity (mPa · s / 25 ° C.) = 3700, weight average molecular weight by GPC = 1079.
[0085]
FT-IR of the obtained polyester macromonomer was measured, and the FT-IR measurement results are shown in Table 5.
[0086]
Example 13
121.2 g of the PET waste pulverized product was added to 282.3 g of tricyclodecane dimethanol ethylene oxide 4 mol adduct (Mole ratio of ester group of glycol: glycol = 1: 1.2), 240 ° C. under nitrogen, Decomposed for 2 hours. The decomposition product had an OH value of 3.61 mol / kg, an OH equivalent of 274.0 g / mol, an acid value of 1.8 mg KOH / g, and a weight average molecular weight by GPC of 1039.
[0087]
To 200.0 g (0.722 OH gram equivalent) of the decomposed product, 54.0 g (0.749 mol, molar ratio 1: 1.04) of acrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone were added. While stirring, the mixture was heated, refluxed, dehydrated and subjected to esterification for 6 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. Yield: 85.0%, acid value = 1.5 mgKOH / g, refractive index (n_D ^{twenty five}) = 1.500, viscosity (mPa · s / 25 ° C.) = 3600, weight average molecular weight by GPC = 1020.
[0088]
Example 14
121.2 g of the PET waste pulverized product was added to 282.3 g of tricyclodecane dimethanol ethylene oxide 4 mol adduct (Mole ratio of ester group of glycol: glycol = 1: 1.2), 240 ° C. under nitrogen, Decomposed for 2 hours. The decomposition product had an OH value of 3.61 mol / kg, an OH equivalent of 274.0 g / mol, an acid value of 1.8 mg KOH / g, and a weight average molecular weight by GPC of 1039.
[0089]
20.0 g (0.375 mol, molar ratio 1: 0.52) of acrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid and 0.5 g of hydroquinone were added to 200.0 g (0.722 OH gram equivalent) of the decomposition product. While stirring, the mixture was heated, refluxed, dehydrated and subjected to esterification for 6 hours. After completion of the reaction, the mixture was washed with a 10% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and toluene was distilled off under reduced pressure. Yield is 84.0%, acid value = 1.4 mgKOH / g, refractive index (n_D ^{twenty five}) = 1.500, viscosity (mPa · s / 25 ° C.) = 3650, weight average molecular weight by GPC = 1015.
[0090]
[Table 4]

[0091]
[Table 5]

[0092]
The result of having determined the structural component of the product of an Example by the measurement of NMR is collectively shown in Table 4 and FIGS. 1-3. FIG. 1 shows the component amounts of the constituents of the products based on Examples 1, 2, 4, 5 and 6. FIG. 2 shows the component amounts of the constituent components of the product based on Example 7. FIG. 3 shows the component amounts of the components of the product based on Example 3.
[0093]
It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
[0094]
【The invention's effect】
According to the present invention, a polyester macromonomer can be easily produced, and industrially useful raw materials can be obtained from a saturated polyester resin or its waste. And the polyester macromonomer synthesize | combined from the glycol decomposition product of a waste can be utilized as a high added value monomer.
[Brief description of the drawings]
FIG. 1 is a diagram showing component amounts of constituents of products based on Examples 1, 2, 4, 5 and 6. FIG.
FIG. 2 is a diagram showing component amounts of constituent components of a product based on Example 7.
FIG. 3 is a view showing component amounts of constituent components of a product based on Example 3.

Claims (3)

  A method for producing a polyester macromonomer, comprising decomposing a saturated polyester resin with glycol and reacting the decomposition product with methacrylic acid or acrylic acid to produce a polyester macromonomer having a methacryloyl group end or an acryloyl group end. . The method for producing a polyester macromonomer according to claim 1 , wherein the saturated polyester resin is waste. The method for producing a polyester macromonomer according to claim 1 or 2 , wherein the saturated polyester resin is polyethylene terephthalate.

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