# Ionic Liquids Applied to Improve the Dispersion of Coagent Particles in an Elastomer

Authors: Magdalena Maciejewska; Marian Zaborski
Journal: Journal of Composites
 (2013)

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## Abstract

The aim of this work was to study the activity of several ionic liquids (alkylimidazolium salts) that are used to improve the dispersion of coagent particles in peroxide-cross-linked hydrogenated acrylonitrile butadiene elastomer (HNBR). Hydrotalcite grafted with monoallyl maleate was applied as a coagent for the HNBR vulcanization. In this paper, we discuss the effect of the ionic liquids (alkylimidazolium salts) with respect to their anion (bromide, chloride, tetrafluoroborate, and hexafluorophosphate) and the length of alkyl chain in the cation (allyl-, ethyl-, butyl-, hexyl-, and octyl-) on the vulcanization kinetics of rubber compounds. The influence of ionic liquids on the cross-link density, the mechanical properties of the vulcanizates, and their resistance to weather ageing were also studied. Alkylimidazolium salts seem to improve the dispersion of the coagent particles and to be active in the cross-linking of HNBR with peroxide. The type of ionic liquid considerably influences the activity of the coagent particles toward the HNBR. The application of ionic liquids increases the cross-link density of the vulcanizates and improves their resistance to weather aging.


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## Body

## 1. Introduction

Ionic liquids (ILs) are generally defined as salts with melting points below 100°C [1, 2]. The definition of ILs clearly distinguishes them from other molten salts. Research on ILs has been one of the most rapidly growing fields in chemistry and industry in recent years. This rapid growth is mainly due to the many unique properties of ionic liquids. They are able to solvate a large variety of polar and nonpolar organic compounds and show potentially “environmentally friendly” characteristics (negligible vapor pressure, flammability) [3]. Their chemical and physical properties can be tuned for a wide range of potential applications by varying the cations and anions. The antielectrostatic properties of ILs have also been recognized [3]. In the past few years, ILs not only have been employed as solvents for various types of polymerization [4, 5] but also have been used to dissolve polymers [6, 7], to impart functionality and to create new polymer composites [8]. Applications of ILs as solvents for polymerization processes, as components of polymeric matrices (such as polymer gels), as templates for porous polymers, and as novel electrolytes for electrochemical polymerizations have been reviewed [9, 10]. However, the application of ILs to improve the dispersion of coagents based on hydrotalcite for elastomer cross-linking with peroxides has not yet been reported. Thus, this work represents an innovative solution.Coagents are applied to improve the physical properties and processing of peroxide-cross-linked elastomers. Coagent application allows for the generation of materials with higher tensile and tear strengths, higher modulus and hardness values, and better abrasion resistance and adhesion to metal [11, 12]. Most coagents are relatively polar compounds, which are difficult to mix with nonpolar polymers. Despite being homogeneously dispersed in a polymer matrix, coagent molecules can agglomerate again, form domains, and then homopolymerize [13]. The polymerized coagent domains are most likely covalently bonded to the surrounding polymer matrix [14]. Commonly used coagents for cross-linking of polymers are diallyl terephthalate, triallyl cyanurate, and zinc acrylates. They are incorporated into the polymer network because of the covulcanization of their domains with the surrounding polymer matrix [15]. However, the use of these coagents has one major disadvantage that restricts their industrial application: deterioration of the mechanical properties of the vulcanizates. This is most likely due to the presence of rigid aromatic structures of coagent molecules, which form hard domains during vulcanization that are strongly bonded to the surrounding “soft” elastomer. Stress is then concentrated near the hard coagent domains, which leads to the destruction of the sample upon deformation [16]. Recently, we reported the high activity of hydrotalcite grafted with monoallyl maleate as the coagent in the peroxide cross-linking of saturated elastomer [17]. The application of this coagent allowed for the realization of vulcanizates with considerably improved mechanical properties and a higher cross-link density compared with vulcanizates cross-linked only with peroxide. However, the ionic cross-link content and tensile strength of vulcanizates decreased with the increase in the amount of coagent in the elastomer because of the agglomeration of the coagent particles in the elastomer. Therefore, it is necessary to develop a substance to improve the dispersion of coagent particles in the elastomer. We applied long-chain ILs with different numbers of alkyl groups to improve the dispersion of the coagent. It is believed that ILs could polymerize during vulcanization and create a structure in the elastomer composed of soft domains of in situpolymerized IL, similar to the mechanism proposed by Lu et al. [18] for interactions between a polar elastomer and zinc dimethacrylate. A structure consisting of poly-IL domains could be deformed upon the application of external stresses, improving the mechanical strength of the material. It is also possible that ILs could participate in the formation of additional noncovalent cross-links in the elastomer network. Elastomer composites with this type of morphology should reveal the ability to relax stress upon external deformation of the sample. The ability of imidazolium salts containing vinyl groups covalently introduced on IL cation or anion moieties to facilitate polymerization has been confirmed [19, 20]. Moreover, its application was shown to improve silica dispersions in elastomers and the mechanical performance of the vulcanizates. The positive effect of ILs on the dispersion of zinc oxide in the elastomer and the mechanical properties of vulcanizates was also confirmed [21].In this work, we employed hydrotalcite grafted with monoallyl maleate (HTA/MMA) as a coagent for the cross-linking of HNBR with dicumyl peroxide. This method allowed hydrotalcite to act as the filler and coagent simultaneously. To improve the dispersion of HTA/MMA particles in the elastomer, ILs (alkylimidazolium salts) were applied. The influence of ILs on the cure kinetics of rubber compounds and their cross-linking efficiency, vulcanizate cross-link density, tensile strength, and resistance to weather aging was discussed.


## 2. Experimental Section

### 2.1. Materials

Hydrogenated acrylonitrile-butadiene elastomer HNBR (Therban A3407) containing 34 wt% acrylonitrile was obtained from Bayer Co. The Mooney viscosity was (ML1+4 (100°C): 70). It was vulcanized with dicumyl peroxide DCP (Aldrich). Synthetic hydrotalcite (HTA, Aldrich) with the molecular formula Mg6Al2(CO3)(OH)16 · 4H2O was grafted with monoallyl maleate (MMA, Technical University of Lodz) with the procedure described previously [22]. The characteristics of the ionic liquids applied are presented in Table 1.Table 1
Characteristics of ionic liquids (ILs).
ILs
Producer
Symbol
1-allyl-3-methylimidazolium bromide
Aldrich
AMIBr
1-ethyl-3-methylimidazolium bromide
Aldrich
EMIBr
1-butyl-3-methylimidazolium bromide
Aldrich
BMIBr
1-allyl-3-methylimidazolium chloride
Aldrich
AMICl
1-ethyl-3-methylimidazolium chloride
Aldrich
EMICl
1-butyl-3-methylimidazolium chloride
Aldrich
BMICl
1-hexyl-3-methylimidazolium chloride
Aldrich
HMICl
1-ethyl-3-methylimidazolium tetrafluoroborate
Aldrich
EMIBF4
1-butyl-3-methylimidazolium tetrafluoroborate
Aldrich
BMIBF4
1-hexyl-3-methylimidazolium tetrafluoroborate
Aldrich
HMIBF4
1-methyl-3-octylimidazolium tetrafluoroborate
Aldrich
OMIBF4
1-ethyl-3-methylimidazolium hexafluorophosphate
Aldrich
EMIPF6
1-butyl-3-methylimidazolium hexafluorophosphate
Aldrich
BMIPF6
1-hexyl-3-methylimidazolium hexafluorophosphate
Aldrich
HMIPF6


### 2.2. Preparation and Characterization of Rubber Compounds

Rubber compounds containing 100 phr of HNBR, 2 phr of dicumyl peroxide, 5 phr of coagent (HTA/MMA), and 1.5 phr of IL were prepared using a laboratory two-roll mill. The samples were cured at 160°C until they developed a 90% increase in torque, which was measured by an oscillating disc rheometer. The kinetics of rubber compound vulcanization was studied using a DSC1 (Mettler Toledo) analyzer by decreasing the temperature from 25 to −60°C at a rate of 10°C/min and then heating to 250°C with the same heating rate.The cross-link density (νT) of the vulcanizates was determined by their equilibrium swelling in toluene based on the Flory-Rehner equation [23]. The Huggins parameter of the elastomer-solvent interaction (χ) was calculated from the equation
(1)χ=0.501+0.273Vr.
See [22], where Vr is the volume fraction of the elastomer in the swollen gel. To determine the content of noncovalent cross-links in the elastomer network, samples were swollen in toluene in a desiccator with saturated ammonia vapor (25% aqueous solution). The content of noncovalent cross-links (Δν) was calculated from (2), where νA is the cross-link density determined for samples treated with ammonia vapor:
(2)Δν=νT-νAνT·100%.The tensile properties and stress relaxation tests of the vulcanizates were measured according to ISO-37 using a ZWICK 1435 universal machine. The strain rate of tensile tests was 500 mm/min. To determine the stress relaxation properties, a sample was subjected to prolonged constant tension at a constant temperature. Deformation was recorded at specified time intervals (0–10 s, 10–100 s, and 100–1000 s), and a stress relaxation versus time diagram was plotted. The slope of the curve at any point was the stress relaxation rate.The dispersion of the coagent in the elastomer matrix was estimated using Scanning Electron Microscopy with a ZEISS SEM. The vulcanizates were broken down in liquid nitrogen, and the surfaces of their fractures were examined. Prior to the measurements, the samples were coated with carbon.The aging of vulcanizates under weather conditions was carried out for 100 hours with an Atlas CI 4000 “Xenon Arc Weather-Ometer” instrument. The aging process followed a simulated day-night cycle with the following parameters: day (102 minutes, irradiation of 60 W/m2, 367 kJ, humidity 50%, spray, temperature: black panel 80°C, panel chamber 38°C); night (18 minutes, irradiation 60 W/m2, 64 kJ, humidity 5%, no spray, temperature: black panel 80°C, panel chamber 38°C). To estimate the resistance of the samples to weather aging, their mechanical properties and cross-link density after aging were determined and compared with the values ​​obtained for the composites before aging. An aging factor (K) was calculated as the numerical change in the mechanical properties of the samples upon aging (3):
(3)K=(TS·EB)afteraging(TS·EB)beforeaging.


## 2.1. Materials

Hydrogenated acrylonitrile-butadiene elastomer HNBR (Therban A3407) containing 34 wt% acrylonitrile was obtained from Bayer Co. The Mooney viscosity was (ML1+4 (100°C): 70). It was vulcanized with dicumyl peroxide DCP (Aldrich). Synthetic hydrotalcite (HTA, Aldrich) with the molecular formula Mg6Al2(CO3)(OH)16 · 4H2O was grafted with monoallyl maleate (MMA, Technical University of Lodz) with the procedure described previously [22]. The characteristics of the ionic liquids applied are presented in Table 1.Table 1
Characteristics of ionic liquids (ILs).
ILs
Producer
Symbol
1-allyl-3-methylimidazolium bromide
Aldrich
AMIBr
1-ethyl-3-methylimidazolium bromide
Aldrich
EMIBr
1-butyl-3-methylimidazolium bromide
Aldrich
BMIBr
1-allyl-3-methylimidazolium chloride
Aldrich
AMICl
1-ethyl-3-methylimidazolium chloride
Aldrich
EMICl
1-butyl-3-methylimidazolium chloride
Aldrich
BMICl
1-hexyl-3-methylimidazolium chloride
Aldrich
HMICl
1-ethyl-3-methylimidazolium tetrafluoroborate
Aldrich
EMIBF4
1-butyl-3-methylimidazolium tetrafluoroborate
Aldrich
BMIBF4
1-hexyl-3-methylimidazolium tetrafluoroborate
Aldrich
HMIBF4
1-methyl-3-octylimidazolium tetrafluoroborate
Aldrich
OMIBF4
1-ethyl-3-methylimidazolium hexafluorophosphate
Aldrich
EMIPF6
1-butyl-3-methylimidazolium hexafluorophosphate
Aldrich
BMIPF6
1-hexyl-3-methylimidazolium hexafluorophosphate
Aldrich
HMIPF6


## 2.2. Preparation and Characterization of Rubber Compounds

Rubber compounds containing 100 phr of HNBR, 2 phr of dicumyl peroxide, 5 phr of coagent (HTA/MMA), and 1.5 phr of IL were prepared using a laboratory two-roll mill. The samples were cured at 160°C until they developed a 90% increase in torque, which was measured by an oscillating disc rheometer. The kinetics of rubber compound vulcanization was studied using a DSC1 (Mettler Toledo) analyzer by decreasing the temperature from 25 to −60°C at a rate of 10°C/min and then heating to 250°C with the same heating rate.The cross-link density (νT) of the vulcanizates was determined by their equilibrium swelling in toluene based on the Flory-Rehner equation [23]. The Huggins parameter of the elastomer-solvent interaction (χ) was calculated from the equation
(1)χ=0.501+0.273Vr.
See [22], where Vr is the volume fraction of the elastomer in the swollen gel. To determine the content of noncovalent cross-links in the elastomer network, samples were swollen in toluene in a desiccator with saturated ammonia vapor (25% aqueous solution). The content of noncovalent cross-links (Δν) was calculated from (2), where νA is the cross-link density determined for samples treated with ammonia vapor:
(2)Δν=νT-νAνT·100%.The tensile properties and stress relaxation tests of the vulcanizates were measured according to ISO-37 using a ZWICK 1435 universal machine. The strain rate of tensile tests was 500 mm/min. To determine the stress relaxation properties, a sample was subjected to prolonged constant tension at a constant temperature. Deformation was recorded at specified time intervals (0–10 s, 10–100 s, and 100–1000 s), and a stress relaxation versus time diagram was plotted. The slope of the curve at any point was the stress relaxation rate.The dispersion of the coagent in the elastomer matrix was estimated using Scanning Electron Microscopy with a ZEISS SEM. The vulcanizates were broken down in liquid nitrogen, and the surfaces of their fractures were examined. Prior to the measurements, the samples were coated with carbon.The aging of vulcanizates under weather conditions was carried out for 100 hours with an Atlas CI 4000 “Xenon Arc Weather-Ometer” instrument. The aging process followed a simulated day-night cycle with the following parameters: day (102 minutes, irradiation of 60 W/m2, 367 kJ, humidity 50%, spray, temperature: black panel 80°C, panel chamber 38°C); night (18 minutes, irradiation 60 W/m2, 64 kJ, humidity 5%, no spray, temperature: black panel 80°C, panel chamber 38°C). To estimate the resistance of the samples to weather aging, their mechanical properties and cross-link density after aging were determined and compared with the values ​​obtained for the composites before aging. An aging factor (K) was calculated as the numerical change in the mechanical properties of the samples upon aging (3):
(3)K=(TS·EB)afteraging(TS·EB)beforeaging.


## 3. Results and Discussion

### 3.1. Cure Characteristics and Cross-Link Density of Vulcanizates

The influence of ILs (alkylimidazolium salts) on the vulcanization process was estimated based on rheometer measurements. The cure characteristics of HNBR compounds and cross-link densities of vulcanizates are given in Table2.Table 2
Cure characteristics and cross-link density of HNBR vulcanizates containing ILs.
ILs
Δ
G (dNm)
t
90 (min)
t
p (min)
ν
T
*
10
-
4 (mol/cm3)
Δ
ν (%)
—
40.6
35
183
29.5
10.3
AMIBr
38.9
35
182
24.4
8.3
EMIBr
44.3
30
184
36.4
10.4
BMIBr
39.3
30
194
35.6
10.1
AMICl
38.9
30
170
24.0
8.2
EMICl
39.2
30
170
35.6
16.6
BMICl
36.7
25
192
35.5
14.6
HMICl
37.3
30
188
34.9
16.6
EMIBF4
42.8
30
186
40.9
18.3
BMIBF4
41.7
25
162
34.8
10.9
HMIBF4
43.7
25
162
32.4
13.9
OMIBF4
45.6
30
182
26.3
18.6
EMIPF6
42.9
32
204
36.0
14.4
BMIPF6
38.3
25
168
35.0
12.6
HMIPF6
41.7
28
188
34.9
12.9
Δ
G: increment of torque in the rubber compound during vulcanization; t90: optimal vulcanization time; tp: scorch time; νT: cross-link density of vulcanizates; Δν: noncovalent cross-link content.The rubber compound cross-linked only with dicumyl peroxide and the coagent. Without the addition of ILs, the rubber compound was characterized by an increase of torque during vulcanization of approximately 40 dNm. The application of ILs did not considerably affect the torque increment compared with the reference rubber compound. There was no correlation between the torque increment and the structure of the cation or anion in the IL molecules.The ILs had a catalytic effect on the vulcanization process. The vulcanization time of HNBR compounds decreased to as little as 25 minutes when EMICl, BMICl, HMIBF4, and BMIPF6 were present.In terms of the influence of the IL structure, it was noted that the rubber compounds containing ILs with butyl- and hexyl-chains in the cation and chloride, hexafluorophosphate, or tetrafluoroborate anions showed the shortest vulcanization times (Figures1 and 2). However, this was not a significant effect from a technological point of view.Figure 1
Vulcanization time for rubber compounds containing ILs with tetrafluoroborate anions.Figure 2
Vulcanization time for rubber compounds containing ILs with 1-butyl-3-methylimidazolium cations.ILs caused changes of approximately 20 seconds in the scorch time compared with the time observed for the rubber compound containing only coagent. The shortest scorch time was exhibited by rubber compounds containing BMIBF4 and HMIBF4 (approximately 162 s).To estimate the influence of ILs on the vulcanization temperature and the energetic effect of the vulcanization process, a DSC analysis was used. The results are presented in Table3. ILs had no influence on the vulcanization kinetics. The vulcanization of HNBR is an exothermic process that took place in the temperature range of 155–202°C and had an energetic effect of 15.4–23.4 J/g.Table 3
Vulcanization temperature and energetic effect of vulcanization determined by DSC.
ILs
Vulcanization temperature range (°C)
Temperature of vulcanization peak (°C)
Energetic effect of vulcanization(J/g)
—
161–201
184
21.8
AMIBr
156–202
183
23.4
BMIBr
161–197
182
15.4
BMICl
155–195
180
16.5
EMIBF4
160–201
185
20.9
BMIBF4
160–201
185
21.0
HMIBF4
161–201
185
21.4
MOIBF4
160–202
185
20.1
BMIPF6
161–196
186
21.9ILs are used as catalysts in interfacial reactions. Cross-linking reactions occur at the interface, so IL application may increase the cross-link density of vulcanizates. The effect of ILs on the cross-link density and on the content of noncovalent cross-links in the elastomer network is presented in Table2 and Figures 3 and 4.Figure 3
Cross-link density of vulcanizates containing ILs with tetrafluoroborate anions.Figure 4
Cross-link density of vulcanizates containing ILs with 1-ethyl-3-methylimidazolium cations.ILs considerably increased the cross-link density in comparison with the reference HNBR vulcanizate. Only ILs with 1-allyl-3-methylimidazolium cations decreased the vulcanizates cross-link density. These ILs could most likely promote the ionic decomposition of part of the dicumyl peroxide, deteriorating the cross-linking efficiency.Based on vulcanizates containing tetrafluoroborates, the effect of the IL cation structure was studied (Figure3). The cross-link density of vulcanizates increased with the length of alkyl chains attached to the imidazolium ring in the IL cation. Similar results were obtained for rubber compounds containing hexafluorophosphates.In terms of the influence of IL anions, the highest cross-link density was obtained for vulcanizates containing tetrafluoroborates; the influence of the other anions was negligible (Figure4).The application of a coagent resulted in the formation of noncovalent cross-links in the elastomer network; the cross-link content was approximately 10%. These were ionic cross-links, which decomposed when the samples were treated with ammonia vapor. Because of their ionic character, most of the examined ILs increased the content of ionic cross-links in the vulcanizates, up to 18% in the case of tetrafluoroborates. Another reason for the increased number of cross-links could be more the homogeneous dispersion of coagent particles in the elastomer containing IL, which leads to better accessibility of the coagent functional groups for interactions with the elastomer and a higher activity of the coagent in the cross-linking process. The increase in the number of ionic cross-links is important because the cross-links are able to rearrange inside the elastomer network upon external deformation of the vulcanizate, resulting in an improvement in the tensile strength. The lowest activity was observed for bromides (no influence on the ionic cross-link content) or ILs containing 1-allyl-3-methylimidazolium cations (decrease in the ionic cross-link content by 2% compared with the reference vulcanizate) (Figure5).Figure 5
Ionic cross-link content in vulcanizates containing ILs with 1-ethyl-3-methylimidazolium cations.


### 3.2. Mechanical Properties of Vulcanizates

Having established the influence of ILs on the vulcanization process and on the cross-link density of vulcanizates, we then examined their mechanical properties. The results are given in Table4.Table 4
Mechanical properties of HNBR vulcanizates containing ILs.
ILs
TS (MPa)
EB (%)
—
10.1
573
AMIBr
9.0
594
EMIBr
12.0
527
BMIBr
12.0
532
AMICl
8.8
609
EMICl
11.8
560
BMICl
10.9
562
HMICl
11.4
566
EMIBF4
11.9
514
BMIBF4
12.5
537
HMIBF4
12.0
549
MOIBF4
12.3
586
EMIPF6
11.1
524
BMIPF6
12.3
525
HMIPF6
11.8
556
TS: tensile strength; EB: elongation at break, the standard deviation for TS 1.5 MPa, EB 25%.HNBR vulcanizate containing only coagent had a tensile strength of approximately 10.1 MPa and an elongation at break of 573%. ILs did not considerably affect the vulcanizate tensile strength or the elongation at break. The highest tensile strength, approximately 12 MPa, was obtained for vulcanizates containing 1-methyl-3-butylimidazolium bromide, tetrafluoroborate, or hexafluorophosphate, whereas the lowest tensile parameters were achieved in the presence of ILs with 1-allyl-3-methylimidazolium cations. Similar effects were observed for the cross-link density and the ionic cross-link content of the vulcanizates.The application of ILs increased the stress relaxation rates of the vulcanizates at the first stage of the stress relaxation process (Table5). The first stage of stress relaxation was characterized by a rapid rate (n1), which slowed with time. The second stage had a relatively uniform rate (n2). The application of hexafluorophosphate also increased the stress relaxation rate in the second and third stage of the stress relaxation process.Table 5
Stress relaxation rates of HNBR vulcanizates containing ILs.
ILs
n
1
*
10
-
3  (s−1)
n
2
*
10
-
3  (s−1)
n
3
*
10
-
3   (s−1)
—
164
63
38
EMIBr
188
65
24
EMICl
183
70
26
EMIBF4
191
69
45
EMIPF6
175
80
37
n
1, n2, and n3: rates of stress relaxation for the time intervals 0–10 s, 10–100 s, and 100–1000 s, respectively, the standard deviation 10 s−1.These results confirm that the tensile strength improvement of the vulcanizates is also partially caused by the increase of the vulcanizates stress relaxation ability. The considerable chain slippage and reformation of ionic bonds in the elastomer network under external stress contribute to the increase in the vulcanizate tensile strength.


### 3.3. Coagent Dispersion in the Elastomer

The aim of the IL application was to improve the dispersion of HTA/MMA particles in the elastomer matrix. The homogeneous dispersion of coagent particles is crucial for maximizing the activity of the coagent in the cross-linking process. Agglomeration decreases the specific surface area of the coagent and, as a result, the interphase between the particles and elastomer chains. SEM images of the vulcanizate surfaces were taken to directly examine the dispersion of coagent particles in the elastomer. These results are presented in Figures6(a)–6(e).SEM images of vulcanizates containing HTA/MMA: (a) without IL, (b) with BMIBr, (c) with BMIBF4, (d) with BMICl, (e) and with BMIPF6.
(a)
(b)
(c)
(d)
(e)HTA/MMA particles showed a high ability to agglomerate in the elastomer. They formed agglomerates several micrometers in size, which were surrounded with elastomer film (Figure6(a)). Assuming that the coagent particles diffuse through the elastomer matrix and react with elastomer chains, forming ionic cross-links, their agglomeration in the elastomer decreases the activity of the coagent.The dispersion of coagent particles in the presence of ILs containing 1-butyl-3-methylimidazolium cation is presented in Figures6(b)–6(e). It follows that ILs significantly improved the dispersion of HTA/MMA particles in the elastomer. The particles created small agglomerates, approximately 0.5–1 μm in size, which were homogeneously dispersed in the elastomer and tightly bound to the elastomer matrix. Therefore, alkylimidazolium salts seem to be active dispersing agents of hydrotalcite and can be applied to improve the dispersion of HTA used both as a coagent and a filler for HNBR elastomers.


### 3.4. Resistance of Vulcanizates to Weather Aging

Having established the effect of ILs on the dispersion of coagents in the elastomer, we then examined their influence on vulcanizate resistance to weather aging. Saturated elastomers cross-linked with peroxides usually demonstrate a strong aging resistance. Therefore, the substances chosen to increase the activity of the coagent should not deteriorate the vulcanizate’s resistance to weather ageing. The effect of ILs on vulcanizate resistance to weather aging was examined through the changes in the mechanical properties and cross-link density of the vulcanizates.In Figure7, the change in elongation at break upon weather aging is given for vulcanizates containing ILs. Weather aging caused the elongation at break to decrease by approximately 100% in comparison with vulcanizates before aging process. This change was due to the large increase in the cross-link density of the vulcanizates (Figure 8). It could be concluded that aging factors such as UV radiation and elevated temperature resulted in the further cross-linking of the elastomer. However, the increase in the cross-link density was considerably smaller in the case of vulcanizates containing ILs. Weather aging deteriorated the tensile strength of vulcanizates with ILs, as it did to the vulcanizate with HTA/MMA. The smallest change in tensile strength was achieved for vulcanizates containing BMIBr and BMIBF4 (Figure 9).Figure 7
Vulcanizate elongation at break after weather aging.Figure 8
Vulcanizate cross-link density after weather aging.Figure 9
Vulcanizate tensile strength after weather aging.From the results presented in Figures7–9, it follows that it is difficult to determine the resistance of vulcanizates to weather aging by considering changes in the tensile strength and elongation at break separately. Therefore, to quantitatively estimate the change in the mechanical properties of vulcanizates, the aging factor K was calculated (Table 6).Table 6
Weather aging factorK of HNBR vulcanizates containing ILs.
ILs
K (—)
—
0.30
AMIBr
0.54
BMIBr
0.68
BMIBF4
0.72
BMICl
0.55
BMIPF6
0.57
The standard deviation 0.08.The aging factorK is a measurement of the changes in the sample deformation energy caused by the weather aging process. The closer to 1 the values of the K-factor are, the smaller the changes in the mechanical properties of the vulcanizates from the aging process will be. The aging factor (K) for vulcanizate containing only coagent is 0.30. The application of ILs increased the values of K considerably. The highest value of K was observed for the vulcanizate containing the BMIBr and BMIBF4 and was close to 0.7. It can be concluded that ILs provided protection for the HNBR against weather aging, which was most likely due to the limitation of the increase in the vulcanizate cross-link density as a function of the aging factors (UV radiation, increased temperature, and humidity).


## 3.1. Cure Characteristics and Cross-Link Density of Vulcanizates

The influence of ILs (alkylimidazolium salts) on the vulcanization process was estimated based on rheometer measurements. The cure characteristics of HNBR compounds and cross-link densities of vulcanizates are given in Table2.Table 2
Cure characteristics and cross-link density of HNBR vulcanizates containing ILs.
ILs
Δ
G (dNm)
t
90 (min)
t
p (min)
ν
T
*
10
-
4 (mol/cm3)
Δ
ν (%)
—
40.6
35
183
29.5
10.3
AMIBr
38.9
35
182
24.4
8.3
EMIBr
44.3
30
184
36.4
10.4
BMIBr
39.3
30
194
35.6
10.1
AMICl
38.9
30
170
24.0
8.2
EMICl
39.2
30
170
35.6
16.6
BMICl
36.7
25
192
35.5
14.6
HMICl
37.3
30
188
34.9
16.6
EMIBF4
42.8
30
186
40.9
18.3
BMIBF4
41.7
25
162
34.8
10.9
HMIBF4
43.7
25
162
32.4
13.9
OMIBF4
45.6
30
182
26.3
18.6
EMIPF6
42.9
32
204
36.0
14.4
BMIPF6
38.3
25
168
35.0
12.6
HMIPF6
41.7
28
188
34.9
12.9
Δ
G: increment of torque in the rubber compound during vulcanization; t90: optimal vulcanization time; tp: scorch time; νT: cross-link density of vulcanizates; Δν: noncovalent cross-link content.The rubber compound cross-linked only with dicumyl peroxide and the coagent. Without the addition of ILs, the rubber compound was characterized by an increase of torque during vulcanization of approximately 40 dNm. The application of ILs did not considerably affect the torque increment compared with the reference rubber compound. There was no correlation between the torque increment and the structure of the cation or anion in the IL molecules.The ILs had a catalytic effect on the vulcanization process. The vulcanization time of HNBR compounds decreased to as little as 25 minutes when EMICl, BMICl, HMIBF4, and BMIPF6 were present.In terms of the influence of the IL structure, it was noted that the rubber compounds containing ILs with butyl- and hexyl-chains in the cation and chloride, hexafluorophosphate, or tetrafluoroborate anions showed the shortest vulcanization times (Figures1 and 2). However, this was not a significant effect from a technological point of view.Figure 1
Vulcanization time for rubber compounds containing ILs with tetrafluoroborate anions.Figure 2
Vulcanization time for rubber compounds containing ILs with 1-butyl-3-methylimidazolium cations.ILs caused changes of approximately 20 seconds in the scorch time compared with the time observed for the rubber compound containing only coagent. The shortest scorch time was exhibited by rubber compounds containing BMIBF4 and HMIBF4 (approximately 162 s).To estimate the influence of ILs on the vulcanization temperature and the energetic effect of the vulcanization process, a DSC analysis was used. The results are presented in Table3. ILs had no influence on the vulcanization kinetics. The vulcanization of HNBR is an exothermic process that took place in the temperature range of 155–202°C and had an energetic effect of 15.4–23.4 J/g.Table 3
Vulcanization temperature and energetic effect of vulcanization determined by DSC.
ILs
Vulcanization temperature range (°C)
Temperature of vulcanization peak (°C)
Energetic effect of vulcanization(J/g)
—
161–201
184
21.8
AMIBr
156–202
183
23.4
BMIBr
161–197
182
15.4
BMICl
155–195
180
16.5
EMIBF4
160–201
185
20.9
BMIBF4
160–201
185
21.0
HMIBF4
161–201
185
21.4
MOIBF4
160–202
185
20.1
BMIPF6
161–196
186
21.9ILs are used as catalysts in interfacial reactions. Cross-linking reactions occur at the interface, so IL application may increase the cross-link density of vulcanizates. The effect of ILs on the cross-link density and on the content of noncovalent cross-links in the elastomer network is presented in Table2 and Figures 3 and 4.Figure 3
Cross-link density of vulcanizates containing ILs with tetrafluoroborate anions.Figure 4
Cross-link density of vulcanizates containing ILs with 1-ethyl-3-methylimidazolium cations.ILs considerably increased the cross-link density in comparison with the reference HNBR vulcanizate. Only ILs with 1-allyl-3-methylimidazolium cations decreased the vulcanizates cross-link density. These ILs could most likely promote the ionic decomposition of part of the dicumyl peroxide, deteriorating the cross-linking efficiency.Based on vulcanizates containing tetrafluoroborates, the effect of the IL cation structure was studied (Figure3). The cross-link density of vulcanizates increased with the length of alkyl chains attached to the imidazolium ring in the IL cation. Similar results were obtained for rubber compounds containing hexafluorophosphates.In terms of the influence of IL anions, the highest cross-link density was obtained for vulcanizates containing tetrafluoroborates; the influence of the other anions was negligible (Figure4).The application of a coagent resulted in the formation of noncovalent cross-links in the elastomer network; the cross-link content was approximately 10%. These were ionic cross-links, which decomposed when the samples were treated with ammonia vapor. Because of their ionic character, most of the examined ILs increased the content of ionic cross-links in the vulcanizates, up to 18% in the case of tetrafluoroborates. Another reason for the increased number of cross-links could be more the homogeneous dispersion of coagent particles in the elastomer containing IL, which leads to better accessibility of the coagent functional groups for interactions with the elastomer and a higher activity of the coagent in the cross-linking process. The increase in the number of ionic cross-links is important because the cross-links are able to rearrange inside the elastomer network upon external deformation of the vulcanizate, resulting in an improvement in the tensile strength. The lowest activity was observed for bromides (no influence on the ionic cross-link content) or ILs containing 1-allyl-3-methylimidazolium cations (decrease in the ionic cross-link content by 2% compared with the reference vulcanizate) (Figure5).Figure 5
Ionic cross-link content in vulcanizates containing ILs with 1-ethyl-3-methylimidazolium cations.


## 3.2. Mechanical Properties of Vulcanizates

Having established the influence of ILs on the vulcanization process and on the cross-link density of vulcanizates, we then examined their mechanical properties. The results are given in Table4.Table 4
Mechanical properties of HNBR vulcanizates containing ILs.
ILs
TS (MPa)
EB (%)
—
10.1
573
AMIBr
9.0
594
EMIBr
12.0
527
BMIBr
12.0
532
AMICl
8.8
609
EMICl
11.8
560
BMICl
10.9
562
HMICl
11.4
566
EMIBF4
11.9
514
BMIBF4
12.5
537
HMIBF4
12.0
549
MOIBF4
12.3
586
EMIPF6
11.1
524
BMIPF6
12.3
525
HMIPF6
11.8
556
TS: tensile strength; EB: elongation at break, the standard deviation for TS 1.5 MPa, EB 25%.HNBR vulcanizate containing only coagent had a tensile strength of approximately 10.1 MPa and an elongation at break of 573%. ILs did not considerably affect the vulcanizate tensile strength or the elongation at break. The highest tensile strength, approximately 12 MPa, was obtained for vulcanizates containing 1-methyl-3-butylimidazolium bromide, tetrafluoroborate, or hexafluorophosphate, whereas the lowest tensile parameters were achieved in the presence of ILs with 1-allyl-3-methylimidazolium cations. Similar effects were observed for the cross-link density and the ionic cross-link content of the vulcanizates.The application of ILs increased the stress relaxation rates of the vulcanizates at the first stage of the stress relaxation process (Table5). The first stage of stress relaxation was characterized by a rapid rate (n1), which slowed with time. The second stage had a relatively uniform rate (n2). The application of hexafluorophosphate also increased the stress relaxation rate in the second and third stage of the stress relaxation process.Table 5
Stress relaxation rates of HNBR vulcanizates containing ILs.
ILs
n
1
*
10
-
3  (s−1)
n
2
*
10
-
3  (s−1)
n
3
*
10
-
3   (s−1)
—
164
63
38
EMIBr
188
65
24
EMICl
183
70
26
EMIBF4
191
69
45
EMIPF6
175
80
37
n
1, n2, and n3: rates of stress relaxation for the time intervals 0–10 s, 10–100 s, and 100–1000 s, respectively, the standard deviation 10 s−1.These results confirm that the tensile strength improvement of the vulcanizates is also partially caused by the increase of the vulcanizates stress relaxation ability. The considerable chain slippage and reformation of ionic bonds in the elastomer network under external stress contribute to the increase in the vulcanizate tensile strength.


## 3.3. Coagent Dispersion in the Elastomer

The aim of the IL application was to improve the dispersion of HTA/MMA particles in the elastomer matrix. The homogeneous dispersion of coagent particles is crucial for maximizing the activity of the coagent in the cross-linking process. Agglomeration decreases the specific surface area of the coagent and, as a result, the interphase between the particles and elastomer chains. SEM images of the vulcanizate surfaces were taken to directly examine the dispersion of coagent particles in the elastomer. These results are presented in Figures6(a)–6(e).SEM images of vulcanizates containing HTA/MMA: (a) without IL, (b) with BMIBr, (c) with BMIBF4, (d) with BMICl, (e) and with BMIPF6.
(a)
(b)
(c)
(d)
(e)HTA/MMA particles showed a high ability to agglomerate in the elastomer. They formed agglomerates several micrometers in size, which were surrounded with elastomer film (Figure6(a)). Assuming that the coagent particles diffuse through the elastomer matrix and react with elastomer chains, forming ionic cross-links, their agglomeration in the elastomer decreases the activity of the coagent.The dispersion of coagent particles in the presence of ILs containing 1-butyl-3-methylimidazolium cation is presented in Figures6(b)–6(e). It follows that ILs significantly improved the dispersion of HTA/MMA particles in the elastomer. The particles created small agglomerates, approximately 0.5–1 μm in size, which were homogeneously dispersed in the elastomer and tightly bound to the elastomer matrix. Therefore, alkylimidazolium salts seem to be active dispersing agents of hydrotalcite and can be applied to improve the dispersion of HTA used both as a coagent and a filler for HNBR elastomers.


## 3.4. Resistance of Vulcanizates to Weather Aging

Having established the effect of ILs on the dispersion of coagents in the elastomer, we then examined their influence on vulcanizate resistance to weather aging. Saturated elastomers cross-linked with peroxides usually demonstrate a strong aging resistance. Therefore, the substances chosen to increase the activity of the coagent should not deteriorate the vulcanizate’s resistance to weather ageing. The effect of ILs on vulcanizate resistance to weather aging was examined through the changes in the mechanical properties and cross-link density of the vulcanizates.In Figure7, the change in elongation at break upon weather aging is given for vulcanizates containing ILs. Weather aging caused the elongation at break to decrease by approximately 100% in comparison with vulcanizates before aging process. This change was due to the large increase in the cross-link density of the vulcanizates (Figure 8). It could be concluded that aging factors such as UV radiation and elevated temperature resulted in the further cross-linking of the elastomer. However, the increase in the cross-link density was considerably smaller in the case of vulcanizates containing ILs. Weather aging deteriorated the tensile strength of vulcanizates with ILs, as it did to the vulcanizate with HTA/MMA. The smallest change in tensile strength was achieved for vulcanizates containing BMIBr and BMIBF4 (Figure 9).Figure 7
Vulcanizate elongation at break after weather aging.Figure 8
Vulcanizate cross-link density after weather aging.Figure 9
Vulcanizate tensile strength after weather aging.From the results presented in Figures7–9, it follows that it is difficult to determine the resistance of vulcanizates to weather aging by considering changes in the tensile strength and elongation at break separately. Therefore, to quantitatively estimate the change in the mechanical properties of vulcanizates, the aging factor K was calculated (Table 6).Table 6
Weather aging factorK of HNBR vulcanizates containing ILs.
ILs
K (—)
—
0.30
AMIBr
0.54
BMIBr
0.68
BMIBF4
0.72
BMICl
0.55
BMIPF6
0.57
The standard deviation 0.08.The aging factorK is a measurement of the changes in the sample deformation energy caused by the weather aging process. The closer to 1 the values of the K-factor are, the smaller the changes in the mechanical properties of the vulcanizates from the aging process will be. The aging factor (K) for vulcanizate containing only coagent is 0.30. The application of ILs increased the values of K considerably. The highest value of K was observed for the vulcanizate containing the BMIBr and BMIBF4 and was close to 0.7. It can be concluded that ILs provided protection for the HNBR against weather aging, which was most likely due to the limitation of the increase in the vulcanizate cross-link density as a function of the aging factors (UV radiation, increased temperature, and humidity).


## 4. Conclusions

Hydrotalcite combined with monoallyl maleate was used as a coagent for peroxide cross-linking of hydrogenated acrylonitrile butadiene elastomers. ILs (alkylimidazolium salts) consisting of different anions (bromides, chlorides, tetrafluoroborates, and hexafluorophosphates) and cations (imidazolium rings with allyl-, ethyl-, butyl-, hexyl-, and octyl- chains) were used to improve the dispersion of the coagent in the elastomer.HTA/MMA particles agglomerated in the elastomer matrix, forming clusters of particles several micrometers in size. ILs significantly improved the dispersion of the coagent particles in the elastomer, resulting in a higher activity of the coagent in the cross-linking process. The use of ILs yielded vulcanizates with a higher cross-link density and content of noncovalent cross-links compared with vulcanizates containing only coagent. The ILs did not considerably influence the vulcanizate tensile strength. ILs increased the resistance of vulcanizates to weather aging. Further cross-linking of the elastomer containing ILs upon aging was greatly reduced in comparison with the vulcanizate containing only the coagent.The structure of ILs had an impact on their activity in the cross-linking process and the properties of the vulcanizates. The length of the alkyl chains attached to the imidazolium ring in the IL cations was particularly important; the effect of the anion was smaller. Analyzing the results obtained for tetrafluoroborates, it can be concluded that cross-linking density and tensile strength of vulcanizates decreased with increasing alkyl chain lengths.



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*Source: 286534-2013-04-17.xml*