In-situ Intercalative Polymerization of Poly(lactic acid)/HTCC-saponite Nanocomposites and Their Properties Characterization†

doi:10.7503/cjcu20141059

Abstract

Abstract:

Water-soluble N-(2-hydroxyl)propyl-3-trimethyl ammonium chitosan chloride(HTCC) was synthesized with 2,3-epoxypropyl trimethyl ammonium chloride(GTA) grafting to the amino groups of chitosan by two-step method. Then, chitosan quaternary ammonium intercalated saponite(HTCC-saponite) was synthesized with HTCC and saponite under ultrasonication. Moreover, poly(lactic acid)(PLA)/HTCC-saponite nanocomposites were prepared by means of in-situ intercalative polymerization with HTCC-saponite and lactide. Orthogonal experiment showed the optimization polymerization parameters of PLA/HTCC-saponite were as follows: the polymerization temperature was 150 ℃, the amount of stannous caprylate was 2%(mass fraction), the amount of HTCC saponite was 1%(mass fraction) and the polymerization time was 16 h. The morphology analysis showed that the HTCC-saponite appeared with intercalative or partially exfoliated structure. The microstructure, morphology and thermal properties of PLA/HTCC-saponite nanocomposites were characterized by XRD, TEM, TG-DTG and DSC, respectively. The results showed that HTCC-saponite obviously promoted the crystallinity and thermal stability of PLA. The antibacterial results showed that HTCC-saponite had good antimicrobial properties, which was endowed in PLA/HTCC-saponite nanocomposites.

Key words: Poly(lactic acid)(PLA), Quaternized chitosan, Saponite, In-situ intercalative polymerization, Nanocomposite

CLC Number:

O631

TrendMD:

XI Xi, ZHEN Weijun, BIAN Shenzhen. In-situ Intercalative Polymerization of Poly(lactic acid)/HTCC-saponite Nanocomposites and Their Properties Characterization^†[J]. Chem. J. Chinese Universities, 2015, 36(3): 559.

Figures/Tables 15

Scheme 1 Synthesis routes of HTCC

Fig.1 FTIR spectra of CTS(a) and HTCC(b)

Fig.2 1H NMR spectrum for HTCC

Fig.3 XRD patterns of HTCC intercalated saponite with different mass ratios Mass ratio of saponite to HTCC: a. 1:0; b. 3:8; c. 2:1; d. 1:1.

Fig.4 SEM(A, B) and TEM(C, D) images of saponite(A, C) and HTCC-saponite(B, D)

Fig.5 GPC spectra of PLA(a) and PLA/HTCC-saponite(b)

Table 1 Molecular weight of PLA and PLA/HTCC-saponite

Sample	M_n	M_w	M_z	Polydispersity index
PLA	25861	49002	69708	1.89
PLA/HTCC-saponite	27684	51302	77432	1.85

Fig.6 XRD patterns of HTCC-saponite(a), PLA(b) and PLA/HTCC-saponite nanocomposites(c)

Fig.7 TEM image of PLA/HTCC-saponite nanocomposites

Fig.8 DSC curves of PLA(a) and PLA/HTCC-saponite nanocomposites(b)

Fig.9 TG(A) and DTG(B) curves of PLA(a) and PLA/HTCC-saponite nanocomposites(b)

Fig.10 POM images of PLA(A) and PLA/HTCC-saponite nanocomposites(B) isothermally crystallized at 130 °C for 15 min

Table 2 Minimum inhibitory concentration(MIC) values of saponite, HTCC-saponite antibacterial agents against E. coli, Bacillus subtilis, Aspergillus and Penicillium

Sample	MIC value/(mg·mL^-1)
Sample	E. coli	Bacillus subtilis	Aspergillus	Penicillium
Saponite	3.00	4.50	7.00	9.00
HTCC-saponite	2.50	2.75	4.25	4.75

Fig.11 Antimicrobial activity of PLA(A1—D1) and PLA/HTCC-saponite(A2—D2) antibacterial agents against E.coli(A1, A2), Bacillus subtilis(B1, B2), Aspergillus(C1, C2) and Penicillium(D1, D2)

Table 3 Antibacterial area of PLA and PLA/HTCC-saponite antibacterial agents against E.coli,Bacillus subtilis, Aspergillus and Penicillium

Sample	Bacteriostatic rings area/cm²
Sample	E. coli	Bacillus subtilis	Aspergillus	Penicillium
PLA	3.14	3.14	2.83	2.54
PLA/HTCC-saponite	7.06	4.52	4.90	6.64

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