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 activity can be noted in the heterogenized state [12]. These
hydrosilylation reactions [1,2], but the discovery by Speier et properties are useful in meeting the demands of the
al. [3] that hexachloroplatinic acid is a very active catalyst self-healing polymer composite systems designed by this
even under ambient conditions has led to Pt complexes be- group [13,14].
coming the catalyst of choice for these reactions. Pt-based Based on previous results, the authors designed an “im-
catalysts are not only useful when alkyl and alkoxysilanes are plant” system aimed at developing new self-healing polymer
employed, but they are also not deactivated by chlorosilanes. composites [14], which was discovered by Dry et al. [15–17]
This versatility and their remarkable turnover frequency ex- and further developed by Brown et al. [18–25]. In this de-
plain the dominance of these catalysts in industrial processes signed system, healing is accomplished by incorporating a
[4]. microencapsulated healing agent dispersed in a matrix and a
Carrier-supported metal complex catalysts are used more supported catalyst on particulate or fiber fillers. The catalyst is
and more widely for their high efficiency. Transition metal a supported platinum catalyst, which can catalyze the hy-
complexes can be immobilized on inorganic substrates [5] drosilylation reaction quickly in ambient atmosphere. The
(such as carbon black [6,7], silica [8,9], Ȗ-Al2O3, and carbon healing agent can be any kind of organosilane or organosi-
nanotubes [10]) or organic polymers [5,11] (such as polysty- loxane that contains Si–H bonds and Si–vinyl bonds. A de-
rene, polyamides, and polyphenylsilanes) and are commonly veloping crack in the polymer would rupture the embedded
anchored through some functional linkages. Generally, the microcapsules to release the healing agent into the plane of
catalytic activities of all types of immobilized complexes (in- the crack through capillary action. Hydrosilylation of the
cluding Pt, Rh, Ni, and Pd) are comparable to that of their healing agent is triggered by contact with the catalyst sup-
homogenous analogs. Sometimes an increase in selectivity or 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- 1.2 Hydrosilylation of styrene and methyldiethoxysilane
chanical properties of the composite material are recovered to
some extent. This system possesses a number of important Methyldiethoxysilane was prepared by an alcoholysis reac-
merits over the previous self-healing methodology, including: tion of methyldichlorosilane. Methyldichlorosilane (0.25 mol,
(1) the mechanical properties are not compromised by the 26.0 ml) was added to a three-necked flask containing xylene
addition of the catalyst because the catalyst is supported on (100 ml) equipped with a condenser/N2 inlet and mechanical
the surface of the filler and the healing reaction occurs in the stirrer, which was airproof. Anhydrous alcohol (0.45 mol,
interface between the filler and the matrix; (2) this system is 26.2 ml) was charged into the flask in 30 min. Methyldieth-
more readily adapted for the fiber/particle reinforced plastics, oxysilane was purified by fractional distillation under vacuum
which is more common in the industry; (3) the amount of after reaction at 30ºC for 6 h and characterized by FTIR and
1
catalyst required is decreased while maintaining healing effi- H NMR. IR (neat. cm1): 3467, 2969, 2929, 2909, 2167,
ciency. 1407, 1262, 1102, 1046, 962, 891, 848, 807, 768; 1H-NMR
In this paper, the authors report on the preparation and (CDCl3): 4.58 (SiH), 3.80 (SiOCH2CH3), 1.24 (SiOCH2CH3),
structure of a novel glass fiber-supported platinum catalyst 0.20 (SiCH3).
that can meet the demand of self-healing polymer composites. To a solution of methyldiethoxysilane (0.402 g, 0.003 mol)
Its merits include: (1) it is effective enough for the hydrosily- and styrene (0.312 g, 0.003 mol, Shanghai Chemical Reagent
lation reaction at room temperature; (2) the catalyst acts as Factory, China), catalyst GF-Pt (0.02 g) was added at 25ºC,
both a reactant and a catalyst, which enhances the interaction and the moment of this addition was marked as the beginning
between the silane from the healing reaction and matrix. of the reaction. The disappearance of starting materials and
formation of products were recorded by gas chromatography
1 Experimental (GC).

1.1 Preparation of the platinum-based catalyst supported 1.3 Catalyst characterization

on glass fiber grafted with D4Vi
1
H NMR spectra were recorded on an Avance DMX 500
The glass fiber (GF) was obtained from Hangzhou instrument (Bruker, Germany) at 25ºC and referenced to
Saint-Gobain Vetrotex Fiber Glass Co. Ltd., China, and TMS. GC–MS data were obtained on a Trace GC 2000/Trace
treated with Piranha solution prior to use. The glass fiber (2 g) MS (ThermoQuest, USA) equipped with an HP-5MS capillary
was placed in toluene (50 ml) containing methyldichlorosilane column and an electron impact ionizer (70 keV). The Fourier
(5 ml, Xinan Chemical and Industrial Group Co. Ltd., China) transform infrared spectroscopy (FTIR) study was carried out
under a nitrogen atmosphere. The mixture was stirred at reflux at room temperature using a Bruker Vector 22 FTIR instru-
temperature for 48 h. The glass fiber was taken away from the ment with a resolution of 2 cm1. The spectra obtained were
mixture after cooling. The silanized glass fiber was then analyzed in the range 4000–400 cm1. Thermogravimetric
washed three times with an excess amount of aqueous ace- (TG) experiments were carried out on an SDT Q600 TG in-
tone. The silanized glass fiber was obtained after drying under strument (TA, USA), and the measurements began from 50 to
vacuum. 800ºC at a heating rate of 10ºC/min. The scanning electron
A mixture of sodium bicarbonate (0.10 g), H2PtCl6·H2O microscopy (SEM) and X-ray energy dispersion spectroscopy
(0.20 g, Shanghai Chemical Reagent Factory, China), (EDX) data of the samples were acquired using a
1,3,5,7-tetravinyl-1,3,5,7-tetramethyl cyclotetrasiloxane SIRION-100 field emission scanning electron microscope
(D4Vi, 0.40 g, Shanghai Jiancheng Industrial and Trade Co. (FEI, Holland) with an EDX spectrometer.
Ltd., China), and ethanol (30 ml) were stirred at 70ºC for 24
h. The mixture was then purged with nitrogen to remove the 2 Results and discussion
volatiles, followed by the addition of 20 ml of D4Vi. A yel-
low liquid, the Pt(0)-D4Vi complex, was obtained after the 2.1 Structure of the glass fiber-supported Pt complex
mixture was cooled to room temperature and filtered. catalyst
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 FTIR spectroscopy of the parent glass fiber gave the lattice
stirring at 60ºC for 12 h, the solution was decanted from the and O–H vibrations at approximately 1635 and 3442 cm1,
mixture, and the solid was washed five times with an excess respectively (Fig. 1(1)). After silanization of the glass fiber
amount of aqueous ethanol. It was then dried under vacuum with methyldichlorosilane, the bands corresponding to Si–H
(70ºC, 26 kPa) to yield the desired glass fiber-supported Pt (2165 cm1) and Si–C (1406 cm1) vibration modes are also
complex catalyst (denoted GF-Pt). 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

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.
Fig. 1 FT-IR spectra of the glass fiber (GF) (1), silanized glass Further evidence was provided by SEM photos (Fig. 3). A
fiber (2), and GF-Pt catalyst (3) uniform coating was observed after the treatment with me-
thyldichlorosilane, whereas the parent glass fiber showed a
In addition, the strength of the bond between D4Vi and the clear and slick surface. There was a thicker coating on the
glass fiber was measured using TG experiments (Fig. 2). For surface after being further treatment with the D4Vi-Pt com-
the parent glass fiber, there were two weight loss peaks below plex.
100ºC and at approximately 300ºC corresponding to the re- The EDX results in Table 1 are not very accurate for calcu-
lease of physisorbed H2O (ca. 3.5%) and dehydroxylation, lating the percentages of the elements on the surface because
respectively (Fig. 2(1)). The release of H2O (ca. 1%) was less hydrogen cannot be detected by EDX, but they do reflect the
upon the silanization with methyldichlorosilane (Fig. 2(2)). trends of the elements. On the basis of the above results, the
Additional dehydroxylation and the loss of alkoxysilane change of the surface structure shown in Scheme 1 is pro-
fragments occurred with this material above 200ºC. Finally, posed.
the very low weight loss (0.2%) at low temperature for the
GF-Pt provided evidence of the high hydrophobicity of the 2.2 Reactivity of the glass fiber-supported Pt complex
surface (Fig. 2(3)). On the other hand, the weight loss occur- catalyst
ring at 450ºC very likely corresponded to the release of D4Vi
after Si–C bond cleavage. The hydrosilylation reaction between methyldiethoxysilane
Besides, a very clear shift from a hydrophilic surface (glass (Me(EtO)2SiH) and styrene was used to determine the relative
fiber) to a hydrophobic surface was observed in the surface activity of this new catalyst. Fig. 4 shows the conversion ver-
treated experiment. Thus, the structure of the bonding be- 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. hydrosilylation catalyst has to be designed. One way to de-
The conversion was over 95% after reaction at 25ºC for 1 h. velop a new heterogeneous catalyst from an effective ho-
mogenous catalyst is to support the latter on high surface area
2.3 Potential for use in the self-healing polymer compos- solids such as graphite, Al2O3, SiO2, zeolite, and so on. The
ites type of the support material and the surface modifier fre-
quently plays a crucial role in the performance of the resulting
To meet the special demand of self-healing polymer com- supported catalyst. Basically, the support has to be thermally
posites, a novel catalyst that is different from a conventional 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

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.

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