Polymer Bulletin (2020) 77:2873–2887

https://doi.org/10.1007/s00289-019-02886-w

ORIGINAL PAPER

A comparative analysis of the preparation of cellulose

acetate butyrate and the characteristics of applying
in pearlescent coating film

Aimin Huang1 · Liping Wei1 · Zengyan Zhao1 · Guodong Wei1 ·

Yanjuan Zhang1,2 · Zuqiang Huang1,2   · Xuanhai Li1 · Huayu Hu1 ·
Xingzhen Qin1 · Mei Yang1,2

Received: 24 November 2016 / Revised: 16 January 2018 / Accepted: 22 July 2019 /

Published online: 27 July 2019
© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
A simple, green, and efficient mechanical activation-assisted esterification (MAE)
technology was developed for the preparation of cellulose acetate butyrate (CAB),
which was used as film-former for pearlescent coating. In addition, CAB was also
prepared by a traditional liquid phase esterification (LPE) method for comparing
the structures and characteristics of the CABs prepared by these two technologies.
1
H and 13C NMR confirmed that CAB was successfully produced, and the degree
of substitution of acetyl and butyryl groups was also calculated. The crystal struc-
ture and molar mass of the CABs prepared by MAE and LPE methods were dis-
similar, ascribing to different reaction systems and characteristics. FTIR, SEM, and
transparency analyses were used to investigate the chemical structure and surface
characteristics of CAB films, and appearance, glossiness, rub resistance, and ethanol
resistance measurements were carried out to investigate the surface and wear char-
acteristics of CAB/pearlescent coating films. The results indicated that the surface
and wear characteristics of the films based on MAE- and LPE-prepared CABs were
similar to the same reaction time, and the interfacial adhesion and compatibility
among components significantly affected the characteristics of the films.

Keywords  Cellulose · Mechanical activation · Esterification · Coating film · Surface

characteristics · Wear characteristics

* Yanjuan Zhang
zhangyj@gxu.edu.cn
* Zuqiang Huang
huangzq@gxu.edu.cn
1
School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
2
State Key Laboratory of Non‑Food Biomass and Enzyme Technology, Guangxi Academy
of Sciences, Nanning 530007, China

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Introduction

Cellulose esters are widely prevailing in many application fields for the renewable
and biodegradable characteristics [1, 2]. Cellulose acetate butyrate (CAB), one
of the most common commercial cellulose esters, is commonly used in coating
industry as a film-former, additive, or modifying resin. CAB provides advantages
to coatings including improved flow and leveling, good sprayability, cold-crack
and moisture resistance, good chlorine tolerance and chemical stability, and acts
as a stable carrier dispersion medium for pigments [3, 4]. As the development of
plastic materials, a coating on plastic materials is a common method to enhance
their surface properties, tinct, and anti-wear ability [5–8]. Pearlescent coating,
with the advantages of stable chemical properties, high-temperature resistance,
light resistance, non-conductive, bright color, etc., is usually used for plastic
products to protect them from damnification and show a beautiful appearance.
For using CAB in the coatings of plastic materials, the compatibility between
CAB and other components (pigments, resins, and solvents) and the interfacial
adhesion between coating film and plastic substrates have a crucial effect on
the performances of coatings. CABs prepared by different methods exhibit dif-
ferent structures, physical, and chemical properties, which can be controlled by
manipulating the structure of polymer, including the degree of substitution (DS)
of butyrate, hydroxyl content, and molecular chain length.
Generally, the preparation of cellulose esters can be performed under both
heterogeneous and homogeneous reaction systems with using organic solvents,
including organic acids, dichloromethane, dimethylacetamide/lithium chloride
(DMAc/LiCl), 1-allyl-3-methylimidazolium chloride (AmimCl), toluene/tri-
ethylamine (TEA), dimethyl sulfoxide/tetrabutylammonium fluoride trihydrate
(DMSO/TBAF) [1, 9–12]. For the preparation of CAB, excess butyric acid is
a readily accepted solvent. In addition, native cellulose is difficult to react with
esterifying agents before activation pretreatment because of its stable crystal
structure [13], and cellulose is commonly soaked in acetic acid and acetic anhy-
dride for a long time to enhance its accessibility and reactivity. The large amounts
of used organic acids and acid anhydride are difficult to be effectively recycled.
Therefore, it is significant to reduce the use of organic acids and acid anhydride
to increase economic feasibility and protect the environment.
In order to avoid the use of organic reagents for the activation of cellulose
and reduce the dosage of butyric acid for the preparation of CAB, it is important
to develop a technology to simultaneously activate the hydroxyl groups of cellu-
lose and enhance the reaction between cellulose and esterifying agents. Mechan-
ical activation (MA), usually carried out by high-energy milling to change the
crystalline structure and physicochemical properties of solids, is an effective
and green method for enhancing the reactivity of cellulose [14–18]. In this case,
MA can be used as an assisted means to enhance the esterification of cellulose,
which combines MA and esterification in the same equipment. CAB with desired
DS and properties can be promising to be directly produced by this simple and
environmentally friendly MA-assisted esterification (MAE) technology. In the

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Polymer Bulletin (2020) 77:2873–2887 2875

present study, unconventional MAE method was adopted to produce CAB, which
was then used to prepare pearlescent coating film for acrylonitrile butadiene sty-
rene (ABS) plastic. In order to evaluate the properties of the CABs produced by
unconventional and traditional technologies and investigate the characteristics
and feasibility of MAE technology, CAB was also produced by a traditional liq-
uid phase esterification (LPE) method to compare the structures of CABs and the
surface and wear characteristics of the CAB-based films.

Experimental

Materials

Cotton cellulose with a degree of polymerization of 1010 was obtained from Hubei
Xiangtai Cellulose Co., Ltd. (China). Acetic anhydride, acetic acid, and butyric acid
were purchased from Shanghai Aladdin Industrial Corporation (China). All materi-
als were commercially available reagents of analytical grade and used without fur-
ther purification.

Preparation of CAB by MAE method

The preparation of CAB by MAE method was carried out in a customized stirring
ball mill driven by a commercially available drill press (maximum drilling diameter
= 16  mm) equipped with a speed-tuned motor [19]. A fixed amount of zirconium
oxide milling balls (300 mL, 5 mm diameter) was first added into a jacketed stain-
less steel tank (1200 mL), and then 10 g of cellulose, 66 g of butyric acid, 20 g of
acetic anhydride, and 0.2  mL of concentrated sulfuric acid (catalyst) were added
into the tank. The mixture was subjected to milling at a speed of 375 rpm and reac-
tion temperature of 70 °C by circulating the thermostatic water in the jacket of tank.
When the mixture was milled for different times (milling time = reaction time), the
milling balls were removed from the resulting sample by a sieve. The resulting sam-
ple was treated by a repeated washing–filtration process with 50% aqueous alcohol
and water until the filtrate was neutral. Crude CAB was obtained after oven-drying
at 55  °C. The crude CAB was dissolved in acetone (15  mL acetone/g CAB) and
stirred for 1 h, and then, the mixture was centrifuged at 3060 g for 20 min by a table-
top centrifuge. The supernatant was removed and evaporated by vacuum distillation
at 50 °C, and the solid was oven-dried at 55 °C. The purified CAB samples, which
named MAE-CAB30, MAE-CAB60, and MAE-CAB90 (milling time = 30, 60, and
90 min, respectively), were prepared. The purification yield was the weight ratio of
purified and crude MAE-prepared CAB.

Preparation of CAB by LPE method

Cellulose (10  g) was first immersed in 50  mL of acetic acid and 10  mL of ace-
tic anhydride for 12  h at 30  °C, and then the mixture was filtered to remove the

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pretreatment reagents. The pretreated cellulose, 92 g of butyric acid (excess butyric
acid as solvent), 20 g of acetic anhydride, and 0.2 mL of concentrated sulfuric acid
(catalyst) were put into a flask, and cellulose reacted with the esterifying agents with
magnetic stirring at a constant temperature of 70 °C for 1 h. The mixture was hydro-
lyzed by the addition of 10  mL of deionized water for 1  h. The resulting sample
was treated by a repeated washing–filtration process and purified by acetone (15 mL
acetone/g CAB) as the same processes in MAE method. Then, the CAB sample,
which named LPE-CAB, was obtained. The purification yield was the weight ratio
of purified and crude LPE-prepared CAB.

Characterization of CAB
1
H and 13C nuclear magnetic resonance (NMR) spectra were recorded on a Bruker
Advance HD III 600  MHz spectrometer (Switzerland) at room temperature, and
deuterated chloroform (­CDCl3) and tetramethylsilane (TMS) were used as solvent
and internal standard, respectively. DS values were calculated by signal integration
and correlation of cellulose and substituent protons in 1H NMR spectra of the CAB
samples.
X-ray diffraction (XRD) analysis was carried out by an Ultima IV diffractometer
(Rigaku, Japan) using Cu Kα radiation (λ = 0.154 nm) with a scan range of 5°–40°
and a step size of 0.02° at 40 kV and 30 mA.
Weight–average molar mass (Mw) of the CAB samples were determined by gel
permeation chromatography (GPC) analysis on a SHIMADZU CTO-20A high-
performance liquid chromatography with an RID-10A differential refraction detec-
tor and a PL gel 5 MIXED-C 300 × 7.5 mm (Polymer Laboratories) column using
tetrahydrofuran (THF) as the mobile phase (0.5 mL/min) with injection volume of
20 µL. Prior to GPC analysis, the CAB sample was dissolved in THF (10 mg/mL),
filtered through a 0.45-µm microporous filter and placed in a 2 mL vial. Molar mass
was calibrated using polystyrene standards of 2940–370,000.

Preparation and characterizations of CAB films

CAB film was prepared as follows: 0.5 g of CAB was completely dissolved in 8 mL
of acetone, and then the solution was spread flat on the surface of a clean glass plate
(5 cm × 10 cm). The CAB film was obtained after air-drying.
Fourier-transform infrared spectroscopy (FTIR) analysis of the CAB films was
performed on a Nicolet IS 10 spectrometer (Thermo Scientific, USA) using the KBr
disk technique. The spectra were obtained with at a resolution of 1 cm−1 in a fre-
quency range from 400 to 4000 cm−1.
Surface morphology of the CAB films was observed by scanning electron micros-
copy (SEM) analysis on an S-3400N scanning electron microscope (Hitachi, Japan)
after mounting the films on a sample bench and sputter-coating with gold.
Transparency of the CAB films was measured by a MIT-60 gloss meter. G1 and
G2 were recorded as the glossiness of the glass plate without and with the CAB film,

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and the transparency (T, %) of the CAB films was calculated using the following
equation:
G2
T= × 100%.
G1

Preparation and performance testing of CAB/pearlescent coating films

CAB/pearlescent coating film was prepared as follows: 1.0 g of CAB and 0.025 g
of film-forming additive (ternary chlorine vinegar resin) were added in 20  mL of
solvent (the mixture with the volume ratio of 34% of methylbenzene, 25% of butyl
acetate, 18% of ethyl acetate, 10% of butanol, 6% of acetone, 4% of butanone, and
3% of ethylene glycol butyl ether), stirring until they were fully dissolved. Then,
0.7 g of pearlescent powders and 4 mL of diluent (xylene) were added to the solu-
tion, and the mixture was stirred at the speed of 750 rpm for 5 min. This paint was
evenly brushed on an ABS plastic plate, and the CAB/pearlescent coating film was
obtained after air-drying.
Glossiness of coating films was measured by a MIT-60 gloss meter, and higher
gloss value (Gs) indicated better glossiness. Rub resistance and ethanol resistance
were determined by an A20-339 abrasion tester. For rub resistance test, the CAB
film was wiped by an eraser (6.5 mm diameter) placed on a weight (500 g) at the
speed of 70 times/min, and the times for breaking the film were recorded. For etha-
nol resistance test, the eraser was replaced with cotton yarn containing 95% alco-
hol. More friction times for breaking the film meant better rub resistance or etha-
nol resistance. All tests were performed in triplicate, and the results represented the
mean values of three independent experiments.

Results and discussion

Preparation and characterization of CAB

Cellulose possesses a complex structure due to the existence of crystalline regions

and inter- and intramolecular hydrogen bonds, resulting in low accessibility and
poor reactivity [20]. Generally, pretreatment is needed to disrupt the hydrogen bonds
and activate the hydroxyl groups in cellulose. In this study, acetic acid and acetic
anhydride were used to pretreat the cellulose for the preparation of CAB by LPE
method. In contrast, cellulose did not require to be pretreated for preparing CAB
by MAE method, ascribing to that cellulose was activated by ball milling during
the process of MAE. The acetyl and butyryl substituents in MAE- and LPE-pre-
pared CABs were identified and quantitated by 1H NMR spectroscopy, and the 1H
NMR spectra of different CAB samples are presented in Fig. 1. The DS values of the
grafted acetyl groups (­DSA) and butyryl groups (­DSB) were calculated by integrat-
ing the characteristic signals of methyl protons of acetyl and butyryl chains and cel-
lulose backbone protons, and the total DS ­(DST) was the sum of ­DSA and ­DSB. DS
values and purification yields of different CABs are shown in Table 1. The CABs

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Fig. 1  1H NMR spectra of different CABs in ­CDCl3

Table 1  DS values, yields, and Sample DSA DSB DST Yield (%) Mw
Mw of different CABs
MAE-CAB30 0.96 1.21 2.17 35 ± 2 292,680 ± 9070
MAE-CAB60 1.07 1.49 2.56 84 ± 4 98,460 ± 2560
MAE-CAB90 1.26 1.33 2.59 69 ± 2 75,880 ± 1540
LPE-CAB 1.21 1.36 2.57 89 ± 3 114,410 ± 2060

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Polymer Bulletin (2020) 77:2873–2887 2879

with desired DS values were successfully prepared by both MAE and LPE methods,
and the optimum reaction time for MAE could be considered to be 60 min, which
presented satisfied ­DSB and purification yield. When the milling time prolonged to
more than 60 min, both the D ­ SB and yield decreased, resulting from that the hydrol-
ysis rate of cellulose esters was faster than the esterification rate when the esterifica-
tion came to a certain extent [21]. After acid pretreatment of cellulose, an average
DS value of CAB above 2.8 is often obtained by LPE method. However, CAB with
a very high DS value is inapplicable in terms of its use in direct commercial applica-
tions due to the lack of desired hydroxyl content, and the partially substituted CAB
with the DS value ranging from 2.5 to 2.8 is more widely applied in industry. There-
fore, hydrolysis of the completely acylated cellulose is generally required to obtain
a desired hydroxyl content, making the process complicated and poorly reproduc-
ible. In comparison, MAE could directly and simply produce the CAB with desired
DS value and hydroxyl content, which avoided special pretreatment and reduced the
dosage of reagents and reaction time. A comparison of MAE and LPE technologies
for the preparation of CAB is presented in Table 2, which clearly shows the charac-
teristics of each method. By combining MA and esterification in the same equip-
ment, the active hydroxyl groups generated from the destruction of stable crystalline
structure and strong hydrogen bonding of cellulose induced by intense milling could
be directly contacted with esterifying agents, leading to efficient preparation of CAB
[14, 22].
Figure 2 presents the 13C NMR spectra of different CAB samples. For all of these
spectra, the C-6, C-2,3,5, C-4, and C-1 carbons of the anhydroglucose unit (AGU)
backbone exhibit signals at 62.0, 71.0–73.4, 76.0, and 100.4 ppm, respectively [23].
The most important signals for confirming the acylation of cellulose are shown at
169.0–170.5 and 171.5–173.0 ppm, which are the carbonyl carbon signals in acetyl
(C-7a) and butyryl groups (C-7b), respectively. The methyl carbons in acetyl groups
(C-11) and butyryl groups (C-10) exhibit signals at 31.5 and 13.5 ppm, respectively,
and peaks at 20.4 and 18.0  ppm correspond to the methylene carbons in butyryl
groups (C-8,9). These distinct carbon signals of substituents indicate that acetyl and
butyryl groups had undoubtedly grafted on cellulose.
The crystal structure of cellulose and different CAB samples was measured by
XRD analysis, and the XRD patterns are presented in Fig.  3. The cotton cellu-
lose exhibits three main planes of cellulose I crystal with the characteristic peaks
at around 2θ = 15.0°, 16.4°, 22.6°, and 34.8°, which are assigned to the 101, 10-1,
002, and 040 diffraction planes, respectively [24]. For all the XRD patterns of CAB

Table 2  Comparison of MAE and LPE technologies for the preparation of CAB

MAE technology LPE technology

Pretreatment – 50 mL of acetic acid and 10 mL

of acetic anhydride for 12 h
Butyric acid dosage 66 g 92 g
Hydrolysis – 10 mL of deionized water for 1 h

The dosages of reagents were based on 10 g of cellulose

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Fig. 2  13C NMR spectra of different CABs in ­CDCl3

Fig. 3  XRD patterns of cellulose and different CABs

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Polymer Bulletin (2020) 77:2873–2887 2881

samples, the characteristic peaks of cellulose gradually disappeared, and a new peak
appeared at about 7.1°. These indicate that both MA and esterification remarkably
destroyed the crystal structure of cellulose and led to the decrease in crystalline
phase. Both MA and chemical modification reduced the crystallinity of cellulose,
but the introduced acyls could lead to the crystallization of these substituent chains.
Therefore, the new peak occurring in the XRD patterns of esterified cellulose could
ascribe to the formation of newly ordered structures associated with the crystalliza-
tion of acyl side chains.
The Mw of different CAB samples was determined by GPC analysis, and the
results are shown in Table 1. With the increase in milling time, the molar mass of
CAB remarkably decreased, indicating that intense mechanical actions caused the
degradation of cellulose chains, which obviously increased the numbers of small
CAB molecules [25]. For the CAB prepared by LPE, the molecular chains of cellu-
lose were also degraded during the processes of acid pretreatment, esterification, and
hydrolysis. However, compared with MAE-CAB60, the molar mass of LPE-CAB
with the same reaction time was higher, implying that MA had more remarkable
effect on the destruction of the molecular chains of cellulose. It is well known that
with the increase in Mw of cellulose esters, toughness and melting point increase,
and compatibility and solubility decrease [3]. Thus, the molar mass of CAB can sig-
nificantly affect the film-forming ability and the characteristics of CAB-based coat-
ing films.

Chemical structure and surface characteristics of CAB films

Native cellulose with high crystallinity demonstrates poor solubility in common sol-
vents. After esterification, the modified cellulose is changed to thermoplastic poly-
mer with amorphous structure, which can be dissolved in common solvents accord-
ing to the degree of modification [26]. CAB is a very good film-forming material
with good flow and leveling, which can be determined by the surface characteris-
tics of CAB film. For this purpose, the functional groups, surface morphology, and
transparency measurements were first carried out to study the chemical structure and
surface characteristics of different CAB films, evaluating the feasibility for using the
CABs prepared by different technologies in coating applications.
The functional groups in different CAB films were measured by FTIR analysis,
and the spectra are presented in Fig.  4. The characteristic absorption bands that
appeared at 1750 and 2880 cm−1 in all the spectra, corresponding to the stretching
vibration of the ester carbonyl groups (C=O) and the characteristic absorption peak
of methylene associated with butyryl substituents [14], are the most convincing evi-
dence of successful esterification of cellulose to prepare CAB. The absorption peaks
at 1376, 1238, and 1050 cm−1 were assigned to C–H bending, C–O–C ester stretch-
ing vibration, and C–O stretching in glycosidic linkages, respectively. A broad band
centered at 3455  cm−1 is attributed to O–H stretching vibration [22], indicating a
certain amount of hydroxyl groups in CABs. MAE-CAB30 film exhibited more
hydroxyl groups than other CABs film as the stronger O–H stretching vibration in its
spectrum, ascribing to the lower substitution of hydroxyl groups.

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Fig. 4  FTIR spectra of a MAE-CAB30, b MAE-CAB60, c MAE-CAB90, and d LPE-CAB films

SEM analysis was applied to observe the CAB films, and the SEM micrographs
of MAE-CAB30, MAE-CAB60, MAE-CAB90, and LPE-CAB films are displayed
in Fig.  5. MAE-CAB30 film shows many cavities on the surface, but the MAE-
CAB60, MAE-CAB90, and LPE-CAB films are relatively compact without obvi-
ous pores or cavities. Moreover, the surface of MAE-CAB60 and LPE-CAB films
is more homogeneous and smooth than the other two films, ascribing to the suit-
able hydroxyl content and molecular chain length. The MAE-CAB30 with a higher
hydroxyl content led to the formation of inter- and intramolecular hydrogen bonds
during the preparation process of film, which caused poor dispersion in solvent and
poor interfacial adhesion between CAB and substrate. As subjected for longer mill-
ing time, esterified cellulose was degraded to many smaller molecules, which were
easy to agglomerate, and so MAE-CAB90 film was rougher than MAE-CAB60 and
LPE-CAB films.
In general, the transparency of cellulose esters films is related to the state of dis-
persion in solvents or substrates, which may affect the technologically important
qualities of cellulose esters. The transparency of MAE-CAB30, MAE-CAB60,
MAE-CAB90, and LPE-CAB films was determined to be 83.9%, 92.7%, 87.9%,
and 93.6%, respectively. It is clearly showed that the transparency of MAE-CAB60
and LPE-CAB films was higher than that of MAE-CAB30 and MAE-CAB90 films,
which was consistent with the result of SEM analysis. The chemical substitution of

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Fig. 5  SEM micrographs of a MAE-CAB30, b MAE-CAB60, c MAE-CAB90, and d LPE-CAB films

hydroxyl groups by acetyl and butyryl groups destroyed the ordered crystal structure
of cellulose and improved its solubility, and higher DS led to better solubility in
organic solutions. In addition, CAB molecules with suitable molar mass possessed
good dispersibility in solution and substrate. As a result, the films prepared from
MAE-CAB60 and LPE-CAB with better solubility and dispersibility presented bet-
ter light transmittance.

Surface and wear characteristics of CAB/pearlescent coating films

CAB has played an important role in solvent-borne coatings for a long time. For the
use of CAB as major additive or film-former, different coating applications require
different properties [3]. It is important to determine the relationships between the
properties of CAB and the performances of CAB-based coating films. Therefore, the
appearance, glossiness, rub resistance, and ethanol resistance of CAB/pearlescent
coating films were investigated to obtain the effect of preparation technology and
properties of CAB on the surface and wear characteristics of CAB-based coating
films.
Figure 6 presents the pictures of the appearance of different CAB/pearlescent
coating films, and their glossiness is shown in Table  3. Apparently, the MAE-
CAB30/pearlescent coating film shows the worst color uniformity and glossi-
ness, ascribing to the poor dispersion of pearlescent powders in CAB-based

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Fig. 6  Pictures of the appearance of a MAE-CAB30/pearlescent, b MAE-CAB60/pearlescent, c MAE-

CAB90/pearlescent, and d LPE-CAB/pearlescent coating films

Table 3  Glossiness, rub resistance, and ethanol resistance of different CAB/pearlescent coating films
Sample Glossiness (Gs) Rub resistance (friction Ethanol resistance
times) (friction times)

MAE-CAB30 69 ± 2 64 ± 2 21 ± 3

MAE-CAB60 81 ± 4 89 ± 5 23 ± 2
MAE-CAB90 78 ± 3 73 ± 4 22 ± 2
LPE-CAB 84 ± 2 92 ± 2 22 ± 3

film-forming solution [27]. The surface of pearlescent powders was coated

on some strong polar ­TiO2 particles, which could adsorb water molecules and
make the polarization of water molecules to form surface hydroxyl groups [28].
These hydroxyl groups were easy to form hydrogen bonds with the hydroxyl
groups of CAB. When the hydrogen bonding force exceeded the force of ori-
entation arrangement of pearlescent powders by CAB, the pearlescent powders
could congregate, leading to the non-uniformity of glossiness and the uneven-
ness of surface. Clearly, the appearance of MAE-CAB60, MAE-CAB90, and
LPE-CAB/pearlescent coating films was relatively more uniform and smooth,
and the glossiness was also better. Moreover, among these three coating films,
the MAE-CAB60 and LPE-CAB coating films exhibit similar appearance and the
LPE-CAB coating film shows the best glossiness. The CAB with higher molar
mass possesses better film-forming properties, contributing to better interfacial
adhesion between CAB and pearlescent powders. Therefore, the CAB with suit-
able DS value and molecular chain length is reasonable to prepare the coating
film with desired appearance and glossiness.
Rub resistance and ethanol resistance are crucial indexes for evaluating the
performances of coating films. Table  3 presents the rub resistance and ethanol

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resistance of different CAB/pearlescent coating films. Rub resistance is the com-

prehensive reflection of hardness, adhesion, and cohesion, which are related to the
properties of film-former materials and substrate. With the increase in ­DST and
­DSB of CAB, the introduction of acyls, especially the low polar butyryl groups,
was beneficial to decrease the interaction between cellulose molecules and reduce
the internal stress of the coating film, thereby enhancing the adhesion between
CAB/pearlescent coating film and the substrate. As a result, the rub resistance
of MAE-CAB30/pearlescent coating film was the worst among these four coat-
ing films. Moreover, the chemical resistance and hardness decreased with the
increase in butyryl substitution in CAB, and the higher molar mass of CAB led
to better interfacial adhesion among CAB, pearlescent powders, and substrate,
contributing to that the rub resistance of MAE-CAB60-based coating film was
slightly worse than that of the LPE-CAB-based coating film. The determination
of ethanol resistance of CAB/pearlescent coating film is to investigate the interfa-
cial adhesion between the coating film and substrate and the compatibility among
pearlescent powders, CAB, film-forming additive, and solvent. It shows that all
of the four CAB-based coating films had good ethanol resistance, and there was
no obvious difference between these coating films, indicating that both MAE-
and LPE-prepared CABs could provide satisfied properties of the coating film to
resist the erosion of alcohol.

Conclusion

CAB was successfully prepared by an unconventional MAE technology, which com-

bined MA and esterification in a stirring ball mill, avoiding a separate process of pre-
treatment and improving the production efficiency. Comparing the XRD and GPC
analyses of the MAE- and LPE-prepared CABs, the results showed that their molecular
structure and molar mass were dissimilar, ascribing to the different reaction systems
and characteristics. The surface characteristics of CAB films and the surface and wear
characteristics of CAB/pearlescent coating films indicated that the performances of the
films based on MAE-prepared CAB were similar to those based on LPE-prepared CAB
with the same reaction time. Consequently, CAB is feasible to be produced by this sim-
ple, environmentally friendly, and efficient MAE technology, and the desired properties
of CAB can be obtained by further optimizing the process conditions.

Acknowledgements  This research was supported by National Natural Science Foundation of China (Nos.
51463003 and 21666005), Guangxi Natural Science Foundation of China (No. 2017GXNSFEA198001),
Guangxi Science and Technology Plan Project of China (No. 2016AB12018), Guangxi Distinguished
Experts Special Foundation of China, and the Scientific Research Foundation of Guangxi University
(Grant No. XJPZ160713).

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