Terminal chains

While living polymers can be prepared, there are some substances like water, alcohols, and carbon dioxide which are highly effective in terminating chain growth ... 

Although the main uses for benzoic acid are as a chemical raw material, it also has numerous direct uses. Benzoic acid is used in substantial quantities to improve the properties of various alkyd resin coating formulations, where it tends to improve gloss, adhesion, hardness, and chemical resistance. Benzoic acid terminates chain propagation in alkyd resins (qv) and promotes crystallinity in the final product. 

Glycogen Branching Occurs by Transfer of Terminal Chain Segments... 

However, upon terminating chains with thiols, sulphur centered low-molecular weight radicals are formed that are able to start a polymerization of the remaining monomer B. Therefore, formation of homopolymer consisting of B is inevitable if thiols are used. A suitable alternative to the classical transfer additives are degra-dative chain transfer agents, such as allylmalonic acid... 

Since the experiment is no longer reliant on the dithiocarbatnyl radical to both initiate and terminate chains (cf Section 9.3.2.1), lower reaction temperatures may be used (where the dithiocarbamyl radical is slower or unable to add monomer) and better control over the polymerization process can be obtained. The transfer constants for the benzyl dithioearbamates in polymerization of acrylic and styrcnic... 

Various side reactions that are likely to lead to a slow loss of "living" ends have been described. With disulfide initiators, one (initiation by the dithiocarbamyl radical) is unavoidable since the experiment relies on the same radical species to both initiate polymerization and terminate chains. 

Table 2 shows a list of collagen model peptides which have teen prepared. Many efforts have been made to prevent racemization. The polycondensation reaction seemed to be more sensitive to racemization than the coupling steps preparing the monomeric tripeptide. Therefore, the sequence of the monomer was selected with Gly or Pro at the C-terminal chain end, because racemization is mostly favored at the carboxy-activated amino acid, and these amino acids cannot racemize. 

Fig, 18a,b, The polymorphic behaviour of the phasmidic-like mesogens a molecular model with six terminal chains b phase diagram for the binary mixture of double swallow-tailed compound (I) with conventional rod-like mesogen (II) (adapted from Letko et al. [123])... 

LDPE polymerization reaction consists of various elementary reactions such as initiation, propagation, termination, chain transfer to polymer and monomer, p-scission and so forth [1-3], By using the rate expression of each elementary reaction in our previous work [4], we can construct the equations for the rate of formation of each component. 

The two conditions stated above do not assure the occurrence of gelation. The final and sufficient condition may be expressed in several ways not unrelated to one another. First, let structural elements be defined in an appropriate manner. These elements may consist of primary molecules or of chains as defined above or they may consist of the structural units themselves. The necessary and sufficient condition for infinite network formation may then be stated as follows The expected number of elements united to a given element selected at random must exceed two. Stated alternatively in a manner which recalls the method used in deriving the critical conditions expressed by Eqs. (7) and (11), the expected number of additional connections for an element known to be joined to a previously established sequence of elements must exceed unity. However the condition is stated, the issue is decided by the frequency of occurrence and functionality of branching units (i.e., units which are joined to more than two other units) in the system, on the one hand, as against terminal chain units (joined to only one unit), on the other. 

Any real network must contain terminal chains bound at one end to a cross-linkage and terminated at the other by the end ( free end O of a primary molecule. One of these is indicated by chain AB in Fig. 92, a. Terminal chains, unlike the internal chains discussed above, are subject to no permanent restraint by deformation their configurations may be temporarily altered during the deformation process, but rearrangements proceeding from the unattached chain end will in time re-... 

The total number of chains, both internal and terminal, is v+Nj as is evident from Fig. 91,b. For every primary molecule there will be two terminal chains, i.e., a total of 2N. The number of internal chains must therefore be v — N. Hence a fraction of the chains given by... 

Under all ordinary circumstances the average lengths of terminal chains and of internal chains will be the same, or nearly so hence represents the weight fraction of the structure which is active in deformation. For certain applications, as for example to crystallization induced by stretching, 8a is an appropriate measure of the effective portion of the... 

A terminal chain may rearrange similarly, but each of a pair of entangled internal chains is prevented from doing so by the permanent chemical structure, as is clear from Fig. 93. Inasmuch as the terminal chains are not thus involved, we should expect the correction factors for terminal chains occurring in Eqs. (30) and (30 ) to be valid. The correction for entanglements should be expected to enter as a factor modifying the entire expression for Ve. Unfortunately, there is at present no theoretical basis from which to estimate this factor, except to note that it presumably will be a function of p. 

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