Colloid and Polymer Science

https://doi.org/10.1007/s00396-018-4389-5

ORIGINAL CONTRIBUTION

Biodegradable multiblock copolymers containing

poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)], poly(ε-caprolactone),
and polyhedral oligomeric silsesquioxane: synthesis, characterization,
and tensile property
Sainan Xia 1 & Ying Shen 1 & Yuqi Zhou 1 & Pengfei Yao 1 & Qingsheng Liu 1,2,3 & Bingyao Deng 1

Received: 10 December 2017 / Revised: 17 June 2018 / Accepted: 24 July 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Biodegradable multiblock copolymers based on poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV), poly(ε-
caprolactone) (PCL), and polyhedral oligomeric silsesquioxane (POSS) were synthesized by one-step copolymerization with
1,6-hexamethylene diisocyanate (HDI) as a coupling agent. The chemical structures, molecular weight, and polydispersity index
of the PHBV/PCL/POSS multiblock copolymers were confirmed by 1H NMR, FTIR, and gel permeation chromatography
(GPC). XRD analysis illustrated that PHBV and POSS blocks in multiblock copolymers with high content of PHBV and
POSS could crystallize to form separate crystalline phases. DSC analysis indicated that the mutual interference of crystallization
of PHBV, PCL, and POSS blocks existed. Compared with the crystallinity of PHBV-diol and original PHBV, the crystallinity of
PHBV block decreased from 54.8 (original PHBV) and 49.5 (PHBV-diol) to 25.5%. TG measurement revealed that thermal
degradation of the multiblock copolymers proceeded by a four-step degradation process and the thermal degradation behavior of
PHBV block was similar to that of the original PHBV. The melt processing window of multiblock copolymers was much wider
than that of the original PHBV. The results of tensile testing showed that the tensile strength at break of the fibrous membranes of
multiblock copolymers increased by 37.5% from 0.8 to 1.1 MPa and the elongation at break reached 307.8%.

Keywords Poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV) . Poly(ε-caprolactone) (PCL) . Polyhedral oligomeric

silsesquioxane (POSS) . Multiblock copolymers

Introduction and energy reserve from agriculture feedstocks such as sugars

and plant oils under unbalanced growth conditions [1, 2].
Poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV) is a Moreover, PHBV behaves similarly to conventional
biodegradable, biocompatible, and thermoplastic polyester syn- petroleum-derived thermoplastics such as polypropylene (PP)
thesized by various microorganisms as an intracellular carbon [3, 4]. PHBV has recently attracted much public and industrial
interest as substitute of the fossils fuels, which has been evalu-
ated for a variety of applications, including environmentally
* Qingsheng Liu friendly materials and biomedical materials [3, 4]. However,
lqs_1980@hotmail.com
PHBV suffers from its high crystallinity, narrow melt process-
* Bingyao Deng ing window because of a high melting temperature and low
bydeng168@163.com
thermal degradation temperature, and brittleness. These short-
1 comings have impeded use of PHBV in many plastics and
Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan
University, Wuxi 214122, China biomedical materials [5]. Some researches on modification of
2 PHBV have been conducted, including physical blending and
Key Laboratory of Pulp and Paper Science & Technology of Ministry
of Education/Shandong Province, Qilu University of Technology, chemical copolymerization, to overcome its shortcomings.
Jinan 250353, China Physical blending is a simple way of acquiring new materials
3
The School of Materials, The University of Manchester, with improved properties. The second components blended
Manchester, UK with PHBV included nanoparticles, polymers, and small

molecules [5]. Unfortunately, physical blending does not often
improve effectively the physical properties of PHBV [5, 6].
Block copolymerization is one of the effective ap-
proaches to modify PHBV. Several biodegradable polymers
have been introduced into PHBV or PHB backbone by
block copolymerization, such as poly(ε-caprolactone)
(PCL) [7–9], poly(ethylene glycol) (PEG) [2, 5, 8], poly(-
ethylene oxide) (PEO) [10], and polylactide (PLA) [11, 12].
Among them, PCL is a kind of biodegradable, biocompat-
ible, non-toxic, and flexible polymer with a melting point of
about 60 °C and a low glass transition temperature of about
− 60 °C [7, 13]. Incorporation of PCL soft block into PHBV
chains can enhance toughness of PHBV significantly,
broaden the melt processing window, and influence the
crystallization behavior due to mutual interference between
PHBV and PCL blocks [7]. Hirt et al. [9] and Saad et al [14]
synthesized polyurethane block copolymers by coupling
reaction using PHBV or polyhydroxybutyrate (PHB) as
hard block, and PCL as soft block. The obtained copoly-
mers were ductile plastics, exhibiting much higher elonga-
tion at break than that of the original PHBVor PHB. Saad et
al. [14] found the crystallization of PHB in the copolymers
was restricted by PCL block and the rate of the non-
isothermal crystallization of PHB block was lower than that
of the corresponding homopolymer. In our previous studies
[7, 15], the block copolymers containing PCL and PHBV
units also were synthesized by coupling reaction. The crys-
tallization competition between PCL and PHBV blocks was
observed. Chen et al. [13] prepared PHB/PCL block copol-
ymers by transesterification and discovered that the melting
temperature of PHB blocks in the block copolymers shifted
to lower temperature as the PCL content increased.
Introduction of soft block into the PHBV backbone can
lead to a significant increase in some properties, particular-
ly elongation at break [14]. However, it is possible that the
tensile strength of the block copolymers decreases with the
increase of PCL soft block content. The polyhedral oligo-
meric silsesquioxane (POSS) itself is an organic-inorganic
hybrid material. A typical POSS molecule possesses an
inorganic silica-like core (Si8O12), which is surrounded by
a shell of eight organic-reactive or organic-non-reactive
Fig. 1 Schematic diagram of the
electrospinning device
Colloid Polym Sci
corner groups [16–18]. The reactive groups such as amino
and hydroxyl are able to introduce POSS into the polymer
matrix by covalent connection. According to previous re-
ports [19–21], inclusion of inorganic POSS nanocage with-
in the matrix can improve the tensile strength; besides,
POSS can influence crystallization rate and the crystallinity
of the matrix. Therefore, here, POSS also was introduced to
PHBV/PCL block copolymers. PHBV/PCL/POSS
multiblock copolymers were synthesized by one-step copo-
lymerization with 1,6-hexamethylene diisocyanate (HDI)
as a coupling agent. Chemical structures, molecular weight,
and polydispersity index of the copolymers were character-
ized by proton nuclear magnetic resonance ( 1H NMR),
Fourier transform infrared (FTIR), and gel permeation
chromatography (GPC). The crystallization and melting be-
haviors of the copolymers were analyzed by DSC. The
thermal degradation behavior of the copolymers was stud-
ied by TG. In addition, the copolymer with a large molec-
ular weight was selected to prepare fibrous membranes by
electrospinning and the mechanical properties were
investigated.
Materials and methods
Materials
PHBV with about 2 mol% 3-hydroxyvalerate (HV) was pur-
chased from Tianan Biologic Material Co., Ltd. (Ningbo,
China). The number-average molecular weight (Mn) and
weight-average molecular weight (Mw) of PHBV are 1.57 × 105
and 2.61 × 105, respectively. TMP diollsobutyl-POSS was ob-
tained from Hybrid Plastics Co. (Hattiesburg, MS, USA). PCL-
diol with Mn of 2000 and HDI (99%) were supplied from Acros
Organics (Geel, Belgium). Dibutyltin dilaurate (> 90%), diglyme,
1,2-dichloroethane, ethanol (> 99.7%), chloroform (LC grade),
and deuterated chloroform were purchased from Guoyao Group
Chemical Reagent Co., Ltd. (Shanghai, China). 1,2-
Dichloroethane was distilled over anhydrous calcium chloride
(CaCl2) before use, while other reagents were used as received.
Colloid Polym Sci

Synthesis of telechelic hydroxylated PHBV

(PHBV-diol)

Telechelic hydroxylated PHBV (PHBV-diol) was prepared by

the method described previously [7, 22]. Original PHBV
(30 g) and ethylene glycol (60 mL) were heated in diglyme
(300 mL) at 140 °C under a nitrogen atmosphere in a 500-mL
four-necked flash with a mechanical stirrer. The reaction was
started with the addition of dibutyltin dilaurate (0.3 g) as a
catalyst. After 7.5 h, the products were precipitated from
diglyme using ethanol and then separated by filtration follow-
ed by drying in a vacuum oven at 60 °C for 48 h. The Mn of
PHBV-diol, measured by GPC, was 1.92 × 103.

Synthesis of PHBV/PCL/POSS multiblock copolymers

PHBV/PCL/POSS multiblock copolymers were synthe-
sized by one-step copolymerization with HDI as a cou-
pling agent. PHBV-diol (9.6 g) and a mixture of POSS
and PCL (10 g) were added into a 250-mL four-necked
flask containing the dry 1,2-dichloroethane (150 mL) un-
der a nitrogen atmosphere. Any trace water of the stirred
mixture was removed through azeotropic distillation, with
only 1,2-dichloroethane (50 mL) being left in the flask.
After the flask was cooled to 75 °C, a certain volume of
HDI and ten drops of dibutyltin dilaurate were added se-
quentially. The mole ratio of NCO and OH groups is 1.2:1.
The reaction mixture was stirred at 75 °C under dried
nitrogen for 16 h. After 16 h, the resultant products were
precipitated in the mixture of ethanol and deionized water
(30/70). The precipitated PHBV/PCL/POSS multiblock
copolymers were separated by filtration followed by
Fig. 3 GPC traces of PHBV/PCL/POSS multiblock copolymers and
PHBV-diol
drying in a vacuum oven at 50 °C for 48 h. The PHBV/
PCL/POSS multiblock copolymers with different contents
of POSS and PCL blocks were obtained by adjusting the
molar ratio of POSS to PCL.
Preparation of fibrous membrane
Fibrous membranes of the investigated PHBV/PCL/POSS
multiblock copolymer and original PHBV were prepared by
solution electrospinning. The schematic diagram of the
electrospinning device is shown in Fig. 1. PHBV/PCL/POSS
multiblock copolymer solution in chloroform was prepared
with the concentration of 20 wt%, and delivered by a syringe
pump with the flow rate of 1.5 mL/h. The distance between

Fig. 2 Synthesis process of PHBV/PCL/POSS multiblock copolymers

 Colloid Polym Sci

Table 1 The molecular was recorded between 4000 and 400 cm−1 with 16 scans at a
weight and Samples Mn × 104 Mw × 104 PDI
resolution of 4 cm−1 at room temperature.
polydispersity index
(PDI) of PHBV/PCL/ PPP20K 2.02 2.43 1.21
POSS multiblock PPP37K 3.73 4.38 1.17
copolymers Proton nuclear magnetic resonance
PPP52K 5.18 6.29 1.21
1
H NMR spectra of the samples were obtained on Bruker
Advance III 400 MHz system in 5-mm tubes at room temper-
needle tip and collection drum was 15 cm and positive voltage
ature. Each sample was dissolved in CDCl3 with a concentra-
applied to the solution was 15 kV. In addition, neat PHBV
tion of about 60 mg/mL.
(4 wt%) solution was electrospun with the same spinning pro-
cess. The obtained fibrous membranes were dried in a vacuum
oven at 50 °C for 48 h to constant weight. X-ray diffraction

The crystalline structures of the samples were characterized by

Gel permeation chromatography
The molecular weight and polydispersity index (PDI) of the
samples were characterized by the Wyatt WH2-08GPC sys-
tem. Chloroform was used as the eluent with a flow rate of
1.0 mL/min at 35 °C. Each sample was dissolved in chloro-
form at a concentration of 5.0 mg/mL.
Bruker D8 diffraction system. This equipment employed Cu
Kα (λ = 1.5406 Å) as radiation source and was operated at
40 kV and 40 mA. Scans were carried out in the 2θ range of
5–60° at 4°/min.
Differential scanning calorimeter

The melting and crystallization behaviors of the samples were

Fourier transform infrared spectroscopy studied by DSC Q200 under nitrogen atmosphere. The sam-
ples (4–6 mg) were heated from room temperature to 200 °C
FTIR spectra of the samples were acquired by employing (100 °C for PCL) at 30 °C/min and kept at the temperature for
Nicolet iS10 FTIR with an ATR accessory. Each spectrum 3 min to erase thermal history, and subsequently cooled to −

Fig. 4 1H NMR spectrum of

PHBV/PCL/POSS multiblock
copolymer (PPP20K)
Colloid Polym Sci

Table 2 Chemical composition of PHBV/PCL/POSS block hydroxylated PHBV (PHBV-diol) with relatively low molec-
copolymers
ular weight by transesterification with ethylene glycol. Then,
Samples PHBV (wt%) PCL (wt%) POSS (wt%) HDI (wt%) the PHBV/PCL/POSS multiblock copolymers are synthesized
with PHBV-diol as the hard segment, PCL-diol as the soft
PPP20K 42.9 25.4 21.6 10.1 segment, HDI as the coupling agent, and 1,2-dichloroethane
PPP37K 44.3 36.7 9.9 9.1 as the solvent in the presence of dibutyltin dilaurate as the
PPP52K 44.1 44.3 2.9 8.7 catalyst. The molecular weight and dispersity index of the
multiblock copolymers were characterized by GPC and the
results are listed in Fig. 3 and Table 1. The multiblock copol-
40 °C (0 °C for PHBV-diol, POSS, and PCL) at 10 °C/min and
ymers based on PHBV, POSS, and PCL are called PPP20K,
then heated to 200 °C (100 °C for PCL) at 10 °C/min.
PPP37K, and PPP52K, respectively, where the number re-
ferred to the Mn of the multiblock copolymers.
Thermogravimetric analysis The chemical structure of the PHBV/PCL/POSS
multiblock copolymers was characterized by 1H NMR. A typ-
Thermal degradation behaviors of the samples were investigated by ther- ical 1H NMR spectrum of PPP20K in CDCl3 is shown in
mogravimetric analysis (TGA) using TGR Q500. The samples (5–6 mg) Fig. 4. In Fig. 4, the signal at k (4.76 ppm) is related to –
were heated from 50 to 600 °C (500 °C for PCL) at the rate of 10 °C/min NH– of urethane linkage [8]. The resonances at b
in nitrogen atmosphere at a flow rate of 60 mL/min. (1.25 ppm), d+e (2.50 ppm), and c (5.22 ppm) are related to
PHBV block. The resonances at f (2.28 ppm) and j (4.04 ppm)
Tensile property of fibrous membrane are assigned to PCL block [23, 24]. The resonances at a
(0.083 ppm), r (0.57 ppm), t+u (0.92 ppm), and s
Tensile properties of the fibrous membranes were studied by a (1.82 ppm) are assigned to POSS block. The existence of
Shimadzu EZ-LX tensile testing machine. The dimension of the characteristic peak of PHBV block, PCL block, POSS block,
samples is 60 mm in length, 10 mm in width, and 61–124 μm in and urethane junction unit indicates that the PHBV/PCL/
thickness. Tests were carried out at a cross-head speed of 5 mm/ POSS multiblock copolymers are synthesized successfully.
min and gauge length of 40 mm at room temperature. For each From the 1H NMR spectra of the PHBV/PCL/POSS
sample, the test was repeated at least five times. multiblock copolymers, the molar content of PHBV, PCL,
and POSS blocks can be calculated. The results are shown
in Table 2. The content of PHBV block in the three multiblock
Results and discussion copolymers nearly keeps constant (42.9–44.1 wt%). The con-
tent of PCL blocks from PPP20K, PPP37K to PPP52K in-
Synthesis of PHBV/PCL/POSS multiblock copolymers creases while that of POSS blocks decreases. Tables 1 and 2
show that the molecular weight of the PHBV/PCL/POSS
The synthesis process of PHBV/PCL/POSS multiblock copol- multiblock copolymers decreases as POSS content increases,
ymers is shown in Fig. 2. The natural source PHBV with high probably due to the presence of bulk Si–O core of POSS and
molecular weight is first converted into telechelic the polarity of oxygen of POSS cage [25].

Fig. 5 FTIR spectra of PHBV/PCL/POSS multiblock copolymers and their corresponding precursors. a 4000–500 cm−1. b 1300–600 cm−1

Fig. 6 XRD traces of PHBV/PCL/POSS multiblock copolymers and
their corresponding precursors
FTIR also was used to characterize the chemical structures
of PHBV/PCL/POSS multiblock copolymers. The FTIR spec-
tra of the PHBV/PCL/POSS multiblock copolymers and their
corresponding precursors are shown in Fig. 5. The bands at
2934 cm−1 and 2865 cm−1 are assigned to CH2 stretching
vibration. The sharp peak at 1723 cm−1 is attributed to C=O
stretching vibration of PHBV and PCL blocks [4]. The shoul-
der peak around 1121 cm −1 and the band at 777 cm −1
corresponded to asymmetric stretching of Si–O–Si and ab-
sorption peak of Si–C of POSS block, respectively [26, 27].
In contrast to spectra of the precursors, two new characteristic
peaks at 3367 cm−1 and 1529 cm−1 in the PHBV/PCL/POSS
multiblock copolymers are observed. They are assigned to N–
H stretch in urethane linkage which results from the reaction
between hydroxyl groups of the precursors and isocyanate
groups of HDI [5, 8]. These results further confirm the forma-
tion of the PHBV/PCL/POSS multiblock copolymers.
Fig. 7 DSC curves of PHBV/PCL/POSS multiblock copolymers and their corresponding precursors. a Cooling process. b Second heating process
Colloid Polym Sci
Crystal structures
The crystal structures of PHBV/PCL/POSS multiblock copol-
ymers and the corresponding precursors were studied by XRD
and the diffraction patterns are presented in Fig. 6. The strong
characteristic refraction peaks at 2θ value of 13.5°and 17.0° of
PHBV-diol corresponded to (020) and (110) crystalline
planes, respectively [7]. The main characteristic refraction
peaks of PCL-diol appear at 21.5° and 23.9°, which
corresponded to (110) and (200) crystalline planes, respective-
ly. The characteristic reflection peaks of POSS appear at
8.12°, 10.8°, and 18.8°, corresponding to (101), (110), and
(122) crystalline planes, respectively [28]. The diffraction pat-
terns in Fig. 6 show that the PHBV block formed a separate
crystalline phase in all the PHBV/PCL/POSS multiblock co-
polymers. In the PPP52K with the low POSS content of
2.9 wt%, the crystals of POSS block are not observed while
in the PPP20K and PPP37K with the relatively high POSS
content of 21.6 and 9.9 wt%, the crystals of POSS block
appear. However, the characteristic peaks of the PCL crystals
are not detected in the diffraction patterns of all the PHBV/
PCL/POSS multiblock copolymers. This indicates that the
crystallization of PCL block is restricted significantly by other
blocks in the multiblock copolymers.
Melting and crystallization behaviors
of PHBV/PCL/POSS multiblock copolymers
The melting and crystallization behaviors of the PHBV/PCL/
POSS multiblock copolymers and corresponding precursors
were studied by DSC. The curves are given in Fig. 7 and the
parameters are listed in Table 3. Figure 7a shows the DSC
cooling curves at 10 °C/min. For PPP20K and PPP37K, the
content of PCL block is relatively low and that of POSS block
is relatively high. No melt-crystallization peaks of PHBV and
Colloid Polym Sci

Table 3 The parameters of

crystallization and melting Samples Tm (°C) Tmc (°C) Tcc (°C) χc (%)
behaviors of PHBV/PCL/POSS
block copolymers and their PHBV PCL POSS PHBV PCL POSS PHBV PCL PHBV
corresponding precursors
Original PHBV 170.0 – – 89.9 – – – – 54.8
PHBV-diol 147.8 – – 63.0 – – – – 49.5
PCL – 47.2 – – 24.6 – – – –
POSS – – 123.6 – – 108.2 – – –
PPP20K 147.8 – 113.6 – – 105.9 41.4 – 25.5
PPP37K 143.7 43.3 110.9 – – 97.0 37.7 1.7 26.9
PPP52K 142.8 42.3 – – −12.1 – 37.1 −6.3 31.9

PCL blocks in the DSC cooling curves of PPP20K and
PPP37K can be observed. Only a small melt-crystallization
peak around 100 °C appears, which corresponded to POSS
block. For PPP52K, the content of PCL block is relatively
high (44.3 wt%) and that of POSS block (2.9 wt%) is relative-
ly low. No melt-crystallization peaks of PHBV and POSS
blocks in the DSC cooling curve of PPP52K can be observed.
Only a small melt-crystallization peak at − 12.1 °C appears,
which is attributed to the crystallization of PCL block. It is
known from the above analysis that the PHBV block of the
three PHBV/PCL/POSS multiblock copolymers cannot crys-
tallize during cooling process and the crystallization tempera-
tures of POSS and PCL blocks are lower than those of their
corresponding precursors, which indicates that crystallization
of the three blocks is hampered mutually.
Figure 7b shows the second heating DSC curves of PHBV/
PCL/POSS multiblock copolymers and corresponding precur-
sors. The exothermic peaks in the relatively low temperature
district from − 20 to 10 °C in the DSC heating curves of the
PHBV/PCL/POSS multiblock copolymers are attributed to
the cold-crystallization of PCL blocks. The exothermic and
endothermic peaks in the middle temperature district from
20 to 60 °C corresponded to the cold-crystallization of
PHBV blocks and the melting of PCL blocks, respectively.
The cold-crystallization peak of PHBV block and the melting
peak of PCL block are partly overlapped. For PPP20K, the
cold-crystallization and melting peaks of PCL block cannot be
observed while a melting peak at 113.6 °C of POSS block
appears. The endothermic peaks at 120–160 °C corresponded
to the melting of PHBV blocks. The melting temperature
(Tms) of PHBV blocks is about 20 °C lower than that of the
original PHBV. In addition, the Tms of PHBV blocks de-
creases with the increase of PCL content.
The relative crystallinity (χc) of PHBV block in the PHBV/
PCL/POSS multiblock copolymers and corresponding precur-
sors is determined using the following equation:
ΔH m −ΔH cc
χc ¼  100% ð1Þ
w  ΔH 0m
where ΔHm is the melting enthalpy of PHBV component, ΔHcc
is the cold-crystallization enthalpy of the PHBV component.
ΔHm0 is the melting enthalpy of the perfectly crystallized
PHBV, which is approximately equal to 146 J/g [8]. The w is
the weight fraction of PHBV block in the PHBV/PCL/POSS
multiblock copolymers. The calculated results are listed in
Table 3. In the PHBV/PCL/POSS multiblock copolymers, the

Fig. 8 TG (a) and DTG (b) curves of PHBV/PCL/POSS block copolymers and their corresponding precursors
 Colloid Polym Sci

Table 4 The parameters of thermal degradation behaviors of PHBV/ PHBV/PCL/POSS multiblock copolymers undergo a four-
PCL/POSS block copolymers and their corresponding precursors
step degradation process. Based on thermal degradation be-
Samples T5% (°C) Tmax (°C) Tf (°C) haviors of the corresponding precursors, the probable degra-
dation process of PHBV/PCL/POSS multiblock copolymers
Original PHBV 265.6 284.1 290.7 is as follows. The first step is assigned to the degradation of
PHBV-diol 262.7 289.7 301.4 PHBV block with Tmax of around 275.2–276.8 °C, mainly due
PCL 275.0 322.1 337.9 to a non-radical random chain scission [29]. The second step is
POSS 1st 276.2 296.7 535.0 attributed to the degradation of PCL block with Tmax of 292.7–
2nd 448.2
300.7 °C, mainly due to statistical rupture of the polyester
3rd 507.0
chains [30]. The third step with Tmax of 342.0–365.0 °C and
PPP20K 1st 257.5 275.2 517.2
fourth step with Tmax of 427.1–455.5 °C corresponded to vol-
2nd 292.7
atilization and thermal cracking of chemical bonds (Si–C) of
3rd 342.0
POSS block, respectively [31].
4th 429.4
It can be seen from Fig. 8 and Table 4 that PCL and POSS
PPP37K 1st 259.7 275.8 512.4
2nd 299.8 have better thermal stability than PHBV. However, thermal
3rd 365.0 stability of the PHBV/PCL/POSS multiblock copolymers is
4th 455.5
not improved by incorporation of POSS and PCL blocks to
PPP52K 1st 257.1 276.8 441.9
PHBV. T5% and Tmax that corresponded to PHBV block of the
2nd 300.7 PHBV/PCL/POSS multiblock copolymers are a bit lower than
3rd 361.1 those of PHBV homopolymer, and the values of the T5% and
4th 427.1 Tmax do not almost change as the content of POSS and PCL
changes. It is noteworthy that compared with original PHBV,
melt processing window of multiblock copolymers has been
crystallinity of PHBV block is lower than that of the original enhanced significantly because of the decrease of the melting
PHBV and varies with the content of PCL and POSS blocks. temperature and constant degradation temperature of PHBV
The probable reasons are as follows. Firstly, incorporation of block.
POSS into the PHBV backbone disturbs the regularity of
PHBV chains. Secondly, the mutual interference of the three
blocks results in the decrease of crystallinity of the PHBV block. Electrospun fibrous membranes

PPP52K with a large molecular weight was selected as raw

Thermal degradation behaviors
Thermal degradation behaviors of the PHBV/PCL/POSS
multiblock copolymers were characterized by TG. Figure 8
presents TG and differential thermogravimetry (DTG) curves
of PHBV/PCL/POSS multiblock copolymers and correspond-
ing precursors. The parameters of thermal degradation behav-
ior including the temperature at 5% weight loss (T5%), the
temperature corresponding to the maximum degradation rate
(Tmax), and the complete decomposition temperature (Tf) are
summarized in Table 4. The thermal degradation of PHBV-
diol is a one-step process with Tmax of 289.7 °C while the
materials to prepare fibrous membranes. Figure 9 shows SEM
photographs of fibrous membranes of PPP52K and original
PHBV. Figure 9 illustrates that the fiber surface of original
PHBV fibrous membrane is rough while that of PPP52K fi-
brous membranes is smooth. In addition, some fibers break in
the original PHBV fibrous membrane while the broken fibers
in PPP52K fibrous membrane cannot be observed.
Figure 10 shows DSC curves from − 80 to 190 °C of fi-
brous membranes of PPP52K and original PHBV at the
heating rate of 10 °C/min. The crystallinities of original
PHBV fibrous membrane and the PHBV block in PPP52K
fibrous membrane are calculated by DSC curves, which are

Fig. 9 SEM photographs of

original PHBV (a) and PPP52K
(b) fibrous membranes
Colloid Polym Sci

Table 5 Tensile properties of original PHBV and PPP52K fibrous

membranes

Sample Tensile at CV (%) Elongation CV (%)

break (MPa) at break (%)

Original PHBV 0.8 14.2 5.2 4.2

PPP52K 1.1 24.0 307.8 23.8

Figure 11 and Table 5 show that the fibrous membrane of

Fig. 10 DSC heating curves of original PHBV and PPP52K fibrous
membranes
57.1 and 37.9%, respectively. The crystallinity of the PHBV
block in PPP52K fibrous membrane is much lower than that
of the original PHBV fibrous membrane.
Tensile properties of the fibrous membranes were investi-
gated. The stress-strain curves for fibrous membranes of
PPP52K and original PHBV are shown in Fig. 11 and the
results of tensile properties are presented in Table 5.
the original PHBV ruptures with low elongation at break
(5.2%). No yield point can be observed in the stress-strain
curve and the fibrous membrane of the original PHBV has a
high initial modulus. The fibrous membrane of the original
PHBV presents a typical brittle fracture. Compared with fi-
brous membrane of the original PHBV, the stress-strain curves
of PPP52K fibrous membrane exhibit a low initial modulus
and a high elongation at break (307.8%). During the tensile
procedure, an obvious yielding phenomenon can be observed
and the elongated PPP52K fibrous membrane after fracture
shrinks gradually. The PPP52K fibrous membrane presents a
typical ductile fracture. Figure 11 and Table 5 show that the
tensile strength of PPP52K fibrous membrane increases by
37.5% in comparison with that of the original PHBV fibrous
membrane, probably due to the nanoscale reinforcement of
POSS cage in the PHBV/PCL/POSS multiblock copolymers

Fig. 11 Tensile stress-strain curves of original PHBV (a) and PPP52K (b) fibrous membranes

[18]. The enhancement of toughness of PPP52K fibrous mem-
brane is attributed mainly to the decrease of crystallinity be-
cause of introduction of PCL and POSS.
Conclusions
The PHBV/PCL/POSS multiblock copolymers based on
PHBV, PCL, and POSS were synthesized by the coupling
reaction. 1H NMR and FTIR verified that the PHBV/PCL/
POSS multiblock copolymers were synthesized successfully.
GPC results showed that the molecular weight decreased with
the increase of POSS content. DSC analysis indicated that the
crystallization of PHBV, PCL, and POSS blocks was restrict-
ed mutually. The melting temperature of PHBV block in the
PHBV/PCL/POSS multiblock copolymers was about 20 °C
lower than that of the original PHBV and decreased as the
content of PCL block increased. The crystallinity of the orig-
inal PHBV was 54.8% while that of PHBV block in PPP20K
was only 25.5%. In comparison with the original PHBV, the
thermal stability of the PHBV/PCL/POSS multiblock copol-
ymers was not improved and the degradation process took
place via a four-step degradation process. In addition, the
PHBV/PCL/POSS multiblock copolymer with a large molec-
ular weight (PPP52K) was selected to prepare fibrous mem-
branes by electrospinning and the results of tensile properties
showed that tensile strength and elongation at break of the
fibrous membrane of the PHBV/PCL/POSS multiblock co-
polymer were higher than those of the original PHBV fibrous
membranes. Especially, the elongation at break of fibrous
membrane of the PHBV/PCL/POSS multiblock copolymer
reached 307.8%.
Funding information This research was supported by the National
Natural Science Foundation of China (51403084), the Key Research
and Development Program (Industry Forward and Common Key
Technology) Project of Suqian City (H201708), the Jiangsu Overseas
Research Training Program for University Prominent Young and
Middle-Aged Teachers and Presidents, the Natural Science Foundation
of Jiangsu Province (BK20130142), the Foundation of Key Laboratory of
Pulp and Paper Science and Technology of Ministry of Education/
Shandong Province of China (KF201714), the 111 Project (B17021),
the Priority Academic Program Development of Jiangsu Higher
Education Institutions, and the Top-notch Academic Programs Project
of Jiangsu Higher Education Institutions (PPZY2015B147).
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
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