Author's personal copy

Reactive & Functional Polymers 71 (2011) 502–511

Contents lists available at ScienceDirect

Reactive & Functional Polymers

journal homepage: www.elsevier.com/locate/react

Synthesis and characterization of novel room temperature vulcanized (RTV)

silicone rubbers using octa[(trimethoxysilyl)ethyl]-POSS as cross-linker
Dongzhi Chen a,b, Shengping Yi a,b, Pengfei Fang c, Yalan Zhong a, Chi Huang a,b,⇑, Xiaojun Wu a
a
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, PR China
b
Engineering Research Center of Organosilicon Compound and Material, Ministry of Education of China, Wuhan 430072, PR China
c
School of Physics and Technology, Wuhan University, Wuhan 430072, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A novel cross-linker octa[(trimethoxysilyl)ethyl]-POSS (OPS) based on a Vinyl-POSS derivative was firstly
Received 28 July 2010 prepared via hydrosilylation chemistry. The novel POSS cross-linker was applied to hydroxyl terminated
Received in revised form 13 December 2010 polydimethylsiloxane (HPDMS) matrix to prepare a series of novel RTV silicone rubbers. The chemical
Accepted 19 December 2010
incorporation of novel POSS cross-linker into PDMS by hydrolytic condensation reaction was verified
Available online 25 December 2010
by attenuated total reflection (ATR) infrared spectroscopy. Morphology, thermal properties and mechan-
ical properties of these novel RTV silicone rubbers have been studied by means of scanning electron
Keywords:
microscope (SEM), thermal gravimetric analysis, universal tensile testing machine and dynamic mechan-
Cross-linker
Octa[(trimethoxysilyl)ethyl]-POSS
ical analysis, respectively. The results displayed a pronounced enhancement effect of the novel cross-lin-
RTV silicone rubber ker OPS on thermal stabilities and mechanical properties of RTV silicone rubbers as compared with the
Thermal stability PDMS polymers prepared with tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and methyltrime-
Mechanical property thoxysilane (MTMOS) cross-linkers. Subsequently, the thermal decomposition of representative novel
RTV silicone rubber in nitrogen was monitored by TGA coupled with real-time IR, and the degradation
residues were also characterized by FTIR. It was found that the POSS cages were beneficial to increasing
the degradation residues. The striking enhancements in thermal properties and improvements on
mechanical properties could be attributable to the synergistic effect of the increasing dimensionality of
cross-linking networks resulting from three-dimensional structure of OPS cross-linker, the plasticization
of self-cross-linked OPS cross-linker and uniform distribution of POSS-rich domains.
Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.

1. Introduction blending as reinforcing nano-filler. POSS with n = 8 nano-struc-

Polyhedral oligomeric silsesquioxanes (POSS) with their com-
bined organic/inorganic properties have attracted considerable
attention in the field of organic/inorganic hybrid materials [1,2]
in the last few years. POSS chemicals with 1–3 nm in diameter
can be thought as the smallest spherical silica. POSS with a generic
empirical formula (RSiO1.5)n is a class of promising nano-sized
building blocks. The inert inorganic caged framework is made up
of silicone and oxygen (SiO1.5)n (n is an even number, n > 4). The
substituent groups (R) connected with silicon atoms can be divided
into hydrogen, reactive organic groups and inert organic groups.
POSS derivatives are now available with reactive functionalities
for polymerization or grafting and inert functionalities for blending
[3]. Hence POSS derivatives can be easily incorporated into a large
number of polymeric systems via chemical bonds or physical
⇑ Corresponding author at: College of Chemistry and Molecular Sciences, Wuhan
University, Wuhan 430072, PR China. Tel.: +86 18971088222; fax: +86 27
68754067.
E-mail address: chihuang@whu.edu.cn (C. Huang).
tured cage has been explored extensively, and several reviews
[4–6] have been published recent years.
The incorporation of POSS derivatives into polymeric materials
can lead to pronounced improvements in comprehensive proper-
ties, such as used temperatures, decomposition temperatures, oxi-
dation resistance, surface hardening, mechanical properties,
flammability resistance, heat evolution and so on [4]. These
improvements have also been shown to apply to polymeric PDMS
systems. Over the past decades, PDMS polymers have become a
class of the most important polymers in our daily lives, which have
still been intensively explored for their unique physical and chem-
ical properties, such as low glass transition temperature, excellent
thermal stability, low toxicity, low surface tension, high permeabil-
ity and low chemical reactivity [7–10].
However, a few researches [11–15] on polymeric polysiloxanes/
POSS hybrid materials have been published up to present. The
aforementioned investigations mostly involved mechanical prop-
erties of high temperature vulcanized silicone rubbers (HTV), addi-
tion type curable (ATC) silicone rubbers and room temperature
vulcanized (RTV) silicone rubbers except for our recent work

1381-5148/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2010.12.010