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AZ9RBAYCAN KIMYA JURNALI № 2 2017
UDC 541.64
THE RESEARCH OF COPOLYMERIZATION REACTIONS OF ALLYL AND VINYL ACETYLSALICYLATES WITH MALEIC ANHYDRIDE
N.Sh.Rasulzade, A. H.Az iz ov, G.M.Safarova, N.Sh.Rasulov
The Institute of Polymer Materials of ANAS [email protected] Received 18.05.2016
The copolymerization reactions of allyl- and vinyl ether of salicylic acid with maleic anhydride (MA) have been researched. It was shown that with transferring charge copolymer monomer pairs make complex and these complexes form rotational structure macromolecules with entering polymerization reaction easily. Equilibrium constant of complex among monomer pairs was defined with the help of PMR spectrums: for Alasp .. .MA couple Kc=0.097 and for Vasp.. .MA Kc=0.028. Via Chromatographic method -Jaaks equation relative activities of monomers have been identified. For Alasp-MA comonomer is r1=0.022, r2=0.038 and for V^p- MA comonomers r1=0.036, r2=0.028. Being close to zero of relative activities of monomer in both case in copolymerization reactions prove that, those monomer pairs are inclined to co-polymerization. The relativity of monomer pairs and the influence to the reaction of the concentration of monomer mixture in the copolymerization reactions of Vasp and MA is studied. The nature of curves is proved that the copolmerization reactions occurs by "mixture" mechanizm by the presence of free monomers and monomer complex.
Keywords: allylacetilsalicylic ether, vinylacetilsalicylic ether, copolymerization, complexes made by
transfer of charge.
Introduction
Recent years the interest to the synthesis of polymers keeping biological active groups is increasing. Thus, such kind of polymers are widely used in obtaining long effective medications, antiseptic polymer coverings, paint and so on.
On the other hand, such kind of polymers being used as bactericidal additions in obtaining antibacterial polymer composites are considered more perspective. Because washing out polymer additions from material surface happens during longer time in comparison with little molecular antibacterial compounds and using time of such coverings increases. One of the polymers with antibacterial property are polymers containing salicylic groups. One of the obtained methods of polymers is polyvinyl salicylate polymers obtained with mutual effects of poly-vinyl alcohol and acetylsalicylic acid by polymer analogy conversion method [1]. In our earlier investigations it was shown that polymers keeping salicylic groups have high antibacterial properties [2].
In our earlier investigations the obtaining methods of monomers - (met)acryloyl salicylates keeping salicylic groups and copolymers on the base of them were reported. It was
shown that these monomers and also methyl methacrylate copolymers obtained on their base have high antibacterial properties [3].
The purpose in presented work is the research of copolymerization reaction of allyl and vinyl ethers (Alasp and Vasp) of acetylsalicylic acid with maleic anhydride (MA) for the obtaining polymers keeping acetylsalicylic group. MA is chosen as comonomer because of the solubility of obtained copolymers.
Experimental part
The synthesis of monomers. Vasp monomer was obtained due to mutual effect of vi-nylacetate with aspirin by trans-vinylization reaction [4]. d2° =0.93 and n D° =1.4200. The synthesis of Alasp monomer was carried out on the base of exchange reaction of Na salt of aspirin with allylchloride [5].
The synthesis of copolymers of Vasp and MA. 0.059 mol (10.30 g) vinylacetil salicylic ether (Vasp), 0.05 g (4.99 mol) maleic anhydride, 0.2% benzoyl peroxide and 35 ml dioxane mixture are poured into the glass ampoule. After freezing solution its air is take off with nitrogen. Reaction product is precipitated in methanol, is washed with ether and dried at
400C temperature in vacuum wardrobe till it gets constant weight.
The obtained white power polymer me-thyl-ethyl-ketone is solved well in benzol and chlorine hydrocarbon. Yield is 9.89 g (68%) ^mei - 1310C, characteristic viscosity is identified in benzol solution in "Ubbelohde" visco-zimetry 0.11dl/g were recorded.
The kinetics of copolymerization reaction is studied by dilatometric way [6].
The content of monomer mixture before and after reactions is identified by the "Chrom-5" gas-liquid chromatograph.
IG spectrums in "VARIAN", PMR spectrums were recorded in dayterium chloroform in "Bruker" spectrometry.
Results and their discussions
The formation of donor (D)-acceptor (A) type complexes (complexes formed by charge transfer) among the molecules of allylacetilsa-licylate maleic anhydride was mentioned ago [7]. Taking into account this PMR spectrum of monomers in separate and in different proportions mixture have been recorded. Rate change of chemical sliding of protones belonging to MA molecule in PMR spectrum of different composition mixtures of MA and Vasp monomers show the formation of [D... A] type complex.
D A
CH2 II 2 HC
+ II ^O
X-CH HC -C%
CH2 HC—C
■h—2—
X-CH HC—C
,O
:o
O
OCOCH
X =
3
COO—
OCOCH
|r COO-CH2
The changing in sliding rate increases with enhancing of mol proportion of donor in monomer mixture. Equilibrium constant (Kc) of complex forming process was graphically calculated by Ketalaar equation [8] (Table 1).
[D M A D...A],
[ D...A] ^ =[D] [A] .
Table 1. Indicators for the calculation of complex forming constants (Kc) of allyl and vinyl acetylsalicylates (D) with maleic anhydride
Monomer [A], [D], 1/Aeks, 1/D,
pairs mol/l mol/l ppm l/mol
Alasp-MA 0.1 1.0 42.0 1.00
0.1 2.0 17.0 0.50
0.1 4.0 12 0.25
VaSp-MA 0.1 1.0 71.0 1.0
0.1 2.0 39.0 0.50
0.1 4.0 11.0 0.25
According to the calculation for Alasp-MA monomer pairs is Kc=0.097 and for Vasp-MA monomer couple is Kc=0.028.
Rates of copolymerization constants of Alasp and Vasp with MA were calculated by chromatographic Jaaks method [9] (Table 2).
Table 2. Results of copolymerization reactions of allyl and vinyl acetylsalicylic ethers with maleic anhydride
Preliminary Composition of
composition of monomer
monomer mix- mixture after r\ r2
ture, mol.% reaction, mol.%
№ [M2]0 [MjL [MJt
AI -^"•asp MA
10 90 8.73 89.53 0.022 0.038
90 10 85.6 5.85
Vasp MA
10 90 8.47 89.53 0.036 0.028
90 10 87.9 8.76
For Alasp-MA monomer pair r1=0.022, r2=0.038 and n=0.036, r2=0.028 for Vasp-MA monomer pair. Being close to zero of rates of relative and activities in copolymerization reactions in monomers prove that copolymers have alternative structure. Having C=O (1725 sm-1), C-O-C (1150 sm-1) copolymer strips in IR spectrums and (1630-1640) absorption strips belonging to C=C contact are one the factors proving copolymer formation.
One may come to conclusion that, complex formed among monomers effect their relative reactivity. MA macro radicals formed from monomer pairs MA molecule cannot join MA molecule and (MA...Vasp) complex by MA component. The created complex behaves like free monomer. The dependence on the composition of monomer mixture of general speed of copolymerization reactions for Vasp-MA monomer pairs was studied (Figure).
36
N.SH.RASULZADE et al.
6
> 5
1 4 о 3
* 2
1
220
40
880
6600
[MA], mol.%
The dependence of initial velocity of the copolymerization reaction Vasp and MA's on content of MA at different summary concentrations of monomers [M] in the reaction system: mixture with: A - [M]=4.0 mol/l, B - [M]=3.2 mol/l, C - [M]=2.8 mol/l.
As is seen in the Figure this dependence is extremal. Displacement of curves depending on the general concentration of monomer mixture of maximum is observed. This fact proves participation of both free monomers and complex in copolymerization reaction [10].
References
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2. Rasulzada N.§., Safarova G.M., Çatirova M.i. Ase-tilsalisil turçusunun vinil efirinin sintezi va tadqiqi. Monomerlar va polimerlar kimyasinin muasir problemlari III respublika konfransinin materiallari. 05-06 noyabr. Sumqayit - 2015. S. 25-26.
3. Пат. 2298016 США. Высокомолекулярные полимеры, содержащие боковые группы салициловой кислоты / Квадир Мурат, Филлипс Эверетт, Бреммер Ларри Мл. 2005.
4. Пат. 2051143 США. Способ перевинилирова-ния / Р.Ю.Муррей. 1995.
5. Расулов Нк.Ш., Зейналова Г.Л., Гасанова У.А., Расулов Н.Ш. Сополимеризация малеинового ангидрида с аллиловым эфиром ацетилсалициловой кислоты. VI Бакинская международная Мамедалиевская конф. по нефтехимии, посвященная 100-летию акад. Ю.Г.Мамедалиева. Сентябрь 27-30. Баку-2005. Тезисы докл. C. 130.
6. Торопцева А.М., Белогородская К.В, Бонда-ренко В.М. Лабораторный практикум по химии и технологии высокомолекулярных соединений. М.: Химия, 1972. 415 с.
7. Рзаев З.М. Полимеры и сополимеры малеинового ангидрида. Баку: Элм, 1984. 157 с.
8. Ketelaar J.A.A. Molecular complexes of iodine with olefinic compounds // Rec. Trav. Chim. Pays-Bas. 1952. V 71. P. 805-808.
9. Jaacks V.V. A novel method of determination of reactivity ratios in binary and ternary copolymerizations // Makromol Chem 1972. V. 161. P. 161-172.
10. Георгиев Г.С., Голубев В.Б., Зубов В.П. Кинетический метод определения вклада донор-но-акцепторных комплексов в реакцию роста цепи чередующейся радикальной сополиме-ризации // Высокомолек. соед. А. 1978. T. 20. № 7. C. 1608-1615.
ALLIL- УЭ VINILASETILSALISILATLARIN MALEIN ANHIDRIDI ILO SOPOLiMERLO§MO REAKSiYALARININ TODQiQi
N.Ç.Rasulzada, A.H. Ozizov , G.M.Safarova, N.§.Rasulov
Salisil turçusunun allil va vinil efirlarinin malein anhidridi ils sopolimerlaçma reaksiyalan tadqiq edilmiçdir. Gôstarilmiçdir ki, sopolimerlaçan monomer cütlari yükün ötürülmasi ils kompleks amala gatirir ki, hamin komplekslar asanliqla polimerlaçma reaksiyalarina daxil olaraq növbali quruluçlu makromolekullar amala gatirir. Monomer cütlari arasinda yaranan kompleksin tarazliq sabitlari PMR spektrlarin kömayila tayin olunmuçdur: Alasp...MA cütü ûçûn Kc=0.097 va Vasp...MA cütü üçün isa Kc=0.028. Xromatoqrafik üsulla - Jaaks tanliyinin kömayila monomerlarin nisbi aktivliklari tayin edilmiçdir. Alasp-MA somonomerlari üQün r1= 0.022, r2= 0.038 va Vasp-MA somonomerlari üçün isa r1=0.036, r2=0.028-dir. Sopolimerlaçma reaksiyalarinda har iki halda monomerin nisbi aktivliklarinin sifira yaxin olmasi hamin monomer cütlarinin sopolimerlaçmaya meyilli oldugunu sübut edir. Vasp va MA-nin sopolimerlaçmasi reaksiyalarinda monomer cütlarinin nisbatinin va monomerlarin ümumi qatiliginin reaksiyanin baçlangic süratina tasiri ôyranilmiçdir. ilkin monomerlarin ekvimolyar nisbatlarinda w maksimum qiymatlarinda müxtalif ümumi qatiliqlarinda sopolimerlaçmanin baçlangic süratinin MA-nrn tarkibindan asililigi ayrilarinin ekstremal xarakteri zancirin böyümasinin ham sarbast monomerlarin, ham da monomer-kompleksin içtiraki ila baç verdiyini sübut edir.
Açar sözlzr: allilasetilsalisil efiri, vinilasetilsalisil efiri, sopolimerh§m3, sopolimerh§m3 sürsti, yükün ötürülmasib yaranan kompleks.
ИССЛЕДОВАНИЕ РЕАКЦИИ СОПОЛИМЕРИЗАЦИИ АЛЛИЛ- И ВИНИЛОВЫХ ЭФИРОВ АЦЕТИЛСАЛИЦИЛОВОЙ КИСЛОТЫ С МАЛЕИНОВЫМ АНГИДРИДОМ
Н.Ш.Расулзаде, А. Г. Азиз о в , Г.М.Сафарова, Н.Ш.Расулов
Исследован реакции сополимеризации аллил- и виниловых эфиров ацетилсалициловой кислоты (Alasp и Vasp) с малеиновым ангидридом (MA). Показано, что мономерные пары образуют комплексы с переносом заряда (КПЗ), которые легко превращаются в сополимер чередующейся структуры. Константы комплексообразования вычислены на основе спектров ПМР-смеси сомономеров методом Кетаалара; для Аlasp...MA Кс = 0.097, для Vasp^MA Кс = 0.028. Относительные активности мономеров при сополимеризации определены методом Яакса с использованием данных хроматографического анализа смеси мономеров до и после реакции сополимеризации. Они соответственно равны ^=0.022, г2=0.038 для мономеров А^- MA и ^=0.036, г2=0.028, для мономеров Vasp-MA. В обоих случаях относительные активности сополимеризующихся мономеров близки к нулю, что доказывает высокую тенденцию к сополимеризации мономерных пар. Изучены зависимости начальной скорости реакции сополимеризации Vasp и МА от состава исходной мономерной смеси при различных суммарных концентрациях мономеров в реакционной смеси. Экстремальный характер кривых зависимости начальной скорости сополимеризации от содержания МА при различных суммарных концентрациях мономеров с максимумами значений V при эквимольном соотношении исходных мономеров позволяет предположить протекание роста цепи с участием свободных или комплексно-связанных мономеров.
Ключевые слова: аллиловый эфир ацетилсалициловой кислоты, виниловый эфир ацетилсалициловой кислоты, сополимеризация, комплекс с переносом заряда.
