聚丁二烯/二氧化硅杂化新材料等温结晶动力学及结晶形态的研究

朱寒; 答迅; 卢晨; 吴一弦

doi:10.11777/j.issn1000-3004.2017.170241

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聚丁二烯/二氧化硅杂化新材料等温结晶动力学及结晶形态的研究

研究论文 | 更新时间：2021-01-26

- 聚丁二烯/二氧化硅杂化新材料等温结晶动力学及结晶形态的研究
- Isothermal Crystallization Kinetics and Crystal Morphology of Polybutadiene/Silica Hybrid Materials
- 高分子学报 2018年0卷第5期页码：656-664
- 作者机构：
  
  北京化工大学化工资源有效利用国家重点实验室　北京 100029
- 作者简介：
  
  E-mail: wuyx@mail.buct.edu.cn Yi-xian Wu, E-mail: wuyx@ mail.buct.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21634002，51573008)和国家重点基础研究发展计划(973计划，项目号 2015CB654700)资助()
- DOI：10.11777/j.issn1000-3004.2017.170241
  中图分类号：
- 纸质出版日期：2018-5，
  
  收稿日期：2017-8-27，
  
  修回日期：2017-9-29，
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朱寒, 答迅, 卢晨, 吴一弦. 聚丁二烯/二氧化硅杂化新材料等温结晶动力学及结晶形态的研究[J]. 高分子学报, 2018,0(5):656-664.

Han Zhu, Xun Da, Chen Lu, Yi-xian Wu. Isothermal Crystallization Kinetics and Crystal Morphology of Polybutadiene/Silica Hybrid Materials[J]. Acta Polymerica Sinica, 2018,0(5):656-664.
朱寒, 答迅, 卢晨, 吴一弦. 聚丁二烯/二氧化硅杂化新材料等温结晶动力学及结晶形态的研究[J]. 高分子学报, 2018,0(5):656-664. DOI： 10.11777/j.issn1000-3004.2017.170241.

Han Zhu, Xun Da, Chen Lu, Yi-xian Wu. Isothermal Crystallization Kinetics and Crystal Morphology of Polybutadiene/Silica Hybrid Materials[J]. Acta Polymerica Sinica, 2018,0(5):656-664. DOI： 10.11777/j.issn1000-3004.2017.170241.

摘要

研究了所合成的新型高顺式聚丁二烯键合纳米二氧化硅杂化材料(PB-Si)的顺式-1

4微观结构、特性黏数([

])、微观形态及热稳定性与键合纳米二氧化硅含量的关系等，并采用示差扫描量热仪(DSC)和配有在线冷热台的偏光显微镜(POM)研究了杂化材料PB-Si中SiO

含量及微观链结构特点对其低温下等温结晶动力学及结晶形态、球晶增长速率的影响. 结果表明：当SiO

含量小于2.5%时，杂化材料PB-Si的特性黏数和顺式-1

4结构含量均基本保持不变，短支链结构的杂化材料(PB-Si-Ni)的顺式-1

4结构含量约为96.6%，高度线性链结构的杂化材料(PB-Si-Nd)的顺式-1

4结构含量约为98.6%，热稳定性均随着SiO

含量增加而有所提高；在PB顺式-1

4微观结构及SiO

结合含量基本相同的前提下，与共混物PB/SiO

相比，杂化材料PB-Si具有更快的结晶速率，且随着杂化材料PB-Si中SiO

结合量增大，其结晶速率加快，半结晶时间(

1/2

)缩短；若杂化材料中顺式-1

4微观结构含量和SiO

结合量同时增加，杂化材料PB-Si的结晶速率进一步加快；在顺式结构含量及SiO

含量确定的情况下，聚合物的拓扑结构对其结晶速率也有明显影响，高度线性结构(PB-Si-Nd)比短支链结构(PB-Si-Ni)的杂化材料也具有更快的结晶速率；杂化材料PB-Si在低温等温结晶过程中均呈现三维球晶的生长方式，Avrami指数(

)在2.0 ~ 3.0之间，球晶增长速率也随SiO

结合量增加而加快.

Abstract

Effect of SiO

content on

cis

-1

4 microstructure content of butadiene (Bd) units

intrinsic viscosity ([

]) and thermal stability of hybrid materials (PB-Si) were studied

in which SiO

nanoparticles were covalently attached and pendants along high

cis

polybutadiene (PB) macromolecular chains. Isothermal crystallization characteristics and SiO

dispersion in PB matrix of PB-Si hybrid and PB/SiO

blend (PB/Si) with the same SiO

contents were conducted. The microstructure of Bd units in PB-Si was characterized by Fourier transform infrared spectroscopy (FTIR) and the

cis

-1

4 content was determined based on the characteristic absorption in FTIR spectrum. The SiO

content of PB-Si was measured by thermal gravimetric analysis (TGA). The intrinsic viscosity of PB-Si in toluene was tested by Ubbelohde viscometer. Effects of SiO

content and microstructure (

cis

-1

4 configuration) on the isothermal crystallization kinetics

crystal morphology and spherulite growth rate of the hybrid materials at low temperatures were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) equipped with

in situ

heating and cooling device. The results show that the intrinsic viscosity and the

cis

-1

4 contents of Bd units of PB-Si remained almost the same

and thermal stability could be improved with increasing SiO

content in the materials when SiO

content was less than 2.5%. For two series of PB-Si-Ni and PB-Si-Nd hybrids

their

cis

-1

4 contents were determined to be around 96.6% and 98.6% respectively. PB-Si hybrid materials exhibited a much higher crystallization rate compared to PB/Si blends by keeping the

cis

-1

4 contents and SiO

content at the same. The crystallization rate increased by introducing a small amount of covalently linked SiO

nanoparticle pendants along the macromolecular chains. The crystallization of PB-Si hybrid materials could be accelerated and the half-crystallization time (

1/2

) decreased with increasing SiO

content. PB-Si-Nd hybrid materials with highly linear chains possessed a higher crystallization rate than PB-Si-Ni with short branched chains by keeping

cis

-1

4 content and SiO

at the same. The crystallization rate of PB-Si-Nd hybrid materials could be further increased with increasing both SiO

and

cis

-1

4 contents. The Avrami exponents (

) for PB-Si hybrid materials with various topological structures were determined to be in the range of 2.0 − 3.0

which indicated a three-dimensional spherulite growth of PB-Si under isothermal condition at low crystallization temperature. The growth rate of spherulites increased with the increase in SiO

content while keeping other conditions almost the same. The crystallization rate could increase with increased

cis

-1

4 content

linearity of chain structure and SiO

content.

关键词

高顺式聚丁二烯杂化材料链结构等温结晶动力学

Keywords

High cis polybutadieneHybrid materialsChain structureIsothermal crystallization kinetics

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