Quaternary Ammonium Salt

8/6/2020 Quaternary Ammonium Salt - an overview | ScienceDirect Topics
Quaternary Ammonium Salt

Quaternary ammonium salts (QAS) are cationic compounds
containing alkyl groups in a chain length of C8–C18, which are
water soluble and can be used as disinfectants in textile industries.
From: Functional Textiles for Improved Performance, Protection and Health, 2011
Related terms:
Anion, Amine, Tertiary Amine, Chloride, Ionic Liquid, Halide, Cation, Ion, [Alpha],
Antimicrobial Agent
Antibacterial textile materials for medical applications

G. Sun, in Functional Textiles for Improved Performance, Protection and Health,
2011
16.3.2 QAS and similar compounds

QAS are ionic compounds having a quaternary ammonium nitrogen, four alkyl or aryl
groups connected to this nitrogen, and an anionic ion such as chloride or bromide.
Among four alkyl groups, one is a long alkyl chain group containing more than eight
hydrocarbons and also serves as the hydrophobic group. Hydrophobic groups on
QAS tend to affect their antimicrobial functions (Tiller et al., 2001; Zhao and Sun,
2007). With stronger hydrophobicity, the more powerful antimicrobial functions the
QAS has (Zhao and Sun, 2008) (Fig. 16.1 and Table 16.1). Many QAS compounds
have surfactant functions. QAS are effective biocides when used in aqueous solutions
and as liquid disinfectants. When QAS are chemically connected to fiber surfaces their
functions can be impeded depending on how they are connected and the final
structures of QAS on surfaces. Physically incorporated QAS in fibers can provide
antimicrobial functions by gradually releasing them from fiber's surfaces during
usage, which could provide the intended functions of the materials but may present a
durability concern.
https://www.sciencedirect.com/topics/chemistry/quaternary-ammonium-salt 1/19
16.1. Structures of different QAS (Zhao and Sun, 2008).
Table 16.1 . Antimicrobial effects of the QAS (Zhao and Sun, 2008)
Concentration to cause a 6-log reduction of bacteria in contact time
QAS 1 min (E. coli) 5 min (E. coli) 1 min (S. aureus) 5 min (S. aureus)
(ppm) (ppm) (ppm) (ppm)
ALPC 100 100 100 50
AALPC 100 100 100 50
BADPB 50 50 50 10
NADPB 50 10 50 10
QAS based antimicrobial textiles have been widely reported by researchers since
1970s (Isquith et al., 1972) and more recently (Cai and Sun, 2004; Kim and Sun,
2002; Son and Sun, 2003; Son et al., 2006; Zhao and Sun, 2008). Commercial QAS
finishing agents have been developed and marketed, and the most popular one is
Dow Corning 5700, which employs siloxyl groups to bind QAS to cellulose surfaces.
QAS could be chemically incorporated to nylon and protein fibers (Son and Sun,
2003; Zhu and Sun, 2004; Zhao and Sun, 2007) and acrylic fibers (Cai and Sun, 2004;
Kim and Sun, 2002) directly with ionic interactions, or by bridging with other reactive
groups to cellulose (Son et al., 2006); all provide the textiles with proper antimicrobial
functions and durability, particularly washing durability.
Due to their effective antimicrobial functions, the QAS moieties were introduced onto
polymer surfaces and dye molecules to produce functional polymers or dyes (Liu and
Sun, 2008a; Ma et al., 2003; Tiller et al., 2001). When QAS structures are covalently
connected to anthraquinone dyes (Fig. 16.2), the new dye molecules exhibited
excellent biocidal properties in diluted solutions. However, when these dyes are
incorporated onto acrylic fibers, following a basic dyeing process, the dyed fabrics
showed limited antimicrobial properties, and these properties could be affected by
surfactants and other species in water (Liu and Sun, 2009b). Results indicated that
surface fixed QAS compounds or combined QAS molecules had reduced
antimicrobial functions. Only the dissociated QAS could demonstrate the ideal
antimicrobial functions, and this result is consistent with the accepted antimicrobial
mechanisms of QAS (Hashemi and Sun, 2010). In fact, this limitation is pretty
universal to all QAS antimicrobial agents.
16.2. Structure of the antimicrobial colorants (n = 3, 7, 11 or 15) (Liu and Sun,
2008a).
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URL: https://www.sciencedirect.com/science/article/pii/B9781845697235500162
Antibacterial colorants for textiles

F. Alihosseini, G. Sun, in Functional Textiles for Improved Performance, Protection
and Health, 2011
17.2.3 Quaternary ammonium antibacterial dyes

Quaternary ammonium salts (QAS) are cationic compounds containing alkyl groups
in a chain length of C8–C18, which are water soluble and can be used as disinfectants
in textile industries. All of these compounds are membrane active agents and can
damage cell walls of gram-positive bacteria. The damaged membrane could lead to
leakage of intracellular constituents, resulting in cytolysis (Russell and Chopara, 1996).
QAS have been successfully applied on wool and nylon fabrics and possess durable
and powerful antibacterial activity (Kim and Sun, 2000, 2001; Zhao and Sun, 2007,
2008).
Two series of dyes containing both anthraquinone and QAS groups were reported,
with a long alkyl chain varying from C4 to C12. The dyes with alkyl chain length
longer than C8 showed good antimicrobial activities against both E. coli and S. aureus
(Ma et al., 2003; Ma and Sun, 2004). However, the washing durability and hydrolytic
stability of the dyes were very limited since the anthraquinone and QAS were
connected by an amide bond, which could be hydrolyzed in alkaline solution (Ma and
Sun, 2005). To overcome the low hydrolytic stability of the amide bond, two new
series of dyes were synthesized (Fig. 17.4) using amine bond as a new connection
between the anthraquinone and QAS groups. These dyes are very stable under both
alkaline and acidic conditions (Liu and Sun, 2008), and have different alkyl chains with
different lengths varying from C4 to C16. The dyes containing alkyl chain lengths of
C8 and C12 demonstrated the most powerful antimicrobial activity, and the dyes with
two quaternary ammoniums sites were stronger than these with one site in
antimicrobial activities. The minimum inhibition concentration of the dyes was as low
as 10 ppm in solutions (Liu and Sun, 2008).
17.4. Chemical structures of antimicrobial cationic dyes (Liu and Sun, 2008).
An antimicrobial reactive dye that can work on cellulosic fabrics as well as nylon, silk
and wool fabrics was produced with QAS as biocidal site (Zhao et al., 2008). The dye
showed the desired antimicrobial functions in solutions, but when it was incorporated
to fabrics, the antimicrobial functions were unexpectedly lost. No matter what
process, reactive or basic dyeing, was employed the dyed fabrics lost antimicrobial
functions even though the dyes are strong biocides in vitro. Several factors could cause
this effect. One is that only surface dyes could be in contact with bacteria cells and
provide the functions, while they also can be easily washed off during laundering.
Another reason may be that all detergents are anionic compounds which could form
insoluble ion pairs with the cationic sites. Most QAS exhibit the functions in
dissociated ionic form in solutions. Anionic surfactants could form precipitates with
QAS in solutions and could thus reduce the antimicrobial efficacy (Liu and Sun, 2008).
However, if the anionic surfactant concentration is higher than its CMC (critical
micelle concentration) the biocidal functions of the QAS will not be affected (Hashemi
and Sun, 2010). It was also found that the immobilized QAS on substrates still
demonstrated the functions (Tiller et al., 2001). In addition, some cationic species such
as calcium and magnesium could also affect antimicrobial properties of the dyes
(Hashemi and Sun, 2010). The comparison of antibacterial efficacy of pyridinium
structures revealed that more hydrophobic moieties could increase antimicrobial
power of the substrates (Zhao et al., 2008).
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Smart anti-microbial composite coatings for textiles

and plastics
Xuehong Ren, Jie Liang, in Smart Composite Coatings and Membranes, 2016
9.3 Quaternary ammonium salts

Quaternary ammonium salts, particularly those containing 12–18 carbon atoms
chains, have been widely used as antimicrobial agents in manufacturing antimicrobial
textiles [41,42]. These compounds carry a positive charge at N atoms after immersed
in water solution and inflict a variety of negative effects on microbes. They adsorb
onto phosphate containing cell walls of bacteria through an ionic interaction,
penetrate the cell wall, and then attach to the cytoplasmic membrane, thus causing
the denaturation of proteins and resulting in leakage of intracellular components and
the death of bacteria [43,44]. During inactivation of bacteria, quaternary ammonium
groups remain intact and retain their antimicrobial ability as long as the compounds
are attached to textiles. However, because of the slow release mechanism, the
washing durability of treated fabrics is limited due to the amount of biocides
incorporated. Moreover, quaternary ammonium salts have a relatively lower
antibacterial efficacy compared with other antibacterial compounds [45,46]. Today,
new kinds of quaternary ammonium compounds have been synthesized and
successfully treated on textiles.
Organosilicon quaternary salts are a novel type of cationic surfactants with
hydrophobic groups containing silicon. In general, this type of surfactant exhibits
excellent properties such as low critical micelle concentration (CMC), thermal stability,
low temperature flexibility, and chemical inertness. This kind of biocide also has good
antimicrobial activity toward gram-positive and gram-negtive bacteria, yeast, fungi,
and mold. Dow Corning first synthesized an organosilicon quaternry salt (DC-5700,
Figure 9.1). It is a reactive silane that is able to react with many materials such as
cotton, glass, or polyester by the hydrolyzed silanol. The treated materials showed
antibacterial property after repeated washings [47]. The toxicity experiments with DC-
5700 indicated that the median lethal dose is LD50=12.27 g/kg±0.116 g/kg and it
cannot be absorbed into body through treated fabrics [48], which shows that this kind
of organosilicon quaternary salt is probably a safe antibacterial agent.
Figure 9.1. Structure of DC-5700.
Polymeric organosilicon containing quaternary ammonium salt groups is achieved by

reacting polysiloxane-bearing chlorohydrocarbon with tertiary amine (Figure 9.2).
100% cotton treated with the compound had a novel antibacterial activity against E.
Coil and S.aureus when the mass concentration exceeds 1.5% [47,49,50]. Recently, a
novel quaternary ammonium silane containing dimethyl (octyl) ammonium segments
was detected to possess surface antibacterial activity. Cotton fabrics were treated with
a novel perfluorooctryl-containing quaternary ammonium salt, and the treated cotton
samples have good antimicrobial activity and low critical surface energy at the same
time [51].
Figure 9.2. Structure of poly [(3-chloropropyl) methylsiloxane] with

dimethyloctylamine.
In order to improve the antibacterial activity of quaternary ammonium salts, chitosan

derivative was synthesized and applied onto cotton fabrics by a pad-dry-cure process
(Figure 9.3). The cotton fabric treated with 0.2% of HTACC and 1.8% of COS
exhibited 100% bacteria reduction and durable laundering activity [6]. A fiber-reactive
chitosan derivative, O-acrylamidomethyl-N- [(2-hydroxy-3- trimethylammonium)
propyl] chitosan chloride (NMAHTCC) (Figure 9.4), was synthesized and applied onto
cotton fabrics via cold pad-batch method. Over 99% of the antibacterial activity of
treated cotton fabrics was maintained after 50 consecutive home laundering
conditions [24].
Figure 9.3. Structure of N-(2-hydroxy)propyl-3-trimethyl ammonium COS chloride

(HTACC).
Figure 9.4. Structure of NMA-HTCC.
A series of copolymers incorporating N-halamine siloxane and quaternary

ammonium salt siloxane units had been prepared to render them soluble in water
and increase their antibacterial abilities. Poly(2,2,6,6-tetramethyl-4-
piperidylmethacrylate-co-acrylic acid potassium salt) and poly(2,2,6,6-tetramethyl-4-
piperidyl methacrylate-co-trimethyl-2- methacryloxy-ethylammonium chloride)
(PolyPMPQ) (Figure 9.5) were prepared and successfully coated onto cotton fabric via
a layer-by-layer (LbL) assembly technique [52]. Copolymers of an N-halamine siloxane
and a quaternary ammonium salt siloxane were prepared using 5,5-dimetylhydatoin
and trimethylamine as functional groups. The solubility of the siloxane copolymer in
water was dramatically improved. The synthesized polymer, poly [3-(5,5-
dimethylhydantoinylpropyl)-siloxane-co-trimethyl ammoniumpropylsiloxane chloride]
(PHQS) (Figure 9.6), was grafted onto cotton. The treated cotton fabrics with
0.23%-0.26% chlorine loading could inactivate 107 colony forming units (CFU) of S.
aureus and E. coli O157:H7 within 1–5 min of contact [53].
Figure 9.5. Structure of PolyPMPQ.
Figure 9.6. Structure of PHQS.
New surface-active bis-quaternary ammonium salts are widely developed and they
are highly effective against gram-positive and gram-negative bacteria, and yeasts.
DABK (see Figure 9.7) and DABB (Figure 9.8) are new kind of bis-quaternary
ammonium salts that are very water-soluble compounds with extraordinary micelle-
forming properties. Nowadays, DABK and DABB have been used in wool fabrics
against B. pumilus, S. aureus, E. coli, and P. aeruginosa [4].
Figure 9.7. Structure of DABK.
Figure 9.8. Structure of DABB.
Acidic or basic dyeing of fabrics involves ionic interaction between reactive groups on
the substrate and dye molecules. Such interaction can be utilized in functional
finishing of fabric surface. According to this theory, nylon 66 and nylon 6 can get
durable and refreshable antimicrobial functions after dipping in a quaternary
ammonium salt solution. Acid dyes usually contain sulfonate groups, and the anionic
solubilizing groups are interactive with the quaternary ammonium salts. A reaction
could occur between anionic dyes and quaternary ammonium salts to establish
chemical connection. Anionic dyed fabrics treated with quaternary ammonium salts
could have durable antimicrobial activities [5,54]. Nylon fabrics treated with
quaternary ammonium salts were durable in laundering and can survive extensive
machine washing and repeated exposures to bacterial solutions.
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New Developments and Application in Chemical

Reaction Engineering
D.W. Park, ... J.W. Lee, in Studies in Surface Science and Catalysis, 2006
2 EXPERIMENTAL
quaternary ammonium salt catalysts based on different alkyl cations such as
tetrapropylammonium (TPA+), tetrabutylammonium (TBA+), tetrahexylammonium
(THA), tetraoctylammonium (TOA+), tetradodecylammonium (TDodA+), and those
with different anions such as Cl-, Br-, and I- were used.
The transesterification reaction was carried out in a 50 mL stainless steel autoclave
equipped with a magnetic stirrer. For each typical reaction, quaternary ammonium
salt (2 mmol), propylene carbonate (25 mmol) and excess methanol (200 mmol) were
charged into the reactor, and the CO2 was introduced at room temperature to a
preset pressure. The reaction was started by stirring when the desired temperature
and pressure were attained. The reaction was performed in a batch operation mode.
The analysis of the products and reactants was performed by using a gas
chromatograph (HP 6890N) equipped with a FID and a capillary column (HP-5, 5 %
phenyl methyl siloxane). Selectivities to DMC and EG are calculated on the basis of EC
as a limited reactant.
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Ultimate Biodegradation of Ingredients Used in

Cleaning Agents
C.G. van Ginkel, in Handbook for Cleaning/Decontamination of Surfaces, 2007
3.3.2 Quaternary Ammonium Salts

Quaternary ammonium salts are characterised by a nitrogen atom linked to four alkyl
chains. These surfactants are potentially excellent sources for microbial growth.
Among the quaternary ammonium salts, biodegradability of
alkyltrimethylammonium salts has been studied in detail by using pure cultures of
micro-organisms. A bacterium tentatively identified as a Pseudomonas sp., capable of
utilising alkyltrimethylammonium chloride as the sole source of carbon and energy,
has been isolated from activated sludge. This Pseudomonas sp. growing on
hexadecyltrimethylammonium chloride accumulates trimethylamine as a breakdown
product, unequivocally showing that this organism used the alkyl chain as the sole
source of carbon and energy. The cleavage of the Calkyl–N bond of
alkyltrimethylammonium salts is initiated by a mono-oxygenase [87]. Another
demonstration of the cleavage of the Calkyl–N bond as the initial degradation step of
alkyltrimethylammonium salts was presented by Nishiyama et al. [88].
Aeromonas hydrophila sp. K, an organism isolated from soil, is capable of utilising
alkylbenzyldimethylalkylammonium salts as the sole source of carbon and energy.
High-performance liquid chromatography and gas chromatography mass
spectrometry analyses have been used to study the degradation pathway. During
alkylbenzyldimethylammonium chloride biodegradation, formation of
benzyldimethylamine, benzylmethylamine, benzylamine, benzaldehyde and benzoic
acid occurs. Formation of benzyldimethylamine suggests that the cleavage of Calkyl–N
bond occurs as the first step of alkylbenzyldimethylalkylammonium chloride
metabolism [89]. A series of Closed Bottle tests inoculated with unadapted micro-
organisms and micro-organisms adapted to decylbenzyldimethylammonium chloride
also suggests cleavage of the Calkyl–N bond [90]. The alkyl chains of the quaterrnary
ammonium salts are liberated as alkanals. Alkanals are channelled into the β-
oxidation cycle as shown inFigure 2.1.6. Trimethylamine and dimethylbenzylamine are
degraded by other micro-organisms [89,91].
Figure 2.1.6. Main biodegradation pathway via a cleavage of the CalkyI–N bond for the
microbial degradation of fatty amine derivatives. The alkyl chains are channelled into
the β-oxidation cycle
It is obvious that toxicity problems in biodegradability tests should be prevented.

Addition of silica gel or LAS prevents toxicity of alkyltrimethylammonium salts
[10,57,92]. For quaternary ammonium salts, biodegradation percentages of >60 have
been obtained after 28 days in Closed Bottle tests (Table 2.1.7). Nine out of ten
laboratories measured >60% degradation of hexadecyltrimethylammonium chloride
inthe Headspace Carbon Dioxide test. The mean biodegradation percentage of
hexadecyltrimethylammonium chloride found is 75 [57]. The biodegradation of
octadecyltrimethylammonium chloride in the presence of LAS started almost
immediately and reached a biodegradation percentage of approximately 80 within 28
days [92]. Masuda et al. [93] assessed the biodegradability of
alkylbenzyldimethylammonium Chlorides after 10 days in the MITI test.
Alkylbenzyldimethylammonium chlorides with alkyl chains ranging from C8 to C14 are
readily biodegradable. Biodegradation percentages of less than 10 with hexadecyland
octadecylbenzyldimethylammonium chlorides reflect biocidal effects [93]. Ready
biodegradability of alkyltrimethylammonium salts and
alkylbenzyldimethylammonium salts with varying alkyl chain lengths is established
through read-across of the biodegradability data (Table 2.1.7).
Table 2.1.7 . Compilation of ready biodegradability test results obtained with

quaternary ammonium salts
Result at
Substance Test Day 28 (%) Source
Octylbenzyldimethylammonium MITI >80 [93]

chloride
Decylbenzyldimethylammonium Closed Bottle >60 [90]

chloride
Tetradecylbenzyldimethyl- MITI >80 [93]

ammonium chloride
Cocotrimethylammonium Closed Bottle >60 Akzo Nobel,

chloride unpublished
result
Hexadecyltrimethylammonium Headspace 75 a [57]

chloride Carbon Dioxide
Octadecyltrimethylammonium Sturm >70 [92]

chloride
a
Mean of eleven tests
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Lamellar Gel Network

T. Iwata, in Cosmetic Science and Technology, 2017
25.5.2 Quaternary Ammonium Salts

Quaternary ammonium salts, such as cetyl trimethyl ammonium chloride and behenyl
trimethyl ammonium chloride, are widely used conditioning actives in various
cosmetic formulations because of their unique lubricated and conditioned feel. The
trimethylammonium head group, as well as its counterion such as chloride, is
considered bulky and “pushes away” the fatty alcohol or surfactant head group next to
it. This enables the molecule to have space to rotate that prevents crystallization of all
alkyl chains around. This class of materials is widely used in hair conditioners and
treatments due to their cationic charge to selectively bind to the negatively charged
damaged hair surface. Historically, C16 alkyl chain was mainly used in hair
conditioners but C22 has become mainstream in most recent years. This is driven by
the trend is to provide a richer, heavier, more conditioned feel. Such feel is a function
of hydrophobicity of the bilayer due to longer alkyl chains. More recently, the
methosulfate counterion has been used to further increases the hydrophobicity and
rigidity of bilayer compared to the chloride counterion.19
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Synthetic Methods V – Organocatalysis

R. Rios, A. Córdova, in Comprehensive Chirality, 2012
6.15.7 By Quaternary Salts of Cinchona Alkaloids

Quaternary ammonium salts have been extensively used in asymmetric synthesis. In
2004, Floravanti et al. reported their use to induce chirality in the aziridination of 2-
(phenylsulfanyl)-2-cycloalkenones.52 The reaction of these cycloalkenones with ethyl
nosyloxycarbamate under phase transfer conditions provided the corresponding
aziridines in good yields and with moderate to good enantioselectivities as shown in
Scheme 33.
Scheme 33. Aziridination catalyzed by quaternary ammonium salts reported by

Tardella.
In the same context, Siva and Murugan have developed a chiral-phase transfer
catalyzed aziridination of a wide range of electron-deficient olefins, using as nitrogen
source N-acyl-N-aryl hydroxamic acids.53 The reaction furnishes the corresponding
N-arylazidirines in good yields and with high enantioselectivities (Scheme 34).
Scheme 34. Aziridination of olefins with N-acyl-N-aryl hydroxamic acids mediated by

phase-transfer catalysts.
In 2008, Minakata et al. reported a new method for the aziridination of electron
deficient olefins based on the use of N-chloro-N-sodio carbamate.54 These reactions
were promoted by phase-transfer catalysts, concretely chiral ammonium salts derived
from cinchona alkaloids. The corresponding aziridines were obtained in good yields
and with good enantioselectivities, as shown in Scheme 35.
Scheme 35. Aziridination catalyzed by phase-transfer catalysts reported by Minakata,

S.; Murakami, Y.; Tsuruoka, R.; Kitanaka, S.; Komatsu, M. Chem. Commun. 2008, 6363
–6365.
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New Developments and Application in Chemical

Reaction Engineering
K. Anas, ... Il Kim, in Studies in Surface Science and Catalysis, 2006
3 RESULTS AND DISCUSSION

Eight quaternary ammonium salts and seven imidazolium salts were chosen in this
study. The quaternary ammonium salts (QAS) used are (1) tetrapropylammonium
chloride (TPACl) (2) tetrabutylammonium chloride (TBACl) (3) tetrahexylammonium
chloride (THACl) (4) tetraoctaylammonium chloride (TOACl) (5)
tetradodecylammonium chloride (TdodecylACl) (6) tetrabutylammonium bromide
(TBAB) (7) tetramethylammonium bromide (TMAB) and (8) tetrabutylammonium
iodide (TBAI). And the imidazolium salts used are (1) 1-ethy1-3-methylimidazolium
chloride (EMImCl), (2) 1-butyl-3-methylimidazolium chloride (BMImCl), (3) 1-hexyl-3-
methylimidazolium chloride (HMImCl), (4) 1-ethyl-3-methylimidazolium
tetrafluoroborate (EMImBF4), (5)1-Butyl-3-methylimidazolium tetrafluoroborate
(BMImBF4), (6) 1-Octyl-3-methylimidazolium tetrafluoroborate (OMImBF4), and (7)
1-ethyl-3-methylimidazolium hexafluorophosphate (EMImPF6). Figures 1 and 2 show
the plots of propylene oxide consumption versus reaction time obtained by adding
1 mmol of QASs and imidazolium salts, respectively.
Fig. 1. PO consumption rate obtained by adding various QAS cocatalysts at 115°C: (a)
TDACl, (b) TOAC1, (c) TMABr, (d) THACl, (e) TBAI, (f ) TBACl, (g) cat. only, (h) TPACl,
and (i) TBABr. Polymerization conditions: catalyst = 0.1 g, initiator (PPG-750) = 70 g,
and QAS = 1 mmol.
Fig. 2. PO consumption rate obtained by adding various imidazolium salt cocatalysts

at 115 °C: (a) OMImBF4, (b) EMImPF4, (c) BMImBF4, (d) EMImCl, (e) EMImBF4, (f )
BMImCl, (g) HMImCl, and (h) cat. only. Polymerization conditions: catalyst = 0.1 g,
initiator (PPG-750) = 70 g, and imidazolium salt = 1 mmol.
The polymerization reactions exhibit very short induction periods (several minutes) in
comparison with that obtained by DMC catalyst alone under the same conditions. In
the case of DMC catalyst alone it can be seen that the reaction rate decreased
gradually with increased monomer addition. No such deactivation is observed if QASs
are added during polymerizations. The induction period was found to be decreased
with an increase in the number of the carbon atoms in the quaternary ammonium
salt. These results show that the total carbon number of the quaternary ammonium
salts is an important factor influencing the catalytic behavior of DMC compounds.
From Fig. 1, it is clear that the activity of the QAS containing chlorine counterion is
decreasing in the order of TdodecylACl > TOACl > THACl > TBACl > TPACl, while in
the case of bromine as anion the reverse was taking place according to the alkyl chain
length; i.e. TMAB > TBAB. Both the high activity and the short induction period
obtained by simply adding QASs are the best level comparing to reported results so
far.
The similar favorable results were also obtained by adding imidazolium salts (Fig. 2).
The induction period was increased when chloride was an anion with the increase of
the alky chain length. When tetrafluroborate is an anion, the induction period was
decreased with the increase of alkyl chain length.
It is not clear why QAS and imidazolium salt yield favorable results in DMC catalyzed
polymerizations. One possible reason is that since the organic phase reaction is the
rate controlling step, the total carbon number of the quaternary salt which
participates in the formation of the active intermediate of catalyst in the organic phase
is increased with an increase in the total carbon atom of the quaternary ammonium
salt. In addition for anions with high polarizabilities more organophilic QASs are
favorable. However, more detailed mechanistic study seems to be needed to explain
these effects more clearly.
All polymers, regardless of the use of ionic complexes, have high molecular weight
and narrow molecular weight distribution (1.21-1.47) (Table 1). It demonstrates that
the addition of QASs and imidazolium salts (not shown) do not influence the
termination reaction so much. The narrow MWD of polyols keeps the viscosity
molecular low. However, the level of unsaturation of polymer chain became increased
slightly by the addition of QAS and imidazolium salt, demonstrating isomerizations
are activated together with the accelerated propagation reaction. Considering
induction period depends on the exchange equilibrium between the dormant site and
active sites during the initial period of polymerization [3], the QAS and imidazolium
salt additives may prevent the strong coordination of complexing species to the
dormant sites, hence increase the propagation rate and also accelerate various
isomerization reactions resulting in unsaturated chains. The detailed mechanistic
discussion will be made elsewhere. Above results demonstrate that fine-tunings of
DMC catalyst such as activity, induction period, and level of unsaturation are possible
only by using simple additives.
Table 1 . Characterization of polymers obtained by ring-opening polymerization of PO

catalyzed by DMC catalysts in the presence of QASs and imidazolium salts
Compound Mn Mw MWD Unsaturation (meq/ gm) Viscosity
DMC only 6043 7430 1.23 0.009 1465
TPAC1 6553 8821 1.35 0.011 1324
TBAC1 6057 7795 1.28 0.015 1256
THAC1 6247 8560 1.37 0.016 1404
TOAC1 6129 9005 1.47 0.019 1485
TdodecylACl 6176 7794 1.26 0.018 1372
TBABr 5909 7219 1.21 0.013 1150
THAI 5871 7638 1.30 0.011 1180
TMABr 6333 7805 1.23 0.011 1462
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CO2 Chemistry
Yu-Nong Li, ... Zhen-Zhen Yang, in Advances in Inorganic Chemistry, 2014
3.1.1.1 Quaternary ammonium salts catalysts

Quaternary ammonium salts have in the early reports been developed to be efficient
catalysts for selective synthesis of 2-oxazolidinone by cycloaddition of CO2 with
aziridine (Scheme 9.21) (56c). In this regard, tetrabutylammonium bromide (TBAB) is
found to be the efficient catalyst with 95% yield of the target product using THF as
the solvent at ambient temperature and atmospheric pressure. The counter anion has
notable impact on the reaction. Catalytic efficiency order is shown as Br > I > Cl (56c).
Scheme 9.21. Cycloaddition of CO2 with 2-methylaziridine catalyzed by TBAB.

Further investigation illustrates that NH4I-catalyzed reaction runs at extremely mild
reaction conditions, for example, at 0 °C for 4 h, affording the major product 5-
isomer 6 in 96% yield as shown in Scheme 9.22 (55b). Here, I− performs well as the
nucleophilic species to promote the ring opening. The reaction temperature also
affects the regioselectivity, for instance, the isomer 6 yield decreases to less than 80%
as temperature increasing from 25 to 45 °C.
Scheme 9.22. Cycloaddition of CO2 with aziridine catalyzed by NH4I.
The quaternary ammonium bromide covalently bound to PEG (PEG6000(NBu3Br)2) as

an easily recyclable catalyst has then been prepared to catalyze the cycloaddition of
aziridine and CO2 in our group (57a). 5-Aryl-2-oxazolidinones are obtained in yield of
more than 99% with excellent regioselectivity without the use of additional organic
solvents or cocatalyst. The only by-products are trace amounts of 1,4-diethyl-2,5-
diphenylpiperazine and 1,4-diethyl-2,3-diphenylpiperazine. Therefore, excellent
chemoselectivity is attained by using this catalytic process (Scheme 9.23). In addition,
the reactions of aziridines bearing phenyl group at the nitrogen atom proceed more
smoothly than ones with alkyl group presumably due to the formation of self-
oligomers of 2-phenylaziridine.
Scheme 9.23. The proposed mechanism for cycloaddition of CO2 with aziridine.
The proposed mechanism involves three steps: the coordination of CO2 to aziridine
(step I), the ring opening of the aziridine via two different pathways a and b (step II),
and then subsequent cyclization via an intramolecular nucleophilic attack by Br−
leading to oxazolidinones and the catalyst regeneration (step III) (56a). In the case of
R1 = aryl group, the intermediate further giving 9 would be more stable than one to
10; whereas R1 is an alkyl group, the reaction favors the 10 formation (Scheme 9.23)
(57a). In particular, this kind of catalyst can be easily recovered by centrifugation and
reused several times without significant loss of catalytic activity and selectivity. Indeed,
PEG6000(NBu3Br)2 actually shows higher catalytic activity than the simple physical
mixture of Bu4NBr with PEG6000 or the unsupported TBAB. That is because the
physical properties of the reaction mixture, such as low viscosity and the increased
solubility for the reactants, could enhance the catalytic performance. This process
represents a pathway for the environmentally benign CO2 utilization with readily
recoverable catalyst system to selectively form 5-substituted-2-oxazolidinones.
Furthermore, natural occurring α-amino acids with zwitterionic structure can be
employed as eco-friendly and recyclable catalysts to provide a greener process for
synthesis of a series of oxazolidinones from CO2 (Scheme 9.24) (62). Among the 12
kinds of investigated amino acids, proline shows the highest activity, which can be
easily precipitated by the addition of ether after the reaction and recovered by a
simple filtration. Consequently, this strategy opens potential ways for homogeneous
catalyst recycling, which also represents a halogen-free approach without the
utilization of additional organic solvent or cocatalyst, but at higher temperature and
pressure than previously described ammonium salts.
Scheme 9.24. Carboxylation of aziridine with CO2 catalyzed by proline.
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Amines and Amides

Robert J. Ouellette, J. David Rawn, in Organic Chemistry, 2014
Invert Soaps
Some quaternary ammonium salts containing a long carbon chain are invert soaps.
Invert soaps differ from soaps and detergents because the polar end of the ion is
positive rather than negative. As with soaps, the long hydrocarbon tail associates with
nonpolar substances, and the polar head dissolves in water. Thus, invert soaps act by
the same cleansing mechanism described in Section 20.5 for soaps and detergents.
Invert soaps are widely used in hospitals, but for their bactericidal properties rather
than their cleansing properties. They are active against bacteria, fungi, and
protozoans, but they are not effective against spore-forming microorganisms. One
type of invert soap is the family of benzalkonium chlorides. The alkyl groups of these
compounds contain from 8 to 16 carbon atoms. These compounds are effective at
concentrations of 1:750 to 1:20,000. The more complex benzethonium chloride is
also an effective antiseptic.
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8/6/2020 Quaternary Ammonium Salt - an overview | ScienceDirect Topics

Antibacterial textile materials for medical applications

16.3.2 QAS and similar compounds

16.1. Structures of diﬀerent QAS (Zhao and Sun, 2008).

Table 16.1 . Antimicrobial eﬀects of the QAS (Zhao and Sun, 2008)

Concentration to cause a 6-log reduction of bacteria in contact time

ALPC 100 100 100 50

AALPC 100 100 100 50

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Antibacterial colorants for textiles

17.2.3 Quaternary ammonium antibacterial dyes

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Smart anti-microbial composite coatings for textiles

9.3 Quaternary ammonium salts

Figure 9.1. Structure of DC-5700.

Polymeric organosilicon containing quaternary ammonium salt groups is achieved by

Figure 9.2. Structure of poly [(3-chloropropyl) methylsiloxane] with

In order to improve the antibacterial activity of quaternary ammonium salts, chitosan

Figure 9.3. Structure of N-(2-hydroxy)propyl-3-trimethyl ammonium COS chloride

Figure 9.4. Structure of NMA-HTCC.

A series of copolymers incorporating N-halamine siloxane and quaternary

Figure 9.5. Structure of PolyPMPQ.

Figure 9.6. Structure of PHQS.

Figure 9.7. Structure of DABK.

Figure 9.8. Structure of DABB.

New Developments and Application in Chemical

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Ultimate Biodegradation of Ingredients Used in

3.3.2 Quaternary Ammonium Salts

It is obvious that toxicity problems in biodegradability tests should be prevented.

Table 2.1.7 . Compilation of ready biodegradability test results obtained with

Octylbenzyldimethylammonium MITI &gt;80 [93]

Decylbenzyldimethylammonium Closed Bottle &gt;60 [90]

Tetradecylbenzyldimethyl- MITI &gt;80 [93]

Cocotrimethylammonium Closed Bottle &gt;60 Akzo Nobel,

Hexadecyltrimethylammonium Headspace 75 a [57]

Octadecyltrimethylammonium Sturm &gt;70 [92]

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Lamellar Gel Network

25.5.2 Quaternary Ammonium Salts

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Synthetic Methods V – Organocatalysis

6.15.7 By Quaternary Salts of Cinchona Alkaloids

Scheme 33. Aziridination catalyzed by quaternary ammonium salts reported by

Scheme 34. Aziridination of oleﬁns with N-acyl-N-aryl hydroxamic acids mediated by

Scheme 35. Aziridination catalyzed by phase-transfer catalysts reported by Minakata,

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New Developments and Application in Chemical

3 RESULTS AND DISCUSSION

Fig. 2. PO consumption rate obtained by adding various imidazolium salt cocatalysts

Table 1 . Characterization of polymers obtained by ring-opening polymerization of PO

Compound Mn Mw MWD Unsaturation (meq/ gm) Viscosity

DMC only 6043 7430 1.23 0.009 1465

TPAC1 6553 8821 1.35 0.011 1324

TBAC1 6057 7795 1.28 0.015 1256

THAC1 6247 8560 1.37 0.016 1404

TOAC1 6129 9005 1.47 0.019 1485

TdodecylACl 6176 7794 1.26 0.018 1372

TBABr 5909 7219 1.21 0.013 1150

THAI 5871 7638 1.30 0.011 1180

TMABr 6333 7805 1.23 0.011 1462

Read full chapter

Octylbenzyldimethylammonium MITI >80 [93]

Decylbenzyldimethylammonium Closed Bottle >60 [90]

Tetradecylbenzyldimethyl- MITI >80 [93]

Cocotrimethylammonium Closed Bottle >60 Akzo Nobel,

Octadecyltrimethylammonium Sturm >70 [92]