2.  Polyamides, also known as nylons, are the first commercial synthetic polymers entering
modern life.
 Polyamides have a repeating amide group (―CONH―) in their molecular structure.
 The world’s first sytnhetic fiber was invented by Carothers at Du Pont laboratories in
1935 and was called as Nylon 66.
Chemical structure of Nylon 66:
Introduction

3.  PA6 has good stiffness, strength, toughness, resistance to chemicals and thermal stability.
 It is mostly used in electrical, automotive and packaging applications.
 Polyamide 6 is mostly synthesized in melt by the ring opening polymerization of
caprolactam. Molecular weight of the polymer is increased by a solid-state polymerization
process where mobile reactive groups are able to react below the melting temperature of
the polymer.
Polyamide 6

4. Scope of the study
 To improve the properties of PA6 incorporation of different monomers/oligomers/polymers
can be realized according to the desired applications.
 If the modification of PA6 is carried out in solution or in the solid state above the glass
transition but below the melting temperature of PA6 then, the good properties of PA6 can
be retained while some other desired properties can be obtained.
 Using solution or solid state polymerization route, deformation of the crystalline phase is
prevented, which provides good mechanical and thermal properties to PA6. The
modification of the polyamide occurs in the mobile amorphous phase.

5. PART 1: Multiblock polyesteramide synthesis from short polyamide and polyester
blocks for enhanced biodegradability. This was done either following an
isocyanate or epoxide route.
PART 2: Incorporation of a semi-aromatic nylon salt into PA6 backbone by SSP by
making use of transreactions. Salt can be chosen according to the desired
property of the copolymer such as higher Tg, increased hydrophobicity,
flame retardancy, etc.
Two main approaches used in this study

6. Part 1-Isocyanate route
6

7. Synthesis and the thermal properties of the copolymer
10 12 14 16 18 20 22 24 26 28 30
NormalizedRISECsignal
SSP-160 °C
SSP-140 °C
SSP-100 °C
PA6C
TPCL
Elution time (min)
End of solution mixing
SSP-60 °C
SEC chromatograms recorded during the
multiblock copolymer formation.
-40 -20 0 20 40 60 80 100 120 140 160 180 200 220
Temperature (°C)
Heatflow(W/g)Endodown
156.3°C
-7.6°C
36.6°C 199.3°C
206.4°C
TPCL
PA6
PEA-ASM
heating
cooling
43.6°C
DSC traces of the second heating cycle of TPCL, PA6
and the second heating and cooling scans of PEA-
ASM polymer.

8. Biodegradation
Scanning electron micrographs of the polymer
films:
(A) PEA-ASM before degradation,
(B) PEA-ASM after 4 weeks of enzymatic
degradation,
(C) PEA-ASM after 8 weeks of enzymatic
degradation,
(D) Commercial PA6 after 8 weeks of
enzymatic degradation.
Remaining weight (%) of the polymers vs. time
of degradation during
(▪) enzymatic degradation of PA6,
(●) hydrolytic degradation of PEA-ASM,
(▲) enzymatic degradation of PEA-ASM.
0 10 20 30 40 50 60
80
85
90
95
100
Remainingweight(%)
Degradation time (days)

9. PART 2-Incorporation of a semi-aromatic nylon salt into PA6
 Commercial grade, high molecular weight PA6 was
mixed with different amounts of Dytek A/IPA salt in a
common solvent.
 The solvent was removed at 55 °C.
 After drying of the mixture, SSP was carried out at
180 °C which was continued at 200 °C for a total of 24
hours.
Via solid state polymerization:
Via melt polymerization:
 ε-Caprolactam was reacted with different amounts of
Dytek A/IPA salt at 265 °C overnight.
 Unreacted monomers and cyclic compounds were
extracted in demi-water at 100 °C and dried.
Scheme for the incorporation of the
nylon salt into the PA6 backbone of
the PA6 during the solid state
polymerization

10. Molecular weight analysis of the copolyamides
14 16 18 20 22 24 26 28 30 32 34 36 38
NormalizedUVSECsignal Elution time (min)
0 h
0.5 h
1 h
2 h
4 h
8 h
12 h
16 h
24 h
14 16 18 20 22 24 26 28 30
NormalizedRISECsignal
Elution time (min)
0 h
0.5 h
1 h
2 h
4 h
8 h
12 h
16 h
24 h
Dytek A IPA
SEC chromatographs of the copolyamides at different reactions times recorded
with an RI and an UV detector.

11. Thermal properties of the copolyamides
Comparison of the DSC traces of the first (---) and second (―)heating and cooling runs
of PA6, copolymers with 20 wt% salt in feed synthesized via SSP and MP and salt
homopolymer.
40 60 80 100 120 140 160 180 200 220
(CL/DyI20
)M2
(CL/DyI20
)S2
DyI HP
Temperature (ºC)
Heatflow,Endodown(W/g)
PA6
40 60 80 100120140160180200220
Temperature (ºC)
Heatflow,Endodown(W/g)
(CL/DyI20
)M2
(CL/DyI20
)S2
DyI HP
PA6

12. The degree of randomness (R) of the copolyamides
10 15 20 25 30
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Dytek A-IPA salt (wt%)
DegreeofrandomnessR
Melt polymerization
Solid-state modification

13. Local chain conformation and the morphology of the copolyamides
3400 3200 3000 2800
2895
2868
2937
3072
3202
220
o
C
Absorbance[a.u.]
Wavenumber [cm-1
]
Heat
30
o
C
3300
1500 1400 1300 1200 1100 1000 900 800
927
960
1029
1121
1170
1201
1239
1266
1292
1373
1417
1436
14541462
1477
220
o
C
Absorbance[a.u.]
Wavenumber [cm-1
]
Heat
30
o
C
1505
*
* *
* Bands associated with the hydrogen-bonded NH stretching vibration become less
pronounced close to the melting temperatures of the copolymers.
* Bands associated with the methylene units totally disappear upon heating indicating a
Brill transition where the interchain and intersheet distances of the chains become equal
forming a pseudohexagonal phase.
* * * * *

14. 10 15 20 25 30
100
002/202
200
PA6
(CL/DyI20
)S2
(CL/DyI30
)S2
Intensity
2 (deg)
180 160 140 55 50 45 40 35 30 25 20 15 10
ppm
212 °C
193 °C
174 °C
155 °C
136 °C
117 °C
98 °C
79 °C
60 °C
41 °C
t g t t,g g t
C1 C2, C3
C4
C5
IPACOIPA
CO
Local chain conformation and the morphology of the copolyamides
X-ray powder diffraction patterns of the
homopolymer and copolymers of PA6
with 20 wt% and 30 wt% DyI salt in the
feed .
Temperature-dependent solid state 13C CP/MAS NMR
spectra of the copolymer with 20 wt% DyI salt in the
feed.

15. Conclusions
 Polyesteramide multiblock copolymers were synthesized in solution and in the solid
state by using an isocyanate route and an epoxide route. By this way biodegradability
of the PA6 can be enhanced.
 Incorporation of a semi-aromatic nylon salt into the backbone of the high molecular
weight PA6 was performed in the solid state. A comparison with the melt polymerized
samples showed that superior thermal properties were obtained in case of solid-state
modification. The degree of randomness analysis indicated a block structure when SSP
was used.
 Analysis of the PA6-salt copolymers with temperature dependent FTIR showed the
formation of non-hydrogen bonded amide groups with increasing salt content and the
Brill transition at around 160-180 °C. X-Ray and solid-state NMR results were in
agreement indicating no co-crystallization of the salt with the PA6 chains.

16. Acknowledgements
Cor Koning
Thierry Leblanc
Donglin Tang
Lidia Jasinska-Walc
Marko Nieuwenhuizen
Maurizio Villani
Martin Fijten
Rinske Knoop
Rene Kierkels
Rudy Rulkens
Ronald Ligthart
Pim Janssen
Marcel Aussems
Victoria de Bruijn
16
Magnus Eriksson
Mats Martinelle
Max-Planck
Institute for
Polymer Research
Michael Ryan Hansen

18. Part 1-B-Epoxide route

19. Synthesis of polyesteramide copolymers
80 °C, 0.45 wt%
80 °C, 0.90 wt%
100 °C, 0.45 wt%
100 °C, 0.90 wt%
120 °C, 0.45 wt%
120 °C, 0.90 wt%
140 °C, 0.45 wt%
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
2000
3000
4000
5000
6000
7000
8000
9000
10000
MnSEC(g/mol)
Time (h)
0 5 10 15 20 25 30 35 40 45 50
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
Time (h)
MnSEC(g/mol)
80 °C, no cat.
80 °C, 2 wt%
80 °C, 5 wt%
100 °C, no cat.
100 °C, 2 wt%
100 °C, 5 wt%
120 °C, no cat.
Increase in molecular
weight during the
reaction of PA6 and the
oligoester with DMAP as
catalyst.
Increase in molecular
weight during the reaction
of PA6 and the oligoester
with or without TEA as
catalyst.

20. Thermal analysis of the copolymers
DSC heating and cooling scans of
DEPA, PA6 and the polyesteramide
copolymer.
-80 -40 0 40 80 120 160 200
-68.9 °C
205.0 °C
Heatflow(W/g)Endodown
Temperature (°C)
DEPA
PA6
PA6/DEPA
4.9 °C
205.5 °C
-40 0 40 80 120 160 200
169.4 °C
166.1 °C
Temperature (°C)
Heatflow(W/g)Endodown
DEPA
PA6
PA6/DEPA