CC BY
16
Section 12. Chemistry
Section 12. Chemistry
DOI: http://dx.doi.org/10.20534/ESR-17-3.4-118-119
Shikhaliyev Kerem Seyfi, Professor,
Azerbaijan State of Oil and Industry University
Azerbaijan, Baku, E-mail: [email protected] Salimova Nigar Azizaga, Azerbaijan State of Oil and Industry University
Azerbaijan, Baku,
Thermodinamics and mutual distribution of macromolecules in the systems: chlorine-chlorocontaining polymers
Abstract: It is shown that the values of the papameter of solubilite metod and OGH and TDT can utverzhdat?chto for predicting solubilite parameter for polemers.
Keywords: polymer-polymer mixtures, chlorinated polyethylenes (CPE), polymethylmetaacrylate (PMMA), polyethylene of low density (PELD), chlorcarboxylated polyethylene of low density (CCPE) chlorinated PELD (CPE), polyvinyl chloride (PVC), criteria of compatibility, chlorination, upper and lower critical temperature, specific holding of volume, Qibbs mixing energy, parameter of solubility, distribution of macromolecules, chlorine-chlorocontaining polymers, polar groups, thermody-namical compatibility, sorbate, gas-carrier.
Need of industry in new polymer materials, possessing by necessary properties for work in extremal conditions continu-osly increase. It is may be achieved by synthesis of the new types of polymers and creation of polymer compositions where properties of the separate components additively are the complement of one another.
Therefore development of different polymer compositions by simplification of technology its production and processing, shortening expenditures on production of materials with necessary complexes of properties is extremely actual.
For production of the new types ofpolymer materials by use of polymer-polymer mixtures determination of its thermodynamical stability as one of the factors, determing a structure and properties of the final product acquire essential interest.
Use of chlorcontaining polymers in industry, stipulated by complex of enough good properties determine the desire to improvement of series them indices. From this point ofview research of thermodynamical conduct of chlorpolymers mixtures with another chlorpolymers, having in their composition the polar groups of chlorpolymers present a special interest.
In the work the thermodinamical compatibility of chlorinated polyethylenes (CPE) with different chlorination degree, shown that by dominant of dispersion forces compatibility is possible by proximity parameters of solubility and interaction. Analysis of compatible and incompatible pairs shown that:
- by difference in chlorine content, reaching;
- 18 mas% A Hm is relatively high (+0.519 Joul/g).
Owing to big difference in thermal coefficients expansion -T A Sm is positive (+ 0.276 Joul/g). The total energy A Gm is positive (+ 0.795 Joul/g). From this it is conduded that a mixture must be inmixing (incompatible);
- by approximately near content of chlorine (27 and 35 mas%) the dispersion forces between molecule, owing to similarity lead to little interaction degree. By calculation, a big difference in thermal coefficients expansion gives a little negative value A Hm (- 0.108 Joul/g). But this difference causes a big positive -T A Sm (+ 0.761 Joul/g) and in result A Gm (+0.653 Joul/g) doesn't favoruable to mixing.
It have been determined, that uniting criteria of compatibility A Gm < 0 in total case is carried out, although a structural compatibility is possible also by little positive values of A Gm. In all cases the surplus energy A Sm doesn't favourable to mixing, but by proximity ofper cent content of chlorine and coefficient of thermal expansion the compatibility is possible.
In the work the system (CPE - PMMA) have been studied. It was shown that polymethylmetacrylate (PMMA) is compatible with chlorinated polyethylene by appointed chlorination degree of the last and only by appointed temperatures. It have been determined that a mixtures have an upper and lower critical temperatures of solubility.
The present work devotes to study of thermodynamic interaction between components mixture of chlorocontaining polymers, one of which in its composition have a polar carboxylic groupings. By that the method of turned gas chromatography have been used, which at the last time is widely applied for study of polymers compatibility.
As initial raw materials the industrial samples of polymers: chlo-rocarboxylated polyethylene of low density PELD (CCPE) with contact of chlorine equal 27 mas% and carboxylic groups 1.2 mas.% correspondingly, chlorinated PELD (XPE) with chlorine content 35 mas.% and polyvinylchloride (PVC) by brand C-70 have been used, the characteristics of which are presented in the table.
Thermodinamics and mutual distribution of macromolecules in the systems: chlorine-chlorocontaining polymers
Table 1. - Characteristic of investigated polymers
polymer content of chlorine mas.% content of car-boxylic groups, mas.% alchohol ethyl propyl alcohol D: B:0 M-10-4 M-10-3 M/M by 298 K, g/sm 2 k-M0-4 TK c
CCPE 2.7 1.2 - - 3.5 5.7 6.11 1.0713 8.64 239
CPE 35 - - - 3.5 5.8 6.08 1.0713 5.80 263
PVC 57 - - 15.0 47.0 3.19 1.3446 3.09 349
packing products - - - 4:3:1 3.0 10.2 2.95 1.2284 4.63 238
SKEP - - 1.0 - 9.0 30.2 2.98 0.8723 8.59 2.11
D: B:0* - 4.4 - diphenylmethanediisosianate; 1.4 - butadiol: oligoethylenebutyleneglycol adipinate
For research the chromographycal columns with individual polymers and its mixtures by correlation of components 30:40, 50:50, 70:20 have been prepared/In the work the chromatograph "Tsvet-100" with flame ionization detector have been used. As a
gas-carrier the nitrogen and as sorbate ten solvents, relating to different classes (alcohols, ketons and chloroderivatives of aliphatic hydrocarbons) have been used.
