SYNTHESIS AND STUDY OF THE POLYMERIZATION OF N-ALKYL-N-ALLYL-(β-CHLORO)ALLYLAMMONIUM DIHYDROPHOSPHATES Текст научной статьи по специальности «Химические науки»

AZERBAIJAN CHEMICAL JOURNAL No 1 2020 ISSN 2522-1841 (Online)

ISSN 0005-2531 (Print)

UDC 547.315.3; 661.52

SYNTHESIS AND STUDY OF THE POLYMERIZATION OF N-ALKYL-N-ALLYL-(P-CHLORO)ALLYLAMMONIUM DIHYDROPHOSPHATES

A.M.Garamanov, O.B.Abdiev, N.Kh.Husiev, R.A.Ahmadova, D.G.Abdullaev, S.N.Allakhverdieva, M.M.Ibrahimova, M.X.Balaeva

Institute of Polymer Materials, NAS of Azerbaijan

ipoma@science.az

Received 22.02.2019 Accepted 06.09.2019

The polymerization reactions of the synthesized N-alkyl(methyl, n-butyl, n-heptyl, n-dodecyl)-N-allyl-N-(P-chloro)allylamines (AABA) were carried out in solutions of mineral acids (HCl, HNO3, H3PO4) in the presence of thermal initiators - ammonium persulfate (AP) and azo-bis-isobutyric acide dinitrile (ABD). Radical polymerization of AABA was performed using AP and ABD with initiator concentration 4.10-4 mol/l and at a temperature 600C, the reaction was 10-24 hours. In this way, it is not possible to obtain sufficiently high molecular mass of the polymerization products, although PA is more effective than ABD. However, during the photopolymerization of AABA in solutions of concentrated acids in the presence of photoinitiators - uranyldiaquadiacetate and uranyldipivalate with an initiator concentration of 4.10-4 mol/l, water soluble polymers were obtained with sufficiently high characteristic viscosity for a given amine. Keywords: N-alkyl-N-allyl-N-(fi-chloro)allylamines, mineral acids, thermal initiator, photo-initiator, polymerization, water, acetone.

Experimental part

Methylamine - used a "pure" 25% water solution. N-Butylamine - b.p. 77.80C, nf -1.4035, df - 0.7401. n-Heptylamine - b.p. 158.30C, nf - 1.4270, d420 - 0.7770. n-Dode-cylamine - b.p. 248°C, m.p. 27-28°C rashly distilled allylchloride - b.p. 45°C, nf - 1.4154,

df- 0.9379. Freshly distilled (P-chloro)allyl-chloride - 940C, nf - 1.4600, d420 - 1.2080. Sodium hydroxide, sodium chloride, orthophos-phoric acid (85% aqueous solution) brand products "ch. p. ". Thermal initiators - ammonium persulfate (AP) (NH4)2S208 and dinitrile azobisisobutyric acid (ABD) N=C-C(CH3)2-N=N-C(CH3)2-C=N products of the brande

"ch. f. a.". Recrystallized from water (AP) and ethyl alcohol (AID), dried in vacuum to constant mass. Photoinitiators - uranyl diaquadi-acetate UO2(OOCCH3^2H2O (Ua) and uranyl diaquadipivalate UO2[OOC(CH3)3]2'2H2O (UP), brand products "ch. p." [3]. In all experiments, bidistilled water was used. Acetone, ethanol, isopropyl alcohol, diethyl ether were purified by the conventional method [4]: the solvents used corresponding to the table characteristics.

doi.org/10.32737/0005-2531-2020-1-66-70 Introduction

The polymers based on diallyl monomers occupy an important place among synthetic po-lyelectrolytes, which can be used as coagulants, flocculants, soil structuring agents, as well as for purification of drinking and waste water. Therefore, the synthesis of new diallyl monomers and polymers containing functional groups, as well as the corresponding polyelectrolytes with adjustable hydrophilic-hydrophobic balance is a very urgent task.

The study on the radical polymerization processes of diallyl monomers, in particular, on the basis of N-alkyl-N-allyl-N-(P-chloro)allyl-amines is of scientific and practical interest. It should also be noted that there are small date in the literature devoted to the study of the kinetic features of the polymerization of N-alkyl-N-allyl-N-(P-chloro)allylamines and their salts in protonated form, which would contain hydro-phobic N-alkyl substituents.

In the literature, there are no date on the synthesis and polymerization of N-alkyl-N-allyl-N-(P-chloro)allylammonium dihydrophosphates. But there is information about the polymerization N-alkyl-N,N-diallylammonium dihydrophosphates [1, 2].

Synthesis of investigated compounds was made on case N-allyl-N-(P-chloro)aHyl-N-methylamine (ABMA). A two-liter, four-necked flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, pour a portion of a 25% aqueous solution of methylamine 127 g (1 mol) and 76.5 g of allyl chloride drop by drop during 1 h and after 7 h 111 g (mol) (P-chloro)allyl chloride for 1 h and then a 50% aqueous solution of sodium hydroxide (80 g, 2 mol). The feed rate of the reagents is adjusted so that the temperature in the reaction mass does not exceed 300C. To remove excess heat using a water bath with ice. After adding the sodium hydroxide solution, the reaction mass is slowly warmed to 700C. After cooling the reaction mixture, the upper layer is separated and kept over granulated NaOH for 40 h. The amine aged above the alkali is fractionated on a column, keeping the reflux ratio 10:1. During distillation, fractions 68-700C/2.67 kPa, nf - 1.4630, df -

0.9445. Yield 60%. MR^/found 42.43. MR^/calc. 42.26. Found, %: C 57.78, H 8.62, N 9.73, Cl 24.25. C7H12NCL Calculated, %: C 57.73, H 8.31, N 9.62, Cl 24.34.

Synthesis of N-aHyl-N-(P-chloro)aHyl-N-n-butylamine (ABBA). The reaction mixture of 7.3 g (0.1 mol) of butylamine, 7.6 g (0.1 mol) of allylchloride and 11.1 g (0.1 mol) (P-chlo-ro)allylchloride, 0.8 g (0.2 mol) sodium hydroxide granules surrounded on air and 40 ml isopropyl alcohol is transferred to a special ampoule. After this, the reaction mixture is degassed on a vacuum unit and placed in an oil thermostat, where it is maintained at a temperature of 105-1100C for. 7-9 h. Then the reaction mixture is thoroughly washed by water, and the organic part is extracted by ether and after removing the ether, it is distilled by vacuum distillation: b. p. - 102-1030C/0.133 kPa. nf -

1.4640, d2° - 0.9191. Yield - 55%. MR^/found -55.55. MRD/calc. 56.21. Found, %: C 64.12, H 9.71, N 7.39, Cl 18.67. C10H18NCL Calculated, %: C 63.99, H 9.67, N 7.46, Cl 18.89.

In a similar way obtained:

N-allyl-N-(P-chloro)allyl-N-«-heptylamine (ABHA) from heptylamine: b.p. 111-113°C/0.133

kPa. nf - 1.4656, d420 - 0.9052. Yield - 52%.

MRD/found - 70.24. MRD/calc. 70.15. Found, %: C 68.14, H 10.60, N 6.06, Cl 15.35. C13H24NCL Calculated, %: C 67.95, H 10.53, N 6.10, Cl 15.43.

N-allyl-N-(P-chloro)allyl-N-«-dodecyl-amine (ABDA) from dodecyltylamine: b.p. 134-1350C/0.133 kPa. nf - 1.4660, d420 -

0.8870. Yield 50%. MR^/found - 93.66. MR^/ca/c. -93.39. Found, %: C 72.15, H 11.52, N 4.72, Cl 11.74. C18H34NCL Calculated, %: C 72.08, H 11.43, N 4.67, Cl 11.82.

Synthesis of N-allyl-N-(P-chloro)allyl-N-methylammonium dihydrophosphate (MHPh). Pre-dried and distilled N-allyl-N-(P-chloro)-allyl-N-methylamine (ABMA) are placed in a beaker and mixed with an equivalent amount of orthophosphoric acid (85% aqueous solution). Mix thoroughly until a homogeneous mass, while the excess heat is removed in a water bath with ice. The mixture is thoroughly washed with cold ether and dried to a constant mass over P2O5. Purified by recrystallization from a mixture of ether-absolute ethanol in the ratio 10:1. rmelt - 660C. Yield - 75%. Found, %: C 34.67, H 6.28, N 5.69, N 5.69, Cl 14.43, P 12.77, C7H15NOPO4. Calculated, %: C 34.51, H 6.21, N 5.75, Cl 14.55, P 12.72.

In a similar way obtained other compounds.

N-allyl-N-(P-chloro)allyl-N-«-butylam-monium dihydrophosphate (BHPh): m. p. -730C. Yield - 73%. Found, %: C 41.98, H 7.47, N 4.99, Cl 12.49, P 10.94. C10H21NClPO4. Calculated, %: C 42.04, H 7.41, N 4.90, Cl 12.41, P 10.85.

N-allyl-N-(P-chloro)allyl-N-«-heptylam-monium dihydrophosphate (HHPh): m. p. -920C. Yield - 70%. Found, %: C 47.69, H 8.35, N 4.20, Cl 10.92, P 9.52. C13H27NClPO4. Calculated, %: C 47.63, H 8.30, N 4.27, Cl 10.81, P 9.46.

N-allyl-N-(P-chloro)allyl-N-«-dodecyl-ammonium dihydrophosphate (DHPh): m. p. 990C. Yield 65%. Found, %: C 54.40, H 9.43, N 3.43, Cl 8.81, P 7.86. C18H37NQPO4. Calculated, %: C 54.33, H 9.37, N 3.52, Cl 8.91, P 7.79.

Polymerization of N-alkyl-N-allyl-N-(P-chloro)allylamines in the environment of proton-donating acids. A weighed 0.2 mol/l of monomer was placed in concentrated solutions of acids (HCl, HNO3, H3PO4) and the initiator

(410 mol/l) was added. The prepared solutions were divided into two parts and placed in a special ampoule. On part of the ampoules was placed in a thermostat at 600C for 10-24 hours, the other part of the ampoules was photo-polymerized at 0-200C, при X=360 nm. After the reaction was completed, the reaction mixture was gradually poured into dry acetone in portions. The resulting precipitates were filtered, thoroughly washed with dry acetone, and dried over P2O5 to constant mass. Yields are 15-45%.

Results and discussion

In connection with widespread use of cationic polyelectrolytes in various branches of industry, it seems natural for researchers to synthesize new polyelectrolytes which would have a complex of valuable properties with adjustable hydrophilic-hydrophobic balance basis on the diallyl monomers. To this end, we have a number of N-alkyl-N-allyl-N-(P-chloro)allylamines synthesized to the scheme [5, 6]:

R-

NH,

+

CH2=CHCH2C1 2NaOH CH2-CHCH2^ _

ch2=cc1ch2c1 -2NaCl -2H20

ch2=cc1ch2

/

N-R

R=CH3, n-C^, n-C7H15, n-C12H25.

The interaction of N-alkyl-N-allyl-N-ф-chloro)allylamines with of orthophosphoric acid

CH2=CHCH2^

CH2=CC1CH2

/

N-R + H3PO4

obtained N-alkyl-N-allyl-N-(P-chloro)allylam-monium dihydrophosphates:

CH2—CHCH

2\ /R

CH2=CC1CH2

©

h2po4

©

R=CH3, n-C4H9, n-C7H,5, n-C12H

7H15,

12H25

It is known that radical polymerization of tertiary amines in the form of free bases proceeds only with the formation of low molecular mass oligomers. This is due to the side effect of the monomer-radical cleavage of the hydrogen atom of the -CH2 group of the allyl substituent, as is well known, which easily occurs in the case of diallylamines in the basic form. In this case, the chain transfer reaction to the monomer leads to the formation of a weakly reactive allylic transfer radical, the loss of the active radical center and the attenuation of the polymerization process. This reaction is characterized as a degradation chain transfer to the monomer [7]. This is mainly due to the presence of isolated degraded chain transfer to the monomer, which complicates the methods of their deep research. Therefore, the search for approaches to the synthesis of of N-alkyl-N-allyl-N-(P-chloro)allylamines which reduce the

contribution of the degradation chain to the monomer, can open the way to obtaining polymers with desired practical properties and high molecular mass (MM).

The reactions of radical polymerization of the amines synthesized by us earlier were carried out in solutions of various mineral acids (HCl, HNO3, H3PO4) in the presence of a thermal initiators (T=600C) and photochemical method (T=200C).

The radical polymerization of ABMA was performed using UA and AID with an initiator concentration of 410-4 mol/l at 600C, the reaction time was equal to 10-24 h. The results are shown in Table 1. As can be seen from table 1, in this way it is not possible to obtain sufficiently high values of the MM of the polymerization products, although PA is more effective than ABID. The polymer yield in all cases did not exceed 10%.

Table 1. The results of the polymerization reaction ABMA depending on the ratio of amine:acid_

Ratio of [n]

Acid ABMA:acid, dl/g, 0.1 n NaCl Initiator

mol/l

1 1 0.028 AP

HCl 1 2 0.028 AP

1 1 0.028 AID

1 1 0.037 AP

HNO3 1 2 0.037 AP

1 1 0.029 AID

1 1 0.048 AP

H3PO4 1 2 0.048 AP

1 1 0.039 AID

However, during the polymerization of ABMA (200C, X=360 nm) in solutions of concentrated acids in the presence of UA and UP with a concentration of Cin=4'10"4 mol/l, water-soluble polymers were obtained with sufficiently high characteristic viscosity for a given class of compounds. The results of photopolymerization are shown in Table 2, from which it is clear that highest MM polymer values were obtained in the case of ABMA in a solution of ortho-phosphoric acid (85% aqueous solution) in the presence of UA as an initiator, and the MM value does not depend on the amine/acid ratio. The MM values of the obtained polymerization products, as well as the yield of polymers, are higher in the case of polymerization of ABMA in mineral acids than in the case of polymerization in the presence of thermal initiators (600C). It should be noted that in the absence of an initiating system, the reaction of polymerization of ABMA in acid is nit observed.

Table 2' The results of the photopolymerization reaction ABMA depending on the ratio of amine: acid at a temperature of 200C, X=360 nm __

Acid Ratio of ABMA:acid, mol/l Photoinitiator Temperature, [n], dl/l, 0.1n NaCl

1 1 UA 20 0.180

HCl 1 2 UA 20 0.14

1 1 UP 20 0.08

1 1 UA 20 0.29

HNO3 1 2 UA 20 0.25

1 1 UP 20 0.19

1 1 UA 20 0.76

1 2 UA 20 0.77

H3PO4 1 1 UP 20 0.33

1 1 UA 20 0.92

1 1 UP 20 0.41

As can be seen from table 2, UA is fairly effective initiating system. It is known that salts of uranyl when absorbed by a quantum of tight are restored, chemically from U to U4+. When light is absorbed, the uranyl ion goes into an excited state to form the U5+ product.

U022+ + hv (U022+)*

(U022+)* + "OOCR [U02+, R] + C02T

In this case, the radicals either die due to intracellular reactions, or dissociate with the release of the radical R', which initiates polymerization, into the bulk [8]. Chlorine anions have a strong inhibitory effection the rate of photochemical reduction of the uranyl ion U6+ to U4+, nitrate anions have a weak inhibitory effect, and ortho-phosphoric acid anions do not have a marked inhibitory effect [9]. Apparently, this fact contributes to the creation of an effective system in which ABMA is capable of polymerizing with the formation of a soluble polymer in water.

Analysis of 13C NMR spectrum of the polymer suggests that the polymerization proceeds through the double bonds of the formation of a diallyl groups via a cyclo linear mechanism with the formation of a polymer with a pyrrolidine structure [10-12].

Conclusions

1. Radical polymerization of AABA was carried out in solutions of mineral acids (HCl, HNO3, H3PO4) using thermal initiators - PA and ABD (Cin= 4'10-4mol/l, at 600C). It is shown that this method fails to obtain sufficiently high MM values of polymerization products. However, during the photopolymerization of AABA (T=200C, ^=360 nm) in solutions of concentrated acids in the presence of photoinitiators - uranyldiaquadiacetate and ura-nyldipivalate with an initiator concentration of 4'10- mol/l, water-soluble polymers were obtained with sufficiently high characteristic viscosity for a given amine.

2. It was established that the polymerization of AABA proceeds through the double bonds of the diallyl groups via a cyclo linear mechanism with the formation of a polymer with a pyrrolidine structure.

References

1. Begieva M.B., Malkanduev Iu.A. Kineticheskie za-konomernosti radikalnoi termopolimerizatcii N,N-diallil-N-metilammonii digidrofosfata v vodnykh rastvorakh. Problemy nauki i obrazovaniia. 2012. № 9. S. 134-137.

2. Begieva M.B., Malkanduev Iu.A. Radikalnaia sopo-limerizatciia fosfatnykh solei proizvodnykh N-alkil-N,N-diallilamina s N,N-diallil-N,N-dimetilammonii khloridom. Novye polimernye kompozitcionnye materialy. Materialy VIII M/n nauchno-prakti-cheskoi konferentcii. Nalchik. 2012. S. 24-27.

3. Kariakin Iu.V., Angelov I.I. Chistye himicheskie veshchestva. M.: Himiia. 1974. 408 s.

4. Gordon A., Ford R. Sputneyk himika. M.: Mir, 1976. 541 s.

5. Qaramanov O.M., Abdiyev O.B., Qurbanov M.§., Abdullayev D.Q., Hüsiyev N.X., Allahverdiyeva S.N., Balayeva X.M. N-Allil-N-(ß-xlor)allil-N-metilam-monium dihidrofosfatin polimerla§masinin tadqiqi. Tezis. "Funksional monomerlar va xüsusi xassali po-limer materiallar: problemlar, perspektivlar va prak-tiki baxi§lar" mövzusunda Beynalxalq konfrans. 1516 noyabr 2017-ci il. Sumqayit. 2017. S. 153-154.

6. Garamanov A.M., Abdiev O.B., Abdullaev D.G.,

Gusiev N.KH., Gurbanov M.Iu., Rzaeva S.A. Ki-neticheskie zakonomernosti radikalnoi polimeri-zatcii N-allil-N-(ß-khlor)allil-N-metilammonii di-gidrofosfata v vodnykh rastvorakh. Tez. docl. Mezhdunarodnaia nauch. konf. posviashchennoi 110-letnemu iubileiu akad. M.Nagieva. Baku. 3031 oktiabria. 2018. S.

7. Ostroverhov V.G., Brunovskaia L.A., Kornienko A.A. O polimerizatcii nekotorykh N-diallilnykh soedinenii. Vysokomolek. soed. 1964. T. 6. № 5. S. 926-928.

8. Sergeeva G.I., Chibisov A.K., Kariagin A.V. Zhurn. pricl. spektroskopii. 1973. № 3. 419 s.

9. Rabinovich E., Belford R. Fotohimiia uranila. M.: Atomizdat. 1960. 168 s.

10. Butler G.B. Cyclopolymerization. Jn: Encyclopedia of Polymer Science and Technology. Eds. Mark H.F. Caylord N.G., Bicales N.M., New-York: Jnt. Sci. 1966. V. 4. P. 568-598.

11. Brace N.O. Cyclopolymerization: Cyclization of Diallylcyanamide to Pyrrolidine Derivatives. J. Polym. Sci., A-1. 1975. V. 8. № 8. P. 2091-2102.

12. Vorobeva A.I., Vasileva E.V., Guysina Kh.A., Puzin Iu.I., Leplianin G.V. Sopolimerizatciia NN-dialkil-NN-diallilammoniigalogenidov s dvuokisiu sery. Vysokomolek. soed. Seriia A. 1996. T. 38. № 10. S.1663-1667.

N-ALKIL-N-ALLIL-N-(ß-XLOR)ALLILAMMONIUM DIHIDROFOSFATLARIN SINTEZI VO

polímerlo§molorínín todqíqí

O.M.Qaramanov, O.B.Abdiyev, N.X.Hüsiyev, D.Q.Abdullayev, R.O.Ohmadova, S.N.Allahverdiyeva

M.M.ibrahimova, X.M.Balayeva

Sintez edilmi§ N-alkil-N-allil-N-(ß-xlor)allilaminlarin (AABA) polimerla§ma reaksiyalari mineral tur§ular (HCl, HNO3, H3PO4) mahlullarinda termiki inisiatorlar - ammonium persulfat (AP) va azobisizoyag tur§usunun dinitrilinin (ABD) i§tiraki ila aparilmi§dir. AABA-nin radikal polimerla§masi PA va ABD-dan istifada edilmakla inisiatorun 410-4 mol/l qatiligi, 600C temperaturda va 10-24 saat müddatinda apanlmi§dir. Göstarilan üsulla kifayat qadar yüksak molekul kütlali polimerla§ma mahsullan almaq olmur, amma AP AÍD-ya nisbatan daha gox effektlidir. Lakin AABA-nin fotopolimerla§masini (Т=200С, X=360 nm) qati tur§u mahlullannda fotoinisiatorlar - uranil diakvadiasetat va uranil diakvadipivalat i§tiraki ila inisiatorun 410-4 mol/l qatiliginda aparan zaman har bir amin ügün xarakteristik özlülüyün kifayat qadar yüksak qiymatli suda hall olan polimerlari alinmi§dir.

Agar sözlar: N-alkü-N-aUü-N-(ß-xlor)aUüaminhr, mineral tur§ular, termiki inisiator, fotoinisiator, polimerh§m3, su, aseton.

СИНТЕЗ И ИССЛЕДОВАНИЕ ПОЛИМЕРИЗАЦИИ ^АЛКИЛ-^АЛЛИЛ-^ф-ХЛОР)АЛЛИЛАММОНИЙ ДИГИДРОФОСФАТОВ

А.М.Гараманов, О.Б.Абдиев, Н.Х.Гусиев, Д.Г.Абдуллаев, Р.А.Ахмедова, С.Н.Аллахвердиева,

М.М.Ибрагимова, Х.М.Балаева

Реакции полимеризации синтезированных нами ранее ^алкил(метил, н-бутил, н-гептил, н-додецил)-Ы-аллил-N-(ß-хлор)аллиламинов (ААБА) проводили в растворах минеральных кислот (HCl, HNO3, H3PO4) в присутствии термических инициаторов - персульфата аммония (ПА) и динитрила азо-бис-изомасляной кислоты (ДАК). Радикальную полимеризацию ААБА проводили с использованием ПА и ДАК с концентрацией инициатора -410-4 моль/л, температура - 600С, продолжительность реакции - 10-24 ч. Указанным способом не удается получить достаточно высокие значения молекулярных масс продуктов полимеризации, хотя ПА является более эффективным, чем ДАК. Однако при проведении фотополимеризации ААБА (Т=200С, Х=360 нм) в растворах концентрированных кислот в присутствии фотоинициаторов - диаквадиацетата уранила и диаквадипивалата уранила с концентрацией 4.10-4 моль/л были получены водорастворимые полимеры с достаточно высокими значениями характеристической вязкости для изученного амина.

Ключевые слова: ^алкил-^аллил-^ф-хлор)аллиламины, минеральные кислоты, термический инициатор, фотоинициатор, полимеризация, вода, ацетон.