Controllable Preparation and Characterizations of ZIF⁃67/Polyphosphazene Composite Microspheres

doi:10.19491/j.issn.1001-9278.2021.01.001

Abstract

Abstract:

In this study， a new type of ZIF-67/polyphosphazene composite microspheres （ZIF-67@PZS） was designed and prepared by an insitu self-assembly method using poly（cyclotriphosphazene-co-4，4'-dihydroxydiphenylsulfone） microspheres （PZS） as a growth substrate for the ZIF-67 crystals. The optimum structural morphology of ZIF-67@PZS was determined by adjusting the mass ratio of raw materials. Scanning electron microscopy （SEM） characterizations indicated that the prepared ZIF-67@PZS presented a higher quality under a cobalt nitrate hexahydrate/2-methylimidazole/triethylamine molar ratio of 1/4/4 and a PZS/cobalt nitrate hexahydrate mass ratio of 5/1. The thermogravimetric analysis results showed that the initial decomposition temperature of ZIF?67@PZS increased by 119 and 20 °C and its residual char yield at 800 °C increased by 25.4 % and 4.7 % compared to pure ZIF-67 and PZS， respectively， indicating an excellent thermal stability. According to the SEM observation under the gradient time， the possible formation mechanism of ZIF-67@PZS was further deduced.

Key words: polyphosphazene, ZIF-67, synthesis mechanism, morphology control, thermal performance

CLC Number:

TB 333

SONG Kunpeng, WANG Yinjie, FANG Zhuqing, LIU Jiping, RUAN Fang. Controllable Preparation and Characterizations of ZIF⁃67/Polyphosphazene Composite Microspheres[J]. China Plastics, 2021, 35(1): 1-7.

Figures/Tables 12

组别	PZS/ g	Co(NO₃)·6H₂O/g	2?MeIM/g	TEA/g
A	0.364	0.364（1.25 mmol）	0.412（5.02 mmol）	0
B	1.822	0.364（1.25 mmol）	0.413（5.03 mmol）	0
C	0.364	0.364（1.25 mmol）	0.411（5.01 mmol）	0.506（5.00 mmol）
D	1.821	0.364（1.25 mmol）	0.412（5.02 mmol）	0.507（5.01 mmol）

Tab.1. Raw material ratio of ZIF?67@PZS

Fig.1. ZIF?67@PZS synthesis process

Fig.2. Infrared spectrum of PZS

Fig.3. SEM images and TEM images of PZS

Fig.4. SEM of ZIF?67@PZS formation process in group A

Fig.5. SEM of ZIF?67@PZS formation process in group B

Fig.6. SEM of ZIF?67@PZS formation process in group C

Fig.7. SEM of ZIF?67@PZS formation process in group D

Fig.8. Infrared spectrum of ZIF?67@PZS and its synthetic raw materials

Fig.9. XRD pattern of ZIF?67@PZS and its synthetic raw materials

Fig.10. TG curve of PZS, ZIF?67 and ZIF?67@PZS under nitrogen atmosphere

样品	T_onset/℃	T_max/℃	800℃残炭量/%
ZIF?67	364.3	510.3、558.7	34.8
PZS	463.4	520.6	55.5
ZIF?67@PZS	483.5	517.3	60.2

Tab.2. TG data of ZIF?67, PZS and ZIF?67@PZS

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