This is an open access article published under an ACS AuthorChoice License, which permits

copying and redistribution of the article or any adaptations for non-commercial purposes.

http://pubs.acs.org/journal/acsodf Article

Cotton Fabric-Supported Cationic Acrylate Polymer as an Efficient

and Recyclable Catalyst for Williamson Ether Synthesis Reaction in
Solid−Liquid−Liquid Phase Transfer Catalysis System
Hui Peng, Manjun Lei, Lihui Yang, Jie Sun, Lei Yang, and Qiangqiang Zhao*
Cite This: ACS Omega 2020, 5, 21468−21475 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Cotton-based catalytic fabric (CCF) was prepared by the simple

padding-drying method with the copolymer of five functional monomers as the
modifier and was applied in the solid−liquid−liquid phase-transfer catalysis
Downloaded via 49.36.232.126 on February 5, 2025 at 12:53:20 (UTC).

(SLL-PTC) system. Effects of the structure of the function monomer, the

content of the cation, and the loading amount on the catalytic activity of CCF
were investigated. The lipophilicity, disperse extent of cationic center, and the
accessory to the ion for CCF were influenced by the structure and content of
the function monomer. The organic phase was adsorbed on the surface of the
catalytic fabric, and the novel catalytic cycle in the PTC system was initiated.
The anion in the aqueous phase diffuses through the interfacial region to the
site for ion exchange. Bond-forming reaction was initiated in the interfacial
region between the organic phase on the fabric and the aqueous phase. The
conversion rate for Williamson ether synthesis reaction reached 92%, and CCF
could be reused five times in this SLL-PTC system.

1. INTRODUCTION The ammonium salt, phosphonium salt, macrocyclic polyether,

Phase transfer catalysis (PTC) is one of the most widely used or poly ethylene glycol was introduced by the reaction of
synthetic techniques because of the advantage of simple and hydroxyl in the surface.11 However, the size of the inorganic
easy reaction procedure, mild conditions, and inexpensive support was too small and the complicated separation
reagents and has been widely applied in the synthesis of dyes, processes, such as filtration and centrifugation, were required.
pigments, pharmaceuticals, perfumes, and polymers.1,2 Design Filtration and centrifugation of these immobilized catalyst
of the efficient and green PTC system has been one of the commonly required much more time and energy. Polymer of
topics in the PTC field. The introduction of the third phase to styrene, alkyl methacrylate, or vinyl pyridine was used as the
the common biphasic PTC system was considered as the organic support.12,13 The catalytic center was introduced by
efficient way to meet the requirement of the green chemistry, the grafting reaction or the copolymerization of functional
for example, third-liquid PTC (TL-PTC) with the catalyst- monomers. Microporous and macroporous polystyrene resins
philic liquid phase,3,4 solid(catalyst)−liquid−liquid PTC (SLL- crosslinked with divinylbenzene were the most popular
PTC) system with the immobilized catalyst phase,5 and the supports. However, the high specific surface area and the
introduction to the solid-ω-liquid PTC with the omega phase mass-transfer efficiency were hardly obtained at the same time.
(water).6 In these third-phase PTC systems, the reaction rate The catalytic activity would be reduced owning to the
and the reusability of the catalyst were increased.7 However, uncertain interfacial or the low mass transfer rate. Hence, an
the introduction of the third liquid phase into the PTC system urgent requirement is the development of the much practical
always induced that the emulsion between the liquid phases immobilized catalyst to overcome the disadvantage of higher
exited and the separation of the phase was more difficult than initial cost of preparation and lower catalytic activity in the
that in the biphasic PTC system, which limited the application SLL-PTC system.
in industry. The SLL-PTC system with the immobilized
catalyst can overcome these drawbacks and exhibits excellent
easy removal and subsequent reusability of the catalyst.8,9 The Received: April 29, 2020
SLL-PTC system has been one of the most promising Accepted: August 4, 2020
industrial system. Published: August 21, 2020
In the existing SLL-PTC system, the catalyst support can be
divided into two types: inorganic support and organic support.
Silica gel, alumina, and clay were used as inorganic supports.10

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsomega.0c01981

21468 ACS Omega 2020, 5, 21468−21475
ACS Omega http://pubs.acs.org/journal/acsodf Article

Fabric has been used as a support for the catalyst effect of the structure and the amount of the modifier on the
immobilization because of the cheap cost, being facile, and catalytic activity and the practicality and the reusability of the
high specific surface area, such as acrylic fabric and nylon catalytic fabric in Williamson ether synthesis reaction were
fabric.14,15 These immobilized catalysts with the fabric have investigated. The as-synthesized catalytic fabric with out-
exhibited excellent catalytic activity and reusability in the acid, standing recoverability exhibited excellent kinetics perform-
basic, and noble metal catalytic reaction systems.16−25 ance, which provided a new strategy for the immobilization of
However, there are few research studies on the immobilization the catalyst and the design of the new PTC system.
of the phase-transfer catalyst on the fabric.26−28 In the
preparation of the reported catalytic fabric, the pretreatment 2. EXPERIMENTAL SECTION
was required and the active group (NH2 or OH) was 2.1. Materials. All materials were purchased from
introduced on the surface of the fiber. However, the Sinopharm Chemical Reagent Co., Ltd. and used without
pretreatment induced the high cost and complex preparation further purification. Scoured and bleached cotton woven fabric
process. Cotton fabric is the most used textile owing to its (118.2 gm−2) was provided by Zhongheng Dayao Textile
numerous advantages such as good strength, easy processing, Technology Co., Ltd.
and relatively low cost. The hydroxyl group on the surface of 2.2. Synthesis of Quaternary Ammonium Monomers.
cotton fiber can provide the site for functional modification. In In a typical procedure, N-[3-(dimethyl amino)propyl]-2-
real production and processing, the cationization of the cotton methyl-acrylamide (DMAPMA) (0.24 mol), n-butyl bromide
fiber has been one of the useful ways to increase the (0.24 mol), hydroquinone (0.2 g), and acetone (120 mL) were
sustainability and green performance of the dyeing and added into a 250 mL round-bottom four-neck flask. The
finishing processes.29,30 The cationic center was introduced reaction solution was magnetic-stirred under a nitrogen
with the reaction of −OH and the modifier and had the similar atmosphere for 30 h at 60 °C. Then, the reaction mixture
structure to the phase transfer catalyst. In this paper, the cotton was cooled to 4 °C for 12 h. The precipitate was collected,
fabric was chosen as the supporter to prepare the catalytic washed with cold ethyl acetate, and dried under vacuum at 60
fabric. °C (86.23% yield).
Surface grafting and coating are the common ways to modify 2.3. Synthesis of the Polymers. In a typical procedure,
the fiber. However, the surface grafting amount is insufficient butyl methacrylate (10.88 g, 0.077 mol), butyl acrylate (6.54 g,
because the amount of the accessory reaction group on the 0.051 mol), styrene (2.34 g, 0.023 mol), the cationic monomer
surface of the fabric is limited, especially for the bulky modifier (0.026 mol), N-methylol acrylamide (2.08 g, 0.021 mol), and
molecule. Therefore, the simple and feasible coating method 2,2′-azobis(2-methylpropionitrile) (0.16 g, 1 mmol) were
was used. Similar to the porous polystyrene resins, the modifier dissolved in ethanol (76 mL); 20 mL of the solution was
consisted of the long-chain alkyl, cross-linking, quaternary added into the flask, and the rest was added into the constant-
ammonium, and solvent resistant groups (Scheme 1). The pressure dripping funnel. The reactor was degassed by purging
with nitrogen gas for 30 min. The polymerization was then
Scheme 1. Preparation Route Scheme for the Catalytic performed at 65 °C. The remaining solution gradually dropped
Cotton Fabric (1 h). The reaction solution was incubated for 8 h.
2.4. Preparation of the Catalytic Fabric. The catalytic
cotton fabric was prepared by the padding-drying method. The
solid content of the polymer solution was adjusted to 24% with
ethanol, and 0.2 g of phosphoric acid-ethanol solution (12 wt
%) was added. The cotton fabric was dipped into the polymer
solution and padded twice. The weight gain rate was regulated
to 70%. The fabric was cured at 170 °C for 1.5 h and then
washed with ethanol solution.
2.5. Williamson Ether Synthesis Reaction. Cresol
(0.0042 mol), NaOH (0.0048 mol), and deionized water (14
mL) were placed into a 50 mL round-bottom flask. The
solution of 4-nitrobenzyl bromide (0.0014 mol) and dipheny
(0.08 g) in 2,4-dimethyl-3-pentanone (14 mL) was added. The
catalytic fabric was cut in 4 mm widths × 4 mm length and
added into the flask. The reaction mixture was heated at 50 °C
under magnetic stirring (600 rpm). With the completion of the
reaction, the fabric was filtered and then washed twice with
ethanol and water. After dried at 50 °C, the catalytic fabric was
reused. The conversion of benzyl bromide derivates for
Williamson reaction was determined by high-performance
liquid chromatography (HPLC) analysis.31
Samples (about 50 μL) of the reaction mixture were
withdrawn at a regular time interval and put into a test tube.
Subsequently, 0.2 mL of 10% (v/v) HCl solution was added to
quench the reaction, and the solution was diluted to 10 mL
with 50% (v/v) aqueous acetonitrile solution. The composi-
tions of the sample were estimated with an internal standard
method and diphenyl was used as internal standard. HPLC
21469 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 1. SEM images of untreated cotton fabric and catalytic fabric. (a,d) untreated cotton fabric; (b,e) catalytic fabric; (c,f) catalytic fabric reused
five times; (g) FT-IR spectrum of cotton, polymer, and catalytic fabric.

analysis was operated with a mobile phase consisting of 40:60 vibration and the benzene skeleton vibration absorption,
(v/v) water/acetonitrile and a flow rate of 1.0 mL/min. respectively. It should be noted that all the characteristic
Detection wavelength was set at 260 nm, and the column absorption peaks for the modifier could be observed on the
temperature was 30 °C. spectrum of the catalytic fabric, which demonstrated that the
2.6. Adsorption Experiments. A quantity of 20 mL of modifier polymer was deposited on the fabric. Meanwhile, with
dye (C.I. acid red 6) solutions (5 g/L) was placed into a the catalytic fabric reused five times, no change in the structure
conical flask and heated to 30 °C; 0.2 g of the fabric was of the fiber and yarn on the catalytic fabric was observed
added. With the adsorption saturation, the dye concentrations (Figure 1c,f). The result shows that the catalytic fabric is
in the residual solutions were determined, and the equilibrium enough firm to be reused, which also is certified in the
adsorption capacity (Qe) could be calculated. following experiments.
2.7. Characterization. HPLC analysis was performed The reaction conversion rate curve against time for the
using a Zorbax Eclipse XDB-C18 column (150 mm × 0.46 catalytic fabric is shown in Figure 2. Conversion rate curves
mm, 0.5 μm) on an Agilent 1260 system. Contact angle (CA)
analysis was performed with an optical contact angle meter
(12907666, Kruss, Germany). SEM analysis was carried out
using a Phenom desktop scanning electron microscope.

3. RESULTS AND DISCUSSION

3.1. Preparation and Characterization of the Catalytic
Fabric. The properties of the acrylic copolymer depend mainly
on the monomers used and the possible modification. As
shown in Scheme 1, five functional monomers were used. The
long-chain alkyl methacrylate in the copolymer would endow
the high lipophilicity and the solvent resistance. Styrene could
increase solvent resistance. N-methylol acrylamide had been
used as the finishing agent for the cotton fabric and showed
high reactivity with OH in the surface of the cotton fiber.2
Butyl methacrylate would improve the rigidity of the chain
segment. NMR and DSC curves of the copolymers were Figure 2. Reaction conversion rate curve against time for catalytic
fabric curried at 130 °C.
characterized. NMR spectra of the products were in complete
agreement with the expected structures and showed essentially
no contaminants (Figure S1). DSC spectra showed the against reaction time for blank experiments are shown in
polymer could be crosslinked with itself with more than 130 Figure S3. The blank experiments were carried out with no
°C (Figure S2). catalyst, and unmodified cotton fabric was used. The
The SEM picture of the catalytic fabric is shown in Figure conversion rates were less than 3% after 10 h with the
1a−f. It can be seen that the membrane is formed on the unmodified cotton or without the catalyst. With the increase in
surface of the cotton fiber. The gap of the fibers in the yarn was the stirring speed, the conversion rate for 10 h has little change.
filled with the modifier. However, the gap between yarns Without the catalyst, the reactant molecules hardly collided
existed. Therefore, the specific surface area would be still high with each other because of the hindrance between the interface
enough, which was certified in the following kinetics between the aqueous phase and the organic phase. However,
experiments. The FT-IR spectrum of the catalytic fabric and the catalytic fabric can transfer the phenolic from the aqueous
the polymer are shown in Figure 1g. For the polymer modifier, phase into the organic phase, which induced the bond-forming
the absorption peaks 2954.9 and 2935.4 cm−1 are assigned to reaction. For the common phase-transfer catalyst, the lip-
the CH3 and CH2 group in the long-chain alkyl, and peaks at ophilicity and adsorption property are main aspects to
1741.1 and 1649.8 cm−1 are ascribed to the stretching ascertain the catalytic activity. The immobilized catalyst should
vibration of the CO. In addition, the peaks appearing at exhibit the amphiphilicity, and the reactants can be adsorbed at
1538.98 and 1455.9 cm−1 are attributed to N−H deformation the surface. Therefore, CA of the catalytic fabric with water
21470 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475
ACS Omega http://pubs.acs.org/journal/acsodf Article

was characterized. The acid dye was chosen as the adsorbate,

and the corresponding equilibrium adsorption capacity (Qe)
was compared. Moreover, the reaction conversion rate curve
could be fitted well with the first-order model (Figure 2). The
first-order reaction rate constant (kfor) was used to evaluating
the catalytic activity.
3.2. Effect of the Stirring Speed on the Catalytic
Activity. For exploring the influence of the mass transfer
resistance and the interfacial region, Williamson ether synthesis
reaction in the SLL-PTC system was carried out with various
stirring speed for the catalytic fabric curing at 130 °C.
According to the result in Figure 1, the modifier was not firm
and would shed into the reaction mixture on first use. The
solvent resistance for the modifier was not high enough
because the cross-link bond for the copolymer molecule was Figure 4. Effect of the long chain alkyl in the modifier on the catalytic
not completely formed. However, the effect of the stirring activity. Modifier polymer: 15% (mol %) M1, 20% (wt %) loading
speed on kfor on first use was same to that for the second use. amount.
The saturation value reached when the stirring speed was high
than 600 rpm (Figure 3). In the common PTC system, the modifier also can facilitate the dispersion of the cationic
monomer in the synthesis process. Therefore, more cation is
exposed and can enter into the aqueous phase. The increased
absorption property is observed. Moreover, the ion pair of the
cation and the adsorbed anion should be more close to the
substrate layer because of the hydrophobic force. The
adsorption property and the transfer efficiency of the reactant
anion are increased, thus inducing the higher catalytic activity.
The dissolubility of the modifier molecule in the organic phase
decreases with the increasing chain length. Therefore, the
highest fitness is observed for the catalytic fabric with
octadecyl.
3.4. Effect of the Cationic Monomer in the Modifier.
Catalytic fabrics with different cationic monomers were
prepared, and the catalytic activity is shown in Figure 5. It

Figure 3. Effect of the stirring speed on the reaction rate constant.

saturated value reached with higher than 200 rpm for the
extract mechanism while with higher than 600 rpm for the
interfacial mechanism. This is because the interfacial region
area can reach the maximum value with higher than 600 rpm,
and the mass transfer rate can reach the maximum value with
higher than 200 rpm. Therefore, with the catalytic fabric, the
reaction followed the interfacial mechanism and the formation
of the interfacial region is also the vital process for the catalytic
cycle. Interestingly, the shed of the modifier had no influence
on the generation of the interfacial region. This result
demonstrated that enough high interfacial region was also
generated with the catalytic fabric used. Meanwhile, it was Figure 5. Effect of the cationic monomer on the catalytic activity.
observed that the organic phase was adsorbed on the surface of Modifier polymer: 15% (mol %) cationic monomer, 20% (wt %)
the fabric with the addition of the catalytic fabric. Therefore, loading amount, and octadecyl as the long-chain alkyl.
the generation process of the interfacial region in this SLLPTC
system would be different from that of the common SLLPTC can be noticed that kfor and Qe for the dimethylbutyl cation
system. (M1) is higher than those of the dimethylbenzyl cation (M2)
3.3. Effect of the Structure for the Long-Chain Alkyl and diethylbenzyl cation (M3), while kfor and Qe for M2 are
in the Modifier. The effect of the long-chain alkyl in the same with those for M3. The structure of the cationic
copolymer on the catalytic activity was first investigated. As monomer has no influence on CA.
shown in Figure 4, kfor, Qe, and CA increase with the increasing For the quaternary ammonium phase transfer catalyst, the
chain length. Except with octadecyl, kfor for the second time is lipophilicity and accessibility of the catalyst are the main
lower than that for the first time. aspects influencing the catalytic activity. Similar CA also
As the chain length of the alkyl in the modifier increases, the indicates that the catalytic fabric has the same “apparent”
lipophilicity of the modifier broadens, and then, the surface lipophilicity. The cationic monomer is the only hydrophilic
energy of the catalytic fabric drops. The long-chain alkyl in the component in the modifier, and the mole content is 15%. The
21471 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475
ACS Omega http://pubs.acs.org/journal/acsodf Article

lipophilicity of the catalytic fabric is hardly influenced by the has no influence on the catalytic activity in the first time.
structure of the cation center. In other words, the lipophilicity Commonly with the dispersion of the catalyst in the reaction
of the catalytic fabric is mainly determined by the hydrophobic system, the mass transfer rate would increase and the catalytic
monomer. However, the accessibility to the anion is activity would increase. Namely, the interfacial region and the
determined by the structure of the cation monomer. The mass transfer rate are not varied with the dispersion and
content of the cationic monomer remains constant, and the insoluble of the polymer modifier. It is also found that the
density of the cation is same. The volume of the cation center catalytic fabric can adsorb the organic solvent on its surface in
for M1 is the smallest, and the cation is more visible than other the PTC system. The catalytic fabric is wetted by the organic
cations (M2 and M3). The amount of the adsorbed anion phase. In this SLL PTC system, the interfacial region is formed
increases, and the higher adsorption property and catalytic between the wetted fabric and the aqueous phase. The aqueous
activity are observed for the catalytic fabric with M1. Therefore, phase must diffuse through the organic phase to the site for ion
the lipophilicity and accessibility for the catalytic fabric can be exchange.
obtained by the adjustment of the structure of the cationic 3.6. Effect of the Loading Amount for the Modifier.
monomer and the lipophilic monomer, which is difficultly Enough high superficial area is the main aspect to accelerate
obtained for the common homogeneous phase transfer the mass transfer rate in the PTC system with the
catalyst. immobilization catalyst. With the fiber as the support, the
3.5. Effect of the Mole Percent of the Cationic specific surface area should be higher because of the relatively
Monomer in the Modifier. The effect of the cation content low fineness of fibril. However, the polymer modifier will form
in the modifier molecule on the catalytic performance is shown the membrane on the surface of the fabric; therefore, the
in Figure 6. It can be seen that kfor for the first time increased surface area is easily influenced by the loading amount. The
catalytic activity for the fabric with various loading amounts
were studied (Figure 7). It can be seen that kfor remains

Figure 6. Effect of the mole ratio for the cationic monomer on the
catalytic activity. Modifier polymer: M1 as the cationic monomer,
20% (wt %) loading amount, and octadecyl as the long-chain alkyl. Figure 7. Effect of the loading amount for the modifier on the
catalytic activity. Modifier polymer: 15% (mol %) M1, 20% (wt %)
loading amount, and octadecyl as the long-chain alkyl.
with the cationic monomer content varied from 6.67 to
26.67%, while kfor for the second time decreases intensively
with the cationic monomer content varied from 20 to 26.67%. constant with the loading amount varied from 5 to 20%, while
The corresponding CA of the catalytic fabric gradually Qe decreases dramatically. With the further increase in the
decreases, while Qe remains constant as the cation content loading amount to 30%, kfor decreases, while Qe remains
increases. constant.
The hydrophilicity of the modifier increases with the content For this SLL-PTC system, the catalytic fabric not only
of the cationic monomer; thus, the decreasing contact angle is provides the cationic center but also induces the generation of
observed. The adsorption of the anion on the surface of the the interfacial region. The area of the interfacial region is
catalytic fabric is induced by the electrostatic interaction influenced by both the lipophilicity and specific surface area of
between the cation and anion. Normally, the absorption the catalytic fabric. With 5% of the modifier loaded on the
property would increase with the increase in the amount of the fabric, only the thin member is formed on the surface of the
cation charge. The modifier molecule not only reacts with the fiber. The micro/nanostructures exist and much cations are
−OH in the surface of the cotton fabric but also with itself. exposed. The solid−liquid interfacial free energy is reduced,
The crosslink between the molecules causes the aggregation of and a higher contact angle is observed. However, the
the cation center. Therefore, the effective cation charge for the adsorption of the organic phase by the fabric is limited. The
adsorption process is limited. Therefore, the content of the catalytic center is fixed on the fabric, and the area of the
cationic monomer has no influence on the adsorption interfacial region is also limited. With the increase in the
property. According to the results from Qe, the catalytic fabric loading amount, the thickness of the membrane increases and
also has the same adsorption property to the phenolic anion the surface of the polymer becomes flatter. The micro−
and the catalytic activity remains constant. nanostructure disappears, and the amount of the exposed
Decreased kobs for the second catalysis demonstrates that the cationic center also decreases, leading to the decrease in CA
polymer is not firm enough and sheds from the surface of the and Qe. The adsorbed amount of the organic phase for the
catalytic fabric. However, the shed polymer in this PTC system catalytic fabric increases, and the interfacial region in the PTC
21472 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475
ACS Omega http://pubs.acs.org/journal/acsodf Article

system increases. As a result, the catalytic activity also has little nium bromide (TBAB) and triethyl benzyl ammonium
change. With further increase in the loading amount, the gap chloride (TEBAB) and anion-exchange resin (IRA-910 and
between fibers will be filled by the modifier and this fabric can 402) are listed in Table. It can be seen that TBAB exhibit the
be treated as the film. Both the area of the interfacial region highest catalytic activity, and the reaction rate constant is 1.3
and the amount of the active catalytic center decrease. Thus, times of that for the catalytic fabric, while the reaction rate
the catalytic activity decreases intensively. constant for TEAB is 1/10 of that for the catalytic fabric. The
3.7. Williamson Ether Synthesis Reaction in LSL PTC reaction rate constant for the catalytic fabric is three times of
System. Williamson ether synthesis reactions for other phonic that for IRA-910 and six times of that for IRA402. These
derivates and benzyl bromide derivatives were proceeded. The results demonstrate that the catalytic fabric exhibit an excellent
conversion rate and kfor are listed in Table 1. The conversion catalytic activity. For TBAB and TEBAB, the catalyst can easily
enter the organic phase and the aqueous phase. However, for
Table 1. Reaction Rate Constant and the Conversion Rate the support catalyst, the resistance for the mass transfer
Fort Williamson Ether Synthesis Reaction in the SLL-PTC increase intensively. IRA-910 and 402 are the copolymer of
System styrene and divinylbenzene and have a tetramethyl ammonium
cation and an ethyl trimethyl ammonium cation as functional
group, respectively. These ion-exchange resins had been used
as the catalyst for C-alkylation in the phase transfer catalyst
system and exhibited a relatively high catalytic activity.34,35 In
this PTC system, the reaction rate constant for the catalytic
fabric was three times of that for IRA-910 and six times of that
for IRA-402. For TBAB and TEBAB (common LLPTC
system), the catalyst can easily enter into the aqueous phase
and the organic phase. However, the catalytic center was fixed
on the surface of the support catalyst. Therefore, the resistance
for the mass transfer would be higher than that for TBAB.
With the catalytic fabric, the organic phase was adsorbed on
the catalytic fabric. The area of the interfacial region would be
higher than that for ion-exchange resin, and mass transfer
resistance also is lower than that for the ion-exchange resin.
Therefore, the catalytic fabric shows a higher catalytic activity
than the common ion-exchange resin.
3.8. Recyclability of the Catalytic Fabric. To evaluate
catalyst recyclability, the catalytic fabric was reused for five
consecutive cycles. Table 2 shows the conversion rate and

Table 2. Reaction Rate Constant and the Conversion Rate

with the Catalytic Fabric Reused

reaction rate constant obtained in each cycle. Only a 5% loss of

the reaction rate constant is observed, and the conversion rate
does not change. SEM of the catalytic fabric after reusing five
times was characterized (Figure 2). No significant change in
the surface is observed when compared to the unused catalytic
rates for all reactions are higher than 92%. With the increase in fabric. These results demonstrate that the catalytic fabric
the electron-donating ability of the group in the phonic exhibits good recycling performance. The cross-linking
derivates and electron-withdrawing property of the group in monomer in the modifier can react with −OH on the surface
the benzyl bromide derivates, the reaction rate constant of the cotton fabric. Moreover, the self-cross-linking of the
increased, which is the same with that in the common PTC modifier and long-chain alkyl can further enhance the solvent
system.32,33 These results demonstrate that the bond-forming resistance. The slight loss of catalyst activity was mainly caused
reaction in this PTC system is same to those in the by the detachment of the polymer modifier.
homogenous system and the common PTC system. 3.9. Reaction Mechanism of the SLL-PTC System.
The catalytic activity for the catalytic fabric was also According to the abovementioned research, it can be
compared with the commercial homogenous catalyst and ion- concluded that the catalytic fabric not only provides the
exchange resin. Reaction rate constants for tetrabutylammo- support for the catalytic center but also induces the generation
21473 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475
ACS Omega http://pubs.acs.org/journal/acsodf Article

of the interfacial region. The whole catalytic cycle in this SLL- the disperse extent of the cationic center. The organic phase
PTC system contains three steps, namely, adsorption, transfer, was adsorbed on the surface of the catalytic fabric. Interfacial
and regeneration (Figure 8). region area was influenced by the amount of the organic phase
adsorbed and specific surface areas of the fabric. For the
Williamson reaction, the conversion rate can reach to 92% in
this SLL-PTC system, and the catalytic fabric can be reused
five times with no loss in the catalytic activity.

■ ASSOCIATED CONTENT
* Supporting Information
sı

The Supporting Information is available free of charge at

https://pubs.acs.org/doi/10.1021/acsomega.0c01981.
NMR and DSC curves for the copolymer (PDF)

■ AUTHOR INFORMATION
Corresponding Author
Qiangqiang Zhao − Key Laboratory of Science & Technology of
Eco-Textile, Ministry of Education, College of Chemistry,
Chemical Engineering and Biotechnology and National
Engineering Research Center for Dyeing and Finishing of
Textiles, College of Chemistry, Chemical Engineering and
Biotechnology, Donghua University, Shanghai 201620, China;
Engineering Research Center for Eco-Dyeing and Finishing of
Textiles, College of Textile Science and Engineering
Figure 8. Mechanism of Williamson ether synthesis reaction in the (International Institute of Silk), Zhejiang Sci-Tech University,
SLL-PTC system with the catalytic cotton fabric.
Hangzhou 310018, Zhejiang, China; orcid.org/0000-0001-
9192-2921; Email: [email protected]
(1) Because of the lipophilicity of the catalytic fabric, the
organic phase is adsorbed on the surface of the fabric. Authors
The interfacial region was generated between the Hui Peng − Engineering Research Center for Eco-Dyeing and
organic phase and the aqueous phase. The cation center Finishing of Textiles, College of Textile Science and Engineering
is prone to enter the aqueous phase because of the (International Institute of Silk), Zhejiang Sci-Tech University,
hydrophilicity. With the electronic interaction, the ion Hangzhou 310018, Zhejiang, China
pairs of the cation and the ion are quickly generated in Manjun Lei − Engineering Research Center for Eco-Dyeing and
the interfacial region near the aqueous phase. Finishing of Textiles, College of Textile Science and Engineering
(2) After the generation of the ion pair, the catalytic center (International Institute of Silk), Zhejiang Sci-Tech University,
is more lipophilic than the ion pair with Br−. In this case, Hangzhou 310018, Zhejiang, China
the ion pair can quickly return into the center of the Lihui Yang − Engineering Research Center for Eco-Dyeing and
interfacial region. Benzyl bromide also can diffuse into Finishing of Textiles, College of Textile Science and Engineering
the interfacial region. (International Institute of Silk), Zhejiang Sci-Tech University,
(3) The bond-forming reaction is initiated in the interfacial Hangzhou 310018, Zhejiang, China
region and follows a SN2 bimolecular nucleophilic Jie Sun − Engineering Research Center for Eco-Dyeing and
substitution mechanism. The phenolic ion acts as the Finishing of Textiles, College of Textile Science and Engineering
nucleophile to attack the electrophilic carbon. Br− is the (International Institute of Silk), Zhejiang Sci-Tech University,
leaving group and will quickly interact with the catalytic Hangzhou 310018, Zhejiang, China
center. The product diffuses into the organic phase. The Lei Yang − Engineering Research Center for Eco-Dyeing and
catalytic center is regenerated and can enter into the Finishing of Textiles, College of Textile Science and Engineering
aqueous phase to catalyze the next cycle. (International Institute of Silk), Zhejiang Sci-Tech University,
Hangzhou 310018, Zhejiang, China; orcid.org/0000-0002-
0331-8909
4. CONCLUSIONS
Complete contact information is available at:
In conclusion, the cotton-based catalytic fabric immobilized https://pubs.acs.org/10.1021/acsomega.0c01981
with the phase transfer catalyst was successfully prepared by
the padding-dry method with the copolymer containing the Author Contributions
quaternary ammonium cation, long-chain alkyl, and cross-
The manuscript was written through contributions of all
linking group as the modifier. The long-chain alkyl not only
authors. All authors have given approval to the final version of
endowed solvent resistance but also acted as the spacer chain.
the manuscript.
However, the crosslink of the modifier molecule induced the
aggregation of the cation center. The absorption property to Notes
the ion was determined by the accessibility of the cation and The authors declare no competing financial interest.
21474 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475
ACS Omega

■
http://pubs.acs.org/journal/acsodf Article

ACKNOWLEDGMENTS (19) Shi, X.-L.; Hu, Q.; Wang, F.; Zhang, W.; Duan, P. Application
of the polyacrylonitrile fiber as a novel support for polymer-supported
This work was financially supported by the Fundamental copper catalysts in terminal alkyne homocoupling reactions. J. Catal.
Research Funds for the Central Universities (2232020G-04), 2016, 337, 233−239.
National Natural Science Foundation of China (21606206), (20) Shi, X.-L.; Sun, B.; Hu, Q.; Chen, Y.; Duan, P. Fiber-supported
the Public Welfare Technology Application Research Project Fe(III) complex catalyst in spinning basket reactor for cleaner ring-
of Zhejiang Province China (2017C31033, 2017C31089 and opening of epoxides with alcohols. Green Chem. 2019, 21, 3573−
LGG18B060001), and the Initial Research Funds for Young 3582.
Teachers of Donghua University. (21) Xu, G.; Wang, L.; Li, M.; Tao, M.; Zhang, W. Phosphorous acid

■
functionalized polyacrylonitrile fibers with a polarity tunable surface
REFERENCES micro-environment for one-pot C-C and C-N bond formation
reactions. Green Chem. 2017, 19, 5818−5830.
(1) Mąkosza, M.; Fedoryński, M. Phase Transfer Catalysis. Catal. (22) Shi, X.-L.; Chen, Y.; Duan, P.; Zhang, W.; Hu, Q. Conversion
Rev.: Sci. Eng. 2003, 45, 321−367. of CO2 into Organic Carbonates over a Fiber-Supported Ionic Liquid
(2) Wei, L.; Hou, Z. High performance polymer binders inspired by Catalyst in Impellers of the Agitation System. ACS Sustainable Chem.
chemical finishing of textiles for silicon anodes in lithium ion batteries. Eng. 2018, 6, 7119−7127.
J. Mater. Chem. A 2017, 5, 22156−22162. (23) Xiao, L.; Huang, Y.; Luo, Y.; Yang, B.; Liu, Y.; Zhou, X.; Zhang,
(3) Santiago, C. C.; Lafuente, L.; Bravo, R.; Díaz, G.; Ponzinibbio, A. J. Organic Cotton Photocatalysis. ACS Sustainable Chem. Eng. 2018, 6,
Ionic liquids as phase transfer catalysts: Enhancing the biphasic 14759−14766.
extractive epoxidation reaction for the selective synthesis of β-O- (24) Wu, X.; Xiang, Z.; Song, T.; Qi, H. Wet-strength agent
glycosides. Tetrahedron Lett. 2017, 58, 3739−3742. improves recyclability of dip-catalyst fabricated from gold nano-
(4) Katole, D. O.; Yadav, G. D. Process intensification and waste particle-embedded bacterial cellulose and plant fibers. Cellulose 2019,
minimization using liquid-liquid-liquid tri-phase transfer catalysis for 26, 3375−3386.
the synthesis of 2-((benzyloxy)methyl)furan. Mol. Catal. 2019, 466, (25) Kempasiddaiah, M.; Kandathil, V.; Dateer, R. B.; Sasidhar, B.
112−121. S.; Patil, S. A.; Patil, S. A. Immobilizing biogenically synthesized
(5) Jwo, J.-J. Phase Transfer Catalysis: Fundamentals and Selected palladium nanoparticles on cellulose support as a green and
Systems. Catal. Rev.: Sci. Eng. 2003, 45, 397−461. sustainable dip catalyst for cross-coupling reaction. Cellulose 2020,
(6) Yadav, G. D. Insight into Green Phase Transfer Catalysis. Top. 27, 3335−3357.
Catal. 2004, 29, 145−161. (26) Wang, L.; Xu, G.; Xiao, J.; Tao, M.; Zhang, W. Quaternary
(7) Tomoi, M. Triphase catalysis. In Handbook of Phase Transfer Ammonium-Based Functionalized Polyacrylonitrile Fibers with Polar-
Catalysis; Sasson, Y., Neumann, R., Eds.; Springer Netherlands: ity Tunable Inner Surface Microenvironment for C-C Bond Forming
Dordrecht, 1997; pp 424−461. Reactions under Continuous Flow Conditions. Ind. Eng. Chem. Res.
(8) Cozzi, F. Immobilization of Organic Catalysts: When, Why, and 2019, 58, 12401−12410.
How. Adv. Synth. Catal. 2006, 348, 1367−1390. (27) Du, J.; Xu, G.; Lin, H.; Wang, G.; Tao, M.; Zhang, W. Highly
(9) Starks, C. M.; Liotta, C. L.; Halpern, M. E. Insoluble Phase- efficient reduction of carbonyls, azides, and benzyl halides by NaBH4
Transfer Catalysts. In Phase-Transfer Catalysis: Fundamentals, in water catalyzed by PANF-immobilized quaternary ammonium salts.
Applications, and Industrial Perspectives; Springer Netherlands: Green Chem. 2016, 18, 2726−2735.
Dordrecht, 1994; pp 207−265. (28) Shi, X.-L.; Chen, Y.; Hu, Q.; Meng, H.; Duan, P. Fiber-
(10) Feng, D.; Xu, J.; Wan, J.; Xie, B.; Ma, X. Facile one-pot Supported Poly(quaternaryammonium Bromide)s as Supported-
fabrication of a silica gel-supported chiral phase-transfer catalyst-N-(2- Phase Transfer Catalysts in the Spinning Basket Reactor. Ind. Eng.
cyanobenzyl)-O(9)-allyl-cinchonidinium salt. Catal. Sci. Technol. Chem. Res. 2018, 57, 7450−7457.
2015, 5, 2141−2148. (29) Niu, T.; Wang, X.; Wu, C.; Sun, D.; Zhang, X.; Chen, Z.; Fang,
(11) Montanari, F.; Tundo, P. Polymer-supported phase-transfer L. Chemical Modification of Cotton Fabrics by a Bifunctional
catalysts. Crown ethers and cryptands bonded by a long alkyl chain to Cationic Polymer for Salt-Free Reactive Dyeing. ACS Omega 2020, 5,
a polystyrene matrix. J. Org. Chem. 1981, 46, 2125−2130. 15409−15416.
(12) Miguélez, J.; Miyamura, H.; Kobayashi, S. A Polystyrene- (30) Montazer, M.; Malek, R. M. A.; Rahimi, A. Salt free reactive
Supported Phase-Transfer Catalyst for Asymmetric Michael Addition dyeing of cationized cotton. Fibers Polym. 2007, 8, 608−612.
of Glycine-Derived Imines to α,β-Unsaturated Ketones. Adv. Synth. (31) Zhao, Q.; Zhao, X.; Peng, H.; Liu, Y.; Yang, L.; Sun, J.; Yang,
Catal. 2017, 359, 2897−2900. L.; Shen, Y. Static phase transfer catalysis for Williamson reactions:
(13) Wang, M.-L.; Lee, Z.-F.; Wang, F.-S. Phase-Transfer-Catalyzed Pickering interfacial catalysis. Catal. Sci. Technol. 2019, 9, 3445−3453.
Etherification of 4,4′-Bis(chloromethyl)-1,1′-biphenyl with 1-Butanol (32) Yadav, G. D.; Bisht, P. M. Synergism of low energy microwave
by Polymer-Supported Catalysis. Ind. Eng. Chem. Res. 2005, 44, irradiation and solid-liquid phase transfer catalysis for selective
5417−5426. alkylation of phenols to phenolic ethers. Synth. Commun. 2004, 34,
(14) Reichelt, E.; Heddrich, M. P.; Jahn, M.; Michaelis, A. Fiber 2885−2892.
based structured materials for catalytic applications. Appl. Catal., A (33) Simion, A. M.; Hashimoto, I.; Mitoma, Y.; Egashira, N.; Simion,
2014, 476, 78−90. C. O-Acylation of Substituted Phenols with Various Alkanoyl
(15) Lee, J.-W.; Mayer-Gall, T.; Opwis, K.; Song, C. E.; Gutmann, J. Chlorides under Phase-Transfer Catalyst Conditions. Synth. Commun.
S.; List, B. Organotextile Catalysis. Science 2013, 341, 1225. 2012, 42, 921−931.
(16) Shi, X.-L.; Chen, Y.; Hu, Q.; Zhang, W.; Luo, C.; Duan, P. A (34) Varona, F.; Mijangos, F.; Lombraña, J. I.; Díaz, M. Anionic Ion
potential industrialized fiber-supported copper catalyst for one-pot Exchangers As Phase Transfer Catalysts In Alkylation Reactions. In
multicomponent CuAAC reactions in water. J. Ind. Eng. Chem. 2017, Progress in Ion Exchange: Advances and Applications; Dyer, A., Hudson,
53, 134−142. M. J., Williams, P. A., Eds.; Woodhead Publishing, 1997; pp 87−95.
(17) Shi, X.-L.; Xing, X.; Lin, H.; Zhang, W. Synthesis of (35) Gelbard, G. Organic Synthesis by Catalysis with Ion-Exchange
Polyacrylonitrile Fiber-Supported Poly(ammonium Resins. Ind. Eng. Chem. Res. 2005, 44, 8468−8498.
methanesulfonate)s as Active and Recyclable Heterogeneous
Brønsted Acid Catalysts. Adv. Synth. Catal. 2014, 356, 2349−2354.
(18) Shi, X.-L.; Zhang, M.; Li, Y.; Zhang, W. Polypropylene fiber
supported ionic liquids for the conversion of fructose to 5-
hydroxymethylfurfural under mild conditions. Green Chem. 2013,
15, 3438−3445.

21475 https://dx.doi.org/10.1021/acsomega.0c01981
ACS Omega 2020, 5, 21468−21475