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Review

Application of Quaternary Ammonium Compounds as Compatibilizers for Polymer Blends and Polymer Composites—A Concise Review

by
Ahmad Adlie Shamsuri
1,* and
Siti Nurul Ain Md. Jamil
2,3,*
1
Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products, University Putra Malaysia, Serdang 43400, Selangor, Malaysia
2
Department of Chemistry, Faculty of Science, University Putra Malaysia, Serdang 43400, Selangor, Malaysia
3
Centre of Foundation Studies for Agricultural Science, University Putra Malaysia, Serdang 43400, Selangor, Malaysia
*
Authors to whom correspondence should be addressed.
Appl. Sci. 2021, 11(7), 3167; https://doi.org/10.3390/app11073167
Submission received: 9 January 2021 / Revised: 11 February 2021 / Accepted: 15 February 2021 / Published: 2 April 2021
(This article belongs to the Special Issue Polymeric Material Chemistry)
Browse Figures
Versions Notes

Abstract

:
A wide variety of quaternary ammonium compounds (QACs) have escalated the attraction of researchers to explore the application of QACs. The compounds have frequently been synthesized through alkylation or quaternization of tertiary amines with alkyl halides. Recently, QACs have been applied to compatibilize polymer blends and polymer composites in improving their thermo-mechanical properties. This concise review concentrates on the application of two types of QACs as compatibilizers for polymer blends and polymer composites. The types of QACs that were effectively applied in the blends and composites are quaternary ammonium surfactants (QASs) and quaternary ammonium ionic liquids (QAILs). They have been chosen for the discussion because of their unique chemical structure which can interact with the polymer blend and composite components. The influence of QASs and QAILs on the thermo-mechanical properties of the polymer blends and polymer composites is also described. This review could be helpful for the polymer blend and polymer composite researchers and induce more novel ideas in this research area.

1. Introduction

Lately, the application of quaternary ammonium compounds (QACs) in the polymer research has drastically developed because of the effectiveness of these ionic compounds in forming the intermolecular interactions with synthetic and natural polymers. QACs can be synthesized through alkylation of amines by quaternization of tertiary amines with alkylating agents such as alkyl halides [1,2]. Figure 1 demonstrates the schematic of quaternization of N-methyldiethanolamine (tertiary amine) with benzyl chloride (alkyl halide) to produce benzylbis(2-hydroxyethyl)methylammonium chloride (QAC). The quaternization of tertiary amines is commonly carried out in polar solvents such as methanol [3]. The other alkylating agents, for example, benzylic, allylic, and α-carbonylated alkyl halides can also be employed in the synthesis of QACs. On top of that, the quaternization of tertiary amines has been used to produce a wide variety of QACs. The two most important QACs that were employed in various applications are surfactants and ionic liquids. In addition, these compounds are able to utilize for processing polymeric materials, as well as for enhancing the physicochemical properties of the materials [4]. QACs can also be applied as compatibilizers for polymer blends and polymer composites due to their capability to improve the compatibility of the materials.
In general, polymer blends are combinations of two or more polymers, whereas polymer composites are compound made up of polymer matrix and filler components. The preparation of polymer blends and polymer composites is typically intended to obtain materials that have a combination of excellent properties of the different materials. This approach is commonly inexpensive and less time-consuming than the development of new polymeric materials. They are classified as compatible and incompatible materials. Compatible polymer blends and polymer composites have superior thermo-mechanical properties (e.g., degradation temperature, glass transition temperature, melting temperature, tensile strength, flexural strength, impact strength, etc.), while incompatible matters commonly have poor thermo-mechanical properties. The compatibilization is usually done on the incompatible polymer blends and polymer composites because they have a difference in polarity that affected their thermo-mechanical properties. Moreover, the use of compatibilizers in polymer blends and polymer composites is to improve their interfacial adhesion [5,6] by creating the intermolecular interactions between the blend and composite components [7,8]. Table 1 shows the examples of polymer blends compatibilized by QACs.
Table 2 indicates the examples of polymer composites compatibilized by QACs. The selection of the polymer blends and polymer composites in this concise review is not randomly based on the materials compatibilized by QACs, but it is based on the thermo-mechanical properties that were comprehensively studied in the previous research works.
In the past ten years, many compatibilization approaches have been recommended for the intention of enhancing the thermo-mechanical properties of polymer blends and polymer composites. The application of QACs as compatibilizers could provide an advantage because of their unique chemical structure that owns both polar ionic and non-polar lipophilic functional groups [26]. These groups are able to interact with polar hydrophilic and non-polar hydrophobic polymers or materials. The intermolecular interactions could contribute to the compatibilization effect on polymer blends and polymer composites, and consequently improve the interfacial adhesion between their components. Yet, to the authors’ knowledge, there is no concise review prepared concentrating on the application of QACs as compatibilizers for polymer blends and polymer composites. That is the objective of making a categorized review in this paper, which consists of related research works.

2. Polymer Blend and Polymer Composite Materials

2.1. Polymer Blend Materials

The polymer blend materials can be prepared either in the melt, solution, or emulsion condition. The blending process involves at least two different polymers. The melt blending process must be carried out at elevated temperatures, precisely at the fusing temperature of the polymer components [27]. The solution blending process can be conducted in appropriate solvents that are capable to dissolve polymers completely [14]. The emulsion blending process involves dispersion of emulsion of at least two different polymers [28]. The compatible polymer blends have remarkable thermo-mechanical properties based on the complementary behavior of their individual components [29]. The preparation of polymer blend materials is straightforward when conventional blending machines are used [30].
The polymer blends can be made either from synthetic thermoplastic polymers or from natural biodegradable polymers by blending between the synthetic/synthetic polymers, natural/natural polymers, or synthetic/natural polymers. Table 3 shows the examples of polymer blends, blend types, blending conditions, and blending machines. Synthetic thermoplastic polymer blends can be prepared via melt, solution and emulsion blending processes [31]. The chemical structure of the main chains of thermoplastic polymers has allowed them to be processed in such conditions, including the nature of the intermolecular interaction of the polymers. Nevertheless, for natural biodegradable polymer (biopolymer) blends, they are usually prepared through solution blending process; this is because most of them do not melt but decompose at elevated temperatures [14]. The chemical nature of biopolymers has also allowed them to be processed in such condition because they were bonded with hydrogen bonding. Figure 2 exhibits the chemical structures of PET, PBS, PEO, and PHBV. The melt blending process can be done by using compounder or extruder. In contrast, solution and emulsion blending processes can be performed by means of mechanical stirrer, magnetic stirrer, or KPG stirrer.

2.2. Polymer Composite Materials

The polymer composite materials are typically prepared by incorporating a filler into the polymer matrix. The process could be done either in the melt, solution, or emulsion condition [24,33,34]. The polymer composites regularly possess improved thermo-mechanical properties compared to their polymer matrix [35]. The polymer composite materials are easy to prepare, and they also need processing machines such as polymer blends. Table 4 displays the examples of polymer matrices, matrix types, fillers, processing conditions, and processing machines. Thermoplastic polymer composites can be prepared through melt, solution, and emulsion processing. However, for thermosetting polymer composites, they are generally prepared through solution processing before curing because they cannot be melted, emulsified, and reshaped after curing [36]. The chemical nature of thermosetting polymers has allowed them to be processed in such condition because they are bonded with irreversible covalent bonds. Figure 3 displays the chemical structures of PBE, DGEBA epoxy, and PU. On the other hand, biopolymer composites are ordinarily prepared via solution processing [37]. Figure 4 demonstrates the chemical structures of cellulose, chitin, chitosan, and agarose. The melt processing can be made by means of internal mixer, two-roll mill, or extruder. In contrast, the solution and emulsion processing can be operated by using mechanical stirrer, overhead stirrer, sonicator, or magnetic stirrer.

3. Types of QACs for Compatibilization of Polymer Blends and Polymer Composites

3.1. Quaternary Ammonium Surfactants (QASs)

In recent times, QACs have been categorized into two types, specifically quaternary ammonium surfactants (QASs) and quaternary ammonium ionic liquids (QAILs). The category is based on the state of the QACs; for instance, QASs are usually present in solid-state and QAILs commonly exist in a liquid form. QASs possess an amphiphilic character, which contains both a polar functional group and a non-polar functional group [40]. Furthermore, QASs could reduce the surface tension between the polar and non-polar materials [41], including components of the polymer blends and polymer composites. On top of that, QASs have been shown to function in many vital physical processes, serving as an emulsifying agent, wetting agent, dispersing agent, lubricating agent, softening agent, foaming agent, an anti-foaming agent, and an antimicrobial agent [42,43,44]. Table 5 shows the examples of QASs applied for compatibilization of polymer blends and polymer composites. Figure 5 demonstrates the chemical structures of QASs collected in Table 5.

3.2. Quaternary Ammonium Ionic Liquids (QAILs)

Unlike QASs, QAILs have a low melting temperature (<100 °C). QAILs are also non-volatile, non-flammable, exhibit good thermal stability, and able to dissolve organic and inorganic materials [51]. In the past decade, QAILs have been utilized in adsorption/desorption studies [52], catalysis systems, electrochemical studies, metal nanostructures, analytical chemistry including sensors, bio-analytical chemistry, electrochemical biosensors [53], and CO2 capture systems [54]. The exceptional properties of QAILs, such as good interaction with organic and inorganic materials, make them suitable chemical compounds for applying in the polymer blends and polymer composites [55]. Table 6 exhibits the examples of QAILs applied for compatibilization of polymer blends and polymer composites. Figure 6 demonstrates the chemical structures of QAILs collected in Table 6.

4. Influence of QACs on Thermo-Mechanical Properties of Polymer Blends and Polymer Composites

4.1. Influence of QASs and QAILs on Polymer Blends

Table 7 indicates the thermo-mechanical properties of polymer blends influenced by QASs and QAILs. QAS like HTAB (chemical structure is shown in Figure 5) has been applied for compatibilization of Nylon-6/LNR blends [9]. The application of HTAB influenced the degradation temperature, glass transition temperature, tensile strength, tensile modulus, tensile extension, and impact strength of the blends. The degradation temperature of the blends decreased because LNR possessed lower initial degradation temperature than nylon-6, which deteriorated the degradation temperature of the overall blends. The result also shows a decreasing trend with the blends containing high LNR content, which is also due to the low degradation temperature of LNR compared to nylon-6. Furthermore, the glass transition temperature of the blends also decreased because of the improvement of the compatibility between nylon-6 and LNR. This is caused by HTAB, which consisted of polar and non-polar groups that acted as a compatibilizer by creating interactions between them [9]. Moreover, the mechanical properties, such as tensile strength and tensile modulus of the blends decreased because of the increase of their segmental movement. It is considered that LNR acted as a stress dilutor, which is responsible for lowering the tensile strength and the tensile modulus. This is induced by the presence of HTAB that is responsible for better homogeneous distribution of LNR in the blends. However, the tensile extension and impact strength of the blends increased by up to 100% and 35%, respectively, compared to the neat nylon-6. This is attributed to the HTAB-compatibilized Nylon-6/LNR blends, which eventually increased the elongation and toughness of the blends [9].
It can be seen in Table 7 that fewer studies have focused on the influence of the QASs on the thermo-mechanical properties of polymer blends. QAS like BDAC (chemical structure is shown in Figure 5) is applied for compatibilization of PET/PE blends [11]. The application of BDAC influenced the degradation temperature, tensile strength, tensile modulus, and tensile extension of the blends. The degradation temperature of the blends decreased because of the presence of the benzyl group and aromatic structure in BDAC that lowered the thermal stability of the blends. Therefore, BDAC acted as a thermal degradation promoter for the blends, which can catalyze the polymer degradation with a thermal dependence. This decreasing trend also occurred in the PP/Nylon-6 blends compatibilized by PP-g-MA [64]. However, the mechanical properties, such as tensile strength and tensile modulus of the blends increased by up to 14% and 24%, respectively, compared to the neat PET/PE blend. This is attributed to the vital role of the BDAC, which acted as a compatibilization agent between PET and PE [11]. Nevertheless, the tensile extension of the blends decreased because of their lower ductility compared to the blend without BDAC [11]. Moreover, the polymer chains of PET/PE blends containing BDAC are stiffer in comparison with the neat blend that reduced the ductility and deformability as well. This effectively decreased the tensile extension of the BDAC-compatibilized PET/PE blends.
On the other hand, QAIL like BmimCl (chemical structure is shown in Figure 6) has been applied for compatibilization of NW/Cellulose blends [10]. The application of BmimCl influenced the degradation temperature, glass transition temperature, tensile strength, tensile modulus, and tensile extension of the blends (Table 7). The thermal properties, such as degradation temperature and glass transition temperature of the blends increased by up to 25% and 33%, respectively, compared to the neat NW. This is attributed to the miscibility between NW and cellulose as well as the formation of strong interaction between these biopolymers generated by BmimCl [10]. Moreover, the mechanical properties, for instance, tensile strength, tensile modulus, and tensile extension of the blends increased by up to 66%, 100%, and 56%, respectively, in comparison with the NW. This is due to the increase of the cellulose content in the blends and also good interfacial adhesion between them [10].
QAIL like DmimNTf2 (chemical structure is shown in Figure 6) has been applied for compatibilization of PBS/RS blends [12]. The application of DmimNTf2 has influenced the degradation temperature, melting temperature, tensile strength, tensile modulus, tensile extension, flexural strength, and flexural extension of the blends (Table 7). The degradation temperature of the blends increased by up to 2.3% compared to the neat PBS/RS blend. This is attributed to the high degradation temperature of DmimNTf2 and the existence of intermolecular interactions between the blend components generated by DmimNTf2. However, the melting temperature of the blends decreased because of the presence of DmimNTf2, which improved the interfacial adhesion between PBS and RS [12]. In the compatible polymer blends, they commonly have the melting temperature lower than their individual components [14]. Thus, it can be considered that the PBS/RS blends containing DmimNTf2 have good compatibility in comparison with the neat blend. Furthermore, the mechanical properties, such as tensile strength, tensile modulus, and flexural strength of the blends decreased since fewer loads are required for withstanding the exerted force. This is, of course, not unusual, the compatible polymer blends are not necessarily linked to the increase of the tensile and flexural strengths. Nevertheless, the tensile extension and flexural extension of the blends increased by up to 233% and 17%, respectively, in comparison with the blend without DmimNTf2. This is caused by the improvement of the compatibility between PBS and RS since DmimNTf2 acted as a compatibilizer [12].
BmimCl has also been applied for compatibilization of PHBV/Cellulose blends [15]. The application of BmimCl influenced the degradation temperature, glass transition temperature, melting temperature, tensile strength, tensile modulus, and tensile extension of the blends (Table 7). The thermal properties, such as degradation temperature and glass transition temperature of the blends increased by up to 20% and 700%, respectively, compared to the neat PHBV. This is attributed to the partial miscibility between PHBV and cellulose in their regenerated form. However, the melting temperature of the blends decreased because of the formation of hydrogen bonding interaction between the blend components regenerated from BmimCl [15]. The lower melting temperature of the polymer blends than their individual components can also be considered as an indicator to show the compatibility between the blend components; this can take place when they have intermolecular interactions. Nonetheless, the mechanical properties, for instance, tensile strength, tensile modulus, and tensile extension of the blends increased by up to 429%, 190%, and 44%, respectively, in comparison with the PHBV. This is because of the presence of interaction between PHBV and cellulose, which improved the compatibility of the blends [15].

4.2. Influence of QASs on Polymer Composites

Table 8 shows the thermo-mechanical properties of polymer composites influenced by QASs. QAS like HTAB has been applied for compatibilization of HDPE/LDPE/Cellulose composites [16]. The application of HTAB has influenced the degradation temperature, melting temperature, tensile strength, tensile modulus, tensile extension, and impact strength of the composites. The degradation temperature of the composites decreased because of the lower initial degradation temperature of HTAB than other composite components, which affected the degradation temperature of the overall composites. Nevertheless, the melting temperature of the composites remains unchanged because of the presence of crystal lattice of HTAB in the composites [16]. Moreover, the mechanical properties, such as tensile strength and tensile modulus of the composites increased by up to 25% and 25%, respectively, compared to the neat HDPE/LDPE/Cellulose composite. This is attributed to the existence of HTAB, which enhanced the interfacial adhesion between HDPE/LDPE matrix and cellulose filler, as a result, improved the stress transfer from HDPE/LDPE to cellulose. However, the tensile extension and impact strength of the composites decreased caused by the excess of the crystal lattice of HTAB in the composites, which increased their brittleness [16]. This is related to the increase of the stiffness property of the composites. It is a well-known fact that the crystal lattice with higher content in the matrix can decrease the tensile extension and impact strength of the composites as a rule of mixture.
QAS like OTAB (chemical structure is shown in Figure 5) has been applied for compatibilization of PBE/BN composites [18]. The application of OTAB has influenced the thermal conductivity, flexural strength, flexural modulus, and impact strength of the composites (Table 8). The thermal conductivity of the composites increased by up to 79%, compared to the neat PBE/BN composite. This is attributed to the improvement of interfacial adhesion between PBE matrix and BN filler, which induced heat transfer across the interface efficiently [18]. Moreover, the mechanical properties, such as flexural strength, flexural modulus, and impact strength of the composites increased by up to 38%, 8.5%, and 11%, respectively, in comparison with the neat composite. This is because of the long alkyl chain length of OTAB, which effectively adsorbed on the surface of the composites [18]. Therefore, the compatibilization by applying OTAB not only increased the thermal conductivity of the composites but also improved their flexural and impact properties as well.
HTAB has also been applied for compatibilization of HDPE/Agar composites [22]. The application of HTAB has influenced the degradation temperature, melting temperature, tensile strength, tensile modulus, tensile extension, and impact strength of the composites (Table 8). The thermal properties, such as degradation temperature and melting temperature of the composites decreased compared to the neat HDPE/Agar composite. This is due to the presence of interactions between HDPE matrix and agar filler generated by HTAB [22]. Moreover, the mechanical properties, for instance, tensile strength and tensile modulus of the composites decreased because of their ductile behavior with the presence of HTAB. The existence of ductile behavior leads to the decrease of brittleness of the composites, which also reduced the stiffness property of the composites. This is induced by HTAB that improved the interfacial adhesion between HDPE and agar. Nevertheless, the tensile extension and impact strength of the composites increased by up to 72% and 24%, respectively, in comparison with the neat composite. This is attributed to the compatibilization effect of HTAB, which improved the compatibility between the composite components, as a result, increased the ductility of the HDPE/Agar composites [22].
Besides, QAS like IDAB (chemical structure is shown in Figure 5) has been applied for compatibilization of SBR/Bentonite composites [20]. The application of IDAB has influenced the degradation temperature, tensile strength, tensile modulus, and tensile extension of the composites (Table 8). The degradation temperature of the composites is expected to be lower compared to the neat SBR/Bentonite composite. This is because of the low degradation temperature of IDAB compared to other components in the composites [20]. However, the mechanical properties, such as tensile strength and tensile modulus of the composites increased by up to 20% and 34%, respectively, in comparison with the neat composite. This is attributed to the increase of the cross-linking density of the SBR, which is caused by the presence of interactions between SBR matrix and bentonite filler, as a result, improving the compatibility between them [20]. Nonetheless, the tensile extension of the composites decreased because of the increase of their stiffness property with the presence of IDAB. The result indicated that the compatibilization of the composites by IDAB has allowed bentonite to restrict the movement of SBR chains. Consequently, it increased the rigidity property, which reduced the strain behavior of the composites and led to the lower tensile extension.
The compatibilization by applying QASs is not only limited to conventional polymer composites, but they can also be applied in polymer nanocomposites [43]. HTAB is applied for compatibilization of Nylon-6/LNR/MMT nanocomposites [24]. The application of HTAB influenced the degradation temperature, glass transition temperature, tensile strength, tensile modulus, tensile extension, and impact strength of the nanocomposites (Table 8). The thermal properties, such as degradation temperature and glass transition temperature of the nanocomposites increased by up to 19% and 81%, respectively, compared to the neat Nylon-6/LNR matrix. This is attributed to the formation of intermolecular interactions between Nylon-6/LNR matrix and MMT filler generated by HTAB [24]. Moreover, the mechanical properties, for instance, tensile strength, tensile modulus, and impact strength of the nanocomposites increased by up to 48%, 149%, and 6.5%, respectively, in comparison with the neat matrix. This is due to the compatibilization by HTAB that has effectively provided a reinforcing effect on the nanocomposites [24]. Nevertheless, the tensile extension of the nanocomposites decreased because of the increase of their stiffness property. This typical phenomenon can occur not only in the conventional polymer composites but also in the polymer nanocomposites due to the compatibilization effect of HTAB.

4.3. Influence of QAILs on Polymer Composites

Table 9 displays the thermo-mechanical properties of polymer composites influenced by QAILs. QAIL like HmimPF6 (chemical structure is shown in Figure 6) has been applied for compatibilization of XSBR/RBC composites [17]. The application of HmimPF6 influenced the degradation temperature, glass transition temperature, tensile strength, tensile modulus, and tensile extension of the composites. The degradation temperature of the composites decreased because of the hydrolyzation of HmimPF6 induced by water that is released from RBC at a temperature above 100 °C. This is due to HmimPF6 being sensitive to hydrolyzation, especially at elevated temperature. Therefore, the polymer composites heated above 100 °C released water from RBC, and it hydrolyzed HmimPF6. As a result, it decreased the degradation temperature of the polymer composites. However, the glass transition temperature of the composites increased by up to 3.4% compared to the neat XSBR/RBC composite. This is attributed to the mobility of XSBR macromolecular chains which was restricted with the presence of HmimPF6 [17]. Moreover, the mechanical properties, such as tensile strength, tensile modulus, and tensile extension of the composites increased by up to 31%, 13%, and 7.0%, respectively, in comparison with the neat composite. This is due to the formation of interactions between XSBR matrix and RBC filler generated by HmimPF6 [17].
QAIL like BmimCl has been applied for compatibilization of Agarose/Tc composites [19], it is blended with urea to increase its efficacy. The application of BmimCl has influenced the degradation temperature, glass transition temperature, tensile strength, tensile modulus, and tensile extension of the composites (Table 9). The degradation temperature of the composites decreased because of the lower thermal resistance of urea than other composite components, which affected the degradation temperature of the overall composites. Nonetheless, the glass transition temperature of the composites increased by up to 23% in comparison with the neat Agarose/Tc composite. This is attributed to the formation of strong interactions between agarose matrix and the talc filler with the presence of BmimCl [19]. Furthermore, the mechanical properties, such as tensile strength and tensile modulus of the composites increased by up to 26% and 62%, respectively, compared to the neat composite. This is because of the composites having strong and stiff properties, as well as BmimCl acted as a coupling agent or compatibilizer for the composites. However, the tensile extension of the composites decreased because the motion of agarose molecular chains was restricted by the talc filler [19]. The result also confirmed that the stiffness property of the composites increased with the presence of compatibilizer, which enhanced the rigidity of the composites, thus moving the tensile extension to lower values.
On the other hand, QAIL like EmimAc (chemical structure is shown in Figure 6) has been applied for compatibilization of DGEBA epoxy/Chitin composites [21]. The application of EmimAc influenced the degradation temperature, glass transition temperature, tensile strength, tensile modulus, tensile extension, and impact strength of the composites (Table 9). The degradation temperature of the composites remains unchanged because of the small content of chitin in the composites; thus, the overall thermal degradation behavior is similar to the neat DGEBA epoxy matrix. Nonetheless, the glass transition temperature of the composites increased by up to 9.0% compared to the neat matrix. This is attributed to the presence of chitin, which restricted the mobility of DGEBA epoxy chains prompted by intermolecular hydrogen bonding [21]. Moreover, the mechanical properties, such as tensile strength, tensile modulus, tensile extension, and impact strength of the composites increased by up to 34%, 8.4%, 80%, and 91%, respectively, in comparison with the neat matrix. This is because of the better dispersion of chitin filler within the DGEBA epoxy matrix with the presence of EmimAc [21].
Besides, QAIL like BmimPF6 (chemical structure is shown in Figure 6) has been applied for compatibilization of PU/SiO2 composites [23]. The application of BmimPF6 influenced the degradation temperature, glass transition temperature, thermal conductivity, flexural strength, and flexural extension of the composites (Table 9). The thermal properties, such as degradation temperature and glass transition temperature of the composites increased by up to 10% and 13%, respectively, compared to the neat PU/SiO2 composite. This is attributed to the presence of BmimPF6 that has significantly enhanced the thermal stability of the composites. Nevertheless, the thermal conductivity of the composites decreased because of the low thermal conductivity of SiO2 filler, which is well dispersed in the cell walls of the PU matrix [23]. In addition, the BmimPF6-compatibilized composites improved the interfacial adhesion between PU and SiO2, which reduced the heat transfer on the matrix, thus decreasing the thermal conductivity of the composites. The flexural strength of the composites increased by up to 15% in comparison with the neat composite. This is because of the reinforcing effect of SiO2 and compatibilization effect of BmimPF6. However, the flexural extension of the composites decreased because of the existence of SiO2 aggregates that acted as defects within the PU matrix [23]. The aggregates normally exist at high content of SiO2 filler in the matrix. Hence, the formation of aggregates can be avoided or minimized during the preparation of the composites.
The compatibilization by applying QAILs is not only limited to conventional polymer composites, but they can also be applied in polymer nanocomposites as QASs. BmimCl is applied for compatibilization of RC/MMT nanocomposites [25]. The application of BmimCl influenced the degradation temperature, tensile strength, tensile modulus, and tensile extension of the nanocomposites (Table 9). The degradation temperature of the nanocomposites increased by up to 154% compared to the neat RC matrix. This is attributed to the good dispersion and exfoliation of MMT filler within the RC matrix regenerated from BmimCl [25]. Furthermore, the mechanical properties, such as tensile strength and tensile modulus of the nanocomposites increased by up to 12% and 47%, respectively, in comparison with the neat matrix. This is caused by the presence of MMT that provided high rigidity property to the nanocomposites. Nonetheless, the tensile extension of the nanocomposites decreased because the slippage movement of RC chains was restrained by MMT filler [25]. This increased the stiffness property of the composites, which reduced the strain behavior and led to the lower tensile extension.

5. Conclusions

Polymer blends and polymer composites compatibilized by quaternary ammonium compounds (QACs) were concisely reviewed in this paper. The focal thermo-mechanical properties, for instance, degradation temperature, glass transition temperature, melting temperature, tensile strength, flexural strength, and impact strength of the polymer blends and polymer composites were also ascertained in this concise review. QACs can be applied for compatibilization of polymer blends and polymer composites because they own multipurpose features. QACs applied for different types of polymer blends and polymer composites are mainly classified into two types, namely quaternary ammonium surfactants (QASs) and quaternary ammonium ionic liquids (QAILs). The appropriate compatibilizations of polymer blends by QASs and QAILs could effectually create intermolecular interactions between the blend components. Furthermore, the polymer composites compatibilized by QASs and QAILs could also effectively form intermolecular interactions between the polymer matrices and fillers. The presence of the interactions might improve the interfacial adhesion and compatibility between the components of polymer blends and polymer composites. The improved compatibility has consequently enhanced the thermo-mechanical properties of the polymer blends and polymer composites.

Author Contributions

Conceptualization, A.A.S. and S.N.A.M.J.; methodology, A.A.S.; validation, A.A.S. and S.N.A.M.J.; formal analysis, S.N.A.M.J.; investigation, A.A.S.; resources, S.N.A.M.J.; data curation, A.A.S.; writing—original draft preparation, A.A.S.; writing—review and editing, S.N.A.M.J.; project administration, A.A.S.; funding acquisition, S.N.A.M.J. All authors have read and agreed to the published version of the manuscript.

Funding

This concise review was funded by the Universiti Putra Malaysia (vote number: 9001103).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors would like to thank Jacek Nowaczyk from the Nicolaus Copernicus University in Toruń for inspiring the authors to write this concise review.

Conflicts of Interest

The authors declare no conflict of interest. The funder had no role in the design of the review; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

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Applsci 11 03167 g001 550
Figure 1. Schematic of the quaternization of N-methyldiethanolamine with benzyl chloride to produce benzylbis(2-hydroxyethyl)methylammonium chloride.
Figure 1. Schematic of the quaternization of N-methyldiethanolamine with benzyl chloride to produce benzylbis(2-hydroxyethyl)methylammonium chloride.
Applsci 11 03167 g001
Applsci 11 03167 g002 550
Figure 2. Chemical structures of thermoplastic polymers and the abbreviations are explained in Table 1.
Figure 2. Chemical structures of thermoplastic polymers and the abbreviations are explained in Table 1.
Applsci 11 03167 g002
Applsci 11 03167 g003 550
Figure 3. Chemical structures of thermosetting polymers and the abbreviations are explained in Table 2.
Figure 3. Chemical structures of thermosetting polymers and the abbreviations are explained in Table 2.
Applsci 11 03167 g003
Applsci 11 03167 g004 550
Figure 4. Chemical structures of (a) cellulose, (b) chitin, (c) chitosan, and (d) agarose.
Figure 4. Chemical structures of (a) cellulose, (b) chitin, (c) chitosan, and (d) agarose.
Applsci 11 03167 g004
Applsci 11 03167 g005 550
Figure 5. Chemical structures of QASs and the abbreviations are explained in Table 5.
Figure 5. Chemical structures of QASs and the abbreviations are explained in Table 5.
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Applsci 11 03167 g006 550
Figure 6. Chemical structures of QAILs and the abbreviations are explained in Table 6.
Figure 6. Chemical structures of QAILs and the abbreviations are explained in Table 6.
Applsci 11 03167 g006
Table
Table 1. Examples of polymer blends compatibilized by quaternary ammonium compounds (QACs).
Table 1. Examples of polymer blends compatibilized by quaternary ammonium compounds (QACs).
Polymer BlendAbbreviationReferences
Nylon-6/liquid natural rubberNylon-6/LNR[9]
Natural wool/celluloseNW/Cellulose[10]
Polyethylene terephtalate/polyethylenePET/PE[11]
Polybutylene succinate/rice starchPBS/RS[12]
Poly(ethylene oxide)/chitosanPEO/Chitosan[13]
Agar/rice starchAgar/RS[14]
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulosePHBV/Cellulose[15]
Table
Table 2. Examples of polymer composites compatibilized by quaternary ammonium compounds (QACs).
Table 2. Examples of polymer composites compatibilized by quaternary ammonium compounds (QACs).
Polymer CompositeAbbreviationReferences
High-/low-density polyethylene/celluloseHDPE/LDPE/Cellulose[16]
Carboxylated styrene butadiene rubber/rice bran carbonXSBR/RBC[17]
Poly(Bisphenol-A-co-epichlorohydrin)/boron nitridePBE/BN[18]
Agarose/talcAgarose/Tc[19]
Styrene-butadiene rubber/bentoniteSBR/Bentonite[20]
Diglycidyl ether of bisphenol A epoxy/chitinDGEBA epoxy/Chitin[21]
High-density polyethylene/agarHDPE/Agar[22]
Polyurethane/silicaPU/SiO2[23]
Nylon-6/LNR/montmorilloniteNylon-6/LNR/MMT[24]
Regenerated cellulose/montmorilloniteRC/MMT[25]
Table
Table 3. Examples of polymer blends, blend types, blending conditions, and blending machines.
Table 3. Examples of polymer blends, blend types, blending conditions, and blending machines.
Polymer BlendBlend TypeBlending ConditionBlending MachineReferences
PET/PESynthetic/syntheticMeltTwin-screw compounder[11]
Agar/RSNatural/naturalSolutionMagnetic stirrer[14]
Chitin/CelluloseNatural/naturalSolutionKPG stirrer[32]
PBS/RSSynthetic/naturalMeltTwin-screw extruder[12]
PEO/ChitosanSynthetic/naturalSolutionMechanical stirrer[13]
PHBV/CelluloseSynthetic/naturalSolutionMagnetic stirrer[15]
Nylon-6/LNRSynthetic/naturalEmulsionMechanical stirrer[9]
Table
Table 4. Examples of polymer matrices, matrix types, fillers, processing conditions, and processing machines.
Table 4. Examples of polymer matrices, matrix types, fillers, processing conditions, and processing machines.
Polymer MatrixMatrix TypeFillerProcessing ConditionProcessing MachineReferences
HDPE/LDPEThermoplasticCelluloseMeltInternal mixer[16]
PEThermoplasticSawdustMeltSingle-screw extruder[38]
PBEThermosettingBNSolutionMechanical stirrer[18]
DGEBA epoxyThermosettingChitinSolutionMechanical stirrer[21]
PUThermosettingSiO2SolutionOverhead stirrer[23]
CelluloseBiopolymerChitosanSolutionSonicator[39]
RCBiopolymerMMTSolutionMagnetic stirrer[25]
AgaroseBiopolymerTcSolutionMagnetic stirrer[19]
SBRElastomerBentoniteMeltTwo-roll mill[20]
Nylon-6/LNRBlendMMTEmulsionMechanical stirrer[24]
Table
Table 5. Examples of quaternary ammonium surfactants (QASs) applied for compatibilization of polymer blends and polymer composites.
Table 5. Examples of quaternary ammonium surfactants (QASs) applied for compatibilization of polymer blends and polymer composites.
QASsAbbreviationCompatibilizationReferences
Dodecyltrimethylammonium bromideDTABBlend/Composite[13,18,45]
N-isopropyl-N, N-dimethyldodecan-1-aminium bromideIDABComposite[20]
Benzylbis(2-hydroxyethyl)dodecylammonium chlorideBDACBlend[11]
Tetradecyltrimethylammonium bromideTTABComposite[46]
Hexadecyltrimethylammonium bromideHTABBlend/Composite[9,22,24,47,48]
N-isopropyl-N, N-dimethylhexadecan-1-aminium bromideIHABComposite[20]
Benzyldimethylhexadecylammonium chlorideBHACBlend[11]
Hexadecylpyridinium chlorideHPCBlend[49]
Octadecyltrimethyl ammonium bromideOTABComposite[18]
Stearyltrimethylammonium chlorideSTACComposite[50]
Table
Table 6. Examples of quaternary ammonium ionic liquids (QAILs) applied for compatibilization of polymer blends and polymer composites.
Table 6. Examples of quaternary ammonium ionic liquids (QAILs) applied for compatibilization of polymer blends and polymer composites.
QAILsAbbreviationCompatibilizationReferences
1-Ethyl-3-methylimidazolium acetateEmimAcBlend/Composite[21,56,57,58]
1-Ethyl-3-methylimidazolium propionateEmimPrBlend[32]
1-Ethyl-3-methylimidazolium trifluoromethanesulfonateEmimOTfComposite[59]
1-Allyl-3-methylimidazolium bromideAmimBrComposite[60]
1-Allyl-3-methylimidazolium chlorideAmimClBlend[61]
1-Butyl-3-methylimidazolium acetateBmimAcComposite[62]
1-Butyl-3-methylimidazolium chlorideBmimClBlend/Composite[14,19,25,39,63]
1-Butyl-3-methylimidazolium hexafluorophosphateBmimPF6Composite[23]
1-Hexyl-3-methylimidazolium hexafluorophosphateHmimPF6Composite[17]
1-Dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imideDmimNTf2Blend[12]
Table
Table 7. Thermo-mechanical properties of polymer blends influenced by QASs and QAILs.
Table 7. Thermo-mechanical properties of polymer blends influenced by QASs and QAILs.
Polymer BlendQASs/QAILsThermo-Mechanical Properties *References
TdTgTmTSTMTEFSFEIS
Nylon-6/LNRHTAB⇩⇩-⇩⇩⇧--⇧[9]
PET/PEBDAC⇩--⇧⇧⇩---[11]
NW/CelluloseBmimCl⇧⇧-⇧⇧⇧---[10]
PBS/RSDmimNTf2⇧-⇩⇩⇩⇧⇩⇧-[12]
PHBV/CelluloseBmimCl⇧⇧⇩⇧⇧⇧---[15]
Td = degradation temperature, Tg = glass transition temperature, Tm = melting temperature, TS = tensile strength, TM = tensile modulus, TE = tensile extension, FS = flexural strength, FE = flexural extension, and IS = impact strength. * The symbol “⇧” corresponds to an increase in the properties and “⇩” a decrease in the properties while “-” describes not available.
Table
Table 8. Thermo-mechanical properties of polymer composites influenced by QASs.
Table 8. Thermo-mechanical properties of polymer composites influenced by QASs.
Polymer CompositeQASsThermo-Mechanical Properties *References
TdTgTmkTSTMTEFSFMIS
HDPE/LDPE/CelluloseHTAB⇩-⇳-⇧⇧⇩--⇩[16]
PBE/BNOTAB---⇧---⇧⇧⇧[18]
HDPE/AgarHTAB⇩-⇩-⇩⇩⇧--⇧[22]
SBR/BentoniteIDAB⇩---⇧⇧⇩---[20]
Nylon-6/LNR/MMTHTAB⇧⇧--⇧⇧⇩--⇧[24]
Td = degradation temperature, Tg = glass transition temperature, Tm = melting temperature, k = thermal conductivity, TS = tensile strength, TM = tensile modulus, TE = tensile extension, FS = flexural strength, FM = flexural modulus, and IS = impact strength. * The symbol “⇧” corresponds to an increase in the properties and “⇩” a decrease in the properties while “-” and “⇳” describe not available and unchanged, respectively.
Table
Table 9. Thermo-mechanical properties of polymer composites influenced by QAILs.
Table 9. Thermo-mechanical properties of polymer composites influenced by QAILs.
Polymer CompositeQAILsThermo-Mechanical Properties *References
TdTgkTSTMTEFSFEIS
XSBR/RBCHmimPF6⇩⇧-⇧⇧⇧---[17]
Agarose/TcBmimCl⇩⇧-⇧⇧⇩---[19]
DGEBA epoxy/ChitinEmimAc⇳⇧-⇧⇧⇧--⇧[21]
PU/SiO2BmimPF6⇧⇧⇩---⇧⇩-[23]
RC/MMTBmimCl⇧--⇧⇧⇩---[25]
Td = degradation temperature, Tg = glass transition temperature, k = thermal conductivity, TS = tensile strength, TM = tensile modulus, TE = tensile extension, FS = flexural strength, FE = flexural extension, and IS = impact strength. * The symbol “⇧” corresponds to an increase in the properties and “⇩” a decrease in the properties while “-” and “⇳” describe not available and unchanged, respectively.
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Shamsuri, A.A.; Jamil, S.N.A.M. Application of Quaternary Ammonium Compounds as Compatibilizers for Polymer Blends and Polymer Composites—A Concise Review. Appl. Sci. 2021, 11, 3167. https://doi.org/10.3390/app11073167

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Shamsuri AA, Jamil SNAM. Application of Quaternary Ammonium Compounds as Compatibilizers for Polymer Blends and Polymer Composites—A Concise Review. Applied Sciences. 2021; 11(7):3167. https://doi.org/10.3390/app11073167

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Shamsuri, Ahmad Adlie, and Siti Nurul Ain Md. Jamil. 2021. "Application of Quaternary Ammonium Compounds as Compatibilizers for Polymer Blends and Polymer Composites—A Concise Review" Applied Sciences 11, no. 7: 3167. https://doi.org/10.3390/app11073167

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