polymers

Article
Synthesis and Properties of Moisture-Cured Reactive
Polyurethane Containing Castor Oil and
Oxime Compounds
Zheng-Ying Wu
Footwear & Recreation Technology Research Institute, No. 11, 8th Rd., Industrial Park, Taichung 407, Taiwan;
wilsonwu389@hotmail.com or 0903@bestmotion.com




Received: 12 July 2020; Accepted: 14 August 2020; Published: 17 August 2020


Abstract: Reactive polyurethane hot-melt resin (moisture-cured reactive polyurethane, PUR)

could successfully be prepared from poly(tetramethylene ether) glycol (PTMG), castor oil and
dimethylglyoxime (DMG) by one or two-stage synthesis. Fourier-transform infrared spectroscopy
(FTIR) analysis showed that the synthesis resins belonged to NCO-capped castor oil-based
polyurethane. The thermal behaviors of the cured PUR were analyzed by differential scanning
calorimeter (DSC) and dynamic mechanical analyzer (DMA) instruments. The results showed that
the cured resin provided remeltable properties under the dosages of 3 wt% DMG. Furthermore,
the phenomenon could be proved by FTIR analysis according to the characteristic absorption peak of
NCO groups after the cured resin was heated. Comparing different syntheses, the resin prepared by
one-stage synthesis showed random distribution of DMG with PUR structure and that prepared by
two-stage synthesis had distribution of DMG with branching structure in the prepolymer. The former
obtained lower remeltable temperatures from 90 to 130 ◦ C than the latter temperatures, which had
temperatures above 125 ◦ C. The tensile test showed that all of the PUR films exhibited typical tough
behavior. Thus, the cured resin with DMG dosages of 3 wt% provided remeltable and mechanical
properties at the same time. Overall, the crosslinking density and numbers of dynamic bonds should
be kept in balance for preparation of remeltable PUR.

Keywords: castor oil; dimethylglyoxime; polyurethane; remeltable property; thermal property

1. Introduction
Reactive polyurethane hot-melt resin (moisture-cured reactive polyurethane, PUR) is a non-solvent
and NCO-capped prepolymer material. PUR is widely applied in films, foams, coatings and
adhesives [1,2]. When PUR is exposed in the surroundings, the irreversible or non-meltable chemical
crosslinking reaction goes through between the NCO of PUR and ambient moisture. Cross-linked
PUR has excellent physical properties and other characteristics (e.g., chemical resistance, hydrolysis
resistance and flexibility). However, the thermosets do not have reshaping, reprocessing or recycling
ability. Recently, the design of polymer networks faces great challenges related to friendly polymers
with excellent performance and recyclability. For this purpose, a large number of dynamic covalent
bonds have been introduced into polymer networks. For the development of repairable crosslinked
PUR the general method involves implanting dynamic bonds or redundant nucleophilic hydroxy
groups on demand [3].
Polyols are the main raw materials for synthesis of PUR and the other primary materials are
isocyanate compounds. All these materials are produced from petroleum-based compounds. To reduce
dependence on petroleum resources, among them, polyols are the most likely to be replaced by biomass
polyols derived from plants such as castor oil [4,5] and dimer acid-based derivatives [6]. Moreover,

Polymers 2020, 12, 1838; doi:10.3390/polym12081838 www.mdpi.com/journal/polymers

Polymers 2020, 12, 1838 2 of 9

CO2 -based polyols are another available resource [7]. Among them, castor oil (Ricinus communis,
ricinoleic acid, s12-hydroxy-9-cis-octadecenoic acid) has hydroxyl groups in the chain without further
derivatization, making it suitable for several applications in the synthesis of polyurethane [8–10].
In conclusion, the process of synthesizing PUR with castor oil and the properties of the remeltable
chemical crosslinking reaction are bound to be interesting subjects. Therefore, for the purpose of
simplifying the synthesis processes, we decided to prepare PUR containing castor oil and oxime
compounds by one or two-stage synthesis and to evaluate the properties of PUR under various
synthesis modes.

2. Materials and Methods

2.1. Materials
Poly(tetramethylene ether) glycol (PTMG, Mw = 1000), dimethylglyoxime (DMG), methylene
diphenyl diisocyanate (MDI-50, MDI, Wanhua Chemical Group Co., Ltd., Yantai, China), castor oil
(OH = 116.12, Young Sun Chemtrade Co., Ltd., Kaohsiung, Taiwan), dibutylamine (DBA) and
hydrochloric acid (HCl). All these chemicals were used without further purification.

2.2. Synthesis of Moisture-Cured Reactive Polyurethane

The moisture-cured reactive polyurethane (reactive polyurethane hot-melt resin; PUR) with the
formulations shown in Table 1 were prepared. All the polyols and DMG were heated in a vacuum oven
at 60 ◦ C until free of moisture. The polyols, PTMG and castor oil with weight of 100/20 were charged
into a four-neck glass reaction flask. The dosage of MDI was calculated by the ratio of NCOMDI to
OH(PTMG+Castor oil) in 2. Then, MDI weighing 63 g was added and polymerization was allowed to
proceed with mixing at 100 ◦ C under vacuum until the reaction was complete. The PUR product
was the control. For the one-stage synthesis, DMG was used as a chain extender with dosages of
1.5 wt% and 3 wt%, based on the total weights of polyols and MDI, respectively. The polyols and DMG
were added to the mix until the solution was homogeneous in the flask before polymerization. Then,
synthesis of PU occurred after the MDI was added. For the two-stage synthesis, DMG was added after
polymerization. The prepolymer reacted with the dosage of DMG. The resulting polymer was placed
in a container under a dry nitrogen headspace to prevent exposure to moisture.

Table 1. Basic properties of various PUR.

First-Step Second-Step Viscosity

NCO%
Synthesis Synthesis (ps/100 ◦ C)
Code of
Resins PTMG 1 Castor oil MDI 1,2 DMG 1,3 DMG 1,3
(g) (g) (g) (wt%) (wt%)
PUR 100 20 63 - - 5.73 71
PUR-I-1.5 100 20 63 1.5 - 4.60 150
PUR-I-3.0 100 20 63 3.0 - 3.48 252
PUR-II-1.5 100 20 63 - 1.5 4.56 181
PUR-II-3.0 100 20 63 - 3.0 3.41 320
1 PTMG: poly(tetramethylene ether) glycol (Mw = 1000); DMG: dimethylglyoxime; MDI: methylene diphenyl
diisocyanate. 2 Calculated by the ratio of NCOMDI to OH(PTMG+Castor oil) in 2. 3 Based on the total weights of polyols
and MDI.

2.3. Preparation of Cured Reactive Polyurethane Film

All the PURs were shaped in a Teflon-coating box (length 20 cm, width 8 cm) and cured at 25 ◦ C
and below 60% relative humidity (RH). The thickness of film was about 0.40–0.50 mm.
Polymers 2020, 12, 1838 3 of 9

2.4. Properties of Moisture-Cured Reactive Polyurethane

The viscosity of PUR was determined by a Brookfield viscometer (DV2T Viscometer, Brookfield,
Middleboro, MA, USA). The measurements were performed using a spindle of NO. 27 at 20 rpm under
100 ± 1 ◦ C by a heater. The NCO contents (NCO%) of PUR were determined according to ASTM D
2572-91. The resin was reacted with an excess of 0.5 N dibutylamine and then titrated with a standard
0.5 N HCl solution. The NCO values could be calculated.

2.5. FTIR Analysis

The infrared (IR) absorption spectra of the samples were measured using an FTIR spectrometer
(PerkinElmer Spectrum 100, Waltham, MA, USA). The test was carried out by the single reflectance
(single ATR) method and at the scanning range of 650–4000 cm−1 .

2.6. DSC Thermo-Analysis

The DSC thermo-analysis was carried out by a differential scanning calorimeter (PerkinElmer
DSC-7, Waltham, MA, USA) with the thermal-scanning method. The sample was heated from 25 to
180 ◦ C at a heating rate of 10 ◦ C/min. The variation in heat flow during the period of heat scanning
was detected and the relative thermal parameters were calculated.

2.7. DMA Thermo-Analysis

The dynamic mechanical analyzer (DMA) thermo-analysis was carried out by a dynamic
mechanical analyzer (Perkin-Elmer DMA 8000, Waltham, MA, USA). The thermal behavior of cured
resins was investigated by the thermal-scanning method. The sample was heated from −80 to 160 ◦ C
at a heating rate of 5 ◦ C/min and an oscillation frequency of 1.0 Hz by the tensile method.

2.8. TGA Thermo-Analysis

A thermal gravimetric analyzer (Perkin-Elmer Pyris 1 TGA-7, Waltham, MA, USA) was employed
to measure the thermal degradation of cured resins. It was conducted under a nitrogen atmosphere by
increasing the temperature from 50 to 700 ◦ C at a heating rate of 10 ◦ C/min.

2.9. Tensile Tests of Cured PUR Films

Tensile tests were carried out at 20 ◦ C and 65% RH using a tensile testing machine (Shimadzu EZ
Tester, Kyoto, Japan). The PUR films were conditioned for 48 h before the test. The sample was loaded
at a crosshead rate of 10 mm/min.

3. Results and Discussion

3.1. Properties of PUR

PUR containing castor oil and oxime compounds were prepared from mixtures of PTMG, castor
oil and MDI. The matrices of PUR were also implanted with DMG as an oxime compound by one
or two-stage synthesis. The reaction pathway and curing reaction of PUR containing castor oil and
DMG are shown in Figures 1 and 2, respectively. In the one-stage synthesis, the raw materials,
including PTMG, castor oil and DMG, reacted with MDI randomly under the condition of NCO/OH > 1.
After that, the resin became an NCO-capped polyurethane. In the two-stage synthesis, the prepolymer
synthesized from PTMG, castor oil and MDI first reacted with DMG. Basic properties of various PUR
are shown in Table 1. Because of the implantment of DMG as a chain extender in PUR, the resins had
less NCO groups and higher viscosity than the control. The viscosity of the resins increased when
increasing the dosages of DMG, especially under the dosages of 3 wt% by two-stage synthesis. It was
the presence of castor oil, due to its greater functionality, that led to significant branch structure in the
resins prepared by two-stage synthesis.
Polymers 2020, 12, x FOR PEER REVIEW 4 of 10

decomposed into NCO and OH groups. After that, the NCO groups generated would react with
moisture or DMG in the resin. Thus, it could have remeltable property due to dynamic covalent bonds
Polymers
in 2020, 12,
polymer 1838
networks [3]. For the melt bonding test, the two cured films containing DMG were4 of 9

overlapped with the treatment of hot press. They could be bonded by heating.

HO NCO NCO
O R R
+ N N OH +
H XOH OH + HO R
OH

PTMG DMG Castor oil MDI

O NH NCO
O
O O R R O
N NH NH O
NCO NH O NH O N
O NH R
O O NCO
X O NH
O
m n O
Z

O OH
R-OH:

NCO NCO
O R R
H OH + HO R OH +
X
OH

PTMG Castor oil MDI

O NH NCO
O R
O R O
NCO NH O O
NH NH R
O
X NCO
O NH
O HO
m
N N O
n
OH

DMG
O
O O
NH O O
NCO O NH O
R NH O N NH
NH O NH NH O N O
O O
R NH
O R
R O n m O
O
NH
m O NH NCO
NH O
O X O R
NCO R O
NCO
NH
O
n X m
O

O OH
R-OH:

Figure 1. Reaction pathway of PUR containing castor oil and oxime compounds with various
Figure
Polymers 12,Reaction
2020,1. pathway
x FOR PEER of PUR containing castor oil and oxime compounds with various syntheses.5 of 10
REVIEW
syntheses.

Figure 2. Curing, remeltable reaction and remeltable bonding of PUR containing castor oil and DMG.
Figure 2. Curing, remeltable reaction and remeltable bonding of PUR containing castor oil and DMG.

3.2. FTIR of PUR

In this study, PTMG, castor oil and DMG were employed to react with the excess of MDI to
prepare NCO-capped polyurethane. FTIR spectra of the raw materials and PUR are shown in Figure
3. As for the characteristic absorption peaks of PTMG, they were at 3200–3500 cm−1 for O–H stretching
−1
Polymers 2020, 12, 1838 5 of 9

Figure 2 showed that the implantment of DMG in PUR became the sites of dynamic covalent
bonds. As the cured
Figure PUR
2. Curing, containing
remeltable DMG
reaction andwas heated,
remeltable the urethane
bonding structures
of PUR containing from
castor oilDMG decomposed
and DMG.
into NCO and OH groups. After that, the NCO groups generated would react with moisture or DMG
in the
3.2.resin.
FTIR ofThus,
PUR it could have remeltable property due to dynamic covalent bonds in polymer
networks [3]. For the PTMG,
In this study, melt bonding test,
castor oil andthe two were
DMG curedemployed
films containing DMGthe
to react with were overlapped
excess of MDI towith
the treatment of hot press.
prepare NCO-capped They couldFTIR
polyurethane. be bonded
spectra by heating.
of the raw materials and PUR are shown in Figure
3. As for the characteristic absorption peaks of PTMG, they were at 3200–3500 cm−1 for O–H stretching
3.2. vibrations,
FTIR of PUR 2700–3000 cm−1 for C–H asymmetric and symmetric stretching vibrations of methyl
groups
In thisand 1100 PTMG,
study, cm−1 for C–O–C stretching
castor oil and DMG(etherwere
groups) in the structure.
employed to reactThe
withFTIRthespectra
excessofof
castor
MDI to
oil was characterized with O–H and C–H stretching vibrations, with ester
prepare NCO-capped polyurethane. FTIR spectra of the raw materials and PUR are shown in Figure groups (C=O) in the 3.
structure at 1744 cm−1. In the spectra of the control and PUR-I-3.0, it was hard −1 to distinguish the
As for the characteristic absorption peaks of PTMG, they were at 3200–3500 cm for O–H stretching
implantment of DMG.−1The spectra showed that the characteristic absorption peak of NCO groups
vibrations, 2700–3000 cm for C–H asymmetric and symmetric stretching vibrations of methyl groups
was at 2722 cm−1. The bands at 3200–3400 cm−1, 1534 cm−1 and 1730 cm−1 were NH stretching
and 1100 cm−1 for C–O–C stretching (ether groups) in the structure. The FTIR spectra of castor oil was
vibrations, N–H for amide bands and ester groups (C=O) in urethane structure, respectively [11]. This
characterized withboth
illustrates that O–Hresins
and C–H
were stretching vibrations,
characterized with ester
as NCO-capped groups (C=O)
polyurethane. Mostincharacteristic
the structure at
−1
1744absorption
cm . In the spectra ofwere
the control
peaks of PUR close to and
thosePUR-I-3.0,
with PTMG it serving
was hard to distinguish
as the main polyols. the implantment
Moreover, the of
DMG. The spectra showed that the characteristic absorption peak
peak strength of C–H increased slightly due to the presence of castor oil. of NCO groups was at 2722 cm−1 .
The bands at 3200–3400
Figure cm−1
4 shows the , 1534
FTIR cm−1ofand
spectra 1730
cured cm−1 were
PUR-I-3.0 NHand
before stretching vibrations,
after heat treatment.N–HWhen forthe
amide
bands andPUR-I-3.0
cured ester groups (C=O)atinthe
was heated urethane structure,
temperature °C for 10 min[11].
of 120respectively °C for
or 135This illustrates that both resins
10 min, respectively,
werethe characteristicas
characterized absorption
NCO-cappedpeakspolyurethane.
of NCO groupsMost occurred in the spectra.
characteristic This could
absorption explain
peaks whywere
of PUR
the dynamic bonds of PUR-I-3.0 had an effect with the implantment of DMG.
close to those with PTMG serving as the main polyols. Moreover, the peak strength of C–H increased
slightly due to the presence of castor oil.

Figure 3. FTIR spectra of PTMG, castor oil and various cured PUR.

Figure 4 shows the FTIR spectra of cured PUR-I-3.0 before and after heat treatment. When the
cured PUR-I-3.0 was heated at the temperature of 120 ◦ C for 10 min or 135 ◦ C for 10 min, respectively,
the characteristic
Polymers 2020, 12,absorption peaks of NCO groups occurred in the spectra. This could explain
x FOR PEER REVIEW why the
6 of 10

dynamic bonds of PUR-I-3.0 had an effect with the implantment of DMG.

Figure 3. FTIR spectra of PTMG, castor oil and various cured PUR.

Figure FTIR
4. 4.
Figure FTIRspectra
spectra of
of cured PUR-I-3.0before
cured PUR-I-3.0 before and
and after
after heatheat treatment.
treatment.

3.3. Thermal Behavior of Cured PUR

To realize the thermal behavior of the cured PUR, DSC and DMA thermal analyses were utilized
to trace the heat flow and modulus of the resins by thermal scanning, as shown in Figures 5 and 6,
respectively. In DSC thermal analysis, the results showed that PUR-I-3.0 and PUR-II-3.0 had apparent
 Polymers 2020, 12, 1838 6 of 9

3.3. Thermal Behavior of Cured PUR

To realize the thermal behavior of the cured PUR, DSC and DMA thermal analyses were utilized
to trace the heat flow and modulus of the resins by thermal scanning, as shown in Figures 5 and 6,
respectively. In DSC thermal analysis, the results showed that PUR-I-3.0 and PUR-II-3.0 had apparent
endothermic heat flow, however, the control (PUR), PUR-I-1.5 and PUR-II-1.5, did not. This illustrates
that crosslinking density and the numbers of dynamic bonds should be kept in balance to prepare
remeltable PUR. In this case, the PUR with dosages of 3 wt% DMG could retain the remeltable property.
However, the endothermic heat flow of cured PUR-I-3.0 was different from that of cured PUR-II-3.0.
The former showed a broad curve of heat flow at lower temperatures from 90 to 130 ◦ C. This resulted
from the random distribution of DMG in the PUR structure in the one-stage synthesis. The latter
showed a broad curve of heat flow at higher temperatures above 125 ◦ C. This resulted from the
Polymers 2020, 12, x FOR PEER REVIEW 7 of 10
distribution
Polymers 2020, 12,of DMG
x FOR onREVIEW
PEER the branch structure of the prepolymer. 7 of 10

Figure 5.
Figure 5. DSC
DSC thermal
thermal analysis
analysis of
of various cured PUR.
various cured PUR.
Figure 5. DSC thermal analysis of various cured PUR.

Figure
Figure 6. Dynamic mechanical
6. Dynamic mechanical analyzer
analyzer (DMA)
(DMA) analysis
analysis of
of various
various cured
cured PUR.
PUR.
Figure 6. Dynamic mechanical analyzer (DMA) analysis of various cured PUR.
Furthermore,
3.4. TGA the storage
Thermo-Analysis modulus
of Cured PUR and tan δ of the cured PUR were analyzed by DMA, as shown
3.4. TGA Thermo-Analysis of Cured PUR
in Figure 6. For the control, its storage modulus was higher than PUR-I-3.0 and PUR-II-3.0 at negative
Figures 7 and
temperature. 8 show the TGAthe and DTG curves of the cured resins. Their TGA parameters are
Figures 7 The
and results
8 showillustrated
the TGA anddifference
DTG curves in mechanical
of the curedstrength.
resins.Thus,
TheirtheTGAcontrol had a higher
parameters are
shown
rigid in Table 2.property
mechanical As shown by the TGA curves, the thermal degradation of the cured PUR occurred
shown in Table 2. As shownthan by thePUR-I-3.0 and PUR-II-3.0
TGA curves, the thermalbecause of theof
degradation higher crosslinking
the cured density.
PUR occurred
at temperatures of 180 °C to 500 °C. DTG analysis showed that the control had two stages of thermal
atIttemperatures
was similar toof the trend
180 in 500
°C to the tensile
°C. DTG tests of cured
analysis PUR films.
showed Forcontrol
that the three resins, theirstages
had two moduli ofdecreased
thermal
degradation,
with increasingthetemperature
temperatures of which
due to were
phase 300 to 400
transition °C glassy
from and 400state
to 500
to °C, respectively.
rubber state. From However,
the tan
degradation, the temperatures of which were 300 to 400 °C and 400 to 500 °C, respectively. However,
all of the cured PUR containing DMG had lower temperatures of thermal degradation from 180 ◦to
allδ curves of thePUR
of the cured curedcontaining
resins, it showed
DMG had thatlower
theirtemperatures
glass transition of temperature (Tg) wasfrom
thermal degradation about 18012 toC.
250 °C.
Further, This
we could
observed be due
the to the
variation decomposition
in storage of
moduli urethane
of the linking
resins with
from 60 DMG.
to 160 With
◦ C. increasing
The results
250 °C. This could be due to the decomposition of urethane linking with DMG. With increasing
temperatures
revealed of 300
thatofthe to 400 °C,notdecomposition of most urethane and urea heated
bonds were observed [12,13].
temperatures 300control
to 400 did have a remeltable
°C, decomposition of mostproperty
urethaneafter
and being
urea bonds were as aobserved
thermoset. As for
[12,13].
The DTG
PUR-I-3.0 peaks
and of of the cured
PUR-II-3.0, PUR containing DMG were similar to each other and shifted to higher
The DTG peaks the cured their
PUR storage moduli
containing DMGdecreased
were similarwithtoincreasing
each othertemperature,
and shifted todropping
higher
temperatures than the control. This was caused by the decomposition of partial urethane groups
temperatures than the control. This was caused by the decomposition of partial urethane groups
during the early stage of thermal degradation. The heat resistance of the PU structure varied from
during the early stage of thermal degradation. The heat resistance of the PU structure varied from
high to low in the following order: cyanuric acid, urea, urethane, biuret and allophanate [14,15]. The
high to low in the following order: cyanuric acid, urea, urethane, biuret and allophanate [14,15]. The
stage from 400 to 500 °C was the fast dissociation phase of MDI, PTMG and castor oil chain scission
stage from 400 to 500 °C was the fast dissociation phase of MDI, PTMG and castor oil chain scission
[16,17]. All of the cured PUR had similar trends of thermal degradation with weight loss from 59% to
[16,17]. All of the cured PUR had similar trends of thermal degradation with weight loss from 59% to
Polymers 2020, 12, 1838 7 of 9

rapidly after the temperatures reached 90 ◦ C and 110 ◦ C, respectively. This phenomenon illustrated
the remeltable property of cured resin. The storage modulus of PUR-II-3.0 was higher than that of
PUR-I-3.0 after the temperatures reached 90 ◦ C. The results could precisely illustrate the difference in
the mechanical properties of the resins in the remelt state. It provided PUR-II-3.0 in the remelt state
with a higher molecular due to the distribution of DMG on the branch structure of the prepolymer.

3.4. TGA Thermo-Analysis of Cured PUR

Figures 7 and 8 show the TGA and DTG curves of the cured resins. Their TGA parameters are
shown in Table 2. As shown by the TGA curves, the thermal degradation of the cured PUR occurred at
temperatures of 180 ◦ C to 500 ◦ C. DTG analysis showed that the control had two stages of thermal
degradation, the temperatures of which were 300 to 400 ◦ C and 400 to 500 ◦ C, respectively. However,
all of the cured PUR containing DMG had lower temperatures of thermal degradation from 180 to
250 ◦ C. This could be due to the decomposition of urethane linking with DMG. With increasing
temperatures of 300 to 400 ◦ C, decomposition of most urethane and urea bonds were observed [12,13].
The DTG peaks of the cured PUR containing DMG were similar to each other and shifted to higher
temperatures than the control. This was caused by the decomposition of partial urethane groups
during the early stage of thermal degradation. The heat resistance of the PU structure varied from high
to low in the following order: cyanuric acid, urea, urethane, biuret and allophanate [14,15]. The stage
from 400 to 500 ◦ C was the fast dissociation phase of MDI, PTMG and castor oil chain scission [16,17].
Polymers 2020, 12, x FOR PEER REVIEW 8 of 10
All of the
Polymers cured
2020, PUR
12, x FOR hadREVIEW
PEER similar trends of thermal degradation with weight loss from 59% to 64%.
8 of 10

Figure 7. TGA
Figure 7. TGA curves
curves of
of various
various cured
cured PUR.
PUR.
Figure 7. TGA curves of various cured PUR.

Figure 8.
Figure DTG curves
8. DTG curves of
of various
various cured
cured PUR.
PUR.
Figure 8. DTG curves of various cured PUR.
Table 2. TGA parameters and mechanical properties of various PUR.
Table 2. TGA parameters and mechanical properties of various PUR.
TGA Parameters Mechanical Properties
II TGA ParametersIII Mechanical Properties
I II III
I II
Onse III
Ons 650 °C
Code of I
Weig II
Weigh III
Weig Tensile Young’s Elongatio
I
Onset Onse
t Ons
et 650 °C
Residue
Code of
Resins Weig
ht Weigh
t Weig
ht Tensile
strength Young’s
modulus Elongatio
n
Polymers 2020, 12, 1838 8 of 9

Table 2. TGA parameters and mechanical properties of various PUR.

TGA Parameters Mechanical Properties

Code of I I II II III III ◦C

650 Tensile Young’s
Resins Onset Weight Onset Weight Onset Weight Elongation
Residues Strength Modulus
Temp. Loss Temp. Loss Temp. Loss (%)
(%) (MPa) (MPa)
(◦ C) (%) (◦ C) (%) (◦ C) (%)
PUR - - 318.7 32.1 435.9 62.5 5.0 22.1 8.8 108.5
PUR-I-1.5 186.1 1.8 312.7 31.6 426.1 63.2 5.1 23.1 8.8 100.1
PUR-I-3.0 195.2 4.1 315.5 30.1 418.5 59.3 6.5 25.1 8.9 77.2
PUR-II-1.5 188.5 1.3 317.2 31.1 434.1 61.2 4.6 20.1 7.8 96.1
PUR-II-3.0 191.5 3.5 319.2 30.5 435.2 62.1 4.9 20.3 7.9 71.4

3.5. Mechanical Property of Cured PUR

Figure 9 shows the stress-strain curves of various PUR films. Table 2 summarizes the tensile
strength, Young’s modulus and elongation at break of various cured PUR. The pure PUR film exhibited
a typical tough behavior with tensile strength of 22.1 MPa and elongation at break of over 100%.
For PUR containing DMG films, their tensile strength was from 20 to 25 MPa. Among them, the films
with one-stage synthesis had more toughness. This was caused by the aggregation of the hard segment
in the PU structure. Their elongation at break of 100% to 71% reduced as the dosage of DMG increased
because2020,
Polymers the 12,
crosslinking
x FOR PEER density
REVIEW of films decreased. 9 of 10

Figure 9.
Figure Stress–strain curves
9. Stress–strain curves of
of various
various cured
cured PUR.
PUR.

4. Conclusions
4. Conclusions
The preparation of PUR containing castor oil and DMG by one or two-stage synthesis is feasible.
The preparation of PUR containing castor oil and DMG by one or two-stage synthesis is feasible.
According to FTIR, the thermal behavior and tensile tests of PUR, the cured resins with the dosages of
According to FTIR, the thermal behavior and tensile tests of PUR, the cured resins with the dosages
3 wt% DMG provided with remeltable and mechanical properties. Comparing different syntheses,
of 3 wt% DMG provided with remeltable and mechanical properties. Comparing different syntheses,
the endothermic heat flow of cured PUR-I-3.0 appeared at lower temperatures from 90 to 130 ◦ C than
the endothermic heat flow of cured PUR-I-3.0 appeared at lower◦temperatures from 90 to 130 °C than
that of PUR-II-3.0, which appeared at temperatures above 125 C. DMA analysis showed the same
that of PUR-II-3.0, which appeared at temperatures above 125 °C. DMA analysis showed the same
trend. Overall, for preparation of remeltable PUR, the crosslinking density and numbers of dynamic
trend. Overall, for preparation of remeltable PUR, the crosslinking density and numbers of dynamic
bonds should be kept in balance. The remeltable temperature of cured resin was affected by the
bonds should be kept in balance. The remeltable temperature of cured resin was affected by the
distribution of DMG in the PUR structure under various syntheses.
distribution of DMG in the PUR structure under various syntheses.
Funding: This research received no external funding.
Author Contributions: Conceptualization, Z.-Y.W.; Investigation, Z.-Y.W.; Methodology, Z.-Y.W.; Writing–
Conflicts of Interest: The author declares no conflict of interest.
original draft, Z.-Y.W.; Writing–review & editing, Z.-Y.W.

Funding: This research received no external funding.

Conflicts of Interest: The author declares no conflict of interest.

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