Sei sulla pagina 1di 24

Studies in the Functionalisation of

LMWNR Using Different Compounding


Mixing Schemes.

A paper delivered by

Dosu Malomo , PhD


FEDERAL UNIVERSITY OYE EKITI, NIGERIA

At
TIRE TECHNOLOGY EXPO, COLLOGNE, GERMANY
10TH FEBRUARY 2015
INTRODUCTION
Natural rubber is obtained in commercial quantity from the tropical tree of Hevea brasiliensis
Standard NR grades are good produced by Malaysian, Indonesia, Singapore, Thailand and
Nigeria.
It has wide applications in manufacturing industry, medicine and
pharmaceuticals due to the following reasons:
High tensile strength
High tear resistance
Availability
Cheap price
But it suffers stiff competition from synthetics such as SBR, IR, NBR, EPDM due to some limitations
such as follows
Poor oil resistance
Poor resistance to hydrocarbon solvents
High permeability to gases
High sensitivity to oxygen and ozone
Inconsistency in quality
NOTE: the production of tyres and tyre based gods can almost depend exclusively on the use of NR.
The aim of the research work is to produce low molecular weight natural rubber which is self-peptizing
and plasticizing and changing mixing orders of compounding ingredients for maximisation of mixing
benefits and vulcanizate properties which are likely to meet tire production standards.

The depolymerisation and functionalisation processes are expected to impact chemical peptization
which should improve the homogienighty
The reduction in fossil material used as additives will reduce thereby encouraging the green
compounding principles.
The major objectives of the work include:
Characterisation of NSR Latex-NIG 902
Characterisation of The Crumb Rubber
Depolymerisation of the NSR Latex
Epoxidation
Thioglycollisation
Compounding with 3 mixing orders
Characterisation of Vulcanizates
TARGET PROPERTIES
The new set of NR is believed to have the following properties:
Improved processing
High loading due to faster filler incorporation.
Reduced scorching
Lower energy consumption
Improved mould flow
Lower plasticity
Non volatile
Improved green tack
Easy vulcanization with conventional networks
Better dispersion of compound ingredients
Improved blending properties.
The technology of tire production encourages
Improved rolling Resistance
Wet grip properties
Fuel economy
Improved processing characteristics
Excellent dynamic properties
Tread wear resistance

The following researchers among several have reported efforts towards achieving these benefits
Isabella J Rahmn Optimizing tire properties with Naphthenic oils- TIRE EXPO 2014
Saikit Das Gupta Non linear rheology prediction of rubber behaviour-TIRE EXPO 2014
Fernanda Albina New modified NdBR rubbers processing aid for green tires.-TIRE EXPO 20-14
This work stands to achieve these desired benefits through depolymerisation, functionalisation and
changes in mixing orders.
EXPERIMENTAL DESIGN
Materials used
Natural rubber latex of 902 clone were collected from RUBBER
RESEARCH INSTITUTE OF NIGERIA
All chemical used were of analytical grades

Equipment Used
Ubelhode Viscometer
UV-V Spectrophotometer
FTIR
XRF
Preparation of LMWNR (LNR)
Different samples of 20% DRC natural rubber stabilised with sodium
laurate were prepared by using 0.5, 1.0, 1.5, 2.0 and 2.5% nitrobenzene.

Nine samples of each concentration were prepared and continuously


stirred (60rpm) for 0.0, 0.5, 1.0,1.5, 2.0, 4.0.6.0, 8.0 and 10 hours.

Total of 45 samples were therefore studied.

At the end of each reaction time, LMWNR was recovered by using


formic acid solution.
Characterisation of LMWNR
Molecular weight determination was carried out by using the viscosity
measurements in Toluene.

The time taken for the pure solvent and various polymer solutions were
recorded and used for calculations of the molecular weights.
The Mark Houwinks equation
= KMva
where
is intrinsic viscosity
Mv is viscosity average molecular weight
K and a are polymer constants in specific solvents
EPOXIDATION
The method by Okwu et al was used. Latex was depolymerised
with the formic acid-hydrogen peroxide mixture.

THIOGLYCOLLISATION
The ELMWNR produced was dissolved in Chloroform and
reacted with thioglycolic acid for 20hrs and recovered with
formic acid to give ELMWNR-TGA
SCHEME 1- NR + MODIFIED RUBBER + COMP INGR
SCHEME 2- NR + COMP INGR + MODIFIED RUBBER
SCHEME 3- MODIFIED RUBBER + COMP INGR + NR

RHEOLOGICAL PROPERTIES
This was done at 175oC WITH ALPHA ODR 2000 Rheometer ISO3417

CURING PROCEDURE: DOUBLE DAY LIGHT PRESS AT 150-170OC


PHYSICO-MECHANICAL PROPERTIES : TENSILE STRENGHT, COMP SET
HARDNESS AND ABRASSION RESISTANCE
RESULTS AND DISCUSSION
Table 1: Characterization of the latex

Parameters NIG (902)


Total Solid Content (TSC) % 40.01.32
Dry Rubber Content (DRC) % 36.01.32
Mechanical Stability Time (MST) Sec. 655.01.2
Coagulum Content (CC) % 0.0461.4
Sludge Content (SC) % 0.101.2
Volatile Fatty Acids (VFA) % 0.160.19
Table 2: Dilute solution viscosity measurements of LMWNR using 0.5%
nitrobenzene, others are 1.0, 1.5, 2.0 and 2.5% nitrobenzene
Reaction Time Concentration ts ts/to (ts/to)-1 sp/C
0.0 h
0.04 24.00 1.1180 0.1180 2.95
0.08 27.00 1.2561 0.2561 3.20
0.12 30.50 1.4143 0.4143 3.45
0.16 34.50 1.6082 0.6082 3.80
0.20 38.50 1.7944 0.7944 3.97

NOTE
SAME WAS REPEATED FOR 0.5,1.0,1.5,2.0,4.0,6.0,8.0 and 10.0 HOURS
REACTION TIMES
Reaction time(h)

Concentrations 0.0 0.5 1.0 1.5 2.0 4.0 6.0 8.0 10.0
Of LMWNR g/100ml

0.04 2.95 2.95 2.55 2.08 1.70 1.43 1.35 1.35 1.28

0.08 3.20 3.20 2.82 2.40 2.00 1.70 1.60 1.60 1.50

0.12 3.45 3.45 3.20 2.80 2.30 1.95 1.83 1.84 1.75

0.16 3.80 3.80 3.50 3.10 2.60 2.20 2.10 2.08 2.02

0.20 3.97 3.97 3.76 3.48 2.90 2.45 2.40 2.40 2.25
4.5 0 hr
4
0.5 hr
3.5
1.0 hr
3
1.5 hrs
sp/C

2.5
2 2.0 hrs
1.5 4.0 hrs
1 6.0 hrs
0.5 8.0 hrs
0
10 hrs
0 1 2 Conc. g/100ml
3 4 5 6

Fig 1: Huggins plots of reduced viscosities versus concentrations of


LMWNR obtained by using 0.5% nitrobenzene at various
reaction times
Table 4.0: Variation of molecular weight of natural rubber as a
function of time using different concentrations of nitrobenzene

Reaction Viscosity average molecular weight (Mv) x 104


Time (h)
Concentration of nitrobenzene (% DRC of Latex)
0.5 1.0 1.5 2.0 2.5
0.0 3.57 3.57 3.48 3.57 3.53
0.5 3.57 3.57 3.48 3.12 3.12
1.0 2.77 2.68 2.43 2.35 2.18
1.5 1.95 1.95 1.87 1.64 1.43
2.0 1.47 1.49 1.49 1.22 1.22
4.0 1.15 1.02 1.02 0.95 0.95
6.0 1.02 0.97 0.83 0.89 0.89
8.0 1.02 0.93 0.83 0.89 0.89
10.0 0.89 0.89 0.87 0.83 0.83
Table 5: Extent of epoxidation of low molecular weight
natural rubber with time at varying ratios of 90% formic acid
to 30% Hydrogen peroxide
Extent of Epoxidation (% Epoxide)

Composition of epoxidisng mixture (90% Formic acid in 30% Hydrogen peroxide)

Reaction Time (hr) 20 % Composition 25 % Composition 30 % Composition 35 % Composition

3 10 13 15 17

3.5 13 17 17 22

4 18 21 22 28

4.5 20 24 24 32

5 23 27 26 34

5.5 25 29 31 35

6 26 30 31 35
20 % Composition 25 % Composition
30 % Composition 35 % Composition
40.00
Extent of Epoxidation

30.00

20.00
(%)

10.00

0.00
0 1 2 3 4 5 6 7
Reaction Time (hrs)
Figure 2. The extent of epoxidation (% epoxide) at different
reaction time using various concentrations of performic acid
0.02 Conc. 0.04 Conc. 0.06 Conc.
0.08 Conc. 0.1 Conc. 0.12 Conc.
25.00
Level of thioglycollic

20.00
15.00
10.00
acid

5.00
0.00
0 1 2 3 4 5
Reaction time (hrs)

Figure 3 Variation in the level of Thioglycollic acid modification of ELMWNR


with reaction time using various concentrations of Thioglycollic
acid
Table 7.0: Physico-mechanical Properties of the Vulcanizates from NR and
LMWNR (18,700Mv) ELMWNR (35%) and TGA ELMWNR (20%)
Parameter Scheme 1 Scheme 2 Scheme 3

LMWNR (ELMWNR) TGA- LMWNR (ELMWNR) TGA- LMWNR (ELMWNR) TGA-


ELMWNR ELMWNR ELMWNR

Tensile strength 25.50 28.20 26.40 22.00 25.00 24.10 17.7 18.90 21.20
(Mpa)

Modulus at 50% 2.90 3.20 2.80 2.70 2.90 2.60 2.40 2.30 2.20
elongation (Mpa)

Modulus at 100% 6.60 8.10 6.70 5.40 7.30 5.70 4.70 6.40 4.60
elongation (Mpa)

Modulus at 200% 8.70 9.90 9.40 6.50 8.70 8.80 6.30 7.90 7.90
elongation (MPa)
Table 7.0 Continued
Parameter Scheme 1 Scheme 2 Scheme 3

LMWNR (ELMWNR) TGA- LMWNR (ELMWNR) TGA- LMWNR (ELMWNR) TGA-


ELMWNR ELMWNR ELMWNR
Elongation at 810.00 962.00 876.00 920.00 903.00 829.00 989.00 843.00 788.00
break (%)

Hardness 59.00 57.00 55.00 55.00 54.00 53.00 54.00 54.00 50.00
(IRHD)
Compression 44.00 45.00 43.00 42.00 44.00 43.00 42.00 42.00 41.00
set (%)
Abrasion 63.00 66.00 64.00 59.00 63.00 62.00 60.00 62.00 59.00
Resistance (%)
Figure 4 Variation in Tensile Properties with the three
schemes
Figure 5 Variation in Hardness, Compression set, Abrasion Resistance
and Elongation at Break for the three schemes
Conclusion
This study has shown that incorporation of 50% depolymerised
rubber into NR impacted a plasticizing effect on the polymer
blend. Owen et al11 reported similar observation for the ELNR -30
blended with PVC in 20:80 ratio. Epoxidizing the depolymerised
rubber further improved the quality of the vulcanizate
properties. It is believed that the inherent swelling and solubility
challenges of NR may be controlled by the presence of the epoxy
groups which polarise the polymer thereby increasing its dipole
moment. Attack by conventional solvents and hydrocarbon oils
will be minimal. Such vulcanizates may be suitable for
producing tires for vehicles.
The mixing orders affected the physico mechanical properties.
APPRECIATION:
RUBBER RESEARCH INSTITUTE OF NIGERIA
FEDERAL UNIVERSITY OYE EKITI, NIGERIA
Dr AK AKINLABI OF FED UNIVERSITY OF AGRIC
ABEOKUTA, NIGERIA

THANK YOU FOR LISTENING