CHAPTER III

3.1 Experimental

3. 1.1 Materials used

1\cryiJc <Krd (GC Purity ()9%,), procured from Thomas Baker. India . dccyl

ak;(llwl ((i( Purity 08io) ubtamed from S D Fuw \ 'hcrmcals i ttL lnclra ->tvrenc

,Jhtamcd from Merck PrPdu~.:h. ( iennany and hydwqumone procured from S D. Fine
Chemicals Ltd, lndw, were used. 8enzuyl pero\.Jtk ( ( ,( Punty lJS"'o) procured from
r nha Chem1cais Pvi Ltd lmha. and was purified by ;;rystallization from methanol

Pu t\ '' l ,,btamed frum .\Aerck !mila . were used as a solvent

~. 1.2. Esterification of den! anylate (l)A.I from a(.rylic acid and dccyl alcohol

De.. \ l acrvlat(' vv:b prcpan.d by reacting acryl1c acid with decyl alcohol ( l.ll

molar ralln rhc rca,twr; '"ii' Jrncd 11Ut m <1 nsm kc11le ll1 the presence of cataJytrc
,J!ll\Hll1t ,r ''rh:cntratcd -..ulphunc ac1d. ii ~~,)~;, hydroqun10ne (with respect to the
mon(Hnen as pulymcruatwn :nh1bttor t(,r lcryllc actd. and toluene a-; a solvt:nt under
1 slow stream nf deoxygenated nitrogen. The reactants. which were mixed with
toluene. were heated gradually tiom room wmp~;ratun: tu 403K using a well-
' on trolled thermostat. The progress or the reactwn was followed by monitoring the
amount of liberated water frnm the reaction mixture to g1ve the ester. decyl acrylate

J.I.J. Purification of the prepared ester

The prepared ester was purified according to the following procedure: a

suitable amount of charcoal was added to the ester, allowed to reflux for 3 h, and then
filtered off The filtrate was washed with 0.5N sodium hydroxide in a separating
funnel and then shaken welL The entire process was repeated several times to ensure
complete removal of unreacted acid. The purified ester was then washed several times
with distilled water to remove any traces of sodium hydroxide, the ester was then left
overnight on calcium chloride and was then removed by distillation under reduced

139
pressure and was used m the polymerization process.

3.1.4. Preparation of homopolymer of DA and its copolymer \Yith styrene and

their purification

The polymerization was carried out in a four necked round bottom t1ask
-~qmpped with a stirreL condenser. thennometeL an inlet for the introduction of
:utrngen and a dropping tunnel tP add styrene drop w1se ln the t1ask was placed
des1rcd mass ,)1 DA and mmator iB/Pl fo!lmvcd hy the des1red mass of styrene wa~

added dropw ISL' f\n ) h m the prcs-.nc~. 'll. toluene as solvent The reaction temperature
was mamtamed at ~5~ K for 6 h. i\1 thL end ut the reactwn tnnc. the reactiPn mtxture
va..: poured mto methanol w1th ~tlrnng to terminate the polymenzat10n and to
preclpttalL lill P''i~ Tl l" \'.:l lurlh,r punt!ed npcated prcclpllalmn ,,j

nwtham1! tnllowed lw drymg under vacuum at 313K. /\

a.s ,;nmlarlv prepared and punfied under th~: ,,amc dmdttlo!~:-c

li.'r usc m n.:lernwc l'Xpcnmcnh

140
 Scheme I
Esterification:

Cone. H 2 S0 4
H 2C=CHCOOH Toluene, HQ inhibitor
Dean Stark
Apparatus

Scheme-l!
Homopolymen~a twn:

I nluene. fVP
.....
---
XO"< 6hr

Scheme-Ill
Copolymeri ..;;ation:

\ H;C"' CH-l:OUG ,,,Hl, j

' /
......
r,,Ju.:n, B/P

. CH=:::CH.

J. 1.5. Spectroscopic Measurements

IR -;pectra \\ere recorded on a Shimudzu FT-1 R X300 Spectrometer using 0.1 mm

KBr cells and the -;pectra were recorded at room temperature within the wave number
range 400 to 4000 1:m ' NMR spectra were recorded m a Brucker Avancc 100 MHz
FTNMR spectrometer using 'i mm BBO probe CDC!, was used as solvent and IMS
as reference materiaL

3.1.6. Viscometric Measurements

Viscosities were determined at 313K in chloroform and toluene, using an

Ubbelohde OB vtscometer placed m a thetmostatically controlled bath. The
temperature was measured close to the capillary by a thermometer with an accuracy of

141
0.0 l K. Experimental determination was l:arriecl out by counting time flow at least six
ditterent concentrations uf the sample solutions. The time flow of the solution was
manually detern1ined by using a cbmnometer. ln a single measurement the lowest
value of solution concentration was chosen for the calculation. The viScometeJ was
calibrated frequently with distilled water. The viscosity results were checked against
viscosity of known solutions and uncertainty was found to be nearly 0. J 7 %.
Precautions regarding prevention of evaporation of the solvent were taken m all the

r\ll the hmary -:nlut10ns were prepared hy d1ssolving a measured we1ght of the
polymer tn chloroform and toluene and dilutmg to a measured volume. All the ternary
snlutwns were rrepared hy dissnlving ;l Int;':lS\lrerl weight of the polymers with a DA

tlluene and then dilutinl!- tu a measured volume.

~or the vtscnsJtv ;lvera[!e molecular we1ght determmat1on. the :onstanh K.

'; IHHX' ell g and <1 P Tl:" !'-~! 461 were emploved m toluene and the unc.tanh K

11 004XO dl g and a () XO [47] were employed m chlorof(nm

J. 1.7. Evaluation of prepared additiH as pour point depressants (PPDs) in base

oils

!'he prepared addit1ves were evaluated as pour pomt depressant using two
di tTercnt hase \)lis collected from the ...;a me source. (Table 5) through the poll! pomt
te-.:1 accordmg tn the A ST!\11 !) .. )7 method usmg WI L -4 71 cloud and pour puml test

apparatus Model 3 (India). The effect of additive concentratiOn was investigated by

using different doping concentration for individual polymers (binary) and polymer
blends (ternary). All the ternary blend solutions were prepared by dissolving a
measured weight of the polymers with DA: copolymer of DA with styrene at the
weight ratio of 3:1, I: 1 and 1:3 in base oils. The etTect of additive concentration was
mvcstigatcd by using different doping concentrations from 0.25% to 3% (w/w). The
cxperiment.:1l data were noted by taking an average of three experimental results under
identical conditions.

142
3.1.8. Evaluation of prepared additive as viscosity index improvers (VIIs) in base
oils

Different binary and ternary blends were prepared by using two ditTerent types
of base oil. Viscosities and the viscosity index (VI) of these oils were calculated
according to i\STM [)2'70 Different weight percentages of concentration from 0.25
hl ~.0 were used 1P ;.,tudv the effect nf concentration on V! of the additive-doped lube
.1tl The cxpenment \v<l'- dune f(n h\Jth binary and temary blends. In th1s respect. the
kinematic \'1'-'l'O'>ll~ , ,i Jh,: nd contammg different concentratiOns ,,f the prepared
polymers. ,:opolymers and polymer hlends ware detem1ined at 313K and 373KThe
experimentai data \\Trt" m>ted hv takmg an average of three expenmental results under

Jdenllca! ''

J.2. Referenct'\

'l l L S . {Meth)/\crylate copolymer pour pomt

!l!

~~ R . Svnthesi;; and characteri/ation of nm~.i

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