Posters

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P01

EFFECT OF SAN/EPDM BLENDS COMPOSITION ON MORPHOLOGY AND MECHANICAL PROPERTIES

A. PTIČEK^a, Z. KATANČIĆ^a, Z. HRNJAK-MURGIĆ^a, J. JELENČIĆ^a, Ž. JELČIĆ^b

The modification of a polymeric material by adding one or more other polymers is highly economical way to achieve superior performance instead of synthesizing new materials.Polymer blends are usually thermodynamically immiscible and, when blended, usually display poor properties, owing to their unstable morphology and poor adhesion between the phases. Compatibilizer in polymer blends reduces the interfacial tension of immiscible polymers and increases the adhesion between their phases. By blending of styrene-acrylonitrile copolymer (SAN) and ethylene-propylene-dieneterpolymer (EPDM), their good properties can be combined, including weatherability and good mechanical strength.

Polymer blends were prepared by twin-screw extrusion of the SAN and EPDM polymers, at ratio 95/5, 90/10, 85/15, 80/20 and 60/40. Polymer blends 90/10 was further studied by adding high impact polystyrene (HIPS) as compatibilizer, in different amounts: 5, 7.5, 10 and 15 phr, respectively. Mechanical properties (tensile strength, elongation at break and impact strength) were measured on the injection-molded specimens. Fractured surface morphology of injection-molded blend specimens was followed by scanning electron microscopy (SEM). From the results it is obvious that enhanced compatibility of polymer blends has significant influence on mechanical and physical properties.

P02

MECHANICAL RECYCLING OF PET BY PREPARING PET/HDPE BLENDS

L. KRATOFIL, Z. HRNJAK-MURGIĆ, J. JELENČIĆ

Recycling of polymers, with the aim of environmental protection and economical benefits, is important procedure, which is constantly developing. Poly(ethylene terephthalate), PET, can be successfully recycled by several methods. For example, it is very interesting to study mechanical recycling of PET through preparation of different polymer blends. Collected PET usually contains some small fraction of high-density polyethylene (HDPE) impurities. In this work physical and mechanical properties of recycled PET containing some amount of HDPE were studied.

PET/HDPE polymer blends were prepared by extrusion in ratio 97/3, 95/5, 90/10 and 85/15.

Then compatibilizer was prepared as EPDM/HDPE masterbatch. Furthermore, this compatibilizer was mixed with all prepared PET/HDPE blends. Mechanical properties (tensile strength, elongation at break and impact strength) and rheological property (melt flow rate, MFR) were determined for all prepared blends. Samples were further characterized by differential scanning calorimetry (DSC). Results show that EPDM compatibilizer has the significant influence on compatibility of PET/HDPE blends.

P03

PREPARATION OF ISOCYANATE-MULTIFUNCTIONALIZED POLYISOBUTYLENE BY ONE-POT SYNTHESIS. AMPHIPHILIC NETWORKS COMPOSED OF POLYISOBUTYLENE AND POLY(HYDROXYALKYL METHACRYLATE)S

L. TOMAN*, M. JANATA, J. SPĚVÁČEK, A. SIKORA, P. VLČEK, M. PEKÁREK, P. LÁTALOVÁ, J. MICHÁLEK, P. HOLLER, B. MASAŘ

In recent years, rapid advances in the field of cationic polymerization of isobutylene (IB) have led to numerous opportunities for the synthesis of new (co)polymers. Amphiphilic networks (APN), i.e., polymer networks composed of covalently bonded hydrophobic (PIB) and hydrophilic segment, represent a novel class of specialty hydrogels.^1-4 Generally, radical copolymerization of methacrylate-telechelic PIB (MA-PIB-MA) with water-soluble monomers have been used successfully for the synthesis of APNs. Most of the hydrophilic segments are well-known for their high biocompatibility, such as poly(2-hydroxyethyl methacrylate) (PHEMA) or poly(ethylene glycol) (PEG). However, PIB-based APNs have been prepared by five sequential synthesis using the site-transformation techniques, e.g., Cl-PIB-Cl → CH₂=CH-PIB-CH=CH₂ → HO-PIB-OH→ MA-PIB-MA→ APNs.⁴ Recently, a novel method of one-pot synthesis of multifunctionalized PIB bearing pendant methacrylate groups along the chain (PIB(MA)_n, where n ~ 3-12) was developed.⁵ Cationic copolymerization of IB and 3-isopropenyl-α,α-dimethylbenzyl isocyanate gives rise to the multifunctionalized PIB bearing pendant isocyanate groups along the chain (PIB(NCO)_n).⁶ The isocyanate groups were subsequently transformed to methacrylate groups by the dibutyltin dilaurate-catalyzed reaction with HEMA giving PIB(MA)_n.⁵

In the present work, we prepared PIB(MA)_n (M_n = 8 200 with an average functionality F_n ~ 5 per chain) in a one-pot synthesis. The PIB(MA)_n is then used as a polymeric crosslinking agent in radical copolymerization of HEMA, glyceryl methacrylate (GMA; 2,3-dihydroxypropyl methacrylate) and poly(ethylene glycol) methacrylate (PEGMA; M_n ~ 360 and 526) giving rise to a rubbery PHEMA-PIB, PGMA-PIB and PEGMA-PIB networks containing 50-60 wt % isobutylene. The amphiphilic nature of the networks has been demonstrated by swelling in both n-heptane and water. We have characterized PIB(MA)_n by SEC and ¹H NMR and APNs by solid state ¹³C NMR and DSC analysis.

Acknowledgement: Financial funding of this research provided by the Grant Agency of the Czech Republic (Grant 203/04/1050) is greatly appreciated.

References

1. B. Iván, J. P. Kennedy, P.W. Mackey, Polym. Prepr. 31(2), 215 (1990).

2. B. Iván, J. Feldthusen, A.H.E. Müller, Macromol. Symp. 102, 81 (1996).

3. B. Iván, J. P. Kennedy, P.W. Mackey, Polym. Prepr. 31(2), 217 (1990).

4. J. P. Kennedy, M. Hiza, J. Polym. Sci., Polym. Chem. Ed. 21, 1033 (1983).

5. L.Toman, P. Vlček, J. Vacík, J. Michálek, Czech Patent 290817 (2002).

6. L. Toman, P. Vlček, Czech Patent 291062 (2003); 290909 (2002).

P04

PHASE SEPARATION OF FUNCTIONALIZED POLYESTER POLYURETHANES

J. ČULIN^a, I. ŠMIT^a, M. ANDREIS^a, Z. VEKSLI^a, A. ANŽLOVAR^b, M. ŽIGON^b

Segmented polyurethanes are one of the most widely investigated classes of synthetic polymers. It is generally agreed that their unique and interesting properties are predominantly the result of a two-phase morphology. One method for tailoring properties of polyurethanes is incorporation of additional functional groups that may provide the change in the degree of phase mixing and domain structure. Polyester polyurethanes based on isophoronediisocyanate, polycaprolactone, and 1,4-butandiol with different amounts of functional groups introduced into the hard segments via second chain extender, 2,2¢-bis-(hydroxymethyl) propionic acid, were prepared. The concentration of carboxylic groups varied from 0 to 0.45 mmol g^-1. In order to examine the effect of functional group content on the phase separation, degree of ordering within domains and the motional heterogeneity wide-angle X-ray diffraction, WAXD, optical microscopy, differential scanning calorimetry and electron spin resonance, ESR-spin label method have been employed. Polarized micrographs and the extent of ordering from WAXD measurements reveal the changes of phase morphology with the carboxylic groups content. The degree of crystallinity and the separation of spherulitic rings increase with increase of functional group content. However, above a certain concentration of functional groups degree of phase separation decreases. Analysis of composite ESR spectra suggests similar behaviour of motional heterogeneity. The effect of functional groups in PU on the hard and soft segment mixing is discussed in terms of additional noncovalent interactions and chain structure which at critical level of interactions lead to a formation of more open hard segment structure accessible to interaction with the soft segment.

P05

ARCHITECTURE OF NANOCYLINDER COMPOSITES COMPOSED OF METAL CLUSTERS USING DOUBLE-CYLINDER-TYPE COPOLYMER BRUSHES AS TEMPLATES

K. ISHIZU, H. KAKINUMA

The well-defined poly(t-butyl methacrylate) cylinders: PSD-graft-PBMA (PBMA-C) were prepared by grafting from photo-induced ATRP of BMA initiated by multifunctional polystyrene (PSD) having N,N-diethyldithiocarbamate (DC) pendant groups in the presence of CuCl/bpy under UV irradiation. A complex, CuCl/bpy, reversibly activated the dormant polymer chains via a DC transfer such as Cu(DC)Cl/bpy. Subsequently, the nanocylinders consisting of graft block copolymers [PSD-graft-(PBMA-block-poly(methyl methacrylate) (PMMA))] were prepared by similar photo-induced ATRP with PBMA-C precursor as a polyinitiator with the controlled/living radical mechanism. Next, we derived to PSD-graft-[poly(methacrylic acid) (PMA)-block-PMMA] amphiphilic cylinders by hydrolysis of PBMA blocks. Nanocylinder composites were constructed by forming the metal clusters (Cu etc.) with internal PMA cylinders as templates followed by reduction of corresponding metal ions. Because the internal metal clusters were stabilized sterically with the external PMMA cylinder parts (hydrophobic sequences), such nanocylinder composites were soluble in some kinds of organic solvents.

P06

CORRELATION BETWEEN GAS PERMEATION AND THE FILLER ASPECT RATIO FOR THERMOSET POLYMER - LAYERED SILICATE NANOCOMPOSITES

V. MITTAL

Adhesive nanocomposites of organically modified layered silicates with polyurethane and epoxy matrices have been developed to be used in packaging laminates. The chemical structure of the filler surface modification was varied in order to study its interactions with the polymer and its effect on the final composite properties. Oxygen and water permeation through the thin composite films was correlated with the inorganic volume fraction of the clay. The oxygen permeation through the nanocomposite films was observed to be influenced strongly by the chemical structure of the modification. A reduction of 70% in the oxygen permeation was observed in epoxy composites containing 5 vol% of filler platelets modified with benzyl dibutyl (2-hydroxyethyl) ammonium ions on the surface. Water vapour permeation in the composites was generally decreased by 50% at 5 vol% filler fraction. As permeation is a function of aspect ratio of the platelets and their volume fraction in the composite, it was of interest to determine the filler aspect ratio in the composites developed in the study. But the bending, folding and misorientation of platelets in the composites makes it almost impossible to determine aspect ratio. As a solution, a macroscopic volume averaged aspect ratio for the organo-montmorillonite platelets in the composite was tried to be determined from the relative permeability values by comparison of the experimental values with the numerical predictions of gas permeation through the composites with mis-aligned disks. An average aspect ratio of about 250-300 was observed for the platelets in the 5 vol% epoxy composite with montmorillonite surface modified with benzyl dibutyl (2-hydroxyethyl) ammonium ions, the composite with maximum reduction in the oxygen permeation. Much lower aspect ratios were observed for the other polyurethane and epoxy composites.

P07

Recycling of PET/PC blends FOR A CONSTRUCTION APPLICATIONS

F. FRAÏSSE, V. VERNEY, S. COMMEREUC, M. OBADAL, J-C. MARECHAL

Polyvinylchloride (PVC) is the most common used polymeric material in building construction. Nowadays, PVC recycling brings a lot of problems because PVC contains heavy metals and its degradation takes place during a recycling process. Thus, efforts aimed at the substitution of PVC in building applications have been intensified noticeably. The idea of our work is to use a recycled polyethylenetereftalate (PET) as a supplement of PVC and therefore this study focuses on detailed study of PET recycling.

However, PET recycling is complicated process because of chemical and mechanical degradation of PET during its recycling and therefore this process has to be carried out with utmost caution. The first step, before the PET recycling, is to determine the level of the PET degradation caused by photo ageing and resulting properties. In addition, the properties can be improved by addition of polycarbonate (PC). Thus, our work is also aimed to use wastes of these polymers for blend preparation.

Mentioned subject has many interests, which can be summarized as follows:

• an academic one - to study an elementary behavior of blends prepared from PET and PC, miscibility of which is limited. Furthermore, their compatibility can be improved by process of transesterification.
• a technological one - to find relations between process of transesterification, method of blend preparation and properties.
• an environmental one - to recycle polymeric wastes.
• an economic one.

First of all, characterization of both PET and PC wastes was carried out. Then, the transesterification of PET and PC wastes was studied. For these purposes, PET and PC blends in various compositions (80/20, 70/30 and 50/50 wt.%) were prepared using twin-screw extruder. Consequently, properties of the blends were studied. The results show that extrusion is necessary prerequisite in order to obtained applicable properties. The transesterification seems to be detected in all blends, however, PET/PC (80/20 wt.%) blend shows the best properties, which can be, except impact characteristics, comparable to properties of PVC.

P08

NEW APPROACHES IN POLYURETHANE ELASTOMERS, FILMS AND BLENDS DERIVED FROM HARD SEGMENTS OF VARIABLE GEOMETRY

C. PRISACARIU

A new approach to block copolymer structure and morphology of polyurethane elastomers (PU), films and blends, by changes in the hard block chemical structure has been made. The infrared and mechanical data all indicate that replacement of the -CH2- spacer group between the two aromatic rings of diisocyanate by a -CH2CH2- spacer group results in a different, much more dense packing structure in the hard domains of the so-obtained novel PU. Due to the specific conformational mobility of the new 4,4'- dibenzyl diisocyanate (DBDI), in the corresponding PU it observes an unusual large range of mechanical, physical and chemical properties [1-2]which are associated with a specific pronounced separation into a domain - matrix morphology, and with a much higher tendency of crystallization [3]. Thus these polymers make possible the study of effects due to varying crystallinity in polyurethanes otherwise not possible. The characterization of novel DBDI based PU block copolymers consisting of blocks of different mechanical, physical and chemical properties was made to study the correlation between the PU properties and the chemical structure of the constituent polymer blocks The investigation of the compatibility of classical and novel DBDI based PU microphase (hard and soft block) on the physical/mechanical properties of polymers was made. The effect of hard segment conformational mobility on the PU deformation and fracture behaviour was followed to assess the structural modifications which appear during mechanical stresses. Stress-strain, stress relaxation and the energy loss during unload-reloading were undertaken and the effect of hydrogen bonding on the PU mechanical performance was studied. Experimental, DSC, IR dichroism, X-ray diffraction and SEM techniques were employed to investigate the specific phase separation, crystallization and orientation phenomena occurring in selected systems PU elastomers, films and blends.

References

[1] A.A Caraculacu, I Agherghinei, M Gaspar and C Prisacariu, J.Chem.Soc. Perkin Trans. 2. 1990,pp 1343-1348.

[2] C. Prisacariu and I Agherghinei, J.M.S.-Pure Appl. Chem., A37 (7), pp. 785-806 (2000)

[3] C. Prisacariu, PhD Thesis, Technical University "Gh. Asachi, Iasi, Romania, (1998).

P09

CAN POLYMER-POLYMER AND POLYMER-SOLVENT MOLECULAR INTERACTIONS ESSENTIALLY CHANGE THE COURSE OF THE COPOLYADDITION PROCESS?

C. PRISACARIU*, C.P. BUCKLEY**, V.A. PRISACARIU***

In the present paper, we proposed to study what are the limit situations that can be attained in the synthesis of polyurethanes (PU) when approaching the 'one shot' synthesis route in two distinct cases, e.g. when employing 4,4'-diphenyl methane diisocyanate (MDI) as a classical diisocyanate with a rigid geometry [1], and respectively when using 4,4'- dibenzyl diisocyanate (DBDI) as our novel diisocyanate which displays a variable geometry due to the presence of a rotation axis -CH₂-CH₂ between two aromatic rings bearing the two NCO groups [2]. The questions which were studied were the following: (a) - to elucidate why an apparently small change in the diisocyanate structure (1 or 2 -CH₂- spacers between two aromatic nucleus) can change dramatically the course of polyaddition, by splitting the process course into two phases e.g. in solution and in parallel in suspension, respectively; (b) - what is the difference in the molecular suprastructure of the mixture of the 2 copolymers which can appear simultaneously in different reaction conditions. Two systems of polyurethane elastomers (PU) based on MDI and on dibenzylic (DBDI) structures respectively have been synthesized. When employing MDI, irrespective of the approached synthesis route it obtained homogeneous soluble polymers inseparable in fractions, by selective dissolution in DMF. As shown [3], the sequence of ordering on the macromolecular chain differs from a PU synthesis route to another. DBDI displays approximately the same reactivity as MDI against n - butanol. Starting from the diisocyanates of variable geometry, a novel series of polyurethane thermoplastic blends were obtained. As seen, on employing the 'one shot' technique either in solution or in melt and using a diisocyanate of variable geometry it obtained PU composites made up by two copolymers with a different composition, separable by selective dissolution in dimethylformamide (DMF). In opposition, in the case when under the same conditions there were used commercial isocyanates of rigid structure as MDI, it obtain homogeneous soluble polymers inseparable in fractions.

References

[1] Oertel G, 'Polyurethane Handbook', Ed.Hanser Publishers - Munich - Vienna - N.Y. 1985

[2] Prisacariu C., , Doctorate Thesis, Technical University "Gh. Asachi", Iasi, Romania, June, 1998.

[3] Caraculacu A.A., .Agherghinei I., Prisacariu C., and Cozan V., .J Macromol. Sci.- Chem.,A27 (12), 1547-1570 (1990).

P10

Polypropylene-clay nanocomposites: application of Chlorosulfonated polypropylene as a coupling agent

J. Kotek, I. Kelnar, M. Studenovský, J. Baldrian, M. Šlouf

Polypropylene (PP) is interesting thermoplastic material due to its balanced properties and favourable price/performance ratio. Therefore, its clay nanocomposites have attracted great research interest. They are relatively difficult to obtain by melt compounding because PP does not contain any polar groups and layered silicates even if modified with nonpolar alkyl groups are polar and thus incompatible. In this work, we added a chlorosulfonated polypropylene as a coupling agent to overcome the polarity difference between the layered silicate and polypropylene.

Chlorosulfonated polypropylenes (CS-PP) differing in the degree of functionalization were prepared by reaction of polypropylene powder with sulfuryl chloride. The reaction was carried out at elevated temperature under UV irradiation in the presence of a small amount of pyridine as catalyst. In this way, sulfochloride groups SO₂Cl were introduced into polymer chains, together with a certain amount of chlorine atoms Cl.

Chlorsulfonated polypropylenes were melt compounded with organofilized montmorillonites (Cloisite 15A and Cloisite 20 A) to produce the masterbatches. The masterbatches were subsequently blended with commercial isotactic polypropylene. The effect of various processing procedures was examined as well.

It has been shown that the presence of polar groups led to increased gallery distance. Nevertheless, the full exfoliation of the clay platelets has not been achieved. TEM confirmed the coexistence of both intercalated and exfoliated structures in nanocomposites containing the coupling agent. Typically, the layers with larger lateral dimensions retained a parallel registry and formed intercalated structures, whereas smaller layers dispersed throughout the matrix. The observed morphologies were correlated with mechanical properties. The best nanocomposites exhibited 1.5 times higher tensile modulus than neat polypropylene, and, at the same time, the tensile strength was also higher than that of neat polypropylene.

This work was supported by the Academy of Sciences of the Czech Republic in the frame of "Projects of targeted research and development" (Project IBS 4050351 ).

P11

VARIOUS METHACRYLATE POLYMERS FOR USE IN DENTAL COMPOSITES*

I. KÜÇÜK^a, A. SARAÇ^b, S. KEYF^a, H. YILDIRIM^b

Aesthetic concepts have been particularly important in guiding the development of dental materials in the last few years. Researcher, patients and dentists are looking for materials that can replace amalgams and other metals while keeping the colors and glare as close as possible of the original teeth. Polymeric composites have been used in dental applications and new developments on polymeric composites for restorative filling materials are mainly focused on the reduction of polymerization, shrinkage and improvement of the biocompatibility, wear resistance and processing properties. Dental materials based on polymer composites are processed by photopolymerizing dimethacrylate monomers to yield materials with high strength. Although their properties and behaviour have been systematically improved, they still are not able to produce dental restorations chemically, dimensionally and mechanically stable for long periods of time.

In this work, to produce polymeric dental restorative composites, 2,-hydroxyethyl methacrylate (HEMA) and 2-hydroxypropyl methacrylate (HPMA) monomers were partially polymerized with ethyleneglycol dimethacryalate (EGDM) as crosslinking agent. Gel periods were determined depending on time during polymerization thus oligomers were prepared by stopping reaction before gelation time. Composite paste was cured with uv radition. Prepared samples were characterized by FTIR and SEM. Their crosslinking degree was investigated by swelling in different solvents.

This research has been supported by State Planning Organization of Turkey (Project Number:24-DPT-07-04-01),
and Yildiz Technical University Scientific Projects Coordination Department (Project Number:24-07-01-08).

P12

REMOVING BORON AND POLYCYCLIC AROMATIC HYDROCARBONS FROM WATER

I. KUCUK^a, S. PEKGUNDUZ^b, U. BEKER^a, F.S. GUNER^b, A.T. ERCIYES^b, A. KUYULU^a

Increasing concern for public health andenvironmental quality has lead to the establishment of limits on the acceptable environmental levels of specific pollutants. Consequently there has been growing interest in developing and implementing various methods of removing specific organics from water. Although there are a number of methods for removing organics from aqueous systems such as aeration, biological degradation, oxidation and adsorption, the last one is often preferred seperation process, since it can be used for removing a variety of organics from aqueous systems.

Polymeric resins have been widely used in the seperation and purification processes. The aim of this work is to prepare resins with different characteristics and to use them for removal of boron and polycyclic aromatic hydrocarbons (PAH) containing different aromatic rings number (naphthalene (Np) and pyrene (Py) in water. For this purpose polyurethane resins, methylmethacrylate (MMA)-ethyleneglycoldimethacrylate (EGDM) copolymers, methylolated abiatic acid were sythesized. In addition, abiatic acid was included in this study.

It was found that functional group content in polyurethane, abiatic acid and methyl abiatic acid resins was the important parameters that affect the removal properties of the resins. In addition, porous structure of MMA-EGDM copolymer beads without functional groups were effected removal of boron and poly aromatic hydrocarbons.

This research has been supported by Istanbul Technical University Scientific Research Projects Department (Project Number: 1515)

P13

SEMICONTINUOUS EMULSION COPOLYMERIZATION OF VINYL ACETATE AND BUTYL ACRYLATE WITH A NEW PROTECTIVE COLLOID. EFFECT OF DIFFERENT INITIATORS*

H. BERBER, A. SARAC, H. YILDIRIM

Copolymerization of vinyl acetate with acrylic monomers can lead to the production of latex having a wide range of mechanical and molecular properties depending on the molecular structure of the emulsifier, copolymer composition, initiating system and protective colloid in the polymerization.

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate and potassium persulfate as initiators, a nonionic emulsifier (30 mole ethoxylated nonylphenol, NP 30), and a new oligomeric stabilizator by changing monomer ratios from 100:0 to 0:100 for VAc:BuA.

The effects of different initiator with the relating BuA percentage increased in the copolymer composition on the physicochemical properties of emulsion copolymers obtained were investigated. The conversions of the copolymer latexes were pointed out by gravimetric method, by viscometric method, and of copolymers and molecular weight distributions of copolymers were measured by GPC.

*This research has been supported by State Planning Organization of Turkey (Project Number:24-DPT-01-02-02).

P14

SYNTHESIS AND CHARACTERIZATION OF NOVEL POLYIMIDES FROM BENZOPHENONE-3,3', 4,4'-TETRACARBOXYLIC DIANHYDRIDE DERIVATIVES

G.J. SHIN*, J.C. JUNG

Polyimides, particularly aromatic polyimides, were originally developed for applications as long-term structural materials due to their outstanding thermal, thermooxidaative, and dimensional stability and high-energy radiation resistance.

We designed novel aromatic polyimides from 3,3',4,4'-benzophenonetetracarboxylic dianhydride containing hydroxyl groups. The novel monomeric dianhydride 2,2'-dihydroxy-3,3',4,4'-benzophenonetetracarboxylic dianhydride (BHTDA) were synthesized by cyclodehydration of 2,2'-dihydroxy-3,3',4,4'-benzophenonetetracarboxylic, respectively with 2,2'-dimethoxy-3,3',4,4'-benzophenonetetracarboxylic followed by deprotecting of the methyl groups. The monomeric dianhydride was characterized by FT-IR, ¹H-NMR, ¹³C-NMR spectroscopic methods and used to prepare polyimides with a number of diamines such as PDA, MDA, ODA, and BPDA. Polyimides were characterized by FT-IR, TGA, DSC and inherent viscosity measurements. The properties of obtained polyimides such as solubility, phase transitions and structure were investigated by means of DSC, TGA, X-Ray.

P15

SYNTHESIS AND LIGHT-EMITTING PROPERTIES OF CONJUGATED POLYMERS CONTAINING ETHYNYLENE UNIT IN THE MAIN CHAIN

J.H. CHI, J.C. JUNG

Polymers with extended π-conjugated system are drawing a great attention due to their potential application as luminescent materials. Poly(phenylene ethynylene)s (PPEs) have been the material class of many researches to develop applications as molecular wires, electro- and photoluminescent device materials.

In the present work, we studied the electro- and photoluminescent device characteristics of a novel PPE, polymer containing ethynylene unit in the main chain. The ethynylene unit is introduced into the polymer main chain to achieve enhanced luminescence performance and electric conductivity. Conductivity of the polymers was measured by the conventional four-probe method after doped with iodine. Light-emitting devices of construction ITO/PEDOT/PPEs/Mg:Ag/Ag were fabricated from double-layer films of the polymer and their electrical performances were measured and discussed with respect to the chemical structure of the polymer

FIG.1. I-V-L curve of device

P16

RELAXATION PROCESSES DURING MICROHARDNESS MEASUREMENTSRELAXATION PROCESSES DURING MIKROHARDNESS MEASUREMENTS

G. ZAMFIROVA

The deformation processes occurring in the material under the Vickers indenter during microhardness measurements are complicated. The material is subjected simultaneously to stretch and pressure, moreover irregularly under different parts of the pyramid. The deformation components (elastic, plastic and viscoelastic) dependent on the nature of the material are included in different interrelations under the sides, edges and the top of the pyramid.

The deviations of the imprint form from ideal square shape, possibly appearance of cracks and causes provoking this, as well as the relaxation processes of the imprint have been investigated.

The materials under study are of different relation between deformation components giving an idea how the appearance of the imprint gives tentative rough information about the structure and mechanical properties of the sample investigated.

The relaxation of the imprint has been studied on linear low-density polyethylene (LLDPE) as a material with expressed viscoelastical deformation.

Usually the indentation base lies on the plane of the sample surface. In the case of LLDPE the indentation base is under the sample surface. Material around the indentor is involved by it and indirectly deformed without getting into any contact with the indentor. It could be explained by the presence of some quantity of physical entanglements in the amorphous phase, which play the role of a crosslinker.

Since the local deformations are different, the local relaxation replays of the material after removing the intender are different in the different parts of the imprint. During the relaxation process of the indentation the size of the diagonals does not change because of the the much larger local deformation under the edges and the top of the Vickers pyramid. Only the change in the indentation depth with time takes place.

P17

POSITRON ANNIHILATION AND MICROHARDNESS AS COMPLEMENTARY METHODS FOR POLYMER INVESTIGATION

G. ZAMFIROVA^a, V. GAYDAROV^a, N. DJOURELOV^b, E. NEDKOV^c, J. PERENA^d

Microhardness measurements, which are sensitive to many structural parameters, include Vickers microhardness (MHV), connected with the irreversible component of the deformation, and total microhardness (MHT), connected with the total deformation.

Positron annihilation lifetime spectroscopy (PALS) is a modern method for direct investigation of the amorphous phase structure, mainly the size, distribution and quantity of the nanopores.

Both methods are sensitive to the presence of the free-volume holes in the polymers but the correlation is not always simple.

A linear dependence between fractional free volume and degree of crystallinity has been established in the case of UHMWPE. It is known that MHV in semicrystalline polymers is proportional to the degree of crystallinity. Therefore in this case MHV depends linearly on the fractional free volume.

In the case of amorphous norbornene-ethylene copolymers with relatively high norbornene content an illogical monotonically increasing of MHV and MHT with increasing of the fractional free volume has been established at a first glance. Bicyclical olefins such as norbornene impart rigidity to the main polymer chain. With increasing the rigidity increases the nanoporous size and intensity and respectively the fractional free volume. Thus the conclusion is that the microhardness measurements and free volume measurements have a similar sensitivity to the micromechanical properties of the chains.

With the physical ageing of liquid crystalline polymers an increase in the total microhardness as well as in the Vickers one has been observed. The changes in the mechanical properties during the ageing process are due to the decrease of the distance between macromolecular segments in the amorphous area i.e. to a decrease in the size of nanopores of the disordered phase.

P18

THE INFLUENCE OF ACIDITY ON THE POLYANILINE FILM FORMATION: FTIR SPECTROSCOPIC STUDY

I. ŠEDĚNKOVÁ, M. TRCHOVÁ, E.N. KONYUSHENKO, J. STEJSKAL

A conducting polymer, polyaniline (PANI) [1], was prepared by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium of strong (sulfuric) or weak (acetic) acids. The progress of polymerization was monitored in situ by FTIR spectroscopy after depositing a droplet of the reaction mixture on a ZnSe crystal (Fig. 1) [2]. The growth of PANI film at the crystal surface, as well as changes proceeding in the surrounding aqueous phase, are reflected in the spectra. It has been shown that in solution of sulfuric acid, granular PANI was produced, in solutions of acetic acid, PANI nanotubes were obtained. The morphology of PANI, granular or tubular, depends on the acidity conditions during the reaction rather than on the chemical nature of acid. FTIR spectra show distinct differences in the chemistry of aniline polymerization. While in strong acid the induction period was followed by exothermic process, in weak acid, two exothermic processes proceed in succession. The changes occurring during polymerization are discussed with the help of differential spectra. The hypothesis that the kinetics of polymerization is controlled by the acidity level and its changes during the polymerization, rather than by the chemical nature of an acid, has been tested.

Fig. 1

[1] J. Stejskal, R.G. Gilbert, Pure Appl. Chem. 74, 857 (2002).

[2] M. Trchová, I. Šeděnková, J. Stejskal, Synth. Met., in press.

P19

MULTIWALL CARBON NANOTUBES MODIFIED WITH A POLYANILINE CONDUCTING POLYMER

E.N. KONYUSHENKO^a, J. STEJSKAL^a, M. TRCHOVÁ^a, J. PROKEŠ^a, J.Y. HWANG^b, K.-H. CHEN^b

Polyaniline (PANI) is typically prepared by the oxidative polymerization of aniline with ammonium peroxydisulfate in the acidic aqueous medium [1]. Any surface in contact with the reaction mixture becomes coated with a PANI film with a thickness of ~100 nm [2]. When carbon nanotubes (CNT) are suspended in the reaction mixture, they become also coated and, depending on the amount of polyaniline generated, may be accompanied by a PANI precipitate. The ethanol (50 vol.%) has been added into the polymerization medium. The goal of the synthesis was to improve the wettability of carbon nanotubes as required in some applications, e.g., in fuel-cell electrodes. The surface-modified CNT are hydrophilic when coated with protonated form of PANI, as proved by contact‑angle measurements. The composites of CNT with PANI have been characterized with FTIR and Raman spectroscopies.

The conductivity of CNT coated with conducting protonated PANI increased from 0.6 S cm^-1 to 8 S cm^-1 as the content of CNT in the composite approached 80 wt.%. The conductivity behaviour of simple mixtures of PANI hydrochloride with CNT is similar.

Conducting protonated PANI form was converted to a non-conducting PANI base. The conductivity of PANI-coated CNT increased from 10^-8 S cm^-1 (PANI base) to the conductivity of neat CNT. The compositional dependence of conductivity, however, was different from the mixtures of CNT with a non-conducting PANI base, which had a percolation threshold at 5 wt.% of CNT. The distribution of conducting polymer and CNT within the composite is different in PANI-coated nanotubes and in the mixture of both components.

[1] J. Stejskal, R.G. Gilbert, Pure Appl. Chem. 74, 857-867 (2004).

[2] I. Sapurina, A. Riede, J. Stejskal, Synth. Met. 123, 503-507 (2001).

P20

STARCH ModifIED with phosphate salts for APPLICATIONS in different branches of industry

S.I. Nazarov, O. M. Yariev, M.S. Sharipov, D.Ch.Muzaffarov, I.I. Nazarov

The first synthesized phosphate of starch taken by Kerb in 1919 year [1]. In operation presence of calcium carbonate was processed solution of starch by chlorine monoxide of phosphorus. The calcium salt starch phosphate dissolute in water and treating with ferment «taka-diastase" gave D-glucose phosphate. In 1922 Samec and Mayer have described cooking ethers of a phosphoric acid at interplay of an amylopectin with phosphorus oxychloride on a way, to a similar method Kerb [2]. Per the last years the methods of obtaining phosphates of starch which improved with applying ortho- and three polyphosphates.

We investigated of process the chemical modify of the soft wheat starch with sodium phosphates salts. Starch of wheat is mixed with sodium salts of phosphate acid, and heated in 165 ⁰C about 80 minute. Obtained starch phosphates melt in a warm water well and will have high viscosity of glue in 60⁰C.

The rheological properties of obtained starch phosphate is learned with areas of applications and used in a laboratory conditions to produce of food creams for pastries. Also we have elaborated many prescriptions of thickeners for pressing cotton fabrics based on obtaining starch phosphates in laboratory mini textile industrial conditions. The models of cloths, printed with the use of starch phosphates, are characterized the satisfactory flatly of press, lowered by the degree of the penetration of printing ink into the cloth. Thus obtained starch phosphates may be use as structure forming agents in nutritional creams for cookies and other confectionery products, both as thickeners in process of printing cotton fabrics with active and cold dyes. The operation not only brings economical benefits, but also utilizing domestic raw resources it's possible receive competitor capable materials place of import products used both in food, and in textile industry sparing energy resources

References

• Kerb J. -"Biochem. Z.", 1919, 100, 3; "Chem. Abstr.", 1920, 14, 2341.
• Samec M., Mayer A. "Koll Chim. Beihefte", 16, 89 (1922); "Chem. Abstr.", 17, 270 (1923).

P21

Geopolymerization

R. Slavik^a, O. Skoba^a, V. Bednarik^a, M. Vondruska^a, T. Hanzlicek^b

Geopolymerization is a polycondensation of aluminosilicates which runs at high alkali reaction conditions, room temperature and normal pressure. Reactive aluminosilicate material dissolves in the solution rapidly and creates free [SiO₄] and [AlO₄] tetrahedral units. During the reaction, water splits out gradually and the tetrahedral units are linked to polymeric precursors by sharing an oxygen atom between two tetrahedral units. Thereby amorphous material called geopolymer, hydroceramics or chemically bonded ceramics (CBC) is formed. There are no CO₂ emissions during the manufacture of geopolymers. Geopolymers can be made of recycled mineral waste. They have good resistance to fire, freeze-thaw cycles, as well as excellent ability to stabilize heavy metal ions within the geopolymer structure. Therefore, geopolymers can be used as a substitute for flammable organic material used as heat-resistance. These properties also make geopolymers a strong candidate for substitution of Portland cement applied in the field of civil, hydraulic and military engineering. Preparation of geopolymers from several types of raw materials containing SiO₂ and Al₂O₃ was studied in this work. Prepared materials were studied by chosen analytic methods.

P22

PEROXIDE-CURABLE RUBBER COMPOUND CONTAINING HIGH-ISOPRENE BUTYL RUBBER

A.GRONOWSKI, R. RESENDES

Commercial butyl rubber is a copolymer of isobutylene with a low amount (0.5-2.5 mol. %) of isoprene. This rubber can be vulcanized with sulfur and accelerators, quinoid systems and polymethylol phenol resins. However, commercial butyl rubber decomposes under the action of organic peroxides. A special grade of butyl rubber (XL-10000) - a terpolymer of isobutylene, isoprene and divinylbenzene - can be cured with peroxides. However, the manufacturing of XL-10000 is more cumbersome and the polymer contains very significant amounts of gel (ca. 70-80 wt. %) leading to difficulties in processing.

The present study involves an experimental butyl rubber with the isoprene content up to 8.0 mol. % which was synthesized via a cationic continuous process in a commercial butyl rubber plant. The rubber had moderate Mooney viscosity (ML 1+8 / 125 ºC) between 35 and 40 MU, while typical values for XL-10000 are 60-75 MU. In addition, the content of a crosslinked fraction in the high-isoprene butyl rubber was below 5 wt. %.

It was found that the high-isoprene butyl rubber, unlike the conventional butyl rubber, was peroxide curable on its own. However, the state of cure was relatively low. Further experiments utilized HVA-2 (m-phenylene-bis-maleimide) as a cure promoter to intensify curing of the rubber compound with peroxides. It was found that such compounds based on high-isoprene butyl rubber could achieve a higher cure state than XL-10000 cured with peroxides alone. In addition, there was no evidence of cure reversion. This was different than the rubber compounds containing regular butyl rubber cured with peroxides and HVA-2, where a low cure state and a pronounced reversion was seen. The results demonstrated that a higher content of isoprene in the rubber contributed to curing with peroxides and the high-isoprene butyl rubber could potentially replace XL-10000 in applications requiring peroxide vulcanization.

P23

NEW SELF-ASSEMBLED COPPER 1D- AND 2D-COORDINATION POLYMERS AS CATALYSTS FOR BIPHASIC PEROXIDE OXIDATION OF CYCLOHEXANE UNDER MILD CONDITIONS

E. YU. KARABACH^a, A. M. KIRILLOV^a, M. N. KOPYLOVICH^a, M. F. C. GUEDES DA SILVA^a, M. HAUKKA^b, A. J. L. POMBEIRO^a

Copper-containing coordination polymers are important class of compounds in view of their significance, e.g. as molecular magnets, optical materials, porous solids, sensors, and in supramolecular chemistry and catalysis. Of particular interest are water-soluble polymeric materials as biological models of copper enzymes involved in various types of catalytic oxidations.

Herein we report the easy self-assembly synthesis of novel copper 1D- and 2D-coordination polymers, including water-soluble ones, constructed from soluble building blocks based on copper dimers containing amino-alcohol ligands such as triethanolamine or methyldiethanolamine, and linear-type spacers e.g. terephthalic or pyromellitic acid. All the compounds have been characterized by IR-spectroscopy, elemental and X-ray diffraction structural analyses which prove a 1D- or 2D-character of polymeric architectures comprising parallel chains in neighbouring layers and hosting water molecules.

The obtained polymers act as new selective and active catalysts for liquid biphasic (MeCN-H₂O) peroxidative oxidation of cyclohexane, under mild conditions (room temperature, atmospheric pressure) and in the absence of any additives or co-catalysts, to a mixture of cyclohexanol and cyclohexanone. The effects on the catalytic activity of various parameters, e.g. the type of catalyst, oxidant-to-catalyst and substrate-to-catalyst molar ratios, reaction time and influence of radical trapping agents, are reported.

This work has been partially supported by the Human Resources and Mobility Marie Curie Research Training Network (AQUACHEM project, CMTN-CT-2003-503864) and the Foundation for Science and Technology (FCT), grant BD/6287/01, and its POCTI programme (FEDER funded).

P24

Characterization of molecular structure of alkyd resins using SEC with MALS detectION

D. VareČkova, S. Podzimek, J. LebduŠka

Alkyd resins belong to a broad generic class of polymers known as polyesters. They are the condensation products of polyfunctional alcohol (e.g. glycerol, pentaerythritol), of polybasic acid or its anhydride (mostly phtalic anhydride) and of oil or monobasic fatty acid. Even though they have been used in protective coatings for over 50 years, they still rank among the most important synthetic coating resins because of their superior solubility in low-cost organic solvents and good film properties and cross-linking ability. Their importance increases with the possibility to synthesize them from vegetable oils, i.e. from natural and renewable resources.

The molar mass is one of the most important parameters controlling the properties and end-use of polymers. The molar mass distribution of alkyds is usually determined by means of conventional size exclusion chromatography (SEC) with column calibration established by polystyrene standards. However, alkyd resins are branched polymers of broad molar mass distribution and their molecules are more compact compared to polystyrene molecules of the same molar mass, therefore, the molar mass values of alkyds determined by conventional SEC with polystyrene calibration are mostly significantly underestimated.

An on-line multi-angle light scattering (MALS) detector coupled to a concentration detector allows obtaining the absolute values of molar mass and root mean square (RMS) radius for each elution volume without need for column calibration.

In addition to the determination of true molar mass, SEC-MALS method allows distinguishing among particular samples with respect to their degree of branching using the ratio of M_w determined by conventional SEC, M_w(SEC), to the true M_w obtained by the MALS detector. This ratio decreases with increasing degree of branching and besides the characterization of branching also illustrates the fault of molar mass determination of alkyds by SEC with polystyrene calibration.

Acknowledgement. This work was supported by the Ministry of Education of the Czech Republic, Project MSM 21627501.

P25

SEMICONTINUOUS EMULSION COPOLYMERIZATION OF VINYL ACETATE AND BUTYL ACRYLATE USING A NEW PROTECTIVE COLLOID: EFFECT OF DIFFERENT EMULSIFIERS*

A. SARAC, H. YILDIRIM

Emulsion copolymers of vinyl acetate are generally water based, milky-white liquids containing 48-55 % solids, the balance being water and small amounts of emulsifiers or emulsifier mixtures, protective colloids or free and other additives. The stabilizing of aqueous homopolymer or copolymer latexes succeeded by using emulsifiers (anionic, nonionic) and/or their mixture, steric stabilizators (polyvinyl alcohol, hydroxyethyl cellulose, polyethylene glycol etc.), and polymerizable surface active agents, in general.

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate and potassium persulfate initiators, emulsifiers having different character such as nonionic emulsifiers, anionic, and anionic+nonionic, and Amol as new protective colloid in a classical glass reactor. The monomer ratio was chosen 85:15. In the case of mixture emulsifiers, the series of non-ionic emulsifiers which have 10 to 40 moles ethoxylated nonyl phenol except 20 moles were combined with Nansa 66 (sodium dodecyl benzene sulfonate).

The effects of different emulsifiers on the physicochemical properties of copolymers were investigated at a constant temperature of 70°C by measuring conversion, viscosity, molecular weight and molecular weight distribution and particle size, respectively by using gravimetric method, Brookfield viscometer, gel permeation chromatograpy (GPC), and Zeta-sizer.

*This research has been supported by State Planning Organization of Turkey (Project Number:24-DPT-01-02-02).

P26

VINYL ACETATE AND BUTYL ACRYLATE EMULSION COPOLYMERIZATION: EFFECT OF PROTECTIVE COLLOIDS ON SOME MECHANICAL PROPERTIES*

H. BERBER, A. SARAC, H. YILDIRIM

Emulsion homopolymers and copolymers (latexes) are widely used in architectural interior and exterior paints, adhesives, and textile industries. The stabilizing of aqueous latexes succeeded by using emulsifiers (anionic, nonionic) and/or their mixture, steric stabilizators (polyvinyl alcohol, hydroxyethyl cellulose, polyethylene glycol etc.), and polymerizable surfaces active agents, in general. Literatures about the using of nonionic emulsifiers for this purpose are very limited. That type emulsifiers give high molecular weights and a broad molecular weight distribution, especially in the presence of protective colloids.

Semi-continuous emulsion copolymerization of vinyl acetate (VAc) and butyl acrylate (BuA) was carried out using a nonionic emulsifier (30 mole ethoxylated nonylphenol, NP 30), conventinal protective colloid (polyvinyl alcohol) and a new oligomeric stabilizator (Amol), and ammonium persulfate (APS) as initiator by changing monomer ratios from 90:10 to 10:90 for VAc:BuA.

The effects of oligomeric stabilizator with the relating BuA percentage increased in the copolymer composition on some mechanical properties of emulsion copolymers obtained were investigated. The latex particle morphologies were studied using scanning electron microscopy (SEM) and the thermomechanical properties of the resulting latex films were investigated using differential scanning calorimetry (DSC). The surface tensions of the produced latexes were measured by using a ring-detachment method with a torsion tensiometer and a platinium ring at 25°C.

*This research has been supported by State Planning Organization of Turkey (Project Number:24-DPT-01-02-02).

P27

SYNTHESIS OF POLY(VINYL ACETATE-co-BUTYL ACRYLATE) LATEXES IN THE LOOP REACTOR: EFFECT OF MONOMER RATIO*

K. TURHAN, A. SARAC, H. YILDIRIM

Emulsion homo and copolymers can be synthesized by applying different production process and using different reactors, such as continuous stirred tank reactor (CSTR), the multi-reactor train and the tubular or loop reactor (LR). Especially in the last three decade, many kinds of reactor had been developed by several researchers. LR is one of the most important and an attractive alternative production method for the emulsion homo and copolymers. Vinyl acetate emulsion homopolymers and copolymers (latexes) are widely used as binders in water-based interior and exterior architectural paints, coatings, and adhesives, since they have higher mechanical and water resistance properties than the homopolymers of both monomers.

Semi-batch emulsion copolymerization of vinyl acetate (VAc) and butyl acrylate (BuA) was carried out using a nonionic emulsifier (30 mole ethoxylated nonylphenol, NP 30), a new oligomeric stabilizator, and ammonium persulfate (APS) as initiator by changing monomer ratios from 100:0 to 0:100 for VAc:BuA.

The effects of oligomeric stabilizator with the relating BuA percentage increased in the copolymer composition on the physicochemical properties of emulsion copolymers obtained were investigated. The conversions of the copolymer latexes were pointed out by gravimetric method, by viscometric method, and of copolymers and molecular weight distributions of copolymers were measured by GPC.

*This research has been supported by State Planning Organization of Turkey (Project Number:24-DPT-01-02-02).

P28

SYNTHESIS OF POLY(VINYL ACETATE-co-BUTYL ACRYLATE) LATEXES IN THE LOOP REACTOR: EFFECT OF VARIOUS EMULSIFIERS*

K. TURHAN, A. SARAC, H. YILDIRIM

Copolymerization of vinyl acetate with acrylic monomers can lead to the production of latex having a wide range of mechanical and molecular properties depending on the molecular structure of the emulsifier, copolymer composition, initiating system and protective colloid in the polymerization.

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate as initiator, nonionic emulsifiers, anionic, and (anionic+ nonionic), and a new oligomeric stabilizator in a loop reactor. The monomer ratio was chosen 85:15. In the case of mixture emulsifiers, the series of non-ionic emulsifiers which have 10 to 40 moles ethoxylated nonyl phenol except 20 moles were combined with Nansa 66 (sodium dodecyl benzene sulfonate).

The effects of different emulsifiers on the physicochemical properties of copolymers were investigated at a constant temperature of 70°C by measuring conversion, viscosity, molecular weight and molecular weight distribution and particle size, respectively by using gravimetric method, Brookfield viscometer, gel permeation chromatograpy (GPC), and Zeta-sizer.

*This research has been supported by State Planning Organization of Turkey (Project Number:24-DPT-01-02-02).

P29

Photoluminescence and Electroluminescence IN Poly(p-phenylenevinylene) Derivatives with m-Terphenyl or 2,6-Diphenylpyridine Segments along the Backbone

V. Cimrová¹, D. Výprachtický¹, H. HLÍDKOVÁ¹, P. Karastatiris², I.K. Spiliopoulos², J.A. Mikroyannidis²

Steady-state and time-resolved photoluminescence (PL), electrochemical behaviour, and electroluminescence (EL) of PPV-based polymers that contain along the backbone structure of m-terphenyl (PC) or 2,6-diphenylpyridine (PN) were studied. An intensive green PL broad band emission with maxima at 516 nm and 527 nm was observed from thin films of PC and PN polymers, respectively, red-shifted compared with the PL emission spectra measured in THF solutions. PL decay dynamics revealed the existence of more than one excited species and the decay curves were best described by three-term exponential functions with the dominant lifetime about 1 ns. The results of time-resolved PL and the steady-state PL study indicated excimer or aggregate formation. Both polymers oxidized irreversibly. A reversible reduction was observed in PN polymer, whereas in PC polymer both reduce irreversibly. Light-emitting devices with an indium-tin oxide hole-injecting and aluminium electron-injecting electrodes were prepared and studied. They emitted a green light and their EL spectra were similar to those of PL thin films. The current characteristics can be explained in the frame of the space-charge-limited currents, while the dependence of the EL intensity on the electric field shows a Fowler-Nordheim-like behavior.

The authors would like to acknowledge support of the Grant Agency of the Academy of Sciences of the Czech Republic (grant No. IAA4050409) and the Grant Agency of the Czech Republic (grant No. 203/04/1372).

P30

CHITOSAN BLOCK COPOLYMERS FOR CREATION OF ANTIBACTERIAL MATERIALS

N.Yu. SOLOMKO^a, O.G. BUDISHEVSKA^a, S.A. VORONOV^a

The purpose of this work is to create chitosan (CN) block-copolymers with grafted chains containing peroxide fragments while retaining the useful properties of primary CN, and also to obtain lattices modified by copolymers of CN.

Block-copolymers were prepared by radical grafted copolymerisation of CN and peroxide monomers 5-tert-butylperoxy-5-methyl-1-hexen-3-yne (PM). Peroxide fragments containing grafted blocks on CN-graft-PM copolymer can initiate radical reactions at the interface. As a result of such reactions grafting of macromolecules of CN-graft-PM copolymer to the polymer surface is achieved. Depending on the CN/PM ratio copolymers with the content of PM links in the range 1-30% were obtained. It was shown that the grafted CN-graft-PM block-copolymers possess antibacter. property, in particular, in relation to the bacter. culture of S. flava.

CN-graft-PM copolymer was used as initiator of emulsion polymerization of styrene (St) in the presence of cation-active emulsifier "Dinoram". Emulsion polymerisation was conducted at a 9:1 volume correlation of water phase to St, emulsifier concentration of 2% wt and CN-graft-PM copolymer concentration of 1% wt with respect to St at 343К. The rate of polymerization of St depending on the content of PM peroxide fragments in copolymerwas in the range 4.5×10^-5- 6.5×10 ^-5 mol/l×sek. Latex particle size was in the range 120-135 nm.

Initiation of radical emulsion polymerization of St occurred by the macro- and tert-butoxyl radicals generated upon homolytic decomposition of the peroxide fragment contained in CN-co-PM copolymer. Thus, initiation originates from the surface of polymer-monomer particle by the initiating radical being adsorbed at the surface and by thermolysis of adsorbed macromolecules of CN-graft-PM copolymer. As a result of the reactions of initiation, chain transfer and recombination grafting of CN-graft-PM copolymer to the polymer-monomer particle occurs at the interface. It was shown that the polystyrene obtained after destruction of the latex, also possesses antibacter. activity in relation to the bacter. culture of S. flava.

P31

POLY(ESTERAMIDE)S FROM AROMATIC BIS(2-OXAZOLINES) AND AROMATIC DICARBOXYLIC ACIDS

KRONEK J.¹, MARKUS O.¹, JANIGOVÁ I.¹, BÖHME F.², KOMBER H.², LUSTOŇ J.¹

2-Oxazolines provide thermally initiated addition reactions with a wide range of reagents, for example with carboxylic acids, phenols, thiols and amines [1]. These reactions can be used for the preparation of tailor made materials by polyaddition reactions of bis-(2-oxazoline)s with difunctional reagents or by the construction of AB_x monomers containing a 2-oxazoline unit and another functional group which reacts with 2-oxazoline [2,3].

The reaction between 2-oxazolines and acids results in opening of oxazoline ring and formation of ester-amide structure. When bis(2-oxazoline)s and dicarboxylic acids are used for the reaction, poly(ester-amide)s are formed. This mode represents a typical polyaddition reaction of the AA + BB type. We used 1,3-bis(2-oxazolin-2-yl)-benzene (IBOX) and 1,4-bis(2-oxazolin-2-yl)benzene (TBOX) and several aromatic dicarboxylic acids for the preparation of these materials in melt and in a solution. Thermal properties of the designed materials were studied. The prepared polymers have good thermal stability that depends on the reactants used.

The authors acknowledge the partial financial support of the Slovak grant agency VEGA (project No. 2/3033/24).

REFERENCES:

1. Kronek J., Lustoň J., Böhme F., Chem. Listy, 92, 475 (1998)

2. Kobayashi S., Prog. Polym. Sci., 15, 751(1990)

3. Culbertson B.M., Prog. Polym. Sci., 27, 579 (2002)

P32

POLY(ESTER AMIDE)S OF THE AA-BB AND AB TYPE CONTAINING BIPHENYL UNITS

J. LUSTOŇ¹, J. KRONEK¹, F. BÖHME²

2-Oxazolines provide thermally initiated addition reactions with a wide range of reagents, for example with carboxylic acids, phenols, thiols and amines [1]. These reactions can be used for the preparation of tailor made materials by polyaddition reactions of bis-(2-oxazoline)s with difunctional reagents or by the construction of AB_x monomers containing a 2-oxazoline unit and another functional group which reacts with 2-oxazoline [2,3].

Two different structures containing a potentially liquid crystalline biphenyl structural unit, 4,4'-bis(2-oxazilin-2-yl)biphenyl (1) and 4-hydroxy-4'-(2-oxazolin-2-yl)biphenyl (2) were synthetized. These compounds were used for the preparation of poly(ester amide)s by the reaction of 1 with dicarboxylic acids and by thermally initiated homopolyaddition reaction of 2.

The preparation of both groups of polymers will be described and thermal properties of the prepared polymers will be presented.

The authors acknowledge the partial financial support of the Slovak grant agency VEGA (project No. 2/3033/24).

REFERENCES:

1. Kronek J., Lustoň J., Böhme F., Chem. Listy, 92, 475 (1998)

2. Kobayashi S., Prog. Polym. Sci., 15, 751(1990)

3. Culbertson B.M., Prog. Polym. Sci., 27, 579 (2002)

P33

CHARACTERIZATION OF RECYCLED PVC/PP BLEND CONTAINING SURFACE-MODIFIED NANOFILLER

B. ANDRIČIĆ^a, T. KOVAČIĆ^a, I. KLARIĆ^a AND M. LESKOVAC^b

Polymeric waste generated in the processing of coverings made of soft poly (vinyl chloride) (PVC) reinforced with polypropilene (PP) fibres is rather hard to recycle due to the incompatibility of PVC and PP. To enhance the interphase properties of those polymers the commercially CaCO₃ filler was partially replaced with precipitated and surface modified CaCO₃ (nanofiller). The samples were prepared on laboratory roller mill in the sheet form in a way that the polymeric waste was added to the virgin PVC formulation.

Morphology of such blends was monitored using SEM and followed by EDAX analysis. Microphotographs show distinction between organic (PVC) matrix and inorganic filler, only.

Surface free energy was determined by contact angle measurements and shows that the PP from waste has no significant effect on the total surface free energy. On the other hand, surface modified filler reduces total surface free energy due to the low surface free energy of the filler.

According to the DSC measurements crystallinity degree of PP in the blends were reduced. Perhaps the crystallization of PP is partially disabled due to its low content.

Thermal degradation in air was performed thermogravimetically up to the 650°C. TG curves differ only in the number of degradation steps as well as in the residual mass.

P34

NEW POLY(ESTER-IMIDE)S DERIVED FROM 3,6- BIS(4-TRIMELLITIMIDOPHENOXY)BENZONORBORNANE AND AROMATIC DIOLS

H. BEHNIAFAR

A series of new alternating aromatic poly(ester-imide)s having inherent viscosities of 0.19-0.41 dl.g^-1 was prepared by the diphenylchlorophosphate (DPCP) activated direct polycondensation of a preformed imide ring-containing diacid, 3,6-bis(4-trimellitimidophenoxy)benzonorbornane (1) with various aromatic diols (3a-3f) in the presence of pyridine and lithium chloride. With due attention to structural similarity and owing to comparison of the characterization data, a model compound (2) was also synthesized by the reaction of 1 with phenol, previously. The optimum condition of polymerization reaction was obtained via study of the model compound synthesis. All of the polymers were fully characterized by spectroscopic methods and elemental analyses. The ultraviolet λ_max values of the poly(ester-imide)s were also determined. All of the poly(ester-imide)s exhibited an excellent solubility in common organic solvents. Crystallinity nature of the polymers was estimated by means of WXRD. The resulted poly(ester-imide)s exhibited nearly an amorphous nature, except poly(ester-imide)s derived from hydroquinone and 4,4^'-dihydroxy biphenyl. From DSC thermograms, the polymers showed T_g^, s between 257 and 304 ºC. Thermal behaviors of the poly(ester-imide)s were characterized by TGA, and the 10% weight loss temperatures of the poly(ester-imide)s were found to be in the range between 407 and 454 ºC in nitrogen.

P35

AN EFFICIENT ROUTE FOR THE SYNTHESIS OF SOLUBLE AND THERMALLY STABLE POLY(URETHANE-IMIDE)S BASED ON BENZONORBORNANE

H. BEHNIAFAR

A new aromatic dicarbonylazide (3) bearing two preformed imide rings and norbornane pendant group was synthesized by treating 3,6-bis(4-trimellitimidophenoxy)benzonorbornane with thionyl chloride followed by a nucleophilic reaction with sodium azide. A novel family of fully aromatic poly(urethane-imide)s with inherent viscosities of 0.15-0.23 dL.g^-1 were prepared from triimide-dicarbonylazide 3 and various aromatic diols. The polyaddition reactions readily proceeded in desirable yields as one-pot reactions starting from 3 without separately synthesis of the corresponding diisocyanate. All of the resulted polymers were thoroughly characterized by spectroscopic methods and elemental analyses. The poly(urethane-imide)s exhibited an excellent solubility in a variety of polar solvents. Crystallinity nature of the polymers was estimated by means of WXRD. The glass transition temperatures of the polymers determined by DSC method were in the range of 176-205 ºC. The 10% weight loss temperatures of the poly(urethane-imide)s from their TGA/DTG curves were found to be in the range of 349-386 ºC in nitrogen. The films of the polymers were also prepared by casting the solution. No flexibility behavior was observed and the resulting transparent films had a brittle nature.

P36

SYNTHESIS OF POLYSTYRENE-LAYERED SILICATE NANOCOMPOSITES BY IN-SITU SUSPENSION POLYMERISATION

C.M. LIAUW, P. LIMPANAPITTAYATORN, G.C. LEES, A.N. WILKINSON

PS matrix nanocomposites have been formed via in-situ free radical suspension polymerisation of styrene/organo-montmorillonite (o-MMT) dispersions.

These composites displayed evidence of large interfacial area relative to the volume fraction of montorillonite added. This was manifested as a reduction in melt flow rate, broadening of the molar mass distribution (increase in M_w) and an increase in thermal stability, relative to the unfilled matrix. However, wide angle X-ray diffraction (WXRD) patterns of the composites revealed a strong (001) reflection (d = 3.3-3.4 nm) together with clear (002) and (003) reflections as shown in Fig. 1.

Fig. 1. XRD Pattern of in-situ polymerised composite containing 10 % w/w o-MMT.

Therefore a mixed intercalated/flocculated morphology, with no significant exfoliation into single platelets, was indicated.

The o-MMT's used in this study were prepared in the semi solid state in a Brabender Plasticorder W50E chamber and the effect of alkyl ammonium chloride intercalant (quat) level and structure was investigated. The semi-solid state treatment method used eliminates the large quantities of water normally required for o-MMT preparation. It was found that mono-stearyl (or hydrogenated tallow) quats and those featuring benzyl groups were most suitable intercalants for the in-situ polymerised PS matrix nanocomposites produced. The distearyl (or dihydrogenated tallow) quats generally led to reduced interfacial effects in the composites and reduced toluene dispersion viscosity. The latter was used to gauge compatibility of the o-MMT with styrene monomer.

P37

EFFECT OF MONODISPERSE POLYMERIC PARTICLES PROPERTIES ON CHARACTERISTICS OF PHOTONIC CRYSTAL

N. SHEVCHENKO^a, A. BILIBIN^a, A. MENSHIKOVA ^b, B. SHABSELS^b, A. SEL'KIN ^c, A. BAZHENOVA ^c

There has been great interest into close-packed three-dimensional ordered structures which demonstrate the properties of photonic crystals (PC) and are potentially valuable both for basic and applied research. In this respect, self-assembling of monodisperse polymeric particles of submicron size is promising way to build lattices desired.

Monodisperse particles were synthesized by emylsifier-free emulsion polymerization styrene and methacrylic acid using K₂S₂O₈ as an initiator. In order to vary diameter of monodisperse particles in the range of 230-450 nm the effects of chain-transfer agents, K₂S₂O₈ concentration, and initial pH were investigated subsequently. Electrosurface properties and a full surface charge of the particles were also studied.

The particles obtained self-assembled from water or ethanol dispersions into ordered arrays packing a face-centred cubic (FCC) lattice. The best thin films were achieved at high enough ionization degree of surface carboxylic groups and at the humidity about 90%. Furthermore, luminescent dyes with emission in the range 450-550 nm were used to impregnate the FC thin films.

The experimental reflection spectra were obtained for polarized light at different angles of incidence and were well simulated in the two basis approaches: planar medium approximation and Bloch mode formalism approximation at θ<45^o. The multiple Bragg diffraction effect from (111) and (11) planes at θ>45^o was shown to be taken into account. Thus, obtained polymeric PC thin films can be used as appropriate models for studding light interaction with crystal lattices.

Carboxylated polymeric particles with distribution in particle diameters less than 2% seemed to be an excellent building blocks for the preparation of photonic crystals. Surface structure and charge of the particles were also shown to effect strongly on formation of perfect lattices and their PC properties.

P38

THE EFFECT OF THE NATURE OF FIBERS AND MATRIX ON THE PROPERTIES OF MICROCOMPOSITES

Kh. ALLABERDIEV

The effect of nature the fibers and the epoxy matrices on mechanical the properties of microcomposites is investigated. The mechanical properties of microcomposites were determined by temperatures 25⁰ and 150⁰C.

In order to investigate of the effect of fibers nature on tensile strength and elongation of microcomposites various fibers such as aromatic polyamides, class and carbon were used.

As objects the matrices for microcomposites researched two pure (96-99%) tetrafunctional epoxy resins (N,N,N¹,N¹-tetraglycidyldiaminodiphenylmethane(TGDDM),N,N,N¹,N¹-tetraglycidyldiaminodiphenyl(TGB) and commercial epoxy resin MY-720(oligomer of TGDDM) cured with 4,4¹-diaminodiphenylsulfone(DDS).

The mechanical properties of microorganocomposites depends on the polyamides of the nature and decreases in the order:armos>svm>terlon.This difference is due to structural characteristics of the fibers.

The properties of microcomposites also depend on the structure of the epoxy resins used. The mechanical properties of microcomposites on base of experimental epoxy systems compared favorably to a commercial epoxy system (MY-720/DDS).Both of the experimental systems exhibited higher tensile strength on microcomposites than based a commercial the epoxy resin. Results of the research indicate that the TGB is promising epoxy system

The tensile strength of microcomposites based on tetrafunctional epoxy systems curing with DDS is observed for temperatures 25⁰ and150⁰C in the ranges 2.60-4.12GPa and 1.69-3.74GPa, respectively.

The elongation values all except of microcarboncomposites have of 2.0-3.8%.

The properties microcomposites are unchanged with time (after 12 years).

P39

MODIFICATION OF SURFACE, ADHESIVE AND MECHANICAL PROPERTIES OF POLYOLEFINS THROUGH BLENDING WITH MALEINIZED PARAFFIN WAX

I. KRUPA^a, I. NOVÁK^a, A.S. LUYT^b

The results of the modification of polarity and adhesive properties of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE) and isotactic polypropylene (iPP) through blending with paraffin wax (Fischer-Tropsch synthesis) grafted by maleic anhydride (MA), are reported in this presentation.

The amount of 10 wt. % of grafted paraffin wax increases the polar component of the SFE of LDPE 13.8 times, for LLDPE, 10 wt. % of grafted paraffin wax increases the polar component of the surface free energy 6.2 times and for iPP 10 wt.% of grafted paraffin wax increases the polar component of its SFE 10.7 times. An increase in polarity of the blends has an influence on the adhesion of the blends to the metallic (alumina) substrate. The strength of the adhesive joint as well as the shear strength of the adhesive joint has increased for the all investigated blends.

The conservation of good mechanical properties, namely stress at break elongation at break and Young's modulus of LLDPE and iPP blended with grafted wax was observed up to 5 wt. % of wax. As far LDPE matrix, conservation of good mechanical properties was observed in the all investigated concentration region (up to 10 wt. %).

P40

THE INFLUENCE OF UV IRRADIATION ON POLY(ACRYLIC ACID)/POLY(ETHYLENE OXIDE) COMPLEXES

A. SZALLA^a, H. KACZMAREK

The poly(acrylic acid) (PAA) - poly(ethylene oxide) (PEO) complexes with different stoichiometric ratio were obtained from aqueous solutions. Prepared complexes and pure components as reference samples were UV- irradiated (l = 254 nm) in air atmosphere.

The course of photochemical reactions was monitored using FTIR spectroscopy, which also gives an information about specific interactions between PAA and PEO macromolecules. The formation of hydrogen bonds between the carboxylic acid groups of PAA and the PEO ether oxygen atoms was proved. Moreover, thermal stability of PAA/PEO was studied using thermogravimetry.

It was found that photooxidative degradation is less efficient in PAA/PEO complexes than that in PAA and PEO exposed separately. The most photostable among the samples studied was PAA/PEO (50/50) blend. The irregularities observed in the intensities of main IR absorption bands indicate that competitive photoreactions take place in UV-irradiated samples.

However, thermal stability of PAA/PEO complexes is lower comparing to pure components. UV-irradiation does not cause significant changes in thermal resistance of blends studied. It is caused by breaking of the hydrogen bonds upon raised temperature and mutual interactions of degradation products.

On the basis of the above results, one can conclude that complexation of polymers in the blend enhances their resistance to UV - irradiation. This process does not effect the thermal decomposition of PAA/PEO comparing to pure polymers degraded at the same conditions.

P41

INFLUENCE OF ULTRASONIC IRRADIATION ON THE LINEAR VISCOELASTIC PROPERTIES OF HIGH-DENSITY POLYETHYLENE /POLYAMIDE 6 BLENDS

V. KUTHANOVÁ^a, B. HAUSNEROVÁ^a, J. LI^b, M. LIANG^b, S. GUO^b

To overcome limited miscibility of majority of polymeric materials, additive or reactive compatibilization methods are commonly employed. This study discusses an alternative possibility based on ultrasonic irradiation (UI) of the blend carried out simultaneously with extrusion. The experimental material was blend composed of high density polyethylene (HDPE) and polyamide 6 (PA6). It was found, and confirmed by the variations in linear viscoelastic properties, that ultrasonic irradiation leads to both degradation and compatibilization of the blend. As can be seen in Fig. 1, degradation predominates compatibilizing effect for higher content of PA6. The improved compatibility is indicated by the increasing slope of storage versus loss modulus dependence in the terminal region (Fig. 2). Among other factors, the processing temperature and content of PA6 significantly influence the effectiveness of UI. Overall, the results have shown that ultrasonic irradiation can be considered a potential alternative for compatibilization of HDPE/PA6 blends.

Fig. 1 Effect of ultrasonic irradiation on |η*| of HDPE/PA6 blends at 235 °C.	Fig. 2 G' versus G'' of HDPE/PA6 80/20 blends at 235 °C.

Legends (Figs. 1,2): HDPE/PA6; HDPE/PA6+UI; HDPE/PA6+compatibilizer

P42

FRACTIONATION AND CRYSTAL MORPHOLOGY OF RIGID POLY(p-PHENYLENEBENZOBISTHIAZOLE)

K. SHIMAMURA, N. MICHIAKI

Fractionation of the rigid polymer, poly(p-phenylene benzobisthiazole) (PBZT) was carried out in dilute solution in concentrated methane sulfuric acid using silica gels as packing material of a column.　Several combinations of the average chain length of the fractionating materials and the average pore diameter of the gels were examined to improve fractionation resolution. The gels with average pore diameter near the average chain length resulted in high fractionation resolution. Single crystals of the fractionated and unfractionated PBZTs were observed by transmission electron microscopy(TEM).　Both single crystals were fundamentally composed of rod crystals with the chain orienting normal to the rods.　The unfractionated PBZT made a cluster of parallel rod crystals, where longer chains penetrated a few rod crystals leaving their chain ends within the neighboring crystalline core. On the contrary, with the fractionated polymer, extended-chain rod-like crystals were dispersed, isolated from each other. TEM lattice fringe showed no chain cilium in the crystalline core.　This structure enabled us to estimate the chain length, corresponded to the rod crystal thickness. Thus we can obtain the molecular weight visibly by TEM, for which a few milligrams of the material is enough for the observation.

P43

SYNTHESIS, MODIFICATION AND CHARACTERIZATION OF AMPHIPHILIC DI AND TRI BLOCK COPOLYMERS OF STYRENE AND 5-VINYLTETRAZOLE OR QUATERNIZED 4-VINYLPYRIDINIUM SALTS

D. GROMADZKI¹, J. LOKAJ¹, M. JANATA¹, P. ŠTĚPÁNEK¹, O. DIAT², F. NALLET³

Well-defined amphiphilic block copolymers composed of hydrophobic polystyrene block and hydrophilic/ionizable block can self-assemble into nanoscopically ordered structures. The aim of this project was the praparation and morphological characterization of diblock and triblock copolymers that can be used as model membranes for fuel cell applications.

Block copolymers comprising poly(styrene-co-acrylonitrile) and polystyrene-b-poly(styrene-co-acrylonitrile) were synthesized by nitroxide-mediated radical polymerization (NMP) [1]. In the second step the acrylonitrile groups were reacted with sodium azide by using the 1,3-polar cycloaddition reaction to yield copolymers with 5-vinyltetrazole units [2,3].

Several AB and ABA block copolymers of styrene and 4-vinylpyridine were transformed to quaternized products using methyl iodide or 1-bromooctane [4,5]. The film flexibility of the quaternized polymers were improved by blending with appropriate amount of dioctylphthalate. The obtained materials were characterized by IR spectroscopy, dynamic light scattering, DSC, X-ray diffraction, AFM microscopy and conductivity measurements.

This work has been supported by European Sience Foundation (ESF) and from the Grant Agency of the Academy of Sciences of the Czech Republic.

1. J. Lokaj, L. Brozova, P. Holler, Z. Pientka, Coll. of Czech. Chem. Commun. Vol. 67(2): 267-278, (2002)
2. P.N. Gaponik, O.A. Ivashkevich, V.P. Karavai, A.I. Lesnikovich, N.I. Chernavina, G. T. Sukhanov, G. A. Gareev, Die Angewandte Makromolekulare Chemie 219, 77-78 (Nr. 3823), (1994)
3. N.V. Tsarevsky, K.V. Bernaerts, B. Dufour, F.E. Du Prez, K. Matyjaszewski, Macromolecules 37, 9308-9313, (2004)
4. S. Gauthier and A. Eisenberg, Macromolecules 20 760-767 (1987).
5. A. Huang, Ch. Xiao, L. Zhuang, J. of Appl. Pol. Sci., Vol. 96, 2146-2153 (2005)

P44

CARBON-CHAIN POLYMERS WITH 1,3,4-OXADIAZOLE RINGS

V.N. KIZHNYAEV, F.A. POKATILOV, L.I. VERESHCHAGIN, A.I. SMIRNOV

Heterochain polymers, containing 1,3,4-oxadiazole cycles in the basic chain, are well known and widely applied as chemo- and thermoresistant, semi-conductive, fibre-forming and gas separating materials. At present, there is lack of information about synthesis and properties of the carbon chain polymers with side oxadiazole cycles. The vinyl monomers with 1,3,4-oxadiazole cycles can be obtained from 5-vinyltetrazole at one stage under the action of acylating agents on them. By analogical way poly-5-vinyltetrazole is converted into poly-2-vinyl-5-R-1,3,4-oxadiazoles.

If the synthesis of vinyl monomers is conjugated with some restrictions on account of a high vinyl group reactivity, the reaction of polymer analogical covertion has no limitations and it makes possible the polyvinyloxadiazoles with different substituentes in the cycle to be obtained.

The vinyl monomers with 1,3,4-oxadiazole cycles are easily polymerized at conditions of radical initiation, creating polymeric products with high yields and molecular masses (up to 4´10⁶). Water has a strong activating effect on oxadiazole monomer polymerization: in water medium the increase of k_p/k_t^0,5 parameter is twenty fold higher than that in aprotonic solvents.

The polymers with 1,3,4-oxadiazole cycles appear either as amorphous powders or rubber-like products, which are decomposing without melting at T> 300 ^oC. Poly-2-vinyl-5-methyl-1,3,4-oxadiazole is non ionogenic, water soluble polymer, capable to complexing with ion of polyvalent metals creating electric-conductive pellicle covering.

P45

PHYSICAL PROPERTIES AND BIODEGRADATION CHARACTERISTICS OF CHITOSAN/PVA BLEND FILMS

T. NAKASHIMA¹, M.I BANDOU², Y. BIN² Y. NAKANO², M. MATSUO²

As one of environmental protections, the physical properties, antibacterial activity and biodegradation characteristic of the chitosan films were studied to check the possibility as new industrial materials. However, the draw-ability of chitosan films was very poor and the improvement of the draw-ability was tried by introducing PVA into chitosan. The biodegradation test was also carried out. Two separate solutions of PVA(3g/100ml) in hot water and chitosan(2g/100ml) in 1% acetic acid were prepared. And then, the two kinds of solution were blended, and the solvent was evaporated at room temperature. The resultant cast films were immersed in 4%NaOH aqueous solution for 2h. The maximum draw ratio of the chitosan/PVA blend film increased with increasing PVA content. The storage modulus E' of the undrawn films decreased with increasing PVA content, while the peak of loss modulus became higher in the range of 30-50^oC. Furthermore, the value of E' increased significantly by elongation because of the preferential orientation of PVA and chitosan crystallites with respect to the stretching direction. The Young's modulus reached ca. 20GPa for the 22/78 composition with 7 times. This indicates that chitosan/PVA blend films have a possibility to be utilized as commercial materials. The XPS measurements provided that the chitosan molecules appear on surface of the blend film with increasing draw ratio. This tendency was in good agreement with an increase in contact angle. As the next step, another subject, the biodegradation tests for the blend films were carried out. The degree of the degradation was judged by the weight loss in soils. The weight loss was faster for the blends with higher chitosan content, which is more significant in paddy soil than the red clay. Especially, the weight loss of the undrawn films is more pronounced. The further trials for the drawn blend films must be taken into consideration.

P46

N-[(METHACRYLOYLOXY)METHYL]NAPHTHALIMIDE SYNTHESIS AND ITS USE AS THERMO- AND LIGHT STABILIZER IN POLYMERS

M.B. RAHIMOVA, U.O. NEKOV, KH.N. MAVLYANOV, O.M. YARIEV, G.Q. SHIRINOV

Heterocyclic connections with the condensed nucleuses containing atoms of nitrogen, in particular naphthalimyds, have high thermo-and lightstabilizing properties and consequently find wide application in manufacture of polymeric materials with the improved operational properties.

In this connection the synthesis of monomers containing naphthalimyd groups and reception of stabilizing itself polymeric systems on their basis is a rather urgent problem. One of perspective ways is the chemical stalization of the basic monomer with rather small (0,5-1 %) quantity of monomers with stabilizing groups.

We synthesized N-(meth)acryloyloximethylennaphthalimyd in three stages on reaction of Mannikh:

reception of N-methylolnaphthalimyd from 1,8-naphthalimyd and phormaldehyde; 2) reception of N-halogenmethylennaphthalimyd-by interaction of N-methylolnaphthalimyd with HHal; 3) reception of N-(meth)acryloyloximethylen-naphthalimyd-by interaction of N-halogenmethylennaphthalimyd with salts of alkaline metals of (meth)acryl acid.

Composition and structure of monomers are confirmed by the data of the element analysis and methods of IK-, UF- and PMR-spectroscopy. It is established that synthesized monomer is actively polymerized on the free-radical mechanism at the presence of the initiators in medium of the organic solvents.

Kinetic law of their radical polymerization with methylmethacrylate and with styrol is investigated.

It is shown that the introduction of small (0,5-1 weights, %) quantities of parts of monomer-stabilizer to the basic chain results in delay of a photo and thermal destructions.

Kinetic laws of high temperature oxidation of the stabilized samples are investigated. It is possible to make of such conclusions from up given and following investigated:

N-(meth)acryloyloximethylennaphthalimyd is synthesized at interaction of N-halogenmethylennaphthalimyd with salts of alkaline metals of methacryl acid.

It is established that synthesized monomer is actively polymerized on the free-radical mechanism at the presence of the initiators in medium of the organic solvents. Kinetic law of their radical polymerization with methylmethacrylate and with styrol is investigated.

P47

Polymeric compositions on the basis of vinyl alcohol as thickener for printed colours

L.B. IDIEVA, B.A. MAVLANOV, G.A. IXtiyarova

For study of intensity of coloring, nature of tint, the stiffness, stability to a soap and dry friction were selected from different compositions for thickenings. By more effective on nourishing to an index have revealed following composition of thickenings of polymeric composition, г/kg: hydrolyzed polyvinyl acetate -7,5; vinyl alcohol -1,0; CMC - 1,0 and starch -55.

The table

Nourishing of the performance of the printed out tissues

In the table the outcomes of study of correctly selected densities and other compounding(drawing up) compositions are retuned, which one attach printed color sufficient stickiness, toughness, plasticity; and also, allow to gain on a tissue the soft elastic, transparent uniform and strongly locked film not sinking brightness strength. It is visible, that the color hue of the printed out tissues for all compositions essentially does not differ, intensity of coloring the most high for the prescriptions HPVA, PVA, CМC , starch. By the same composition thickenings receive also least inequality of colorings, the most luminance and purity of color.

Reference

1. Mavlanov B.A., Idieva L.B., Choriev I.K., Ikhtiyarova G.A., Learning of influencing of vinyl alcohol on flow characteristics of solutions of starch. The conference of young scientists "The main problems of the subject about polymer ". Tashkent. 2004. b.84-85.

P48

Synthesis OF monomers basED on imides

KH.N. Mavlyanov, U.O. Nekov, O.M. Yariev, M.B. Rahimova, N. Khasanova

The problem of synthesis of high molecular connections containing functional-active groups represents the large interest in view of an opportunity of their use not only for synthesis of polymers having valuable properties, but also for realization of the directed chemical updating. In this connection the synthesis of monomers containing imyde groups is a rather urgent problem. From them (meth)acryl derivative imydes and their copolymers with various monomers find the greatest practical application. In this connection in the given work earlier unknown N-(meth)acryl derivative phthalimyd, sunctsinimyd, maleinimyd and 1,8-naphthalimyd is synthesized on reaction of Mannikh:

					OR
							OR
	CH2O		HHal		MeOCC=C2H
Z(CO2)NH		Z (CO2)NCH2OH		Z(CO2)NCHHal		Z(CO2)NCH2O	CC=C2H
			- H2O		- MeHal

where z=org residuum R=H or CH₃; Me=Na or K; Hal=Cl,Br.

Compound and structure of monomers are established on the data of the element analysis and methods of PMR-, UF- and IK of spectroscopy. It is revealed that the synthesized monomers are polymerized easily and enter reaction of copolymerization with other monomers at the presence of the initiators in medium of the organic solvents. The received polymers have high chemical activity and easily enter polymeranalogous transformation with a large number of reagents. It is possible to make of such conclusions from up given and following investigated: N-(meth)acryl derivative phthalimyd, sunctsinimyd, maleinimyd and 1,8 -naphthalimyd are synthesized at interaction of N-halogenmethyl (derivative with alkaline-metallic salts of (meth)acryl acids. Compound and structure of monomers are established on the data of the element analysis and methods of PMR-, UF - and IK - spectroscopy. It is revealed that the synthesized monomers are polymerized easily and enter reaction of copolymerization with other monomers at the presence of the initiators in medium of the organic solvents. The received polymers have high chemical activity and easily enter polymeranalogous transformation with a large number of reagents.

P49

Study of thermal and thermooxidizing destruction of halogen-containing STYRENE copolymers

G.A. KhudaInazarova, B.A. Mavlanov, O.M. Yariev, D. Amonova

Continious growth of production and the use of copolymers on the basis of styrol dictates the necessity of proper study of their conduct on high temperature, on the influence of oxygen, radiation and etc. These factors stipulate processes which bring to the loss of complex of valuable physico-chemical properties and shortening of periods of materials' services and their goods. Because of all these the study of kynetics and the mechanisms of thermal and thermooxidizing destruction of copolymers is of great value.

The investigation of thermal and thermooxidizing destruction of copolymers of 6-Br-benzoxazolonilmethilacrilate (6-Br-BOMA), 6-Br-benzoxazolthionilme-thilacrilate (6-Br-BOTMA) with styrol with the method of monometrical and thermogravimetrical analysis, and also according to the change of indecular masses in the process of destruction.

According to the facts of isothermal thermograviametration polysterol and copolymers of styrol small amounts (0,5-3,0 mass. %) 6-Br-BOTMA, 6-Br-BOMA modified links of monomer stabilizer, had higher thermofirmness than its the homopolymers of styrol. The most effect of thermostabilization of polymers was observed when their containing in structure 0,5-1,0 mass. % links of monomer stabilizer, that testifies of highly effectiveness of intermolecular stabilization.

Kynetic curves of thermooxidizing disintegration of copolymers have S-figurative character. It means, that the mass of investigated samples slowly decreases at the beginning of destruction, later more quickly in relatively tight intervals of temperature. In spite of this, the effective energy of activation of thermooxidizimg destruction, defined according to the method of double logarithming (Raigh's method) rises from 223,4 to 250,0 kjmole. The most powerful stabilizing influence perform the monomer links of 6-Br-BOTMA, in comparison with the links of 6 Br-BOMA, occasionally, the stabilizing effect of sulphurcontaining monomer links as in the case of copolymer with styrol by thermal and thermooxidizing destruction is connected with reality of the effect of "a strange link" and with the formation of little active radicals by the destruction of copolymer.

So, it must be marked, that synthesized high-molecular antioxidant on the basis of hetero cyclic acryl monomers and styrol is considered to be effective thermal and thermooxidizing stabilizer of polystyrol and for other polymers.

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