SSBR/TPI共混体系中TPI的结晶、 成核及动力学研究

doi:10.7503/cjcu20170664

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 1091.doi: 10.7503/cjcu20170664

SSBR/TPI共混体系中TPI的结晶、成核及动力学研究

任惠成, 武营飞, 刘丹丹, 聂华荣, 贺爱华

山东省烯烃催化与聚合重点实验室, 橡塑材料与工程教育部重点实验室,青岛科技大学高分子科学与工程学院, 青岛 266042

收稿日期:2017-09-30 出版日期:2018-01-13 发布日期:2018-01-13
作者简介:
联系人简介: 贺爱华, 女, 博士, 教授, 博士生导师, 主要从事烯烃、二烯烃配位聚合及聚合物结构与性能研究. E-mail: aihuahe@iccas.ac.cn;聂华荣, 女, 博士, 教授, 主要从事反式橡胶新材料结构与性能及Janus粒子在聚合物中的应用研究. E-mail: niehr@iccas.ac.cn
基金资助:
国家重点基础研究发展计划项目[批准号: 2015CB654700(2015CB354706)]、国家自然科学基金(批准号: 51473083, 51773105)、山东省重大基础研究项目(批准号: ZR2017ZA0304)、山东省自然科学基金(批准号: ZR2016EMM05)、泰山学者工程和黄河三角洲学者工程专项经费资助.

Crystallization, Nucleation and Kinetics of TPI in SSBR/TPI Blends^†

REN Huicheng, WU Yingfei, LIU Dandan, NIE Huarong^*, HE Aihua^*

Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization, Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Received:2017-09-30 Online:2018-01-13 Published:2018-01-13
Contact: NIE Huarong,HE Aihua
Supported by:
Supported by the National Basic Research Development Program of China[No.2015CB654700(2015CB354706)], the National Natural Science Foundation of China(Nos.51473083, 51773105), the Major Basic Research Program of Shandong Province, China(No.ZR2017ZA0304), the Natural Science Foundation of Shandong Province, China(No.ZR2016EMM05) and the Special Foundation of Taishan Mountain Scholar Constructive Program and the Yellow River Delta Scholar Program, China.

摘要/Abstract

摘要：

研究了不相容共混体系溶聚丁苯橡胶(SSBR)/反式-1,4-聚异戊二烯(TPI)共混体系的结晶行为. 当SSBR含量较低时, SSBR/TPI共混物的成核密度降低, 晶体生长速率降低, 等温结晶速率降低, 非等温结晶峰移向低温, SSBR抑制了α-TPI 的生成, SSBR/TPI共混体系总结晶度降低, 但TPI的相对结晶度升高, 结晶行为与热力学相容的结晶/非晶共混体系一致; 当SSBR含量较高时, 随着SSBR含量增加, 体系的成核密度增加, 球晶的生长速率显著降低, SSBR显著抑制了α-TPI 的生成, 共混体系以β晶为主.

关键词: 溶聚丁苯橡胶/反式-1, 4-聚异戊二烯(SSBR/TPI)共混体系, 结晶行为, 结晶动力学

Abstract:

Crystallization behavior including polymorphic behavior, nucleation density, crystal growth rate, kinetics of isothermal and non-isothermal crystallization in the immiscible solution polymerized styrene-butadiene rubber(SSBR)/trans-1,4-polyisoprene(TPI) blends were investigated by polarized optical microscopy(POM), wide angel X-ray diffraction(WAXD) and differential scanning calorimeter(DSC). The results show that less than 40%(mass fraction) of SSBR admixing with TPI brings about the suppressed nucleation and crystal growth rate of TPI. The overall crystallinity declines with the addition and increase of amorphous SSBR content, the normalized crystallinity of TPI, however, increases due to the decreased crystallization rate, resulted from the dilution of SSBR components, in turns the reduced equilibrium melting points and the lower undercooling. Additionally, the amorphous component SSBR depresses the formation of α-TPI crystal while enables the formation of β-TPI crystal. Both the reduced crystallization rate of TPI during the isothermal crystallization and the lower crystallization temperature of TPI during non-isothermal crystallization were observed with the increase of SSBR content. All these results are in line with the crystallization behavior of the miscible amorphous/crystalline polymer blends because of the neglectable phase separation arising from the high viscosity of both rubber components leading to the slow dynamic of molecules. However, as the content of SSBR reached a high level, the nucleation density of the system increased with SSBR content increasing due to the phase separation exerting its influence on TPI crystallization.

Key words: Styrene-butadiene rubber/trans-1, 4-polyisoprene(SSBR/TPI) blend, Crystallization behavior, Crystallization kinetics

中图分类号:

O631

TrendMD:

任惠成, 武营飞, 刘丹丹, 聂华荣, 贺爱华. SSBR/TPI共混体系中TPI的结晶、成核及动力学研究. 高等学校化学学报, 2018, 39(5): 1091.

REN Huicheng,WU Yingfei,LIU Dandan,NIE Huarong,HE Aihua. Crystallization, Nucleation and Kinetics of TPI in SSBR/TPI Blends^†. Chem. J. Chinese Universities, 2018, 39(5): 1091.

图/表 9

Fig.1 POM images of SSBR/TPI blends crystallized at 35 ℃ Note:mSSBR/mTPI: (A) 0/100; (B) 10/90; (C) 20/80; (D) 40/60; (E )80/20; (F) 90/10.

Fig.2 Nucleation density versus the SSBR content at 35 ℃

Fig.3 Spherulite growth rate of SSBR/TPI blends at 35 ℃

Fig.4 WAXD patterns of SSBR/TPI blends crystallized at 35 ℃ Note:mSSBR/mTPI: a. 0/100; b. 10/90; c. 20/80; d. 40/60; e. 80/20; f. 90/10.

Table 1 Values of Xα, Xβ, total crystallinity and normalized TPI crystallinity calculated from WAXD

m_SSBR/m_TPI	X_α(%)	X_β(%)	X_c(%)	X_c,TPI(%)
0/100	67.4	32.6	30.1	30.1
10/90	66.1	33.9	29.3	32.5
20/80	65.6	34.4	26.3	32.9
40/60	64.9	35.1	19.9	33.2
80/20	35.2	64.8	9.8	49.2
90/10	5.2	94.8	5.9	53.2

Fig.5 DSC(A) and isothermal crystallization(B) curves of SSBR/TPI blends at 35 ℃ Note: mSSBR/mTPI: a. 0/100; b. 10/90; c. 20/80; d. 40/60; e. 80/20; f. 90/10.

Table 2 Crystallization parameters of SSBR/TPI blends at 35 ℃

m_SSBR/m_TPI	ΔH_c/(J∙g^-1)	ΔH_c,TPI/(J∙g^-1)	t_1/2/min
0/100	42.3	42.3	3.8
10/90	38.4	42.7	6.0
20/80	34.5	43.1	10.8
40/60	26.3	43.8	12.6

Fig.6 DSC curves of SSBR/TPI blends undergoing non-isothermal crystallization with different cooling rates for mSSBR/mTPI of 0/100(A), 10/90(B), 20/80(C) and 40/60(D) Note:Cooling rate/(℃∙min-1): a. 2; b. 5; c. 10; d. 20.

Fig.7 DSC curves of SSBR/TPI blends at 10 ℃/min of cooling rate Note:mSSBR/mTPI: a. 0/100; b. 10/90; c. 20/80; d. 40/60.

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SSBR/TPI共混体系中TPI的结晶、成核及动力学研究

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SSBR/TPI共混体系中TPI的结晶、 成核及动力学研究

Crystallization, Nucleation and Kinetics of TPI in SSBR/TPI Blends†

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SSBR/TPI共混体系中TPI的结晶、成核及动力学研究

Crystallization, Nucleation and Kinetics of TPI in SSBR/TPI Blends^†