Stabilisers grafting

Figure 6.7 Various types of polymeric stabilisers (I) AB block copolymer, (II) AB graft copolymer, (III) super-stabiliser graft copolymer, (IV) terminally grafted homopolymer.

Surface active agents are important components of foam formulations. They decrease the surface tension of the system and facilitate the dispersion of water in the hydrophobic resin. In addition they can aid nucleation, stabilise the foam and control cell structure. A wide range of such agents, both ionic and non-ionic, has been used at various times but the success of the one-shot process has been due in no small measure to the development of the water-soluble polyether siloxanes. These are either block or graft copolymers of a polydimethylsiloxane with a polyalkylene oxide (the latter usually an ethylene oxide-propylene oxide copolymer). Since these materials are susceptible to hydrolysis they should be used within a few days of mixing with water. 

It has been observed that complete immobilisation of the stabiliser through a graft leads to deactivation. However, proper selection of the ratio of phenolic to graftable groups leads to a polymer-bound product which retains sufficient mobility to provide a high level of antioxidant activity. An n/m ratio of 5-10 provides an optimal balance of graftability and antioxidant activity [144]. 

As already shown, it is technically possible to incorporate additive functional groups within the structure of a polymer itself, thus dispensing with easily extractable small-molecular additives. However, the various attempts of incorporation of additive functionalities into the polymer chain, by copolymerisation or free radical initiated grafting, have not yet led to widespread practical use, mainly for economical reasons. Many macromolecular stabiliser-functionalised systems and reactive stabiliser-functionalised monomers have been described (cf. ref. [576]). Examples are bound-in chromophores, e.g. the benzotriazole moiety incorporated into polymers [577,578], but also copolymerisation with special monomers containing an inhibitor structural unit, leading to the incorporation of the antioxidant into the polymer chain. Copolymers of styrene and benzophenone-type UV stabilisers have been described [579]. Chemical combination of an antioxidant with the polymer leads to a high degree of resistance to (oil) extraction. 

Kim el al. [582] have described maleimide-based antioxidants melt grafted onto low-MW PE. IR spectroscopic methods and titration were used for the quantitative determination of the extent of grafting of the monomeric antioxidant. Smedberg el al. [583] have characterised polymer-bound stabilisers by FTIR and NMR. The binding of antioxidants and photostabilisers to polyurethanes was verified by tJV/VIS spectroscopy [584]. 

The formation of stable nanoparticles has been studied using various derivatives of thermosensitive PNIPAM, including diblock and graft copolymers, PNIPAM-b-PEO and PNIPAM-g-PEO [165-172], In these copolymers, the role of the PEO chains is to solubilise/stabilise collapsed PNIPAM at temperatures above its cloud point. Both the graft and the block copolymers, PNIPAM-g-PEO and PNIPAM-fr-PEO, form spherical core-shell structures in... 

In all cases, the cloud-point temperature was slightly dependent on polymer concentration for a given copolymer it increased with decreasing concentration. This effect is enhanced with increasing number of PEO grafts per chain. Also, the PNIPAM collapse seemed to be less abrupt with decreasing concentration. Upon dilution of the solution the distance between polymer chains increases, which favours intrapolymeric interactions over in-terpolymeric attractions. Dilution also enhances the surface stabilisation of the polymer particles by PEO. 

Cross-Linked PVCL Microgels Stabilised with Amphiphilic Grafts... 

The formation of stable particles of PNIPAM [166] or PVCL [182] grafted with PEO was detected earlier and it is expected that the introduction of the amphiphilic PEO-alkyl chains on PVCL, as well, will stabilise the PVCL aggregates upon heating. 

For both kinds of polymer-grafted particles, flocculation was induced either by changing the temperature or by adding a nonsolvent for the stabilising polymer. In this way critical flocculation temperature (c.f.T) and critical flocculation vol. fractions of non-solvent (c.f.v.) values were obtained, in general as a function of . 

Non-aqueous (or-oil-in-oil) emulsions, where the phases are two immiscible organic liquids, have received relatively little attention in the literature. Riess et al. [116-119] have studied the stabilisation of waterless systems with block and graft copolymers, where one of the liquids is a good solvent for one of the blocks and a non-solvent for the other, and vice versa. Thus, poly(styrene-b-methylmethacrylate) copolymers could emulsify acetonitrile/cyclohexane mixtures, and poly(styrene-b-isoprene) was effective for DMF/hexane systems [116]. These, however, are not HIPE systems. 

The idea of the preparation of porous polymers from high internal phase emulsions had been reported prior to the publication of the PolyHIPE patent [128]. About twenty years previously, Bartl and von Bonin [148,149] described the polymerisation of water-insoluble vinyl monomers, such as styrene and methyl methacrylate, in w/o HIPEs, stabilised by styrene-ethyleneoxide graft copolymers. In this way, HIPEs of approximately 85% internal phase volume could be prepared. On polymerisation, solid, closed-cell monolithic polymers were obtained. Similarly, Riess and coworkers [150] had described the preparation of closed-cell porous polystyrene from HIPEs of water in styrene, stabilised by poly(styrene-ethyleneoxide) block copolymer surfactants, with internal phase volumes of up to 80%. 

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