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Synthesis and properties of the phosphonium polymers
Thereby, us is designed new froth pontoon, modified hot climatic condition of the Central Asia. The Practical fire-resistant polymeric composition, not requiring com- application of the development can solve many techno-plex technological registration, available, idle time firm to logical, economic and ecological problems of the republic.
References:
1. Cat M., Wolf O. M., Pustomelinik V. P. Fire-prevention actions on oil reference planes. - M.: Stroyizdat, 2005. - 111 s.
2. The Coachman’s seat V. A. “Guard of the air ambience on chemical and petrochemical enterprise”: - M., Chemistry, 2002, - s.245.
3. Mukhamedgaliev B. A., Khabibullaev S.SH. The Processes of the combustion and fireman safety production enterprise: (the monograph). T.: 2012. - 156 s.
4. Demidov P., Saushev V. S. Combustion and characteristic combustible veschestv. - M.: Chemistry, 1995. 279 s.
Habibullaev Saidaziz Shohsuvarovich, Tashkent State Technical University, Faculty Oil and Gas- Head of department for working with academic lyceums and professional colleagues E-mail: [email protected] Akhrarov Bobur Boxodirovich, Tashkent State Technical University, assistant.
Mukhamedgaliev Baxtiyor Abdukadirovich, Tashkent State Technical University, professor.
E-mail: [email protected] Allamuradov Maxmud Umarovich, Nukus State University, assistant.
Synthesis and properties of the phosphonium polymers
Abstract: Nowadys an Epichlorohydrine [ECG] is widely used for the polymers synthesis, and its high reaction ability made it possible to synthesise some epoxy polymers [1; 2].
The reactions of interaction ECG with amino-units are more studied [1; 3] and as a result, the polymers with high reaction activity were received, which are used as superficial active substances, high-molecular stabilizers, polymer glues, etc.
In this aspect the reaction of interaction ECG with trivalent phosphorus units, which is the same according to structure of trivalent nitrogen, is much more interesting for study. We have studied the reaction of interaction ECG with triphenilphospin [TPP] which is less toxic.
Keywords: polymerization, phosphin, viscosity, kinetics, density, velocity, output, potensiometriya, ion exchange, spontaneous polymerization, spectroscopic investigations.
The Experimental Part
The ECG before using was twice outrun (Boiling T=389 K, nfl20=1.4350; JI, n 20=l,1807). In IR-spectrum the line of absorbtion at 2870-3000 sm 1 ‘is reliable to group (CH2). The middle- intensively absorbing line in 850-800 sm 1. is relating to the valents oscillation of CC1 structure group.
In PMR — spectrum the ECG is characterized by two multiplete signals at 2.5 and 2.75 m. p.
This is explained by the form of these signals which is the same with the signals in PMR spectrum of propilen oxide [5; 6].
The multiplete complex signal situated in more weak fields with a centre 3.45 is reliable to the two proton metilen groups which are connected with chloride atom.
Triphenilphosphin is the white crystals recrystalized twice before using from the mixture of ethanol and diethyl ester.
There are some absorbed zones of weak activity in IR - spectrum.
IR -, PMR - and UV- spectroscopic investigations show that this product is a linear polymer, containing guarternary phosphonium groups in its external bonds.
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Section 9. Chemistry
CH, - CH - CH2C1 + P(C6Hc), —> - CH2 - CH - О -
\ / I
О CH2 (!)
(C6H5)3P+C1-
Accordind to potentiometric titration of the polymers water solution, the polymer contains chlor ions 10+ 1.0%, that is near the theoretical content of chlor ions in polymer, received of equimolecular composition.
Thus the 1-st stage of the polymersization is Menshutkin reaction — the quarternization of TPP by epychlorhydrin.
For the investigation of TPP and ECG interaction the IR and UV-spectrums of the 1-st and final products were registered, so as PMR spectrum of the 1-st components, their mixtures during start and time.
In the polymer IR — spectrum, made on the basis of TPP and ECG interaction, the stripe of deformation oscillation P-Ph is in the low -frequent zone up to 1350 sm” 1 in comparision with the zone in TPP- spectrum. This fact is explained by the low strength of P-Ph unit because of quarternizied phosphor.
The valent oscillation C- Cl unit (850-800 cm’ x) of ECG CH2-group disappears because of formation new stripe in 1350 cm’ *, zone.
In the zone 1050-1100 cm” 1 new intensive absorbtion stripes appear and they are the result of valent oscillation of the simple ester unit (C — O — C) because of the opening of epoxy — groups (1260,93 sm” x) ECG during interaction with TPP. The stripe in the zone of 930 sm” 1 is partially reserved, characterizing epoxy -groups, that was proved by the definition of epoxy number which was equal to 1,18 according to the method (7).
In PMR — spectrum of the polymer the signals of phosphonium benzene rings protons appear by 7,80 m. d. as a multiplete and protons of the qroups O — CH2-CH and P+- CH2 ECG as a multiplete with a centre 3,8 m. d. The groups of multiplete signals by 2,33 m. d. probably because of the polymer chains formation, in which CH and CH2 groups are more shield than in the first components. The ratio charge of the protons signals of benzene and non — benzene rings is about 1:2,2, that practically corresponds to the proposed structure (fig.1).
Fig. 1. PMR-spectrs: 1 - tryphenylphosphin, 2 - epychlorgydrin
Fig. 2. UF-spectrs: 1 - tryphenylphosphin, 2 - epychlorgydrin. 3 - polymer
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Synthesis and properties of the phosphonium polymers
The presence of quarternary phosphonium group in the polymer structure was proved by UV — spectrum (fig.2). So in the zone of 240-260 nm there are absorption stripes which are typical for the quarternary phosphonium group. The spectrum investigation shows that the beginning of TPP and ECG interaction is the quarternization (Menshutkin reaction which involves the epoxy cycle into this one and the opening of this process leads to the receiving of the linear polymers.) What is the mechanizm of this process?
The kinetic regularity of TPP and ECG interaction by dilatometrical method was received. It is proved, that efflctive ingibitors of the radical polymerization
such as hydroquinone, air oxygen, stable imine oxide radicals, 2.2.6.6-tetramethylpiperidine — 1 — oxide don’t influence on the polymerization speed and that proves the non — radical character of the process. In EMR — spectrum of TPP and ECG system with different conditions the formation of radical is not seen. The influence of solvent nature on the starting speed of TPP and ECG interaction has been studied.
The investigations were made taking into account the homogenity of the medium. The results showed that the more the solvent dielectric penetrability the more the reaction speed (fig. 3) and that is connected with the increasing of Menshutkin reaction which is the first stage of the process.
Fig. 3. The dependence of the degree of conversion of the duration of the polycondensation at different temperatures: 1-343 К, 2-353 К, 3-363 К
The study of the temperature influence on the interaction velocity of TPP and ECG proves that the temperature which is move than 10° increases the interaction velocity in 3 times, and its dependence on the temperature is under the meaning in accordance with Arenius equation. The effective energy of activation in accordance with the table in ethanol is 12,79 kkal/mol, that is the same with the activation energy according to Menshutkin reaction and is the 1-st stage of the process.
So we may suppose that Menshutkin reaction is the limited stage of the process.
On the basis of the experimental results (9, 10) we may suppose the following interaction scheme of ECG with TPP. The atom of ECG haloid makes connected with it carbon of chlormethyl group the place of the first nucleophilic attack and the 1-st stage of the process is the quarternization reaction (Menshutkin reaction):
CH, - CH - CThCl + P(C6Hc), —> - CH2 - CH - О
\ / I
о CH2
(C6H5)3P+C1-
(2)
As a result of electron density moving in the quar-ternization molecular the tense of three nominal cycle becomes low and under the pressure of anione haloid
active ion pair of oxirane cycle the opening reaction of the polar carbon — oxygen link is taken place.
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Section 9. Chemistry
CH2 - CH
\ / I
0 CH2 (C6H5)3P+Cr
Cl - CH2 - CH - 0 CH2
(C6H5)3P+
(3)
The quarternization and the opening reaction are the stages influencing on velocity according S M2.
The chain growing is according to anione polymerization while acting particle and then with dimer and trimer, etc.
Cl-CH2-CH-0 + CH2-CH -► Cl-CH2-CH-0- CH2 - CH - CH О I I I
CH2 CH2
(C6Th)3P+ (C6Th)3P+ Cr C6Th)3P+Cf (C6Th)3P+
(4)
The chain break is taken place probably because of acting equimolecular substances or by adding of the solvent
proton with macroanione according to schemes
(5)
For the experimental test of the received kinetic scheme ECG were investigated. The results are shown in Table 1 the kinetic order regularities of the interaction TPP and
Table 1. - The dependence of the starting velocity of the process TPP and ECG interaction on the components concentration. T = 323 K, ethanol
№ [ANG]m ol/l TFF mol/1 v 10 6 mol 1 c - 6+lgv n ndl/r reaction order n
1 0,5 0,05 0,62 0,79 0,105
2 0,5 0,075 1,17 1,06 0,122 1,1
3 0,5 0,1 2,06 1,31 0,183
4 0,5 0,125 3,17 1,47 0,21
5 0,25 0,5 4,66 0,66 0,247
6 0,5 0,5 9,83 0,962 0,18 0,88
7 0,75 0,5 12,10 1,04 0,166
8 1,00 0,5 17,3 1,23 0,131
9 0,25 0,25 3,07 0,127 0,342
10 0,5 0,5 9,83 0,962 0,122 1,9
11 0,75 0,75 17,71 1,27 0,118
12 1,00 1,00 39,28 1,59 0,117
So on the basis of kinetic data (table 2) of TPP and ECG interaction the reaction order was determined according to components which are equal 1,1 and 0,88 correspondingly, so as the general order of reaction which is equal 1,9. The summary 2 — nd order and the components order, which is near 2, confirm our suggestion aboutbimolecular substitution reaction. The equation of general polymerization ECG and TPP is the following: Vcommon = Kcommon [ECG] [TPP]'
This equation is the same as in Menshutkin reaction, which is limited stage of polymerization process, except the difference in reaction order by monomer. The highest
— 0-CH2-CH —>
1"
(ОВД* P+C1
meaning of the order proves that with quarternarized chains of ECG there are non-quarternarized chains. This is confirmed by study of IR — spectres of polymers received during ECG and TPP intereaction and we see that the absorbing zone is not disappeared absolutely at the level of 850-880 sm, relating to the deformation oscillation C-Cl-group.
The difference in the Cl-ion meanings, detennined by potentiometric titration (Cl — 10,01%) in comparison with the element analysis (Cl = 13,6%) is also proves our suggestion.
0-CH2-CH — CH2C1
(6)
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Synthesis and properties of the phosphonium polymers
This is explained by the following together with Zwitter-ion polymerization there is anionic polymerization of the non- quarternarized ECG molecules with the opening of high — polar carbon — oxygen chain of the epoxy cycle as oxides olefines.
Thus the synthesized polymer is a powder of brown colour, stable to long storage with 428 K, the density determined by pycnometer method is 1,388 g/cm 3, it is solved in dymethilphormamid, ethanol, methanol, water and in the other polar solvents. The study ofviscosity proved that it is the typical polyelectrolyte and the dependence of c/n from c for water solvents of the synthesized polyelectrolytes is of linear character which proves that water solvents behavior is described by Fuoss — Strauss equation (12).
The dependence of polymer solution viscosity on the concentration of phosphonium polymers in the presence of strong electrolyte 0,25 KC1 solution is of straight — line character, because of creation screen “fur coat “ anti-ions around macro-molecular ions.
The molecular mass of polymers was determined by the method of high — speed sedimentation using the equation of Flory -Mandelkern which was equal to 51000.
Thus on the basis of kinetic, spectral and chemical methods was studied the reaction of interaction ECG and TPP and supposed polymerization process was shown, that is able to receive the catione polyelectrolyte, contained in the side chains the quarterized groups.
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6. Nuclear- magnetic resonance spectrum of the “ Varian Company”, n. 32, 1968.
7. Kalinina Z., Motorina M., Karaputadze E. “The analysis of condensated polymers”, M., 1986.
8. Loginova N., Govurina R., Kulicheva A. “Copolymerization character investigaation N, N-DMAEMA and its chlorohydric salt”, (high - molecular units), 10B, n.6, 1968, 422 p.
9. Askarov М., Jalilov A. «lonogenic polymers synthesis «, Taskent, 1978, 60 p.
10. Horner L., Jurgeleit H., Klupfel K. Liebigs Ann. Chem 591, Zur amionotropen polymerization saus lousung bu olefinen (phosphine III).
11. Furukava J., Saegusa T. “Aldehydes and oxides polymerization”, - M., 1965, P. 176.
12. Fuoss R. M., Strauss U. P. Polyelectrolites. J. Pol. Sci, 1948, v3. N2. p. 242-263.
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