Chain structure crosslinking

Considerations of the primary chemical structure (e.g., molecular composition, backbone microstructure, chain length, crosslinking) of urethane polymers are... 

Figure 6.5 Illustrations of nanoscale spherical assemblies resulting from block copolymer phase separation in solution are shown, along with the chemical compositions that have been employed to generate each of the nanostructures (a) core crosslinked polymer micelles (b) shell crosslinked polymer micelles (SCKs) with glassy cores (c) SCKs with fluid cores (d) SCKs with crystalline cores (e) nanocages, produced from removal of the core of SCKs (f) SCKs with the crosslinked shell shielded from solution by an additional layer of surface-attached linear polymer chains (g) crosslinked vesicles (h) shaved hollow nanospheres produced from cleavage of the internally and externally attached linear polymer chains from the structure of (g)...

Note 4 For components of chain structures that would be expected to be miscible, miscibility may not occur if molecular architecture is changed, e.g., by crosslinking. 

By using this method, the chemical shifts of the resonances in the spectra of a sulfur vulcanized natural rubber (Fig. 32 expanded aliphatic region in shown in Fig. 33 [top]) are assigned to various units of the polymer network, which arise from structural modifications induced by the vulcanization 194,196 200). Different sulfidic structures are found for unaccelerated and accelerated sulfur vulcanizations, respectively. With increasing amount of accelerator (as compared to the sulfur), the network structure exhibits less crosslinking, fewer main chain structural modifications, and fewer cyclic sulfide structures 197). 

Experimental results show that at low grafting temperature (30°C) the solubility of grafted polymers is highly modified by butadiene-acrylonitrile chains. Precipitation curves look like those of polymers prepared using dichloroethane and therefore seem compatible with a less cross-linked BD-AN chain structure. At high grafting temperature (70°C), the precipitation curve resembles that obtained with DVB crosslinked copolymers. 

For many years, several authors have tried to explain and predict the yield stress of polymers (crosslinked or not), as a function of the experimental test parameters (T, e) and/or structural parameters (chain stiffness, crosslinking density). These models would be very useful to extrapolate yield stress values in different test conditions and to determine the ductile-brittle transition. 

Network structures are still determined by nodes and strands when long chains are crosslinked at random, but the segmental spacing between two consecutive crosslinks, along one chain, is not uniform in these systems which are currently described within the framework of bond percolation, considered within the mean field approximation. The percolation process is supposed to be developed on a Cayley tree [15, 16]. Polymer chains are considered as percolation units that will be linked to one another to form a gel. Chains bear chemical functions that can react with functions located on crosslinkers. The functionality of percolation units is determined by the mean number f of chemical functions per chain and the gelation (percolation) threshold is given by pc = (f-1)"1. The... 

A quantitative analysis of the shape of the decay curve is not always straightforward due to the complex origin of the relaxation function itself [20, 36, 63-66] and the structural heterogeneity of the long chain molecules. Nevertheless, several examples of the detection of structural heterogeneity by T2 experiments have been published, for example the analysis of the gel/sol content in cured [65, 67] and filled elastomers [61, 62], the estimation of the fraction of chain-end blocks in linear and network elastomers [66, 68, 69], and the determination of a distribution function for the molecular mass of network chains in crosslinked elastomers [70, 71]. 

Bain and co-workers [115] studied the field dependence of 13C linewidths for polyacrylates crosslinked to low levels. The linewidth was directly proportional to field strength, consistent with a significant contribution from a dispersion of chemical shifts arising from new chain structures. In addition the authors used the Delays Alternating with... 

When chain segments can move relatively freely in cured polymers, it is most likely due to low crosslink density or the mobility of the molecular chain structure. The glass transition temperature is a measure of the mobility of the molecular chains in the polymer network as a function of temperature. The glass transition is the reversible change in a polymer from (or to) a rubbery condition to (or from) a hard and relatively glassy state condition (Fig. 3.14). This transition occurs at a temperature called the glass transition temperature or Tg. It is... 

In some cases, network structure is modified by aminolysis reactions25. An example is the polymer formed from diglycidylic ester of o-phthalic acid and diaminodiphenilmethane. Aminolysis makes the chain between crosslinks shorter and influences the properties of the polymer (dynamic shear modulus in a rubbery... 

Murayama8> studied a series of resins from diglycidyl ether of Bisphenol A (DGEBA) cured with varying quantities of diaminodiphenylmethane (DDM). These cured resins had the same main chain structure, but differed in the degree of crosslinking. Izumo 25) performed similar studies by using diethylenetriamine (DETA) as a... 

FIGURE 2 Pentameric polypeptide chain structure of human IgM. The IgM heavy chain have five domains with disulfide bonds crosslinking adjacent C/j.3 and C/j.4 domains of different units. Also shown are the carbohydrate side chains and possible location of the J chain. (Reprinted from Roitt et o/.")... 

They possess a gel-type structure due to their styrenic macromolecular chains lightly crosslinked by 1 to 2 % of divinylbenzene. Therefore, the Merrifield resin and its derivatives are able to swell significantly only on good solvents of the polystyrene chain. Their efficiency is therefore strongly lowered in more polar solvents such as alcohol or water. 

Electrochemical polymerisation produces films on an electrode surface.. Under controlled conditions uniform films up to a few mm thick, which carl be removed from the electrode for subsequent study, can be prepared. Physical properties can be modified by choice of the counterions (dopants) included in the film during growth. It is, however, more difficult to control chain structure and crosslinking than in chemical methods. Electrochemically produced polymers are, therefore, less well characterised than the best directly-synthesised polymers. While this is less satisfactory for fundamental investigations, it is of less concern for applications such as battery electrodes, artificial muscles and drug release agents. The two main approaches, direct-synthesis and electrochemical, are described in the following two sections. 

The polymers evaluated are shown in Fig. 1. These twelve polymers cover typical types of organosilicon polymers, such as polysiloxane, ladder type polysiloxane, polysilane, polymethacrylate, polysilyl-styrene, and novolak. Polymers and were supplied by Shin-etsu Chemical Co., Ltd. Actually, polymer" 2 evaluated contains very small amount of vinylsiloxane for crosslinking by deep UV irradiation after coating, because the pure polysiloxane is a fluid at room temperature and is impossible to measure the etching depth. These polymers have Si-0 bonds in the main chain structure. Polymer was purchased from Shin Nisso Kako Co., Ltd. and was purified in house. Polymers 4 to 12 were synthesized in house. Polymers 1J and 12 have Si-0 bonds in side chain structure. Thermal Si02 1J was evaluated as a reference. ... 

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