JP5782027B2 - 構造的に精密なポリ(プロピレンカーボネート)組成物 - Google Patents
構造的に精密なポリ(プロピレンカーボネート)組成物 Download PDFInfo
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- JP5782027B2 JP5782027B2 JP2012518615A JP2012518615A JP5782027B2 JP 5782027 B2 JP5782027 B2 JP 5782027B2 JP 2012518615 A JP2012518615 A JP 2012518615A JP 2012518615 A JP2012518615 A JP 2012518615A JP 5782027 B2 JP5782027 B2 JP 5782027B2
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- propylene carbonate
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Description
本願は、米国特許法第119条(e)項の下、2009年7月5日に出願された米国仮特許出願第61/223,042号、2009年7月9日に出願された米国仮特許出願第61/224,134号の利益を主張し、これらの各々の全体の内容は、本明細書中に参考として援用される。
本発明は、プラスチックの分野に関する。より詳細には、本発明は、構造的に精密なポリ(プロピレンカーボネート)を含有するポリマー組成物およびブレンドならびにそれから作製された物品に関する。
ポリ(プロピレンカーボネート)(本明細書中で以降「PPC」とも呼ぶ)とは、1960年代後半にInoueおよび共同研究者らによって最初に合成されてから知られているポリマーである。最近まで、高分子量のPPCは、酸化プロピレンをCO2と共重合させるためにカルボン酸亜鉛触媒を用いて主に合成されていた。その結果生じる材料は熱心な調査の中心であり、いくつかの企業が日用品の熱可塑性物質としての材料の応用を探索している。現在まで、PPCは、PPCのクリーンな熱分解が有利である応用において犠牲ポリマーとしてのみ商業化されている。熱可塑性の応用のための材料の商業化は、乏しい熱および加工の特性によって複雑となっている。最近、遷移金属複合体がCO2およびエポキシドの共重合のために開発されたが、そのような複合体は、改善されたPPC材料の調製において完全に活用および/または最適化されていない。
本発明には、反応パラメータを注意深く制御して作製したPPCは、有利な特性を有するPPCを生じるという認識が包含される。たとえば、特定の反応パラメータのそのような制御は、以前のPPC組成物よりも構造的に精密なPPCをもたらす。予想外に、この構造的に精密なPPCは、PPCが過去に性能が乏しかった数々の応用においてこの材料を使用することを可能にする、改善された加工特徴を有する。
具体的な官能基および化学用語の定義を、以下により詳細に記載する。本発明の目的のために、化学元素をthe Periodic Table of the Elements、CAS version、Handbook of Chemistry and Physics、第75版、内表紙に従って同定し、具体的な官能基は、その中に記載されているように一般に定義される。さらに、有機化学の一般的原理、ならびに具体的な官能部分および反応性は、そのそれぞれの内容全体が本明細書中に参考として組み込まれている、Organic Chemistry、Thomas Sorrell、University Science Books、Sausalito、1999、SmithおよびMarch、March’s Advanced Organic Chemistry、第5版、John Wiley&Sons,Inc.、New York、2001、Larock、Comprehensive Organic Transformations、VCH Publishers,Inc.、New York、1989、Carruthers、Some Modern Methods of Organic Synthesis、第3版、Cambridge University Press、Cambridge、1987に記載されている。
例えば、本発明は以下の項目を提供する。
(項目1)
ポリ(プロピレンカーボネート)を含む包装材料であって、該ポリ(プロピレンカーボネート)中、平均して少なくとも80%の隣接する単量体単位が頭−尾の配向である、包装材料。
(項目2)
少なくとも85%の隣接する単量体単位が頭−尾の配向である、項目1に記載の包装材料。
(項目3)
少なくとも90%の隣接する単量体単位が頭−尾の配向である、項目1に記載の包装材料。
(項目4)
少なくとも95%の隣接する単量体単位が頭−尾の配向である、項目1に記載の包装材料。
(項目5)
前記ポリ(プロピレンカーボネート)中、平均して少なくとも90%の隣接する単量体単位間の結合がカーボネート結合である、項目1に記載の包装材料。
(項目6)
少なくとも95%の隣接する単量体単位間の結合がカーボネート結合である、項目5に記載の包装材料。
(項目7)
少なくとも99%の隣接する単量体単位間の結合がカーボネート結合である、項目5に記載の包装材料。
(項目8)
隣接する単量体単位間の結合の本質的にすべてがカーボネート結合である、項目5に記載の包装材料。
(項目9)
前記ポリ(プロピレンカーボネート)の数平均分子量が約40,000g/mol〜約400,000g/molである、項目1に記載の包装材料。
(項目10)
前記ポリ(プロピレンカーボネート)の数平均分子量が約50,000g/mol〜約350,000g/molである、項目9に記載の包装材料。
(項目11)
前記ポリ(プロピレンカーボネート)の数平均分子量が約100,000g/mol〜約300,000g/molである、項目9に記載の包装材料。
(項目12)
前記ポリ(プロピレンカーボネート)の数平均分子量が約150,000g/mol〜約250,000g/molである、項目9に記載の包装材料。
(項目13)
前記ポリ(プロピレンカーボネート)の数平均分子量が約180,000g/mol〜約220,000g/molである、項目9に記載の包装材料。
(項目14)
前記ポリ(プロピレンカーボネート)の多分散指数が1.7未満である、項目1に記載の包装材料。
(項目15)
前記ポリ(プロピレンカーボネート)の多分散指数が1.5未満である、項目14に記載の包装材料。
(項目16)
前記ポリ(プロピレンカーボネート)の多分散指数が1.3未満である、項目14に記載の包装材料。
(項目17)
前記ポリ(プロピレンカーボネート)の多分散指数が1.2未満である、項目14に記載の包装材料。
(項目18)
前記ポリ(プロピレンカーボネート)が、式Aを有する鎖:
を、式D 3 を有する鎖:
と組み合わせて含み、式中、Xが、エポキシドを開環させることができる求核剤の結合した形態を表し、
nが、出現するごとに、約50〜約3,000の整数であり、
yおよびy’が、それぞれ独立して0〜6の整数であり、y+y’が2を超え、
が、二酸化炭素または酸化プロピレンと反応してポリマー鎖を開始させることができる2つ以上の官能基を含有する多官能性化合物を表す、項目1に記載の包装材料。
(項目19)
前記ポリ(プロピレンカーボネート)が、式Bの鎖:
をさらに含み、式中、Yが、エポキシドを開環させることができる求核剤の結合した形態であり、
XおよびYが異なる、項目18に記載の包装材料。
(項目20)
式Aの鎖対式D 3 の鎖の比が約1:50〜約50:1の範囲である、項目18に記載の包装材料。
(項目21)
式Aの鎖対式D 3 の鎖の比が約1:50〜約1:1の範囲である、項目18に記載の包装材料。
(項目22)
式Aの鎖対式D 3 の鎖の比が約1:10〜約10:1の範囲である、項目18に記載の包装材料。
(項目23)
式Aの鎖対式Bの鎖の比が約1:2〜約2:1の範囲である、項目19に記載の包装材料。
(項目24)
D 3 が式:
の鎖を含み、式中、qが0〜32の整数(両端を含む)である、項目18に記載の包装材料。
(項目25)
D 3 が式:
の鎖を含み、式中、qが0〜32の整数(両端を含む)である、項目18に記載の包装材料。
(項目26)
D 3 が式:
の鎖を含み、式中、pが1〜200の整数(両端を含む)であり、
R 1 が任意選択で存在し、存在する場合はメチルである、項目18に記載の包装材料。
(項目27)
D 3 が式:
の鎖を含み、式中、R 1 およびR 2 のうちの一方がメチルであり、他方が水素であり、R 3 およびR 4 のうちの一方がメチルであり、他方が水素である、項目26に記載の包装材料。
(項目28)
前記ポリ(プロピレンカーボネート)が少なくとも0.1%の鎖D 3 を含有し、yおよびy’の和が2を超える、項目18に記載の包装材料。
(項目29)
前記ポリ(プロピレンカーボネート)が0.5%〜20%の鎖D 3 を含有し、yおよびy’の和が2を超える、項目28に記載の包装材料。
(項目30)
nの値が出現するごとにほぼ同じである、項目18に記載の包装材料。
(項目31)
フィルムを含む、項目1から30のいずれか一項に記載の包装材料。
(項目32)
前記フィルムが少なくとも10重量%のポリ(プロピレンカーボネート)を含む、項目
31に記載の包装材料。
(項目33)
前記フィルムが少なくとも50重量%のポリ(プロピレンカーボネート)を含む、項目31に記載の包装材料。
(項目34)
前記フィルムが少なくとも90重量%のポリ(プロピレンカーボネート)を含む、項目31に記載の包装材料。
(項目35)
前記フィルムが吹込成形フィルムである、項目31に記載の包装材料。
(項目36)
前記フィルムが押出成形フィルムである、項目31に記載の包装材料。
(項目37)
前記フィルムの厚さが約0.01〜約100milである、項目31に記載の包装材料。
(項目38)
前記フィルムの厚さが約0.1〜約10milである、項目31に記載の包装材料。
(項目39)
前記フィルムの厚さが約0.2〜約5milである、項目31に記載の包装材料。
(項目40)
前記フィルムの厚さが約0.5〜約3milである、項目31に記載の包装材料。
(項目41)
前記フィルムが二軸延伸フィルムを含む、項目31に記載の包装材料。
(項目42)
前記フィルムがラミネートフィルムを含む、項目31に記載の包装材料。
(項目43)
前記フィルムが、充填剤、加工補助剤、難燃剤、着色料、相溶化剤、および可塑化剤からなる群から選択される1つ以上の添加剤を含む、項目31に記載の包装材料。
(項目44)
前記ラミネートフィルム中の層が、ポリオレフィン、ポリエステル、ポリエーテル、ポリアミド、ポリスチレン、ポリ塩化ビニル、ポリエチレンテレフタレート、フッ化ポリマー、およびこれらのうちの任意の2つ以上の混合物からなる群から選択されるポリマーを含む、項目42に記載の包装材料。
(項目45)
前記ラミネートフィルム中の層が、ポリ乳酸、ポリ(ヒドロキシアルカノエート)、ポリ(プロピレンカーボネート)以外の脂肪族ポリカーボネート、芳香族ポリカーボネート、ポリビニルアルコール、ナイロン(商標)、およびこれらのうちの任意の2つ以上の混合物からなる群から選択されるポリマーを含む、項目44に記載の包装材料。
(項目46)
項目1から30のいずれか一項に記載の包装材料を含む射出成形品。
(項目47)
項目1から30のいずれか一項に記載の包装材料を含む吹込成形品。
(項目48)
項目1から30のいずれか一項に記載の包装材料を含む1回分のサッシェ。
(項目49)
項目1から30のいずれか一項に記載の包装材料を含む食品包装フィルム。
(項目50)
項目1から30のいずれか一項に記載の包装材料を含むクラムシェル包装。
(項目51)
ポリ(プロピレンカーボネート)を含む成形用樹脂であって、該ポリ(プロピレンカーボネート)中、平均して少なくとも80%の隣接する単量体単位が頭−尾の配向である、成
形用樹脂。
(項目52)
少なくとも85%の隣接する単量体単位が頭−尾の配向である、項目51に記載の成形用樹脂。
(項目53)
少なくとも90%の隣接する単量体単位が頭−尾の配向である、項目51に記載の成形用樹脂。
(項目54)
少なくとも95%の隣接する単量体単位が頭−尾の配向である、項目51に記載の成形用樹脂。
(項目55)
前記ポリ(プロピレンカーボネート)中、平均して少なくとも90%の隣接する単量体単位間の結合がカーボネート結合である、項目51に記載の成形用樹脂。
(項目56)
少なくとも95%の隣接する単量体単位間の結合がカーボネート結合である、項目55に記載の成形用樹脂。
(項目57)
少なくとも99%の隣接する単量体単位間の結合がカーボネート結合である、項目55に記載の成形用樹脂。
(項目58)
隣接する単量体単位間の結合の本質的にすべてがカーボネート結合である、項目55に記載の成形用樹脂。
(項目59)
前記ポリ(プロピレンカーボネート)の数平均分子量が約40,000g/mol〜約400,000g/molである、項目51に記載の成形用樹脂。
(項目60)
前記ポリ(プロピレンカーボネート)の数平均分子量が約50,000g/mol〜約350,000g/molである、項目59に記載の成形用樹脂。
(項目61)
前記ポリ(プロピレンカーボネート)の数平均分子量が約100,000g/mol〜約300,000g/molである、項目59に記載の成形用樹脂。
(項目62)
前記ポリ(プロピレンカーボネート)の数平均分子量が約150,000g/mol〜約250,000g/molである、項目59に記載の成形用樹脂。
(項目63)
前記ポリ(プロピレンカーボネート)の数平均分子量が約180,000g/mol〜約220,000g/molである、項目59に記載の成形用樹脂。
(項目64)
前記ポリ(プロピレンカーボネート)の多分散指数が1.7未満である、項目51に記載の成形用樹脂。
(項目65)
前記ポリ(プロピレンカーボネート)の多分散指数が1.5未満である、項目64に記載の成形用樹脂。
(項目66)
前記ポリ(プロピレンカーボネート)の多分散指数が1.3未満である、項目64に記載の成形用樹脂。
(項目67)
前記ポリ(プロピレンカーボネート)の多分散指数が1.2未満である、項目64に記載の成形用樹脂。
(項目68)
前記ポリ(プロピレンカーボネート)が、式Aを有する鎖:
を、式D 3 を有する鎖:
と組み合わせて含み、式中、Xが、エポキシドを開環させることができる求核剤の結合した形態を表し、
nが、出現するごとに、約50〜約3,000の整数であり、
yおよびy’が、それぞれ独立して0〜6の整数であり、y+y’が2を超え、
が、二酸化炭素または酸化プロピレンと反応してポリマー鎖を開始させることができる2つ以上の官能基を含有する多官能性化合物を表す、項目51に記載の成形用樹脂。
(項目69)
前記ポリ(プロピレンカーボネート)が、式Bの鎖:
をさらに含み、式中、Yが、エポキシドを開環させることができる求核剤の結合した形態であり、
XおよびYが異なる、項目68に記載の成形用樹脂。
(項目70)
式Aの鎖対式D 3 の鎖の比が約1:50〜約50:1の範囲である、項目68に記載の成形用樹脂。
(項目71)
式Aの鎖対式D 3 の鎖の比が約1:50〜約1:1の範囲である、項目68に記載の成形用樹脂。
(項目72)
式Aの鎖対式D 3 の鎖の比が約1:10〜約10:1の範囲である、項目68に記載の成形用樹脂。
(項目73)
式Aの鎖対式Bの鎖の比が約1:2〜約2:1の範囲である、項目69に記載の成形用樹脂。
(項目74)
D 3 が式:
の鎖を含み、式中、qが0〜32の整数(両端を含む)である、項目68に記載の成形用樹脂。
(項目75)
D 3 が式:
の鎖を含み、式中、qが0〜32の整数(両端を含む)である、項目68に記載の成形用樹脂。
(項目76)
D 3 が式:
の鎖を含み、式中、pが1〜200の整数(両端を含む)であり、
R 1 が任意選択で存在し、存在する場合はメチルである、項目68に記載の成形用樹脂。
(項目77)
D 3 が式:
の鎖を含み、式中、R 1 およびR 2 のうちの一方がメチルであり、他方が水素であり、R 3 およびR 4 のうちの一方がメチルであり、他方が水素である、項目76に記載の成形用樹脂。
(項目78)
前記ポリ(プロピレンカーボネート)が少なくとも0.1%の鎖D 3 を含有し、yおよびy’の和が2を超える、項目68に記載の成形用樹脂。
(項目79)
前記ポリ(プロピレンカーボネート)が0.5%〜20%の鎖D 3 を含有し、yおよびy’の和が2を超える、項目78に記載の成形用樹脂。
(項目80)
nの値が出現するごとにほぼ同じである、項目68に記載の成形用樹脂。
(項目81)
少なくとも50重量%のポリ(プロピレンカーボネート)を含む、項目51から80のいずれか一項に記載の成形用樹脂。
(項目82)
少なくとも70重量%のポリ(プロピレンカーボネート)を含む、項目81に記載の成形用樹脂。
(項目83)
少なくとも90重量%のポリ(プロピレンカーボネート)を含む、項目81に記載の成形用樹脂。
(項目84)
加工補助剤、難燃剤、着色料、相溶化剤、抗酸化剤、充填剤および可塑化剤からなる群から選択される1つ以上の添加剤をさらに含む、項目51から80のいずれか一項に記載の成形用樹脂。
(項目85)
ポリオレフィン、ポリエステル、ポリエーテル、ポリアミド、ポリスチレン、ポリ塩化ビニル、ポリエチレンテレフタレート、フッ化ポリマー、およびこれらのうちの任意の2つ以上の混合物からなる群から選択されるポリマーをさらに含む、項目51から80のいずれか一項に記載の成形用樹脂。
(項目86)
ポリ乳酸、ポリ(ヒドロキシアルカノエート)、ポリ(プロピレンカーボネート)以外の脂肪族ポリカーボネート、芳香族ポリカーボネート、ポリビニルアルコール、ナイロン(商標)、およびこれらのうちの任意の2つ以上の混合物からなる群から選択されるポリマーをさらに含む、項目51から80のいずれか一項に記載の成形用樹脂。
(項目87)
項目51から80のいずれか一項に記載の成形用樹脂を含む射出成形品。
(項目88)
項目51から80のいずれか一項に記載の成形用樹脂を含む吹込成形品。
(項目89)
項目51から80のいずれか一項に記載の成形用樹脂を含むボトル。
(項目90)
項目51から80のいずれか一項に記載の成形用樹脂を含む押出物品。
(項目91)
項目51から80のいずれか一項に記載の成形用樹脂を含む熱成形物品。
一部の実施形態では、本発明には、構造的に精密なポリ(プロピレンカーボネート)組成物から製造された物品が包含される。これらの物品を作製するポリ(プロピレンカーボネート)組成物は、不均一亜鉛触媒系の存在下で酸化プロピレンおよび二酸化炭素の重合によって典型的に形成される従来技術のポリ(プロピレンカーボネート)組成物からそれらを区別する物理的特徴を有する。
B2およびCの鎖を含むPPCの合成。
A2、B2、およびCの鎖を含むPPCの合成。
B2、C、およびD5の鎖を含むPPCの合成。
B2、C、およびD8の鎖を含むPPCの合成。
B2、C、およびD9の鎖を含むPPCの合成。
実施例2〜4からのポリマーのゲル浸透クロマトグラフィー(GPC)を得た(図1)。実施例2〜4からのPPCのGPCの追跡を図1に示す。実施例2から生じる試料は二峰性の分子量分布を有しており、主に約120kg/molのMwの鎖(D5およびC型の鎖の混合物)、ならびにB2型の鎖の混合物に対応する約60kg/molのMwの鎖のより小さな集団を含有する。実施例3および4からの試料は、それぞれGPCにおいて特徴的な三峰性の分子量分布を示す。3つの構成成分は、B2型の鎖(低分子量集団)、C型の鎖を含有する中央集団およびD8(実施例3)またはD9(実施例4)型の鎖に対応する高Mwの集団に対応する。
本発明のPPCを、4インチのフィルムダイを備えた一軸スクリュー押出機に供給した。押出機の温度は170℃に維持した。100ミクロン、200ミクロン、500ミクロン、および900ミクロンのフィルムは、ダイの開口部を調節することによって得られた。水冷ロールを備えたロールシステムに通すことによってフィルムを冷却した。得られたフィルムは透明かつ強靭であり、様々な物品の熱成形に使用することができた。
真空システムを備えたIllig SB53−C1熱成形機を用いて、実施例6のPPCフィルムのそれぞれから小さなカップを形成した。PPCフィルムの熱成形条件を以下に要約する。
**熱成形では、加工は、セラミック加熱器の照射によって加熱されたPPCシートの温度を監視する高温計によって達成される温度によって、制御される。すなわち、表面温度が設定点である130℃に達した際に雄型が上に動き、真空が作動する。
実施例1に記載のものに類似のPPC(Novomer PPC)を供給ホッパーから射出成形機械に供給した。バレル内に入った際、樹脂は170℃まで加熱され、型に供給される。以下に記載のようにASTMの標準に従って試験するドッグボーンおよびフラットバーを成形した。
2.曲げ試験:ASTM D790(ISO178)
3.ノッチ付アイゾッド衝撃:ASTM D256、ISO180
4.加熱撓み温度(または負荷下の撓み温度):ASTM D648、ISO75。
本実施例では、本発明のPPC(Novomer PPC)をポリオレフィンとブレンドし、フィルム、射出成形品目および吹込成形ボトルを含めた様々な物品へと作製した。予想外に、本発明のPPCは押出加工を乗り切り、ポリオレフィンとの有用なブレンドを提供した。
Claims (21)
- ポリ(プロピレンカーボネート)を含む包装材料であって、該ポリ(プロピレンカーボネート)中、平均して少なくとも80%の隣接する単量体単位が頭−尾の配向であり、該包装材料が、押出成形フィルムを含み、該ポリ(プロピレンカーボネート)が、異なる平均分子量を有する2つ以上のポリ(プロピレンカーボネート)のブレントを含む、包装材料。
- 前記ポリ(プロピレンカーボネート)中、平均して少なくとも90%の隣接する単量体単位間の結合がカーボネート結合である、請求項1に記載の包装材料。
- 前記ポリ(プロピレンカーボネート)の数平均分子量が40,000g/mol〜400,000g/molである、請求項1に記載の包装材料。
- 前記ポリ(プロピレンカーボネート)の数平均分子量が100,000g/mol〜300,000g/molである、請求項3に記載の包装材料。
- フィルムを含む、請求項1から7のいずれか一項に記載の包装材料。
- 請求項1から7のいずれか一項に記載の包装材料を含む吹込成形品。
- 請求項1から7のいずれか一項に記載の包装材料を含む1回分のサッシェ。
- 請求項1から7のいずれか一項に記載の包装材料を含む食品包装フィルム。
- 請求項1から7のいずれか一項に記載の包装材料を含むクラムシェル包装。
- 押出物品の製造における使用のためのポリ(プロピレンカーボネート)を含む成形用樹脂であって、該ポリ(プロピレンカーボネート)中、平均して少なくとも80%の隣接する単量体単位が頭−尾の配向であり、該ポリ(プロピレンカーボネート)が、異なる平均分子量を有する2つ以上のポリ(プロピレンカーボネート)のブレントを含む、成形用樹脂。
- 前記ポリ(プロピレンカーボネート)中、平均して少なくとも90%の隣接する単量体単位間の結合がカーボネート結合である、請求項13に記載の成形用樹脂。
- 少なくとも99%の隣接する単量体単位間の結合がカーボネート結合である、請求項14に記載の成形用樹脂。
- 前記ポリ(プロピレンカーボネート)の数平均分子量が100,000g/mol〜300,000g/molである、請求項14に記載の成形用樹脂。
- 加工補助剤、難燃剤、着色料、相溶化剤、抗酸化剤、充填剤および可塑化剤からなる群から選択される1つ以上の添加剤をさらに含む、請求項13から19のいずれか一項に記載の成形用樹脂。
- 請求項13から19のいずれか一項に記載の成形用樹脂を含む吹込成形品。
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US8748555B2 (en) | 2014-06-10 |
EP2451860A2 (en) | 2012-05-16 |
KR101813019B1 (ko) | 2017-12-28 |
EP2451860A4 (en) | 2014-08-20 |
WO2011005664A2 (en) | 2011-01-13 |
KR20120048600A (ko) | 2012-05-15 |
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JP2012532233A (ja) | 2012-12-13 |
CN102471473A (zh) | 2012-05-23 |
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