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1.生命有机磷化学及化学生物学教育部重点实验室清华大学化学系 北京 100084
2.中国科学院仿生材料与界面科学重点实验室中国科学院理化技术研究所 北京 100190
Published:20 October 2017,
Received:22 May 2017,
Revised:11 June 2017,
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Yang Yang, Zhang Xi-qi, Wei Yen, Ji Yan. A Liquid Crystalline Vitrimer with Better Actuation Repeatability. [J]. Acta Polymerica Sinica (10):1662-1667(2017)
Yang Yang, Zhang Xi-qi, Wei Yen, Ji Yan. A Liquid Crystalline Vitrimer with Better Actuation Repeatability. [J]. Acta Polymerica Sinica (10):1662-1667(2017) DOI: 10.11777/j.issn1000-3304.2017.17134.
通过高温下酯交换反应的进行,含酯键的液晶型类玻璃高分子(liquid crystalline vitrimer),能够通过简单拉伸进行取向,获得随温度变化可逆伸缩的智能材料.在目前已报道的此类主链型高分子中,酯交换剧烈发生需要的临界温度(
T
v
),与液晶弹性体发生可逆形变的温度(
T
i
,即液晶相-各向同性相转变温度)相隔较近,导致材料的使用温度范围比较窄,而且多次升降温后,取向及可逆形变会消失.为解决此问题,本文在原来体系的基础上,通过共聚合另外一种液晶基元,有效地降低了
T
i
,从而拓宽
T
i
与
T
v
之间的距离.这不仅使材料的使用次数明显增加,还能延长此类液晶弹性体的使用期限.
Liquid crystalline elastomers (LCEs) can show reversible shape change when the materials go through isotropic-liquid crystal phase transition (
T
i
). To get such actuation
LCEs have to be aligned into monodomain samples
in which the mesogens are orientated more or less in a uniform direction. Normally
LCEs are covalently cross-linked
which makes the alignment very difficult. We have previously shown that this problem can be solved by designing LCEs with exchangeable links. The material for demonstration was synthesized by reacting an epoxy-terminated biphenyl mesogen with sebacic acid in the presence of triazobicyclodecene catalyst for transesterification. The resultant material is in fact a liquid crystalline vitrimer. When the material is stretched above the topology freezing transition temperature (
T
v
)
the accelerated transesterification reaction allows topology adjustment. The alignment can be fixed by cooling afterwards. However
as the
T
i
is very close to
T
v
in this sample
it is easy for the alignment to disappear when the temperature increases to above
T
i
to trigger the actuation. This not only limits the operating temperature range
but also destroys the alignment after multiple heating-cooling cycles. Consequently
it is desirable to increase the distance between
T
i
and
T
v
by reducing
T
i
. To this end
a second epoxy-terminated cyanostilbene mesogen (EP11) was added into the main chain of the liquid crystalline vitrimer. The result shows that the copolymerization of the two types of mesogens can effectively decreases
T
i
without affecting the
T
v
too much. It broadens the range between
T
i
and
T
v
. The more EP11
the lower
T
i
. When the content of EP11 is 20 mol%
T
i
is 82 ºC
which is 31 ºC lower than the previous liquid crystalline vitrimer. The copolymer can also be used to make into monodomain LCE by stretching at high temperature. The resultant monodomain LCE has a similar reversible elongation-contraction actuation ratio as the previous liquid crystalline vitrimer. More importantly
the large distance between
T
i
and
T
v
makes it possible to trigger the actuation by heating it to a temperature of 15 ºC above
T
i
without destroying the alignment. Little fatigue has been identified after repeating the reversible elongation-contraction actuation for 120 times.
液晶弹性体类玻璃高分子液晶态转变温度(Ti)可逆驱动
Liquid crystal elastomerVitrimerLiquid crystal-isotropic phase transition temperature (Ti)Reversible actuation
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