Controllable preparation of hydrolysis⁃resistant crystalline poly（glycolic acid） using poly（epoxypropoxy） silsesquioxane

doi:10.19491/j.issn.1001-9278.2024.11.003

Abstract

Abstract:

Poly（epoxypropoxy） silsesquioxane （PESQ） was designed and synthesized and then melt blended with poly（glycolic acid）（PGA） at loadings of 0.5 wt%， 1.0 wt%， 2.0 wt% and 4.0 wt% to prepare the hydrolysis⁃resistant crystalline PGA. The changes in the rheological， hydrolysis， and crystallization properties of the PESQ⁃modified PGA was investigated to study the effect of PESQ modification on PGA. The results indicated that a combination of PESQ and PGA in a chain expansion form effectively improved the hydrolytic performance of PGA through increasing its viscosity， resulting in a reduction in the mass loss by 21.1 % after degrading for 10 days. Furthermore， PESQ could facilitate the crystallization of PGA. With an increase in the addition amount of PESQ， the crystallization temperature of the modified PGA increased to 179.5 ℃， which was higher than that of pure PGA by 6.8 ℃. There is a decrease in the initial crystallization activation energy of the modified PGA， indicating that PESQ contributed to heterogenous nucleation.

Key words: poly（glycolic acid）, poly（epoxypropoxy） silsesquioxane, hydrolytic property, crystallization property

CLC Number:

TQ325.1

WEN Wei, GONG Weiguang, MENG Xin. Controllable preparation of hydrolysis⁃resistant crystalline poly（glycolic acid） using poly（epoxypropoxy） silsesquioxane[J]. China Plastics, 2024, 38(11): 14-20.

Figures/Tables 16

Fig.1. Structural formula and crystal structure of PGA

Fig.2. Synthesis mechanism of PESQ

Fig.3. Reaction illustration of the PGA modified by PESQ

Fig.4. FTIR spectra of the PESQ

Fig.5. Effect of PESQ modification on dynamic scanning frequency of the PGA

Fig.6. Contacting angle of the PESQ modified PGAs

Fig.7. Mass loss ratio of the PESQ modified PGAs degraded for 10 days

Fig.8. Morphology of the PESQ modified PGAs degraded for 10 days

Fig.9. DSC curves of the PESQ modified PGAs

样品	结晶峰温度/℃	结晶焓/J·g^-1	低温熔融峰温度/℃	高温熔融峰温度/℃	二次熔融焓/J·g^-1	结晶度/%
PGA	172.7	80.8	—	221.3	84.6	46.2
PGA/0.5PESQ	175.9	84.0	208.0	221.5	86.4	47.2
PGA/1PESQ	177.8	86.7	208.5	221.2	87.2	47.6
PGA/2PESQ	179.4	87.5	208.9	221.1	88.6	48.4
PGA/4PESQ	179.5	93.3	209.2	221.4	90.1	49.2

Tab.1. Crystallization performance of the samples

Fig.10. XRD patterns of the PESQ modified PGAs

Fig.11. Crystallization curves of the PGA/PESQ system at different cooling rate

Fig.12. Changes of relative crystallinity of the PGA/PESQ systems with temperature

样品	结晶速率/℃·min^-1	结晶峰温度/℃	半结晶时间/s
PGA	2.5	184.3	884.2
	5.0	179.3	585.8
	10.0	173.1	179.0
	20.0	165.2	32.7
	30.0	159.4	25.8
PGA/4PESQ	2.5	190.5	383.3
	5.0	185.8	89.8
	10.0	180.0	41.4
	20.0	173.0	21.7
	30.0	167.4	23.5

Tab.2. Crystallization temperature and half⁃crystallization time of the PGA/PESQ system at different cooling rate

Fig.13. Friedman curves of the PESQ modified PGAs

Fig.14. Relationship between activation energy and relative crystallinity of the PESQ modified PGAs

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