1989 Fiscal Year Annual Research Report

メタクリル酸エステルの重合機構の解明とポリマ-の構造制御

Research Project

Project/Area Number	61430022
Research Institution	Osaka University
Principal Investigator	畑田耕一大阪大学, 基礎工学部, 教授 (60029402)
Co-Investigator(Kenkyū-buntansha)	右手浩一大阪大学, 基礎工学部, 助手 (30176713) 北山辰樹大阪大学, 基礎工学部, 助手 (60135671) 岡本佳男大阪大学, 基礎工学部, 助教授 (60029501)
Keywords	ポリメタクリル酸エステル / 重水素化開始剤 / 末端基 / NMR / アルキルリチウム / グリニヤ-ル試薬 / 重水素NMR / カルボニル付加
Research Abstract	1.前年度までの研究からtーC_4H_9MgBrによるトルエン中でのメタクリル酸メチル(MMA)の重合では末端に正確に1個のtーC_4H_9基を有するインタクチックPMMAが生成することが明らかになったので、部分重水素化開始剤CH_3(CD_3)_2CMgBrを合成し、これによるMMAの重合で得られるポリマ-の末端基CH_3(CD_3)_2C-基の定量を^1HNMRと^2HNMRの両面から行なった。その結果、^2HNMRによる末端基定量が正確度、くり返し測定の精度とも十分に高いものであることが確認できた。 2.(1)部分重水素化エチルリチウムCH_3CD_2LiによるMMA、メタクリル酸エチル(EMA)、イソプロピル(iPMA)およびtーブチル(tBMA)の重合をトルエンあるいはテトラヒドロフラン(THF)中で行なった。生成ポリマ-の^2HNMRには開始末端のCH_3CD_2基の吸収とともに、モノマ-のカルボニル基への開始剤の付加で生成するエチルイソプロペニルケトン(EIPK)単位のCH_3CD_2CO基の吸収が認められ、ブチルリチウムによるMMAの重合の場合と同様、これらの重合においてもカルボニル付加反応の生起が重合反応を左右する鍵となっていることが明らかになった。ポリマ-1分子当りのEIPK単位の数はモノマ-のエステル基がかさ高くなるほど減少しており、エステル基の立体障害がカルボニル付加を抑制することを示している。 (2)CH_3CD_2MgBrによる上述のモノマ-の重合を行ない、生成ポリマ-中のEIPK単位の数を定量したところ、その数はやはりエステル基の大きいものほど少なくなったが、特にtーBMAのポリマ-ではケトン単位が導入されなくなり、CH_3CD_2Liより塩基性の低いCH_3CD_2MgBrによる重合ではカルボニル付加に対するエステル基の立体効果がより大きいものと考えられる。 3.重水素化開始剤は比較的安価に合成でき、広範囲のモノマ-に適用できる。また、^2Hの天然存在比が極めて低く、NMR試料の汚染を受けにくいので、今後重合反応機構の研究に重要な役割を果すと思われる。

Research Products

(17 results)

All Other

All Publications (17 results)

[Publications] Koichi Hatada: "The NMR Chemical Shifts between the Nonequivalent Methylene Protons of Polymer and Oligomers of Methyl Methacrylate:the Revised meso/racemo Assignments for the omega-End Dyad Sequences" Polymer Journal. 21(5). 447-449 (1989)
[Publications] Tatsuki Kitayama: "Tacticity Dependence of Thermal Degradation of PMMAs with the Same Chemical Structure" Polymer Bulletin. 21(4). 433-437 (1989)
[Publications] Koichi Hatada: "On-line GPC/NMR Analyses of Block and Random Copolymers of Methyl and Butyl Methacrylates Prepared with t-C_4H_9MgBr." Polymer Bulletin. 21(5). 489-495 (1989)
[Publications] Tatsuki Kitayama: "Living and Highly Syndiotactic Polymerization of Methyl Methacrylate and Other Methacrylates by tert-Butyllithium-Trialkylaluminium in Toluene" Makromol.Chem.Supplement. 15. 167-185 (1989)
[Publications] 畑田耕一: "立体規則性・共重合体のモノマ-連鎖分布" 高分子. 38(6). 430-434 (1989)
[Publications] 岡本佳男: "アニオン重合" 高分子. 38(9). 912-915 (1989)
[Publications] Yoshio Okamoto: "High-Performance Liquid Chromatography Using Stereoregular Poly(methyl methacrylate)s as Stationary Phases" Polymer Journal. 21(10). 795-801 (1989)
[Publications] 畑田耕一: "オンラインGPC/NMRによるポリマ-の構造解析" 高分子. 38(11). 1029 (1989)
[Publications] Koichi Ute: "Stereoregular Oligomers of Methyl Methacrylate III.^1H and ^<13>C NMR Spectra of the Pure-Isotactic and Pure-Syndiotactic Oligomers from Dimers to Octamers" Polymer Journal. 21(12). 1027-1041 (1989)
[Publications] Koichi Hatada: "Stereoregular Oligomers of Methyl Methacryalte.4.Supercritical Fluid Chromatography of the Isotactic and Syndiotactic Oligomers of MMA" Polymer Bulletin. 23(2). 157-162 (1990)
[Publications] Koichi Hatada: "Preparation of Random,Block and Graft Copolymers of High Stereoregularity and Their Characterization" "Progress in Pacific Polymer Science",Proceedings of First Pacific Polymer Conference Springer-Verlag,Heidelberg. (1990)
[Publications] Koichi Hatada: "Determination of Molecular Weight of Poly(methyl methacrylate)by Deuterium NMR and Its Reliability" Polymer Journal.
[Publications] Tatsuki Kitayama: "Synthesis of Stereoregular Polymers and Copolymers of Methacrylate by Living Polymerization and Their Characterization by NMR Spectroscopy" British Polymer Journal.
[Publications] Koichi Ute: "Studies on the Anionic Polymerization of Methyl Methacrylate with Butyllithium and Butylmagnesium Chloride Using Deuterated Monomer and Initiator" Polymer Journal.
[Publications] Koichi Ute: "Deuterium NMR Analysis of the Polymethacrylates Prepared with Ethyllithium-1,1-d_2 and with Ethylmagnesium-1.1-d_2 Bromide" Polymer Journal.
[Publications] Tatsuki Kitayama: "Stereoregular Oligomers of Methyl Methacrylate V.Stereochemical Effect on the Fragmentation in Mass Spectrometry." Makromol.Chem.Rapid Commun.
[Publications] Tatsuki Kitayama: "NMR Analysis of Dimer,Trimer and Tetramer of Methyl Methacrylate Formed in the Polymerization with Triphenylphosphine-Triethylaluminum in Toluene at -78℃" Polymer Journal.

1989 Fiscal Year Annual Research Report

メタクリル酸エステルの重合機構の解明とポリマ-の構造制御

Principal Investigator

畑田 耕一 大阪大学, 基礎工学部, 教授 (60029402)

Research Products

[Publications] Koichi Hatada: "The NMR Chemical Shifts between the Nonequivalent Methylene Protons of Polymer and Oligomers of Methyl Methacrylate:the Revised meso/racemo Assignments for the omega-End Dyad Sequences" Polymer Journal. 21(5). 447-449 (1989)

[Publications] Tatsuki Kitayama: "Tacticity Dependence of Thermal Degradation of PMMAs with the Same Chemical Structure" Polymer Bulletin. 21(4). 433-437 (1989)

[Publications] Koichi Hatada: "On-line GPC/NMR Analyses of Block and Random Copolymers of Methyl and Butyl Methacrylates Prepared with t-C_4H_9MgBr." Polymer Bulletin. 21(5). 489-495 (1989)

[Publications] Tatsuki Kitayama: "Living and Highly Syndiotactic Polymerization of Methyl Methacrylate and Other Methacrylates by tert-Butyllithium-Trialkylaluminium in Toluene" Makromol.Chem.Supplement. 15. 167-185 (1989)

[Publications] 畑田耕一: "立体規則性・共重合体のモノマ-連鎖分布" 高分子. 38(6). 430-434 (1989)

[Publications] 岡本佳男: "アニオン重合" 高分子. 38(9). 912-915 (1989)

[Publications] Yoshio Okamoto: "High-Performance Liquid Chromatography Using Stereoregular Poly(methyl methacrylate)s as Stationary Phases" Polymer Journal. 21(10). 795-801 (1989)

[Publications] 畑田耕一: "オンラインGPC/NMRによるポリマ-の構造解析" 高分子. 38(11). 1029 (1989)

[Publications] Koichi Ute: "Stereoregular Oligomers of Methyl Methacrylate III.^1H and ^<13>C NMR Spectra of the Pure-Isotactic and Pure-Syndiotactic Oligomers from Dimers to Octamers" Polymer Journal. 21(12). 1027-1041 (1989)

[Publications] Koichi Hatada: "Stereoregular Oligomers of Methyl Methacryalte.4.Supercritical Fluid Chromatography of the Isotactic and Syndiotactic Oligomers of MMA" Polymer Bulletin. 23(2). 157-162 (1990)

[Publications] Koichi Hatada: "Preparation of Random,Block and Graft Copolymers of High Stereoregularity and Their Characterization" "Progress in Pacific Polymer Science",Proceedings of First Pacific Polymer Conference Springer-Verlag,Heidelberg. (1990)

[Publications] Koichi Hatada: "Determination of Molecular Weight of Poly(methyl methacrylate)by Deuterium NMR and Its Reliability" Polymer Journal.

[Publications] Tatsuki Kitayama: "Synthesis of Stereoregular Polymers and Copolymers of Methacrylate by Living Polymerization and Their Characterization by NMR Spectroscopy" British Polymer Journal.

[Publications] Koichi Ute: "Studies on the Anionic Polymerization of Methyl Methacrylate with Butyllithium and Butylmagnesium Chloride Using Deuterated Monomer and Initiator" Polymer Journal.

[Publications] Koichi Ute: "Deuterium NMR Analysis of the Polymethacrylates Prepared with Ethyllithium-1,1-d_2 and with Ethylmagnesium-1.1-d_2 Bromide" Polymer Journal.

[Publications] Tatsuki Kitayama: "Stereoregular Oligomers of Methyl Methacrylate V.Stereochemical Effect on the Fragmentation in Mass Spectrometry." Makromol.Chem.Rapid Commun.

[Publications] Tatsuki Kitayama: "NMR Analysis of Dimer,Trimer and Tetramer of Methyl Methacrylate Formed in the Polymerization with Triphenylphosphine-Triethylaluminum in Toluene at -78℃" Polymer Journal.

畑田耕一大阪大学, 基礎工学部, 教授 (60029402)