JP6788679B2 - ポリ乳酸の天然油とのエステル交換 - Google Patents
ポリ乳酸の天然油とのエステル交換 Download PDFInfo
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- JP6788679B2 JP6788679B2 JP2018540049A JP2018540049A JP6788679B2 JP 6788679 B2 JP6788679 B2 JP 6788679B2 JP 2018540049 A JP2018540049 A JP 2018540049A JP 2018540049 A JP2018540049 A JP 2018540049A JP 6788679 B2 JP6788679 B2 JP 6788679B2
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- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
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- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
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- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
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- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、一般にポリマーのエステル交換に関し、より詳細にはポリマーポリ乳酸と天然油とのエステル交換反応に関する。
過去には、いくつかのタイプのポリマー骨格が、ひまし油及び大豆油などの特定の天然油でエステル交換されている。これらのポリマー骨格にはポリ乳酸骨格は含まれていなかった。ポリ乳酸骨格は、グリコール又はカプロラクトンでエステル交換されている。いずれの場合も、エステル交換プロセスが改善された特性を有するポリマーをもたらすであろうことが期待されていた。
エステル交換プロセスは、さまざまな反応性成分について当技術分野で知られている。エステル交換反応全体では、アルコールが触媒の存在下でエステルと反応し、エステル上の1つのR基が、アルコール上のR基と交換される:R’−OH+R”−O−C(O)−R→R”−OH+R’−O−C(O)−R。天然油を使用したエステル交換反応は、ポリ乳酸には適用されていなかった。本発明の方法に供された従来のポリ乳酸ポリマーは、エステル交換されたポリ乳酸ポリマーをもたらす。エステル交換されたポリ乳酸ポリマーは、ポリ乳酸と比較すると、室温において液体又はワックス状固体の状態であることや、様々な溶媒中での溶解性の向上など、望ましい改善された特性を有する。
各サンプルのヒドロキシル価は、当業者に知られている標準的な手順を使用してKOHによる滴定を使用して測定した。結果は、材料1g当たりのKOHのmgとして示す。ヒドロキシル価は、化学物質中の遊離ヒドロキシル基の含量の尺度であり、通常、化学物質1グラムのヒドロキシル含量に相当する、ミリグラム単位での水酸化カリウム(KOH)の質量の単位で表される。ヒドロキシル価を決定するために使用される分析方法は、従来、該物質の遊離ヒドロキシル基のピリジン溶媒中での無水酢酸によるアセチル化を含む。反応終了後、水を添加し、そして残りの未反応の無水酢酸を酢酸に変換し、水酸化カリウムを用いた滴定によって測定する。
大豆油(Soybean)−PLA−400と表記した第1の例では、撹拌機、温度計、加熱マントル、還流冷却器、及び窒素フラッシュ注入口を備えた500mlの丸底フラスコに、以下のように仕込んだ:ジエチレングリコール60g(565.40ミリモル)、次いで、80,000g/モルのポリ乳酸原料110g(.375ミリモル)を添加した。触媒であるチタン(IV)ブトキシドを、先ずイソプロパノール中に0.1g/mlのレベルで溶解し、次いでこの溶液0.4mlをフラスコに投入した。反応混合物を撹拌しながら150℃〜165℃に加熱してポリ乳酸を溶融させた。反応全体を窒素ブランケット下で行った。いったん溶液が完全に溶解したら、天然油である大豆油30gを反応混合物に添加し、温度を170〜180℃に上昇させ、そして撹拌しながら3時間この温度に維持した。3時間後、温度を190〜200℃に上昇させ、撹拌しながらさらに4時間この温度に維持した。4時間後、温度を210〜220℃に上昇させ、反応生成物が目視で透明で均質な単一層になるまで、撹拌しながら少なくとも7時間又はそれ以上この温度に維持した。加熱マントルを取り外し、生成物を取扱いに好都合な温度まで冷却させ、次いでエステル交換ポリ乳酸生成物を取り出した。
Claims (18)
- a)反応混合物の総重量に基づいて50〜85重量%の量で存在するポリ乳酸;
b)前記反応混合物の前記総重量に基づいて13〜30重量%の量で存在する少なくとも1種の天然油;
c)前記反応混合物の前記総重量に基づいて2〜36重量%の量で存在するジオール;及び、
d)任意選択でエステル交換触媒
を含む反応混合物の反応から生じるエステル交換ポリ乳酸であって、
前記エステル交換ポリ乳酸が、エステル交換ポリ乳酸1グラム当たり10〜600ミリグラムのKOHのヒドロキシル価を有する、エステル交換ポリ乳酸。 - 前記エステル交換ポリ乳酸が、エステル交換ポリ乳酸1グラム当たり40〜600ミリグラムのKOHのヒドロキシル価を有する、請求項1に記載のエステル交換ポリ乳酸。
- 前記ジオールが、ジエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール、ネオペンチルグリコール、プロピレングリコール、ジプロピレングリコール、ヘキサンジオール、エチレングリコール、2−メチル−1,3プロパンジオール、ブタンジオール、ポリテトラヒドロフラン、及びそれらの混合物からなる群から選択される、請求項1又は2に記載のエステル交換ポリ乳酸。
- 前記ポリ乳酸が、前記反応混合物の前記総重量に基づいて50〜80重量%の量で存在する、請求項1〜3のいずれか一項に記載のエステル交換ポリ乳酸。
- 前記少なくとも1種の天然油が、大豆油、ひまし油、キャノーラ油、ヒマワリ油、ベニバナ油、コーン油、ピーナッツ油、アーモンド油、オリーブ油、ココナツ油、パーム油、トール油、及びそれらの混合物からなる群から選択される、請求項1〜4のいずれか一項に記載のエステル交換ポリ乳酸。
- 前記ポリ乳酸の数平均分子量が2,000〜200,000である、請求項1〜5のいずれか一項に記載のエステル交換ポリ乳酸。
- 請求項1〜6のいずれか一項に記載のエステル交換ポリ乳酸を含む組成物。
- ポリ乳酸をエステル交換する方法であって、以下の工程:
a)ジオール、ポリ乳酸、及び任意選択でエステル交換触媒を一緒に組み合わせて反応混合物を形成し、それを第1の温度まで加熱して溶融反応混合物を形成する工程;
b)溶融反応混合物に少なくとも1種の天然油を添加し、第1の温度よりも高い第2の温度まで加熱し、該第2の温度を所定の時間維持する工程;
c)第2の温度よりも高い第3の温度まで加熱し、該第3の温度を所定の時間維持する工程;
d)第3の温度よりも高い第4の温度まで加熱し、該第4の温度を所定の時間維持する工程;及び、
e)反応混合物を冷却し、エステル交換ポリ乳酸反応生成物を回収する工程
を含む、方法。 - 工程a)におけるポリ乳酸の量が、工程a)及び工程b)の組合せの総重量の50〜85重量%を構成する、請求項8に記載の方法。
- 工程a)におけるポリ乳酸の量が、工程a)及び工程b)の組合せの総重量の50〜80重量%を構成する、請求項8又は9に記載の方法。
- 工程b)における天然油の量が、工程a)及び工程b)の組合せの総重量の13〜30重量%を構成する、請求項8〜10のいずれか一項に記載の方法。
- 工程a)におけるポリ乳酸が、2,000〜200,000の数平均分子量を有するポリ乳酸を含む、請求項8〜11のいずれか一項に記載の方法。
- 工程a)におけるジオールが、工程a)及び工程b)の組合せの総重量の2〜36重量%の量で存在する、請求項8〜12のいずれか一項に記載の方法。
- 工程b)における少なくとも1種の天然油が、大豆油、ひまし油、キャノーラ油、ヒマワリ油、ベニバナ油、コーン油、ピーナッツ油、アーモンド油、オリーブ油、ココナツ油、パーム油、トール油、及びそれらの混合物からなる群から選択される、請求項8〜13のいずれか一項に記載の方法。
- 工程a)におけるエステル交換触媒がチタンアルコキシドである、請求項8〜14のいずれか一項に記載の方法。
- エステル交換触媒がチタン(IV)ブトキシドである、請求項15に記載の方法。
- エステル交換ポリ乳酸が、エステル交換ポリ乳酸1グラム当たり10〜600ミリグラムのKOHのヒドロキシル価を有する、請求項8〜16のいずれか一項に記載の方法。
- 工程a)におけるジオールが、ジエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール、ネオペンチルグリコール、プロピレングリコール、ジプロピレングリコール、ヘキサンジオール、エチレングリコール、2−メチル−1,3プロパンジオール、ブタンジオール、ポリテトラヒドロフラン、及びそれらの混合物からなる群から選択される、請求項8〜17のいずれか一項に記載の方法。
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