Preparation and secondary processing test of dynamic reversible cross⁃linked poly（vinyl chloride）

doi:10.19491/j.issn.1001-9278.2022.03.014

Abstract

Abstract:

Dimercapto?terephenylborate was synthesized using α?thioglycerol and 1，4?benzenediboronic acid as monomers， and it was cross?linked with poly（vinyl chloride）（PVC） through melt blending. The resultant PVC with a dynamic reversible cross?linking structure was analyzed by infrared spectroscopy and hydrogen nuclear magnetic resonance spectroscopy to confirm the structure of dimercapto?terephenylborate. Meanwhile， dimercapto?terephenylborate was thermally analyzed to verify its feasibility as a cross?linking agent for PVC. The chemical structure， stress relaxation， creep properties， mechanical properties， and secondary processing performance of cross?linked PVC were further investigated. The results indicated that the dimercapto?terephenylborate?crosslinked PVC achieved an improvement in comprehensive properties， and it could be processed secondarily under the condition of higher gel degree with 90 % of the original mechanical properties retained after processing.

Key words: poly（vinyl chloride）, dimercapto?terephenylborate, reversible crosslinking, secondary processing

CLC Number:

TQ325.3

JIA Yao, ZHANG Ze, YU Zhengfa, CUI Yongyan. Preparation and secondary processing test of dynamic reversible cross⁃linked poly（vinyl chloride）[J]. China Plastics, 2022, 36(3): 82-88.

Figures/Tables 14

Fig.1. Reaction mechanism of thioglycerin and p?phenyldiboric acid

Fig.2. Reversible exchange mechanism of crosslinking agent dimercapto?terephenylborate

样品编号	PVC	DOP	Hst	二巯基对苯硼酸酯	KH⁃590	MgO	TMPD
1^#	100	30	0.5	0	0	2.5	1
2^#	100	30	0.5	0~5	0	2.5	1
3^#	100	30	0.5	0	3	2.5	1

Tab.1. Experimental formula

Fig.3. Molecular structure analysis of dimercapto?terephenylborate crosslinking agent

Fig.4. Thermal analysis of dimercapto?terephenylborate crosslinking agent

Fig.5. Reaction principle of sulfhydryl group with active chlorine in PVC

Fig.6. Infrared spectra of PVC and crosslinked PVC

Fig.7. Torque change of crosslinked PVC at 160 ℃

Fig.8. Swelling of crosslinked PVC at cyclohexanone for 48 hours

Fig.9. Influence of dimercapto?terephenylborate dosage on the gelation rate of PVC samples

Fig.10. Influence of dimercapto?terephenylborate dosage on the tensile properties of PVC samples

Fig.11. Influence of dimercapto?terephenylborate dosage on Tg of PVC samples

Fig.12. DMA test of cross?linked PVC samples

二巯基对苯硼酸酯含量/份	加工过程	拉伸强度/MPa	断裂伸长率/%
1	首次热压	21.867	295.878
1	二次热压	20.978	272.886
3	首次热压	26.054	234.878
3	二次热压	24.439	201.950
5	首次热压	29.514	220.101
5	二次热压	25.586	168.460

Tab.2. Mechanical properties of reversible cross?linked PVC before and after secondary processing

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