REACTIVE PEROXIDE MACROINITIATOR FOR CROSS-LINKING BIOCOMPATIBLE POLYMERS

2018;
226-235
1
Lviv Polytechnic National University
2
Lviv Polytechnic National University
3
Ivan Franko National University of Lviv
4
Lviv Polytechnic National University
5
Lviv Polytechnic National University

The series of reactive peroxide macroinitiators (RC) based on acryl amide (AcAm), butyl methacrylate (BMA), maleic anhydride (MA) and peroxidic monomer 5-ter-butylperoxy-5-methyl-1-hexene-3-yne (PM), which can be used for biocompatible polymer cross-linking, were synthesized via radical copolymerization in organic solvent.

The studies of polymerization kinetics witness that the copolymerization of PM:AcAm binary mixture is going slowly due to the low values of the rate constants of crossover propagation. At the same time, for three- and four-component systems the polymerization process proceeds with high rate and up to high conversions. An increase in the content of peroxidic monomer PM in the reaction mixture causes a decrease in the rate of polymerization, which is explained by the action of PM as a weak inhibitor of polymerization. The content of monomer units in the synthesized copolymers was determined and the influence of the components concentration of the reaction mixture on RC composition was investigated. The content of the monomer units in the copolymers changes symmetrically with the content of the corresponding monomers in the reaction mixture, and the composition of the copolymer is close to the ratio of monomers in the initial solution due to high conversion of monomers. The increase in the peroxide monomer concentration results in the decrease of molecular weight of the obtained peroxide-containing copolymers because of chain transfer reactions to PM molecules. The synthesized copolymers are characterized by a unimodal distribution of molecular weights, with a rather high polydispersity index – kpol = 3.7-3.9. The structure of the copolymers was confirmed by gas chromatography, FTIR and 1H NMR spectroscopy, elemental analysis, reverse potentiometric titration.

The dependence of the surface activity of peroxide-containing RС on their chemical structure was studied. The resulting peroxide-containing RC possess surface-active properties, reduce the surface tension at the aqueous-alkaline solution - air phase boundary. The kinetics of decomposition of peroxide-containing copolymers at different temperatures was studied. The process proceeds according to the mechanism described by the first order kinetic equation. The determined activation energy of the decomposition process for peroxide groups was 135-145 kJ/mol depending on RC composition. The results of complex thermal analysis confirm the presence of peroxide fragments in the structure of copolymers. On all derivatograms on the DTA curves the pronounced peaks are present in the region 420-520 K, which correspond to the exothermic effect of the decomposition of PM peroxide groups.

The series of reactive peroxide macroinitiators (RC) based on acryl amide (AcAm), butyl methacrylate (BMA), maleic anhydride (MA) and peroxidic monomer 5-ter-butylperoxy-5-methyl-1-hexene-3-yne (PM), which can be used for biocompatible polymer cross-linking, were synthesized via radical copolymerization in organic solvent.

The studies of polymerization kinetics witness that the copolymerization of PM:AcAm binary mixture is going slowly due to the low values of the rate constants of crossover propagation. At the same time, for three- and four-component systems the polymerization process proceeds with high rate and up to high conversions. An increase in the content of peroxidic monomer PM in the reaction mixture causes a decrease in the rate of polymerization, which is explained by the action of PM as a weak inhibitor of polymerization. The content of monomer units in the synthesized copolymers was determined and the influence of the components concentration of the reaction mixture on RC composition was investigated. The content of the monomer units in the copolymers changes symmetrically with the content of the corresponding monomers in the reaction mixture, and the composition of the copolymer is close to the ratio of monomers in the initial solution due to high conversion of monomers. The increase in the peroxide monomer concentration results in the decrease of molecular weight of the obtained peroxide-containing copolymers because of chain transfer reactions to PM molecules. The synthesized copolymers are characterized by a unimodal distribution of molecular weights, with a rather high polydispersity index – kpol = 3.7-3.9. The structure of the copolymers was confirmed by gas chromatography, FTIR and 1H NMR spectroscopy, elemental analysis, reverse potentiometric titration.

The dependence of the surface activity of peroxide-containing RС on their chemical structure was studied. The resulting peroxide-containing RC possess surface-active properties, reduce the surface tension at the aqueous-alkaline solution - air phase boundary. The kinetics of decomposition of peroxide-containing copolymers at different temperatures was studied. The process proceeds according to the mechanism described by the first order kinetic equation. The determined activation energy of the decomposition process for peroxide groups was 135-145 kJ/mol depending on RC composition. The results of complex thermal analysis confirm the presence of peroxide fragments in the structure of copolymers. On all derivatograms on the DTA curves the pronounced peaks are present in the region 420-520 K, which correspond to the exothermic effect of the decomposition of PM peroxide groups.

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