JP6148006B2 - 環式エステルおよび環式カボネートのイモータル開環重合用触媒系 - Google Patents
環式エステルおよび環式カボネートのイモータル開環重合用触媒系 Download PDFInfo
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- JP6148006B2 JP6148006B2 JP2012507764A JP2012507764A JP6148006B2 JP 6148006 B2 JP6148006 B2 JP 6148006B2 JP 2012507764 A JP2012507764 A JP 2012507764A JP 2012507764 A JP2012507764 A JP 2012507764A JP 6148006 B2 JP6148006 B2 JP 6148006B2
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- alcohol
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- polymerization
- sime
- butyl
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YBLVILVQEZRPFO-UHFFFAOYSA-N calcium;bis(trimethylsilyl)azanide Chemical compound [Ca+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C YBLVILVQEZRPFO-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 235000019136 lipoic acid Nutrition 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004355 nitrogen functional group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000001196 time-of-flight mass spectrum Methods 0.000 description 1
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- AFVLVVWMAFSXCK-UHFFFAOYSA-N α-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C(O)C=C1 AFVLVVWMAFSXCK-UHFFFAOYSA-N 0.000 description 1
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- C08G63/78—Preparation processes
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Description
(1)非毒性の亜鉛(非特許文献19〜23)
(2)アルミニウム(非特許文献24〜28)
(3)3族金属およびランタニド(非特許文献29〜31)
しかし、さらに改良する余地は十分にある。
本発明の他の目的は、このフェノキシ-ベースのリガンドを使用して二価金属錯体を製造することにある。
本発明のさらに他の目的は、この金属錯体を使用して環式エステルおよび環状カボネートの制御されたイモータルROP用の触媒系を提供することにある。
本発明のさらに他の目的は、末端が官能化されたPLAを製造することにある。
本発明のさらに他の目的は、ラクチドおよびスチレンのコポリマーのインサイチュー(in situ)合成を促進することにある。
本発明の上記目的の少なくとも一部は本発明によって達成される。
R3はR1と同じか、1〜20の炭素原子を有するヒドロカルビル、好ましくはメチル、エチル、イソプロピル、tert-ブチル、ネオペンチル、クミル、トリチルの中から選択されアルキルか、フェニル、2,4,6−トリメチルフェニル、2,6−ジイソプロピルフェニルの中から選択されるアリールである]
Zheng et al. (Z. Zheng, G. Zhao, R. Fablet, M. Bouyahyi, CM. Thomas, T. Roisnel, O. Casagrande, J.-F. Carpentie、New Journal of Chemistry, 32, 2279, 2008)
プロ-リガンドおよび金属複合体を製造するための本発明方法は下記文献に記載の方法の一変形例である。
Schanmuga et al. (S. Shanmuga Sundara Raj, M. N. Ponnuswamy, G. Shanmugam, M. Kandaswamy, J. Crystallogr, Sp.beta.ctrosc. Res., 1993, 23, 607-610) Teipel et al. (S. Teipel, K. Griesar, W. Haase, B. Krebs, Inorg. Chem., 1994, 33, 456-464)
本明細書では各基の名前を下記の下記略称で表すことがある:
Me メチル
Et エチル
iPr イソプロピル
tBu tert−ブチル
Ph フェニル
CH 2 Ph ベンジル
ここで、
MはZn、Mg、Ca、SrまたはBaであり、
Xはヒドロカルビルまたはアルコキシド基OR''であり(ここでR''はヒドロカルビル、アリール、シリルまたはアミノ基NR* 2であり)(ここで、R*はSiMe3、イソ−プロピル、メチルまたはエチルであり)(好ましいヒドロカルビルはエチルである)
[LO]は2−R1、4−R2、6−R3−C6H2Oである(ここで、R1、R2およびR3は上記で記載のもの)
[M]:有機金属フラグメント
ktr:変換速度定数
kp:成長速度定数
M. Jalabert, C. Fraschini, R. E. Prud'homme, J. Pol. Sci. Part A: Polym. Chem., 2007, 45, 1944-1955 M. Save, M. Schappacher, A. Soum, Macromol. Chem. Phys., 2002, 203, 889-899 I. Palard, M. Schappacher, B. Belloncle, A. Soum, S. M. Guillaume, Chem. Eur. J., 2007, 13, 1511-152
全ての取扱いは、不活性雰囲気の下で実行した。グローブ・ボックス中で金属ベースの開始剤と精製モノマーとを直ちに大きいシュレンクチューブに入れた。管を封止してグローブ・ボックスから取り出す。以下の操作は全て標準的なシュレンクテクニックを使用しシュレンクラインで実行した。必要に応じて、トルエン、THFまたはスチレンから選択されるドライな脱気した溶剤の必要量をシュリンジで加えた。次に、iPrOH、ベンジルアルコール、HEMA、AA−OHまたはTEMPO−OHの中から選択されるアルコールを、開始剤とモノマーを収容したシュレンクチューブに添加して金属錯塩活性化させた。迅速に添加後、シュレンクチューブを所望温度に予熱されたオイルバス中に漬けた。この時から重合時間を計測する。MeOH(1%、HCl)を添加して反応を停止し、ポリマーはメタノール中に沈澱させる。ジクロロメタンまたはTHFを溶剤として使用し、メタノールを非溶媒として使用て再沈殿で精製した。次いで、10-2 mbar以下の動的減圧下でポリマーを恒量乾燥した。
プロ−リガンド:2,6-ビス(モルホリノメチル)-4-t−ブチル−フェノール([L01]H)2,4-ジ−t−ブチル-6-(モルホリノメチル)−フェノール([LO2]H)および2,4−ジt−ブチル-6−[(1-アザ-15-クラウン-5)メチル]−フェノール([LO3]H)の製造方法は下記の反応概要1に示す。
11.7mlのホルムアルデヒド(138.3mmol、37重量%水溶液)を9.0gの4-t−ブチルフェノール(60.6mmol)と10.3mlのモルホリン(10.2g、118.2mmol)のジオキサン溶液60mlに加えた。得られた混合液を120℃の温度で一晩還流した。揮発性画分は減圧除去し、得られた固体をトルエン/水で抽出した。トルエン層を合せ、硫酸マグネシウム硫酸マグネシウム上で乾燥した。濾過後、黄色の溶液を減圧濃縮し、-24の温度で一晩保存した。大きな無色の結晶[LO1]Hが収率77%で得られた。この化合物の(1Hおよび13C{1H}NMR)の分光分析データは文献報告値と一致した。純度は元素分析で確認した。[LO1]Hはエーテル、塩素化溶剤および芳香族炭化水素に完全溶解し、脂肪族炭化水素にはわずかに溶ける。
12.2gの2,4-ジ- t−ブチル−フェノール(59.1mmol)と、5.9mlのホルムアルデヒド(67.5mmol、水中37重量%)と、6.2mlのモルホリン(6.2g、70.9mmol)と黄色溶液を120℃の温度で一晩、90mlのジオキサン中で還流した。揮発油はポンプで排気し、得られた粘着性の固形物をトルエンおよびNaCl飽和水溶液で抽出した。有機層を合せ、MgSO4上で乾燥し、トルエンを排気するとオフホワイトの固形物が生ずる。それを減圧下に恒量乾燥して17.0gを得た(収率94%)。X線回折に適した単結晶[LO2]Hは +4℃の温度に一晩維持した濃縮ペンタン溶液から成長させて、その構造を決定した。それを[図1]に示す。
1.03gの2,4-ジ-t−ブチル−フェノール(5.0 mmol)、0.5 mlのホルムアルデヒド(6.2 mmol、37重量%水溶液)および1.25gの1-アザ-15-クラウン-5(5.7 mmol)の混合液を20mlのジオキサン中で120℃の温度で24時間還流した。溶剤を減圧除去して得られるオレンジ油を恒量乾燥して2.23gの粗生成物を得る。移動層として純粋なクロロホルムを使用した薄層クロマトグラフィで精製して所望生成物を完全に精製した。クロロホルムを蒸発後、1.78gの化合物が81%の収率で得られた。[LO3]Hの分光分析データは公知の文献値と一致した。[LO3]Hは黄色の粘性のあるオイルで、全ての有機溶媒に充分に溶ける。
亜鉛、マグネシウムおカルシウムをベースにした錯体の合成方法を下記の反応概要2に示す。
[2,6-ビス(モルホリノメチル)-4-tBu-フェノキシ]亜鉛-エチル([LO 1 ]ZnEt)の合成
3.5gの[LO1]-H(10.0mmol)のトルエン溶液75 mlを-45℃の温度で20分かけて10.2 mlのZnEt2(ヘキサン中1.0のM溶液、10.2 mモル)のトルエン溶液125 mlに加えた。得られた混合液を-45℃の温度で60分間攪拌し、さらに室温で2時間攪拌すると白い懸濁が生じる。沈降物を濾過分離し、減圧乾燥して分析的に純粋な4gの白い粉末を91%の収率で得た。{[LO1]ZnEt}2 C6H5の無色単結晶を濃縮ベンゼン溶液から室温で成長させ、その固体物理構造をX線結晶学で決定した。
元素分析:C22H36N2O3Zn(440.20グラム/モル):
理論値:C 59.79、H 8.21、N 6.34%
分析値:C 59.78)H 8.21、N 6.05%
1.06gの[LO2]-H、3.47 mmol)のトルエン溶液20 mlトルエン溶液を-25℃の温度で3.50mlのZnEt2(3.50 mmol、1.0Mヘキサン溶液)のトルエン40 mlに20分かけてゆっくり加える。さらに-25℃の温度で40分間攪拌し、アルカン除去後に無色溶液を得る。溶剤を蒸発させて得られた白い固形物を20 mlのペンタンで3回洗浄し、減圧乾燥して1.18gの錯体を85%の収率で得た。
元素分析:C21H35NO2Zn(397.20グラム/モル):
理論値:C 63.23、H 8.84、N 3.51%
分析値:C 63.09、H 8.73、N 3.51%
[LO 2]ZnEtの合成で記載したのと同じ手順で、0.94gの[LO1]H(2.70 mmol)と3.0mlのMgBu2(3.50 mmol、1.0Mヘプタン溶液)のトルエン22.0 mlとの反応によって、[LO1]MgBuを82%の収率で得た。
元素分析:C24H40N2O3Mg(428.90グラム/モル):
理論値:C 67.21、H 9.40、N 5.67%
分析値:C 67.32、H 9.89、N 6.19%
1.32gの[LO1]H(3.79 mmol)のTHF溶液20 mlを室温で45分かけて1.71gのCa[N(SiMe3)2]2(THF)2(3.39 mmol)のTHF溶液20 mlに加えた。黄色の溶液を室温で一晩攪拌し、溶剤を減圧蒸発させると白い粉末が得られる。熱いヘキサン(ヘプタンまたは高級炭化水素も使用できる)での抽出を繰り返した後、溶剤を真空乾燥して77%の収率で分析的に純粋なヘテロレプティック(heteroleptic)な化合物が得られる。[[LO1]N(SiMe3)2の単結晶は室温でTHF溶液中にヘキサンをゆっくり拡散させて成長させて得た。その固体物理構造はX線回折で確認した。
元素分析:026H49N3O3Si2Ca(547.29グラム/モル:
理論値:C 56.99、H 9.01、N 7.67%
分析値:C 56.88、H 8.95、N 7.51%
普通の有機溶媒への[LO1]N(SiMe3)2の溶解性は脂肪族炭化水素でも良から優である。溶液中での安定正も非常に良く、NMRチューブでCeDe溶液中に5日間貯蔵した後でも劣化の兆候は見られない。しかも、そのヘテロレプティック性は溶液中でも保存される。すなわち、[LO1]N(SiMe3)2のみでシュレンク-タイプの平衡無しに80℃でC6D6中で長時間反応させた後でも保存される。Ca[N(SiMe3)2および[LO1]2Caが生じる兆候はない。
Hawker et al. (C. J. Hawker, G. G. Barclay, A. Oreliana, J. Dao, W. Devonport, Macromotecules, 1996, 29, 5245-5254 Asri et al. (M. Asri Abd Ghani, D. Abdaliah, P. M. Kazmaier, B. Keoshkerian, E. Buncel, Can. J. Chem., 2004, 82, 1403-1412
アルコールのトランスファー剤の存在下での上記の新規な開始剤[LO1]ZnEtを用いたLAのイモータルROPは極めて迅速であり、良く制御され、これに匹敵する公知のROP触媒系は文献にはない。重合条件および結果は[表1]にまとめた。
トルエン中でiPrOHを使用した大量のL-LAのイモータルROPでの開始剤(BDI)ZnN(SiMe3)2、[LO1]ZnEt、[LO2]ZnEt、[LO1]MgBuおよび[LO1]CaN(SiMe3)2の有効度を決定するための一連の実験を実施した。重合条件および結果は[表5]にまとめてある。
(1) 連鎖移動剤の最大100〜500当量用いてLAを数万当量の量でイモータルROPする場合の最高の候補はZn-ベースの開始剤である。
(2) 条件が全く同じ場合、[LO1]ZnEtが[LO2]ZnEtより効率的である。
(3) 重合速度、[LO1]ZnEt(および[LO2]ZnEt)を活性化するために必要な誘導時間に対して有害効果は反応時間が90分以上では無視できる。
反応階段はシェーマ5に、重合条件および結果は[表6]に示してある。
反応階段はシェーマ6に、重合条件および結果は[表7]に示した。
反応階段はシェーマ7に、重合条件および結果は[表8]に示した。
反応階段はシェーマ9に、重合条件および結果は[表10]に示した。
10当量のiPrOHの添加で、[LO1]ZnEtは200〜500当量のrac-BBLを定量的に数時間以内に容易に変換した。得られたポリマーのPDIは非常に狭く、一般に約1.10であり、分子量(GPCまたはMALDl-TOF質量分析で決定)は実験値と理論値とで極めて良く一致した。実施例84および実施例85に示すように、公知の(BDi)Zn-N(SiMe3)2と比較して、[LO1]ZnEtは活性および制御性の両方に優れている。
Claims (11)
- R2がtert-ブチルである請求項1に記載の金属錯体。
- R3がR1と同じであるか、tert-ブチルである請求項1または2に記載の金属錯体。
- 請求項1〜3のいずれか一項に記載の二価金属錯体を含む系とアルコールまたはポリオールとの存在下で、環式エステル又は5−、6−若しくは7−員環の環状カーボネートをイモータル開環重合する方法。
- アルコールまたはポリオールの量が金属に対して1〜10,000当量である請求項5に記載の方法。
- アルコールがR'OHである(ここでR'は一級または二級アルキル残基またはベンジル基である)請求項5または6に記載の方法。
- R'がイソプロピル(iPr)またはベンジルである請求項7に記載の方法。
- 4−ヒドロキシ−2,2,6,6−テトラメチルピペリジン−1−オキシル(TEMPO)−OH、2−ヒドロキシエチル−メタアクリレート(HEMA)またはヒドロキシ−アルコキシアミンの中から選択される官能化されたアルコールを用いてスチレン中で開環重合を実行する、末端官能化ポリマーを製造するための請求項5〜9のいずれか一項に記載の方法。
- 上記の官能化されたアルコールが1−ヒドロキシ−2−フェニル−2−(2',2',6',6'−テトラメチル−1'−ピペリジニルオキシ)−エタン(AA−OH)である請求項10に記載の方法。
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US9371418B2 (en) | 2012-06-15 | 2016-06-21 | Total Research & Technology Feluy | Method of copolymerizing ethylene carbonate with one or more cyclic esters |
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