Interfacial Interaction Mechanism of Etherified PBS and CMC Liquid Composites†

doi:10.7503/cjcu20140792

Abstract

Abstract:

Poly(butylene succinate)(PBS) was etherified by polyethylene glycol(PEG), and blended with carboxymethylcellulose(CMC). A novel liquid composite(PEG/PBS)-CMC was successfully prepared in water solution. The interaction mechanism of (PEG/PBS)-CMC composite was investigated by molecular simulation. The results showed that the desired structure of PEG/PBS with good hydrophilicity was achieved. Molecular simulation displayed that the polarity and flexibility of PEG/PBS was enhanced by introducing PEG to PBS. The interactions of (PEG/PBS)-CMC were hydrogen bonding, van der Waals, hydrophobic bond and adsorption. This results were explained by the deviation of absorption peak frequency on functional groups such as —OH, —OCO—, —COOH and —C—O—C— in Fourier transform infrared(FTIR) and the binding energy transfer of C and O element in X-ray photoelectron spectroseopy(XPS). Non-covalent interaction existed between composites displayed in polarizing optical microscope(POM) and X-ray diffraction(XRD). The closely integrated interface of (PEG/PBS)-CMC in scanning electron microscope(SEM) showed that the binding forces and the compatibility were enhanced after etherification modification.

Key words: Etherified polycbutylene suceinate, Carboxymethyl cellulose, Liquid composite, Dynamics simulation, Interaction

CLC Number:

O631
TQ31

TrendMD:

ZHANG Min, XU Xiaoling, SONG Jiqing, HE Wenqing. Interfacial Interaction Mechanism of Etherified PBS and CMC Liquid Composites^†[J]. Chem. J. Chinese Universities, 2015, 36(4): 808.

Figures/Tables 12

Scheme 1 Synthesis routes of PBS and PEG/PBS copolymer

Table 1 1H NMR date information of PBS and PEG/PBS copolymer

Polymer	δ	Ownership	Structural unit
TMS	0	—CH₃	(CH₃)₄Si
PBS	1.72	—CH₂—	BDO
	2.62	—CH₂—C ＝O	SA
	4.13	—CH₂—O—	BDO
PEG/PBS(50/50)	3.68	—CH₂—O—	PEG
	4.28	—CH₂—OOC—	PEG
Solvent	7.26	—C—D—	CDCl₃

Fig.1 Contact angle of PBS and PEG/PBS

Fig.2 Structures of CMC(A, stick mode), PBS(B, ball mode) and PEG/PBS(C, ball mode) Carbon: gray; hydrogen: white; oxygen: red.

Fig.3 Dynamics simulation models of CMC-CMC(A), PBS-CMC(B) and (PEG/PBS)-CMC(C) in aqueous solution Carbon: gray; hydrogen: white; oxygen: red.

Table 2 Energy of CMC-CMC, PBS-CMC and (PEG/PBS)-CMC by dynamics simulation

Composity	10^-4 E_Mixing / (kJ·mol^-1)	10^-3E_Dihedral / (kJ·mol^-1)	10^-3 E_Angle / (kJ·mol^-1)	10^-3 E_Bond / ( kJ·mol^-1)	10^-3 E_Vdw / (kJ·mol^-1)
CMC-CMC	-11.26	6.23	5.78	13.22	21.25
PBS-CMC	-2.47	3.21	1.54	3.21	4.59
(PEG/PBS)-CMC	-8.18	3.25	4.76	10.52	15.28

Fig.4 Energy distribution of CMC-CMC(a), PBS-CMC(b) and (PEG/PBS)-CMC(c) (A) EMixing; (B) EDihedral; (C) EAngle; (D) EBond; (E) EVdw.

Fig.5 FTIR spectra of CMC-CMC(a), PBS-CMC(b) and (PEG/PBS)-CMC(c)

Fig.6 XPS spectra of composites(A) and the energy distribution of C1s(B), O1s(C),Na1s(D) of CMC-CMC(a), PBS-CMC(b) and (PEG/PBS)-CMC(c)

Table 3 Atomic composition of composites from XPS

Sample	E_B(C₁_s)/eV				E_B(O₁_s)/eV			E_binding(Na₁_s)/eV
Sample	—C—C—, C—H	—C—O—	C=O	—O—C=O	—C—O—	—C=O	—O—C=O	—COONa
CMC	282.61	284.15	285.70	290.61	529.08	530.48	533.68	1068.82
PBS-CMC	282.01	283.32	284.87		528.15	529.69	532.57	1068.22
PEG/PBS-CMC	282.23	283.55	286.01	289.85		530.05	532.75	1068.47

Fig.7 POM images(A—C) and XRD spectra(D) of CMC-CMC(A,a), PBS-CMC(B,b) and (PEG/PBS)-CMC(C,c)

Fig.8 SEM images of CMC-CMC(A), PBS-CMC(B) and (PEG/PBS)-CMC(C)

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