SVIBOR - Project code: 1-07-003

MINISTRY OF SCIENCE AND TECHNOLOGY

Strossmayerov trg 4, HR - 10000 ZAGREB
tel.: +385 1 459 44 44, fax: +385 1 459 44 69
E-mail: ured@znanost.hr

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Project code: 1-07-003


MIXTURES OF REACTIVE ALTERNATING AND STATISTICAL COPOLYMERS


Main researcher: VUKOVIĆ, RADIVOJE (53914)


Assistants
Type of research: applied
Duration from: 01/01/91. to 12/31/93.
Papers on project (total): 71
Papers on project quoted in Current Contents: 30
Institution name: INA, Razvoj i istraživanje, Zagreb (61)
Department/Institute: INA-Industrija nafte, Research and Development
Address: Savska cesta 41/X
City: 10000 - Zagreb, Croatia
Communication
Phone: 385 (0)1 233-16-66/2033
Phone: 385 (0)1 21-63-16
Fax: 385 (0)1 21-52-73
Phone: 385 (0) 1 611-55-11
Summary: Studies of the miscibility behaviour of polymers are extended to the mixtures of the modified PPO with polystyrene derivatives and functional alternating copolymers prepared by copolymerization of electron-donor-acceptor monomers. The copolymerization was performed in the presence of free radical initiators. Alternating copolymers which contain mesogenic groups in side chains were prepared, thus enabling the extension of the mean-field theory to blends which contain rigid groups capable to form densely packed domains of regular structures. During the course of our studies on the preparation of new polymeric materials the water-soluble alternating copolymers as potential additives in the oil fields exploration were prepared. A part of the studies was the preparation and characterization of thermostable polymers of low flammability. Studies of the mechanism of alternating copolymerization of ŕ-methylstyrene with N-substituted maleimides under the participation of CT-complexes was extended to the copolymers which contain the macrocyclic polyethers in the side chains of N-substituted maleimides. By means of WAXD and SAXD it was established that homopolymers and copolymers show interplanar spacings characteristic for the comb-like polymers with the structures attributable to 3-one helix. Significant difference in the ability of complexation of polymers which contain macrocyclic polyethers and low molecular mass analogues was found in equilibrium extraction of sodium and potassium ions from aqueous solution. Starting from the Flory's equation of state (EOS) the group - contribution version EOS for polymer solutions was developed by our group and successfully applied for liquid-liquid equilibria (LLE) calculations in polymer systems. All polymers prepared as well as their blends were characterized by means of thermal analysis, spectrometric methods, by WAXD and SAXD, HPGPC, mass spectrometry, polarized light microscopy.

Keywords: Synthesis, alternating copolymers, random copolymers, water soluble polymers, electron-donor-acceptor monomers, mesogenic groups, comb-like structure, miscibility, segmental interaction parametars, phase separation, mean-field theory, GC-Flory EOS, LLE

Research goals: Aims of the present research program are the studies of the relationship between properties and structure of polymeric materials on molecular and supermolecular level. This approach enables the preparation of new polymeric materials with the desired properties. Of special interest in the development of these, often called high performance materials, is the preparation of polymer-polymer blends. However, the prediction of properties of new blends on the basis of the mean-field-theory, usually used, is limitted due to the lack of model parameters, i.e. interaction parameters between polymer segments. One of the approaches which can extend the knowledge of the miscibility laws are studies of the properties of blends which consist of polymers and copolymers of known chemical and macromolecular strucure. This also enables the estimation of more model parameters. With this aim a number of new copolymers of St, ŕ-MeSt, á-MeSt and phenylvinyl alkyl ethers (alkyl = Et, sec-Bu) with N-substituted maleimides (RMI) are prepared: R = H, Me, Et, n-Pr, iso-Pr, n-Bu, terc-Bu, n-Hex, benzo-15-crown-5, 2,4,6-tribromphenyl, p-C6H4COOcholesteryl, (CH2)5-COOcholesteryl, 4-phenoxyphenylene. The water soluble copolymers of St and MAn and copolymers of vinylaromatic components of pyrocondensate with MAn are also prepared. Steric parametars are controlled by the selection of side chain substituents, while microtacticity was controlled by solvent, concentration and temperature. In order to study the miscibility of statistical and alternating copolymers, a series of sulfonylated PPO copolymers were prepared. As far as we know this type of studies has not been described so far. Several copolymers prepared in our laboratories contain rigid mesogenic groups in side chains of comb-like polymers. These copolymers having characteristic mesomorphic properties are of interest as additives in the preparation of polymer blends. Liquid-liquid equilibria (LLE) calculations for polydisperse polymer solutions were performed, taking in the consideration the molecular weight distribution in the case of the homopolymer solutions, and both, the molecular weight and the comonomers composition distributions in the case of copolymer solutions. We have also considered the extent of LLE calculations to which we can obtained a qualitative or semiquantitative understanding of miscibility in polymer blends through the use of the Entropic-FV and the GC-Flory EOS thermodynamic models. The capability of mentioned models to predict miscibility/immiscibility in polymer blends was evaluated and the obtained results were compared with the experimental results as well as with mean-field theory.

COOPERATION - PROJECTS


  1. Name of project: JF-902 (NSF) Effect of the chemical structure on polymer miscibility
    Name of institution: University of Massachusetts, Polymer Science and Engineering Department
    City: 01003 - Amherst MA, USA

COOPERATION - INSTITUTIONS


  1. Name of institution: Institut "Ruđer Bošković"
    Type of institution: State institute
    Type of cooperation: Occasional exchange of information
    City: 10000 - Zagreb, Croatia
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