JP5190002B2 - ポリ乳酸ブロック共重合体の製造方法 - Google Patents
ポリ乳酸ブロック共重合体の製造方法 Download PDFInfo
- Publication number
- JP5190002B2 JP5190002B2 JP2009031667A JP2009031667A JP5190002B2 JP 5190002 B2 JP5190002 B2 JP 5190002B2 JP 2009031667 A JP2009031667 A JP 2009031667A JP 2009031667 A JP2009031667 A JP 2009031667A JP 5190002 B2 JP5190002 B2 JP 5190002B2
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- JP
- Japan
- Prior art keywords
- pdla
- plla
- lactic acid
- lactide
- poly
- 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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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 53
- 239000004626 polylactic acid Substances 0.000 title claims description 52
- 229920001400 block copolymer Polymers 0.000 title claims description 42
- 238000000034 method Methods 0.000 title description 30
- 230000008569 process Effects 0.000 title description 4
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 113
- 238000004519 manufacturing process Methods 0.000 claims description 58
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 50
- 229940022769 d- lactic acid Drugs 0.000 claims description 38
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 28
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 27
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 17
- 229920001434 poly(D-lactide) Polymers 0.000 description 91
- 238000006243 chemical reaction Methods 0.000 description 37
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 31
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 28
- -1 polyethylene terephthalate Polymers 0.000 description 25
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 24
- 239000013078 crystal Substances 0.000 description 23
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- 238000000113 differential scanning calorimetry Methods 0.000 description 16
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- 239000002184 metal Substances 0.000 description 15
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- 238000002844 melting Methods 0.000 description 14
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- YWFOKXPDJMYPQR-UHFFFAOYSA-N 1-(2-hydroxypropyl)pyrrole-2,5-dione Chemical compound CC(O)CN1C(=O)C=CC1=O YWFOKXPDJMYPQR-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- 150000002596 lactones Chemical class 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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Description
ディールス・アルダー反応の原料となる、末端にアントラセニル基を有するポリ−L−乳酸(本明細書では、単にA−PLLAとも称する)、または末端にアントラセニル基を有するポリ−D−乳酸(本明細書では、単にA−PDLAとも称する)は、以下のような構成を有する。
ディールス・アルダー反応のもう一方の原料となる、末端にマレイミド基を有するポリ−L−乳酸(本明細書では、単にM−PLLAとも称する)、または末端にマレイミド基を有するポリ−D−乳酸(本明細書では、単にM−PDLAとも称する)の構成については、末端がアントラセニル基からマレイミド基に代わること以外、上記の「(末端にアントラセニル基を有するポリ−L−乳酸またはポリ−D−乳酸)」の項で説明した通りであるので、ここでは説明を省略する。また、M−PLLAおよびM−PDLAの製造方法についても、アントラセン化合物の代わりにマレイミド化合物を重合開始剤として用いること以外は、上記の「(末端にアントラセニル基を有するポリ−L−乳酸またはポリ−D−乳酸)」の項で説明した製造方法と同様の製造方法を採用することができる。すなわち、重合開始剤としてマレイミド化合物を用い、L−ラクチドを開環重合するか、またはL−乳酸を脱水縮合すればM−PLLAが得られる。重合開始剤としてマレイミド化合物を用い、D−ラクチドを開環重合するか、またはD−乳酸を脱水縮合すればM−PDLAが得られる。
本発明のポリ乳酸ブロック共重合体の製造方法は、上記A−PLLAと上記M−PDLAとをディールス・アルダー反応させる工程か、または上記A−PDLAと上記M−PLLAとをディールス・アルダー反応させる工程を含むことを特徴とする。
500MHz 1H−NMRは、Bruker社製、ARX500を用い、内部標準としてテトラメチルシラン(TMS)を0.3体積%含む重クロロホルムを溶媒として用いた。
GPC法により、ポリスチレン換算の値を測定した。使用した測定機器等の測定条件は下記表2の通りであった。分子量分布(MwD)は、測定された重量平均分子量(Mw)と数平均分子量(Mn)とから、前記数式1によって算出した。
示差走査熱量測定計(株式会社島津製作所製DSC−50)を用いた。試料3mgをアルミニウムパンに入れ、下記表3に示す(a)〜(c)の条件で、20ml/分の流速で窒素ガスを流して測定を行った。
株式会社リガク製の粉末X線回折装置RINT−2500を用い、Cu−Kα線、40kV、50mA、5〜40°、スキャン速度4°/分の条件で測定した。
<A−PLLAの合成>
試験管に、L−ラクチド 1g(7mmol)、および2−(ヒドロキシメチル)アントラセン 20.8mg(0.1mmol)を入れ、室温(20℃)で3時間、真空乾燥した。オクチル酸スズ 0.05mmolを含む0.1mLの触媒溶液(溶媒:トルエン)を、窒素雰囲気下で試験管に加えた。混合物全体を、トルエンを蒸発させるために室温(20℃)で5時間真空乾燥し、120℃に加熱して3時間攪拌した。加熱後1時間以内に、溶融状態の混合物が固化し、結晶の色が黄色くなった。よって、その後は攪拌せずに、固体状態で反応を続けた。得られた重合物を、ジクロロメタンに溶かし、過剰のメタノール中に再沈殿させて、濾過分離し乾燥し、A−PLLAを得た。A−PLLAの収率は91%(収量:0.91g)であった。1H−NMRのスペクトルデータを、下記表4に示す。
<M−PDLAの合成>
試験管に、D−ラクチド 1g(7mmol)、および2−(ヒドロキシメチル)マレイミド 14mg(0.1mmol)を入れ、室温(20℃)で3時間、真空乾燥した。オクチル酸スズ 0.05mmolを含む0.1mLの触媒溶液(溶媒:トルエン)を、窒素雰囲気下で試験管に加えた。混合物全体を、トルエンを蒸発させるために室温(20℃)で5時間真空乾燥し、120℃に加熱して3時間攪拌した。加熱後1時間以内に、溶融状態の混合物が固化し、結晶の色が黄色くなった。よって、その後、攪拌せずに、固体状態で反応を続けた。得られた重合物を、ジクロロメタンに溶かして、過剰のメタノール中に再沈殿させて、濾過分離し乾燥し、M−PDLAを得た。M−PDLAの収率は92%(収量:0.92g)であった。重合体の数平均分子量は、1H−NMRスペクトルにより決定した。1H−NMRのスペクトルデータを、下記表5に示す。
<A−PDLAの合成>
L−ラクチドの代わりに、D−ラクチドを用いたこと以外は、製造例1と同様にしてA−PDLAを得た。収率は91%(収量:0.91g)であった。1H−NMRのスペクトルデータを、下記表6に示す。
<M−PLLAの合成>
D−ラクチドの代わりに、L−ラクチドを用いたこと以外は、製造例2と同様にしてM−PLLAを得た。収率は90%(収量:0.90g)であった。1H−NMRのスペクトルデータを、下記表7に示す。
製造例1で得られたA−PLLAおよび製造例2で得られたM−PDLAを、それぞれジクロロメタンに溶解し、濃度が5mM(0.5g/L)である溶液を調製した。最初に、両方の溶液を、A−PLLAとM−PDLAのモル比が1:1となるように混合し、室温(20℃)で120分間激しく攪拌・混合した。得られた溶液を、過剰のメタノール中に再沈殿させた。沈殿物を、濾過分離し乾燥した。次に、乾燥後の沈殿物を窒素雰囲気下の試験管に入れ、室温(20℃)で3時間真空乾燥した後、135℃で12時間攪拌した。その後、冷却し、生成物であるポリ乳酸ブロック共重合体(本明細書では、単に「PLLA−b−PDLA」とも称する)を得た。得られたPLLA−b−PDLAの1H−NMRのスペクトルデータを、下記表8に示す。
A−PLLAの代わりに製造例3で得られたA−PDLAを用い、M−PDLAの代わりに製造例4で得られたM−PLLAを用いたこと以外、実施例1と同様の方法で、ポリ乳酸ブロック共重合体(本明細書では、単に「PDLA−b−PLLA」とも称する)を得た。得られたPDLA−b−PLLAの1H−NMRのスペクトルデータを、下記表9に示す。
Claims (2)
- 末端にアントラセニル基を有するポリ−L−乳酸と末端にマレイミド基を有するポリ−D−乳酸とを、ディールス・アルダー反応させる工程を含む、ポリ乳酸ブロック共重合体の製造方法。
- 末端にアントラセニル基を有するポリ−D−乳酸と末端にマレイミド基を有するポリ−L−乳酸とを、ディールス・アルダー反応させる工程を含む、ポリ乳酸ブロック共重合体の製造方法。
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