scholarly journals Complex-radical copolymerization of vinylcyclohexyl ketones with maleic anhydride and N-p-tolylmaleimide

2016 ◽  
Vol 1 (1) ◽  
pp. 17 ◽  
Author(s):  
Zakir M. O. Rzaev ◽  
Güneri Akovali ◽  
E.Yu. Kuliyeva ◽  
N.Yu. Lezgiev
Keyword(s):  
Charge Transfer ◽  
Maleic Anhydride ◽  
Random Copolymer ◽  
Radical Copolymerization ◽  
Photochemical Reactions ◽  
Vinyl Ketone ◽  
Chain Growth ◽  
Charge Transfer Complexes ◽  
Alternating Copolymer ◽  
Mobile Hydrogen

<p>Some features of the formation and photochemical reactions of cyclohexylketone containing macromolecules including copolymers of vinylcyclohexyl ketone (VCHK) and its derivatives (V-a-Cl-CHK and V- d-C1-CHK) with maleic anhydride (MA) and N-p-tolylmaleimide (TMI) have been revealed. It has been established that keto-enol tautomerism is the only reaction realized in the vinylcyclohexylketone molecules having mobile hydrogen atom at a -position in the cyclohexane ring, enol form of which is formed by charge-transfer complexes with anhydride or imide of maleic acid as acceptor monomers. The kinetic parameters of these reactions, including complex-formation and copolymerization constants, as well as the ratios of chain growth rates for the participation of monomeric charge-transfer complexes and free monomers, are all determined. It is shown that an alternative copolymerization is realized with the monomer systems containing VCHK and V- d -C1-CHK, which are carried out through a complex-mechanism due to the keto-enol tautomerism; while random copolymer enriched with vinyl ketone units is formed with the system containing oc-substituted VCHK. It is found that characteristics of photochemical reactions of alternating copolymer synthesized depend on the type of substitutation in the vinyl ketone molecule; unlink VCHK-MA(TMI) and V-d-C1-CHK-MA(TMI) copolymers case which easily crosslink upon UVirradiation, and the N-substituted derivatives of these copolymers which decompose under similar condition.</p>

Study on Synthesis and Characterization of Styrene-Maleic Anhydride Random Copolymer by Xylene

2013 ◽  
Vol 750-752 ◽  
pp. 1075-1078
Author(s):  
Ting Ting Li ◽  
Zhi Ming Zhang ◽  
He Ti Li ◽  
Jie Cao
Keyword(s):  
Maleic Anhydride ◽  
Molar Fraction ◽  
Evaluation Criteria ◽  
Random Copolymer ◽  
Radical Copolymerization ◽  
Alternating Copolymer ◽  
Styrene Maleic Anhydride ◽  
Maleic Anhydride Copolymer ◽  
Alternating Copolymerization

Radical copolymerization of styrene (St) and maleic anhydride (MA) were typically alternating copolymerization, which generated copolymer styrene-maleic anhydride (SMA). The copolymer was synthesized by solution polymerization method,with benzoyl peroxide (BPO) as initiator and xylene as solvent, and using the yield of copolymer as evaluation criteria, the reaction conditions were researched. The maleic anhydride of molar fraction was 45% in the copolymer measured by chemical titration, combined with the theoretical that the synthesis of styrene-maleic anhydride copolymer was confirmed to be the alternating copolymer. The structure and character of the copolymer was also confirmed by IR. The glass-transition temperature of the alternating copolymer was tested by DSC.

Alternating Copolymers by Complexed Copolymerization

1973 ◽  
Vol 46 (4) ◽  
pp. 1068-1076 ◽  
Author(s):  
M. Hirooka ◽  
K. Mashita ◽  
S. Imai ◽  
T. Kato
Keyword(s):  
Glass Transition ◽  
Physical And Mechanical Properties ◽  
Random Copolymer ◽  
Radical Copolymerization ◽  
Random Copolymers ◽  
Acrylonitrile Copolymer ◽  
Alternating Copolymers ◽  
Alternating Copolymer ◽  
Sequential Structure ◽  
Acrylic Ester

Abstract There have been few studies on how the nature of copolymers is affected by their sequential structure. This is because, in the past, the sequential structure of most copolymers could not be controlled at will. However, such studies have been realized since it was found that alternating sequential regulation can be attained from many monomer combinations, from which only random copolymers had been obtained previously, provided the copolymerization was carried out in the presence of a Lewis acid, such as an alkylaluminum halide. This kind of reaction is termed complexed copolymerization, as distinguished from the conventional alternating copolymerization. Furukawa and coworkers indicated that alternating butadiene—acrylonitrile copolymer is superior in various properties to the corresponding 1:1 random copolymer. Yabumoto and coworkers noticed that 1:1 styrene—acrylonitrile copolymer obtained in the presence of zinc chloride had a higher glass transition temperature than that of the corresponding 1:1 random copolymer made by radical copolymerization. Moreover, the former was hardly colored due to substantial absence of acrylonitrile—acrylonitrile bonds. Thus, it is very interesting how the properties of eopolymers are affected by sequential structure. The present paper describes various properties of alternating copolymers. The first part of this paper introduces a newly developed alternating copolymer of isobutylene and an acrylic ester and compares it with the corresponding homo-polymers. The latter part deals with comparison of alternating and random copolymers. Equimolar copolymers of styrene and acrylonitrile are compared in physical and mechanical properties. Glass transition temperatures of equimolar alternating and random copolymers of various vinyl compounds are compared. An interesting correlation is shown and discussed on the basis of a thermodynamic treatment.

Photochemical reactions of charge-transfer complexes. III. Molecular orbital studies of the charge-transfer complexes between 1,2-dimethoxyethylenes and 1,2-dicyanoethylenes

1981 ◽  
Vol 59 (6) ◽  
pp. 974-981 ◽  
Author(s):  
Po Cheong Wong ◽  
Russell J. Boyd
Keyword(s):  
Charge Transfer ◽  
Ab Initio ◽  
Molecular Orbital ◽  
Photochemical Reactions ◽  
Charge Transfer Complexes ◽  
Double Bonds ◽  
Mo Calculations ◽  
Model Compounds ◽  
Projected Distance

Ab initio and PCILO molecular orbital (MO) calculations for the four π–π* charge-transfer complexes formed between maleonitrile (MN) and fumaronitrile (FN), and cis (CS) and trans-1,2-dimethoxyethyIene (TR) are reported. The donor and the acceptor molecules are stacked in parallel planes. Trans and cis-l,2-dihydroxyethylene are used as the model compounds for TR and CS in the determination of the optimum geometries of the complexes. Both types of MO calculations indicate that the eclipsed geometry (with the two central double bonds parallel and the centres of the double bonds centred over one another) is relatively unstable. With limited geometry searching, we find that the slipped geometry (with the two central double bonds parallel but separated at a projected distance of 2.2 Å and the oxygen atoms above the cyanocarbon atoms) is the preferred structure. According to the ab initio calculations the relative order of the calculated heats of formation (ΔHθ's) for these complexes is: MN−CS > FN−CS > FN−TR > MN−TR.

Sign in / Sign up

Export Citation Format

Share Document