Structural Changes in Poly(trimethylene adipate) and Poly(trimethylene succinate) During Melt Crystallization Studied Using In Situ Infrared Spectroscopy
Restricted accessResearch articleFirst published online November, 2017
Structural Changes in Poly(trimethylene adipate) and Poly(trimethylene succinate) During Melt Crystallization Studied Using In Situ Infrared Spectroscopy
This paper investigates the structural changes occurring in poly(trimethylene adipate) (PTAd) and poly(trimethylene succinate) (PTSu) during melt crystallization using differential scanning calorimetry (DSC) and in situ Fourier transform infrared (FT-IR) spectroscopy. Cooling thermograms revealed that PTAd had a faster crystallization rate than PTSu. Infrared (IR) bands of the two polyesters were assigned by correlating with the IR bands of polymers containing the trimethylene and the diacid segments. The bands at 1478, 1459, 1393, and 1364 cm−1 in PTAd and 1475, 1459, 1393, and 1361 cm−1 in PTSu were designated to the CH2 of the trimethylene segment. Changes in the IR band absorbance intensities of the CH2 and the C–O–C groups were monitored with time during melt crystallization. Structural changes of the trimethylene and diacid segments of PTAd occurred synchronously, while in PTSu the two segments changed sequentially. Normalized band intensities showed a time lag between the trimethylene and succinic acid segments. The acid segment showed a faster change compared to the trimethylene segment. Fourier transform infrared spectroscopy is shown to be a useful technique to study conformational changes during crystallization in polymers.
SasanumaY.NonakaY.YamaguchiY.“Conformational Characteristics and Configurational Properties of Poly(ethylene succinate) and Poly(tetramethylene succinate) and Structure–Property–Function Relationships of Representative Biodegradable Polyesters”. Polymer. 2015. 56: 327–339.
2.
KimH.J.KimS.B.KimJ.K.JungY.M.et al.“Phase Behavior of a Weakly Interacting Block Copolymer by Temperature-Dependent FT-IR Spectroscopy”. Macromolecules. 2006. 39(1): 408–412.
3.
KisterG.CassanasG.VertM.“Effects of Morphology, Conformation and Configuration on the IR and Raman Spectra of Various Poly(lactic acid)s”. Polymer. 1998. 39(2): 267–273.
4.
TashiroK.SasakiS.GoseN.KobayashiM.“Microscopically-Viewed Structural Change of Polyethylene During Isothermal Crystallization from the Melt I. Time-Resolved FT-IR Spectral Measurements”. Polym J. 1998. 30(6): 485–491.
5.
ZhangJ.DuanY.ShenD.YanS.et al.“Structure Changes During the Induction Period of Cold Crystallization of Isotactic Polystyrene Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy”. Macromolecules. 2004. 37(9): 3292–3298.
6.
RohindraD.R.TanakaM.KuboyamaK.OugizawaT.“Behavior of Pressure Dependence of Melting Temperatures in Aromatic Polyesters: Influence of Polymer Structure”. J. Polym. Sci. B. Polym. Phys. 2009. 47(18): 1799–1808.
7.
RohindraD.KuboyamaK.OugizawaT.“Dominant Factors Affecting the Pressure Dependence of Melting Temperatures in Homologous Series of Aliphatic Polyesters”. Eur. Polym. J. 2012. 48(10): 1768–1776.
8.
YamenM.OzkayaS.VasanthanN.“Structural and Conformational Changes During Thermally-Induced Crystallization of Poly(trimethylene terephthalate) by Infrared Spectroscopy”. J. Polym. Sci. B. Polym. Phys. 2008. 46(14): 1497–1504.
9.
BikiarisD.N.AchiliasD.S.“Synthesis of Poly(alkylene Succinate) Biodegradable Polyesters I. Mathematical Modelling of the Esterification Reaction”. Polymer. 2006. 47(13): 4851–4860.
10.
ChuahH.H.“Orientation and Structure Development in Poly(trimethylene Terephthalate) Tensile Drawing”. Macromolecules. 2001. 34(20): 6985–6993.
11.
KimK.J.BaeJ.H.KimY.H.“Infrared Spectroscopic Analysis of Poly(trimethylene Terephthalate)”. Polymer. 2001. 42(3): 1023–1033.
12.
HuangJ.M.ChangF.C.“Miscibility, Melting, and Crystallization of Poly(trimethylene Terephthalate)/Poly(ether Imide) Blends”. J. Appl. Polym. Sci. 2002. 84(4): 850–856.
13.
HuangJ.M.JuM.Y.ChuP.P.ChangF.C.“Crystallization and Melting Behaviors of Poly(trimethylene Terephthalate)”. J. Polym. Res. 1999. 6(4): 259–266.
14.
ChungW.T.YehW.J.HongP.D.“Melting Behavior of Poly(trimethylene Terephthalate)”. J. Appl. Polym. Sci. 2002. 83(11): 2426–2433.
15.
WuP.L.WooE.M.“Correlation Between Melting Behavior and Ringed Spherulites in Poly(trimethylene Terephthalate)”. J. Polym. Sci. B. Polym. Phys. 2003. 41(1): 80–93.
16.
SrimoaonP.DangseeyunN.SupapholP.“Multiple Melting Behavior in Isothermally Crystallized Poly(trimethylene Terephthalate)”. Eur. Polym. J. 2004. 40(3): 599–608.
17.
YunJ.H.KoboyamaK.OugizawaT.“High Birefringence of Poly(trimethylene Terephthalate) Spherulites”. Polymer. 2006. 47(5): 1715–1721.
18.
HoR.M.KeK.Z.ChenM.“Crystal Structure and Banded Spherulite of Poly(trimethylene Terephthalate)”. Macromolecules. 2000. 33(20): 7529–7537.
19.
ChenZ.YanS.“Structural Differences Between Cold- and Melt- Crystallized Poly(trimethylene Terephthalate) Samples”. Appl. Spectrosc. 2013. 67(3): 307–313.
20.
ZhangJ.“Effective Nucleating Chemical Agents for the Crystallization of Poly(trimethylene Terephthalate)”. J. Appl. Polym. Sci. 2004. 93(2): 590–601.
21.
JakewaysR.WardI.M.WildingM.A.HallI.H.et al.“Crystal Deformation in Aromatic Polyesters”. J. Polym. Sci. Poly. Phys. Ed. 1975. 13(4): 799–813.
22.
WardI.M.WildingM.A.BrodyH.“The Mechanical Properties and Structure of Poly(m-methyleneterephthalate) Fibers”. J. Polym. Sci. Polym. Phys. Ed. 1976. 14(2): 263–274.
23.
ZhangJ.TsujiH.NodaI.OzakiY.“Structural Changes and Crystallization Dynamics of Poly(L-lactide) during the Cold-Crystallization Process Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy”. Macromolecules. 2004. 37(17): 6433–6439.
24.
ZhengK.LiuR.HuangY.“A Two-Dimensional IR Correlation Spectroscopic Study of the Conformational Changes in Syndiotactic Polypropylene during Crystallization”. Polym J. 2010. 42(1): 81–85.
25.
IannaceS.NicolaisL.“Isothermal Crystallization and Chain Mobility of Poly(L-lactide)”. J Appl. Polym. Sci. 1997. 64(5): 911–919.
26.
HealeyA.M.HendraP.J.WestY.D.“A Fourier-Transform Raman-Study of the Strain-Induced Crystallization and Cold Crystallization of Natural-Rubber”. Polymer. 1996. 37(18): 4009–4024.
27.
ZhuX.YanD.FangY.“In Situ FT-IR Spectroscopic Study of the Conformational Change of Isotactic Polypropylene during the Crystallization Process”. J. Phys. Chem. B. 2001. 105(50): 12461–12463.
28.
DuanY.ZhangJ.ShenD.YanS.“In Situ FT-IR Studies on the Cold-Crystallization Process and Multiple Melting Behavior of Isotactic Polystyrene”. Macromolecules. 2003. 36(13): 4874–4879.
29.
JiangaY.GuaQ.LiaL.ShenaD.-Y.et al.“Conformational Changes in the Induction Period of Crystallization as Measured by FT-IR”. Polymer. 2003. 44(10): 3509–3513.
30.
ZhangJ.TsujiH.NodaI.OzakiY.“Weak Intermolecular Interactions during the Melt Crystallization of Poly(l-lactide) Investigated by Two-Dimensional Infrared Correlation Spectroscopy”. J. Phys. Chem. B. 2004. 108(31): 11514–11520.
31.
ZhangJ.M.LiC.W.DuanY.X.DombA.J.et al.“Glass transition and Disorder-to-Order Phase Transition Behavior of Poly(L-lactic Acid) Revealed by Infrared Spectroscopy”. Vib. Spectrosc. 2010. 53(2): 307–310.
32.
ZhangJ.SatoH.NodaI.OzakiY.“Conformation Rearrangement and Molecular Dynamics of Poly(3-hydroxybutyrate) During the Melt-Crystallization Process Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy”. Macromolecules. 2005. 38(10): 4274–4281.
33.
MeaurioE.ZuzaE.Lopez-RodrıguezN.SarasuaJ.R.“Conformational Behavior of Poly(L-lactide) Studied by Infrared Spectroscopy”. J. Phys. Chem. B. 2006. 110(11): 5790–5800.
34.
ZhangY.GuM.ZhangT.YuanY.et al.“Phase Transition Behavior of PLLA Ultrathin Film Studied by Grazing Angle Reflection Absorption Infrared Spectroscopy”. Vib Spectrosc. 2012. 63: 338–341.
35.
LiX.YangL.LiuD.“In situ FT-IR Spectroscopy Study on the Crystallization Process of Isotactic Polypropylene in Isotactic Polypropylene/Polyethylene-glycol Blends”. AMR. 2012. 476–478: 2223–2226.
36.
PapageorgiouG.Z.BikiarisD.N.“Crystallization and Melting Behavior of Three Biodegradable Poly(alkylene Succinates). A Comparative Study”. Polymer. 2005. 46(26): 12081–12092.
37.
SoccioM.LottiN.FinelliL.GazzanoM.et al.“Miscibility of Biodegradable Poly(proplyne Succinate)/Poly(propylene Adipate) Blends: Effect of the Transesterrification Reactions”. Eur. Polym. J. 2009. 45(3): 3236–3248.
38.
ZorbaT.ChrissafisK.ParaskevopoulosK.M.BikiarisD.N.“Synthesis, Characterization and Thermal Degradation Mechanism of Three Poly(alkylene Adipate)s: Comparative study”. Polym. Degrad. Stabil. 2007. 92(2): 222–230.
39.
BikiarisD.N.PapageorgiouG.Z.PapadimitriouS.A.KaravasE.et al.“Novel Biodegradable Polyester Poly(Propylene Succinate): Synthesis and Application in the Preparation of Solid Dispersions and Nanoparticles of a Water-Soluble Drug”. AAPS J. 2009. 10(1): 138–146.
40.
NanakiS.G.PantopoulosK.BikiarisD.“Synthesis of Biocompatible Poly(ɛ-caprolactone)- Block-poly(propylene Adipate) Copolymers Appropriate for Drug Nanoencapsulation in the Form of Core-Shell Nanoparticles”. Int. J. Nanomedicine. 2011. 6: 2981–2995.
41.
BikiarisD.KaravelidisV.KaravasE.“Novel Biodegradable Polyesters. Synthesis and Application as Drug Carriers for the Preparation of Raloxifene HCl Loaded Nanoparticles” Molecules. 2009. 14(6): 2410–2430.
42.
NanakiS.G.PapegeorgiouG.BikiarisD.“Crystallization of Novel Poly(e-caprolactone)-block-poly(propylene Adipate) Copolymers”. J. Thermal Anal. Calorim. 2012. 108(2): 633–645.
43.
YanC.ZhangY.HuY.OzakiY.et al.“Melt Crystallization and Crystal Transition of Poly(tetramethylene Adipate) Revealed by Infrared Spectroscopy”. J Phys Chem B. 2008. 112(11): 3311–3314.
44.
BikiarisD.N.PapageorgiouG.Z.GiliopoulosD.J.StergiouC.A.“Correlation Between Chemical and Solid-State Structures and Enzymatic Hydrolysis in Novel Biodegradable Polyesters. The Case of Poly(propylene alkanedicarboxylate)s”. Macromol. Biosci. 2008. 8: 728–740.
45.
PapageorgiousG.Z.BikiarisD.N.“Biodegradable Poly(alkylene Succinate) Blends: Thermal Behavior and Miscibility Study”. J. Polym. Sci., Part B. 2006. 44: 584–597.
46.
RohindraD.KuboyamaK.OugizawaT.“High Pressure Analysis of the Multiple Melting Peaks of Poly(ethylene Succinate) and Poly(butylene Succinate)”. J. Macro. Sci. B. Phys. 2010. 49(3): 470–478.
47.
QuiZ.B.KomuraM.IkeharaT.NishiT.“DSC and TMDSC Study of Multiple Melting Behavior of Poly(butylene Succinate) and Poly(ethylene Succinate)”. Polymer. 2003. 44(26): 7781–7785.
48.
QuiZ.B.KomuraM.IkeharaT.NishiT.“Melting Behavior of Poly(butylene Succinate) in Miscible Blends with Poly(ethylene Oxide)”. Polymer. 2003. 44(10): 3095–3099.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
