Styrene 4-vinyl pyridine

Many vinyl monomers were reported to have been grafted onto fluoropolymers, such as (meth)acrylic acid and (meth)acrylates, acrylamide, acrylonitryl, styrene, 4-vinyl pyridine, N-vinyl pyrrolidone, and vinyl acetate. Many fluoropolymers have been used as supports, such as PTFE, copolymers of TFE with HFP, PFAVE, VDF and ethylene, PCTFE, PVDF, polyvinyl fluoride, copolymers ofVDF with HFP, vinyl fluoride and chlorotrifluoroethylene (CTFE). The source of irradiation has been primarily y-rays and electron beams. The grafting can be carried out under either direct irradiation or through the use of preliminary irradiated fluoropolymers. Ordinary radical inhibitors can be added to the reaction mixture to avoid homopolymerization of functional monomers. 

Figure 3.38. Force-displacement curves measured for interactions between a scanning force microscope s tip and a layer of styrene-4-vinyl pyridine block copolymer (the degrees of polymerisation of the styrene and 4-vinyl pyridine blocks were 200 and 20, respectively) in toluene. The solid curve is the prediction of self-consistent field theory. After Ovemey et al. (1996).

Similarly, styrene-4-vinyl pyridine and styrene-Al-vinyl pyrolidone stabilized Fe nanoparticles have been prepared starting from Fe(CO)5. ... 

PoIy(styrene sulphonic acid) + poIy(styrene sulphonates) + aqueous solutions Copoly(styrene-4-vinyl pyridine) +... 

Useful brominating resins (containing vinylpyridinium hydrobromide per bromide units) were prepared by functionalizing terpolymers of styrene, 4-vinyl-pyridine and divinylbenzene with bromine and HBr. The resins were stable over long periods and gave excellent yields in the bromination of alkenes and ketones. The spent reagent was readily removed after reaction and could be regenerated easily. ... 

The isoprene units in the copolymer impart the ability to crosslink the product. Polystyrene is far too rigid to be used as an elastomer but styrene copolymers with 1,3-butadiene (SBR rubber) are quite flexible and rubbery. Polyethylene is a crystalline plastic while ethylene-propylene copolymers and terpolymers of ethylene, propylene and diene (e.g., dicyclopentadiene, hexa-1,4-diene, 2-ethylidenenorborn-5-ene) are elastomers (EPR and EPDM rubbers). Nitrile or NBR rubber is a copolymer of acrylonitrile and 1,3-butadiene. Vinylidene fluoride-chlorotrifluoroethylene and olefin-acrylic ester copolymers and 1,3-butadiene-styrene-vinyl pyridine terpolymer are examples of specialty elastomers. 

The formation of coagulum is observed in all types of emulsion polymers (i) synthetic rubber latexes such as butadiene-styrene, acrylonitrile-butadiene, and butadiene-styrene-vinyl pyridine copolymers as well as polybutadiene, polychloroprene, and polyisoprene (ii) coatings latexes such as styrene-butadiene, acrylate ester, vinyl acetate, vinyl chloride, and ethylene copolymers (iii) plastisol resins such as polyvinyl chloride (iv) specialty latexes such as polyethylene, polytetrafluoroethylene, and other fluorinated polymers (v) inverse latexes of polyacrylamide and other water-soluble polymers prepared by inverse emulsion polymerization. There are no major latex classes produced by emulsion polymerization that are completely free of coagulum formation during or after polymerization. 

Styrenes, vinyl pyridines and C6o (for another example see Section VILA.8 above) have been shown to be good dipolarophiles 415,416... 

Membranes which may be used in the removal of alkali metal ions by electrodialysis are those which are impermeable to anions, but which allow the flow therethrough of cations. Such cation-selective membranes should, of course, possess chemical durability, high resistance to oxidation and low electrical resistance in addition to their ion-exchange properties. Homogeneous-type polymeric membranes are preferred, for example, network polymers such as phenol, phenosulfonic acid, formaldehyde condensation polymers and linear polymers such as sulfonated fluoropolymers and copolymers of styrene, vinyl pyridine and divinylbenzene. Such membranes are well known in the art and their selection for use in the method of the invention is well within the skill of the art. 

Only types (l)-(4) fall within the scope of this chapter. No further reference will be made to emulsion-polymerized prolybutadiene rubbers, because they are now of little industrial significance relative to the styrene-butadiene rubbers. Poly(vinyl chloride) is discussed elsewhere in this book. Brief reference will also be made in this chapter (Section 15.5) to the production and properties of carboxylated variants of styrene-butadiene rubber latexes. It may also be noted that latexes of rubbery terpolymers of styrene, vinyl pyridine and butadiene, produced by emulsion polymerization, have long been of considerable industrial importance for the specialized application of treating textile fibres (e.g., tyre cords) in order to improve adhesion between the fibres and a matrix of vulcanized rubber in which they are subsequently to be embedded. 

Figure 6.16. Segregation of a deuterium-labelled styrene-vinyl pyridine block copolymer to an interface between polystyrene and poly(vinyl pyridine), revealed by forward recoil spectrometry. The block copolymer was initially imiformly distributed in the upper, polystyrene film after annealing for 8 h at 178 °C an interfacial excess of 100 A has developed. After Shull etal. (1990).

Figure 7.9. Interfacial reinforcement of a polystyrene/poly(vinyl pyridine) interface by a high relative molecular mass deuterated styrene-vinyl pyridine block copolymer, with degrees of polymerisation of each block 800 and 870, respectively. Circles (right-hand axis) show the measured interfacial fracture energy as a function of the areal chain density of the block copolymer 2, whereas crosses show the fraction of dPS found on the polystyrene side of the interface after fiacture. The discontinuity in the curves at 2 = 0.03 nm is believed to reflect a transition from failure by chain scission to failure by crazing. After Kramer et al. (1994).

Rubber products such as tyres, belts and hose rely on reinforcement by textiles to achieve the required physical properties. To effect reinforcement, textile and rubber must be adequately bonded together, and to promote adhesion, there is a range of treatments to suit most fibre-rubber systems. The adhesion-promoting material (dip) is usually a terpolymer latex of butadiene-styrene-vinyl pyridine (or a blend of SBR and vinyl pyridine), which bonds well to the fibres, together with a resorcinol formaldehyde precondensate, which, on curing, bonds well to mbber a three-dimensional resin network is formed. 

Frequently it is necessary to combine materials having quite dissimilar solubility parameters, and often differing in modulus as well. An important example, the manufacture of tires, is discussed in the chapter, Bonding Textiles to Rubber. Use is made of a hybrid adhesive, RFL, containing heat-resistant resorcinol-formaldehyde for good attachment primarily to the polar, high modulus fiber, plus an elastomer of moderate solubility parameter, butadiene-styrene-vinyl pyridine terpolymer latex, mainly for the rubber. 

The toughness of interfaces between immiscible amorphous polymers without any coupling agent has been the subject of a number of recent studies [15-18]. The width of a polymer/polymer interface is known to be controlled by the Flory-Huggins interaction parameter x between the two polymers. The value of x between a random copolymer and a homopolymer can be adjusted by changing the copolymer composition, so the main experimental protocol has been to measure the interface toughness between a copolymer and a homopolymer as a function of copolymer composition. In addition, the interface width has been measured by neutron reflection. Four different experimental systems have been used, all containing styrene. Schnell et al. studied PS joined to random copolymers of styrene with bromostyrene and styrene with paramethyl styrene [17,18]. Benkoski et al. joined polystyrene to a random copolymer of styrene with vinyl pyridine (PS/PS-r-PVP) [16], whilst Brown joined PMMA to a random copolymer of styrene with methacrylate (PMMA/PS-r-PMMA) [15]. The results of the latter study are shown in Fig. 9. 

As previously described, all microspheres discussed in this chapter were synthesized from AB type diblock copolymers. Precursor block copolymers, poly(styrene-b-4-vinyl pyridine) (P[S-b-4VP]) diblock copolymers, were synthesized using the additional anionic polymerization technique [13]. The basic properties of the block copolymers were determined elsewhere [24,25] and are listed... 

The poly(styrene-b-isoprene) (P(S-b-IP)) and poly(-styrene-b-2-vinyl pyridine) (P(S-b-2VP)) block copolymers with narrow molecular weight distributions for blending with the microspheres were also synthesized using the additional anionic polymerization technique. The number-average molecular weights (Mns) and PS contents are also shown in Table 1. 

Various substituted styrenes have been also polymerized by NMP. These include 1 03-1 07, p-chloromethylstyrene (108), p-halostyrenes, and p-aceloxystyrene. Vinyl pyridines (e.g. 109) are amenable to NMP21 and may be quaternized post-polymerization to provide water-soluble polymers. 

Examination of the mass spectrum of P2VPY taken during the maximum decomposition rate reveals the major decomposition products as methylpyridine (93 a.m.u.), protonated vinyl pyridine (106 a.m.u.), and protonated dimer (211 a.m.u.) with ion ratios 74 100 59 respectively. Trimeric and tetrameric protonated species (316 and 421 a.m.u.) are also observed but in relatively small amounts. Protonated ions, rather than the simple monomers and dimers observed for the decomposition of poly(styrene) by MS11, may be created by a mechanism similar to that reported for the decomposition of 2-(4-heptyl)pyridine12 in the mass spectrometer. 

One component of a terpolymer of butadiene, styrene and vinyl pyridine used in latex form to promote good adhesion between rubber and textiles, particularly rayon and nylon. Viscoelasticity... 

Hazardous when exposed to oxygen due to peroxide formation and subsequent peroxide initiation of polymerization Styrene Butadiene Tetrafluoroethylene Chlorotrifluoroethylene Vinyl acetylene Vinyl acetate Vinyl chloride Vinyl pyridine Chloroprene... 

Grafting of these preformed monoliths with dormant radicals is achieved by filling the pores with a monomer solution and heating to the desired temperature to activate the capped radicals. For example, a functionalization of poly(styrene-divinylbenzene) monolith with chloromethylstyrene and vinyl-pyridine to obtain material with up to 3.6 mmol/g of functionalities has been demonstrated [88]. 

Radiation Induced Reactions. Graft polymers have been prepared from poly(vinyl alcohol) by the irradiation of the polymer-monomer system and some other methods. The grafted side chains reported include acrylamide, acrylic acid, acrylonitrile, ethyl acrylate, ethylene, ethyl methacrylate, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinyl pyridine and vinyl pyrrolidone (13). Poly(vinyl alcohols) with grafted methyl methacrylate and sometimes methyl acrylate have been studied as membranes for hemodialysis (14). Graft polymers consisting of 50% poly(vinyl alcohol), 25% poly(vinyl acetate) and 25% grafted ethylene oxide units can be used to prepare capsule cases for drugs which do not require any additional plasticizers (15). 

QPVP = partially quaternized PVP with ethylbromide DBQP = partially crosslinked PVP with dibromobutane PSP = copolymer of styrene and 4-vinyl pyridine PVIm = poly(N-vinylimidazole)... 

To 5.3 g of 4-vinylpyridine is added to THE up to a volume of 50 ml 5 ml of this solution (containing 5 mmol 4-vinyl pyridine) are added in the same way to the above solution containing the "living" polystyrene, with vigorous agitation. After 15 min another 40 mmol of styrene are added, followed 15 min later by another 5 mmol of 4-vinylpyridine this operation is repeated once more. 15 min after the last addition of monomer the block copolymer is precipitated by dropping the solution into a mixture of 300 ml of diethyl ether and 300 ml of petroleum ether.The polymer is filtered, washed with ether,filtered again, and dried in vacuum at room temperature. 

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