Novel, fully biobased semicrystalline polyamides

Article abstract of DOI:10.1021/ma200256v

Novel, semicrystalline polyamides and co(polyamides) were synthesized from biobased sebacic acid (SA), 2,5-diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol (diaminoisoidide, DAII) as well as from 1,4-diaminobutane (DAB), also known as putrescine in nature. Low

Full text of DOI:10.1021/ma200256v

ARTICLE
pubs.acs.org/Macromolecules
Novel, Fully Biobased Semicrystalline Polyamides
,
†,||,§
‡
†,#,||
#,||
^
‡
Lidia Jasinska,*
Maurizio Villani, Jing Wu, Daan van Es, Enno Klop, Sanjay Rastogi, and
,†,||
Cor E. Koning*
†
Laboratory of Polymer Chemistry, Eindhoven University of Technology, Den Dolech 2, P.O. Box 513, 5600 MB Eindhoven,
The Netherlands
Dutch Polymer Institute DPI, PO Box 902, 5600 AX Eindhoven, The Netherlands
§
Department of Polymer Technology, Chemical Faculty, Gdansk University of Technology, G. Narutowicza Str. 11/12, 80-952 Gdansk,
Poland
‡
Laboratory of Polymer Technology, Department of Chemical Engineering, Eindhoven University of Technology, P.O. Box 513,
5
600MB Eindhoven, The Netherlands
#
Wageningen University and Research Centre, Bornse Weilanden 9, 6700AA Wageningen, The Netherlands
^Research Institute, Teijin Aramid BV, P.O. Box 5153, 6802 ED Arnhem, The Netherlands
S Supporting Information
b
ABSTRACT: Novel, semicrystalline polyamides and co-
(
2
polyamides) were synthesized from biobased sebacic acid (SA),
,5-diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol (diaminoisoidide,
DAII) as well as from 1,4-diaminobutane (DAB), also known as
putrescine in nature. Low molecular weight polyamides were
obtained by melt polycondensation of the salts based on these
monomers or by interfacial polycondensation. In order to increase
their molecular weights the polyamide prepolymers were submitted
to a solid state polymerization (SSP) process. The chemical
structure of the polymers was confirmed by 2D NMR correlation
spectra (COSY), heteronuclear multiple-bond correlation spectra (HMBC) and by FT-IR spectroscopy. In the present work, FT-IR and
X-ray techniques were used as a tool for the investigation of the crystal structure of the polymers after SSP. The X-ray diffractograms of the
polyamides point to crystals containing both 4.10- and DAII.10-based repeat units. Because of the presence of diaminoisoidide residues the
synthesized fully renewable products exhibit tunable polarities and melting points. Since most commercial polyamides have a much higher
melting point than their end application requires, especially for fiber applications, this simple adaption can result in a significant reduction of
energy consumption during processing.
’
INTRODUCTION
polyamides have been intensively studied. The application of such
monomers for the synthesis of biobased polyamides with different
spacial separation between the amide groups, and thus with different
hydrogen bond densities, may be a powerful method of tailoring their
thermal and mechanical properties.
Their good physicochemical and mechanical properties as well as
low cost make polyamides (PA) interesting candidates for high
performance engineering thermoplastics and for fibers. Numerous
studies, reporting advantages of polyamides over other thermoplas-
tic polymers, have been published so far. However, it is known
that many of the commonly used polyamides like polyamide 6
1
ꢀ5
Currently, very promising and revealing opportunities for bio-
based monomers are offered by 1,4;3,6-dianhydrohexitols with
endoexo, endoendo or exoexo conformation. Examples are 1,4;3,6-
dianhydro-D-glucidol (isosorbide), 1,4;3,6-dianhydro-D-mannitol
6
ꢀ8
9ꢀ11
and polyamide 6.6
are based on petrochemical building blocks.
Therefore, following the driving force toward the production of
environmentally friendly and sustainable materials, the development
of biomass-based polymers is entirely justified.
2
7
(
isomannide), 1,4;3,6-dianhydro-L-iditol (isoidide), and their
28,29
diamino derivatives (see Supporting Information, Figure S1).
However, due to the formation of intramolecular hydrogen bonds
and due to steric hindrance by one of the rings, the endo-oriented
hydroxyl or amino groups reveal relatively low reactivity. On the
other hand, the use of monomer moieties with L-ido conformation
Of significant interest and extensively reported are biobased
12ꢀ16
17ꢀ20
polyamides from brassylic acid,
obutane (see Supporting Information, Figure S1).
Although succinic acid is also a renewable dicarboxylic acid, the
manufacturing of these polyamides is difficult because the formation
of a stable five-membered imide ring limits molecular weight and
results in discoloration. Along with different synthetic approaches the
morphology and crystalline transitions of these renewable
sebacic acid
or 1,4-diamin-
4
,5,19,21ꢀ26
Received: February 4, 2011
Revised:
March 23, 2011
Published: April 07, 2011
r 2011 American Chemical Society
3458
dx.doi.org/10.1021/ma200256v
|Macromolecules 2011, 44, 3458–3466

Macromolecules
ARTICLE
Scheme 1. Chemical Structure of Sebacic Acid/1,4-Diami-
nobutane and Sebacic Acid/Diaminoisoidide Repeat Units in
the Synthesized Co- and Homopolyamides
melt. SSP provided the ability to achieve biobased polyamides with
number-average molecular weights above 18 000 g/mol. The
chemical structure of the synthesized polymers was confirmed
using 2D NMR and FT-IR spectroscopy. To investigate the
influence of diaminoisoidide on the crystal structure and melting
points of the polyamides wide-angle X-ray diffraction, FT-IR, and
DSC techniques were applied. To the best of our knowledge, these
fully biomass-based co(polyamides) have not yet been described in
the literature.
’
EXPERIMENTAL SECTION
Materials. 2,5-Diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol (diamin-
oisoidide, DAII) was prepared by the published method from 1,4:3,6-
2
9
dianhydro-D-mannitol. Sebacic acid (99%), sebacoyl chloride (99%),
1
9
,4-diaminobutane (99%), 1,4:3,6-dianhydro-D-mannitol (isomannide,
5%), p-toluenesulfonyl chloride (g99%), potassium phthalimide
(
g99%), dimethyl sulfoxide (g99.9%), hydrochloric acid (reagent grade
or modified products with enhanced reactivity may provide fully
30
37%), ethanolic HCl solution (1.25 N), Amberlyst A26-OH, potassium
carbonate (g99%), chloroform-d (99.8 atom %D), and benzene-d (99
biobased polymers including liquid-crystalline materials. Thiem
28
6
et al. presented a series of polyamides synthesized by interfacial
polycondensation of aromatic or aliphatic diacyl chlorides with
isomannide- (DAIM), isosorbide- (DAIS), and isoidide-derived
atom %D) were purchased from Sigma-Aldrich. Irganox 1330 was
available from Ciba Specialty Chemicals. Magnesium sulfate (99%) was
purchased from Acros Organics. Acetic acid (glacial, 99ꢀ100%), pyridine
(
DAII) diamines. They found that by using DAII or DAIS in
(
99.5%), and D O (99.8 atom %D) were purchased from Merck.
2
combination with e.g. sebacoyl chloride polyamides with high
Trifluoroacetic acid-d (99.5 atom %D) was purchased from Cambridge
Isotope Laboratories, Inc. Activated carbon was purchased from Norit.
1
degrees of polymerization and T values in the range 50ꢀ70 ꢀC
g
31,32
can be obtained. Recent studies of Bartolussi
focused on
,1,1,3,3,3-Hexafluoro-2-propanol (HFIP), diethyl ether, methanol, etha-
interfacial polycondensation, microwave-assisted polymerization
and Higashi's method as synthetic routes toward biobased poly-
amides. In these studies isosorbide was derivatized into the corre-
sponding diamine or diacyl chloride and used for the preparation of
optically active products. The comparative analysis performed by
these authors proved that microwave-assisted polycondensation
leads to the highest molecular weight of the studied polyamides
nol and dry chloroform were purchased from Biosolve. All the chemicals
were used as received, unless denoted otherwise.
29
1,4;3,6-Dianhydro-2,5-di-O-p-tosyl-D-mannitol. To a solution
of isomannide (50.0 g, 0.34 mol) in pyridine (150 mL) at 0 ꢀC was added a
solution of p-toluenesulfonyl chloride (130.5 g, 0.68 mol) in pyridine
(350 mL) dropwise. The mixture was stirred under Ar atmosphere for 3 h
and subsequently stored for 24 h at 0ꢀ3 ꢀC. The reaction product was
poured into 2.5 L of an ice/water mixture, stirred and allowed to warm up to
room temperature. The resulting precipitate was filtered and the product was
recrystallized from ethanol to afford isomannidebistosylate as white crystals
(
140 000 g/mol) with thermal stabilities ranging up to 400 ꢀC.
In several papers on biodegradable polymers, poly-
esterꢀamides) based on 1,4;3,6-dianhydrohexitols attracted
(
3
3ꢀ35
1
special attention.
These biobased products were success-
(142.9 g, 92%). H NMR (CDCl ): δ = 7.75 (d, 4H), 7.30 (d, 4H), 4.80 (m,
3
13
fully obtained by the reaction of p-toluenesulfonic acid salts
2H), 4.43 (m, 2H), 3.86 (dd, 2H), 3.66 (dd, 2H), 2.41 (s, 6H). C NMR
(CDCl ): δ = 145.33, 132.85, 129.94, 127.91, 79.94, 77.96, 70.05, 21.65.
2,5-Diphthalimido-2,5-dideoxy-1,4;3,6-dianhydroiditol.
0
of O,O -bis(R-aminoacyl)-1,4;3,6-dianhydro-D-glucitol with bis-
3
2
9
(
p-nitrophenyl) esters of dicarboxylic acids and tested for their
thermal properties and enzymatic degradation. The analyses
have shown a particular suitability of these polyamides as drug
delivery systems. Another application for biobased poly-
Isomannidebistosylate (50 g, 0.11 mol) and potassium phthalimide (45.4
g, 0.25 mol) in DMSO (500 mL) were stirred at 130 ꢀC for 24 h under Ar
atmosphere. The solution was then cooled to room temperature and
water (1 L) was added. The mixture was extracted with chloroform (3 ꢁ
36
(
esterꢀamides) was proposed by Philip and Sreekumar. These
5
4
00 mL) and thecombined organicextracts were washed with water (4 ꢁ
authors synthesized optically active materials, having biphenolic
4
00 mL), dried over MgSO , decolorized with activated carbon and
azo chromophores and isosorbide as T -increasing building
g
concentrated under reduced pressure to give 2,5-diphthalimido-2,5-
blocks, with a potential application in electro-optic devices.
In this paper, we present synthetic routes, the structural char-
acterization, the thermal properties and some XRD analysis of the
semicrystalline polyamides and co(polyamides) from the renewable
monomers diaminoisoidide (DAII, prepared from isomannide),
1
dideoxy-1,4;3,6-dianhydroiditol as a yellow solid (36.4 g, 82%). H
3
NMR (CDCl ): δ = 7.84 (m, 4H), 7.72 (m, 4H), 5.36 (s, 2H), 4.89
1
3
(
3
m, 2H), 4.34 (m, 2H), 3.97 (m, 2H). C NMR (CDCl ): δ = 167.52,
134.26, 131.63, 123.40, 88.07, 71.06, 55.71.
2
,5-Diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol Dihy-
1
,4-diaminobutane (DAB, in nature known as putrescine) and the
29
drochloride. 2,5-Diphthalimido-2,5-dideoxy-1,4;3,6-dianhydroiditol
20.2 g, 0.05 mol) and 6 N HCl/AcOH (125 mL, 4:1, v/v) were stirred
castor oil-derived sebacic acid (see Scheme 1). The monomer
combination was chosen in view of their natural origin and
possibility to obtain relatively high molecular weight polymers,
while by using the more readily available succinic acid the growth of
the polyamide chain can be limited by the formation of five-
membered imide rings, acting as a chain stopper. One of the two
synthetic methods is based on interfacial polycondensation of the
diacyl chloride derivative of sebacic acid with DAII, while the second
method involves solvent-free bulk polycondensation accomplished
by solid state polymerization (SSP) after a prepolymerization in the
(
at 135 ꢀC for 24 h. The solution was allowed to cool and crystallized
phthalic acid was filtered off. The filtrate was washed with diethyl ether (3 ꢁ
150 mL) and evaporated to dryness. The crude product was dissolved in
methanol (25 mL) at 50 ꢀC and then ethanol (25 mL) was added.
Subsequently, methanol was distilled and ethanolic HCl solution (50 mL)
was added dropwise to precipitate 2,5-diamino-2,5-dideoxy-1,4;3,6-dianhy-
1
droiditol dihydrochloride as a brownish/white solid (7.3 g, 67%). H NMR
(D O): δ = 5.15 (s, 2H), 4.34 (m, 2H), 4.20 (m, 2H), 4.17
2
13
(m, 2H). C NMR (D O): δ = 84.49, 70.46, 56.20.
2
3
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Macromolecules
,5-Diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol (Diaminoi-
ARTICLE
2
The data acquisitions were performed using Viscotek OmniSec 4.0 and
Waters Empower 2.0 software.
29
soidide). 2,5-Diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol dihydro-
chloride (7.0 g, 0.032 mol) was dissolved in demineralized water
2D NMR spectra were recorded on a Varian Unity 500 plus spectro-
meter at room temperature. Chemical shifts were referenced to residual
signals of C D . Correlation spectra (COSY) were acquired using
(100 mL) and stirred with activated carbon (50 mg) at 35 ꢀC for 30
min. The mixture was filtered and sonificated with washed Amberlyst A-26-
OH (28.0 g, 0.035 mol) in an ultrasonic bath at room temperature for 1 h.
The aqueous solution was filtered and evaporated to dryness to afford 2,5-
6
6
standard programs provided by a Varian spectrometer library with the
following parameters: spectral width SW1 = SW2 = 6075.3 Hz, acquisi-
tion time 0.221 s, relaxation delay 1.4 s, and number of scans 8 ꢁ 300
increments. Heteronuclear multiple-bond correlation spectra (HMBC)
diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol as a white solid (4.3 g, 93%).
1
H NMR (D
H). C NMR (D O): δ = 85.69, 71.55, 55.96.
2
O): δ = 4.67 (s, 2H), 3.94 (dd, 2H), 3.77 (dd, 2H), 3.67 (m,
13
1
2
2
were recorded with pulse field gradients. The spectral windows for H
1
3
DiaminoisoidideꢀSebacic Acid Salt. To a solution of sebacic
and C axes were 6075.3 and 21367.4 Hz, respectively. The data were
collected in a 2560 ꢁ 210 matrix and processed in a 1K ꢁ 1K matrix. The
spectra were recorded with the acquisition time 0.211 s, relaxation delay
acid (3.0 g, 0.015 mol) in ethanol (10 mL) at 50 ꢀC a solution of
diaminoisoidide (2.2 g, 0.015 mol) in an ethanol/water mixture (6 mL,
1
5:1, v/v) was added dropwise. During the addition, a precipitate was
1.4 s and number of scans equal to 144 ꢁ 210 increments. H NMR and
1
3
formed. The mixture was stirred at 80 ꢀC for 1 h and then at 50 ꢀC for 1 h.
x
C NMR spectra were recorded using a Varian Mercury V spectro-
1
The crude product was filtered and recrystallized from ethanol/water
meter with the frequency of 400 MHz. For H NMR experiments the
spectral width was 6402.0 Hz, acquisition time 1.998 s, and the number
of recorded scans equal to 64. C NMR spectra were recorded with the
spectral width 24154.6 Hz, acquisition time 1.300 s, and the number of
recorded scans equal to 256.
1
mixture (8:1, v/v) to afford the salt as white crystals (4.7 g, 86%). H
1
3
2
NMR (D O): δ = 4.84 (s, 2H), 4.05 (dd, 2H), 3.89 (d, 2H), 3.86 (m, 2H),
2.12 (m, 4H), 1.42 (m, 4H), 1.17 (m, 6H).
1
,4-DiaminobutaneꢀSebacic Acid Salt. To a solution of
sebacic acid (3.0 g, 0.015 mol) in ethanol (10 mL) at 50 ꢀC a solution
of 1,4-diaminobutane (1.3 g, 0.015 mol) in ethanol (3 mL) was added
dropwise. During the addition, a precipitate was formed. The mixture
was stirred at 80 ꢀC for 1 h and then at 50 ꢀC for 1 h. The crude product
was filtered and recrystallized from ethanol/water mixture (10:1, v/v) to
afford the salt as white crystals (4.1 g, 95%). H NMR (D
Thermogravimetric analyses (TGA) were performed on a TA
Instruments Q500 TGA in a nitrogen atmosphere. Samples were heated
from 50 to 600 ꢀC with a heating rate of 10 ꢀC/min.
DSC measurements were performed using a DSC Q100 from TA
Instruments. The measurements were carried out in a nitrogen atmo-
sphere with a heating rate of 10 ꢀC/min. The transitions were deduced
from the second heating and cooling curves.
1
2
O): δ = 2.86
(m, 4H), 1.97 (m, 4H), 1.58 (m, 4H), 1.36 (m, 4H), 1.13 (m, 6H).
Fourier transform infrared spectra (FT-IR) were obtained using a
Varian 610-IR spectrometer equipped with an FT-IR microscope. The
spectra were recorded at 30 ꢀC in transmission mode with a resolution of
Polymerization of Salt Monomers. This example is represen-
tative for all conducted co(polymerizations). A mixture of diaminoisoi-
dideꢀsebacic acid salt (0.66 g) and 1,4-diaminobutaneꢀsebacic acid salt
ꢀ
1
2
cm . PA films obtained from HFIP were analyzed on a zinc selenium
(
2.0 g), 1,4-diaminobutane (0.2 g, 2.3 mmol), diaminoisoidide (0.066 g,
disk and heated using a Linkam TMS94 hotstage and controller. Varian
Resolution Pro software version 4.0.5.009 was used for the analysis of the
spectra.
X-ray diffraction patterns were obtained employing a Bruker AXS HI-
STAR area detector installed on a P4 diffractometer, using graphite-
monochromatedCuKRradiation(λ= 1.5418 Å) and a 0.5 mm collimator.
The data were collected at room temperature on SSP-synthesized powder
contained in glass capillaries. The 2D data were subsequently background-
corrected and transformed into 1D profiles via integration.
0
.45 mmol) was stirred in a three-necked round-bottom flask equipped
with a mechanical stirrer, vigreux column and a DeanꢀStark type
condenser. The reaction mixture was heated at 160 ꢀC for 0.5 h and
then the temperature was raised to 190 ꢀC. The polycondensation
process was conducted in the presence of Irganox 1330 (0.026 g) as an
antioxidant. The reaction was carried out for 2 h under argon atmo-
sphere. The low molecular weight polyamide was ground into powder,
washed with demineralized water at 80 ꢀC for 12 h, filtered, and dried
under reduced pressure at 80 ꢀC. In order to increase the molecular
weight of the polyamide prepolymer solid state polymerization (SSP)
was applied. SSP of the polyamide powder was carried out in a glass tube
reactor (2.5 cm diameter) equipped with a sintered glass plate at the
bottom on which the polyamide prepolymer powder was deposited.
Below this glass plate the SSP reactor contained an inert gas inlet
through which the heated gas was introduced. During the reaction
course the temperature was raised gradually from 200 to 205 ꢀC for 27 h
and maintained 10ꢀ15 ꢀC below the melting point of the polyamide
’
RESULTS AND DISCUSSION
Synthesis and Molecular Characterization of the (Co)poly-
amides. Co(polyamides) (co-PAs) were prepared via melt and
solid state bulk polycondensation of the salts obtained from
sebacic acid, diaminoisoidide and 1,4-diaminobutane, as de-
scribed in the Experimental Section. This method was also used
for the synthesis of the homopolyamide PA1 based on sebacic
acid and 1,4-diaminobutane (DAB), polyamide 4.10. The purity
prepolymer. The reactor was heated using a salt mixture of KNO (53 wt %),
NaNO (40 wt %), NaNO (7 wt %). SSP was carried out in Ar
2 3
atmosphere at a gas flow rate of 2.5 L/min.
3
37
1
of the salts was confirmed by H NMR spectroscopy while their
Interfacial Polycondensation. To a solution of diaminoisoidide
thermal transitions and stability were determined using DSC and
TGA, respectively. These parameters are highly important in
view of selecting the time/temperature conditions of the poly-
condensation. The melting points of the sebacic acid/DAII and
sebacic acid/DAB salts were 133 and 130 ꢀC, respectively.
Despite the relatively low melting points of both salts and the
high thermal stability of the sebacic acid/DAB salt (maximum
rate of decomposition at Tmax = 468 ꢀC) the low thermal stability
of the synthesized sebacic acid/DAII salt (maximum rate of
decomposition at Tmax = 266 ꢀC) restricted the temperature of
the polycondensation reaction of the salt mixtures in the melt. An
extensive duration of the polymerization above 200 ꢀC should be
(
(
0.72 g, 0.005 mol) and potassium carbonate (1.38 g, 0.01 mol) in water
35 mL) a solution of sebacoyl chloride (1.19 g, 0.005 mol) in dry
chloroform (5 mL) was added dropwise. The heterogeneous mixture
was stirred at room temperature for 2 h under Ar atmosphere. The
obtained polyamide was filtered, washed with water, ethanol, and dried
under reduced pressure at 80 ꢀC (1.42 g, 92%).
Measurements. Size exclusion chromatography analyses (SEC) in
,1,1,3,3,3-hexafluoro-2-propanol were performed using a setup
1
equipped with a Shimadzu LC-10AD pump and a waters 2414 differ-
ential refractive index detector. PSS (2 ꢁ PFG-lin-XL, 7 μm, 8 ꢁ 300
mm) columns were used. The eluent flow rate was 1.0 mL/min.
Calibration of the measurements was carried out with PMMA standards.
3
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ARTICLE
Figure 1. 500 MHz heteronuclear multiple-bond correlation spectrum (HMBC) of co(polyamide) coPA5.
Table 1. Characteristics of Co- and Homopolyamides from Sebacic Acid, 1,4-Diaminobutane, and Diaminoisoidide (DAB = 1,4-
Diaminobutane, DAII = Diaminoisoidide)
a
b
c
c
d
d
symbol monomer feed, mol ratio (DAB/DAII)
built-in composition (DAB/DAII)
M
n
(g/mol) prepolymer PDI
n
M (g/mol) after SSP PDI
PA1
1.0/0
1.0/0
9600
6500
5000
5500
2500
4200
2.3
2.0
1.8
1.8
1.7
2.3
21 900
21 300
18 700
20 400
3900
-
3.0
2.7
2.7
2.9
1.9
-
coPA2
coPA3
coPA4
coPA5
0.91/0.09
0.83/0.17
0.78/0.22
0.55/0.45
0/1.0
0.89/0.11
0.86/0.14
0.80/0.20
0.57/0.43
e
PA6
0/1.0
c
a
b
Determined by weighed-in monomers. Determined by NMR. Determined for polyamides before solid state polymerization using the SEC method
with PMMA standards in HFIP solvent. Determined for polyamides after solid state polymerization using SEC method with PMMA standards in HFIP
d
e
solvent. PA obtained via interfacial polymerization, PA1 = PA 4.10, coPA2 = PA 4.10/DAII.10ꢀ2, coPA3 = PA 4.10/DAII.10ꢀ3, coPA4 = PA 4.10/
DAII.10ꢀ4, coPA5 = PA 4.10/DAII.10ꢀ5, PA6 = PA DAII.10.
avoided and so a two-step method for the synthesis of co-PAs
their properties, including molecular weight and polydispersity
index. The melt prepolymerizations yielded products with Mn
ranging between 2500 and 9600 g/mol (Table 1). The homo-
leading to white products with M above 18 000 g/mol was
n
applied. In a first step (bulk melt-polycondensation for 2 h at
1
90 ꢀC) low molecular weight, semicrystalline prepolymers with
polymer PA1 based on DAB and sebacic acid exhibits an M value
n
variable molar ratios DAB/DAII were obtained, which were
subsequently subjected to solid state polymerization (see
Table 1), 10ꢀ15 ꢀC below their melting points.
around 9600 g/mol, decreasing to approximately 2500 g/mol
with increasing DAII monomer residue concentration. These
results clearly reflect the lower reactivity of the secondary amine;
diaminoisoidide, in comparison to 1,4-diaminobutane. It is well-
known, that mechanical and thermal properties of polyamides
As expected, the presence of diaminoisoidide in the polymer
backbone of the synthesized copolymers significantly affected
3
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Macromolecules
ARTICLE
are directly related to their molecular weight. Higher molecular
weights promote higher melting points and better mechanical
properties (toughness, tensile strength, elongation at break etc.),
Scheme 2. Possible Sequences of Monomer Residues of
Sebacic Acid, Diaminoisoidide, and 1,4-Diaminobutane in the
Co- and Homopolyamides
18
at least as long as the molecular weight is below a critical value.
Therefore, the M values of the prepolymers needed to be
n
enhanced to values above this critical value, which for aliphatic
polyamides is ca. 12 000ꢀ15 000 g/mol. Taking into account the
low thermal stability and high weight loss above 260 ꢀC of both
DAII and the sebacic acid/DAII salt, the use of SSP for obtaining
the targeted polymers with number-average molecular weights
above 15 000 g/mol turned out to be a suitable method
(Table 1). Because of the low melting temperature of the coPA5
prepolymer (see below) and hence the need for carrying out the
SSP of this specific prepolymer at 150 ꢀC, which is not sufficient
for proper polycondensation, for coPA5 the SSP treatment only
resulted in a very modest enhancement of the Mn.
2
D NMR spectra of the synthesized co(polyamides) provided
detailed information regarding the chemical structure, purity and
possible changes of the stereochemistry of DAII, which could
occur during the synthesis of the PAs. The analysis of the
COSY correlation spectra (see Supporting Information, Figure S2)
and heteronuclear multiple-bond correlation spectra (HMBC)
9
10
9
8
(
Figure 1) confirmed the incorporation of DAII into the
H /H and H /H at 3.38 ppm in the corresponding COSY
spectrum (see Supporting Information, Figure S2). Additional
evidence for the presence of this structural fragment in the
co(polyamides) are the signals at 3.38/25.0 ppm, 3.38/180.5
structure of the co(polyamides). Because of the absence of
separated signals related to the amine end-groups of PAs,
although these should be present from the statistical point of
view, the calculation of their molecular weights from NMR
spectra was impossible. However, given the structure of the
synthesized polyamides and the possible sequence of the differ-
ent monomer residues (Scheme 2), 2D NMR spectra should
clearly display the signals related to the repeat units of diami-
noisoidide, 1,4-diaminobutane and sebacic acid residues of which
both functional groups had been transferred into amides.
The analysis of the signals originating form DAII residues was
9
10
ppm, 1.57/42.0 ppm, and 8.43/180.5 ppm assigned to H /C ,
9
15
10
9
8
15
H /C , H /C , and H /C in the HMBC spectrum, as shown
in Figure 1.
To fully accomplish the proton and carbon peak assignment
the analysis of sebacic acid units in PA was performed. In the
COSY spectrum the cross-peaks at 2.32 ppm, 1.52 ppm, 1.21
1
2
2
3
3
2
ppm are described as H /H , H /H and H /H signals and are
related to sebacic acid residues bonded to diaminoisoidide. This
unit sequence was also confirmed by the HMBC spectrum by the
presence of the signals at 2.32/26.0 ppm, 2.32/28.5 ppm, 1.52/
35.2 ppm, 1.52/28.5 ppm, 1.21/26.0 ppm, 1.21/35.2 ppm from
1
1
successfully accomplished by the study of Hꢀ H COSY and
1
13
7
4
4
6
4
Hꢀ C HMBC spectra. The cross-peaks H /H , H /H , H /
0
0
6
6
6
5
4
H , H /H , and H /H found in the COSY spectrum at 7.78,
7
1
2
1
3
2
1
2
3
3
2
3
1
4
.46, 4.02, 3.96, and 4.80 ppm prove the presence of protons H ,
H /C , H /C , H /C , H /C , H /C , and H /C correlations.
1 14 2 14
0
4
6
6
5
H , H , H , and H , respectively. Moreover, two- and three-bond
Two- and three-bond correlations between H /C and H /C
correlations between these protons and carbons were verified by
are found at 2.32/180.5 ppm and 1.52/180.5 ppm (Figure 1).
Similarly, the presence of sebacic acid units bonded to 1,4-
diaminobutane is evidenced by the cross-peaks at 1.21, 1.58,
HMBC spectra. The HMBC signals at 4.80/57.8, 4.80/71.5,
5
4
.80/86.2, and 4.46/86.2 are assigned to the correlations H /
0
4
5
6
5
5
4
5
6
4
6
4
6
5
13
12
11
C , H /C , H /C , and H /C , while H /C , H /C , H /C ,
and 2.50 ppm, depicted as H , H , H (Scheme 2 and Figure
S2, Supporting Information). A careful examination of the
HMBC spectrum allows to indentify these signals as H/C
correlations at 1.21/36.0 ppm, 1.21/34.0 ppm, 1.58/34.0 ppm,
2.50/26.0 ppm, 2.50/28.5 ppm. Additional evidence of sebacic
acid units bonded to 1,4-diaminobutane were the signals at 2.50/
0
6
5
and H /C signals are found at 4.02/57.8 ppm, 3.96/57.8 ppm,
.02/86.2 ppm, and 3.96/86.2 ppm. Further assignments of the
signals at 4.46/180.5 ppm, 7.78/180.5 ppm, 7.78/57.8 ppm, and
4
4
14
7
14
7
4
7
6
7
.78/71.5 ppm for H /C , H /C , H /C , and H /C corre-
spond to the linkage between diaminoisoidide and sebacic acid
units. On the basis of the NMR results, it should be noted that in
view of the presence of the singlet at 4.67 ppm of diaminoisoidide
monomer and the signal at 4.80 ppm of DAII-based polyamides
the bicyclic building blocks have L-ido conformation and epimer-
ization of the initial L-ido into the D-manno conformation of the
diamine during synthesis can be excluded. Nonetheless, even
after the purification procedure of the polyamides, a set of weak
11
15
12 15
180.5 ppm and 1.58/180.5 ppm from H /C and H /C ,
respectively. Finally, due to the presence of the signals at 2.30/
184.0 ppm and 1.52/184.0 ppm and originating from two- and
17
16
18 16
three-bond correlations of H /C and H /C , it was possible
to prove the existence of sebacic acid units as end groups of the
PA (Figure 1).
Polyamide based exclusively on sebacic acid and diaminoisoi-
dide (entry 6 in Tables 1, 2, and 3) was obtained via interfacial
polycondensation of diaminoisoidide and sebacoyl chloride in a
water/chloroform emulsion. The reaction was carried out in the
presence of potassium carbonate. As reported by Thiem and
1
signals at around 3.9, 2.1, and 1.4 ppm in the H NMR spectra
can be seen. These signals can be associated with the presence of
trace amounts of the polyamide salts, which were used in the
synthesis of the polymers (see also Supporting Information,
Figure S3).
The sequence of 1,4-diaminobutane bonded with sebacic acid
units (Scheme 2) is confirmed by the presence of the cross-peaks
28
Bachmann the formation of polyamides during interfacial
polycondensation takes place in the organic solvent near the
aqueous phase. Simultaneously, the results presented by these
3
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Macromolecules
ARTICLE
authors clearly indicate that the molecular weight of polyamides
based on DAII is dependent on many factors such as tempera-
ture, type of organic solvent or molar ratio of the used mono-
mers. SEC data show that the molecular weight of the polyamide
based on diaminoisoidide and sebacic acid is slightly above 4000
g/mol (Table 1). This low molecular weight might be explained
by the high solubility of diaminoisoidide in water, reducing the
tendency to accumulate around the interface, and possible
hydrolysis of diacid chloride resulting in a change of the molar
18
1
ratio of the reactive compounds. The H NMR spectrum
presented in Figure 2 provides information regarding the che-
mical structure of the PA based on sebacic acid and diaminoi-
soidide (entry 6 in Table 1, see also Scheme 2 for the labeling of
7
the protons). The signals at 8.05 ppm are related to H protons
1
Figure 2. 400 MHz H NMR spectrum of the homopolyamide based
from the amide group. The peaks at δ = 4.33, 4.07, 3.80, and 3.58
0
5
4
6
6
on diaminoisoidide and sebacic acid.
ppm are assigned to DAII protons H , H , H , and H . They do
not suggest any conformational change of the DAII structure
during the synthesis. As expected, the signals related to sebacic
1
2
3
acid units H , H , and H are observed at 2.05, 1.44, and 1.20
ppm, respectively.
Figures 3 and S4 (in the Supporting Information) show FT-IR
spectra of the synthesized polyamides and co(polyamides) recorded
at 30 ꢀC. The spectra were normalized according to the area under
the symmetric and asymmetric methylene bands in the interval
ꢀ
1
2
800ꢀ3000 cm . In Figure S4 (Supporting Information) the
ꢀ
1
spectral range from 2800 to 3500 cm is presented. It shows
several significant differences between the synthesized materials with
different DAII contents. The signals at 3301ꢀ3315, 3201, and
ꢀ1
3
060ꢀ3072 cm are assigned to the NH stretch, NH stretch and
amide (I þ II overtone), and NH stretch with amide II overtone
38ꢀ41
vibrations, respectively.
It is interesting, however, that for the
polyamides with increasing content of DAII (coPA2-PA6), these
bands appear broader and weaker, which suggests a decrease of the
crystalline order and a reduction of the hydrogen bond density. This
phenomenon is consistent with the appearance and growth of the
ꢀ
1
Figure 3. FT-IR spectra of homopolymers PA1 and PA6 and copoly-
intensity of the bands around 1720 cm associated with “free” non-
42
mers coPA2, coPA3, coPA4, and coPA5, recorded at 30 ꢀC. The spectra
hydrogen-bonded carbonyl groups (Figure 3). The infrared
ꢀ1
ꢀ
1
show frequency ranges 1750ꢀ800 cm
.
spectra in the region 1800ꢀ800 cm show signals related to amide
ꢀ
1
I (CO stretch, 1636ꢀ1642 cm ), amide II (in-plane NH deforma-
ꢀ
1
tion with CO and CN stretches, 1542ꢀ1543 cm ), amide III
coupled with hydrocarbon skeleton (1358, 1291, 1189ꢀ
directly related to the content of diaminoisoidide residues in the
polymers. With increasing DAII content in the polyamides a
reduction in their thermal stability was observed. Upon heating of
PA1 (PA 4.10) a 5 wt % weight loss was observed around 420 ꢀC.
The temperature at 5% weight loss decreases to 300 ꢀC (entry 6 in
Table 2) with increasing DAII content. However, for the composi-
tions with a DAB/DAII mol ratio of 0.80/0.20 the differences in
thermal stability, compared to PA 4.10, were less pronounced (5%
weight loss T5% = 377 ꢀC). The explanation of this phenomenon
might be oxidation at the carbon atom in the R-position of the ether
oxygens in the diaminoisoidide residues, resulting in a lower thermal
stability of the materials containing DAII units. This decrease in the
thermal stability of the co- and homopolyamides containing diami-
noisoidide units in comparison to the commercially available PA
4.10, PA 6, or PA 6.6 can restrict their melt processing and further
applications at high temperature working conditions. Nevertheless,
the thermal stabilities in combination with the corresponding
melting points should enable melt processing of all co(polyamides)
synthesized in this work. Moreover, TGA measurements carried out
for the co(polyamides) with a DAII content lower than 43 mol %
show that these materials can be still valuable for many demanding
applications, similar to those found for PA 4.10 (see Table 2).
ꢀ
1
1
9
190 cm ), and the amide IV “crystallinity band” (CꢀCO stretch,
ꢀ
1 40,41,43
46 cm ).
Interesting information is also provided by the
1
ꢀ
presence of bands at 1476, 1466, and 1418 cm , which are assigned
to CH scissoring next to NH groups with trans conformation and
2
visible exclusively for PA 4.10 and copolymers having 1,4-diamino-
butane residues, CH scissoring not adjacent to the amide group, and
2
CH scissoring next to the CO group with trans conformation,
2
3
9,41
ꢀ1
respectively.
Furthermore, the weak bands at 1135ꢀ1142 cm
were identified and are assigned to skeletal CꢀC stretch, gauche
44
conformation. In the analyzed spectral region also bands related to
ꢀ
1
CꢀO stretching vibrations at 1080ꢀ1100 cm , CH wagging/
2
ꢀ
1
twist vibrations at 1392 and 1314 cm , skeletal CꢀC stretch
ꢀ
1
vibrations at 1255 and 1231 cm , CH rocking vibrations at
2
ꢀ
1
9
71 cm and amide stretching vibrations in the “crystalline phase”
at 903 cm are observed.
ꢀ
1
44ꢀ46
ꢀ1
The “crystalline”signals at 903 cm
are visible for the polymers containing DAII units and give strong
evidence for the presence of DAII residues in the crystalline phase of
these polyamides.
Thermal Properties of the Polyamides. From the thermo-
gravimetric and DSC analysis data, presented in Table 2, it is clear
that the thermal stability of the novel renewable polyamides is
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ARTICLE
Table 2. Thermal Stability, Melting and Crystallization
Temperatures, and Enthalpy of the Transitions Analyzed from
a
the Second DSC Heating and Cooling Runs
symbol T5% (ꢀC) Tmax (ꢀC) T
m
(ꢀC) ΔH
m
(J/g) T
c
c
(ꢀC) ΔH (J/g)
PA1
424
388
379
377
321
300
483
457
460
456
455
437
246
67.3
57.3
50.6
40.9
32.8
15.1
221
209
201
198
156
96
75.4
56.0
47.8
45.3
39.3
11.4
coPA2
coPA3
coPA4
coPA5
PA6
242
236
232
179, 198
152
a
T
5% = temperature of 5% mass loss, Tmax = temperature of maximal rate
of decomposition, T = melting point, T = crystallization temperature,
ΔH = enthalpy of the transition.
m
c
Figure 5. X-ray powder diffraction patterns of as-prepared co- and
homopolyamides with different contents of diaminoisoidide measured
at room temperature. The indices correspond to the packing mode of the
R-phase and the β-phase of common polyamides.
Wide-Angle X-ray Diffraction. The synthesized polyamides are
semicrystalline in the entire studied range of copolymer compo-
sitions (see Figure 5). The X-ray diffraction profiles of all
copolymers present strong analogueies with the X-ray diffraction
patterns of the corresponding homopolymers. In particular the
patterns of samples with a DAII content lower than 43 mol % are
similar to that of the sebacic acid/DAB homopolymer, displaying
the typical four polyamide reflections in the 2θ ranges 3ꢀ7ꢀ,
1
0ꢀ12ꢀ, and 18ꢀ25ꢀ, indexed as 001, 002, 100, and 010/110
(
Table 3). Therefore, it can be concluded that coPAs with DAII
Table 3. X-ray Diffraction Spacings for Co- and Homopo-
lyamides with Different Contents of Diaminoisoidide
Figure 4. DSC traces of the second heating cycle of the co- and
homopolyamides with different contents of diaminoisoidide.
X-ray diffraction (nm)
002 100 010/110 001 002
1.561 0.776 0.442
2θ (deg)
100 010/110
To investigate the melting and crystallization of the polyamides,
DSC analyses were performed. From the data presented in Table 2,
taken from the second heating and cooling scans, it follows that a
partial replacement of DAB units by diaminoisoidide in the structure
of polyamide 4.10 influences the melting point. The co(polyamides)
containing diaminoisoidide have lower melting and crystallization
temperatures in comparison to the homopolymer based on sebacic
acid and 1,4-diaminobutane. The synthesized, fully renewable
co(polyamides) exhibit tunable polarities and melting points. As
mentioned, lower melting points, and therewith lower processing
temperatures of the obtained DAII-containing co(polyamides), can
facilitate processing of these materials. The presence of DAII in the
structure of the PAs influences ΔH of the observed transitions. With
increasing DAII content in the polymers the enthalpy of the
transitions is strongly reduced compared to entry PA1 in Table 2.
These changes can be understood in terms of a reduction of the
hydrogen bond density in the co(polyamides), as was found by FT-
IR spectroscopy discussed above, less perfect chain packing of DAII-
containing polymers and a reduction of the lamellar crystal
symbol 001
PA1
0.379
0.380
0.380
0.380
-
5.66 11.38 20.00
5.68 11.46 20.00
5.68 11.46 20.00
5.68 11.40 20.00
23.46
23.44
23.44
23.44
-
coPA2 1.555 0.771 0.442
coPA3 1.555 0.771 0.442
coPA4 1.555 0.775 0.442
coPA5 1.686
PA6 1.624
-
-
0.442
0.442
5.24
5.44
-
-
20.00
20.00
-
-
contents lower than 43 mol % have a crystal structure similar to
that of the polyamide 4.10 based on 1,4-diaminobutane and
sebacic acid. This structure consists of stacked hydrogen-bonded
sheets, in which the polymer chains are arranged side-by-
24,48
side.
The 100 peak corresponds to the interchain distance
and the 010/110 peak to the intersheet distance. With increasing
DAII content the 010/110 reflection decreases in intensity, but it
does not show any shift in position. This suggests that the
intersheet distance is not affected by increasing the DAII content
for coPAs with a DAII content lower than 43 mol %.
43
thickness. Moreover, the widely reported effect related to struc-
47
tural rearrangement and the resulting two-peak melting was
especially visible for the copolymer containing around 43 mol %
of DAII (see Figure 4). This phenomenon can be explained by
melting of imperfect crystals (low temperature peak), recrystalliza-
tion upon heating and remelting of the more perfectly formed
crystals (high temperature peak).
The XRD pattern of the co(polyamide) with a DAII content of
43 mol % shows close resemblance to that of the sebacic acid/
DAII homopolymer, i.e. it gives only two strong reflections in the
2θ range 3ꢀ7ꢀ and 15ꢀ25ꢀ (see Figure 5). The latter single peak
in the 2θ range of 15ꢀ25ꢀ indicates that the material has
crystallized into a close to hexagonal packing of polymer chains.
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ARTICLE
1
In the XRD patterns of the coPA5 and SA/DAII-based
homopolyamide the reflection indexed as 001 shifts to lower
θ values compared to the same reflection of the other poly-
amides. This shift reveals an increase of the c-axis dimension of
spectrum of co(polyamide) coPA5, H NMR spectrum of the
DAII/sebacic acid salt and FT-IR spectra of the polyamides recorded
ꢀ
1
2
at 30 ꢀC in the frequency range 3500ꢀ2800 cm . This material is
available free of charge via the Internet at http://pubs.acs.org.
coPA5 due to cocrystallization of the two comonomers in the
4
9
same crystal lattice.
’ AUTHOR INFORMATION
Further and more detailed information will be described in a
following publication concerning crystallographic studies of the
new biobased co(polyamides). It will be also shown that for the
copolymers having up to 20 mol % of DAII the comonomer units
are included in the crystalline PA 4.10 phase, even though visible
changes of the unit cell dimensions do not occur.
Corresponding Author
E-mail: (C.E.K.) c.e.koning@tue.nl; (L.J.) l.jasinska@tue.nl.
Telephone: þ31-40-2472527. Fax: þ31-40-2463966. Address:
Laboratory of Polymer Chemistry, Eindhoven University of
Technology.
*
’
CONCLUSIONS
’
ACKNOWLEDGMENT
Fully biobased polyamides from sebacic acid, 1,4-diaminobutane,
This work forms part of the research program of Dutch
and diaminoisoidide (prepared from isomannide) were successfully
synthesized by either bulk melt polycondensation followed by solid
state polymerization (SSP) or by interfacial polycondensation. The
molecular weight and chemical structure of the polymers were
characterized by SEC, FT-IR, and 2D NMR, viz. by recording
COSY correlation spectra and heteronuclear multiple-bond correla-
tion spectra (HMBC). After a short melt polycondensation followed
by SSP white products with number-average molecular weights
above 18 000 g/mol and polydispersity indexes below 3.0 were
obtained. However, the interfacial polymerization route led to a
polymer with a significantly lower molecular weight, most probably
caused by hydrolysis of diacid chloride during the course of the
reaction. The analysis of 2D NMR spectra proved the presence of
diaminoisoidide, 1,4-diaminobutane and sebacic acid units as chain
fragments, while sebacic acid residues were also found as end-groups
of the macromolecules. More characterization details were provided
by FT-IR spectroscopy which showed that the presence of DAII
influenced the hydrogen bond density in the co(polyamides).
Moreover, FT-IR analysis also allowed to distinguish bands at
around 903 cm related to DAII residues incorporated into the
crystal structure also XRD analysis showed that the new biobased
co(polyamides) are semicrystalline. The XRD data indicate that with
increasing DAII content the typical polyamide structure with
different interchain and intersheet distances is preserved for samples
with DAII content lower than 43 mol %. At higher DAII contents the
structure changes into a structure with a close to hexagonal packing
of polymer chains. As expected, with the introduction of DAII into
the main chain of the polyamides the melting temperature decreased.
Significant differences between the melting points of the homo-
Polymer Institute (Project No. 656). We kindly thank Dr. Eng.
Pawez Sowi nꢀ ski for recording the 2D NMR spectra.
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2
(
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dx.doi.org/10.1021/ma200256v |Macromolecules 2011, 44, 3458–3466