Polymerizable structures

The most reliable information on the structure of the polymer has been derived from X-ray diffraction and Raman-spectroscopic studies. In a few cases it has been possible to determine in detail the structures of both the monomer and the corresponding polymer. From such measurements and other optical studies the process is considered to be 132 — 133 for a symmetric diacetylene. In polymerizable structures the diacetylene rods are inclined at about 45° to the translation (stack) axis, with the ends of each diacetylene moiety approaching the adjacent triple-bond systems to a distance of s4 A. The polymer is a planar system in extended conformation and having alternate R groups trans to one another. 

In an attempt to consider some extent of fragmentation of the monomer as well as to explain polymerization of simple organic molecules that are not considered monomers, plasma polymerization mechanisms are often explained by assuming plasma-induced precursors, which have polymerizable structures. The precursor concept is detailed in Figure 10.3. It is significantly different from the simple process described in Figure 10.2 however, it still depends on a simple deposition process from precursors to plasma polymer. This concept intuitively assumes that the structure of a plasma polymer can be predicted from the structures of precursors. 

Plasma-induced polymerization is essentially conventional (molecular) polymerization that is triggered by a reactive species created in an electric discharge. In order for one to form polymers by plasma-induced polymerization, the starting material must contain polymerizable structures, such as olefinic double bonds, triple bonds, or cyclic structures. 

In plasma state polymerization, the polymer is formed by the repeated stepwise reaction described above. It should be noted that plasma-induced polymerization does not produce a gas phase by-product, because the polymerization proceeds via the utilization of a polymerizable structure. The process can be schematically represented by tiie following chain propagation mechanism ... 

Apart from these direct uses as macromonomers, epoxydized vegetable oils have also been employed as precursors to other polymerizable structures, follow-... 

HRs functionalized with COOH groups can be diversified by saponification or esterification. The latter process allows the binding of some polymerizable structures (i.e., alkyl acrylates) [35]. 

There are no reports of ferro-, pyro- or piezoelectric properties being exhibited by LB polymers, although in principle there is no reason why such materials should not exhibit electroactive behaviour of this type. By incorporating suitable functional groups into polymerizable structures, it should be possible to produce useful LB pyro- and piezoelectric polymers... 

While most vesicles are formed from double-tail amphiphiles such as lipids, they can also be made from some single chain fatty acids [73], surfactant-cosurfactant mixtures [71], and bola (two-headed) amphiphiles [74]. In addition to the more common spherical shells, tubular vesicles have been observed in DMPC-alcohol mixtures [70]. Polymerizable lipids allow photo- or chemical polymerization that can sometimes stabilize the vesicle [65] however, the structural change in the bilayer on polymerization can cause giant vesicles to bud into smaller shells [76]. Multivesicular liposomes are collections of hundreds of bilayer enclosed water-filled compartments that are suitable for localized drug delivery [77]. The structures of these water-in-water vesicles resemble those of foams (see Section XIV-7) with the polyhedral structure persisting down to molecular dimensions as shown in Fig. XV-11. 

Uchida M, Tanizaki T, Gda T and Ka]iyama T 1991 Control of surface chemical-structure and functional property of Langmuir-Blodgett-film composed of new polymerizable amphiphile with a sodium-sulfonate Maoromoieouies 24 3238-43... 

Organic peroxide-aromatic tertiary amine system is a well-known organic redox system 1]. The typical examples are benzoyl peroxide(BPO)-N,N-dimethylani-line(DMA) and BPO-DMT(N,N-dimethyl-p-toluidine) systems. The binary initiation system has been used in vinyl polymerization in dental acrylic resins and composite resins [2] and in bone cement [3]. Many papers have reported the initiation reaction of these systems for several decades, but the initiation mechanism is still not unified and in controversy [4,5]. Another kind of organic redox system consists of organic hydroperoxide and an aromatic tertiary amine system such as cumene hydroperoxide(CHP)-DMT is used in anaerobic adhesives [6]. Much less attention has been paid to this redox system and its initiation mechanism. A water-soluble peroxide such as persulfate and amine systems have been used in industrial aqueous solution and emulsion polymerization [7-10], yet the initiation mechanism has not been proposed in detail until recently [5]. In order to clarify the structural effect of peroxides and amines including functional monomers containing an amino group, a polymerizable amine, on the redox-initiated polymerization of vinyl monomers and its initiation mechanism, a series of studies have been carried out in our laboratory. 

Gandini and Rieumont26,119 have carried out an extensive examination of the polymerizability of several vinyl esters of furan carboxylic acids and of the causes of the autoinhibition which most of them display with free-radical initiation. The compounds studied were the vinyl esters of 2-furoic, 2-furylacetic, 2-furylpropionic, 2-furylacrylic and sorbic acid. All these derivatives, showed the same strong indifference towards radical polymerization. Only when treated with large doses (10—30%) of initiator did they give small yields of oligomers. The structure of all these products was carefully studied by spectroscopic and other techniques. Invariably, it was... 

In this section, we consider the kinetics of propagation and the features of the propagating radical (Pn ) and the monomer (M) structure that render the monomer polymerizable by radical homopolymerization (Section 4.5.1). The reactivities of monomers towards initiator-derived species (Section 3.3) and in copolymerizalion (Chapter 6) arc considered elsewhere. 

Limited data suggest that the cntropic term may be as important as the enthalpic term in determining polymerizability. The value of AA(, is lowered >20 J moh1 K."1 by the presence of an a-melhyl substituent (Table 4.10, compare entries for AN and MAN, S and AMS). This is likely to be a eonscqucncc of the polymers from a-methyl vinyl monomers having a more rigid, more ordered structure than those from the corresponding vinyl monomers. 

Emulsion polymerization is the most important process for production of elastic polymers based on butadiene. Copolymers of butadiene with styrene and acrylonitrile have attained particular significance. Polymerized 2-chlorobutadiene is known as chloroprene rubber. Emulsion polymerization provides the advantage of running a low viscosity during the entire time of polymerization. Hence the temperature can easily be controlled. The polymerizate is formed as a latex similar to natural rubber latex. In this way the production of mixed lattices is relieved. The temperature of polymerization is usually 50°C. Low-temperature polymerization is carried out by the help of redox systems at a temperature of 5°C. This kind of polymerization leads to a higher amount of desired trans-1,4 structures instead of cis-1,4 structures. Chloroprene rubber from poly-2-chlorbutadiene is equally formed by emulsion polymerization. Chloroprene polymerizes considerably more rapidly than butadiene and isoprene. Especially in low-temperature polymerization emulsifiers must show good solubility and... 

From the kinetic viewpoint the polymerizability of 61 is considered to be higher than that of e-caprolactam, which is polymerized usually at temperatures above 135 °C63,64 Thermodynamically, the polymerization of 61 appears to be more favored than that of a-pyrrolidone, for which no polymerization is observed in THF63-65 The higher polymerizability of 61 may be attributed not only to its highly strained bicyclic structure but also to the activation of the anion 66 by the... 

In total, many possibilities of propagation result for the ions formed by the attack on the C = 0 double bond. According to the calculations, 4 of the structures which can be formed theoretically by interaction of an acrolein chain end with an acrolein monomer possess energetic preference. Two of them are the structures c and d. These results agree with the experimental cationic polymerizability ofacroleine(R = —CHO), as well as with the fact that in the cationically polymerized polyacroleine the following structures alternate with each other88) ... 

A novel polymerized vesicular system for controlled release, which contains a cyclic a-alkoxyacrylate as the polymerizable group on the amphiphilic structure, has been developed. These lipids can be easily polymerized through a free radical process. It has been shown that polymerization improves the stabilities of the synthetic vesicles. In the aqueous system the cyclic acrylate group, which connects the polymerized chain and the amphiphilic structure, can be slowly hydrolyzed to separate the polymer chain and the vesicular system and generate a water-soluble biodegradable polymer. Furthermore, in order to retain the fluidity and to prepare the polymerized vesicles directly from prev lymerized lipids, a hydrophilic spacer has been introduced. 

Microgels which have been prepared in emulsions or microemulsion have a more compact structure than those obtained by polymerization in solution. For microemulsion copolymerization, preferentially self-emulsifying comonomers, such as unsaturated polyesters, are used as polymerizable surfactants, because no emulsifier must be removed after the reaction. By choosing suitable monomer combinations the composition, size and structure of microgels can be widely varied, thus adjusting these macromolecules to special applications. 

We have discussed the structure and synthesis of the library of molecular catalysts for polymerization in Section 11.5.1. In the present section we want to take a closer look at the performance of the catalyst library and discuss the results obtained [87], The entire catalyst library was screened in a parallel autoclave bench with exchangeable autoclave cups and stirrers so as to remove the bottleneck of the entire workflow. Ethylene was the polymerizable monomer that was introduced as a gas, the molecular catalyst was dissolved in toluene and activated by methylalumoxane (MAO), the metal to MAO ratio was 5000. All reactions were carried out at 50°C at a total pressure of 10 bar. The activity of the catalysts was determined by measuring the gas uptake during the reaction and the weight of the obtained polymer. Figure 11.40 gives an overview of the catalytic performance of the entire library of catalysts prepared. It can clearly be seen that different metals display different activities. The following order can be observed for the activity of the different metals Fe(III) > Fe(II) > Cr(II) > Co(II) > Ni(II) > Cr(III). Apparently iron catalysts are far more active than any of the other central metal... 

One approach could be the attempt to include the lipids into the stabilization process. Lipid molecules bearing polymerizable groups can actually be arranged as planar monolayers or as spherical vesicles and polymerized by high energy irradiation within these membrane like structures under retention of the orientation of the molecules (8,9,36). 

Influence of subphase temperature, pH, and molecular structure of the lipids on their phase behavior can easily be studied by means of this method. The effect of chain length and structure of polymerizable and natural lecithins is illustrated in Figure 5. At 30°C distearoyllecithin is still fully in the condensed state (33), whereas butadiene lecithin (4), which carries the same numEer of C-atoms per alkyl chain, is already completely in the expanded state (34). Although diacetylene lecithin (6) bears 26 C-atoms per chain, it forms both an expanded and a condensed phase at 30°C. The reason for these marked differences is the disturbance of the packing of the hydrophobic side chains by the double and triple bonds of the polymerizable lipids. At 2°C, however, all three lecithins are in the condensed state. Chapman (27) reports about the surface pressure area isotherms of two homologs of (6) containing 23 and 25 C-atoms per chain. These compounds exhibit expanded phases even at subphase temperatures as low as 7°C. 

Before leaving the diacetylenes we must note some of the stereochemical varieties available in their polymers. Triynes, 138, also polymerize in the crystal by 1,4-addition (213). Also, cyclic di- and polyenes give polymeric products on irradiation. The exact structure of the polymer, however, has been established only in the polymer 135. Note that alternate side chains in this polymer are on opposite sides of the plane of the main chain the polymer is thus meso. However, in principle such a reaction could give rise to optically active polymers in suitable structures. The cyclic tetradiyne 139 crystallizes in a polymerizable phase containing interstitial chloroform (209). The polymerization reaction, which involves... 

Finally, reference should be made to copolymerization in this series. The diacetylene 142 is (homo)-polymerizable by high-energy radiation, whereas 143, though structurally very similar, is not. This difference in reactivity is apparently due to the difference between the crystal axial lengths in the direction in which polymerization would be expected to proceed this length is 4.37 A for 142 and 4.55 A for 143 (216). The two monomers are miscible in all proportions in the... 

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