Photopolymerization Kinetics of Poly(Acrylate Acid) Hydrogels Induced by Blue Light †

doi:10.7503/cjcu20190362

Abstract

Abstract:

In order to establish the photopolymerization kinetics model of the blue light induced photo-polymerization and crosslinking of hydrogels, camphorquinone/ diphenyl iodonium hexafluorophosphate(CQ/DPI) were chosen as initiator, and acrylic acid(AA), polyethylene glycol diacrylate(PEGDA, $M ? n$ =1000) were chosen as monomer and crosslinker, respectively. Such hydrogel precursor was examined by photo-DSC and photo-rheology analysis under ca. 450 nm blue light to gain insight into the polymerization mechanism and evaluate the polymerization process. CQ/DPI photoinitiator exhibited a high efficiency which was advantageous to photopolymerization in aqueous solution. The maximum polymerization rate was found to be proportional to the square root of the initiator system w_CQ, w_DPI and illumination intensity(I), and the quantum yield and free volume effect played an important role in the polymerization rate and double bond conversion. The elastic modulus G', gel point time, delay time and cross-linking rate have different functional relationships with the initiator system(w_CQ, w_DPI and I). Based on the power law relationship between elastic modulus G' and I , w_CQ and w_DPI, the linear relationship between delay time and $w CQ 0.5$ , $w 0.5 DPI$ and I ^0.5, the linear relationship between crosslinking rate and $w CQ 0.5$ , $w DPI 0.5$ , I ^0.5 and monomer concentrations(w_AA), an empirical model describing the mechanical properties of blue-light initiate photopolymerization of PAAc hydrogels was proposed. Such model provides an approach to predicating the gelation process which was advantageous to developing and constructing new hydrogel structures.

Key words: Blue light polymerization, Poly(acrylic acid) hydrogel, Polymerization kinetics, Crosslinking structure, Elastic modulus

CLC Number:

O631.5

TrendMD:

SUN Guangdong, PAN Xiaopeng, ZHONG Yuhao, CHEN Enyu, HUANG Yi, SHAO Jianzhong. Photopolymerization Kinetics of Poly(Acrylate Acid) Hydrogels Induced by Blue Light ^†[J]. Chem. J. Chinese Universities, 2019, 40(11): 2404.

Figures/Tables 8

Scheme 1 Experimental equipment for testing photorheological properties of hydrogel precursors

Fig.1 Polymerization rates(A—C) and kinetic fitting curves(D—F) of the polymerization precursor at different CQ(A, D), DPI(B, E) amounts and light intensity(C, F) (A, D) wDPI=0.25%, wAA=30%, I=22.2 mW/cm2; (B, E) wCQ=0.5%, wAA=30%, I=22.2 mW/cm2; (C, F) wCQ=0.5%, wDPI=0.25%, wAA=30%.

Fig.2 Double bond conversion of the polymerization precursor at different CQ(A), DPI(B) concentrations and light intensity(C) (A) wDPI=0.25%, wAA=30%, I=22.2 mW/cm2; (B) wCQ=0.5%, wAA=30%, I=22.2 mW/cm2; (C) wCQ=0.5%, wDPI=0.25%, wAA=30%.

Scheme 2 Diagram of the mechanism of CQ/DPI initiation system

Fig.3 Damping factor of the polymerization precursor at different CQ(A) and AA concentrations(B) (A) wDPI=0.25%, wAA=30%, I=22.2 mW/cm2; (B) wCQ=0.5%, wDPI=0.25%, I=22.2 mW/cm2.

Fig.4 Storage modulus of the polymerization precursor at different CQ(A) and AA concentrations(B) (A) wDPI=0.25%, wAA=30%, I=22.2 mW/cm2; (B) wCQ=0.5%, wDPI=0.25%, I=22.2 mW/cm2.

Fig.5 Fitting curves of the polymerization precursor at different CQ(A) and AA concentrations(B) (A) wDPI=0.25%, wAA=30%, I=22.2 mW/cm2; (B) wCQ=0.5%, wDPI=0.25%, I=22.2 mW/cm2.

Fig.6 Crosslinking rates(A, B) and onset times(C, D) of the polymerization precursor at different CQ(A, C) and AA concentrations(B, D) (A, C) wDPI=0.25%, wAA=30%, I=22.2 mW/cm2; (B, D) wCQ=0.5%, wDPI=0.25%, I=22.2 mW/cm2.

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