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43Section 4. Petrochemistry
Musayeva Minakhanim Anvar gizi, ANAS Academician A. M. Guliyev Institute of Chemistry of Additives, PhD in Chemistry E-mail: aki0S@mail.ru Hamidova Jeyhun Shafayatgizi, PhD in Chemistry, associate professor E-mail: c.hamidova@mail.ru Isakov Elxan Urshan ogli, PhD in Chemistry, associate professor E-mail: vmsh_14@mail.ru Hasanova Elnara Ismatgizi, ANAS Academician A. M. Guliyev Institute of Chemistry of Additives, PhD in Chemistry E-mail: amea.elnara@mail.ru
Copolymer allylnaphthenate-styrene as the viscosity additive for petroleum oils
This work was supported by the Science Development Foundation under the President of the Republic of Azerbaijan — Grant № EIF 2013-9 (l5)-46/21/4-M-38 Abstract: The results of synthesis of copolymers of allyl naphthenate with styrene by method radical polymerization in the presence of the initiator are given in this article. The synthesized copolymers were studied as viscosity additives for petroleum oils.
Keywords: allyl naphthenate, styrene, coopolymerization, viscosity additives, thermal stability.
Lubricating oil is the system with multicomponent, they are used in order to ensure the long-term exploitation of machine and mechanisms. One of the most important components in the content of the lubricating oil is viscosity additives. The viscosity of the lubricating oil is the most important exploitation parameter and its price determines the viscosity class of the lubricating oil. The simplest and faithful among the different ways of gaining the oil having the good viscosity-temperature property is considered the usage of the viscosity additives — from the polymer combinations. Some polymers — as well as, polyisobutylen, poly-alkylmethacrylates, polyvinylbutyle ether are used as the viscosity additives. But the additives shown today are considered “classics” and they aren’t used, because they don’t meet the requirements of the modern technique [1, 139].
At last times the results of the analysis of the researches carried out in the field of viscosity additives
shows that, the modified polyalkylmethacrylates are used as the viscosity additives that is the polymers with the compound type of ether have the better exploitation properties rather than hydrocarbon. This priority shows itself especially in the properties such as viscosity-temperature, especially the low temperature of the condensed oil. From other side the viscosity admditives with polyalkylmethacrylate type are gained on radical mechanism and they are free from the undesirable cases such as cleaning of the catalyzer belonging to ion polymerization, that is they are gained on clear technology clear ecologically [2, 36-52].
It is necessary to mention that, the interest on any chemical product is determined with its raw material reserves. We have noted in the above that — alkyl (met)acrylate is considered the most interesting unsaturated compound ether for gaining the viscosity additive [3, 31-32]. The monomer shown in our Republic has no production.
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Copolymer allylnaphthenate-styrene as the viscosity additive for petroleum oils
The other way of gaining the unsaturated ether may be the etherification of carbon acids saturated with the unsaturated alcohols. The simplest unsa-tured alcohol is allyl alcohol. The oil acids which are in the content of Baku petroleum may be used as the carbon acid. So, the researchers have been carried out in the direction of gaining to viscosity additives with the compound ether type on the basis of the local raw material. Naphthenic acids — oil acids separated from the light fraction of the oil are changed into the nafthenate — the salt solving in the water processing with the alkali and are separated from other oil products. Then it becomes the mixer of naphthenic acids effecting with the chloride acid. If the clearance degree isn’t satisfactory, the operation is repeated. The gained product is distilled and is entered the etherification reaction with allyl alcohol. The process is conducted in the flask provided with Din-Stark keeper.
For azeothropic sending offwater decomposing at the result of reaction toluene is used, that is the process is carried out in toluene solution. As an accelerant КУ-2 cation is used. Upon termination of a process acquired product is washed, dried and distilled.
As it is clear that allyl monomers while decomposing they polymerizated difficult and it is impossible to get polymer combinations out of them possessing high molecule weight. Therefore allyl ether we synthesized is included into polymerization reaction together with styrene — vinyl monomer
which is polymerizated easy. Use of styrene as a co monomer is explained in such a way that styrene is a cheaper raw material of oil chemistry after ethylene and propylene. Along with it including aromatic fragments into polymer chain, increases resistance of acquired viscosity additives against thermo oxidation.
Polymerization of allyl naphthenate with styrene is carried out on radical mechanism using benzoic peroxide as an initiator. Impact of various factors over the process such as temperature, comparison of monomers, duration of reaction, initiator expense is studied. It was determined that increase of amount of styrene in monomer mixture causes increase of molecular weight of acquired polymer. It is explained in following way that styrene enters radical polymerization very fast.
Taking initiator expense less than 0.7 % (with regard to mixture of monomers) causes decrease of extension of polymer. Therefore initiator expense is taken in the interval of 0.7-1 %.
Study ofperiod of carrying out of reaction made clear that process ends approximately in 4-5 hours.
It is expedient to carry out polymerization process in the interval of 65-67 °C.
So, necessary reaction condition under which acquiring of high extension and molecular weight will be ensured is defined.
Conducted reactions can be given schematically as follows:
1) Synthesis of allylnaphthenate (RH — radical of naphthenic acids):
kat
Rh-COOH + CH=CH-CH2OH ---------- CH =CH
-Hp 2 I
ch2-oco-rh
allylnaphthenates
2) Polymerization of allylnaphthenate with styrene:
The results of carried out reactions show that at the result of polymerization of allylnaphthe-
nates with styrene real combined polymers are acquired.
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Section 4. Petrochemistry
Structure of combined polymers is studied by IQ- spectrographic method.
Absorbing line observed in spectrum 1780 cm1 show that there is complex ether group. 1600 cm-1 absor-bing line is the evidence that there is no aromatic ring.
So, spectral researches approve correctness of a structure which is discussed.
Polymer of synthesized allylnaphthenates with styrene is light yellow color viscous flowing water solved easily in mineral and synthetic oil.
Acquired polymer combination applied in petroleum oil as a viscosity mixture. Schedule indicates impact of density of combined polymer synthesized on viscosity-temperature features of M-6 oil. Molecular weight of used combined polymer is 8000; amount of styrene units in composition of combined polymer is 30 %.
As it is seen from the schedule that by adding 3-7 % combined polymer to M-6 oil it is possible to get base oil for motor oil of M-8 ± 0.5 mm 2/s type
which meets up to date requirements as to viscosity index rate (it should not be less than 93).
Comparative study of thermal degradation of synthesized combined polymer by certain viscosity additives showed that samples of experiment as for this feature prevail over polyisobutylene and poly-alkylmethacrylates.
It is from one hand is explained by stabilizing impact of styrene fragment which is included in composition of combined polymer. From other hand as allyl monomers are polymerizated hardly distribution of combined polymer as for its molecular weight is not extensive and at the result polymer combinations with much more physical-mechanical features are acquired.
So, for the first time allylnaphthenate-sty-rene combined polymer synthesized and studied as viscosity admixture. Rate of molecular weight of combined polymer and its density in oil is defined depending upon concrete demand to acquired oil.
Table 1. - Influence of allylnaphthenate-styrene copolymer to viscosity-temperature properties of M-6 oil
Density of copolymer, % (weight) Properties of condensed M-6 oil
Viscosit v, mm2/s Index of viscosity
100 °C 40 °C
0 6.60 47.02 88
1 6.85 48.65 92
3 7.54 54.76 98
5 8.00 58.60 102
7 8.60 64.30 104
9 9.20 70.11 106
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3. Ахмедов А. И., Аскерова Х. А., Исаков Э. У, Гамидова Д. Ш. Синтез вязкостных присадок к смазочным маслам сополимеризацией бутилметакрилата с аллилнафтенатами и а-олефинами С6-С.// Журнал «Нефтепереработка и нефтехимия». - № 5. - 2009. - С. 31-32. 30
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