A
Novel Polymer Based On Coconut Oil and Rosin for Detergent
Pravin A. Dhakite1, Dr. B. B.
Gogte2* and Dr. B. W. Phate3
1Department
of Applied Chemistry, Datta Meghe
Institute of Engg., Technology and Research, Sawangi Meghe, Wardha.(MS)
2Department
of Applied Chemistry, Shri. Shankarprasad
Agnihotri College of Engg. Ramnagar, Wardha -442001
3Department of Applied Chemistry, Priyadarshini Indira Gandhi
College of Engineering, Nagpur
ABSTRACT:
Alkyd resin is normal raw material for
paints, printing inks, and water thin able coatings. In the present work, we
have successfully prepared a very Novel Alkyd Polymer using high proportion of
rosin. The other ingredients are coconut oil, maleic
anhydride and glycerol. Various parameters like temperature, time of heating
and mole ratio have been studied. All the sample have been analyzed for physiochemical
characteristics like acid value, saponification
Value, HLB ratio, viscosity, and cleaning performance on soiles
cloth .Two samples AR-1, AR-2 have given good results so these samples have
been used after neutralization with KOH in powder detergent compositions .These
polymer are based on raw materials of vegetable origin. The above result
indicates that Novel polymer can be used as replacement of petroleum based acid
slurry. The use of coconut oil and rosin gives good foaming and cleaning properties.
These products will support green chemistry as the raw materials are of
vegetable origin.
INTRODUCTION:
A novel polymeric surfactant based on coconut oil1,
maleic anhydride2 and rosin3
has been synthesized, technically it is a rosinated
short oil alkyd resin4. Short oil alkyd5 resin has been
successfully used as polymeric surfactants in various powder and liquid
detergents. In this piece of research work, the mole ratio, catalyst and
heating schedule has been standardized to get an alkyd resin with molecular
weight in the range of 3000 to 5000. The conditions have been worked out to get
desired acid value, hydrophilic-lipophlic balance5,
viscosity and solubility chacteristics.
An effort has
been made to replace crude petroleum based acid slurry and alpha olefin sulphonate (AOS) with novel polymers. Two selected polymers
have been used for formulation of powder. (Given in table no.1) The special
feature of our polymers is use of 50 to 60% rosin which is abundantly
available. The other ingredients are minor proportions of coconut oil 25 to
30%, glycerol 10% and maleic anhydride 7.5%. The
combined used of rosin and coconut oil gives good foaming and cleaning
properties.
India Coconut Oil
Production by Year
|
Market Year
|
Production
|
Unit of Measure
|
change
|
|
2008
|
25
|
(1000 MT)
|
0.00 %
|
|
2009
|
25
|
(1000 MT)
|
0.00 %
|
|
2010
|
25
|
(1000 MT)
|
0.00 %
|
The World
production of coconut oils is of order of 25000MT per annum. These figures
indicate steadily and abundant supply of coconut oil throughout the year.
Table No: 1 Composition of
Novel polymers
|
Sr. No
|
Ingredient
|
% By weight
|
|
AR1
|
AR 2
|
|
1
|
Coconut oil
|
30
|
25
|
|
2
|
Maleic anhydride
|
7.5
|
7.5
|
|
3
|
Rosin
|
52.5
|
57.5
|
|
4
|
Glycerol
|
10
|
10
|
Catalyst used: 1.5% sodium Bisulphate And 0.5% sodium bisulphite on weight of total mass.
EXPERIMENTAL:
Preparation of Novel Polymers:
The polymer was prepared in a three neck glass reactor
fitted with stirrer condenser and temperature control of +/-2 0C. A
novel catalyst 1.5% sodium bisulphite and 0.5% sodium
bisulphate has been used for this reaction. The composition cooking schedule
and analysis of novel polymer is given in table no .2.
Table No.2 Cooking schedule of
Novel Polymers
|
Sr. No.
|
Time (Hr)
|
Temp(0c)
|
|
1
2
3
4
|
0.00— 2.00
2.00— 4.00
4.00— 6.00
6.00— 8.00
|
130
225
200
200
|
Neutralization of novel Polymer
with aqueous KOH: - 100 gm
of Novel polymer was heated to 70 0C
the calculated amount of 30%KOH was added to novel polymer with constant
stirring so as to get slightly alkaline solution of polymer with PH of 8.
Preparation of Detergent
Powders;
Detergent powder was prepared in a laboratory blender
mixer and finally moisture content of 4-5% has been maintained in finished
powder. Two type of detergent powder have been prepared one based totally on a
novel polymer and in other sample 50% of novel polymer has been replaced by
alpha olefin sulphonate and acid slurry.
Surface Tension6: The surface tension of powder detergents
was measured using stalagnometer with standard
techniques.
Foam volume7: foam is a dispersion of gas relatively in a
small amount of liquid. This was measured by Cylinder Method using stoppered glass of one thousand ml capacity.
Detergency Test8: This includes the following steps:
Preparation of Soil Medium8: The soil medium was prepared in following
manner. The mixture of carbon black (28.4%) and lauric
acid (17.9%) along with mineral oil (17.9%) was taken in a pastle
mortal. The contents were grind for about 1-2hours. About 2gm of above paste
was dispersed in 500ml of carbon tetrachloride. This solution was used for
soiling of fabrics.
Fabrics Washing9: The solutions of 1% concentration of powder
detergents in distilled water were prepared. These solutions were heated to 600C
and stained fabrics were dipped in it for five minutes. Ten to and fro hand
washes in tap water were given with equal strokes. After washing, the test
materials were rinsed in running tap water, dried and ironed. The same parallel
technique was adopted for commercial scale. The %detergency was found out by
using Lambert and Sanders formula9.
(Rw
– Rs) x 100
% Detergency =
(Ro – Rs)
Where,
Rw, Rs and Ro are the reflectance measured on washed
fabrics, stained fabrics (before washing) and clean fabrics respectively. The
reflectance was measured with a Digital Gloss Meter-Model-RSPT-20.
Table No .3 – Analysis of
Novel Polymers
|
Sr. No
|
Analysis
|
Result
|
|
AR1
|
AR 2
|
|
1
|
Acid value
|
28.71
|
32.57
|
|
2
|
% solid
|
83%
|
84%
|
|
3
|
HLB
|
13.21
|
13.20
|
|
4
|
PH
|
4.7
|
4.42
|
|
5
|
Solubility
|
CCl4
|
CCl4
|
|
6
|
Mol. Wt
|
4245
|
4027
|
|
7
|
Viscosity (By ford
Cup No.4 in sec.)
|
293
|
281
|
|
8
|
Saponification value
|
320.571
|
352.09
|
|
9
|
Oxygen-oxygen
content
|
16.45
|
16.30
|
RESULT AND DISCUSSION
1) The composition of Novel polymers are given in table
no. 1; A large quantity of rosin has been used. Rosin gives good foam,
solubility and brilliant appearance to various soap and detergent compositions.
However we are using large proportion of rosin, which will also act as a chain
stopper for alkyd synthesis. The cooking schedule has been standardized. The
time of heating was 8 hours. The higher oxygen-oxygen, HLB value of 13.00,
viscosity and molecular weight of novel polymers suggest their use in detergent
compositions. Analysis of polymers is given in table no. 3.
2) The composition of detergent powders is given in
table no. 4 the concentration of novel polymer has been varied from 10 to 20%.
In the subsequent compositions novel polymer has been replaced by 50% alpha
olefin sulphonate. The concentration of all other ingredients has been maintained
at a constant level EDTA helps in Ca and Mg sequisterizetion
, sorbitol gives
smooth and pleasant feel to the powder.
3) The foam volume measured at various concentrations
is given in table no.7. The samples totally based on polymer have a low foaming
capacity but reduction in surface tension is appreciable. The polymer based
formulations can also give an excellent detergency from 88 to 98%. This data
certainty indicates that rosinated novel polymer has
all the desirable chacteristics at 0.25%
concentration. Various cloths like terricot, cotton
and polyester give the same positive results.
Table No .4 –
Composition of powder detergents
|
Sr.
No.
|
Ingredients
|
Sample
(% by weight)
|
|
PD1
|
PD2
|
PD3
|
PD4
|
PD5
|
PD6
|
PD7
|
PD8
|
|
1.
|
Sodium carbonate
|
8.5
|
8.5
|
8.5
|
33.25
|
33.25
|
47.50
|
47.50
|
47.50
|
|
2.
|
Alkyd Polymer (AR-1)
|
---
|
5.34
|
10.68
|
4.45
|
8.9
|
---
|
---
|
---
|
|
3.
|
Alkyd Polymer (AR-2 )
|
---
|
---
|
---
|
---
|
---
|
---
|
5.34
|
10.68
|
|
4.
|
Acid slurry
|
9.96
|
4.98
|
---
|
4.15
|
---
|
---
|
---
|
---
|
|
5.
|
Sodium lauryl Sulphate
|
5.0
|
5.0
|
5.0
|
5.0
|
5.0
|
---
|
---
|
---
|
|
6.
|
Sodium silicate
|
--
|
--
|
--
|
3.0
|
3.0
|
---
|
---
|
---
|
|
7.
|
Sodium sulphate
|
30.0
|
30.0
|
30.0
|
15.0
|
15.0
|
14.0
|
14.0
|
14.0
|
|
8.
|
Dolomite
|
20.0
|
20.0
|
20.0
|
14.0
|
14.0
|
---
|
---
|
---
|
|
9.
|
Salt
|
12.0
|
12.0
|
12.0
|
10.0
|
10.0
|
10.0
|
10.0
|
10.0
|
|
10.
|
Sodium tripolyphosphate
|
3.0
|
3.0
|
3.0
|
---
|
---
|
5.0
|
5.0
|
5.0
|
|
11.
|
Urea
|
---
|
---
|
---
|
---
|
---
|
5.0
|
5.0
|
5.0
|
|
12.
|
Additives
|
1.75
|
1.75
|
1.75
|
1.75
|
1.75
|
2.1
|
2.1
|
2.1
|
|
13.
|
EDTA
|
0.5
|
0.5
|
0.5
|
0.5
|
0.5
|
0.5
|
0.5
|
0.5
|
|
14.
|
CMC
|
---
|
---
|
---
|
---
|
---
|
0.5
|
0.5
|
0.5
|
|
15.
|
alpha olefin sulphonate
|
4.35
|
4.35
|
4.35
|
4.35
|
4.35
|
10.44
|
5.22
|
---
|
|
16.
|
%moisture
|
4.94
|
4.58
|
4.22
|
4.55
|
4.25
|
4.96
|
4.84
|
4.72
|
Abbreviations: EDTA-
Ethylene diamine tetra acidic acid; CMC-Carboxyl
Methyl Cellulose
Additives:- 2% Robin Blue powder was churered with sorbitol for 2
hours in a pastel mortel. The homogenized paste was
used as additives.
Table No .5:- Detergency
evaluation of Individual Novel Polymers and conventional Soft Slurry and Alpha
Olefin Sulponate
|
Cloth
|
Medium for Staining
|
Conc.
in %
|
% detergency
|
Commercial Products
|
|
AR1
|
AR 2
|
Acid Slurry
|
Alpha Olefine Sulponate
|
|
Cotton
|
Soil solution
|
0.1%
|
44
|
63.32
|
62.00
|
58.20
|
|
0.25%
|
54
|
67.76
|
66.50
|
63.60
|
|
0.5%
|
66
|
71.46
|
70.85
|
69.80
|
|
1.0%
|
84.61
|
83.33
|
85.00
|
83.33
|
|
2.0%
|
78.46
|
81.66
|
87.25
|
86.28
|
|
3.0%
|
73.84
|
78.12
|
89.00
|
87.50
|
Table No .6 – Evaluation of
detergency
|
Cloth
|
Medium for Staining
|
Conc. in %.
|
% Detergency by detergent powder
|
|
PD1
|
PD2
|
PD3
|
PD4
|
PD5
|
PD6
|
PD7
|
PD8
|
CD1
|
|
Cotton
|
Soil Solution
|
0.1
|
71.50
|
78.86
|
77.52
|
82.12
|
81.75
|
83.31
|
82.37
|
79.79
|
80.12
|
|
0.25
|
73.84
|
79.12
|
78.32
|
83.10
|
83.67
|
85.11
|
84.31
|
81.17
|
83.31
|
|
0.5
|
78.46
|
81.86
|
80.32
|
85.32
|
84.01
|
86.32
|
86.17
|
83.27
|
85.00
|
|
1.0
|
84.61
|
83.33
|
81.66
|
87
|
86.12
|
87.67
|
88.12
|
85.11
|
81.77
|
|
Tea Solution
|
0.1
|
89.25
|
89.56
|
90.63
|
89.74
|
89.88
|
90.56
|
90.25
|
89.25
|
89.25
|
|
0.25
|
89.56
|
89.23
|
89.22
|
89.54
|
89.74
|
89.45
|
89.75
|
89.85
|
90.12
|
|
0.5
|
89.75
|
89.56
|
89.96
|
89.45
|
89.74
|
88.56
|
89.69
|
89.54
|
89.23
|
|
1.0
|
90.12
|
91.23
|
91.45
|
93.12
|
92.56
|
93.45
|
93.25
|
94.23
|
93.84
|
|
Coffee Solution
|
0.1
|
84.23
|
85.23
|
84.21
|
86.25
|
85.56
|
89.23
|
86.23
|
85.40
|
84.25
|
|
0.25
|
85.23
|
84.56
|
85.25
|
85.56
|
85.65
|
85.54
|
85.56
|
84.25
|
85.23
|
|
0.5
|
86.77
|
89.75
|
88.23
|
87.54
|
88.56
|
88.23
|
87.23
|
88.23
|
89.21
|
|
1.0
|
89.56
|
89.23
|
90.23
|
91.25
|
91.58
|
92.65
|
93.14
|
92.45
|
93.12
|
4) Use of 50% alpha olefin sulphonate
gives good foam height, further reduction in surface tension andexcellent stain removing properties. A perfect synergism
is observed at 50:50 levels of alpha olefin sulphonate
and Novel Polymer.
5) The detergent powder based on acid slurryand novel polymer also gives excellent foam height
and stain removing properties10. Detergent Powder totally based on
Novel Polymer give reduction in surface tension and effective at lower dosage
of detergent (0.1%).
CONCLUSION:
- The following conclusions
stand confirm in the light of above experimental work
1) A useful novel polymer of desired molecular
weight and acid value11 can be prepared based on higher proportions
of rosin and smaller proportions of coconut oil, maleic
anhydride and glycerol. The order of reaction, time of heating, cooking
schedule and catalyst has been standardized. The method of cooking is simple,
easy to operate and without complications. Normally polymer cooking requires a
heating schedule of 12 to 15 hours while our heating schedule is of 8 hours
duration. This is certainly saving time and energy, the process is smooth and
easy to operate.
Table No
.7-Analysis of Detergent Powders
|
Powder
Detergent
|
Concentration
In
%
|
Foam
volume
|
PH
|
Surface
tension
(dyne/cm)
|
|
0
|
5
|
10
|
15
|
|
PD -1
|
0.1
|
600
|
600
|
550
|
500
|
8.5
|
24.26
|
|
0.25
|
600
|
600
|
550
|
500
|
8.0
|
23.85
|
|
0.5
|
650
|
650
|
600
|
600
|
8.0
|
21.21
|
|
1
|
700
|
700
|
650
|
600
|
8.0
|
20.92
|
|
PD-2
|
0.1
|
500
|
450
|
450
|
400
|
8.0
|
30.12
|
|
0.25
|
500
|
450
|
400
|
350
|
8.0
|
29.20
|
|
0.5
|
550
|
500
|
450
|
400
|
8.5
|
28.96
|
|
1
|
600
|
550
|
500
|
450
|
8.5
|
28.26
|
|
PD-3
|
0.1
|
450
|
400
|
400
|
300
|
8.0
|
29.16
|
|
0.25
|
450
|
400
|
400
|
400
|
8.0
|
28.35
|
|
0.5
|
500
|
500
|
450
|
400
|
8.5
|
27.98
|
|
1
|
600
|
600
|
550
|
500
|
8.5
|
27.29
|
|
PD-4
|
0.1
|
400
|
400
|
350
|
300
|
8.0
|
34.34
|
|
0.25
|
450
|
400
|
400
|
350
|
8.0
|
33.78
|
|
0.5
|
500
|
500
|
450
|
450
|
8.5
|
32.64
|
|
1
|
600
|
600
|
550
|
450
|
8.5
|
31.98
|
|
PD-5
|
0.1
|
400
|
350
|
350
|
300
|
7.5
|
35.01
|
|
0.25
|
450
|
400
|
350
|
300
|
7.5
|
34.18
|
|
0.5
|
500
|
450
|
400
|
350
|
8.0
|
33.31
|
|
1
|
500
|
550
|
500
|
450
|
8.0
|
32.78
|
|
PD-6
|
0.1
|
450
|
400
|
400
|
300
|
7.5
|
42.45
|
|
0.25
|
500
|
450
|
450
|
400
|
7.5
|
41.89
|
|
0.5
|
550
|
550
|
450
|
400
|
8.0
|
41.11
|
|
1
|
600
|
550
|
550
|
500
|
8.0
|
40.12
|
|
PD-7
|
0.1
|
400
|
350
|
350
|
300
|
7.5
|
42.88
|
|
0.25
|
400
|
350
|
300
|
300
|
7.5
|
42.07
|
|
0.5
|
450
|
400
|
350
|
300
|
8.0
|
41.51
|
|
1
|
500
|
450
|
400
|
350
|
8.0
|
40.97
|
|
PD-8
|
0.1
|
350
|
300
|
300
|
250
|
7.5
|
27.51
|
|
0.25
|
400
|
400
|
350
|
300
|
7.5
|
26.19
|
|
0.5
|
450
|
400
|
350
|
300
|
8.0
|
20.01
|
|
1
|
500
|
450
|
450
|
400
|
8.0
|
25.01
|
|
Commercial sample CD-1
|
0.1
|
500
|
450
|
450
|
400
|
7.5
|
25.98
|
|
0.25
|
550
|
500
|
450
|
400
|
7.5
|
25.41
|
|
0.5
|
600
|
550
|
500
|
450
|
8.0
|
24.63
|
|
1
|
650
|
600
|
600
|
550
|
8.0
|
24.33
|
2) The physicochemical analysis of novel
polymer12 shows that this is a polymer with acid value 28 to 35 and
HLB ratio of 13 to 14.The neutralization of this polymer is easy and feasible
as it has higher acid value. So we can convert this polymer into water soluble
product by neutralization with various alkalies .The
HLB ratio point out the possibility of using this novel polymer in liquid,
powder and cake detergents.
3) Various powder detergent compositions based
on novel polymer give excellent detergency13 and reduction in
surface tension. The foam volume of various composition and foam stability is
also good. These entire ecofriendly samples have excellent detergency
characteristics comparable to commercial sample.
4) A synergetic combination of alpha olefin sulphonate and novel polymer give extraordinary result in
reference to surface tension reduction, detergency, stain removing and foaming
properties. A 50:50 combination of alpha olefin sulphonate
and novel polymer give optimum results sample P-4 and P-7 shows extra ordinary
excellent result. Thus formulation P-4 and P-7 can be recommended for pilot
scale and commercial studies.
5) Sample P-3 and P-8 which is total
replacement of acid slurry and alpha olefin sulphonate
is also showing appreciable results. A synergetic combination of acid slurry
and novel polymer give excellent performance characteristics i.e. sample P-2
and P-4.
6) Individual detergency test of Novel
Polymer at 1% concentration are 83-84% which is comparable or more than
individual detergency of commercial active ingredient i.e. acid slurry, sodium lauryl sulphate and alpha olefin sulphonate this again shows that our Novel Polymer can
totally replace petroleum based acid slurry.
7) Raw material cost of this detergent
powder cum stain remover is around Rs. 28/kg which is certainly an attractive
preposition. There is an urgent need to take up these compositions on pilot
plant and commercial scale. Our samples are not only comparable but in some
instance superior to commercial samples.
REFERENCE:
1. Fulzele S.V., SatturwarP.M,
GogteB.B.,DorleA.K, email:fsuniket@yahoo.co.in.
2. Gogte B. B., Bhagwat A.M,j .Soaps Deter.
Toilet rev, 36(2004) 20-25
3. Gogte B.B., Dontulwar
J.R., Asian journal of chemistry, 16(2004)1385-1390
4. Kirk, o., Encyclopedia of chemical
technology,(11)269-270 http:/www.nirri.org
5. Garrett H.E., Surface active chemicals
Programmer press, New York,
1972
6. ASTM standard method 6.01, d1639-70(for acid
value of organic coating material), published by the American Society for
Testing Material, Philadelphia,
1981.
7. Jellinia, Stephan, J, Encyclopedia of chemical
technology, 20, John Wiley and sons, New
York, 1982, p-780
8. Harris, J.C. Detergency Evaluation and
Testing Inters science publisher, inc., New
York, 1984
9. National institute of Hand Book
of industrial Research, Hand Book of Soaps, Detergent and acids Slurry by
N.I.I.R. Board.
10. Bauvy, A. Leversidge,
Paint India,
March-1985, p.45-52.
11. Kirk Othmer,
“Encyclopedia of chemical Technology,” 20, John Willey and Sons, New York, 1982, p.
780-805.
12. Suri S.K, “Synthetic Detergent powder changing
Trends –I, Soaps Detergents and Toiletries Review,” September-200, p.14-18.
13. Kharkate, S.K. Kardbhajne
.V.Y. and Gogte, B.B: Journal of Scientific and
industrial research, vol.64, October 2005, p .752-755.