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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 3 2021 ISSN 0005-2531 (Print)
UDC 541.64:547.538.141 POLYMERIZATION OF 8-ACETOXYTETRACYCLO[4.4.12'5.1710.01'6]DODEC-3-ENE AND ITS COPOLYMERIZATION WITH ACRYLIC ACIDS
E.K.Makhmudova, R.A.Rasulova, V.S.Kadyrly, M.J.Ibrahimova, J.H.Ismailova
Y.H.Mamedaliyev Institute of Petrochemical Processes NAS,of Azerbaijan
Received 31.05.2021 Accepted 16.06.2021
The reaction of radical polymerization of 8-acetoxytetracyclo[4.4.12,5.17,10.01,6]dodec-3-ene as weH as its copolymerization with methacrylic acids in the presence of BF3OEt2 in bulk and in the medium of organic solvent, particularly in benzene was investigated. The influence of various factors: the amount of catalyst, temperature and reaction time on the process of polymerization, as well as the influence of the monomer ratio on the copolymerization process was studied. The structure of the obtained homo- and copolymers was confirmed by IR spectroscopy and the thermal stability of the obtained polymers and their cured products was studied.
Keywords:8-acetoxytetracyclo[4.4.12'5.17'10.0L6]dodec-3-ene,polymerization, BF3 OEt2, copolymerization, acrylic acid, methacrylic acid.
doi.org/10.32737/0005-2531-2021-3-31-37 Introduction
The development of simple methods for the synthesis of alicyclic monomers of various functionality, as well as methods for their polymerization and copolymerization to obtain polymeric materials with a wide range of applications is one of the challenges facing the chemistry of macromolecular compounds [1-7].
The presence of cyclic fragments in the composition of ester molecules cause an increase in viscosity and thermal stability of based on polymers. Polycyclic esters of saturated
acids are plasticizers for polymeric materials improve their performance [8-10].
This article presents the results of studies on radical polymerization of 8-acetoxy-tetracyclo[4.4.12,5.17,10.01.6]dodec-3-ene (ATCD) and its copolymerization with (meth)acrylic acids in the presence of BF3OEt2.
The synthesis of ATCD was carried out according to the method developed by us by the interaction of tricyclo[5.2.1.02,6]deca-3,8-diene with vinyl acetate in the presence of a nano-TiO2 catalyst [11]:
O
o
,/ .. nano-TiO? m //+ CH2=CH-0-C-CH3-^ CH3-C-O
Experimental part
The synthesized ATCD and acrylic acids used as comonomers were characterized by the offered constants below after purification by distillation.
ATCD - Bp. 122-1240C/2 mm Hg; d.
20
1.1152; n 20 1.5012.
Acrylic acid - B.p. 1410C; df 1.062;
n 20 1.4224.
Methacrylic acid - B.p. 160-160.50C; df 1.018; n2D° 1.4315.
The degree of purity of all the above reagents according to chromatographic data (U,BeT-100) is 99.7%.
Polymerization of ATCD and its copol-ymerization with (meth)acrylic acids were carried out in sealed glass ampoules immersed in a
thermostated bath (the bath temperature was controlled with an accuracy of±10C) in an inert gas atmosphere. The process was carried out both in bulk in the presence of boron trifluoride etherate - BF3OEt2, and in a solvent medium -benzene.
BF3 OEt2 was distilled under vacuum over calcium hydride before use, B p. - 460C/10
mm Hg, d420 - 1.1540.
The isolation of the obtained polymer from the unreacted part of the monomer was carried out by dissolving the reaction mass in benzene and precipitation in ethyl alcohol. Then the resulting polymer was filtered and dried to constant mass in a thermostat with air access at 1000C. The samples were weighed on an analytical balance with an accuracy of 0.0001 g.
IR spectral analysis of polymer products was carried out on a spectrophotometer "ALPHA IQ FURYE" recorded by the German company "Bruker" in the range of numbers 600-4000 cm-1.
The molecular mass of the polymers was determined by the cryoscopic method, and the hardness (pendulum device M-3), elasticity (scale SHQ-1), impact strength (device U-1A), and adhesive strength were also determined by the method of lattice notch of coatings based on them.
Results and discussion
The influence of various factors: amount of catalyst, temperature and reaction time on the process of ATCD polymerization in bulk was studied. The results are shown in Table. 1. Studies have shown that monomer polymerization is not observed in the temperature range 50-800C under the studied conditions. When the temperature rises to 1200C with the amount of catalyst of 2 mass % within 10 h, the yield of polymer is 40%, and with an increase in the amount of catalyst, a sharp increase in the yield of polymer is observed. Under the above conditions the yield of poly-8-acetoxytetracyclo[4A12'5.17'10.01'6]dodec-3-ene at a polymerization time of 10 h and a catalyst amount of 5% is 49.6%, at 10% - 77.2%.
With an increase in the reaction time to 15 h, the yield of polymer remains practically unchanged and makes up 77.7% (Table 1).
Table 1. Influence of various factors on polymerization
of ATCD
Amount of catalyst, % Time, h T,0C Yield of polymer, %
2 10 50 -
2 10 80 -
2 10 100 33.7
2 10 120 40.0
5 10 120 49.6
10 10 120 77.2
10 15 120 77.7
Polymerization of ATCD was also investigated by carrying out the process in solution. Benzene was used as a solvent. The yield of polymer was 87 % at 1:0.5 ratio of ATCD to benzene, amount of catalyst - 10 mass %, polymerization temperature 1200C and reaction time 10 h. The observed increase in the yield of polymer in the process carried out in solution under similar conditions is apparently associated with the high viscosity of the obtained polymer and, thereby, complicated the conversion of the monomer.
Copolymerization process of ATCD with acrylic (AA) and methacrylic (MAA) acids was also studied:
h,c-c-o
The results of the researches are shown in Table 2.
Table 2. Influence of the molar ratio of monomers on the yield of copolymer at 1200C
Molar ratio of monomers T, h Catalyst, % Yield of copolymers, %
ATCD:AA ATCD:MAA
10:90 - 10 10 -
30:70 - 10 10 13.1
50:50 - 10 10 46.3
- 50:50 10 10 45.0
As is evident from Table 2, at a reaction temperature of 1200C, the amount of BF3-OEt2 catalyst is 10 mass % within 10 h, the yield of the copolymer of ATCD with AA and MAA is 46.3 and 45 mass % respectively at 50:50 monomers ratio.
The IR spectra of poly-ATCD obtained by bulk polymerization and in benzene solution are characterized by the presence of identical absorption bands. In particular, the spectra exhibit absorption bands characteristic on the bending and stretching vibrations of C-H bonds of CH3 groups (1364 and 2941 cm-1), bending and stretching vibrations of C-H bonds of CH2 groups in the cycle (972-965 cm-1), stretching vibrations of C=O groups (1736 cm-1), as well as absorption bands (1242 cm-1) related to stretching vibrations of the C-O bond connection of the ester group (Figure 1).
The IR spectrum of a sample of ATCD copolymer with acrylic acid (Figure 2) is cha-
racterized by the presence of the following absorption bands:
- stretching vibrations of the C=O group of the carboxyl fragment - 1720-1724 cm-1;
- stretching vibrations of C-O bonds -1162, 1242 cm-1;
- bending and stretching vibrations characteristic for C-H bonds of the CH3 group -750, 364, 1451 cm-1;
- absorption band of C-H bonds of CH2 group - 2938 cm-1.
It should be noted that absorption bands characteristic for C=C bonds are also not observed in the IR spectra of the polymer and copolymers.
As is known, inclusion of cyclic fragments into composition of the macro chain contributes to an increase in the thermal stability of the final product. The thermal stability of the synthesized polymer and copolymers in air at a heating rate of 100C per minute has been investigated by the method of thermogravimetric analysis (TGA). Differential thermal analysis of the samples of the synthesized polymer and co-polymer with acrylic acid was carried out on LINSESIS STA PT 1600 apparatus.
The curves of thermogravimetric analysis of poly-ATCD (Figure 3) and the product of its copolymerization with acrylic acid at an equal ratio of components are given in Figure 4.
- u
(2) § / 452.50 — < 1365.59 -t 1 JO
r 1 — >
< N 5 i>
C ;
s s -
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
Fig. 1. IR spectra of poly-ATCD obtained in mass (1) and in benzene (2).
Fig. 2. IR spectrum of copolymer ATCD with acrylic acid. AZERBAIJAN CHEMICAL JOURNAL № 3 2021
Fig. 3. TGA curves of the poly-ATCD.
Fig. 4. DTA curves of the poly-ATCD.
Analysis of the obtained data on the mass loss of the polymer (Table 3) indicates that the homopolymer of ATCD is characterized by a sufficiently high thermal stability and the mass loss of the polymer is not observed up to 3000C, on the contrary, the mass of the polymer in-
creases by 13%, may be associated with an increase in air temperature. A slight weight loss is observed at 370 that and at 4000C is 8% mass. Further, with an increase in temperature, intensive destruction of the sample proceeds and at 6000C the mass loss is 81% by mass. With a
further increase in temperature to 6200C, a slight increase in mass loss (1.6 mass %) is observed and the degradation process is practically completed at a residual polymer mass of 17.4 mass %.
Analysis of the curves of TGA of the ATCD/acrylic acid copolymer indicates that at already insignificant mass loss is observed (1% by mass) at temperature of 1000C and at 3000C the mass loss is 8.5 mass %. With increasing temperature, the intensity of the process of destruction of the copolymer increases.
Comparison of DTA curves of the polymer and copolymer with acrylic acid showed a relatively high thermal stability of the polymer with respect to the latter. So, if the mass loss of the polymer is 52% at 5000C, the mass loss of the copolymer reaches 71.2% at the same temperature copolymer with (Table 3) and at 6200C the mass loss is 92.4% and the degradation process is practically completed.
Table 3. Indicators of change in the mass of polymer and copolymer based on ATCD
Sample mass loss (%), temperature (0C)
100 200 300 400 500 600
Polymer +5 +9 +13 -8 -52 -81
Copolymer -1 -.8 -8.5 -38 -71.2 -91
Conclusion
It can be noted that the homopolymer of 8-acetoxytetracyclo- [4.4.12,5.17,10.01,6]dodec-3-ene is characterized by relatively higher thermal stability than the synthesized copolymer based on it, and when heated up to 350 C it exhibits thermal stability, then, with an increase in temperature, the destruction process proceeds with a relatively moderate decrease in the mass of the sample to 6000C.
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8-ASETOKSiTETRATSiKLO[4.4.12'5.1710.ö'6]DODETS-3-ENiN POLiMERLO§MOSi VO AKRlL
TUR§ULARI iLO BiRGOPOLiMERLO^MOSi
E.Q.Mahmudova, R.A.Rasulova, M.C.ibrahimova, V.S.Qadirli, C.H.ismayilova
8 -Asetoksitetratsiklo [4.4.12'5.1710.016]dodets-3 -enin radikal polimerla§masi va akril tur§ulari ila birgapolimerla§masi reaksiyalari katalizator BF3OEt2 i§tiraki ila ham kütlada, ham da üzvi halledici benzolda tadqiq edilmi§dir. Müxtalif amillarin: katalizatorun miqdari, temperaturun va vaxtin polimerla§ma reaksiyasiyasina, hamginin monomerlarin nisbatinin birgapolimerla§ma reaksiyalarina tasiri öyranilmi§dir. Sintez edilmi§ homo- va birgapolimerlarin qurulu§u iQ-spektroskopiya üsulu vasitasi ila tasdiqlanmi§ va onlarin stmkturla§ma mahsullarinin termiki stabilliyi ara§-dinlmi§dir.
Agar sözlsr: 8-asetoksitetratsiklo[4.4.12"5.17"10.01"6]dodets-3-en, polimerb§m3, BF3 OEt2, birg3polimerb§m3, akril tur§usu, metakril tur§usu.
ПОЛИМЕРИЗАЦИЯ 8-АЦЕТ0КСИТЕТРАЦИКЛ0[4.4.12'5.1710.0'6]Д0ДЕЦ-3-ЕНА И ЕГО СОПОЛИМЕРИЗАЦИЯ С АКРИЛОВЫМИ КИСЛОТАМИ
Э.К.Махмудова, Р.А.Расулова, М.Д.Ибрагимова, В.С.Кадырлы, Дж.Г.Исмайлова
Исследована реакция радикальной полимеризации 8-ацетокситетрацикло[4.4.12'5.17'10.01'6]додец-3-ена, а также его сополимеризация с (мет)акриловыми кислотами в присутствии BF3OEt2 как в массе, так и в среде органического растворителя, в частности, бензола. Изучено влияние различных факторов: количества катализатора, температуры и продолжительности реакции на процесс полимеризации, а также влияние соотношения мономеров на процесс сополимеризации. Структура полученных гомо- и сополимеров подтверждена методом ИК-спектроскопии и изучена термическая стабильность полученных полимеров и продуктов их отверждения.
Ключевые слова: 8-ацетокситетрацикло[4.4.12"5.17"10.01"6]додец-3-ен, полимеризация, BF3 OEt2, сополимеризация, акриловая кислота, метакриловая кислота.
