Cocontinuous Cellulose Acetate Polyurethane Electrospinning
Cocontinuous Cellulose Acetate Polyurethane Electrospinning
Cocontinuous Cellulose Acetate Polyurethane Electrospinning
2
Fujian Key Laboratory of Polymer Materials, Fuzhou 350007, China
3
Laboratory of Cellulose and Lignocellulosic Chemistry, Guangzhou Institute of Chemistry,
Chinese Academy of Sciences, Guangzhou 510650, China
Cocontinuous cellulose acetate (CA)/polyurethane (PU) down to submicrometers or even 10s of nanometers [1].
composite nanofibers were obtained through electro- Nanofiber possesses the characteristic features of high
spinning of partially miscible CA and PU in 2:1 N,N- length-to-diameter ratio and specific surface areas, ena-
dimethylacetamide (DMAc)/acetone mixture solvent.
Their structures, mechanical, and thermal properties bling it to be applied for protective clothing, filter, cata-
were characterized by scanning electron microscopy lyst support, reinforced composite, and tissue engineering
(SEM), transmission electron microscopy (TEM), and dif- [2]. Recently, there is growing interest in the design and
ferential scanning calorimetry (DSC). The structures and preparation of novel composite nanofiber with improved
morphologies of the nanofibers were affected by com- properties, because it may combine the merits of each
ponent ratio in the binary mixtures. PU component not
only facilitated the electrospinning of CA at CA concen- component. One type of composite nanofibers reported so
tration down to 12 wt%, but reinforced the tensile far are prepared by multiple-jet electrospinning [3, 4],
strength of CA/PU nanofibrous mats, while semirigid mainly because a cosolvent is hard to be found for each
component CA in the composite nanofibers could component. For instance, cellulose acetate (CA)/poly(vi-
greatly improve the rigidity and dimensional stability of nyl alcohol) (PVA) composite nanofiber was generated by
CA/PU nanofibrous mats. In a series of nanofibrous
mats with varied CA/PU composition ratios, CA/PU 20/ side-by-side electrospinning of CA in 2:1 acetone/dime-
80 showed excellent tensile strength and Young’s modu- thylacetamide and PVA in water [4]. It was found that the
lus. The residual product after selective removal of any mechanical properties of the CA nanofibrous mats are sig-
one of the components in CA/PU composite nanofibers nificantly enhanced with the increasing of PVA component
by washing with proper solvent maintained the fiber in the CA/PVA composites [4]. Nevertheless, this type of
structure but greatly reduced the fiber size, suggesting
CA/PU composite fibers showed a cocontinuous nano-
composite nanofibrous mat is composed of two kinds of
fiber structure due to phase separation in the spinning nanofibers formed by individual pure polymers. Another
solution and in the course of electrospinning. POLYM. type of composite nanofiber is synthesized from electro-
ENG. SCI., 48:1296–1303, 2008. ª 2008 Society of Plastics Engineers spinning of polymer blends in a cosolvent. Most composite
nanofibers of this type consist of two components. One
component is hard to be electrospun into nanofiber alone
INTRODUCTION such as chitosan and Bombyx mori silk, and the other is a
good nanofiber-forming polymer such as poly(ethylene ox-
Electrospinning is a simple and versatile technique in
ide) [5–7]. Generally, such nanofibers are of the ‘‘islands-
the generation of continuous ultrafine fibers with diameter
in-the-sea’’ structure with the former dispersing into the
latter, which is continuous fiber morphology due to phase
Correspondence to: Haiqing Liu; e-mail: [email protected] separation and fast solvent evaporation during fiber forma-
Contract grant sponsor: Initiative Fund for the Returned Overseas Chi- tion. Selective removal of the dispersed component often
nese Scholar administered by the State Education Ministry and the Key results in nanoporous nanofibers with higher specific sur-
Project of Natural Science Foundation of Fujian Province; contract grant
face areas than untreated nanofibers, whereas the removal
number: E0620001.
DOI 10.1002/pen.21090 of the fiber-forming component would cause complete dis-
Published online in Wiley InterScience (www.interscience.wiley.com). integration of the composite nanofiber [8, 9]. With special
V
C 2008 Society of Plastics Engineers design of the spinneret, side-by-side [10] or core-sheath
[11] bicomponent polymer nanofibers have been reported DMAc and 2:1 (v/v) DMAc/acetone. To facilitate their
as well. Obviously, none of these bicomponent composite capabilities in the fiber formation during electrospinning,
nanofibers presents a well-blended and cocontinuous fiber the latter was chosen as the cosolvent for CA and PU. All
structure within a single nanofiber. materials were used as received.
Cocontinuous composite nanofiber is defined as each
component forms fiber structure in the composite. Com-
paring with the composite nanofibers from the side-by-
Electrospinning
side electrospinning, the cocontinuous structure enables
the components in the nanofiber to be blended in the Precalculated amount of CA and PU was dissolved in
nanolevel, and to interact with each other through molec- 2:1 DMAc/acetone mixture solvent to make CA/PU com-
ular forces such as hydrogen bonding. Such structure position ratio of 100/0, 80/20, 60/40, 40/60, 20/80, and 0/
would certainly impart new mechanical and thermal prop- 100. The total polymer weight concentrations were 20%
erties for the composite nanofiber. However, little work by weight. It was observed that the miscibility of these
on the cocontinuous composite nanofiber has been found two polymers in solutions is poor, because the blend solu-
so far [9]. In this work, we aim to prepare cocontinuous tions are not completely transparent. The CA/PU spinning
composite nanofibers of CA/PU through electrospinning solution was added to a 10-ml syringe attached to a stain-
their blends in cosolvent N,N-dimethylacetamide (DMAc)/ less needle with an inner diameter of 0.84 mm. An elec-
acetone. Each component alone is readily to form nano- trode was clamped on the needle and connected to a
fiber through electrospinning. CA nanofibers show poor power supply. Grounded counter electrode was connected
mechanical property with stress of 1.3 MPa, but good to collector aluminum foil. All solutions were electrospun
dimensional stability with strain as small as 0.007% due at ambient temperature, flowing rate at 10 ll/min, 10 kV,
to its semirigid chain structure [12, 13]. Moreover, it can and a 20-cm distance between the collector and needle
be easily deacetylated to regenerate more biocompatible tip. The products were dried under vacuum at 508C for
and reactive cellulose nanofiber [14]. PU nanofiber exhib- 5 h to remove any residual solvents.
its excellent tensile strength of over 10 MPa but high
strain of more than 300% [15]. Depending on the struc-
ture, PU nanofibers have been tested in the application
Selective Removal of One Component from
areas of protective clothing [16] and tissue engineering
CA/PU Nanofiber
[17]. CA/PU cocontinuous composite nanofibers are possi-
ble to exhibit excellent mechanical strength and relative To remove PU component in the composite nanofiber,
stable dimensionality. To test this assumption, the electro- the CA/PU nanofibrous mat was first hydrolyzed in 0.05
spinning of CA/PU is investigated in terms of composi- M NaOH/ethanol solution to turn CA to cellulose at room
tion ratio in the binary mixtures. The structure, morphol- temperature for 24 h. Because cellulose is hard to dissolve
ogy, mechanical behavior, and thermal property of the in many solvents, the hydrolyzed fibrous mats were subse-
CA/PU composite nanofibers are examined. The structure quently immersed in DMAc for 24 h to dissolve PU com-
of residual nanofibers obtained from selective removal of ponent while cellulose nanofiber mat was left behind.
one of the components from the CA/PU composite nano- Such obtained cellulose nanofibrous mat was further
fiber is characterized. washed with DMAc three times, acetone two times to
completely remove PU component. The selective removal
of CA component was achieved by immersing CA/PU
EXPERIMENTAL nanofibrous mat in acetone for 12 h. After it was washed
with acetone five times, PU nanofiber was remained. The
residual cellulose and PU nanofibrous mats were vacuum
Materials
dried at 508C for 10 h. The mass of dried nanofibrous
Cellulose acetate (Mn ¼ 3.0 3 104, acetyl content 39.8 mat before and after selective removal of CA or PU com-
wt%) was from Aldrich Chemical Company. Elastollan ponent was measured to calculate the weight loss. Scheme
B64D, a polyester-based polyurethane, was purchased 1 illustrated the preparation and treatment procedure of
from BASF Company. Both CA and PU can dissolve in CA/PU nanofiber.
composite nanofibers. However, actual PU loss after treat- deacetylation of CA in NaOH/EtOH solution, and the
ment of hydrolyzed mat with DMAc was less than that of deacetylation of CA and PU removal are processed com-
theoretical PU content. Considering that the actual total pletely. In another parallel hydrolysis experiment in
loss closely matches theoretical loss, we believe that part NaOH/H2O (values in the last two rows in Table 1), we
of the polyester-based PU is hydrolyzed along with the found that the actual mass loss is a little bit more than
that theoretical acetyl content after hydrolysis, with no results suggest that aq. NaOH has little effect on the hy-
significant hydrolytic degradation of PU. PU is almost drolysis of PU, which is believed to be caused by the
removed in the subsequent treatment with DMAc. These poor penetration of aq. NaOH solution into the hydropho-
TABLE 1. Mass changes of CA/PU nanofibrous membranes after hydrolyzed in NaOH/EtOH or NaOH/H2O and washed in DMAc.
a
The values in the last two rows were from hydrolysis in the NaOH/H2O.
FIG. 3. TEM images of CA/PU 40/60 composite nanofibers. (a) as-electrospun, (b) after hydrolyzed in
NaOH/EtOH and washed with DMAc, and (c) after washed with acetone.