Preparation of two carboxylate nucleating agents and their nucleation effect on polypropylene

doi:10.19491/j.issn.1001-9278.2022.12.015

Abstract

Abstract:

Two types of α⁃form nucleating agents with a similar chemical structure， sodium bicyclo［2.2.1］hept⁃5⁃ene⁃2，3⁃dicarboxylate （NA₁） and sodium bicyclo［2.2.1］heptane⁃2，3⁃dicarboxylate （NA₂）， were synthesized， and their nucleation effects on the crystallization behavior of isotactic polypropylene （iPP） was studied. The crystallization temperature and crystal morphology of iPP nucleated with the two nucleating agents were investigated using differential scanning calorimetry and polarized optical microscope （PLM）. The results indicated that the crystallization peak temperature of iPP increased by 14.5 ℃ and 16.0 ℃ at 0.3 wt % NA₁and NA₂， respectively. Meanwhile， the two nucleating agents could refine the spherical crystal size of iPP significantly. The nucleated iPP was characterized using wide⁃angle X⁃ray diffraction. Both of two nucleating agents were found to induce the formation of α⁃form crystalline polypropylene， indicating good α⁃form nucleation effectiveness. The mechanical properties of the nucleated polypropylene were characterized. The nucleated polypropylene exhibited an increase in tensile strength and flexural modulus at first and then tended to be stable with increasing the contents of two nucleating agents. Compared to pure iPP， the tensile strength of the nucleated iPP increased by 4.6 % and 8.6 % at 0.05 wt % NA₁and NA₂， respectively. The iPP nucleated with 0.05 wt % NA₁and NA₂ also showed an increase in flexural modulus by 8.2 % and 21.7 %， respectively， and its impact strength keep stable basically.

Key words: isotactic polypropylene, α nucleating agent, crystallization behavior, mechanical property, isothermal crystallization kinetics

CLC Number:

TQ 325.1⁺4

ZHANG Zewen, ZHU Enci, ZHANG Xixiang, WEI Lijuan, ZHAO Shicheng. Preparation of two carboxylate nucleating agents and their nucleation effect on polypropylene[J]. China Plastics, 2022, 36(12): 100-107.

Figures/Tables 11

Fig.1. FTIR spectra of NA1 and NA2

Fig.2. DSC crystallization curves of iPP with different contents of NA1 and NA2

Fig.3. Effect of contents of NA1 and NA2 on the crystallization temperature of iPP

Fig.4. DSC melting curves of iPP with different contents of NA1 and NA2

Fig.5. WAXD pattern of iPP modified by NA1 and NA2

Fig.6. PLM images of iPP before and after modification for different time periods

Fig.7. Mechanical properties of iPP nucleated with different contents of NA1 and NA2

Fig.8. SEM of iPP/NA1 and iPP/NA2 and their elemental mapping images of oxygen and sodium

Fig.9. Isothermal crystallization curves of iPP/NA1 and plots of relative crystallinity vs. time at different temperature

样品	结温温度/℃	K/min^-1	n	t^a_1/2/min	t^b_1/2/min	t_max/min
iPP	125	3.40×10^-6	3.03	1.06	0.94	0.93
	126	1.21×10^-6	3.12	1.28	1.16	1.15
	127	6.74×10^-7	3.10	1.60	1.44	1.43
	128	1.50×10^-7	3.25	2.06	1.87	1.87
	129	6.48×10^-8	3.26	2.55	2.38	2.38
iPP/NA₁	141	2.95×10^-7	2.83	2.95	2.96	2.89
	142	6.87×10^-8	2.97	3.60	3.80	3.74
	143	8.52×10^-8	2.84	4.53	4.54	4.43
	144	8.70×10^-8	2.70	5.88	5.97	5.76
	145	1.35×10^-8	2.87	7.83	8.12	7.95
iPP/NA₂	141	1.90×10^-5	2.27	1.65	1.68	1.53
	142	7.83×10^-6	2.40	1.87	1.89	1.76
	143	4.07×10^-6	2.32	2.97	2.94	2.70
	144	8.20×10^-6	2.03	4.43	4.45	3.82
	145	4.47×10^-6	2.01	6.29	6.36	5.43

Tab.1. Kinetic parameters of isothermal crystallization of iPP and its composites

Fig.10. Plots of ln {-ln [1-X(t)]} of iPP/NA1 vs ln t at different temperature

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