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STUDIES OF THE INITIATION MECHANISM OF VINYL POLYMERIZATION WITH THE SYSTEM PERSULFATE/N-ALKYL SUBSTITUTED ETHYLENEDIAMINE DERIVATIVES

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Chinese Journal of Polymer Science 1989年第2期7卷 165-173页

作者：郭新秋丘坤元冯新德 Department of Chemistry Peking University

Effects of N-alkyi substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of different diamine derivatives on vinyl polymerization are in the order of tertiary diamine>secondary diamine>primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups. The initial free radicals produced through the redox reaction of persuifate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.

关键词： Persulfate Ethylenediamine Derivatives ESR Acrylamide Radical Polymerization Redox System

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STUDIES ON THE ORGANIC PEROXIDE-DITERTIARY AMINE INITIATION SYSTEMS

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Chinese Journal of Polymer Science 1985年第1期3卷 76-81页

作者：丘坤元张景义胡元洁冯新德 Department of Chemistry Peking University Beijing The First Branch of Peking University Beijing.

Radical polperization of methyl methacrylate （MMA） initiated with organic peroxide-ditertiaryamine binary systems was studied. Benzoyl peroxide （BPO）, lauroyl peroxide （LPO）, t-butyl hydro-peroxide （TBH）, and t-butyl peroxybenzoate （TBPB） were used as organic peroxide components,aromatic ditertiay amine 4, 4′-tetramethyldiaminodiphenylmethane （TMDAPM） an d aliphatic di-tertiary amine tetramethylethylenediamine （TMEDA） were used as amine components. The polymeri-zation rate RP, the overall activation energy of polymerization Ea, the rate equation of MMA poly-merization, and the end group of polymer formed were determined.

关键词： TMEDA LPO STUDIES ON THE ORGANIC PEROXIDE-DITERTIARY AMINE INITIATION SYSTEMS BPO PMMA

STUDIES ON THE REACTION MECHANISM OF ORGANIC HYDROPEROXIDE AND AMINE SYSTEM INITIATED POLYMERIZATION

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Science in China,Ser.B 1984年第4期27卷 349-360页

作者：孙燕慧丘坤元冯新德 Department of Chemistry Peking University

The initiation mechanism of organic hydroperoxide and amine system has been investigatedsystematically in this paper. It has been confirmed from the IR spectra that organic hydro-peroxide could form hydrogen-bonded complex with amine. The reactive intermediate of theamine and its effect on initiating polymerization have been determined by using ESR techni-que, and further proved by the results of polymer end group analysis and graft copolymeri-zation of vinly monomer onto the amino-containig polymer. Finally, water, as one of the finalproducts of ROOH-amine reaction has been detected through chromatographic analysis, fromwhich the conversion reaction of the reactive intermediate is verified.

关键词： DMT TB STUDIES ON THE REACTION MECHANISM OF ORGANIC HYDROPEROXIDE AND AMINE SYSTEM INITIATED POLYMERIZATION PMMA NDMA

THE EFFECTS OF MORPHOLINES ON METHYL METHACRYLATE RADICAL POLYMERIZATION

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Chinese Journal of Polymer Science 1986年第1期4卷 92-99页

作者：丘坤元沈一兵冯新德 Department of Chemistry Peking University Beijing

The effects of Morpholine, N-methyl morpholine, and N-ethyl morpholine on methyl methacrylatepolytherization initiated with organic peroxides were studied. The polymerization rate Rp, theoverall activation energy of p... 详细信息

关键词： NEMP MMP MMA THE EFFECTS OF MORPHOLINES ON METHYL METHACRYLATE RADICAL POLYMERIZATION BPO LPO

STUDIES ON THE PEROXYDISULFATEALIPHATIC AMINE INITIATION SYSTEMS

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Science in China,Ser.B 1987年第9期30卷 897-906页

作者：郭新秋丘坤元冯新德 Department of Chemistry Peking University

The effect of some types of water-soluble aliphatic amines on the polymerization of acrylamide initiated by peroxydisulfate has been investigated in this paper. It was found that the primary and secondary aliphatic amines enhanced the rate of the polymerization effectively as well as tertiary amines and the promoting effect of these amines varied with their different structures. A new method of detecting the aliphatic amine end-group of the polymer has been developed, i.e. 'CTC Spectrum Method'. The kinetic equation and overall activation energies of the polymerization have been determined and the initiation mechanism of peroxydisulfate-aliphatic amine system was proposed.

关键词： TMEDA KPS STUDIES ON THE PEROXYDISULFATEALIPHATIC AMINE INITIATION SYSTEMS

STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

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Chinese Journal of Polymer Science 1983年第1期 53-59页

作者：丘坤元张景义冯新德 Department of Chemistry Peking University Beijing

Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine （DMT, DHET, DMA） redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET>DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine （DMT, DHET, DMA） alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET>DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of RP=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol （8.2 Kcal/mol）. Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

关键词： DMT STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES MMA DMA BPO

STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLY(ETHER-URETHANE)

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Chinese Journal of Polymer Science 1983年第2期 182-188页

作者：孙燕慧丘坤元冯新德 Department of Chemistry Peking University

A new method of graft copolymerization of acrylamide (AAM) on poly(ether-urethane) (PEU) which was prepared from poly(tetramethylene ether) glycol (PTMG), 4,4’-diphenylmethane diisocyanate (MDI) and ethylene diamine or butanediol extender was investigated. Hydroperoxide group was first introduced onto the surface of PEU through photo-oxidation in the presence of hydrogen peroxide, then it was reacted with ferrous ion or N,N-dimethyl toluidine (DMT) to initiate AAM graft copolymerization on PEU surface. The graft reaction could be carried out effectively at low temperature. The formation of graft copolymer has been verified by its water absorption % and the scanning electron microscopy photographs. Some model compounds of PEU soft segment and hard segment were synthesized in order to clarify the site of graft reaction. The results of oxida-tion and graft copolymerization of model compounds showed that this graft copolymerization possesses higher selectivity, and it takes place predominately at the polyether segments, because the ether linkage in soft segment is very sensitive to oxidation and can form hydroperoxide easily. Thus, the grafting site appears to be at α-carbon of the ether linkage.

关键词： PEU STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLY ETHER-URETHANE

THE EFFECTS OF HINDERED AMINES ON METHYL METHACRYLATE POLYMERIZATION

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Chinese Journal of Polymer Science 1985年第4期 373-381页

作者：丘坤元杨英飞冯新德 Department of Chemistry Peking University Beijing

The effects of hindered amines, such as TMP, TMPM, TUV-770, on MMA and St homopoly-merization have been studied. It was found that in the MMA polymerization initiated with BPO orAIBN, the presence of TMPM, TUV-770 prolonged the induction period and a little change on Rp wasobserved. However, in the presence of TMP Rp increased slightly. The activation energy of poly-merization and polymerization rate equation were determined.

关键词： MMA TMPM AIBN BPO THE EFFECTS OF HINDERED AMINES ON METHYL METHACRYLATE POLYMERIZATION

哌啶类化合物和有机过氧化物体系引发甲基丙烯酸甲酯聚合的研究

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高等学校化学学报 1985年第8期6卷 741-746页

作者：张景义丘坤元冯新德北京大学第一分校北京大学化学系

本文研究了四种哌啶类环状脂肪胺哌啶(P)、2,2,6,6-四甲基-4-哌啶醇(TMP)、N-乙基哌啶(NEP)、1,2,2,6,6-五甲基-4-哌啶醇(PMP)分别与有机过氧化物过氧化苯甲酰(BPO)、过氧化月桂酰(LPO)、叔丁基过氧化氢(TBH)、过氧化苯甲酸叔丁酯(TBPB... 详细信息

本文研究了四种哌啶类环状脂肪胺哌啶(P)、2,2,6,6-四甲基-4-哌啶醇(TMP)、N-乙基哌啶(NEP)、1,2,2,6,6-五甲基-4-哌啶醇(PMP)分别与有机过氧化物过氧化苯甲酰(BPO)、过氧化月桂酰(LPO)、叔丁基过氧化氢(TBH)、过氧化苯甲酸叔丁酯(TBPB)组成的引发体系对甲基丙烯酸甲酯(MMA)聚合的影响。测定了聚合反应的表观活化能和动力学方程。

关键词：有机过氧化物叔丁基过氧化氢哌啶醇脂肪胺甲基丙烯酸甲酯过氧化苯甲酰叔丁酯哌啶类

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