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Investigation on Microstructural Evolution of Mesomorphic Propylene/Ethylene Copolymer upon Thermal Treatment
- Acta Polymerica Sinica Issue 9, Pages: 1538-1548(2017)
- 作者机构：
1.中国科学院化学研究所 中国科学院分子科学科教融合卓越中心 中国科学院工程塑料重点实验室 北京 100190
2.中国科学院大学 北京 100049
- 作者简介：
- 基金信息：
DOI：10.11777/j.issn1000-3304.2017.17133
CLC：Published：20 September 2017，
Received：16 May 2017，
Revised：24 June 2017，
扫 描 看 全 文
Qian-hong Jiang, Ying Zhao, Du-jin Wang. Investigation on Microstructural Evolution of Mesomorphic Propylene/Ethylene Copolymer upon Thermal Treatment. [J]. Acta Polymerica Sinica (9):1538-1548(2017)
Qian-hong Jiang, Ying Zhao, Du-jin Wang. Investigation on Microstructural Evolution of Mesomorphic Propylene/Ethylene Copolymer upon Thermal Treatment. [J]. Acta Polymerica Sinica (9):1538-1548(2017) DOI： 10.11777/j.issn1000-3304.2017.17133.
摘要
通过熔体淬冷方式制备了中介相态丙烯-乙烯无规共聚物（PPR），综合使用原位红外光谱、原位X-射线散射（WAXD/SAXS）、示差扫描量热分析（DSC）和动态机械热分析（DMA）等方法系统研究了中介相态PPR在升温过程中的微观结构演变.红外光谱研究结果表明，在连续升温过程中，中介相态PPR在30~50℃之间分子链构象发生了变化，其可能源于刚性无定形区（RAF）中部分链段构象的无序化转变，并发现在RAF中存在长度为
n
≤ 13（
n
为3
1
螺旋序列中丙烯单元的个数）的螺旋序列.中介相态PPR在连续升温过程中经历了RAF中链段构象的无序化转变、中介相向
α
晶的转变、不完善
α
晶的熔融和
α
晶的完善化，以及
α
晶熔融4个转变过程.中介相向
α
晶的转变是一个异相成核生长过程，其结晶活化能Δ
E
=67.94 kJ/mol.
Abstract
Mesomorphic propylene/ethylene copolymer (PPR) was obtained by quenching quiescent melt. Its microstructural evolution during continuous heating process was studied by
in situ
Fourier transform infrared spectroscopy (FTIR)
in situ
wide/small angle X-ray diffraction (WAXD/SAXS)
differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). No structural change was detected by WAXD in temperature range of 30-50℃
while IR results showed the molecular segments experienced conformational changes in this temperature range. Considering the presence of large amount of rigid amorphous fraction (RAF) in the mesomorphic sample
the IR results
in combination with DMA and DSC results of annealed mesomorphic samples
implied that this conformational changes may originate from the helical sequences destruction of partial segments in RAF. The helical conformation regularity bands showed different variation trends during heating. The relative intensity of the conformation bands associated with the long helical sequences (
n
>
13
the number of monomers in helices) showed no evident change in the temperature range of 30-50℃
while the relative intensity of the conformation bands assigned to the helical sequences with medium length (
n
≤ 13) gradually decrease in this temperature range. Therefore
the presence of the helical sequences with
n
≤ 13 was deduced in RAF. Variation of fractions of mesophase
α
crystal and amorphous phase during the continuous heating process was evaluated by
in situ
WAXD. The long periods of the sample at different temperatures during heating were derived from SAXS result. The results of IR and XRD indicated that
during the continuous heating process
the tranformation of mesomorphic PPR mainly experienced four stages:helical conformation destruction of partial segments in RAF
transformation of mesophase to α crystal
perfection of imperfect
α
crystal and melting of
α
crystal. IR results of isothermal crystallization process showed the transformation from mesophase to
α
crystal was a nucleation-growth process
via
heterogeneous nucleation. The activation energy of meso-
α
transformation in isothermal crystallization process was determined to be Δ
E
=67.94 kJ/mol.
关键词
无规共聚聚丙烯中介相红外光谱
Keywords
Polypropylene random copolymerMesophaseInfrared spectroscopy
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