CHINESE JOURNAL OF CATALYSIS

Volume 28, Issue 11, November 2007

Online English edition of the Chinese language journal

Cite this article as: Chin J Catal, 2007, 28(11): 947–952. RESEARCH PAPER

A Novel Glass Fiber-Supported Platinum Catalyst for

Self-healing Polymer Composites:
Structure and Reactivity
YANG Haitang1, FANG Zhengping1,2,*, FU Xiaoyun1, TONG Lifang1,2
1
Institute of Polymer Composites, Zhejiang University, Hangzhou 310027, Zhejiang, China
2
Key Laboratory of Macromolecular Synthesis and Functionalization of Ministry of Education, Zhejiang University, Hangzhou 310027,
Zhejiang, China

Abstract: A platinum-based catalyst supported on glass fiber grafted with 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane
(D4Vi) was prepared and evaluated for the hydrosilylation reaction of styrene and methyldiethoxysilane. The silanization of the glass fi-
ber was carried out with methyldichlorosilane. D4Vi was then anchored on the modified fiber with Si–H bonds through a hydrosilylation
reaction mediated by a Pt(0)-D4Vi complex solution catalyst. Fourier transform infrared spectroscopy, field emission scanning electron
microscopy, X-ray energy dispersion spectroscopy, and thermogravimetric data showed that D4Vi was covalently bonded onto the fiber
surface. The very high density of D4Vi grafting confers a strong hydrophobic character to the modified fiber surface. Fairly good cata-
lytic activity for hydrosilylation between styrene and methyldiethoxysilane was observed on this catalyst.

Key Words: self-healing composite; glass fiber; platinum; supported catalyst; styrene; methyldiethoxysilane; hydrosilylation

Many metal complexes are known to be catalysts for the
hydrosilylation reactions [1,2], but the discovery by Speier et
al. [3] that hexachloroplatinic acid is a very active catalyst
even under ambient conditions has led to Pt complexes be-
coming the catalyst of choice for these reactions. Pt-based
catalysts are not only useful when alkyl and alkoxysilanes are
employed, but they are also not deactivated by chlorosilanes.
This versatility and their remarkable turnover frequency ex-
plain the dominance of these catalysts in industrial processes
[4].
Carrier-supported metal complex catalysts are used more
and more widely for their high efficiency. Transition metal
complexes can be immobilized on inorganic substrates [5]
(such as carbon black [6,7], silica [8,9], Ȗ-Al2O3, and carbon
nanotubes [10]) or organic polymers [5,11] (such as polysty-
rene, polyamides, and polyphenylsilanes) and are commonly
anchored through some functional linkages. Generally, the
catalytic activities of all types of immobilized complexes (in-
cluding Pt, Rh, Ni, and Pd) are comparable to that of their
homogenous analogs. Sometimes an increase in selectivity or
activity can be noted in the heterogenized state [12]. These
properties are useful in meeting the demands of the
self-healing polymer composite systems designed by this
group [13,14].
Based on previous results, the authors designed an “im-
plant” system aimed at developing new self-healing polymer
composites [14], which was discovered by Dry et al. [15–17]
and further developed by Brown et al. [18–25]. In this de-
signed system, healing is accomplished by incorporating a
microencapsulated healing agent dispersed in a matrix and a
supported catalyst on particulate or fiber fillers. The catalyst is
a supported platinum catalyst, which can catalyze the hy-
drosilylation reaction quickly in ambient atmosphere. The
healing agent can be any kind of organosilane or organosi-
loxane that contains Si–H bonds and Si–vinyl bonds. A de-
veloping crack in the polymer would rupture the embedded
microcapsules to release the healing agent into the plane of
the crack through capillary action. Hydrosilylation of the
healing agent is triggered by contact with the catalyst sup-
ported on the fillers (particles or fibers), and the product of

Received date: 2007-03-09.

* Corresponding author. Tel/Fax: +86-571-87953712; E-mail: zpfang@zju.edu.cn
Foundation item: Supported by the National Natural Science Foundation of China (50473036).
Copyright © 2007, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier BV. All rights reserved.
 YANG Haitang et al. / Chinese Journal of Catalysis, 2007, 28(11): 947–952
hydrosilylation bonds the faces of the crack. Thus, the me-
chanical properties of the composite material are recovered to
some extent. This system possesses a number of important
merits over the previous self-healing methodology, including:
(1) the mechanical properties are not compromised by the
addition of the catalyst because the catalyst is supported on
the surface of the filler and the healing reaction occurs in the
interface between the filler and the matrix; (2) this system is
more readily adapted for the fiber/particle reinforced plastics,
which is more common in the industry; (3) the amount of
catalyst required is decreased while maintaining healing effi-
ciency.
In this paper, the authors report on the preparation and
structure of a novel glass fiber-supported platinum catalyst
that can meet the demand of self-healing polymer composites.
Its merits include: (1) it is effective enough for the hydrosily-
lation reaction at room temperature; (2) the catalyst acts as
both a reactant and a catalyst, which enhances the interaction
between the silane from the healing reaction and matrix.
1 Experimental
1.1 Preparation of the platinum-based catalyst supported
on glass fiber grafted with D4Vi
The glass fiber (GF) was obtained from Hangzhou
Saint-Gobain Vetrotex Fiber Glass Co. Ltd., China, and
treated with Piranha solution prior to use. The glass fiber (2 g)
was placed in toluene (50 ml) containing methyldichlorosilane
(5 ml, Xinan Chemical and Industrial Group Co. Ltd., China)
under a nitrogen atmosphere. The mixture was stirred at reflux
temperature for 48 h. The glass fiber was taken away from the
mixture after cooling. The silanized glass fiber was then
washed three times with an excess amount of aqueous ace-
tone. The silanized glass fiber was obtained after drying under
vacuum.
A mixture of sodium bicarbonate (0.10 g), H2PtCl6·H2O
(0.20 g, Shanghai Chemical Reagent Factory, China),
1,3,5,7-tetravinyl-1,3,5,7-tetramethyl cyclotetrasiloxane
(D4Vi, 0.40 g, Shanghai Jiancheng Industrial and Trade Co.
Ltd., China), and ethanol (30 ml) were stirred at 70ºC for 24
h. The mixture was then purged with nitrogen to remove the
volatiles, followed by the addition of 20 ml of D4Vi. A yel-
low liquid, the Pt(0)-D4Vi complex, was obtained after the
mixture was cooled to room temperature and filtered.
One gram of silanized GF was added to a mixture of 0.1 ml
of Pt(0)-D4Vi complex solution and 10 ml of D4Vi. After
stirring at 60ºC for 12 h, the solution was decanted from the
mixture, and the solid was washed five times with an excess
amount of aqueous ethanol. It was then dried under vacuum
(70ºC, 26 kPa) to yield the desired glass fiber-supported Pt
complex catalyst (denoted GF-Pt).
1.2 Hydrosilylation of styrene and methyldiethoxysilane
Methyldiethoxysilane was prepared by an alcoholysis reac-
tion of methyldichlorosilane. Methyldichlorosilane (0.25 mol,
26.0 ml) was added to a three-necked flask containing xylene
(100 ml) equipped with a condenser/N2 inlet and mechanical
stirrer, which was airproof. Anhydrous alcohol (0.45 mol,
26.2 ml) was charged into the flask in 30 min. Methyldieth-
oxysilane was purified by fractional distillation under vacuum
after reaction at 30ºC for 6 h and characterized by FTIR and
1
H NMR. IR (neat. cm1): 3467, 2969, 2929, 2909, 2167,
1407, 1262, 1102, 1046, 962, 891, 848, 807, 768; 1H-NMR
(CDCl3): 4.58 (SiH), 3.80 (SiOCH2CH3), 1.24 (SiOCH2CH3),
0.20 (SiCH3).
To a solution of methyldiethoxysilane (0.402 g, 0.003 mol)
and styrene (0.312 g, 0.003 mol, Shanghai Chemical Reagent
Factory, China), catalyst GF-Pt (0.02 g) was added at 25ºC,
and the moment of this addition was marked as the beginning
of the reaction. The disappearance of starting materials and
formation of products were recorded by gas chromatography
(GC).
1.3 Catalyst characterization
1
H NMR spectra were recorded on an Avance DMX 500
instrument (Bruker, Germany) at 25ºC and referenced to
TMS. GC–MS data were obtained on a Trace GC 2000/Trace
MS (ThermoQuest, USA) equipped with an HP-5MS capillary
column and an electron impact ionizer (70 keV). The Fourier
transform infrared spectroscopy (FTIR) study was carried out
at room temperature using a Bruker Vector 22 FTIR instru-
ment with a resolution of 2 cm1. The spectra obtained were
analyzed in the range 4000–400 cm1. Thermogravimetric
(TG) experiments were carried out on an SDT Q600 TG in-
strument (TA, USA), and the measurements began from 50 to
800ºC at a heating rate of 10ºC/min. The scanning electron
microscopy (SEM) and X-ray energy dispersion spectroscopy
(EDX) data of the samples were acquired using a
SIRION-100 field emission scanning electron microscope
(FEI, Holland) with an EDX spectrometer.
2 Results and discussion
2.1 Structure of the glass fiber-supported Pt complex
catalyst
FTIR spectroscopy of the parent glass fiber gave the lattice
and O–H vibrations at approximately 1635 and 3442 cm1,
respectively (Fig. 1(1)). After silanization of the glass fiber
with methyldichlorosilane, the bands corresponding to Si–H
(2165 cm1) and Si–C (1406 cm1) vibration modes are also
observed (Fig. 1(2)). The significant decrease in the O–H
 YANG Haitang et al. / Chinese Journal of Catalysis, 2007, 28(11): 947–952

band intensity at 3442 cm1 provided evidence of the grafting

of methyldichlorosilane. Finally, the FTIR spectrum of GF-Pt
(Fig. 1(3)) showed a single peak at 1091 cm1, which is the
distinct characterization of the vibration mode of the D4 ring,
instead of a broad band at 1400–1000 cm1 that corresponds to
the vibration of the Si–O–Si chain. Bands at 2980–2890,
1650, and 1450 cm1 appeared in the FTIR spectrum of GF-Pt,
in contrast to that of the parent glass fiber and the silanized
glass fiber. These peaks can be assigned to the –CH2–,
–CH=CH2 (stretching vibration), and –CH=CH2 (scissor vi-
bration) bands, indicating the presence of the D4Vi ring on
the surface of GF-Pt. Furthermore, the significant decrease in
the intensity of the Si–H band revealed that most of the Si–H
bonds on the surface of the glass fiber have reacted with
D4Vi. On the basis of the above results, it can be deduced that
D4Vi molecules were covalently bonded to the glass fiber.
Fig. 2 TG profiles in N2 of the glass fiber (1), silanized glass
fiber (2), and GF-Pt catalyst (3)

Table 1 The results of EDX analysis of the samples

Content (%)
Sample
Si O Mg Al Ca C Pt
Glass fiber 24.67 57.90 2.72 7.49 7.22 — —
Silanized
18.64 36.42 1.45 3.89 4.16 35.44 —
glass fiber
GF-Pt 4.79 25.88 0.01 0.53 0.31 67.30 1.18
GF-silane 4.31 16.19 0.21 0.49 0.48 78.24 0.08

tween the glass fiber and D4Vi can be proposed as shown in

Fig. 1 FT-IR spectra of the glass fiber (GF) (1), silanized glass
fiber (2), and GF-Pt catalyst (3)
In addition, the strength of the bond between D4Vi and the
glass fiber was measured using TG experiments (Fig. 2). For
the parent glass fiber, there were two weight loss peaks below
100ºC and at approximately 300ºC corresponding to the re-
lease of physisorbed H2O (ca. 3.5%) and dehydroxylation,
respectively (Fig. 2(1)). The release of H2O (ca. 1%) was less
upon the silanization with methyldichlorosilane (Fig. 2(2)).
Additional dehydroxylation and the loss of alkoxysilane
fragments occurred with this material above 200ºC. Finally,
the very low weight loss (0.2%) at low temperature for the
GF-Pt provided evidence of the high hydrophobicity of the
surface (Fig. 2(3)). On the other hand, the weight loss occur-
ring at 450ºC very likely corresponded to the release of D4Vi
after Si–C bond cleavage.
Besides, a very clear shift from a hydrophilic surface (glass
fiber) to a hydrophobic surface was observed in the surface
treated experiment. Thus, the structure of the bonding be-
Scheme 1. There was also evidence that the content of plati-
num in GF-Pt was 1.18 at% from the EDX result (Table 1),
which represented the composition of the surface.
Further evidence was provided by SEM photos (Fig. 3). A
uniform coating was observed after the treatment with me-
thyldichlorosilane, whereas the parent glass fiber showed a
clear and slick surface. There was a thicker coating on the
surface after being further treatment with the D4Vi-Pt com-
plex.
The EDX results in Table 1 are not very accurate for calcu-
lating the percentages of the elements on the surface because
hydrogen cannot be detected by EDX, but they do reflect the
trends of the elements. On the basis of the above results, the
change of the surface structure shown in Scheme 1 is pro-
posed.
2.2 Reactivity of the glass fiber-supported Pt complex
catalyst
The hydrosilylation reaction between methyldiethoxysilane
(Me(EtO)2SiH) and styrene was used to determine the relative
activity of this new catalyst. Fig. 4 shows the conversion ver-
sus time for the process of hydrosilylation. It is obvious that
 YANG Haitang et al. / Chinese Journal of Catalysis, 2007, 28(11): 947–952

Scheme 1 The changes of the glass fiber surface during the treatment process

this catalyst has fairly good catalytic activity for this reaction.
The conversion was over 95% after reaction at 25ºC for 1 h.
2.3 Potential for use in the self-healing polymer compos-
ites
To meet the special demand of self-healing polymer com-
posites, a novel catalyst that is different from a conventional
hydrosilylation catalyst has to be designed. One way to de-
velop a new heterogeneous catalyst from an effective ho-
mogenous catalyst is to support the latter on high surface area
solids such as graphite, Al2O3, SiO2, zeolite, and so on. The
type of the support material and the surface modifier fre-
quently plays a crucial role in the performance of the resulting
supported catalyst. Basically, the support has to be thermally
and chemically stable during the reaction and has accessible

Fig. 3 SEM images of the glass fiber (a), silanized glass fiber (b), GF-Pt (c), and GF-silane (d)
 YANG Haitang et al. / Chinese Journal of Catalysis, 2007, 28(11): 947–952
Fig. 4 Conversion versus time in the hydrosilylation of Me(EtO)2-
SiH with styrene over the GF-Pt catalyst
(1) Catalyst-free, (2) With catalyst
and well dispersed active sites. Moreover, the surface modi-
fier should provide the support surface with structures re-
quired by applications. In the earlier work [8,26], the authors
developed an effective SiO2-supported Pt catalyst for hy-
drosilylation, where SiO2 is modified by vinyltriethoxysilane.
Here, glass fiber was selected as the support, considering
that it is widely used in polymer composites and it is stable
during the process. Methyldichlorosilane and D4Vi act as
modifiers sequentially to promote a better dispersion of the
active sites and good reactivity. The above analysis of the
results show that GF-Pt has the structure as shown in Scheme
1, where the D4Vi ring provides more free vinyl to the com-
plex with Pt than the vinyltriethoxysilane modifier. Thus, the
D4Vi ring is dispersed more symmetrical on the surface of the
glass fiber (as shown in Fig. 3), which confirmed that GF-Pt
has a better dispersion of active sites.
After the hydrosilylation reaction was complete, the cata-
lyst was removed from the reaction mixture and washed three
times with aqueous ethanol. The appearance of its surface
(Fig. 3(d)) showed that some products of the hydrosilylation
reaction are bonded to the glass fiber, indicating the existence
of unreacted Si–CH=CH2 on the surface of GF-Pt. This makes
this supported catalyst very promising for use in self-healing
composites because of the strong bond between the healing
agent and fiber.
3 Conclusions
The prepared glass fiber-supported platinum catalyst has
high reactivity for the hydrosilylation reaction between sty-
rene and methyldiethoxysilane. D4Vi is covalently bonded
onto the glass fiber surface through hydrosilylation with si-
lanized glass fiber. The surface structure and composition
suggest that this fiber-supported platinum catalyst has good
potential for use in self-healing polymer composites.
References
[1] Marciniec B. Coord Chem Rev, 2005, 249(21–22): 2374
[2] Tanabe M, Ito D, Osakada K. Organometallics, 2007, 26(3):
459
[3] Speier J L, Webster J A, Barnes G H. J Am Chem Soc, 1957,
79(4): 974
[4] Drake R, Dunn R, Sherrington D C, Thomson S J. J Mol Catal
A, 2001, 177(1): 49
[5] Corma A, Garcia H. Chem Rev, 2002, 102(10): 3837
[6] Marciniec B, Maciejewski H, Duczmal W, Fiedorow R, Kityn-
ski D. Appl Organomet Chem, 2003, 17(2): 127
[7] Meille V. Appl Catal A, 2006, 315: 1
[8] Miao Q J, Fang Zh P, Cai G P. Catal Commun, 2003, 4(12): 637
[9] Corma A, Garcia H. Adv Synth Catal, 2006, 348(12–13): 1391
[10] Planeix J M, Coustel N, Coq B, Brotons V, Kumbhar P S, Du-
tartre R, Geneste P, Bernier P, Ajayan P M. J Am Chem Soc,
1994, 116(17): 7935
[11] Corma A, Garcia H, Leyva A. J Catal, 2006, 240(2): 87
[12] Corma A, Garcia H. Chem Rev, 2003, 103(11): 4307
[13] Fang Zh P, Yang H T, Li R J, Gu A J, Tong L F. 2005 National
Symposium on Polymer. Beijing, China, 2005. 10
[14] Fang Zh P, Yang H T, Xu L H, Gu A J, Tong L F, Xu Zh B. J
Aeronaut Mater, 2006, 26(3): 335
[15] Dry C. Compos Struct, 1996, 35(3): 263
[16] Dry C. Chem Eng News, 2001, 79(11): 8
[17] Dry C, McMillan W. Smart Mater Struct, 1997, 6(1): 35
[18] Brown E N, Sottos N R, White S R. Exp Mech, 2002, 42(4): 372
[19] Kessler M R, Larin G E, Bernklau N. J Therm Anal Calorim,
2006, 85(1): 7
[20] Kessler M R, Sottos N R, White S R. Composite A, 2003, 34(8):
743
[21] Kessler M R, White S R. Composite A, 2001, 32(5): 683
[22] Kessler M R, White S R. J Polym Sci A, 2002, 40(14): 2373
[23] White S R, Sottos N R, Geubelle P H, Moore J S, Kessler M R,
Sriram S R, Brown E N, Viswanathan S. Nature, 2001,
409(6822): 794
[24] Rule J D, Brown E N, Sottos N R, White S R, Moore J S. Adv
Mater, 2005, 17(2): 205
[25] Cho S H, Andersson H M, White S R, Sottos N R, Braun P V.
Adv Mater, 2006, 18(8): 997
[26] Fang Zh P, Yang H T, Miao Q J, Cai G P. Chin Chem Lett,
2006, 17(9): 1155