The Effects of the Addition of Alkanolamide on Carbon Blacks Filled Natural Rubber Compounds

  

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  The effects of the addition of alkanolamide on carbon blacks filled natural rubber compounds _{1 2 3 1} I Surya , M Ginting , H Ismail ₂ Department of Chemical Engineering, University of Sumatera Utara, Medan, Indonesia ₃ Department of Science of Chemistry, University of Sumatera Utara, Medan, Indonesia School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Penang, Malaysia

  E-mail: indradanas@yahoo.com _[20]

  Abstract. The effects of theon of alkanolamide (ALK) on cure characteristics and filler

  dispersion of the two types of carbon black (CB) filled natural rubber (NR) compounds were _[41] investigated. The N-550 and N-220 types of CB were utilised, and each of them was incorporated separately into NR compound with a fixed loading, 30 . 0 phr. The ALK was

  synthesized from Refined Bleach ed Deodorized Palm Stearin he ALK loadings _[22]

  were 3. 0, 5.0 7.0 and 9.0 , phr. It was found that ALK could function as a secondary accelerator _{[22] [22]} and also an internal plasticiser . As a secondary accelerator ; ALK decreased the scd cure _[22] times of the N-550 and N-220 CBs filled NR compounds The higher the ALK loading . , the _{[22] [22]} shorter the scorccure times . As an internal plasticiser ; ALK decreased the minimum _[20] torque and improved the dispersions otypes of CB in NR phases . At a similar ALK _[22] loading ; N-220 exhibited higher cure rate, minimum and maximum torques and torque _[22] difference values . However, degree of filler dispersion of N-220 was poorer .

1. Introduction In rubber technology, a rubber compound contains a group of base rubber and rubber additives.

  

Each of them has a specific function either in processing, curing or end use of the rubber products [1].

Rubber or blend of rubbers will provide rubbery behavior to the compound; rubber additives such as

plasticisers are used to reduce viscosity, enhance deformability and alter properties; vulcanising agents

can crosslink the rubber chains; and accelerators improve the action of vulcanising agents to speed up

the cure rate.

  Rubber additives are classified into curative and non curative additives. Curative additives play

an important role in determining the cure characteristics of rubber compounds. They affect the rate and

nature of the vulcanisation process. The popular curative additives are sulphur or other vulcanising

agents, zinc oxide, stearic acid, and accelerators. _[33] Fillers are considered as non curative additives. The main purpose of utilising them is to

enhance the mechanical properties of rubber vulcanisates such as tensile strength, resistances to

_[33]

abrasion, tearing and flexing or cheapen the cost of products. Carbon black (CB) is the most popular

filler in manufacturing of various rubber ts, and normally CB is used to reinforce the rubber

_[24] compounds [

  2 -3]. However at a relatively higher loading, the filler particles tend to form Content from this work may be used under the terms of the Creative Commons Attribution 3. 0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. Innovation in Polymer Science and Technology 2016 (IPST 2016)

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agglomeration and will poor the filler dispersion. Practically, to overcome the filler dispersion

problem, special additives such as processing aid, dispersant aid, oil etc. are used.

  Alkanolamide (ALK) as a relatively new rubber additive is suggested to solve the filler dispersion problem. was synthesized from Refined Bleached Deodorized Palm Stearin (RBDPS) and It

ethanolamine. RBDPS is one type of vegetable oils which comes from palm tree. Physically, the

RBDPS-based ALK is an oily substance. Oil is one type of plasticising agents [4] and hence, ALK

potentially can be utilised to lubricate, plasticise or soften the CB filled NR compounds and improve

the CB dispersion in the rubber phases.

  Some previous works on ALK have been reported. The ALK enhanced the mechanical

properties of the silica-filled NR vulcanisates [5]. The enhancement of the properties was attributed to

the improvement of silica dispersion and the excel that ALK could function as an accelerator and

_[63]

internal plasticiser . Studied on t he comparison of ALK and aminopropyltriethoxy Silane (APTES)-

_[28]

silane coupling agent on the properties of silica-filled NR compounds [ 6] , it was reported that due to

its unique function as an accelerator and internal plasticiser, ALK produced a higher reinforcing

_[20]

efficiency than APTES at a similar loading . Studied on the effect of ALK loading on properties of CB-

filled NR , epoxidised natural rubber (ENR) and styrene butadiene rubber (SBR) compounds revealed

that ALK gave cure enhancement, better filler dispersion and greater rubber−filler interaction to three

different types of rubbers [ 7].

  In this study, the effects of ALK loading on the cure characteristics of CBs filled NR

compounds and degree of CB dispersion in the filled NR compounds were investigated. Two types of

CBs, N-550 and N-220, were used as the fillers. They are different in particle sizes. N-220 has smaller

particle size than N-550 [4].

  2. als and Methods _[20] 2.

  1 Materials NR grade SMR-L was obtained from Guthrie (M) Sdn . Bhd., Seremban, Malaysia. N-550 and _[21]

  

N-220 grades of CB were supplied by Cabot Corporation. Other compounding ingredients such as

suphur, zinc oxide, stearic acid, N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD ) and Mercapto

Benzothiazolyl disulfide (MBTS) were supplied by Bayer (M) Ltd. , Sdn. Bhd., Petaling Jaya,

Selangor, Malaysia. All materials were utilised as supplied. The ALK was synthesized in laboratory

using RBDPS and olamine. The chemical reaction of the preparation of ALK is presented in _[24] Figure 1. Innovation in Polymer Science and Technology 2016 (IPST 2016)

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_{H C O 2 C H C H C OH O 15 31 2 O O} CH CH OH _{3 2 CH} ^{H C O C} + ^{R 3 HN H C OH CH OH 3 CH (CH ) C} _{H C O C H C OH 2 C H RBDPS Diethanolamine Glycerol Alkanolamide O CH CH OH N} ² _{15 31 3} + _{2 2 CH 3 2 14 CH OH} ² _{2 2} ² Figure 1. Chemical reaction of the preparation of Alkanolamide.

  2.2 Laboratory Preparation of Alkanolamide The reaction was carried out at atmosphesure in a 1000 mL reaction vessel fitted with a _{[34] [34]}

stirrer. Typically 1. 0 mol of RBDPS, and 3 . 0 mol each of diethanolamine, sodium methoxide and

methanol (as catalysts) were placed in the reaction flask . The mixture was stirred and heated; the

o

reaction temperature was kept constant at 70 C for about 5 h. The resultant mixture was extracted with

diethyl ether and washed with saturated sodium chloride solution. The crude ALK was purified with

anhydrous sodium sulphate and then concentrated by a rotary evaporator. The cream-coloured and oily

ALK was characterized by Fourier transform infra-red (FTIR) spectroscopy. The infrared spectrum of

ALK presented in Figure 2. is _[20] 2.

  3 Compounding _[30] A semi-efficient vulcanisation system was used for the rubber compounding. The compounding

procedure was done in accordance with the American Society for Testing and Material (ASTM) –

_[20]

  

Designation D 3184 80. – The compounding was performed on a two-roll mill (Model XK-160). Table

1 displays the compound formulation of CBs filled NR compounds with various ALK loading. _[26]

• _* Table 1. The composition of the CBs filled NR compounds.

  Ingredients Content (phr ) SMR-L 100. Zinc oxide

  5.0 Stearic acid

  2.0 IPPD

  2.0 MBTS

  1.5 Sulphur

  1.5 CB (N-220/N- 550)

  30.0

• _* ALK 0.0; 3.0; 5.0; 7.0; 9.0

  parts per hundred part of rubber _[21] 2.

  4 Cure Characteristics The cure characteristics of the CBs filled NR compounds with and without ALK were obtained

using a Monsanto Moving Die Rheometer (MDR 2000) which was employed to determine the scorch Innovation in Polymer Science and Technology 2016 (IPST 2016) _[21]

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time (ts 2 ), cure time (t 90 ), minimum torque (M L ), maximum t(M H ) and torque difference (M H — _[26] o

  M ) according to ISO 3417 . Samples of the respective compounds were tested at 150 C. _[59] L

3. Results and Discussion 3 .

  1 Characterization of ALK Figure 2 shows the typical infrared spectrum of the ALK which was obtained from RBDPS and

ethanolamine. The spectrum clearly shows the presence of wavenumbers of the functional groups of

ALK such as O-H, C=O and C-N groups. _[58] Figure 2. The infrared spectrum of ALK from RBDPS and ethanolamine.

  3.

2 Cure Characteristics

  The effects of ALK loading on the cure characteristics of the two different types of CBs (N-550 _[22]

and N-220) filled NR compounds are presented in Table 2 . The cure characteristics were measured at

o 150 C including scorch and cure times , minimum and maximum torques and torque differences.

  Scorch time is the required time to reach the two torque units rise above the minimum torque.

Scorch time is considered as the required time at which vulcanisation begins, and cure time is the

reque for a rubber compound to reach 90% of the state of cure -9). (8 _[33]

  As presented i Table 2, n it was observed that the scorch times (ts 2 ) of CB filled s NR compounds

with ALK were lower than those of without ALK (control compounds). The higher the ALK loading,

the lower were the scorch times. The curing systems of those two rubber compounds used MBTS as

the accelerator, and it functionally classified as a primary accelerator which usually provides scorch is

delay to a rubber compound (4, 10). The lower the mass ratio of MBTS, the lower was the scorch

safety. The addition of ALK reduced mass ratios of the base rubber (NR) and also rubber additives.

This explained why the scorch times tended to slightly decrease when the ALK was added. _[34]

  Table 2. Cure characteristics of CBs filled NR compounds at various ALK loadings Innovation in Polymer Science and Technology 2016 (IPST 2016)

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  ALK Loadings (phr) CBs filled NR Compounds

  0.0 (Control)

  3.0

  5.0

  7.0

  9.0 N-550 filled ts ^{2 , min}

  3.36

  1.79

  1.35

  1.20

  1.14 t ^{90 , min} _H

  7.21

  4.10

  3.50

  3.26

  3.17 M , dN.m

  6.66

  8.40

  8.66

  8.56

  8.18 M L , dN.m

  0.33

  0.30

  0.16

  0.14

  0.12 M H ―M L , dN.m

  6.33

  8.10

  8.50

  8.42

  8.06 N-220 filled ₂ ts , min

  2.13

  1.42

  1.26

  1.12

  1.08 t ^{90 , min} _H

  5.56

  3.45

  3.16

  2.88

  2.80 M , dN.m _L

  8.42

  11.95

  9.80

  9.52

  9.42 M , dN.m

  0.39

  0.37

  0.33

  0.32

  0.29 M H ―M L , dN.m

  8.03

  11.58 9.

  47

  9.20

  9.13 From Table 2, it was also observed that the addition of each 3.0 phr of ALK into the control

  compounds decreased the cure time (t 90 ). Lower cure time means higher cure rate and hence, a c _[21]

enhancement phenomenon was observed. It was attributed to the function of ALK as a curative agent

(secondary accelerator) in the curing or vulcanisation process. In rubber compounding, amine is

usually utilised not only as an accelerator but also an accelerator activator [7,11]. In the case of the

cure enhancement phenomenon, the amine part of ALK together with zinc oxide and fatty acid,

activated the MBTS-accelerator more pronouncedly and hence, improved tof sulphur reaction

_[33]

of CB filled s NR compounds. It was also observed that the higher the ALK loading, the more

pronounced the cure enhancement. It was simply attributed to a higher amount or mass ratio of amine

in t NR compounds. _[20] At a similar ALK loading, the scorch and cure times of N-220 were shorter than those of N-550. _[21]

It was simply attributed to the difference in sizes of their particles. According to Fetterman [12-13] ,

CB will react with sulphur during vulcanisation and form sulphur bonds that link the rubber chains and

also rubber filler bonds. The nature of rubber filler bond is determined by some factors and one of – – _[61]

is the surface activity of filler. Greater surface area tends to provide greater surface activity [14].

N-220 has a smaller particle-size or greater surface area than N-550 [ 4] and hence, shorter scorch and

cure times of N-220 were due to its greater surface activity which reduced time to complete the rubber

– filler bonds formation.

  Table 2 shows that the additions of 3.0 phr of ALK decreased the minimum torques (M ) of L

both control compounds. The M value is used to measure of the viscosity of a rubber compound ([5].

  L

The lower the M value, the lower is the viscosity. The addition oreduced the viscosity of the

  L _[21]

CBs filled NR compounds. This was attributed to the additional function of ALK as an internal

plasticiser which plasticised, softened and reduced the viscosity of the filled NR compounds, respectively. The higher the ALK loading, the lower was the viscosity. Innovation in Polymer Science and Technology 2016 (IPST 2016)

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  Table 2 also shows that the addition of each 3. 0 phr of ALK increased the torque difference

(M ―M ) values of both control compounds. N-550 and N-220 have different trends of torque

  H L _[69]

differences with further increases the ALK loading. The torque difference of N-550 was further

increased with the addition of ALK up to 5. 0 phr, and decreased beyond the loading. Whilst, the

torque difference220 was increased by the addition of 3.0 phr, and decreased beyond the

_{[26] [30]}

loading. The torque difference indicates the degree of crosslink density of a rubber compound [ 7, 16].

  

The greater the value, the higher is the crosslink density . The increasing of torque difference or

crosslink density up to the optimum loadings of ALK (5.0 phr for N-550; 3.0 phr for N-220) was

attributed to the chemical and physical properties of ALK. The nitrogen atom or the amine constituent

of ALK activated chemically not only the rubber but also the elemental suphur during suphuration or

curing reaction. Together with the others curatives, amine could form intermediate complexes which

attached the available elemental suphur to rubber chains more efficient [4], causing higher degree of

cure. The nitrogen atom also can act as a hydrogen acceptor and amine accelerators can activate the

elemental suphur and/or the rubber for the curing reaction [4].

  Physically, ALK is an oily material and has the function as an internal plasticiser agent. As discussed earlier, ALK reduced the viscosity of the CBs filled NR compounds. improved the CB It _[20] – dispersion and rubber - filler interaction/bond, respectively. The rubber filler defined as is

additional physical crosslinks [17] , and together with sulphide crosslinks contribute to total crosslink

density of a rubber vulcanisate [ 10, 18].

  The reductions of the torque differences, beyond the optimum loadings, were most probably

attributed to the dilution effect of the excessive amounts of ALK which formed some oily layers.

These layers might absorb a part of CB filler and other curatives and coated them together. By this

mechanism, the total crosslink density was reduced. _[38] 3.

3 Filler Dispersion

  Based on torque properties data in Table 2, the degree of CBs dispersion in NR phases, with and without ALK, can be quantitatively calculated by Equation (1 ) [ 7, 19-20].

  L = η r — m r (1)

where: η = [M / M ], and m = [M / M ]; where M and M are the minimum and maximum

r Lf Lg r Hf Hg Lf Hf

torques of the filled compounds, and M and M are the minimum and the maximum torques of the

  Lg Hg

unfilled/gum rubber compound. A lower value of L, at a particular CB loading, meant a better degree

of CB dispersion. The minimum and maximum torques of gum NR compounds were 0.05 and 4.85 , respectively. Innovation in Polymer Science and Technology 2016 (IPST 2016)

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  Figure 3 shows the values of L for CBs dispersion in the NR phases at various ALK loading. It

can be seen that the L values of CB-filled compounds with ALK were lower than those of CB-filled

compounds without ALK. The higher the ALK loading, the lower was the L value. This was attributed

to the plasticisation effect of ALK which reduced minimum torque or viscosity the rubber compounds

and hence, improved the CB dispersion.

  At a similar ALK loading, The L values of N-220 were higher than those of N-550. A higher

value of L, meant a lower degree of filler dispersilibity. Again, it was simply attributed to the particle-

sizes of those CBs. According to Bhakuni [21], decreasing particle-size decreases the dispersilibity of

filler in a rubber compound. The N-220 has smaller particle-size than N-550 and hence, its smaller

particle-size decreased its degree of dispersilibity.

  Figure 3. The effect of ALK loading on value of L of the carbon blacks filled NR compounds.

  4. Conclusions From this study, the following conclusions were drawn:

  

1. Alkanolamide can be function as a curative additive in carbon blacks filled natural rubber

compounds. It act ed as a secondary accelerator and internal plasticiser in the carbon blacks filled natural rubber compounds. Alkanolamide reduced not only the scorch and cure times but also minimum torque of the carbon blacks filled natural rubber. The higher the loading, the more pronounced the acceleration of curing and plasticising effects.

  

2. Alkanolamide improved the torque difference of the carbon blacks filled natural rubber up to the optimum loadings. A 5.0 phr was the optimum loading of Alkanolamide for N-550, and 3.0 phr was for N-220 filled natural rubber compounds. Innovation in Polymer Science and Technology 2016 (IPST 2016)

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3. Alkanolamide also improved the filler dispersions of N-550 and N-220 in natural rubber phases.

  Increasing the Alkanolamide loading further increased the dispersion degrees of the fillers. At a _[65] milar Alkanolamide loading, the filler dispersion of N-220 war poorer than that of N-550.

  Acknowledgement

The authors would like to thank Universiti Sains Malaysia for providing the research facilities for

carrying out the experiment and for making this research work possible. Indra Surya and Mimpin

Ginting are grateful to University of Sumatera Utara for the Penelitian BP PTN research grant under

contract No. 6049/UN5.1.R/PPM/2016.

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• [6] Surya I et al 2014 Polym. Testing 40 24 32 . [7] Surya I et al 2015 Polym. Testing 42 208- 14.

  [8] Ngamsurat S et al 2011 Energy Procedia 9 452- 8. [9] Surya I and Ismail H 2016 Plast Rubber Compos 45(7) 287- 93 . [10] Surya I and Ismail H 2016 Polym. Testing 50 276- 82. [11] Long H 1985 Basic Compounding and Processing of Rubber, Rubber Division. American Chemical Society

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• [13] Fetterman M 1986 Rubber World 194 (1) 38 40. [14] Dannenberg E 1975 Rubber Chem. Technol. 48 (3) 410- 44.

  [15] Ismail H et al 2002 Polym. Testing 21 5) ( 565- 9. [16] Teh P et al 2004 Eur. Polym. J. 40 (11) 2513- 21. [17] Nunes R (1) - et al 2000 Polym. Testing 19 93 103. [18] Polmanteer K and Lentz C 1975 Rubber Chem. Technol. 48 (5) 795-809. [19] Lee B 1979 Rubber Chem. Technol. 52 (5) 1019-29. [20] Pal P and De S 198

  2 Rubber Chem. Technol. 55(5) 1370- 88. [21] Bhakuni R et al 1989 Tires''in``Encyclopedia of Polymer Science and Engineering ` ,''JI Kroschwitz, Editor.

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