• 제목/요약/키워드: free-radical polymerization

검색결과 105건 처리시간 0.027초

Investigation on Chain Transfer Reaction of Benzene Sulfonyl Chloride in Styrene Radical Polymerization

  • Li, Cuiping;Fu, Zhifeng;Shi, Yan
    • Macromolecular Research
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    • 제17권8호
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    • pp.557-562
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    • 2009
  • The free radical polymerization of styrene was initiated with azobis(isobutyronitrile) in the presence of benzene sulfonyl chloride. Analysis of the terminal structures of the obtained polystyrene with $^1H$ NMR spectroscopy revealed the presence of a phenyl sulfonyl group at the ${\alpha}$-end and a chlorine atom at the ${\omega}$-end of each polystyrene chain. The terminal chlorine atom in the polystyrene chains was further confirmed through atom transfer radical polymerization (ATRP) of styrene and methyl acrylate using the obtained polystyrenes as macroinitiators and CuCl/2,2'-bipyridine as the catalyst system. GPC traces of the products obtained in ATRP at different reaction times were clearly shifted to higher molecular weight direction, indicating that nearly all the macroinitiator chains initiated ATRP of the second monomers. In addition, the number-average molecular weights of the polystyrenes increased directly proportional to the monomer conversions, and agreed well with the theoretical ones.

Carboxyl-Terminated Polybutadiene 의 중합 및 특성에 관한 연구 (제1보). 개시제농도가 수율 및 특성에 미치는 영향 (Studies on the Polymerization and Characterization of Carboxyl-Terminated Polybutadiene (Ⅰ). Effects of Initiator Concentration on Yields and various Characteristics)

  • 강정부;유경준;권석기;오동영
    • 대한화학회지
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    • 제24권5호
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    • pp.398-403
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    • 1980
  • 4,4'-azobis-[4-cyano valeric acid]를 개시제로 하여 라디칼 중합에 의해 carboxyl-terminated polybutadiene을 제조하고, 개시제의 농도가 중합체의 물성에 미치는 영향을 조사하였다. 부타디엔 농도를 일정하게 유지하고, 개시제 농도를 변화시켜 중합한 결과, 개시제농도가 증가함에 따라 카르복실기 함량이 감소하고 중합수율은 개시제농도의 1/2 제곱에 정비례하였으며, 관능도가 2.0을넘어 일반적인 라디칼 중합의 경향과 일치하였다.

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Olefin Polymerization Activity and Crystal Structure of Alkyliron(Ⅲ) Porphyrin Complexes

  • Oh, Yung-Hee;Swenson, Dale;Goff, Harold M.
    • Bulletin of the Korean Chemical Society
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    • 제24권2호
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    • pp.167-172
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    • 2003
  • Alkyliron(Ⅲ) porphyrins, n-butyliron(Ⅲ) tetraphenylporphyrin, (TPP)Fe-Bu and n-butyliron(Ⅲ) tetrakis-(pentafluorophenyl)porphyrin, $(F_{20}TPP)Fe-Bu$ have been evaluated as suitable for olefin free-radical polymerization. Butyl radicals dissociated from n-butyliron(Ⅲ) porphyrin initiated the polymerization reaction, but the ratio of the propagation was low. The GCMS analysis of the reaction mixture of nbutyliron(Ⅲ) porphyrin and styrene has revealed several products containing two butyl groups, while traces of b-hydrogen-abstracted products were observed. The crystal structure of (TPP)Fe-Bu has been determined. The structure of the n-butyliron(Ⅲ) porphyrin reveals the compound containing five-coordinated iron with the average Fe-N distance of 1.973(1) Å and Fe-C of 2.030(2) Å. The iron atom is displaced by 0.137Å from a four nitrogen mean plane. Crystal system is triclinic, and space group is P-1.

Preparation and Properties of Polyolefin Graft Polymer available as a Primer for Polyurethane Adhesive (I) Synthesis of polyolefins with cyclic acid anhydride by free radical graft polymerization

  • Ryu, Ki Jung;Kim, Min Jung;Min, Seong Kee;Lee, Won Kee;Park, Chan Young
    • Elastomers and Composites
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    • 제50권2호
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    • pp.119-125
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    • 2015
  • Because of their low surface free energy and absence of polar groups at the surface, polyolefins are substrates whose wetting and adhesion are very difficult. Free radical grafting of monomers to backbone polymer is one of the most attractive ways for the chemical modification of polymers. Synthesis of graft copolymer through graft polymerizations of PE and/or PP with phthalic anhydride (PhAn) was made and FTIR spectra of the graft polymer were the examined. And also the effects of phthalic anhydride content on the grafting ratio, thermal properties and contact angle of the graft polymer were examined.

A Novel Synthetic Route to Highly Cross-Linked Poly(alkylvinylether)s. Synthesis and Free Radical Polymerization of a Vinyl Ether Monomer Containing Electron Acceptors in Side Chain

  • 이주연;이현주;김무용
    • Bulletin of the Korean Chemical Society
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    • 제17권3호
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    • pp.257-262
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    • 1996
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile 2 and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate 3 was prepared by the condensation of p-(2-vinyloxyethoxy)benzaldehyde 1 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2 and 3 polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃. The trisubstituted terminal double bond participated in the vinyl polymerization and radical polymerization of 2 and 3 led to swelling polymers 4 and 5 that were not soluble in common solvents due to cross-linking. Under the same polymerization conditions ethylvinyl ether polymerized well with model compounds of p-methoxybenzylidenemalononitrile 6 and methyl p-methoxybenzylidenecyanoacetate 7, respectively, to give 1:1 alternating copolymers 8 and 9 in high yields. Polymers 4 and 5 showed a thermal stability up to 300 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 8 and 9 were soluble in common solvents such as acetone and DMSO, and the inherent viscosities of the polymers were in the range of 0.36-0.74 dL/g. Films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 59-60 ℃.

Graft Polymerization of Acrylic Acid onto nylon 6

  • Park, Jae ho;Lee, Chong-Kwang
    • Nuclear Engineering and Technology
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    • 제8권3호
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    • pp.159-168
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    • 1976
  • Ceric 염과 ${\gamma}$-선을 계기로 하여 Nylon 직포에 Acrylic acid를 접목반응 시켰다. 접목반응된 Polyacrylic acid의 분자량 분포를 측정한 결과 양 평균분자량과 수 평균분자량의 비는 낮은온도(-184$^{\circ}C$)dptj 보다는 상온에서 더 높았다는 것을 알았다. Polyacrylic acid의 양 평규 sqnswkfid은 Sodium hydroxide용액에서 점도를 측정하여 계산하였다. Nylon에 Acrylic acid가 중합반응될 때에 중합반응에 영향을 주는 요소들을 시험하였다. Nylon의 산화반응은 질소원자에 인접해 있는 methlene group에서 일어나 free-radical이 만들어 진다는 메카니즘을 논의 하였다.

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Rate-acceleration of TEMPO-mediated Polymerization of Styrene in the Presence of Various Acids

  • Hong, Chang-Kook;Jang, Heang-Sin;Hong, Sang-Hyun;Shim, Sang-Eun
    • Macromolecular Research
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    • 제17권1호
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    • pp.14-18
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    • 2009
  • The acceleration effect of various organic acids, such as methanesulfonic acid (MSA), ethanesulfonic acid (ESA), 4,4'-sulfonyldibenzoic acid (SDA), diphenylacetic acid (DPAA), and $\rho$-toluenesulfonic acid (TSA), on the rate of styrene bulk polymerization with 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) and benzoyl peroxide (BPO) was investigated. The addition of organic acids significantly accelerated the rate. Among these organic acids, DPAA showed an efficient rate-accelerating effect with living nature of polymerization. When DPAA was used as a rate-accelerating additive for TEMPO-mediated living free radical polymerization (LFRP), the rate of polymerization was dramatically enhanced, the linearity of reaction kinetics was successfully maintained, and the polydispersity was effectively controlled.