Thiols polymeric

Alcohol or Thiol Polymeric Reagent Alkyl Chloride Yield (%) Reference... 

Liquid photo-curable resin is used in UV nanoimprint lithography (UV-NIL).i Basic ideas of photopolymerization are shown in Chapter 1. Liquid photo-curable resins change from liquid to solid by UV irradiation. The change is produced by polymerization of a monomer or oligomer constituted in the resin. Initiators induce polymerization by UV irradiation. Resins of UV-NIL are classified into several types by polymerization systems radical polymerization, ion polymerization, and ene-thiol polymerization. Details of those systems are described in below. 

Starters. Nearly any compound having an active hydrogen can be used as starter (initiator) for the polymerization of PO. The common types are alcohols, amines, and thiols. Thus in Figure 2 ROH could be RNH2 or RSH. The fiinctionahty is derived from the starter, thus glycerol results in a triol. Some common starters are shown in Table 4. The term starter is preferred over the commonly used term initiator because the latter has a slightly different connotation in polymer chemistry. Table 5 Hsts some homopolymer and copolymer products from various starters. 

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

In general, rubber manufacturers balance thiol reactivity and odor. The stmcture of the thiol plays a significant role in its abiUty to be transported within the polymer matrix, particularly in emulsion polymerizations, ie, mixed water—monomer emulsion. The odor of light thiols is generally too strong for most mbber manufacturers, as it is generally hard to remove residual odors from polymers. 

Often a chain-transfer agent is added to vinyl acetate polymerizations, whether emulsion, suspension, solution, or bulk, to control the polymer molecular weight. Aldehydes, thiols, carbon tetrachloride, etc, have been added. Some emulsion procedures call for the recipe to include a quantity of preformed PVAc emulsion and sometimes antifoamers must be added (see Foams). 

Thus the thiol 0 2 25511 is capable of terminating a growiug chain and also initiating a new chain. If the initiation-rate constant, k is not much slower than the propagation-rate constant, the net result is the growth of a new chain without any effect on the overall polymerization rate (retardation). That represents a tme chain transfer, ie, no effect on the rate but a substantial decrease iu molecular weight (12). 

Treatment of thiiranes with lithium aluminum hydride gives a thiolate ion formed by attack of hydride ion on the least hindered carbon atoms (76RCR25), The mechanism is 5n2, inversion occurring at the site of attack. Polymerization initiated by the thiolate ion is a side reaction and may even be the predominant reaction, e.g. with 2-phenoxymethylthiirane. Use of THF instead of ether as solvent is said to favor polymerization. Tetrahydroborates do not reduce the thiirane ring under mild conditions and can be used to reduce other functional groups in the presence of the episulfide. Sodium in ammonia reduces norbornene episulfide to the exo thiol. 

The procedure described is essentially that of Shioiri and Yamada. Diphenyl phosphorazidate is a useful and versatile reagent in organic synthesis. It has been used for racemlzatlon-free peptide syntheses, thiol ester synthesis, a modified Curtius reaction, an esterification of a-substituted carboxylic acld, formation of diketoplperazines, alkyl azide synthesis, phosphorylation of alcohols and amines,and polymerization of amino acids and peptides. - Furthermore, diphenyl phosphorazidate acts as a nitrene source and as a 1,3-dipole.An example in the ring contraction of cyclic ketones to form cycloalkanecarboxylic acids is presented in the next procedure, this volume. 

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... 

Even in the absence of added transfer agents, all polymerizations may be complicated by transfer to initiator (Sections 3.2.10 and 3.3), solvent (Section 6.2.2.5), monomer (Section 6.2.6) or polymer (Section 6.2.7). The significance of these transfer reactions is dependent upon the particular propagating radicals involved, the reaction medium and the polymerization conditions. Thiol-ene polymerization consists of sequential chain transfer and reinitiation steps and ideally no monomer consumption by propagation (Section 7.5.3). 

Traditionally thiols or mercaptans are perhaps the most commonly used transfer agents in radical polymerization. They undergo facile reaction with propagating (and other) radicals with transfer of a hydrogen atom and form a saturated chain end and a thiyl radical (Scheme 6.6). Some typical transfer constants are presented in Table 6.2. The values of the transfer constants depend markedly on the particular monomer and can depend on reaction conditions.4"1 44... 

Thiols react more rapidly with nucleophilic radicals than with electrophilic radicals. They have very large Ctr with S and VAc, but near ideal transfer constants (C - 1.0) with acrylic monomers (Table 6.2). Aromatic thiols have higher C,r than aliphatic thiols but also give more retardation. This is a consequence of the poor reinitiation efficiency shown by the phenylthiyl radical. The substitution pattern of the alkanethiol appears to have only a small (<2-fokl) effect on the transfer constant. Studies on the reactions of small alkyl radicals with thiols indicate that the rate of the transfer reaction is accelerated in polar solvents and, in particular, water.5 Similar trends arc observed for transfer to 1 in S polymerization with Clr = 1.4 in benzene 3.6 in CUT and 6.1 in 5% aqueous CifiCN.1 In copolymerizations, the thiyl radicals react preferentially with electron-rich monomers (Section 3.4.3.2). 

Thiol-ene polymerization was first reported in 1938.220 In this process, a polymer chain is built up by a sequence of thiyl radical addition and chain transfer steps (Scheme 7.17). The thiol-ene process is unique amongst radical polymerizations in that, while it is a radical chain process, the rate of molecular weight increase is more typical of a step-growth polymerization. Polymers ideally consist of alternating residues derived from the diene and the dithiol. However, when dienes with high kp and relatively low A-, monomers (e.g. acrylates) are used, short sequences of units derived from the diene are sometimes formed. 

One may envisage polymerizations analogous to the thiol-enc process using other bis- or multi transfer agents (e.g. radical-induced hydrosilylation between bis-silanes and dienes). However, none has been described or achieved significance. 

Tung et al21> have reported on the use of a polymeric thiol transfer agent for use in block copolymer production. Various methods have been used for the anion thiol conversion. Near quantitative yields of thiol arc reported to have been obtained by terminating anionic polymerization with ethylene sulfide and derivatives (Scheme 7.27). Transfer constants for the polymeric thiols are reported to be similar to those of analogous low molecular weight compounds.273... 

Triphenylinethyl terminated polymers (41) are formed in polymerizations conducted in the presence of triphenylmethyl thiol (40).9 5 Transfer constants for 40 are similar to other thiols (17.8 for S, 0.7 for MM A, compare Section 6.2.2.1). When the polymers (41) are heated in the presence of added monomer it is presumed that the S-CPh bond is cleaved and triphenylmethyl-mediated polymerization according to Scheme 9.11 can then ensue to yield chain extended or block polymers (42). 

RAFT polymerization can be performed simply by adding a chosen quantity of an appropriate RAFT agent to an otherwise conventional radical polymerization. Generally, the same monomers, initiators, solvents and temperatures are used. The only commonly encountered functionalities that appear incompatible with RAFT agents are primary and secondary amines and thiols. 

RAFT polymerization lends itself to the synthesis of polymers with thiol end groups. Several groups have utilized the property of thiols and dilhioesLers to bind heavy metals such as gold or cadmium in preparing brushes based on gold film or nanoparticles1 8 761 763 and cadmium selenide nanoparticles.763 76 1... 

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