JPWO2014167966A1 - ラクチド−ラクトン共重合体の製造方法 - Google Patents
ラクチド−ラクトン共重合体の製造方法 Download PDFInfo
- Publication number
- JPWO2014167966A1 JPWO2014167966A1 JP2015511172A JP2015511172A JPWO2014167966A1 JP WO2014167966 A1 JPWO2014167966 A1 JP WO2014167966A1 JP 2015511172 A JP2015511172 A JP 2015511172A JP 2015511172 A JP2015511172 A JP 2015511172A JP WO2014167966 A1 JPWO2014167966 A1 JP WO2014167966A1
- Authority
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- Japan
- Prior art keywords
- lactide
- group
- complex
- lactone
- dioxomolybdenum
- 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.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000002596 lactones Chemical class 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 16
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 16
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 41
- -1 molybdenum ion Chemical class 0.000 claims description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims description 33
- 239000011733 molybdenum Substances 0.000 claims description 32
- GCMDLPXRCVHIMG-UHFFFAOYSA-N dioxomolybdenum(2+) Chemical group O=[Mo+2]=O GCMDLPXRCVHIMG-UHFFFAOYSA-N 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 24
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- RTPYACZBQBEDCN-UHFFFAOYSA-N oxomolybdenum(4+) Chemical group [Mo+4]=O RTPYACZBQBEDCN-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000003999 initiator Substances 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 16
- 239000003446 ligand Substances 0.000 description 15
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- 230000015572 biosynthetic process Effects 0.000 description 9
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- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
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- 239000000126 substance Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 6
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- MDYOLVRUBBJPFM-UHFFFAOYSA-N tropolone Chemical compound OC1=CC=CC=CC1=O MDYOLVRUBBJPFM-UHFFFAOYSA-N 0.000 description 6
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- KLDZYURQCUYZBL-UHFFFAOYSA-N 2-[3-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCN=CC1=CC=CC=C1O KLDZYURQCUYZBL-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本願は、2013年4月12日に出願した特願2013-084129号明細書(その全体が参照により本明細書中に援用される)の優先権の利益を主張するものである。
本発明は、ラクチド−ラクトン共重合体の製造方法に関する。
すなわち、本発明は以下の通りである。
R1は、炭素数2〜7の二価の脂肪族炭化水素基であり、
R2、R3、R4、R5、R6、R7、R8及びR9は、独立して、水素、炭素数が1〜4のアルキル基、炭素数1〜4のアルコキシ基、シリル基、アリール基、メトキシメチル基、−Cl、−Br、又は−Iである、項6に記載のラクチド−ラクトン共重合体の製造方法。
ジオキソモリブデン(VI)サレン錯体は、下記の一般式(1)で表される。
R1は、炭素数2〜7の二価の脂肪族炭化水素基であり、
R2、R3、R4、R5、R6、R7、R8及びR9は、独立して、水素(−H)、炭素数が1〜4のアルキル基、炭素数1〜4のアルコキシ基、シリル基、アリール基、メトキシメチル基、−Cl、−Br、又は−Iである。
R3及びR8、並びにR5及びR6はそれぞれ同一であり、
R1は−(CH2)2−、−(CH2)3−、−CH2−C(CH3)2−CH2−、又は−(CH2)4−であり、R5及びR6は水素、−CH3、−CH2CH3、−C(CH3)3、−OCH3、−Cl、−Br、又は−Iであり、R3及びR8は水素、−CH3、−CH2CH3、−C(CH3)3、−OCH3、−Cl、−Br、又は−Iである。
以下の実施例において、別段明記がない限り、NMR、GPC及びDSCは以下の条件で行った。
NMRはBRUKER DRX500 spectrometer (Bruker社製)を用いて測定した。溶媒には標準物質としてTMSを0.03vol%含むCDCl3, DMSO-d6を用いた。
(開始剤消費率)=a/(a+d)
(重合度)=(c+e)/e
GPCはポンプ(LC-10ADVP、株式会社島津製作所)及びRI検出器(RID-10A、株式会社島津製作所)を用い、カラムShodex GPC KF-804L(昭和電工株式会社製)でオーブン温度40℃、THF流速0.5ml/分にて測定した。ポリマー1.8mgに対してTHF0.5mlで試料を作成し、10μl注入して測定した。分子量Mn, Mw及び分子量比Mw/Mnはポリスチレンを標準物質として検量線を作成して計算した。
DSCはDSC 2920(TA Instrument 社製)を用いてHeating rate10℃/minで−80〜200℃の範囲でガラス転移温度(Tg)を測定した。通常測定を行い放冷した後、再び測定しデータとした。
実施例1 ジオキソモリブデンサレン錯体の製造
K. Yamanouchi et al., Inorg. Chim. Acta, 9, 161-164, 1974又はW. E. Hill et al., Inorg. Chim. Acta, 35, 35-41, 1979等を参考にして、下記の表2の反応式におけるようにジアミン(2)とサリチルアルデヒド誘導体(3)からリガンド(4)を合成した。
実施例1で得られたジオキソモリブデンサレン錯体のうち、MoO2(3-OMe)salen、MoO2(3-OMe)saltn、MoO2(3-OMe)Di-Me-saltn、及びMoO2(3-OMe)saltetのcis-α立体異性型について、ε−カプロラクトン:開始剤:触媒=100:10:1(モル比)の条件で、開始剤としてベンジルアルコールを用いてトルエン還流下で1時間反応させてε−カプロラクトン(CL)の開環重合活性を調べたところ(ε−カプロラクトン110μl、ベンジルアルコール10μl、触媒0.1mmol、及びトルエン1mL)、表4のように、いずれの錯体の触媒活性も高かった。反応率及び重合度はCDCl3を溶媒に用いてNMRで測定した。
ε−カプロラクトン:開始剤:触媒=100:1:0.05(モル比)の条件で、開始剤としてシクロドデカノールを用いてメシチレン中110℃で15分反応したところ、表6の様にMoO2(3-OMe)Di-Me-saltnの活性が最も高いことが分かった。
K. Yamanouchi, S. Yamada, Inorg. Chim. Acta, 9, 83-86, 1974に記載された合成方法に従い、サリチルアルデヒド誘導体とモリブデン酸アンモニウムをMethanol-H2Oに溶解し、12M HCl 1mlをゆっくり加えた。その後、室温で4時間反応させ、生じた沈殿をろ過し、各種ジオキソモリブデンサリチルアルデヒド錯体を合成した(下記の化7の反応式、表7)。各錯体の合成方法は以下の通りである。また、同定は元素分析により行った。
Salicylaldehyde 2.2009g (18.02mmol)のMethanol溶液5mlに七モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) 1.2392g (1.003mmol; salicylaldehyde: Mo = 2.5:1) の水溶液15 mlを加え、撹拌しながら12M HCl 1mlをゆっくりと加えた。そのまま室温で4時間反応させ、沈殿をろ過し、Methanolと水のそれぞれで洗浄した後に減圧下で乾燥し、2.4210g (6.540mmol)の黄色結晶を得た。(収率93.2%)
mp=250-267℃ (分解), Anal. Calcd For C14H10O6Mo: C, 45.4; H, 2.72. Found: C, 45.7, H, 2.80.
o-vanillin 2.7393g (18.00mmol) のMethanol溶液5mlに七モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) 1.2347g (0.999mmol)の水溶液15mlを加え、撹拌しながら12M HCl 1mlをゆっくりと加えた。そのまま室温で4時間反応させ、沈殿をろ過し、Methanolと水のそれぞれで洗浄した後に減圧下で乾燥し、2.8222g (6.560mmol)の黄色結晶を得た。(収率93.8%)
mp=160-227℃ (分解), Anal. Calcd For C16H14O8Mo: C, 44.7; H, 3.3. Found: C, 45, H, 3.3.
3-MethylSalicylaldehyde 1.2280g (9.019mmol)のMethanol溶液2.5mlに七モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) 0.6181g (0.5000mmol)の水溶液7.5mLを加え、撹拌しながら12M HCl 0.5 mlをゆっくりと加えた。そのまま室温で4時間反応させ、沈殿をろ過し、Methanolと水のそれぞれで洗浄した後に減圧下で乾燥することで、1.2824g (3.220mmol)の黄色結晶を得た。(収率92.0%)
mp=265-285℃ (分解), Anal. Calcd For C16H14O6Mo: C, 48.3; H, 3.54. Found: C, 49.2, H, 4.0
5-MethoxylSalicylaldehyde 1.3613g (8.950mmol)のMethanol溶液2.5mlに七モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) 0.6183g (0.5002mmol)の水溶液7.5mlを加え、撹拌しながら12M HCl 0.5mlをゆっくりと加えた。そのまま室温で4時間反応させ、沈殿をろ過し、Methanolと水のそれぞれで洗浄した後に減圧下で乾燥することで、1.2032g (2.797mmol)の黄色結晶を得た。(収率79.9%)
mp=160-240℃ (分解), Anal. Calcd For C16H14O8Mo: C, 44.7; H, 3.3. Found: C, 43.4, H, 3.4
5-MethylSalicylaldehyde 1.2337g (9.061mmol)のMethanol溶液20mlに七モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) 0.6234g (0.5044mmol)の水溶液5mlを加え、撹拌しながら12M HCl 0.5mlをゆっくりと加えた。そのまま室温で4時間反応させ、沈殿をろ過し、Methanolと水のそれぞれで洗浄した後に減圧下で乾燥することで、0.8222g (2.065mmol)の黄色結晶を得た。(収率58.5%)
mp=180-250℃ (分解), Anal. Calcd For C16H14O6Mo: C, 48.3; H, 3.54. Found: C, 45.5, H, 3.3
2-Hydroxy-1-naphthaldehyde 1.5537g (9.024mmol)のMethanol溶液2.5mlに七モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) 0.192g (0.5010mmol)の水溶液7.5mlを加え、撹拌しながら12M HCl 0.5mlをゆっくりと加えた。そのまま室温で4時間反応させ、沈殿をろ過し、Methanolと水のそれぞれで洗浄した後に減圧下で乾燥することで、0.9991g (2.1245mmol)の黄色結晶を得た。(収率60.7%)
実施例4で得られたジオキソモリブデンサリチルアルデヒド錯体を、ε−カプロラクトン:開始剤:触媒=100:1:0.05(モル比)の条件で、開始剤としてシクロドデカノールを用いてメシチレン中80℃で反応させてε−カプロラクトン(CL)の開環重合活性を調べたところ、MoO2[(5-OMe)salad]2では15分程度で90%以上の反応が進行し、最も活性が高く、他の錯体も30分でほぼ反応が終了し、活性が高いことが示された(表8)。
MoO2[(5-OMe)salad]2を触媒として用い、ラクチド(LA)とε−カプロラクトン(CL)を種々の割合で加えて重合させた。[LA+CL]:[開始剤]:[触媒]=100:1:0.05(モル比)とし、溶媒はメシチレンとし、110℃で重合させた。反応率、生成したポリマーのモノマー比率はNMRにより測定した(表9)。生じたポリマーの分子量はGPCにて測定した。
MoO2[(5-OMe)salad]2、MoO2[(3-OMe)Di-Me-saltn](cis-α型)、MoO2(acac) 2、及び(NH4)8[Mo10O34]の4種類の触媒を用いて、ラクチドとε−カプロラクトンをモル比50/50で共重合させ、得られたε-CL-LA共重合体のランダム性について調べた。
Claims (11)
- ラクチドとラクトンとを、モリブデン化合物を触媒として使用して、共重合させることを特徴とする、ラクチド−ラクトン共重合体の製造方法。
- 前記ラクトンはε−カプロラクトンである請求項1に記載のラクチド−ラクトン共重合体の製造方法。
- 前記モリブデン化合物は、モリブデンのキレート化合物、ポリオキソモリブデン塩、モリブデンのアルコキシド、モリブデンイオンと有機酸の塩類、又はモリブデンのカルボニル化合物から選択される請求項1又は2に記載のラクチド−ラクトン共重合体の製造方法。
- 前記モリブデン化合物は六価モリブデンの錯体である請求項1又は2に記載のラクチド−ラクトン共重合体の製造方法。
- 前記六価モリブデンの錯体は、ジオキソモリブデン(VI)錯体又はポリオキソモリブデン塩である請求項4に記載のラクチド−ラクトン共重合体の製造方法。
- 前記ジオキソモリブデン(VI)錯体は、ジオキソモリブデン(VI)アセチルアセトナト錯体、ジオキソモリブデン(VI)サレン錯体、又はジオキソモリブデン(VI)サリチルアルデヒド錯体から選択される請求項5に記載のラクチド−ラクトン共重合体の製造方法。
- 前記R1は−(CH2)2−、−(CH2)3−、−CH2CH(CH3)−、−CH2−C(CH3)2−CH2−、−(CH2)4−、1,2−シクロヘキシル基、1,3−シクロヘキシル基、1,4−シクロヘキシル基、1,2−シクロペンチル基、又は1,2−シクロヘプチル基であり、R2、R4、R7、R9は水素又は−CH3であり、R5及びR6は水素、−CH3、−CH2CH3、−C(CH3)3、−OCH3、−Cl、−Br、又は−Iであり、R3及びR8は水素、−CH3、−CH2CH3、−C(CH3)3、−OCH3、−Cl、−Br、又は−Iである、項7に記載のラクチド−ラクトン共重合体の製造方法。
- 前記R1、R2、R3及びR4はそれぞれ独立して水素、−Cl、−Br、−I、−OCH3、−OCH2CH3、−NO2、−OH、−COOH、−CH3、又は−CH2CH3である請求項9に記載のラクチド−ラクトン共重合体の製造方法。
- 前記ポリオキソモリブデン塩は、[Mo3 O10 ]2- 、[Mo6 O20 ]4- 、[Mo7 O24 ]6- 、[Mo8 O26 ]4- 、及び[Mo10O34 ]8- からなる群より選ばれた陰イオンと、アンモニウムイオン、アルキルアンモニウムイオン及びアルカリ金属イオンからなる群より選ばれた陽イオンとの塩である請求項5に記載のラクチド−ラクトン共重合体の製造方法。
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JP6242382B2 (ja) | 2017-12-06 |
EP2985302B1 (en) | 2018-01-10 |
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EP2985302A4 (en) | 2016-11-30 |
WO2014167966A1 (ja) | 2014-10-16 |
US20160053049A1 (en) | 2016-02-25 |
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