Poly stabilisers

PVC. Poly(vinyl chloride) (PVC), a very versatile polymer, is manufactured by the polymerisation of vinyl chloride monomer, a gaseous substance obtained from the reaction of ethylene with oxygen and hydrochloric acid. In its most basic form, the resin is a relatively hard material that requites the addition of other compounds, commonly plasticisers and stabilisers as well as certain other ingredients, to produce the desired physical properties for roofing use. The membranes come in both reinforced and nonreinforced constmctions, but since the 1980s the direction has been toward offering only reinforced membranes. The membrane thickness typically mns from 0.8—1.5 mm and widths typically in the range of 1.5—4.6 m. 

Other polymers can be more troublesome. Poly(vinyl chloride) requires the incorporation of stabilisers and even so may discolour and give off hydrochloric acid, the latter having a corrosive effect on many metals. At the same time some metals have a catalytic effect on this polymer so that care has to be taken in the construction of barrels, screws and other metal parts liable to come into contact with the polymer. 

There are a number of occasions where a transparent plastics material which can be used at temperatures of up to 150°C is required and in spite of its relatively high cost, low impact strength and poor aging properties poly-(4-methylpent-1 -ene) is often the answer. Like poly(vinyl chloride) and polypropylene, P4MP1 is useless without stabilisation and as with the other two materials it may be expected that continuous improvement in stabilising antioxidant systems can be expected. 

It is an interesting paradox that one of the least stable of commercially available polymers should also be, in terms of tonnage consumption at least, one of the two most important plastics materials available today. Yet this is the unusual position held by poly(vinyl chloride) (PVC), a material whose commercial success has been to a large extent due to the discovery of suitable stabilisers and other additives which has enabled useful thermoplastic compounds to be produced. 

An example of the first type is the emulsion stabiliser as exemplified by sodium oleyl sulphate, cetyl pyridinium chloride and poly(ethylene oxide) derivatives. For a number of applications it is desirable that the latex be thickened before use, in which case thickening agents such as water-soluble cellulose ethers or certain alginates or methacrylates may be employed. Antifoams such as silicone oils are occasionally required. 

The solution of poly(vinyl butyral) is diluted with methanol and the polymer precipitated by the addition of water during vigorous agitation. The polymer is then stabilised, washed and dried. 

Epoxidised drying oils have been available for several years as stabilisers for poly(vinyl chloride). They may be considered to have the skeletal structure shown in Figure 26.17. 

The polymetallosiloxanes above may in fact be considered as variants of a series of polymetalloxanes which are akin to the silicones but which contain, for example, tin, germanium and titanium instead of silicon. Of the poly-organostannoxanes, dibutyl tin oxide finds use as a stabiliser for PVC and as a silicone cross-linking agent. Polyorganogermanoxanes have also been prepared (Figure 29.13). 

An alternative mechanism by which additives may protect polymers from photo-oxidation is radical trapping. Additives which operate by this mechanism are strictly light stabilizers rather than antioxidants. The most common materials in this class are the hindered amines, which are the usual additives for the protection of poly (ethylene) and poly (propylene). The action of these stabilisers is outlined in Reactions 8.3-8.5. 

Depending on the nature of the sulfur or phosphorus compound used, the product R2S = O or R3P = O may undergo a number of further reactions with ROOH groups, all of which convert the hydroperoxide group into an alcohol. These compounds tend to be only weakly effective so are generally used in conjunction with synergistic promoters. Suitable mixtures are used to stabilise a variety of polymers including poly(alkenes), ABS, and poly(stryrene). 

The most spectacular results with temperature-programmed LC have been obtained for some notoriously difficult polymeric additives. Characterisation of the oligomeric HALS stabiliser poly [[6-[(l,l,3,3-te-tramethylbutyl) amino]-l,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-l,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidyl)imino]] (I) (Figure 4.12) is difficult for several reasons it has a broad MWD, may contain isomers, and has several amino groups that promote almost irreversible adsorption to silica based column packings in LC. 

Detailed studies led Gandini and Plesch to formulate the concept of pseudocationic polymerisations. These are reactions which show many of the characteristics of cationic polymerisations, but do not involve ions. Since they could see no other alternative compatible with general chemical knowledge, they formulated the reactive species as an ester, and they were able to support this view by direct experiments (formation of the ester in the styrene solution by metathesis). The evidence indicates that in the system styrene, perchloric acid, methylene dichloride, the poly(styryl perchlorate) ester requires four molecules of styrene for its stabilisation. When these are no longer available, the ester ionises, and the residual styrene is consumed by a very fast, truly cationic polymerisation ionisation of the ester is a complicated reaction which has been only partly elucidated. The initiation and propagation of the pseudocationic polymerisation can be represented thus ... 

Polyelectrolytes provide excellent stabilisation of colloidal dispersions when attached to particle surfaces as there is both a steric and electrostatic contribution, i.e. the particles are electrosterically stabilised. In addition the origin of the electrostatic interactions is displaced away from the particle surface and the origin of the van der Waals attraction, reinforcing the stability. Kaolinite stabilised by poly(acrylic acid) is a combination that would be typical of a paper-coating clay system. Acrylic acid or methacrylic acid is often copolymerised into the latex particles used in cement sytems giving particles which swell considerably in water. Figure 3.23 illustrates a viscosity curve for a copoly(styrene-... 

Polyadenylation This process is the addition of many AMP molecules to the 3 end of the RNA molecule. Once bound it is known as a poly A tail, since it is comprised of 100 or more such adenylate (AMP) residues. The tail is thought to stabilise the mRNA molecule in the cytosol, probably by preventing hydrolysis by an RNAase. 

Currently available BAS include cholestyramine, colestipol and colesevelam hydrochloride (colestimide). Cholestyramine comprises a long-chain polymer of styrene with divinylbenzene trimethylbenzylammonium groups, whereas colestipol is a long-chain polymer of l-chloro-2,3-epoxypropane with diethylenetriamine. Colesevelam HCl is poly(allylamine hydrochloride) cross-linked with epichlorohydrin and alkylated with 1-bromodecane and 6-bromo-hexyl-trimethylammonium bromide. Bile-acid binding is enhanced and stabilised in the latter compound by long hydrophobic sidechains, increased density of primary amines, and quaternary amine sidechains. For this reason, colesevelam HCl exhibits increased affinity, specificity and capacity to bind bile acids compared with the other BAS. Colesevelam HCl also binds dihydroxy and trihydroxy bile acids with equal affinity, contrasting with cholestyramine and colestipol that preferentially bind dihydroxy bile acids (CDCA and deoxycholic acid). The latter BAS can lead to an imbalance towards trihydroxy bile acids and a more hydrophilic bile-acid pool. 

Poly(alkylene oxide)-based (PEO-PPO-PEO) triblock and diblock copolymers are commercially successful, linear non-ionic surfactants which are manufactured by BASF and ICI. Over the last four decades, these block copolymers have been used as stabilisers, emulsifiers and dispersants in a wide range of applications. With the development of ATRP, it is now possible to synthesise semi-branched analogues of these polymeric surfactants. In this approach, the hydro-phobic PPO block remains linear and the terminal hydroxyl group(s) are esteri-fied using an excess of 2-bromoisobutyryl bromide to produce either a monofunctional or a bifunctional macro-initiator. These macro-initiators are then used to polymerise OEGMA, which acts as the branched analogue of the PEO block (see Figures 2 and 3). 

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%. 

---