Preparation and Characterisation of Novel Polymer Bound Phenolic Antioxidants and Its Use in Natural Rubber

ABSTRACT: Phenol was chemically attached to low molecular weight chlorinated polyisobutylene and stearic acid respectively. These phenolic antioxidants were characterised by IR, 1H NMR and TGA. The efficiency and permanence of these bound antioxidants were compared with conventional antioxidants in natural rubber vulcanisates. The vulcanisates showed comparable ageing resistance in comparison to vulcanisates containing conventional antioxidants. The presence of liquid polymer bound phenol reduce the amount of plasticiser required for compounding.

Synthesis,Characterisation and Uses of Polymer-bound Antioxidants

Department of Polymer Science and Rubber Technology,Cochin University of Science and Technology

Studies on Polymer Bound Antioxidants

The primary aim of this work has been to prepare efficient and cost effective polymer bound antioxidants by direct’ attachment of conventional antioxidants to a modified polymer. Due to the importance and easy availability of natural rubber in Kerala, it is proposed to make use of low molecular weight natural rubber as the polymer substrate for binding the antioxidant in most cases. The molecular weight of such low molecular weight natural rubber can be easily manipulated by varying the time of mastication, UV—irradiation etc. Further, the bound antioxidant may also get vulcanized during the vulcanization of the elastomer to which it is added, making the antioxidant non—volatile and non extractable. Several methods are proposed to be investigated for attaching the antioxidant to the low molecular weight natural rubber such as modified Friedel-Craft's alkylation reaction, binding during UV—irradiation, binding during aggressive mastication etc. The efficiency of such rubber bound antioxidants is proposed to be compared with that of conventional antioxidants in terms of volatility, extractability in solvents, ageing resistance etc. Naturally occuring antioxidants such as cardanol, are also proposed to be modified by binding them to low molecular weight natural rubber. The study is undertaken with the intention of generating a class of bound antioxidants which can be used in elastomers for aggressive and long term application.

Time controlled photo-oxidation of polyolefins by polymer bound additives

A variety of iron compounds containing vinyl or thiol functional groups (used as photoactivators) have been synthesised and some of these were successfully bound to both polyethylene and polypropylene backbones during processing in the presence of peroxide and interlinking agent. Concentrates (masterbatches) of the photoactivators in PP and PE were prepared and the pro-oxidant effect of the diluted masterbatches in absence and presence of an antioxidant was evaluated. An antioxidant photoactivator (FeDNC ) was found to sensitise the photoactivity of pro-oxidants (Metone A / Metone M) whereas an antioxidant (ZnDNC) was found to stabilise the polymer (PP and PE) containing both of these combinations. It was observed that the lower concentration of FeDNC sensitises the stability of the polymer containing very small concentration of NiDNC whereas higher concentration of FeDNC stabilises the polymer (LDPE) containing same amount of NiDNC compared to FeDNC alone. The photostability of unstabilised PP containing FeAc could be varied by varying the concentration of ZnDEC. Both the induction period and the UV - life time of the polymer increased by increasing concentration of ZnDEC. It is suggested that ligand exchange reaction may take place between FeAc and ZnDNC. A polymer bound UV stabiliser (HAEB) and a thermal stabiliser (DBBA) were used with a non extractable photoactivator (FeAc) in PP. Small concentrations of the stabilisers (HAEB and DBBA) in combination with the photoactivator (FeAc) sensitise the polymer. The antioxidant present in commercial polymer (LDPE and PP) was found to be of a hindered phenol type, which was found to antagonise with ZnDNC when used in combination with the photoactivators.

Stabilisation of polypropylene using polymer-bound antioxidants

variety of hindered phenol and hindered piperidine antioxidants containing vinyl or vinylidine functional groups have been synthesised and some of these were successfully bound to Polypropylene backbone during processing operations in presence of a radical generator. Up to 20% concentrates were prepared using this technique. Commercially acceptable concentrates (MASTERBATCHES) can only be prepared with antioxidants that are only weakly chain breaking such as hindered piperidines. One of the antioxidants, AATP was found to polymrise as well as bind to Polypropylene. Bound antioxidants were found to be resistant to such channels of physical loss as solvent extraction. Temperature and concentration of the additive and radical generator were found to be important parameters in the preparation of the concentrates. The stabilising efficiences of the diluted bound antioxidants alone, and in combination (synergistic) with other antioxidants have been evaluated. Results of both thermal and photo-oxidative stabilities of the bound samples in Polypropylene show that the restriction on free mobility of the bound antioxidants in the polymer has virtually no effect on its stabilising efficiency. Bound AATP was found to generate nitroxyl radicals during the course of its stabilising activities, and in combination with a small amount of Irganox 1076, it was shown to be highly synergistic thermally. A mechanism of catalytic phenol regeneration by the resultant piperidine hydroxylamine was proposed. Although the mechanical properties of the masterbatches were affected by the transformation, this was not found to be carried over to the diluted samples. This work has shown that bound concentrates can be effectively prepared in saturated polymers for subsequent dilution to normal concentrates used in commercial stabilisation.

Concentration effects in polymer-bound antioxidants

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Ca(2+)-mediated thiolysis of peptide-resin linkage as an option for preparing protected peptide thioesters

A mild new procedure for preparing protected peptide thioesters, based oil Ca(2+)-assisted thiolysis of peptide-Kaiser oxime resin (KOR) linkage, is described. Ac-Ile-Ser(Bzl)-Asp(OcHx)-SR (Ac: acetyl; Bzl: benzyl; cHx: cyclohexyl), model peptide, was readily released from the resin by incubating the peptide-KOR at 60 degrees C in mixtures of DMF with n-butanethiol [R = (CH(2))(3)CH(3)] or ethyl 3-mercaptopropionate [R = (CH(2))(2)COOCHCH(3)] containing Ca(CH(3)COO)(2). After serine and aspartic acid side-chain deprotection under acid conditions, Ac-Ile-Ser-Asp-S(CH(2))(2)COOCH(2)CH(3) was successfully obtained with good quality and high yield. This type of C-terminal modified peptide may act as an excellent acyl donor in peptide segment condensation by the thioester method, native chemical ligation and enzymatic methods. (c) 2008 Elsevier Ltd. All rights reserved.

Synthesis and Characterization of Chlorinated Paraffin Wax-Bound Paraphenylenediamine Antioxidant and ItsApplication in Natural Rubber

ABSTRACT: p-Phenylenediamine was chemically attached to low molecular weight chlorinated paraffin wax. The polymer-bound p-phenylenediamine was characterized by vapor-phase osmometry (VPO), proton magnetic resonance spectroscopy ('H-NMR), infrared spectroscopy (IR), and thermogravimetric analysis (TGA). The efficiency and permanence of the polymer-bound p-phenylenediamine as an antioxidant was compared with a conventional amine-type antioxidant in natural rubber vulcanizates. The vulcanizates showed improved aging resistance in comparison to vulcanizates containing a conventional antioxidant. The presence of liquid polymer-bound p-phenylenediamine also reduces the amount of the plasticizer required for compounding.

Characterization and Catalytic Activity of Polymer Supported Ruthenium Schiff Base Complexes Towards Catechol Oxidation

Ruthenium(III) complexes of the Schiff bases formed by the condensation of polymer bound aldehyde and the amines, such as 1,2-phenylenediamine (PS-opd), 2-aminophenol (PS-ap), and 2-aminobenzimidazole (PS-ab) have been prepared. The magnetic moment, EPR and electronic spectra suggest an octahedral structure for the complexes. The complexes of PS-opd, PS-ap, and PS-ab have been assigned the formula [PS-opdRuCl3(H2O)], [PS-apRuCl2(H2O)2], [PS-ab- RuCl3(H2O)2], respectively. These complexes catalyze oxidation of catechol using H2O2 selectively to o-benzoquinone. The catalytic activity of the complexes is in the order [PS-ab- RuCl3(H2O)2] . [PS-opdRuCl3(H2O)] [PS-apRuCl2(H2O)2]. Mechanism of the catalytic oxidation of catechol by ruthenium( III) complex is suggested to take place through the formation of a ruthenium(II) complex and its subsequent oxidation by H2O2 to the ruthenium(III) complex.

Polymer-drug conjugates: current status and future trends

Polymer conjugates are nano-sized, multicomponent constructs already in the clinic as anticancer compounds, both as single agents or as elements of combinations. They have the potential to improve pharmacological therapy of a variety of solid tumors. Polymer-drug conjugation promotes passive tumor targeting by the enhanced permeability and retention (EPR) effect and allows for lysosomotropic drug delivery following endocytic capture. In the first part of this review, we analyze the promising results arising from clinical trials of polymer-bound chemotherapy. The experience gained on these studies provides the basis for the development of a more sophisticated second-generation of polymer conjugates. However, many challenges still lay ahead providing scope to develop and refine this field. The "technology platform'' of polymer therapeutics allows the development of both new and exciting polymeric materials, the incorporation of novel bioactive agents and combinations thereof to address recent advances in drug therapy. The rational design of polymer drug conjugates is expected to realize the true potential of these "nanomedicines".

Transition metal ion co-ordination in hydrophilic polymer membrane

This thesis is concerned with the investigation of transition metal (TM) ion complexation with hydrophilic membranes composed of copolymers of 4-vinyl pyridine & 4-methyl-4'vinyl- 2,2'-bipyridine with 2-hydroxyethyl methacrylate. The Cu(II), CoCII) & Fe(II) complexes with these coordinating membranes were characterised by a variety of techniques, in order to assess the effect of the polymer on the properties of the complex, and vice versa. A detailed programme of work was instigated into the kinetics of formation for the polymer-bound tris(bipyridyl) iron(II) complex; the rate and extent of complex formation was found to be anion-dependent. This is explained in terms of the influence of the anion on the transport properties and water content of the membrane, the controlling factor in the development of the tris-complex being the equilibrium concentration of Fe(II) in the gel matrix. A series of transport studies were performed with a view to the potential application of complexing hydrogel membranes for aqueous TM ion separations. A number of salts were studied individually and shown to possess a range of permeabilities; the degree of interaction between particular metal-ion:ligand combinations is given by the lag-time observed before steady-state permeation is achieved. However, when two TM salts that individually display different transport properties were studied in combination, they showed similar lag-times & permeabilities, characteristic of the more strongly coordinating metal ion. This 'anti-selective' nature thus renders the membrane systems unsuitable for TM ion separations. Finally, attempts were made to synthesise and immobilise a series of N ,0-donor macrocyclic ligands into hydrogel membranes. Although the functionalisation reactions failed, limited transport data was obtained from membranes in which the ligands were physically entrapped within the polymer matrix.

Polymer microspheres: synthesis, characterisation and post-functionalisation by olefin metathesis

Porous polymer particles are used in an extraordinarily wide range of advanced and everyday applications, from combinatorial chemistry, solid-phase organic synthesis and polymer-supported reagents, to environmental analyses and the purification of drinking water. The installation and exploitation of functional chemical handles on the particles is often a prerequisite for their successful exploitation, irrespective of the application and the porous nature of the particles. New methodology for the chemical modification of macroreticular polymers is the primary focus of the work presented in this thesis. Porous polymer microspheres decorated with a diverse range of functional groups were synthesised by the post-polymerisation chemical modification of beaded polymers via olefin cross metathesis. The polymer microspheres were prepared by the precipitation polymerisation of divinylbenzene in porogenic (pore-forming) solvents; the olefin cross-metathesis (CM) functionalisation reactions exploited the pendent (polymer-bound) vinyl groups that were not consumed by polymerisation. Olefin CM reactions involving the pendent vinyl groups were performed in dichloromethane using second-generation Grubbs catalyst (Grubbs II), and a wide range of coupling partners used. The results obtained indicate that high quality, porous polymer microspheres synthesised by precipitation polymerisation in near-θ solvents can be functionalised by olefin CM under very mild conditions to install a diverse range of chemical functionalities into a common polydivinylbenzene precursor. Gel-type polymer microspheres were prepared by the precipitation copolymerisation reaction of divinylbenzene and allyl methacrylate in neat acetonitrile. The unreacted pendent vinyl groups that were not consumed by polymerisation were subjected to internal and external olefin metathesis-based hypercrosslinking reactions. Internal hypercrosslinking was carried out by using ring-closing metathesis (RCM) reactions in toluene using Grubbs II catalyst. Under these conditions, hypercrosslinked (HXL) polymers with specific surface areas around 500 m2g-1 were synthesised. External hypercrosslinking was attempted by using CM/RCM in the presence of a multivinyl coupling partner in toluene using second-generation Hoveyda-Grubbs catalyst. The results obtained indicate that no HXL polymers were obtained. However, during the development of this methodology, a new type of polymerisation was discovered with tetraallylorthosilicate as monomer.

Novel Porphyrin-Incorporated Hydrogels for Photoactive Intraocular Lens Biomaterials

Novel surface-modified hydrogel materials have been prepared by binding charged porphyrins TMPyP (tetrakis-(4-N-methylpyridyl)porphyrin) and TPPS (tetrakis(4-sulfonatophenyl)porphyrin) to copolymers of HEMA (2-hydroxyethyl methacrylate) with either MAA (methacrylic acid) or DEAEMA (2-(diethylamino)ethylmethacrylate). The charged hydrogels display strong electrostatic interactions with the appropriate cationic or anionic porphyrins to give materials which are intended to be used to generate cytotoxic singlet oxygen (1O2) on photoexcitation and can therefore be used to reduce postoperative infection of the intraocular hydrogel-based replacement lenses that are used in cataract surgery. The UV/vis spectra of TMPyP in MAA:HEMA copolymers showed a small shift in the Soret band and a change from single exponential (161 ���­s) triplet decay lifetime in solution to a decay that could be fitted to a biexponential fit with two approximately equal components with ���´ ) 350 and 1300 ���­s. O2 bubbling reduced the decay to a dominant (90%) component with a much reduced lifetime of 3 ���­s and a minor, longer lived (20 ���­s) component. With D2O solvent the 1O2 lifetime was measured by 1270 nm fluorescence as 35 ���­s in MAA:HEMA, compared to 67 ���­s in solution, although absorbance-matched samples showed similar yield of 1O2 in the polymers and in aqueous solution. In contrast to the minor perturbation in photophysical properties caused by binding TMPyP to MAA:HEMA, TPPS binding to DEAEMA:HEMA copolymers profoundly changed the 1O2 generating ability of the TPPS. In N2-bubbled samples, the polymer-bound TPPS behaved in a similar manner to TMPyP in its copolymer host; however, O2 bubbling had only a very small effect on the triplet lifetime and no 1O2 generation could be detected. The difference in behavior may be linked to differences in binding in the two systems. With TMPyP in MAA:HEMA, confocal fluorescence microscopy showed significant penetration of the porphyrin into the core of the polymer film samples (>150 ���­m). However, for TPPS in DEAEMA:HEMA copolymers, although the porphyrin bound much more readily to the polymer, it remained localized in the first 20 ���­m, even in heavily loaded samples. It is possible that the resulting high concentration of TPPS may have cross-linked the hydrogels to such an extent that it significantly reduced the solubility and/or diffusion rate of oxygen into the doped polymers. This effect is significant since it demonstrates that even simple electrostatic binding of charged porphyrins to hydrogels can have an unexpectedly large effect on the properties of the system as a whole. In this case it makes the apparently promising TPPS/DEAEMA:HEMA system a poor candidate for clinical application as a postoperative antibacterial treatment for intraocular lenses while the apparently equivalent cationic system TMPyP/MAA:HEMA displays all the required properties.