Melt copolymer chains are the main (most abundant) reaction product obtained when heating a blend of two (or more) condensation polymers (such as polyester + polycarbonate or polyester + polyamide or polyester + polyester) in which exchange reactions occur. In fact, during the melt-mixing reaction, an AB copolymer is formed and, as a consequence, the sample is a complex mixture made of three components or simply “parts”, referred to as Z1, Z2 and Z3, where Z1 and Z2 are the parts for unreacted homopolymers (A and B), whereas Z3 is the part for the copolymer. In this paper, it is shown that matrix-assisted laser desorption/ionization mass spectrometry (and mass spectrometry in general) can be used to monitor the yield of the reactive blending reaction, YR, by measuring the amount of unreacted homopolymer (Z1 and Z2). In order to allow for comparisons, the paper also discusses conventional methods for measuring Z1 and Z2, such as liquid chromatography and nuclear magnetic resonance.
PorterR.S.WangL.H., “Compatibility And Transesterification In Binary Polymer Blends”, Polymer33, 2019–2030 (1992). doi: 10.1016/0032-3861(92)90866-U
2.
KotliarA.M., “Interchange reactions in condensation polymers”, J. Polym. Sci., Macromol. Rev.16, 367–395 (1981). doi: 10.1002/pol.1981.230160106
3.
LitmanovichA.D.PlateN.A.KudryavtsevY.V., “Reactions in polymer blends: Interchain effects and theoretical problems”, Progr. Polym. Sci.27, 915–970 (2002). doi: 10.1016/S0079-6700(02)00003-5
4.
Transreactions in condensation polymers, Ed by FakirovS., Wiley-VCH, New York, USA (2000).
5.
CollinsS.KenwrightA.M.PawsonC.PeaceS.K.RichardsR.W.MacDonaldW.A.MillsP., “Transesterification in Mixtures of Poly(ethylene terephthalate) and Poly(ethylene naphthalene-2,6-dicarboxylate): An NMR Study of Kinetics and End Group Effects”, Macromolecules33, 2974–2980 (2000). doi: 10.1021/ma9916382
6.
KricheldorfH.R.KreiserI., “Polylactones. 13. Transesterification of poly(l-lactide) with poly(glycolide), poly(β-propiolactone), and poly(ε-caprolactone)”, J. Macromol. Sci.: Chem.A24, 1345–56 (1987).
7.
KrentselL.B.MarkovaG.D.KudryavtsevY.V.FilatovaM.P.VasnevV.A.LitmanovichA.D.PlateN.A., “Transesterification of Poly(4,4-isopropylidene-2,2-dimethyldiphenylene terephthalate) and Poly(ethylene adipate) Blend in Solution”, Macromol. Chem. Phys.206, 2206–2211 (2005). doi: 10.1002/macp.200500265
8.
ImpallomeniG.GiuffridaM.BarbuzziT.MusumarraG.BallistreriA., “Acid Catalyzed Transesterification as a Route to Poly(3-hydroxybutyrate-co-eps-caprolactone) Copolymers from Their Homopolymers”, Biomacromolecules3, 835–840 (2002). doi: 10.1021/bm025525t
9.
DevauxJ.GodardP.MercierJ.P.TouillauxR.DereppeJ.M., “Bisphenol-A polycarbonate-poly(butylene terephthalate) transesterification. II. Structure analysis of the reaction products by IR and 1H and 13C NMR,”J. Polym. Sci.: Polym. Phys. Ed.20, 1881–1894 (1982). doi: 10.1002/pol.1982.180201011
10.
KollodgeJ.S.PorterR.S., “Phase Behavior and Transreaction Studies of Model Polyester/Bisphenol-A Polycarbonate Blends. 2. Molecular Weight, Composition, and End-Group Effects”, Macromolecules28, 4097–4105 (1996). doi: 10.1021/ma00116a008
11.
BertiC.BonoraV.PilatiF.FioriniM., “Reactive Blending of Poly(Ethylene-Terephthalate) And Polycarbonate .1. A Reappraisal of the Reactions Occurring During Melt-Mixing”, Makromol. Chem.–Macromol. Chem. Phys.193, 1665–1677 (1992). doi: 10.1002/macp.1992.021930710
12.
BertiC.BonoraV.PilatiF.FioriniM., “Reactive Blending of Poly(Ethylene-Terephthalate) and Polycarbonate. 2. A Novel Route To Copoly(Ester–Ether)s”, Makromol. Chem.–Macromol. Chem. Phys.193, 1679–1686 (1992). doi: 10.1002/macp.1992.021930711
13.
HoJ.C.WeiK.H., “The kinetics of transesterification in blends of liquid crystalline copolyester and polycarbonate”, Polymer40, 717–727 (1999). doi: 10.1016/S0032-3861(98)00014-7
14.
MontaudoG.PuglisiC.SamperiF., “Mechanism of Exchange in PBT/PC and PET/PC Blends. Composition of the Copolymer Formed in the Melt Mixing Process”, Macromolecules31, 650–661 (1998). doi: 10.1021/ma9712054
15.
WeiK.H.HoJ.C., “The Role of Transesterification on the Miscibility in Blends of Polycarbonate and Liquid Crystalline Copolyester”, Macromolecules30, 1587–1593 (1997). 10.1021/ma9615260
16.
MontaudoG.PuglisiC.SamperiF., “Sequencing Aromatic Copolycarbonate by Partial Ammonolysis and FAB-MS Analysis of the Products”, Polym. Bull.21, 483–488 (1989).
17.
PillonL.Z.UtrackiL.A., “Compatibilization of polyester/polyamide blends via catalytic ester–amide interchange reaction”, Polym. Eng. Sci.24, 1300–1305 (1984). doi: 10.1002/pen.760241706
18.
PrattipatiV.HuY.S.BandiS.MehtaS.SchiraldiD.A.HiltnerA.BaerE., “Improving the Transparency of Stretched Poly(ethylene terephthalate)/Polyamide Blends”, J. Appl. Polym. Sci.99, 225–235 (2006). doi: 10.1002/app.22463
19.
PrattipatiV.HuY.S.BandiS.SchiraldiD.A.HiltnerA.BaerE.MehtaS., “Effect of Compatibilization on the Oxygen-Barrier Properties of Poly(ethylene terephthalate)/Poly(m-xylylene adipamide) Blends”, J. Appl. Polym. Sci.97, 1361–1370 (2005). doi: 10.1002/app.21843
20.
KoulouriE.G.ScourlisE.C.KallitsisJ.K., “Characterization of melt-mixed blends of poly(ether-ester) with various polyamides”, Polymer40, 4887–4896 (1999). doi: 10.1016/S0032-3861(98)00707-1
21.
SamperiF.PuglisiC.AlicataR.MontaudoG., “Essential Role of Chain Ends in the Nylon-6/Poly (ethylene terephthalate) Exchange”, J. Polym. Sci: Part A: Polym. Chem.41, 2778–2793 (2003). doi: 10.1002/pola.10823
22.
SamperiF.MontaudoM.PuglisiC.AlicataR.MontaudoG, “Essential Role of Chain Ends in the Ny6/PBT Exchange. A Combined NMR and MALDI Approach”, Macromolecules36, 7143–7154 (2003). doi: 10.1021/ma0346153
23.
GattigliaE.TurturroA.LamantiaF.P.ValenzaA., “Blends of polyamide 6 and bisphenol A polycarbonate. Effects of interchange reactions on morphology and mechanical properties”, J. Appl. Polym. Sci.46, 1887–1897 (1992). doi: 10.1002/app.1992.070461102
24.
KimW.N.ParkC.E.BurnsC.M., “Ternary Blends of Poly(Amide-6)–Polycarbonate–Poly(Epsilon-Caprolactone)”, J. Appl. Polym. Sci.49, 1003–1011 (1993). doi: 10.1002/app.1993.070490606
25.
VanBennekomA.C.M.PluimersD.T.BussinkJ.GaymansR.J., “Blends of amide-modified polybutylene terephthalate and polycarbonate: Transesterification and degradation”, Polymer38, 3017–3024 (1997). doi: 10.1016/S0032-3861(96)00866-X
26.
MontaudoG.PuglisiC.SamperiF.LamantiaF.P., “Synthesis of AB and ABA Block Copolymers as Compatibilizers in Nylon 6/Polycarbonate Blends”, J. Polym. Sci: Part A: Polym. Chem.34, 1283–1290 (1996). doi: 10.1002/(SICI)1099-0518(199605)34:7<1283::AID-POLA15>3.0.CO;2-5
27.
MontaudoG.PuglisiC.SamperiF., “Exchange reactions occurring through active chain ends: Melt mixing of Nylon 6 and Polycarbonate”, J. Polym. Sci: Part A: Polym. Chem.32, 15–31 (1994). doi: 10.1002/pola.1994.080320103
28.
EerselsK.L.L.AerdtsA.M.GroeninckxG., “Transamidation in Melt-Mixed Aliphatic and Aromatic Polyamides. 2. Molecular Characterization of PA 46/PA 6I Blends as a Function of the Extrusion Time, Extrusion Temperature, and Blend Composition”, Macromolecules29, 1046–1050 (1996). doi: 10.1021/ma950786z
PuglisiC.SamperiF.DiGiorgiS.MontaudoG., “Exchange Reactions Occurring through Active Chain Ends. MALDI-TOF Characterization of Copolymers from Nylon 6,6 and Nylon 6,10”, Macromolecules36, 1098–1107 (2003). doi: 10.1021/ma021348c
31.
SamperiF.MontaudoM.S.PuglisiC.DiGiorgiS.MontaudoG., “Structural Characterization of Copolyamides Synthesized via the Facile Blending of Polyamides”, Macromolecules37, 6449–6459 (2004). doi: 10.1021/ma049575x
32.
EerselsK.L.L.GroeninckxG.MengerinkY.VanderWalS., “Transamidation in Melt-Mixed Aliphatic and Aromatic Polyamides. 3. Molecular Characterization Using Gradient Elution Chromatography (GEC)”, Macromolecules29, 6744–6749 (1996). doi: 10.1021/ma960549b
33.
ShalabyS.W.SifniadesS.SheermanD., “Syntheses and properties of phosporous-containing polyamides”, J. Polym. Sci. Polym. Chem. Ed.14, 2675–2687 (1976). doi: 10.1002/pol.1976.170141109
34.
RandallH., Polymer sequence determination (the 13C method). Academic Press, New York, USA (1977).
35.
MatlengiewiczM, “Tetrad distribution of an aromatic copolyterephthalate”, Macromolecules17, 473–478 (1984). doi: 10.1021/ma00133a039
36.
AdamusG.KowalczukM.MontaudoM.S., “Bivariate distribution in copolymers. A new model”, J. Polym. Sci., Part A: Polym. Chem.40, 2442–2448 (2002). doi: 10.1002/pola.10328
37.
MontaudoM.S., “Determination of the Compositional Distribution and Compositional Drift in Styrene/Maleic-Anhydryde Copolymers”, Macromolecules34, 2792–2799 (2001). doi: 10.1021/ma0010231
Mass Spectrometry of Polymers, Ed by MontaudoG.LattimerR.P., CRC Press, Boca Raton, Florida, USA (2002).
40.
MontaudoG.SamperiF.MontaudoM.S., “Characterization of synthetic polymers by MALDI-MS”, Progr. Polym. Sci.31, 277–357 (2006). doi: 10.1016/j.progpolymsci.2005.12.001
41.
AdamusG.RizzarelliP.MontaudoM.S.KowalczukM.MontaudoG., “MALDI-TOF with SEC fractionation for structural characterization of synthetic aliphatic copolyesters”, Rapid Commun. Mass Spectrom.20, 804–814 (2006). doi: 10.1002/rcm.2365
42.
TillierD.LefebvreH.TessierM.BlaisJ.C.FradetA., “High Temperature Bulk Reaction between Poly(ethylene terephthalate) and Lactones: 1H NMR and SEC/MALDI-TOF MS Study”, Macromol. Chem. Phys.205, 581–592 (2004). doi: 10.1002/macp.200300053
43.
SalhiS.TessierM.BlaisJ.C.El-GharbiR.FradetA., “Synthesis of Aliphatic-Aromatic Copolyesters by a High Temperature Bulk Reaction Between Poly(ethylene terephthalate) and Cyclodi(ethylene succinate)”, Macromol. Chem. Phys.205, 2391–2397 (2004). doi: 10.1002/macp.200400301
