General Method for Evaluation of Alternating Tendency in Copolymerization

A new method for deriving expressions for the mole fractions of alternating n-ads and the average lengths of the alternating sequences of n-component copolymers (n > 2) was developed based on the apparatus of finite Markov chains. These characteristics are considered as indexes of alternating tendency forn-component copolymerization. A specific property of n-component copolymerization (n > 3) compared with binary copolymerization is the fact that alternating n-ads might be constructed by two, three, or more types of monomeric units. In order to express this specific property of three and multi-component copolymers the term, alternating order, is introduced. The method developed in the paper permits the alternating indexes to be determined differentially in dependence of alternating order. Expressions for the average lengths and the compositions of all possible alternating sequences starting with a given monomer unit and ending with unit found only at that position, are derived as well. The alternating indexes for binary radical copolymerization of styrene and methyl methacrylate and for ternary radical copolymerization of styrene, methyl methacrylate, and acrylonitrile were determined.     

Ionic Copolymerizations

It is shown that for the reported instances of “random” copolymerization in cationic systems, N values related to relative reactivity may be derived for monomers. The N values approximate reasonably well the values of the function, exp (-e) - 1.23, where e is the polarity e of the Q-e scheme for free-radical copolymerizations.

In a recent paper [1] it was shown that for the reported instances [2-4] of “random” copolymerization (r₁,r₂ = 1) in cationic systems, N values, related to relative reactivity, might be derived for monomers, employing styrene as a base monomer (N = 1). Thus d[M₁]/d[M₂] =N₁[M₁]/N₂[M₂] (1)

where d[M₁]/d[M₂] is the instantaneous copolymer composition, [M₁]/[M₂] is the ratio of unreacted monomers, and N₁ and N₂ are parameters related to general monomer reactivity of monomers 1 and 2, respectively, in cationic copolymerization.     

Studies in Cyclocopolymerization. X. Cyclocopolymerization of Tetrahydronaphthoquinone and Dimethyl Tetrahydronaphthoquinone with Divinyl Ether

Abstract

Tetrahydronaphthoquinone (THNQ) and dimethyl tetrahydronaphthoquinone (DMTHNQ) were found by UV spectroscopy to form donor-acceptor complexes with divinyl ether (DVE), the latter being the electron donor. Since the participation of such complexed species has been considered in the cyclocopolymerization of a 1,4-diene with a monoolefin such as DVE-maleic anhydride (MA) and DVE-fumaronitrile (FN) systems, radical copolymerization of THNQ and DMTHNQ with DVE was studied. It was found that these copolymers have constant 1:1 composition regardless of the feed composition. The terpolymerization of DVE-THNQ-DMTHNQ confirmed the 1:1 donor-acceptor composition in the polymer. The integration of the NMR spectrum was used in determining the copolymer composition. The spectroscopic data suggest a cyclized repeating unit in which the copolymer main chain consists of only DVE units. There is a marked difference between these copolymers and the typical cyclo-copolymers, such as DVE-MA and DVE-FN, in which the copolymer main chains consist of DVE and the comonomer alternately, with the overall composition being 1:2. These results are interpreted in terms of the steric effect by the bulky acceptor monomers and the electronic interaction between the comonomers. The competition between an acceptor monomer and the charge-transfer (CT) complex toward the cyclized DVE radical in the propagation step appears to favor the CT complex.     

Kinetics of the Thermo-Oxidative Degradation of Nylon 66 by Oxyluminescence Methods

The chemiluminescence from stabilized nylon 66 fibers during oxidation above T_g has been studied to determine the activation energies of the initiation, propagation and termination reactions. When oxygen is admitted to a nylon 66 sample heated in an inert atmosphere, a pulse of chemiluminescence is observed corresponding to a nonstationary alkyl peroxy radical concentration in the polymer. The analysis of the decay to the steady state can provide kinetic data for peroxy radical reactions in the induction period of the oxidation and the effect of stabilizers on these reactions.     

The Fundamental Basis for Cyclopolymerization. VII. A Cyclopolymerization Study of Certain Allylcycloalkenes

The cyclopolymerization characteristics of 3-allylcyclopentene, 3 allylcyclopentene, 3-allylcyclohexene, and 4-allylohexene were studied and the extent of their cyclopolymerization by cationic initiation were compared with previously reported solvolysis results involving the same intermediate carbonium ion. The results of this study were also compared with previously reported results on 4-vinylcyclohexene and 1, 4-dimethylenecyclohexane. The allylcycloalkenes were also polymerized by metal alkyl coordination catalysts and the extent of cyclization in each case was determined. The polymers derived from these monomers invariably contained polymeric fractions (27 to 99%) which were soluble in non-polar organic solvents. Calculations based on NMR spectral data indicated the cationic polymers were 68 to 95% cyclized. The extent of cyclization was found to parallel the interolefinic separation in the monomer. Coordination polymerization yielded somewhat lower ratios of cyclizations (54 to 80%) in all cases except for 4-allylcyclohexene. 4-Allylcyclohexene gave only 5 to 54% cyclization, 4-Vinylcyclohexene, 3-allylcyclopentene, and 3-allylcyclohexene produced soluble copolymers with maleic anhydride. Elemental analysis indicated the composition of these copolymers to be 2:1 molar in maleic anhydride and diene units. A cyclic copolymerization mechanism suggested the formation of a multicyclic repeating unit. The other monomers gave crosslinked polymers since maleic anhydride could not be incorporated into a six-membered ring.     

Copolymerization Parameters of Allyl Glycidyl Ether

Interest in the copolymerizability of allyl glycidyl ether has been stimulated by recent industrial and academic interest in the monomer, because of its epoxy as well as allylic functionality, There is a paucity of information in the literature, however, concerning its copolymerization parameters with other monomers, and none, apparently, concerning its Q and e values.     

Secure Polar Coding for the Primitive Relay Wiretap Channel

With the emergence of wireless networks, cooperation for secrecy is recognized as an attractive way to establish secure communications. Departing from cryptographic techniques, secrecy can be provided by exploiting the wireless channel characteristics; that is, some error-correcting codes besides reliability have been shown to achieve information-theoretic security. In this paper, we propose a polar-coding-based technique for the primitive relay wiretap channel and show that this technique is suitable to provide information-theoretic security. Specifically, we integrate at the relay an additional functionality, which allows it to smartly decide whether it will cooperate or not based on the decoding detector result. In the case of cooperation, the relay operates in a decode-and-forward mode and assists the communication by transmitting a complementary message to the destination in order to correctly decode the initial source’s message. Otherwise, the communication is completed with direct transmission from source to the destination. Finally, we first prove that the proposed encoding scheme achieves weak secrecy, then, in order to overcome the obstacle of misaligned bits, we implement a double-chaining construction, which achieves strong secrecy.