JP5409012B2 - ポリ乳酸のステレオコンプレックス形成促進剤 - Google Patents
ポリ乳酸のステレオコンプレックス形成促進剤 Download PDFInfo
- Publication number
- JP5409012B2 JP5409012B2 JP2008552057A JP2008552057A JP5409012B2 JP 5409012 B2 JP5409012 B2 JP 5409012B2 JP 2008552057 A JP2008552057 A JP 2008552057A JP 2008552057 A JP2008552057 A JP 2008552057A JP 5409012 B2 JP5409012 B2 JP 5409012B2
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- JP
- Japan
- Prior art keywords
- polylactic acid
- anhydride
- stereocomplex
- group
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Description
なお、本発明はその機構が明らかではなく、ポリ乳酸の分子鎖と添加したステレオコンプレックス形成促進剤を構成する各試薬(すなわち前記エポキシ化合物、酸無水物、及び有機過酸化物、以下試薬と言うときもある)とが反応している可能性もある。よって、エポキシ化合物と酸無水物の配合比も幅のあるものとなる。
本発明における前記試薬とポリ乳酸との反応例はなく、有機反応機構上も解明されていない。ポリ乳酸の分子鎖と添加した試薬が反応している可能性もある。したがって、エポキシ化合物と酸無水物との配合比も若干の幅がある。また単純なインターポリマーネットワークとは考え難い。
これら各成分の含有比は、重量比において、3,4−エポキシシクロヘキセニルメチル−3’,4’−エポキシシクロヘキセンカルボキシレート:無水フタル酸:t−ブチルパーオキシラウレート:2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン=100:25〜35:20〜30:20〜30であることが好ましい。
本発明に係るステレオコンプレックス形成促進剤がこのような組成であると、形成されたポリ乳酸の結晶がステレオコンプレックスのみとなり、耐熱性及び耐衝撃性に極めて優れたポリ乳酸を得ることができる。更に、このようにステレオコンプレックス形成促進剤を添加したポリ乳酸は自己消火性を有し、火がついても燃え広がらず、自ら鎮火することができる。
レイシアH400(ポリ−L−乳酸、三井化学社製)に対して、下記の表1に示す組成のステレオコンプレックス形成促進剤を加え、ステレオコンプレックス形成開始剤である、所謂、マスターバッチ(サンプル1〜8)を調製した。なお、表1中の数値の単位は全て重量%である。
1)セロキサイド2021P;3,4−エポキシシクロヘキセニルメチル−3’,4’−エポキシシクロヘキセンカルボキシレート(ダイセル化学工業社製)
2)YDCN700−5;ノボラック型エポキシ樹脂(東都化成社製)
3)リカシッドHT−IA;テトラヒドロ無水フタル酸(新日本理化社製)
4)パーブチルL;t−ブチルパーオキシラウレート(日本油脂社製)
5)パーヘキサ25Z;2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン(日本油脂社製)
加重たわみ温度;JIS K 7191
引張強度;JIS K 7161
伸び;JIS K 7113
曲弾性率;JIS K 7171
アイゾット衝撃強度;JIS K 7110
ガラス転移温度;JIS C 6481
ポリ−L−乳酸(PLLA)(レイシアH400、三井化学社製)に対して、下記の表3に示すように、各種組成のステレオコンプレックス形成促進剤を加え、ステレオコンプレックス形成開始剤(サンプル9〜11)を調整した。
6)ニューザイダー;エポキシダイズ油(日本油脂社製)
表1に記載のサンプル1において、ポリ乳酸(レイシアH400)を表4に示す他の樹脂に替えることにより、樹脂98.4重量%に対し、結晶化促進剤(セロキサイド2012P:無水フタル酸:パーブチルL:パーヘキサ25Z=1:0.3:0.15:0.15(重量比))を2.6重量%添加した樹脂組成物が得られた。これらの樹脂組成物について、DSCにより結晶化温度(Tc)と結晶化エントロピー(ΔH)を測定して、各樹脂に対する前記結晶化促進剤の結晶化促進効果を調べた。結果を表4及び図3〜13に示した。
A:各樹脂のペレットをそのままDSCにより測定した。
B:結晶化促進剤を添加せずに、各樹脂のペレットを押出し機で融解させたものをDSCにより測定した。
C:各樹脂のペレットに結晶化促進剤を添加した後、押出し機で融解させたものをDSCにより測定した。
測定装置:ブルカー・エイエックスエス社製 DSC3100SA
窒素流量:30mL/min
標準試料:α−アルミナ
昇温速度:10℃/min
降温速度:5℃/min
Claims (9)
- 脂肪族環状エポキシ、及び、エポキシ化大豆油からなる群より選ばれる少なくとも1種のエポキシ化合物、
無水コハク酸、無水マレイン酸、無水フタル酸、及び、無水トリメリット酸からなる群より選ばれる少なくとも1種の酸無水物、並びに、
パーオキシケタール、ハイドロパーオキサイド、パーオキシジカーボネート、及び、パーオキシエステルからなる群より選ばれる少なくとも1種の有機過酸化物を含有することを特徴とするポリ乳酸のステレオコンプレックス形成促進剤。 - 前記エポキシ化合物と前記酸無水物との含有比が、重量比において、エポキシ化合物:酸無水物=100:10〜40である請求項1記載のポリ乳酸のステレオコンプレックス形成促進剤。
- 脂肪族環状エポキシ、無水フタル酸、及び、パーオキシエステルからなる請求項1又は2記載のポリ乳酸のステレオコンプレックス形成促進剤。
- 前記脂肪族環状エポキシが、3,4−エポキシシクロヘキセニルメチル−3’,4’−エポキシシクロヘキセンカルボキシレートであり、
前記パーオキシエステルが、t−ブチルパーオキシラウレート、及び、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサンである請求項3記載のポリ乳酸のステレオコンプレックス形成促進剤。 - 各成分の含有比が、重量比において、3,4−エポキシシクロヘキセニルメチル−3’,4’−エポキシシクロヘキセンカルボキシレート:無水フタル酸:t−ブチルパーオキシラウレート:2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン=100:25〜35:20〜30:20〜30である請求項4記載のポリ乳酸のステレオコンプレックス形成促進剤。
- 脂肪族環状エポキシ、及び、エポキシ化大豆油からなる群より選ばれる少なくとも1種のエポキシ化合物、
無水コハク酸、無水マレイン酸、無水フタル酸、及び、無水トリメリット酸からなる群より選ばれる少なくとも1種の酸無水物、並びに、
パーオキシケタール、ハイドロパーオキサイド、パーオキシジカーボネート、及び、パーオキシエステルからなる群より選ばれる少なくとも1種の有機過酸化物をポリ乳酸又はポリ乳酸生成前の中間体中に加え、反応させることによって得られるポリ乳酸のステレオコンプレックス形成開始剤。 - ポリ乳酸又は前記中間体とエポキシ化合物との重量比が100:0.5〜5である請求項6記載のポリ乳酸のステレオコンプレックス形成開始剤。
- 請求項7記載のポリ乳酸のステレオコンプレックス形成開始剤を、1〜10重量%となるように、ポリ乳酸に添加する工程を有することを特徴とする乳酸系ポリマーの製造方法。
- ポリプロピレン、ポリアミド、又は、ポリエチレンテレフタレートの結晶化を促進するためのものであって、
脂肪族環状エポキシ、及び、エポキシ化大豆油からなる群より選ばれる少なくとも1種のエポキシ化合物、
無水コハク酸、無水マレイン酸、無水フタル酸、及び、無水トリメリット酸からなる群より選ばれる少なくとも1種の酸無水物、並びに、
パーオキシケタール、ハイドロパーオキサイド、パーオキシジカーボネート、及び、パーオキシエステルからなる群より選ばれる少なくとも1種の有機過酸化物を含有することを特徴とする結晶化促進剤。
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