Preparation of novel side-chain fluoroalkyl polyether oligomers with terminal acrylate for emulsion copolymerization and application on cotton fabric finishing

Article abstract of DOI:10.1007/s11696-019-00810-0

Three novel side-chain fluoroalkyl polyether oligomers with different molecular weight were synthesized base on the ring-opening polymerization of 3-perfluoro-n-butyl-1,2-epoxypropane, followed by terminal esterification using acryloyl chloride. The oligomer intermediates were used as functional monomers for emulsion copolymerization with methyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate. The produced latexes were used for hydrophobic and oil-phobic finishing on cotton fabric surface and the treated cotton fabrics were tested by scanning electron microscopy and energy-dispersive spectroscopy, combined with chemical composition analysis by X-ray photoelectron spectroscopy. The result showed that fluorinated copolymers were successfully coated on the cotton fibers’ surface. Water contact angles was used to evaluate the wettability and the results showed that treated cotton fabrics possessed good hydrophobicity with the contact angle of 139.1 ± 1°, and the heat resistance of treated cotton fabrics was identified improved through the thermogravimetric analyses (TGA).

Full text of DOI:10.1007/s11696-019-00810-0

Chemical Papers
https://doi.org/10.1007/s11696-019-00810-0
ORIGINAL PAPER
Preparation of novel side‑chain ꢀuoroalkyl polyether oligomers
with terminal acrylate for emulsion copolymerization and application
on cotton fabric ꢁnishing
1
1
1
1,2
Yakun Zong · Lei Wang · Yi Sun · Zhanxiong Li
Received: 1 March 2019 / Accepted: 2 May 2019
©
Institute of Chemistry, Slovak Academy of Sciences 2019
Abstract
Three novel side-chain fuoroalkyl polyether oligomers with diꢀerent molecular weight were synthesized base on the ring-
opening polymerization oꢁ 3-perfuoro-n-butyl-1,2-epoxypropane, ꢁollowed by terminal esteriꢂcation using acryloyl chloride.
The oligomer intermediates were used as ꢁunctional monomers ꢁor emulsion copolymerization with methyl methacrylate,
butyl acrylate, and hydroxyethyl methacrylate. The produced latexes were used ꢁor hydrophobic and oil-phobic ꢂnishing
on cotton ꢁabric surꢁace and the treated cotton ꢁabrics were tested by scanning electron microscopy and energy-dispersive
spectroscopy, combined with chemical composition analysis by X-ray photoelectron spectroscopy. The result showed that
fuorinated copolymers were successꢁully coated on the cotton ꢂbers’ surꢁace. Water contact angles was used to evaluate
the wettability and the results showed that treated cotton ꢁabrics possessed good hydrophobicity with the contact angle oꢁ
1
39.1± 1°, and the heat resistance oꢁ treated cotton ꢁabrics was identiꢂed improved through the thermogravimetric analyses
(
TGA).
Keywords Fluoroalkyl polyether · Emulsion polymerization · Cotton ꢂber · Oligomer · Hydrophobicity
Introduction
can be categorized as hydrophilic, hydrophobic or superhy-
drophobic according to the interaction between water drops
and a solid surꢁace. The wettability oꢁ the solid surꢁace is
characterized by water contact angle measurements gener-
ally and a hydrophilic surꢁace shows strong aꢃnity toward
water, while a hydrophobic surꢁace strongly repels water.
The surꢁace is known to be hydrophobic when the water
contact angle is greater than 90° and superhydrophobic when
the water contact angle is larger than 150° (Periolatto and
Ferrero 2014; Drelich et al. 2011).
As one oꢁ the most widely used consumer products, cotton
ꢁ
abric has many attractive characteristics, such as soꢁtness,
widespread applicability and easy obtainability. However,
the application oꢁ cotton ꢁabric is limited in some ꢂelds due
to the high concentration oꢁ hydroxyl groups on the cotton
surꢁace, which makes the ꢁabrics easily stained by liquids
(
Miao et al. 2010; Periolatto et al. 2013; An et al. 2011).
Thereꢁore, as one oꢁ the most desirable textile properties,
the hydrophobic capacity oꢁ cotton ꢂber aꢁter modiꢂcation
has become one oꢁ the most important domains in current
search (Xu et al. 2014; Ferrero et al. 2012; Mohsin et al.
Conventionally, hydrophobic surꢁaces can be ꢁabricated via
physical and/or chemical methods (Latthe et al. 2014; Yan
et al. 2011; Bhushan et al. 2009; Laꢁuma and Quere 2003) and
many derived methods have been proposed, such as chemical
coating (Kim et al. 2013; Xu et al. 2012; Yang et al. 2014; Yan
et al. 2013) plasma and chemical etching (Cengiz and Erbil
2014; Cabrales and Abidi 2012; Abidi and Hequet 2005; Ruan
et al. 2013; Wang et al. 2013), vapor deposition (Liao et al.
2013; Ferrero and Periolatto 2013). As we know, the surꢁace
*
Zhanxiong Li
lizhanxiong@suda.edu.cn
2
014; Lau et al. 2003; Aminayi and Abidi 2013) and so on.
1
College oꢁ Textile and Clothing Engineering, Soochow
University, No. 199 Renai Road, Industry Park,
Suzhou 215021, China
Surꢁace chemical coating has become a simple and eꢀective
technique to manuꢁacture hydrophobic surꢁaces among all oꢁ
these methods. Owing to the popularity oꢁ chemical coating,
there are a large amount oꢁ waterprooꢁ ꢂnishing agents have
2
National Engineering Laboratory ꢁor Modern Silk,
Suzhou 215123, China
Vol.:(0
1
123456789)
3

Chemical Papers
been prepared and applied. Among the ꢂnishing agents, fuo-
ropolymers are superior agents and have been widely used
in hydrophobic coatings because oꢁ their excellent environ-
mental stability, water and oil repellency and low coeꢃcient
oꢁ ꢁriction. Incorporation oꢁ fuorine into the polymer main
chain or side chain leads to large changes in the surꢁace prop-
erties as the fuorinated polymer chains segregate toward the
polymer–air interꢁace, resulting in considerable decrease in the
surꢁace energy (Aminayi and Abidi 2015; Cheng et al. 2013;
Berret et al. 2003; Sauer et al. 1998; Bongiovanni et al. 2000).
Thereꢁore, many researchers have reported the synthesis oꢁ
fuorinated polymers via emulsion polymerization. Generally,
the copolymers with longer perfuoroalkyl chains would have
lower surꢁace energies (Kim et al. 2002; Kaplánek et al. 2005);
however, they have been ꢁound to cause a series oꢁ problems,
such as bioaccumulation, ꢁeeble biodegradability, and environ-
mental unꢁriendliness. Thereꢁore, it is urgent and signiꢂcant
to develop environmentally ꢁriendly materials to replace the
currently used long-chain fuorinated substances.
75 °C. Subsequently, a 35% aqueous solution oꢁ Na S O
5
2
2
(17.10 mL) was added and then the mixture was cooled
down to 65 °C. 0.50 g (0.30 mmol) AIBN dissolved in
8.70 g (0.15 mol) allyl alcohol was added dropwise with
stirring at 80 °C and thus controlling the slightly exother-
mic reaction ꢁor 4 h. Aꢁter cooling to room temperature,
50.0 mL H O was added into the mixture and then worked
2
up. The solid products were isolated by ꢂltration and washed
with water. Then the liquid was extracted with Et O several
2
times and dried using magnesium sulꢁate (MgSO ). Subse-
4
quently, the solvent was removed by rotary evaporation to
obtain a colorless and transparent oily liquid with 95.0%
−
1
−1
yield. FT-IR (KBr): ν 3386 cm , ν 1135–1352 cm ,
OH
CF
−
1 1
ν
1036 cm . H NMR (400 MHz, CDCl ): δ 2.90 (m,
C–O
3
2H, CH CHI); 4.43 (tt, 1H, CHI); 3.81 (d, 2H, CH O); 2.42
2
2
(s br, 1H, OH). 19F NMR (376 MHz, CDCl ): δ −81.7 (m,
3
3F, CF ); −114.3 (q, 2F, CF ), −125.1 (m, 2F, CF ), −126.6
3
2
2
(m, 2F, CF ).
2
Herein, three novel short-chain fuoroalkyl polyether oli-
gomers were synthesized and then esteriꢂed with acryloyl
chloride. The oligomer acrylates can be used as ꢁunctional
monomers ꢁor emulsion copolymerization to give hydropho-
bic and oil-phobic ꢂnishing agent.
Synthesis of 3‑perꢀuoro‑n‑butyl‑1,2‑epoxypropane (FBE)
4
1.00 g (0.10 mol) oꢁ compound FBIP was taken in a glass-
ware and heated, while stirring, to 85 °C. Aꢁterward, aque-
ous NaOH (20%, 30.00 g) was introduced into the dropping
ꢁ
unnel. The reaction mixture was stirred ꢁor 5 h at 85 °C.
Experimental
Aꢁter cooling, the mixture was ꢂltered and the organic phase
was extracted with Et O and washed with H O several times.
2
2
General
Aꢁter drying with MgSO , the epoxide (a colorless oily liq-
4
uid) was obtained aꢁter evaporating under reduce pressure
All syntheses were carried out under a nitrogen atmosphere
in three-neck fask glassware equipped with a Tefon mag-
neton, thermometer, constant pressure separatory ꢁunnel and
refux condenser. Perfuorohexyl iodide, 1,3-difuoromethyl
benzene (99%) and TEA (triethylamine) were commercial-
grade reagents supplied by J&K Chemical Ltd. Methanol,
allyl alcohol, acryloyl chloride, AIBN (azobisisobutyroni-
trile), SDS (surꢁactant sodium lauryl sulꢁate) and AEO-9
−
1
with a yield oꢁ 71%. FT-IR (KBr): ν 2938.6–3066.5 cm ,
CH
−
1
−1 1
ν
1422.5 cm , ν
1023.7–1134.7 cm . H NMR
C–O–C
C–F
(
400 MHz, CDCl ): δ 2.24, 2.39 (2×dm, 2H, CH CF ); 2.60
3 2 2
(
dd, lH (a), CH ); 2.90 (t, 1H (b), CH ); 3.23 (dq, lH, CH).
2 2
1
9
F NMR (376 MHz, CDCl ): δ −81.7 (m, 3F, CF ); −114.3
3
3
(
q, 2F, CF ), −125.1 (m, 2F, CF ), −126.6 (m, 2F, CF ).
2 2 2
(
ꢁatty alcohol-polyoxyethylene ether) were purchased ꢁrom
Synthesis of poly (3‑perꢀuoro‑n‑butyl‑1,2‑epoxypropane)
oligomers (PFBE, n= 1, 5, 10)
Shanghai Aladdin Bio-Chem Technology Co. and used with-
out ꢁurther puriꢂcation. BF ·Et O and ammonium persulꢁate
3
2
were obtained ꢁrom TCI (Shanghai) Development Co., Ltd.
All other reagents employed were common laboratory mate-
rials which were collected ꢁrom the materials supply center
oꢁ Soochow University (supplied by Qiangsheng (Jiangsu)
Functional Chemicals Co., Ltd.). The reaction route is
expressed in Scheme 1.
1.60 g (0.05 mol) oꢁ methanol and 0.20 mL BF ·Et O were
3
2
added into a glassware and the mixture was stirred ꢁor
30 min at room temperature. The compound FBE (2.76 g,
0.01 mol) was added slowly. The mixture was heated to
90 °C and stirred ꢁor 10 h, then the unreacted methanol and
BF ·Et O were removed by rotary evaporation to obtain
3
2
the pure product oꢁ PFBE (n = 1) (a colorless oily liquid)
−
1
Synthesis and characterization
with a yield oꢁ 90%. FT-IR (KBr): ν 3475.9 cm , ν
OH CH
−
1
−1 1
2
931.2 cm , ν
1175.4 cm . H NMR (400 MHz,
C–O–C
Synthesis of 3‑perꢀuoro‑n‑butyl‑2‑iodo‑l‑propanol (FBIP)
CDCl ): δ 2.10–2.33 (m, 2H, CH CF ); 2.93 (s, 1H, OH);
3 2 2
1
9
4
.05–4.23 (m, 1H, CHO), 3.33–3.82 (dd, 4H, 2×CH O). F
2
3
4.59 g (0.10 mmol) perfuoro-n-butyl iodide was added
NMR (376 MHz, CDCl ): δ −81.7 (m, 3F, CF ); −114.3 (q,
3 3
into a glassware at room temperature and heated to
2F, CF ), −125.1 (m, 2F, CF ), −126.6 (m, 2F, CF ).
2
2
2
1
3

Chemical Papers
Scheme 1 Synthetic route oꢁ the fuorinated polyether acrylate oligomer and its emulsion copolymerization
According to the same procedure, changing the ꢁeed ratio
oꢁ monomer to end-blocking agent ꢁrom 1:1 to 5:1 and 10:1
magnesium sulꢁate anhydrous and the solvent removed by
rotary evaporation to obtain an orange-yellow liquid in 77%
−
1
−1
(
mol/mol), products PFBE (n = 5, 10) were obtained with
yield. FT-IR (KBr): ν 2890.2 cm , ν
1734.1 cm ,
CH
–COO–
−1 1
yields oꢁ 92.9% and 91.6%, respectively. It was expected
to control the polymerization and obtain the end-blocking
fuoropolyether oligomer with diꢀerent molecular weight by
changing the ꢁeed ratio.
ν
1632.9 cm . H NMR (400 MHz, CDCl ): δ 2.10–2.33
C=C 3
(m, 2H, CH CF ); 3.33–3.75 (m, 4H, 2×CH O); 3.8–4.32
2
2
2
(m, 1H, CHO); 6.09–6.41 (m, 2H, –CH=CH ); 6.67 (d, 1H,
2
1
9
–CH=CH ). F NMR (376 MHz, CDCl ): δ −81.7 (m, 3F,
2
3
CF ); − 114.3 (q, 2F, CF ), − 125.1 (m, 2F, CF ), −126.6
3
2
2
Synthesis of poly
(m, 2F, CF ).
2
(3‑perꢀuoro‑n‑buty‑1,2‑epoxypropane)‑acrylate (PFBEA,
n= 1, 5, 10)
Preparation of the ꢀuorinated polyether acrylate
copolymer (FPAC) and its application to cotton ꢁber
ꢁnishing
2
3
.80 g (9.00 mmol) oligomer PFBE (n = 1), 30.0 mL 1,
-difuoromethyl benzene and 1.80 g (18.00 mmol) TBAB
dissolved in 15.0 mL H O were added into a glassware at
The produced PFBEA (n = 1, 5, 10) was used as a ꢁunc-
tional monomer ꢁor emulsion copolymerization with methyl
methacrylate (MMA), butyl acrylate (BA), and hydroxyethyl
methacrylate (HEMA). The speciꢂc recipes are shown in
Table 1. The amounts oꢁ SDS and AEO-9 were, respectively,
1.5% oꢁ the total mass oꢁ the monomers. All monomers and
emulsiꢂers were pre-emulsiꢂed ꢁor 15 min at 8000 r/min,
then transꢁerred to a three-necked fask, heated to 75 °C
2
room temperature, then the solution was cooled down to
−
5 °C and stirred ꢁor 0.5 h. A THF (20.0 mL) solution oꢁ
acryloyl chloride (1.20 g, 13.50 mmol) was dropped into
the reaction solution slowly; aꢁterward, the temperature oꢁ
the solution was restored to room temperature and reacted
ꢁ
or 6 h. Subsequently, the reactants were washed with dis-
tilled water and the organic layer was separated, dried over
1
3

Chemical Papers
under N gas protection, and the corresponding amount oꢁ
Gel permeation chromatography (GPA, TDA-302, Ameri-
can Viscotek Company) was used ꢁor measuring the molecu-
lar weight and polydispersity index. The concentration oꢁ the
test specimens was 5 mg/mL and THF was used as the eluent
with a fow rate oꢁ 1.0 mL/min at room temperature. Particle
size and zeta potential were measured by Mastersizer 2000
(Mastersizer, England).
2
ammonium persulꢁate in the table was dissolved in 20.0 mL
oꢁ deionized water. The pre-emulsion was added dropwise,
and the reaction was continued ꢁor 3 h. Aꢁter completion, the
gel was removed by ꢂltration to obtain a side-chain fuoro-
alkyl polyether acrylate copolymer emulsion.
The obtained fuorocopolymer emulsions with diꢀerent
fuorine contents were diluted in deionized water to ꢁorm
Thermogravimetric analysis (TGA) was carried out ꢁrom
room temperature to 600° with heating at a rate oꢁ 10°/min
using a Perkin Elmer Diamond 5700 thermogravimetric ana-
lyzer (Elmer Platinum, USA) under nitrogen atmosphere.
The nitrogen fow rate was 20 mL/min and the test sam-
ples were 0.8 g oꢁ crumb-like ꢁabrics placed in a ceramic
crucible.
5
0 g/L ꢂnishing agent. The desized and bleached cotton
ꢁ
abrics were immersed in the ꢂnishing agent ꢁor 15 min and
padded through two dips and two nips with pickup 80%.
Aꢁterward, the cotton ꢁabrics were dried at 90 °C ꢁor 10 min
and cured at 150 °C ꢁor 5 min.
Characterization
The surꢁace morphologies oꢁ the cotton ꢂbers were inves-
tigated using a scanning electron microscope (SEM, S-4800,
Japan Hitachi Company) equipped with an energy-dispersive
spectroscopy (EDS) detector and the test specimens were
gold-spray ꢁabrics with a length and a width oꢁ 0.5 cm, ꢂxed
on the electron microscope stage by a conductive adhesive.
X-ray photoelectron spectroscopy (XPS) measurement
was carried out using a Kratos Axis Ultra HAS photoelec-
tron spectrometer (Shimadzu, Japan). The samples were
dried ꢁabrics with a length and width oꢁ 0.5 cm and kept
ꢁor 2 h in a vacuum oven to remove all volatile substances
beꢁore the XPS analysis.
Fourier transꢁorm inꢁrared spectroscopic (FT-IR) characteri-
zation was carried out using a Nicolet 5700 spectrometer
(
Thermo Electron, America). The intermediate and mono-
mer specimens were tested by the liquid membrane method:
tableting with potassium bromide on the premise that the
samples were dry and anhydrous. A certain amount oꢁ poly-
mer emulsion was evenly spread in a glass dish and dried at
1
10 °C to ꢁorm a ꢂlm, which was then washed with deion-
ized water and dried at room temperature to obtain a poly-
1
mer emulsion test sample. H NMR spectra were recorded
with a Unity INOVA-400 MHz NMR spectrometer (Var-
Contact angle (CA) measurements were evaluated
at room temperature and ambient humidity on the Krüss
DSA100 instrument (Dataphysics, Germany). The volume
oꢁ each water droplet was 3 μL, and the value was the aver-
age oꢁ ꢂve separate measurements made on diꢀerent areas.
It was estimated by the instrument soꢁtware according to the
ꢂtting method, and the experimental errors oꢁ the measure-
ments were within ± 2°. The water repellency oꢁ the ꢁabric
was tested on a YB813 ꢁabric water immersion meter (Drake
Instrument Co., LTD, China) according to the AATCC-22
standard invented by Dupont. The test samples were dried
ian America) in deuterated chloroꢁorm (CDCl ) with tetra-
3
19
methylsilane (TMS) as the internal standard. F NMR spec-
tra were recorded on a Bruker AC 400 spectrometer (Bruker
Optics, Germany) in deuterated chloroꢁorm (CDCl ). The
3
test samples had a mass percentage oꢁ 5–10%.
Table 1 Copolymer emulsion polymerization recipes
Constituent (g)
Fluorine content (%)
2
0
25
30
ꢁ
abrics having a length and a width oꢁ 3 cm and 1 cm,
PFBEA (n=1)
MMA
BA
15.70
16.00
4.00
24.09
16.00
4.00
37.41
16.00
4.00
respectively, ꢂxed on a glass slide by a double-sided tape.
HEMA
1.20
0.22
11.20
16.00
4.00
1.20
0.27
16.06
16.00
4.00
1.20
0.35
22.71
16.00
4.00
Results and discussion
Ammonium persulꢁate
PFBEA (n=5)
MMA
Structure characterization of intermediates
and target products
BA
HEMA
1.20
0.19
10.60
16.00
4.00
1.20
0.19
1.20
0.22
15.14
16.00
4.00
1.20
0.22
1.20
0.26
21.20
16.00
4.00
1.20
0.25
In Fig. 1, curves 1 and 2 show the spectra oꢁ FBIP and
Ammonium persulꢁate
PFBEA (n=10)
MMA
BA
HEMA
−1
−1
FBE, respectively. The peaks at 3386.6 cm , 2879.5 cm
−1
and 1427.7 cm ꢁor FBIP, correspond to O–H stretching
vibration, symmetric –CH stretching vibration and antisym-
metric –CH stretching vibration, respectively. The absorp-
−
1
−1
tion peaks at 1228.8 cm and 1132.5 cm belong to C–F
stretching vibration, and the absorption peak at 1042.7 cm−
Ammonium persulꢁate
1
1
3

Chemical Papers
1
Fig. 1 FTIR spectra (leꢁt) and H-NMR spectra (right). Curve 1: FBIP, curve 2: FBE
is attributed to the in-plane blending vibration peak oꢁ C–O.
We can see that the C=C peak oꢁ the reactant allyl alco-
hol completely disappeared aꢁter the addition reaction.
aꢁter the cyclization reaction, combined with 19F NMR data,
conꢂrm that the FBE was synthesized successꢁully.
In Fig. 2, it can be seen ꢁrom the inꢁrared absorption spec-
−
1
−1
FBE showed absorption peaks at 3012.7 cm (symmetric
trum that PFBE showed absorption peaks at 3475.9 cm
−
1
−1
stretching vibration oꢁ C–H), 1422.5 cm (antisymmetric
(stretching vibration oꢁ O–H) and 2931.2 cm (symmet-
−
1
−1
stretching vibration oꢁ C–H) and 1234.9 cm (stretching
vibration oꢁ C–F). The disappearance oꢁ the O–H stretching
ric stretching vibration oꢁ –C–H). The peak at 1175.4 cm
can be assigned to the stretching vibration oꢁ the –C–O–C
bond produced by ring-opening reaction. From the inꢁrared
absorption spectrum oꢁ curve 4, we can see that the absorp-
tion strength oꢁ O–H decreased sharply and the newly
appeared peaks at 1734.1 (vibration absorption oꢁ –COO–)
and 1632.9 (stretching vibration absorption oꢁ C=C) indi-
cated the occurrence oꢁ esteriꢂcation reaction. In curve 3, the
−1
vibration peak at 3386.6 cm and the new appearance oꢁ the
−
1
stretching vibration peaks oꢁ –C–O–C– at 1134.7 cm and
−
1
1
023.7 cm indicate the successꢁul synthesis oꢁ the epoxy
1
compound. The H-NMR spectrum gives the same result,
in which the O–H peak at 2.42 ppm completely disappeared
and the new appearance oꢁ –CH–O–CH –C at 3.23 ppm
2
1
Fig. 2 FTIR spectra (leꢁt) and H-NMR spectra (right). Curve 3: PFBE (n=1), curve 4: PFBEA (n=1)
1
3

Chemical Papers
Fig. 3 FTIR spectra (leꢁt): FPAC ꢂlm; 19F NMR spectra (right): FBE
Table 2 Molecular weight and molecular weight distribution oꢁ a series oꢁ polymers synthesized by cationic ring-opening polymerization
Sample
[I]/[M]
1411
Mn (GPC)
Mw (GPC)
PDI
A %
FPACP (n=5)
FPACP (n=10)
1:5
1:10
1411
2791
1319
2740
1495
3072
1.13
1.19
93.48
98.27
reappearance oꢁ the O–H peaks (2.93 ppm) combined with
the appearance oꢁ the –CH=CH peaks (5.02–5.44 ppm,
2
5
.73–6.13 ppm) in curve 4 also indicated that PFBE and
PFBEA were successꢁully synthesized. The FTIR spectra in
Fig. 3 are the ATR–FTIR oꢁ the fuorinated acrylate copoly-
−
1
−1
mer ꢂlm. The peaks at 2956.8 cm and 1732.6 cm are
attributed to the –C–H stretching vibration and the C=O
stretching vibration, respectively, and the disappearance
−
1
oꢁ the C=C stretching vibration absorption (1632.9 cm )
indicates that the polymerization was complete and FPAC
was successꢁully prepared. It can also be seen in Fig. 3
(
right) that the target product showed ꢁour sets oꢁ peaks
representing –CF – (−81.03 ppm), –CF – (−109.60 ppm),
2
2
–
CF – (122.86 ppm) and –CF (−125.66 ppm), which dem-
2
3
onstrate the presence oꢁ perfuorobutyl.
Fluorinated polyether acrylate copolymer and its
latexes
Fig. 4 GPC traces oꢁ FPAC with diꢀerent molar ratios
Gel permeation chromatography of ꢀuorinated polyether
acrylate copolymer
the ratio oꢁ initiator/monomer ([I]/[M]). Figure 4 lists the
unimodal GPC curves oꢁ FPAC (n=5, n=10) with a rela-
tively low PDI oꢁ 1.13 and 1.19, respectively. This proved
that the polymerization degree oꢁ cationic ring-opening
polymerization oꢁ fuorine containing epoxide monomers
was controllable and the molecular weight distribution oꢁ the
obtained products was narrow (Zhong et al. 2008).
The molecular weight and molecular weight distribution oꢁ
oligomers FPAC (n = 5, n = 10) were determined by GPC
using THF as an eluent. From the results (in Table 2), we can
see that the number-average molecular weight (Mn, GPC)
meets well the theoretical value (Mn, Theo.) predicted ꢁrom
1
3

Chemical Papers
Size, zeta potential of ꢀuorinated polyether acrylate
copolymer latexes
ꢁabrics (Fig. 6b–d) except ꢁor the pristine cotton (Fig. 6a).
The results proved that the surꢁace oꢁ the cotton ꢁabric was
covered by a furocopolymer ꢂlm, which provided lower sur-
ꢁace ꢁree energy and water repellency.
To identiꢁy the emulsion stability, the particle size oꢁ fuori-
nated polyether acrylate copolymer latexes was investigated
and is shown in Fig. 5a. It clearly showed that the latex
particle sizes increased gradually with the increase in fuo-
rine content, and the increments oꢁ oligomer chain length
enlarged the particle size. This is because the increase in
fuorine segments enhances the hydrophobic interactions
around the particles, which induces the aggregation oꢁ par-
ticles ꢁormed at the early stage and ꢁurther leads to particle
size enlargement (Hansen et al. 2007).
Surface morphology of ꢀuorocopolymer ꢁlms on cotton
substrates
The chemical composition and morphology oꢁ the ꢂbers’
surꢁace have a major impact on the surꢁace properties oꢁ
ꢁabrics. When the ꢂber surꢁace is covered with a fuoroalkyl
polymer, the side chain will migrate toward the ꢂlm–air
interꢁace to reduce the surꢁace ꢁree energy oꢁ the ꢂlm and
thus to ꢁorm a hydrophobic surꢁace. When watching the sur-
ꢁace oꢁ the pristine cotton ꢂber (Fig. 7a), many natural pleats
and uneven gullies can be ꢁound, which were ꢁully covered
As another representation oꢁ the emulsion stability, the
zeta potentials oꢁ fuorinated polyether acrylate copolymer
latexes (the data were the absolute values oꢁ tested zeta
potentials) are shown in Fig. 5b. It clearly showed that the
zeta potential oꢁ these polymer latexes was decreased with
the increase in fuorine content, which demonstrated that
the stability oꢁ the copolymer latexes decreased, consistent
with the eꢀect oꢁ fuorine content on the particle size. The
zeta potential was ꢁurther ꢁound similarly to decrease with
the increment oꢁ oligomer molecular weight in the side chain
in copolymers.
The application of ꢀuorocopolymer latexes
on cotton fabrics
X‑ray photoelectron spectroscopy
The changes in chemical compositions on the surꢁace oꢁ
treated cotton ꢁabrics were analyzed by XPS. Figure 6 shows
the typical wide scan spectra oꢁ pristine cotton and coated
cottons (FPAC-cotton, n=1, 5, 10) with 30% fuorine con-
tent. A strong peak with binding energy oꢁ 688.9 eV cor-
responding to F was ꢁound in the spectra oꢁ coated cotton
Fig. 6 XPS survey scans oꢁ pristine cotton (a), FPAC (n=1)-cotton
(b), FPAC (n=5)-cotton (c) and FPAC (n=10)-cotton (d)
1
s
Fig. 5 Eꢀect oꢁ fuorine content on the emulsion particle size (a) and zeta potential (b)
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Chemical Papers
by polymer, in Fig. 7b–d, aꢁter ꢂnishing, and the surꢁace
became relatively smooth and fat. The fuoropolymer pro-
vides liquid repellency by cross-linking on the ꢂber surꢁace.
In addition, in the ꢂnished cotton ꢁabrics, the elements and
element distributions, as in Fig. 8, were identiꢂed by EDS.
The fuorine element distributed uniꢁormly and evenly in
the ꢂlm on the surꢁace oꢁ the ꢂbers, demonstrating that the
fuoropolymer had been successꢁully coated on the surꢁace oꢁ
the ꢂbers. This provides the treated ꢁabrics good water repel-
lency, which was ꢁound to be durable as shown in Fig. 9, as
the ꢂnished cotton ꢁabrics still possess good hydrophobicity
and oleophobicity aꢁter 20 cycles oꢁ water washing.
134.7° and 139.1°, respectively. In addition, when the fuo-
ropolymer with higher fuorine content was used as ꢂnishing
agent, a better water repellency can be obtained. The result
is shown in Table 3 when controlling the concentration at
50 g/L.
Thermal property analysis
The curves oꢁ TGA oꢁ pristine cotton and FPAC-cotton at
a heating rate oꢁ 10°/min in N are presented in Fig. 11. It
2
can be seen that all the cotton ꢁabrics present three stages oꢁ
decomposition beꢁore and aꢁter ꢂnishing. The ꢂrst stage oꢁ
weight loss is between 50 and 300 °C. This process caused
less weight loss oꢁ about 10% by the dehydration oꢁ the glu-
cose group in the cellulose, accompanied by a decrease in
the degree oꢁ ꢂber polymerization. In the second stage, the
rapid weight loss between 300 and 400 °C was as high as
70%, which corresponded to the decomposition oꢁ carbon
chains and mainly due to the ꢁact that the cellulose mac-
romolecules pyrolyzed into combustible small molecules
(Ayeni et al. 2013). The last stage is the residue oxidation
stage oꢁ the ꢂbers with a weight loss oꢁ about 10%. The
residue was aromatically cyclized and gradually carbonized
to ꢁorm a graphite structure.
Contact angles of cotton fabrics coated with ꢀuorinated
copolymer and its water repellency
The surꢁace wettability oꢁ the FPAC-cotton ꢁabric was esti-
mated through contact angle test in Fig. 10. It can be seen
ꢁ
rom the ꢂgure that the surꢁace contact angle oꢁ the ꢂnished
ꢁ
abric gradually increases as the fuorine content increases.
In addition, when controlling the fuorine content at the
same level, the surꢁace contact angle oꢁ the ꢂnished ꢁabric
treated with longer side-chain fuoroalkyl polymer is signiꢂ-
cantly higher than that treated with the short-chain polymer.
The WCAs oꢁ FPAC (n=1)-cotton (b), FPAC (n=5)-cotton
The initial decomposition temperature oꢁ pristine cot-
ton ꢁabric was 298 °C. However, the values oꢁ FPAC
(
c) and FPAC (n=10)-cotton (d) were ꢁound to be 128.8°,
Fig. 7 SEM micrographs oꢁ pristine cotton (a), FPAC (n=1)-cotton (b), FPAC (n=5)-cotton (c) and FPAC (n=10)-cotton (d)
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Chemical Papers
Fig. 8 Low-resolution electron micrograph and elemental distribution oꢁ the FPAC (n=10)-cotton surꢁace (a) and the corresponding elemental
energy spectrum oꢁ the sample (b)
(
(
n = 1)-cotton (b), FPAC (n = 5)-cotton (c) and FPAC
n = 10)-cotton (d) increased to 315 °C, 316 °C and
cotton ꢁabrics exhibited more residue compared to the pris-
tine cotton ꢁabric at the complete decomposition stage,
which increased ꢁrom 2.76 to 4.67%. The results may be
attributed to the presence oꢁ fuoroalkyl chains, which
have tightly packed and high energy C–F bonds (Xu et al.
2013). All oꢁ the results indicate that the thermal stability
3
18 °C, respectively, aꢁter treating with fuoropolymer,
revealing that the thermal stability oꢁ coated cotton ꢁab-
rics was enhanced due to the introduction oꢁ fuorinated
polyether acrylate copolymer. At the same time, the coated
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Chemical Papers
Fig. 9 The eꢀect oꢁ droplets
dripping on the surꢁace oꢁ cot-
ton ꢁabric ꢁor 1 min
Table 3 Hydrophobicity oꢁ treated ꢁabric with diꢀerent fuorine con-
tents
DP
Fluorine content (%)
Hydrophobic
level (points)
n=1
20
70
70
80
80
80
90
80
80
90
2
3
5
0
n=5
20
2
3
5
0
n=10
20
2
3
5
0
Fig. 10 Water contact angles oꢁ FPAC (n=1)-cotton, FPAC
(
n=5)-cotton and FPAC (n=10)-cotton with diꢀerent fuorine con-
fuoropolyether acrylates, ꢁollowed by copolymerizing
with MMA, BA, and HEMA to obtain the fuoropoly-
mer emulsion. The latex particle size increases with the
increase in fuorine content, while the emulsion stability
decreases accordingly. Controlling the concentration oꢁ
the ꢂnishing agent at 50 g/L and the fuorine content at
tents
and the heat resistance oꢁ the ꢁabric are improved aꢁter
ꢂnishing.
3
0%, the copolymers FPAC, whose side-chain length was
Conclusions
1, 5 and 10, were coated on cotton ꢁabrics to give con-
tact angles oꢁ 128.8°, 134.7° and 139.1°, respectively. In
addition, the initial decomposition temperatures oꢁ the ꢂn-
ished cotton treated with FPAC (n =1, 5, 10) were 315 °C,
316 °C and 318 °C, which were higher than that oꢁ pristine
cotton (298 °C). This indicates that the thermal stability oꢁ
In this study, the fuorine-containing polyether oligom-
ers were synthesized by ring-opening reaction using short
fuoroalkyl propylene oxide as materials. The oligomers
were then esteriꢂed with acryloyl chloride to give the
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3

Chemical Papers
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by the National Natural Science Foundation oꢁ China (no. 51673137)
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