Article in Press: Oligo-And Polysilo Xanes

ARTICLE IN PRESS
Prog. Polym. Sci. xx (2004) xxx–xxx

www.elsevier.com/locate/ppolysci
Oligo- and polysilo xanes

Yoshimoto Abe*, Takahiro Gunji
Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science,
2641 Yamazaki, Noda, Chiba 278-8510, Japan
Received 14 January 2003; revised 5 August 2003; accepted 21 August 2003
Abstract
The article reviews the work on the synthesis, properties, and structure of curious oligo- and polysiloxanes which have been
done mainly by the authors, referring the related papers. So far as oligosiloxanes, the topic is especially focused on sila-
functional siloxanes as the building block for the synthesis of ladder or cube oligosiloxanes, while the another is the
polysiloxanes derived from silicic acid and trimethoxysilanes RSi(OMe)3 which are able to form fibers and flexible free-
standing films. The review also refers to the new routes for the selective synthesis of sila-functional oligosiloxanes in addition to
the reaction control based on the relative reactivity of sila-functional groups. Finally, the application of polysiloxanes as the
precursors to ceramics, high performance coatings, and interlayer low dielectric materials are described.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Sila-functional oligosiloxanes; New synthetic routes; Siloxanenols; Cube; Ladder; Polysilicic acid esters; Partially silylated silicic
acids; Polysilsesquioxanes; Spinnablility; Flexible free-standing films; Ceramic precursor; Coatings; Interlayer low dielectrics
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
2. Commercially available sila-functional oligosiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
3. Formation of siloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
3.1. Various oligo- and polysiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
3.2. Reactivity of sila-functional groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
3.3. Siloxane bond formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4. Polysiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4.1. Polysilicic acid esters and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4.2. Polysiloxanes capable of forming fibers and films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4.3. Highly polymerized TEOS stable to self-condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4.4. Flexible free-standing films from RSi(OMe)3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4.5. Base-catalyzed hydrolytic polycondensation of RSi(OMe)3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5. Linear and cyclic sila-functional oligosiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5.1. Facile synthesis routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5.1.1. Vapor phase hydrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5.1.2. Oxidative condensation of dimethyldichlorosilane with dimethyl sulfoxide . . . . . . . . . . . 000
* Corresponding author. Tel.: þ 81-4-7124-1501x3608; fax: þ 81-4-7123-9890.

E-mail address: abeyoshi@rs.noda.tus.ac.jp (Y. Abe).
0079-6700/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2003.08.003
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2 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx
5.1.3. Linear siloxanes with definite chain length by ring opening reaction of Dn . . . . . . . . . . . 000
5.2. IR and NMR spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5.3. Disiloxanols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5.4. Cyclotetrasiloxane tetrols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
6. Ladder oligosilsesquioxane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
7. Cube siloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
8. Application of oligo- and polysiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
8.1. Ceramic precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
8.2. High performance coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
8.3. Interlayer low dielectrics for electronic devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1. Introduction versatile as starting materials. The synthesis and

uses of sila-functional oligosiloxanes are very limited,
Polysiloxanes are versatile materials, many hav- although they can be potential building blocks for
ing excellent chemical, physical, and electrical polysiloxanes and polysilsesquioxanes. The key to
properties; polydimethylsiloxane is an important develop the methods for the synthesis of such
example of this class of polymers. The only precursors should be the controlled reactions of
disadvantage, nevertheless it is one of the excellent silanes with sila-functional groups, with special
properties, of siloxanes is the fact that they are not attention to the reactivity of sila-functional groups.
able to form fibers and films because of their low Subsequently, di- and trifunctional silanes would be
interactions between molecules. In order to afford precursors, with hydrolysis, condensation or elimin-
new functions, the structure of polysiloxanes has ation is as the preferred reactions to provide
been modified by side chain functionalization or oligosiloxanes.
change in the main chain. The dimension of the This review article will focus on the syntheses,
macromolecular structure is a key factor in the properties, and applications of sila-functional oligo-
generation of new properties: ladder and sheet are and polysiloxanes and silsesquioxanes with linear,
two-dimensional structures, while cross-linked cage, cyclic, ladder, cage, and cube structures.
cube, and spheres are three-dimensional structures.
Such structures may find use as materials with
characteristic thermal, optical, electrical, and mech- 2. Commercially available sila-functional
anical properties. The state of association or oligosiloxanes
aggregation of the macromolecules must also be
considered. Recent research trends involve the A variety of organosilicon compounds are com-
synthesis and properties of sila-functional oligo- mercially available. However, so far as oligosiloxanes
and polysiloxanes, silsesquioxanes such as cage, and silsesquioxanes are concerned, very limited
cube, and ladder structures, and their applications as products are available as reagents including sila-
functional materials. functional oligosiloxanes and oligosilsesquioxanes
Although research on siloxanes is attractive like ladder, cage, and cube. The same is also true
because of the multitude of potential applications, for sila-functional silanes. Moreover, as illustrated by
convenient and selective methods for the synthesis of the examples listed in Tables 1 and 2, based on
sila-functional silanes and oligosiloxanes are lacking catalogues issued by several sources [1], the available
Even silanes with sila-functional groups such as reagents are often expensive.
R42n 2 mSi(OR)nXm or (RO)42nSiXn (m ¼ 1; 2; Sila-functional silanes R42nSiXn (n ¼ 2; 3: R ¼
n ¼ 1 , 3, R ¼ alkyl, alkenyl, aryl; X ¼ halogen, alkyl, alkenyl, aryl; X ¼ H, halogen, OR) are versatile
OR0 , OH, NR 2, OCOR, NCO) are not reagents, whereas silanes R 42nSiX n (n ¼ 2; 3;
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Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 3
Nomenclature Mw/Mn polydispersity

NMR nuclear magnetic resonance
Bp boiling point
ORTEP Oak Ridge thermal ellipsoid plot
Bu butyl group, CH3CH2CH2CH2 –
Oct octyl, (CH3)2(CH2)7 –
But tert-butyl group, (CH3)3C –
PC polycarbonate
D3 hexamethylcyclotrisiloxane, (Si(CH3)2O)3
PEOS polyethoxysiloxanes
D4 octamethylcyclotetrasiloxane,
PET polyethylene terephthalate
(Si(CH3)2O)4
PMSQ polymethylsilsesquioxane
D5 decamethylcyclopentasiloxane,
PP polypropylene
(Si(CH3)2O)3
PSSX partially silylated siloxane
DABCO 1,4-diazabicyclo[2.2.2]octane
PVSQ polyvinylsilsesquioxane
DE degree of esterification
Ph phenyl, C6H5 –
DS degree of silylation
Pri isopropyl, (CH3)2CH –
Decomp. decomposition
Qn Siloxane unit, Si(OSi0.5)n(OR)42n ðn ¼
Et ethyl, CH3CH2 –
1 – 4Þ
SEC size exclusion chromatography (or GPC,
SOG spin-on-glass
gel permeation chromatography)
SUS304 stainless steel
HDPE high density polyethylene
TEOS tetraethoxysilane
HPLC high performance liquid chromatography
THF tetrahydrofuran
IR spectrum infrared absorption spectrum
TMOS tetramethoxysilane
JIS K5400 Japan Industrial Standard No. K5400
Td (5%) temperature at the weight loss of 5%
MS mass spectroscopy
Tn siloxane unit, RSi(OSi0.5)n(OR)32n ðn ¼
Me methyl group, CH3 –
1 – 3Þ
MeOH methanol
Vi vinyl, CH2yCH –
Mn number average molecular weight
m-CPBA meta-chloroperbenzoic acid
Mp melting point
d solubility parameter
Mw weight average molecular weight
X ¼ OH, OCOCH3, NR2, NCO) and especially Table 1. It may be noted that only siloxanes with
(RO)42nSiXn (n ¼ 1 , 4; R ¼ Me, Et, Pri, But; n ¼ 1 , 4 are commercially available, as shown at
X ¼ halogen, OR0 , OH, NR2, OCOCH3, NCO) are the bottom of Table 1. Cyclic oligodimethylsiloxanes
so limited as to be supplied for commercial uses. D3,5 are the raw materials for the production of
Many of them may be purchased as order-made or silicone. Usually, the only variations of the functional
obtained as a component product of reaction mixtures group found with sila-functional cyclosiloxanes
or a by-product. Silanediols and triols R42nSi(OH)n (SiMeXO) n are hydrogen and alkoxy groups
(R ¼ Me, Ph) are often used as a potential precursor (n ¼ 3 , 5; X ¼ H, OR). While an appreciable
for the preparation of oligo- and polysiloxanes or number of linear sila-functional oligosiloxanes are
silsesquioxanes. Recently, isocyanato(methyl)silanes listed, most are disiloxanes, as shown in Table 1, and
Me42nSi(NCO)n ðn ¼ 1 , 4Þ have been used as no homologues more than trimers are listed in the
halogen-free coupling reagents, of which reactivity catalogues.
is appreciably higher than that of alkoxysilanes, but Cubes can be a potential building block to
low compared with chlorosilanes [2]. On the other prepare silicon-based materials, but as shown in
hand, it is difficult to synthesize silanes with different Table 2, they are very expensive and limited as
functional groups (RO)4-nSiXn. A few examples commercial products. Therefore, convenient
(X ¼ halogen, OR0 , OH, NR2) are listed in Table 1. methods to provide them as precursors have to be
Linear and cyclic oligosiloxanes are listed in developed.
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Table 1 Table 2
Price list of commercially available oligosiloxanes Price list of commercially available cubes
insoluble products, because base catalysis promotes

hydrolysis to provide gels in the form of powders or
bulk bodies. On the other hand, controlled acid-
catalyzed hydrolysis followed by polycondensation of
silanes provides polysiloxanes with various shapes,
including cyclic, linear, pseudo-ladder, and even
cubic structures, as shown in Schemes 1 and 2.
Acid-catalyzed reactions are preferred to prepare
linear polymers and branched polysiloxanes, from
which silica glass and fibers are prepared via
precursor gels. Base catalysis or template tends
to afford cube and pseudo-ladder silsesquioxanes.
3. Formation of siloxanes
3.1. Various oligo- and polysiloxanes
Bifunctional silanes are used as starting materials

for the preparation of linear and cyclic oligosiloxanes
and polysiloxanes. By contrast, trifunctional silanes
have not been used as raw materials. Now, they have
been recognized as potential materials for the
syntheses of interesting oligo- and polysiloxanes and
polysilsesquioxanes.
Controlled hydrolytic polycondensations with acid
or base catalysis provide oligo- and polysilsesquiox-
anes with various structures which can be the
precursors for silicon-based materials. The hydrolysis
of tri- and tetrafunctional silanes usually gives Scheme 1.
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Scheme 2.
Sol – Gel reactions of sila-functional silanes provide a form siloxane oligomers and polymers, especially with
facile process to obtain the materials mentioned chloro and alkoxy groups. This is also the reaction in the
above. sol –gel process, which is applicable to metallasiloxane
or metalloxane bonds formation using metal-organic
3.2. Reactivity of sila-functional groups compounds. Hetero-functional condensations invol-
ving silanol groups (Eq. (3.2)) are a potential route to
Sila-functional groups, which are essential to the control reactions and/or construct siloxanes with well-
formation of siloxane bonds and/or the synthesis of defined structures, because the cleavage of siloxane
siloxane compounds, make it possible to promote bond by acid or base catalyst is minimized. Therefore,
various types of siloxane formation reactions. In the reactions shown in Eq. (3.2) provide tailor-made
addition, the reactivity plays an important role to siloxanes, such as high molecular weight block,
control reactions and subsequently to result in the random, and alternating copolysiloxanes, as well as
structure control of siloxane compounds. A number of oligosiloxanes. Another type of hetero-functional
sila-functional groups are shown below. Of these, the condensation is illustrated in Eq. (3.3). Similarly,
following are particularly versatile: Halogen, NR2, condensation of silanes with alkoxy and chloro groups
OCOR, NHCONR2, NCO, OH, OR, H, OCRyCR2, may take place in the presence of a suitable catalyst. The
ONyCR2, and ONR2. silicon – silicon bond can be oxidized with peroxides,
There have been no reported quantitative, or even nitrosoamines, ozone, and hydrogen peroxide to form
qualitative estimates of the reactivity of sila-func- siloxanes (Eq. (3.4)). It seems that almost no reports
tional groups. Based on the experimental results [3], have been published about the reaction in Eq. (3.5).
one would anticipate the following order: H, OR, Condensation followed by elimination takes place in
OH , NCO, OCOCH3, , NHCONR2, NR2, Cl. the presence of acid as a catalyst, if controlled, and
would provide polysiloxanes with targeted structures.
3.3. Siloxane bond formation
Siloxane bond formation reactions are represented 4. Polysiloxanes

by the Eqs. (3.1) – (3.5) in Scheme 3. Self-conden-
sations followed by hydrolysis of silanes with sila- A wide variety of industrial applications have been
functional groups (Eq. (3.1)) are a versatile means to developed for polysiloxanes, with excellent chemical,
ARTICLE IN PRESS
Scheme 3.
physical, electrical properties. In recent years, the Silicic acids are potential starting materials, but
requirements of advanced technologies have created they do not react with organic compounds in an
as need for new high performance polysiloxanes. aqueous solution except by means of silylation by
Here, an attention will be focused on polysiloxanes as Lentz [5]. However, alcohols, chlorosilane, acetyl
precursors for coatings, binders, additives, and chloride [6] or even metal chloride [7,8] will react
ceramics. with silicic acids to give derivatives, which may be
extracted by organic solvents. Thus, silicic acid was
4.1. Polysilicic acid esters and their properties extracted with organic solvent from the resulted
aqueous solution after neutralization of sodium
Polyalkoxysiloxanes have been used as industrial metasilicate with hydrochloric acid followed by
raw materials (so called SE 40, 48, and ME 52). salting out. In this procedure, acetone, alcohols such
These are the mixture of oligomers prepared by as 1-propanol, 2-methyl-2-propanol, and 2-propanol,
hydrolysis of tetraethoxysilane TEOS and tetra- and THF were used as solvent. When THF was used,
methoxysilane TMOS. No high molecular weight silicic acid was extracted up to 90% as SiO2 [9]. As a
polyalkoxysiloxanes stable to condensation have result, a silicic acid – THF solution of 1.2 mol/l was
been synthesized. On the other hand, esterification conveniently prepared.
of silicic acid, the reverse reaction of hydrolysis of According to Eq. (4.1), silicic acid is esterified by
tetraalkoxysilane, is reported by Iler [4] to provide alcohol under azeotropic distillation to give poly-
polysilicic acid esters and/or polyalkoxysiloxanes silicic acid esters over a range of molecular weight
unstable to self-condensation, of which silica and degree of esterification (DE: relative degree of
content was up to 66%. However, their properties, alkoxy group among the all functional groups). An
structure, and esterification conditions were not apparatus for this purpose is shown in Fig. 1, and
investigated in detail. example results with 1-butanol are summarized in
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hexane. Especially, gelation of ester was favored

when the DE was less than 60%. Samples decompose
before melting. Solubility and stability increase as the
DE and carbon number of the alkyl group increase.
The esters are soluble in organic solvents and stable to
self-condensation, as silylates are, even the DE is
higher than 60%. Subsequently, the esters of low DE
undergo further condensation to give more high
molecular weight polymers. Esters prepared by
controlled condensation show silica contents up to
70%, and good spinnability, to form precursor fibers,
as indicated in Table 4a.
The structure was estimated by the spectral and
elemental analysis together with the relationship
between viscosity and Mn of esters by the Mark –
Houwink –Sakurada equation (Eq. (4.3)). The esters
are constructed of the structure (Scheme 4). The
composition was estimated from the 1H NMR spectra
to be ðx þ yÞ : z ¼ 0:7 , 0:9 : 1 for the esters
(R ¼ Bu). In addition, the exponential a in the
equation is determined to be 1.2. Consequently, the
esters should be consisted of ladder-like structure as is
supported by the thermal behavior of no melting point
Fig. 1. Apparatus for the esterification of silicic acid. Silicic acid –
THF solution is put in the flask at left side and alcohol and calcium but decomposition [10 –14].
oxide are put in the flask at right side. On heating both flasks
individually, the vapor of alcohol is introduced to the flask at left
side, while the vapor of THF and water is introduced to the flask at
ð4:3Þ
the right side. The esterification of silicic acid is promoted by
dehydration by calcium oxide.
A silicic acid – THF solution is prepared by
Table 3. These are characterized by SEC and 1H NMR extraction of an aqueous silicic acid solution with
analysis after isolation as silylates, stable to conden- THF. A concentrated silicic acid solution, up to about
sation according to Eq. (4.2) [10 – 14]. 6 mol/l, can be obtained by adding hexane into the
silicic acid – THF solution. It was found that an about
6 mol/l silicic acid – THF solution diluted with
methanol provides silica gels like silica glasses on
ð4:1Þ aging in a sharle wrapped with a polyethylene film
with several pin holes to permit slow evaporation of
the solvent [15].
ð4:2Þ
4.2. Polysiloxanes capable of forming fibers and films

The properties of polysilicic acid esters depend
greatly on DE and the ester group. The esters gelled One of the outstanding properties of polysiloxanes
just after the concentration of the reaction mixture or is the weak interaction between molecules, which
isolation as a white powder by precipitation with affords them excellent physical properties, such
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Table 3 Table 4b
Preparation of polysilicic acid butyl esters under atmospheric Solubility of various silicic acid esters
pressure
R DE (%) Spinnable timea (h) Length (cm)
Temp (8C) Time (h) Mp (decomp., 8C) DE (%) Mn
Et 50 28– 32 10–20
135–145 0.5 235 54 13,200 Pri 40 160– 168 50–100
2 230 63 10,000 Bu 43 38– 42 50–100
12 220 90 11,500 Oct 26 70– 90 5–10
140–145 0.5 – 63 22,000 a
The time until a spinnability was observed and spinnable time
1 210 73 24,000 intervals on aging a solution of various esters (7.0 mol/l) at 40 8C.
6 215 85 18,000
Eq. (4.4). The silylates are soluble in organic solvents
and isolated by precipitation with water/MeOH (5/1,
Table 4a
Variation of molecular weights of polysilicic acid butyl ester with v/v) followed by drying in vacuo. Despite a low
DEs on aging molecular weight and dispersion as indicated in
Table 5, concentrated silylate solutions show spinn-
DE (%) Aging time (h) Mn Mn Mw =Mn
ability that is highly dependent on the solvent such as
43 0 3390 4650 1.37
acetone, dibutyl ether, ethyl acetate, dioxane, and THF
12 4480 10,300 2.30 and also on the sila-functional groups of OH, OCOCH3,
19.5 4570 18,200 3.98 and OBu. Thus, remarkable spinnability is observed for
31.5 4300 29,500 6.86 the silylate with DS 70% when in dioxane solution.
38 4930 33,500 6.80
Further, reactions of silylates with acetyl chloride and
55 0 3850 5420 1.41 1-butanol provide the corresponding derivatives in
131 3300 5100 1.55 which the silanol groups are replaced with acetoxy and
226.5 3300 7360 2.23
butoxy groups. The relative spinnability is measured to
85 0 11,400 20,000 1.75 be the order: Bu , OCOCH3 , OH. No spinnability is
194 11,000 15,600 1.42
observed for the completely silylated polymer.
985 10,400 18,300 1.76
Obviously, spinnability highly depends on DS and
solvent and/or the solubility parameter so that spinn-
as a low viscosity coefficient and a small contact
ability is correlated to the intermolecular interactions
angle. However, this can also represent a potential
resulted from the structure of polysiloxane. The
limitation for their use as coating films or fibers. Such
results suggest that structure modification of siloxane
limitations could be overcome by modification or
improvement of the polysiloxane structure. Table 5
As shown in Tables 4a and b, silicic acid esters Spinnability of partially silylated silicic acids PSSX
undergo condensation to form high molecular weight
PSSX Xa Molar ratio Mn Mw Mw =Mn nc Spinnability
polysilicic acid esters. Depending on DE and the ester b
TMCS/SiO2 (cm)
group, some of these show spinnability, and provide
precursor fibers of silica. This may suggest that OH 1 980 1100 1.12 7.3 50
spinnability depends on the DE and/or silanol groups, 2 1150 1370 1.19 6.7 250
3 1270 1500 1.23 6.5 200
in addition to molecular weight. If so, partially silylated 5 1290 1720 1.33 6.5 100
silicic acids would be expected to show spinnability 7 1480 1990 1.34 6.6 80
[16 – 18]. Therefore, silylates with various degrees of 10 1500 2020 1.35 6.6 50
OCOCH3 5 1340 1670 1.25 6.5 80
silylation (DS) were prepared by the reaction of OBu 7 1330 2300 1.73 6.8 50
chloro(trimethyl)silane with silicic acid, according to
a
Functional group in PSSX.
b
Molar ratio of chloro(trimethyl)silane (TMCS) to silicic acid
(SiO2).
c
Scheme 4. Degree of condensation.
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backbone with sila-functional group as a pendant is a importance in sol – gel processing. Depending on
key process to synthesize polysiloxanes capable of whether acid and base catalysis are utilized, linear or
forming not only fibers but also films. cross-linked polymer sols are formed especially on sol –
ð4:4Þ
Silylation of silicic acid with allyl(chloro)(di- gel process of TEOS. However, almost no work has
methyl)silane in the presence of triethylamine gives been done on the isolation and characterization of sols,
partially allyl(dimethyl)silylated silicic acids, of as they are unstable to self-condensation Moreover,
which high molecular weight polymers (M n most efforts are devoted to the preparation and
6000 , 34,000) are separated as a benzene-soluble characterization of ceramic materials. Therefore, the
component from low molecular weight polymers (Mn structure is often investigated by in situ analysis in the
2400 , 4100). Interestingly, the silylates show not solution [20].
only spinnability, but film formation while no flexible Low molecular weight polymer sols are now
films are prepared from partially trimethylsilylated supplied as commercially available products, so
silicic acids. This appears to be the first finding of called SE 40, 48, and MS 52, but they are the
flexible free-standing films prepared from polysilox- mixture of oligomers with low degrees of polym-
anes as a precursor, other than Brown’s phenylsilses- erization. Investigation of the preparation and
quioxane [19]. The results mentioned above reveal properties of polyethoxysiloxane sols stable to self-
that spinnability and film formation are closely condensation by sol – gel reaction of TEOS is of
associated with the structure of polysiloxanes: inter- interest and value to the basic chemistry of polymer
molecular interactions resulted from backbone and sols, and their application as industrial raw
pendant group are the key factor, and mechanical materials.
strength of fibers and films is related to backbone As indicated in Section 4.2, the properties of
structure in addition to molecular weight. polysilicic acid esters largely depends on the DE and
ester groups. Controlled esterification is essential to
4.3. Highly polymerized TEOS stable to self- the preparation of esters with expected properties. The
condensation same is true in the sol – gel process of TEOS, the
reverse reaction of the esterification of silicic acid.
Hydrolytic polycondensation of metal alkoxides is Thus, the sol – gel reaction, if controlled, would
well known as a sol – gel method. It is a potential route to provide polyethoxysiloxanes (PEOS) according to
prepare oxide materials in a range of forms, including Eq. (4.5). The key factor to obtain polyethoxysilox-
bulk bodies, particles, thin films, and fibers. The anes stable to condensation is structure control, based
material properties can be strongly influenced by on the relative ratio of siloxane structural units Qn
the sol and gel precursors. In this regard, control of the (Q2: x, Q3: y, Q4: z) together with the ratios of silanol
hydrolysis and condensation reactions are of central to ethoxy and silanol groups [21].
ð4:5Þ
ARTICLE IN PRESS
Table 6
Preparation of polyethoxysiloxanes
No. Molar ratio H2O/TEOS Time (h) Yield (g) Mw Mw =Mn Ratio of siloxane unita Spinnability at 25 8C (cm)
(%)
Q1 Q2 Q3 Q4
1 1.50 7 17.4 1700 1.3 8 37 45 10 0

2 1.60 7 16.7 2300 1.5 3 24 54 19 0
3 1.70 7 15.9 5400 2.3 2 21 56 21 80
4 1.75 5 15.8 7300 2.9 2 17 58 23 120
5 1.80 2 15.3 11,700 3.8 2 13 62 23 120b
6 1.90 1.5 15.1 Gel – – – – – 0
Scale in operation: TEOS 34.8 g (0.167 mol). Molar ratios: EtOH/TEOS ¼ 2.07, HCI/TEOS ¼ 0.105. Temp.: 80 8C.
a
Calculated based on the 29Si NMR spectra.
b
At 80 8C.
In an investigation of these effects, reactions were analysis indicates silica contents up to 70%. This
carried out in various molar ratios of H2O, HCl, and should be noted considering the fact that the silica
EtOH to TEOS at 70 8C for 3 h with stirring under the contents of industrial ethyl silicates (SE 40, 48) and
nitrogen stream, as shown in Table 6 [22]. The methyl silicate (SM 53) are 40, 48, and 53%,
preparation process is featured by reaction under a respectively. Polyethoxysiloxanes as well as poly-
nitrogen stream (Fig. 2) and evaporation of solvent, silicic acid esters, therefore, can be a potential
hydrogen chloride and excess amount of water, to material as coating, additives, and binders.
maintain steady progress in the condensation at the
late stage, but PEOS with molecular weight up to
11,700. They are identified by 1H, 13C, and 29Si NMR
spectra, IR spectra, and SEC analysis. From these
results, the products were confirmed to be PEOS with
siloxane backbone and side chains of ethoxy and
silanol groups where the siloxane unit structures are
consisted of Q2, Q3, and Q4 (Fig. 3) [21]. Since they
mainly consist of Q3, the structures should not be
linear, but branched-ladder.
Polyethoxysiloxanes are soluble in organic sol-
vents, except for hexane, and stable to self-conden-
sation although they contain an appreciable amount of
silanol groups (the molar ratio OH/Si ¼ 0.4), esti-
mated from elemental analysis. Good spinnability was
also observed by drawing a glass rod up from a
concentrated viscous solution. They undergo conden-
sation either in solution or neat, as illustrated by
the results of an SEC analysis as shown in Fig. 4. Only Fig. 2. Apparatus for the preparation of polyethoxysiloxanes
a slight increase in molecular weight is observed for (PEOS) by the hydrolytic polycondensation of tetraethoxysilane
the controlled reactions at room temperature and (TEOS) under a nitrogen stream. TEOS, ethanol, and hydrochloric
acid are placed in a four-necked flask and nitrogen is introduced
below, except for reactions in a THF solution, trough the reaction. PEOS is produced as a highly viscous liquid. In
showing unexpectedly stability compared with sols this process, the discharge of hydrochloric acid promotes the
generally prepared via a sol – gel process. Elemental condensation reaction.
ARTICLE IN PRESS
4.4. Flexible free-standing films from RSi(OMe)3
Much attention has been paid to hydrolytic

polycondensation of trifunctional silanes RSiX3
(X ¼ Cl, OR 0 ; R 0 ¼ alkyl), as the controlled
reaction provides oligo- and polysiloxanes with
various structures, as shown in Scheme 2 in
Section 3.1. These have potential as precursors to
high performance silicon-based materials, as
demonstrated by the properties of ladder poly-
phenylsilsesquioxanes, synthesized by hydrolytic
condensation followed by base-catalyzed equili-
bration reaction of phenyltrichlorosilane or
phenyltrimethoxysilane.
High molecular weight polymethylsilsesquiox-
anes (PMSQ) soluble in solvents and capable of
forming tough free-standing films had not been
synthesized from the trifunctional silanes until 1992
[23] and 1995 [24]; Brown prepared soluble, film
forming poly-T-phenylsilsesquioxane in 1960, [19],
and allyl(dimethyl)silylated silicic acid was
reported to give flexible free-standing films in
1988 [18].
Fig. 3. 29Si NMR spectra of polyethoxysiloxanes (PEOS). The Qn
denotes the silicon atom substituted with n siloxy groups and 4 2 n According to Eq. (4.6), controlled acid-cata-
alkoxy, aryloxy, or hydroxy groups, which is often described as lyzed hydrolytic polycondensation, characterized
Si(OSi)n(OR)42n (n ¼ 0–4).
Fig. 4. The variation of the molecular weight of polyethoxysiloxanes (PEOS) on aging as neat, THF solution, and EtOH solution at 0 8C (a) and
20 8C (b).
ARTICLE IN PRESS
Fig. 5. Free-standing films prepared by casting a 20 wt% acetone–

methanol (v/v ¼ 1) solution of polymethylsilsesquioxanes (PMSQ)
and heating at 80 8C.
Fig. 6. The variation of the tensile strength and elongation of
polymethylsilsesquioxanes (PMSQ) free-standing films as a func-
tion of molar ratio of H2O/trimethoxy(methyl)silane (MTS) on the
by the reaction method described in Section 4.3, hydrolysis of MTS.
provides PMSQ and polyvinylsilsesquioxanes
(PVSQ), as summarized in Table 7. They are
expected to be broken ladder since the backbone condensation of siloxane bond (DC) increases,
consists of T2 and T3 structures. They are stable tensile strength increases and elongation decreases.
to condensation and have excellent spinnability. At a DC of 70%, films become less flexible, and
No gelation is observed, even after several are rather rigid and brittle. This is also indicated
months in concentrated solution. Free-standing by the stress – strain curves of films: above DC of
films are prepared by casting a 20 wt% acetone- 70%, films are broken at the maximum tensile
methanol (v/v ¼ 1) solution and heating at 80 8C strength about 15 MPa. The results clearly reveal
for 3 weeks (Fig. 5). Films show high transpar- that the mechanical properties of polysilsesquiox-
ency up to 98% (at 500 nm), high thermal anes are closely associated with the structure in
stability, with Td (5%) of 400 8C (PMSQ) and terms of DC and/or cross-linkage of siloxane
600 8C (PVSQ), and appreciable flexibility, with bond and molecular weight.
ð4:6Þ
tensile strength up to 27 (PMSQ) and 17 MPa Polysiloxanes such as polysilicic acid esters,
(PVSQ) and elongation of 1.2 (PMSQ) and partially silylated silicic acids, and polymethyl(vi-
0.8 mm (PVSQ). The tensile strength and nyl)silsesquioxanes have fascinating properties as
elongation of films are represented in Fig. 6 advanced silicon-based materials, suggesting the
as a function of the molar ratio of H2O/MTS on possibility of a wider range of applications than for
the hydrolysis of MTS. As the degree of found with traditional organopolysiloxanes.
ARTICLE IN PRESS
4.5. Base-catalyzed hydrolytic polycondensation of substrate and the reaction temperature were increased.
RSi(OMe)3 Volatile amines provide low molecular weight poly-
siloxanes, but non-volatile amine DABCO yields a
Acid-catalyzed hydrolytic polycondensation of polysiloxane with fairly high molecular weight of
R42nSi(OR0 )n (n ¼ 3; 4) is a desirable way to obtain 6800. On the other hand, sodium hydroxide catalyzes
polysiloxanes as polymer sols, because linear poly- hydrolytic polycondensation effectively, depending on
siloxanes are formed according to the reaction the molar ratio of the base and H2O, to yield
mechanism discussed in the previous sections. polysiloxanes with high molecular weight above
Generally, base-catalyzed condensations provide 35,000. In the higher molar ratio of base, methacryloxy
insoluble gels. Almost no reports have been published groups are hydrolyzed, while molecular weights
on the preparation of soluble polysiloxanes, except by decrease as a white powder is formed.
the hydrolysis of PhSiX3 (X ¼ Cl, OMe) followed by Thus, the reaction conditions investigated in detail
equilibration with potassium hydroxide to form reveal that high molecular weight polysiloxanes are
polysiloxanes with molecular weights around a attainable and, interestingly, consist of almost all T3
thousand [25]. structures, as shown in Table 8. The 29Si NMR spectra
are noted, for the signal due to T3 has two shoulders at
the fields below 2 66.5 ppm (2 64.0 and 2 65.5 ppm),
as shown in Fig. 7. These signals may be ascribed to
ð4:7Þ
an irregular ladder structure due to three-, four-, and
bridged four-membered rings.
Polysiloxanes are soluble in organic solvents,
In order to synthesize high molecular weight except for hexane and methanol Hence, thin films
polysiloxanes, 3-methacryloxypropyl(trimethoxy)si- are formed on various organic and inorganic sub-
lane is hydrolyzed (Eq. (4.7)) with various base strates by dip coating with a 20 wt% acetone-
catalysts such as ammonia, triethylamine, diazabicy- methanol (v/v ¼ 1) solution.
clooctane (DABCO), and sodium hydroxide, using the Recently, tetraalkylammonium hydroxides have
same apparatus as that for acid-catalyzed conden- found use in base catalysis of hydrolytic polyconden-
sations [26]. Table 8 shows the results of reactions with sation of TEOS and RSi(OR0 )3. It is well known that
the bases, as well as acid-catalyzed reactions. For tetraalkylammonium hydroxides serve as a template
reactions in the presence of HCl, soluble polysiloxanes to synthesize cube siloxane Q8(ONR4)8, but no work
with molecular weighs higher than 2300 were not have been reported on their role as a base catalysis on
prepared, even if the molar ratio of HCl and water to the hydrolytic polycondensation. Therefore, it is of
Table 7
Preparation of polymethylsilsesquioxanes and polyvinylsilsesquioxanes
Molar ratio H2O/TEOS Spinnability (cm) Mw £ 103 Mw =Mn State
As prepared After 30 min
PMSQ 1.28 2 40 31.0 9.2 Viscous liquid

1.30 200 300 42.0 11.6 Viscous liquid
1.32 300 0 – – White resin
1.64 – – – – White powder
PVSQ 1.30 0 1 2.4 1.8 Transparent liquid
1.44 20 40 3.8 2.3 Viscous liquid
1.60 200 300 19.0 5.0 Viscous liquid
1.64 300 0 – – White resin
Scale in operation: MTS and VTS 0.167 mol. MeOH: 14 ml. Molar ratio: HCI/TEOS ¼ 0.105. Temp.: 70 8C. Stirring: 150 rpm. N2 flow
rate: 360 ml/min.
ARTICLE IN PRESS
convenient and selective synthesis routes of sila-

functional oligosiloxanes.
5.1. Facile synthesis routes
5.1.1. Vapor phase hydrolysis

The vapor phase hydrolysis reported by Andrianov
is expected to form disiloxanes [27], but the reaction
conditions, procedure, and apparatus were not
Fig. 7. 29Si NMR spectra of poly(3-methacryloxypropyl)siloxanes

prepared by the hydrolysis 3-methacryloxypropyl(trimethoxy)si-
lane using base catalyst. The Tn denotes the silicon atom substituted
with n siloxy groups and 3 2 n alkoxy, aryloxy, or hydroxy groups,
which is often described as RSi(OSi)n(OR0 )32n (n ¼ 0–3).
importance to investigate the reaction mechanisms as

a template and also base catalysis.
5. Linear and cyclic sila-functional oligosiloxanes
Sila-functional oligosiloxanes, as well as silanes,

can be potential building blocks for synthesis of
linear, cyclic, ladder, and cubic siloxanes, although
oligomers without sila-functional groups are less
useful. As indicated in Table 1 in Section 2,
commercially available sila-functional oligosilox-
anes are expensive and limited. In addition,
synthetic routes for these are also limited. Certainly, Fig. 8. Apparatus for the vapor-phase hydrolysis. Four-necked flask
hydrolytic condensation of sila-functional silanes is attached with reflux condenser and flowmeter, that connects to a
R42nSiXn ðn ¼ 3; 4Þ is versatile, but neither attrac- flask. Trifunctional silane, RSiX3 (R ¼ Me, vinyl, Ph; X ¼ Cl,
tive nor preferable for selective synthesis in NCO), is placed in the four-necked flask and water and 1,4-dioxane
are placed in the other flask. On refluxing trifunctional silane under
appreciable yields. Tedious and complicated separ- reduced pressure, a mixed vapor of 1,4-dioxane and steam is
ation processes, resulting in low yields, often follow introduced into the four-necked flask to hydrolyze trifunctional
it. Therefore, it would be desirable to develop silane.
ARTICLE IN PRESS
Scheme 5.
described in detail. The method would provide a the hydrolysis of 50 according to Scheme 7.
convenient route to obtain sila-functional oligosilox-
anes, if the reaction can be carried out under
controlled conditions.
Thus, the hydrolysis of isocyanatosilanes R42n ð5:1Þ
Si(NCO)n (R ¼ Me, vinyl, Ph; n ¼ 3; 4) was inves-
tigated using a simple apparatus [28]. Fig. 8 shows
the vapor phase hydrolysis apparatus, equipped with
a reflux condenser, a thermometer, a flow meter, and
a flask containing water and dioxane. In a four- 5.1.2. Oxidative condensation of
necked flask, the silane, vaporized on heating under dimethyldichlorosilane with dimethyl sulfoxide
reduced pressure, undergoes hydrolysis/condensation Recently, a new method for the preparation of
with a water – dioxane vapor introduced into a flask cyclosiloxanes D3 and D4 by ‘anhydrous hydrolysis’
through a flow meter, to form the oligosiloxane. was reported [30]. It is the reaction of dichloro(di-
Since the oligosiloxane is not vaporized at the methyl)silane with dimethylsulfoxide, which acts as
temperature and pressure, only the starting silane is oxygen donor or oxidizing agent for dichloro(di-
vaporized and selectively hydrolyzed to give methyl)silane according to Scheme 8. This may be
oligosiloxanes. The reaction in the vapor phase preferable to provide D3.
proceeds according to Eq. (5.1).
The method is applied to the synthesis of linear 5.1.3. Linear siloxanes with definite chain length by
oligosiloxanes 2 , 6 and 8 with an even number of ring opening reaction of Dn
silicon atom, but not those with odd number of silicon Hydrolysis of difunctional silanes with chloro and
atoms, nor cyclic oligosiloxanes 30 , 60 . Therefore, alkoxy group is not useful to prepare high molecular
they are synthesized by hydrolysis of linear oligosi- weight polysiloxanes. Thus, acid or base catalyzed
loxanes in the liquid phase according to Schemes 5 ring-opening polymerization of cyclic dimethylsilox-
and 6 [29]. Tables 9 and 10 summarize the results of anes D3, D4, and D5 are the practical and industrial
the synthesis of linear and cyclic oligosiloxanes. methods to produce polydimethylsiloxanes.
Except for cyclotetrasiloxane 40 , which solidifies after
distillation, they are isolated as liquids by distillation
under reduced pressure, and identified by NMR, IR,
and MS spectral analysis. During distillation of 50
from a reaction mixture, the distillate with low boiling
point solidifies. The structure was determined to be a
propellane 500 by X-ray analysis, with the results
shown by the ORTEP drawing in Fig. 9. The
propellane is assumed form via an intermediate on Scheme 6.
ARTICLE IN PRESS
Table 8
Hydrolytic polycondensation of 3-methacryloxypropyl(trimethoxy)silane
Run Catalyst Molar ratios Temp. (8C) Molecular weight Crude yields (g)
Cat./MAS H2O/MAS Mn Mw =Mn Polysiloxane Powder
1 HCl 1.05 £ 1021 1.5 70 2200 1.6

2 100 2200 1.6
3 150 2300 1.7
4 200 Gel Gel
5 NH3 1.0 £ 1021 3.0 70 620 1.9 9.39 –

6 3.2 £ 1021 780 2.1 9.19 –
7 NEt3 1.0 £ 1021 3.0 70 2100 2.0 7.89 –
8 2.7 £ 1021 2400 2.0 7.79 –
9 DABCO 2.7 £ 1021 3.0 70 6800 6.1 7.43 –
25
10 NaOH 5.4 £ 10 3.0 70 2700 1.6 7.76 –
11 2.7 £ 1023 .35,000a –a 7.27 –
12b 2.7 £ 1022 9000 5.9 6.40 0.28
13b 5.7 £ 1022 2900 2.1 6.10 0.27
14b 2.7 £ 1021 390 1.0 0.18 4.97
Scale of operation: 3-methacryloxypropyl(trimethoxy)silane, 10.4 g (4.2 £ 1022 mol); MeOH, 14 ml. Temp.: 70 8C. Time: 3 h. N2 flow
rate: 360 ml/min.
a
Over the exclusion limit of the column.
b
Methacryloxy group was hydrolyzed.
If a ring opening reaction of Dn without equili- trends to behavior for polydimethylsiloxane are
bration is conducted, linear oligosiloxanes with a observed, as shown in Figs. 10 and 11, but the
limited chain length may be derived. One-way to following aspects are revealed: in Fig. 10, a sharp
obtain linear oligo- and polysiloxanes with definite peak at 1041 cm21 for 30 shifts to 1100 cm21 for
and various chain lengths is partial hydrolysis to form 40 , 60 . No further shifts are observed while the
silanol, followed by condensation with a suitable shoulder appears at 1040 cm21 in addition to the peak
chlorosilane. This is also used as a method to prepare broadening. In Fig. 11, on the other hand, the sharp
dendrimers [31,32]. peak at 1099 cm21 for 2 is broaden for 3 , 6 and 8
and splits into two at the peak top. The band at
5.2. IR and NMR spectra 1099 cm21 shows no shift, but the others a low
wavenumber shift from 1079 cm21 (trisiloxane) to
It seems that almost no investigations have 1053 cm21 (octasiloxane).
addressed the IR or 29Si NMR spectra of oligosilox- The pattern of NMR signals for cyclic oligosilox-
anes. The asymmetric stretching vibration nSi – O – Si of anes depends on the structure and/or stereochemical
linear and cyclic dimethylsiloxanes is reported: the configuration, and often shows complicated splittings,
signals appear at 1018 ðn ¼ 3Þ; 1076 ðn ¼ 4Þ; 1081 as expected from the molecular structures. On the
ðn ¼ 5Þ; 1068 ðn ¼ 6Þ; 1060 ðn ¼ 7Þ; and 1056 cm21 other hand, a similar pattern of signal splittings is
ðn ¼ 8Þ for cyclic dimethylsiloxanes (Me2SiO)n, and observed for the 1H, 13C, and 29Si NMR spectra of
also at 1000 , 1100 cm21 for linear dimethylsilox- linear oligosiloxanes 2 , 5: the signals due to the
anes (Me2SiO)n The absorption band is increased, proton, carbon, and silicon attached to the methylsilyl
overlapped, and broaden as the increase of n more groups are shifted to low and high field, respectively.
than three. On the other hand, no work has been The signals at low field due to the terminal groups do
reported on the IR spectra of sila-functional oligosi- not shift regardless of length of siloxane bond, while
loxanes such as those in Tables 9 and 10. Similar those at high field are split into several peaks, and
ARTICLE IN PRESS
Table 9
Spectral and analytical data of cyclic oligosiloxanes 30 –60 and 500
Compound Bp (8C/mm Hg) NMRa (ppm) IRb (cm1) MS/m=z

1 13 29
H C Si
30 79.4–76.5/0.80 0.371 (9H, s, CH3 –Si):cis 22.07 (CH3 –Si): trans 251.2: cis 1041 ðnSiOSi Þ 287 (Mþ-15)
0.398 (6H, s, CH3 –Si): 22.19 (CH3 –Si): trans 251.1: trans 1274 ðdSiCH3 Þ
trans
0.425 (3H, s, CH3 –Si): 22.32 (CH3 –Si): cis 250.8: trans 1457 ðdCH3 Þ
trans
123 (Si–NCO) 2285 ðnNCO Þ
40 133.0– 134.2/3.0 0.36 (12H, m, CH3 –Si) 22.20 (CH3 –Si) 260.4 to 261.1 1030–1107 ðnSiOSi Þ 404 (Mþ-15)
123.0 (Si– NCO) 1270 ðdSiCH3 Þ
1457 ðdCH3 Þ
2290 ðnNCO Þ
50 134.7– 136.8/0.45 0.233–0.501 (15H, 21.74 (CH3 –Si) 262.4 to 262.0 1031–1106 ðnSiOSi Þ 490 (Mþ-15)
br, CH3 –Si)
123 (Si–NCO) 261.1 to 261.0 1274 ðdSiCH3 Þ
260.8 to 260.5 1457 ðdCH3 Þ
2288 ðnNCO Þ
60 136.3– 140.2/0.34 0.234–0.471 (18H, br, 22.04 (CH3 –Si) 262.4 to 262.2 1040–1103 ðnSiOSi Þ 591 (Mþ-15)
CH3 –Si)
123 (Si–NCO) 260.4 1275 ðdSiCH3 Þ
260.1 1456 ðdCH3 Þ
2290 ðnNCO Þ
500 c – 0.281 (6H, s, CH3 –Si) 21.73 (CH3 –Si) 258.0 to 258.5 1033–1114 ðnSiOSi Þ 491 (Mþ-15)
0.349 (3H, s, CH3 –Si) 21.95 (CH3 –Si) 1273 ðdSiCH3 Þ
0.398 (3H, s, CH3 –Si) 22.17 (CH3 –Si) 1454 ðdCH3 Þ
0.404 (3H, s, CH3 –Si) 25.06 (CH3 –Si) 2288 ðnNCO Þ
123 (Si–NCO)
a
Solv. CDCl3. Ref.: TMS.
b
CCl4 soln. method.
c
Mp: 73.6–75.5 8C.
coalesce in a narrow region of several ppms which the condensation is prevented from forming
2 61.3 , 2 62.2 for oligosiloxanes 2 , 6 and 8. silanols with an appreciable stability to self-conden-
From the results, it is expected that no further shifts sation. The synthesis and properties of various
are appeared for higher homologues. A similar trend silanols are reviewed by Lickiss [33].
is observed for the 1H and 13C NMR spectra. Schemes 9 and 10 show 1,3-disiloxanediols
(a) , (c) [33] and (d) [34], together with 1,5-
5.3. Disiloxanols trisiloxanediols ((a), n ¼ 2) and also disiloxanetetrols
(e) and (f). Some of the diols (a) in Scheme 9 are
Disiloxanols (disiloxane polyols) such as disilox- commercially available. Brown reported 1,1,3,3-
anediols and even tetrols are essentially synthesized diphenyldisiloxanetetrol (e) in Scheme 10 by hydroly-
by hydrolysis of the corresponding chlorosilanes. The sis of phenyltriacetoxysilane [35]. Bulky organic
reaction has to be carried out under mild and carefully groups: such as phenyl, t-butyl, hexyl, octyl, decyl
controlled conditions, because the products easily [36], and 1,1,2-trimethylpropyl, are essential to isolate
undergo condensation, especially in the presence of a the tetrols [37]. The disiloxanetetrol with an aryl
trace amount of acid and base, or on heating. A key (trimethylsilyl)amino group (f) by hydrolysis of
factor to isolate silanediol, and especially disiloxane arylamino(trichloro)silane is noted [38], because in
polyols, is the steric hindrance of substituents and general silylamino groups are easily substituted with a
additional intramolecular hydrogen bonding, by hydroxyl group, but this is not true in this case,
ARTICLE IN PRESS
in good yields, for they easily undergo condensation

to form polymerized products, making it difficult to
isolate tetrols. Therefore, few reports have been
published on their preparation and crystal structure.
The method to synthesize tetrols is the hydrolysis of
trichlorosilanes with organic groups such as phenyl
[39], isopropyl and cyclopentyl [40]. The reaction
proceeds via silane triols, where the steric hindrance
and inductive effects of organic groups should play an
important role directing the condensation to form
cyclic tetrols. Hydrolysis is preferably carried out in
water –acetone or methyl ethyl ketone, as is shown in
Eq. (5.2). This is a simple and convenient way,
although the yields are low, around 40% [39]. Another
route is the stepwise synthesis shown in Eq. (5.3).
This is a fine way, but the three-step reaction results in
a total yield of 25% [40]. Sila-functional cyclic
tetrasiloxanes can be a starting material if con-
veniently synthesized by the reaction of sila-func-
tional disiloxanes or sila-functional linear
Fig. 9. ORTEP drawing of propellane 500 .
tetrasiloxanes.
probably due to steric hindrance as well as the low Hydrolysis of 1,3-diisopropyl-1,1,3,3-tetrachloro-
basicity of the amino group. disiloxane in acetone as a solvent [40] yields cyclic
tetrasiloxane tetrol, where all silanol groups arrange in
a cis configuration by hydrogen bonding between the
5.4. Cyclotetrasiloxane tetrols tetrol and water molecules to form a silanol cluster.
The structure is identified by X-ray crystallographic
Cyclotetrasiloxanetetrols are potential precursors analysis. It can be a starting material for
for the preparation of bead, cage, and cube siloxanes. the preparation of cage polysiloxanes by a conden-
However, it is not easy to synthesize them selectively sation reaction, with cyclohexylcarbodiimide
Scheme 7.
ARTICLE IN PRESS
6. Ladder oligosilsesquioxane
Ladder polyphenylsilsesquioxane has excellent

properties, such as enhanced thermal stability, film
formation, and mechanical properties, in addition to
Scheme 8. those of usual polysiloxanes of chemical, physical,
and electrical properties. If the structure is completely
as a dehydrating agent.
ladder, it consist of the T3 structural unit. However, so
called ladder-T-phenylsilsesquioxane virtually con-
ð5:2Þ tains the T2 unit, which means that the structure has
broken ladder defects. Another problem is the
synthesis: at first, oligosiloxanes are prepared by the
hydrolysis of phenyltrichloro- or trialkoxysilanes and
ð5:3Þ
then subjected to base-catalyzed equilibration reac-

tion to provide polyphenylsilsesquioxanes. Therefore,
the reactions may not be controlled, and may not
provide products with definite physical properties. If
the reaction is controlled, high performance ladder
polysilsesquioxanes would be obtained, and it would
be of great interest to investigate their properties.
Since it is difficult to obtain a perfect ladder product,
the present research target is the synthesis of ladder
oligosilsesquioxanes as a model compound.
Brown reported the first synthesis of ladder
oligosilsesquioxane of cyclotetrasiloxane unit-con-
densed three ring system in 1965, by the hetero-
functional condensation of cyclotetrasiloxane tetrol
with dichlorodisiloxane [41], as shown by Eq. (6.1) in
Scheme 11. The results on the measurement of IR and
1
H NMR spectra and elemental analysis in addition to
Mn (815), mp (124 8C), and yield (24%) are cited, but
the structures in solution and crystal were not
described. Later, the two ring systems are also
synthesized by the reaction of tetrachlorodisiloxane
with disiloxane diols in 1973 according to Eq. (6.2)
[42]. No spectral and analytical data were given,
except for IR spectral data and melting point.
Recently, ladder oligosilsesquioxanes with two,
Fig. 10. IR spectra of cyclic oligosiloxanes 30 , 60 . three, and five-ring system [43,44] have been
ARTICLE IN PRESS
synthesized and isolated as one component of several

stereoisomers [44], by means of HPLC through
effective, but tedious, stepwise reaction processes
(Eq. (6.3)). The X-ray crystal structure analysis
reveals the ring system is not linear, but bent to be
face to face against the both terminal sites, which may
result from the reaction with cyclotetrasiloxane tetrol,
where all silanol groups are in the cis configuration.
Interestingly, oxidation of ladder oligosilanes was
reported to give bi- and tricyclic siloxanes (Eq. (6.4)).
This is a new route, which uses not oligosiloxanes, but
ladder oligosilanes as a starting material [45].
The cyclic siloxanes mentioned above bear bulky
organic groups, which means that the starting
materials are not versatile and have to be prepared
via several steps. Vapor phase hydrolysis of commer-
cially available chloro- and isocyanatosilanes con-
veniently provides the di- and tetrasiloxanes. If they
can be used as a precursor, cyclic siloxanes with usual
organic groups of methyl, vinyl, phenyl as a pendant
would be obtained.
A convenient potential route for the synthesis of two
and three ring systems with all methyl or vinyl group as
a pendant has been realized [46]: the hetero-functional
condensation of disiloxane diols with tetraisocyanato-
Fig. 11. IR spectra of linear oligosiloxanes 2 , 6 and 8. disiloxanes or tetraisocyanatocyclotetrasiloxane with
Scheme 9.
Scheme 10.
ARTICLE IN PRESS
disiloxanediols, as is shown in Eqs. (6.5) and (6.6). represented in Eq. (7.1). On the other hand, hydrolysis
This method should be versatile, for the starting of TEOS to give water-soluble silicate ions, followed
materials are simply and selectively synthesized by by condensation, yields complicated condensed
vapor phase hydrolysis, as it is described in Section 5, species. Hoebbel [51] found another cube in 1971:
and a number of ring systems with various pendant in the presence of quaternary ammonium ions, the
groups would be obtained in addition to the preparation silicate ion Si8O20O82 is templated to give an
of more larger ring systems. The products are obtained ammonium salt Q8(NR4)8 in almost quantitative
by distillation in vacuo and the results of spectral yields, according to Eq. (7.2).
analysis indicate ladder oligosilsesquioxanes. To date, many cubes have been synthesized, as
listed in Table 11 [52]. These are classified into three
ð6:5Þ
ð6:6Þ
7. Cube siloxanes groups, (a) alkyl and aryl substituted cubes, (b) carbo-
functional cubes, (c) sila-functional cubes. A large
Oligosilsesquioxanes consist of the (RSiO3/2)n numbers of cubes belong to the groups (a) and (b)
structural unit; the homologues with n ¼ 6; 8, 10, while the residues are the group (c). In the group (a),
and 12 have been isolated [47]. Of these, QX 8 the cubes are prepared by the hydrolysis of trichloro-
( ¼ Q8X8, X denotes substituted group to Q unit) or trialkoxysilanes (Eq. (7.3)). The cubes in the group
and TR8 ( ¼ T8R8, R denotes substituted group to T (b) are synthesized by the hydrosilylation of the
unit), abbreviated ‘cubes’ hereafter, have attracted corresponding carbo-functional olefines with TH 8 (Eq.
considerable attentions from the stand point of (7.4)) prepared by the hydrolysis of trichlorosilane
synthesis and applications: they have a nano-sized HSiCl3 (Eq. (7.1)). The group (c) is the cubes with the
three-dimensional structure consisted of almost inor- sila-functional groups of Cl and OMe together with H
ganic silica backbone with an angstrom level cavity, and ONR4. The cube T(OMe) 8 is synthesized by the
high thermal stability, and reactive functional groups. reaction of methyl formate with TCl 8 which is derived
The first cube TH8 was obtained in 1959 by Muller by chlorination of TH8 (Eq. (7.5)).
et al. as a intermediate, in yield less than 1%, on the Thus, the synthetic route and the starting materials
synthesis of poly(hydridosilsesquioxane) [48]. Frye are limited. Moreover, it is a serious problem that
et al. [49] modified the hydrolysis of HSiCl3 to regardless of the groups, cubes are obtained in low
prepare TH 8 in 13% yield. Later, the cube was obtained yields after long time reactions. In particular, only a
in 27% yield in 1991 by Agaskar [50]. The reaction is few cubes with sila-functional groups are prepared,
ARTICLE IN PRESS
Scheme 11.
as mentioned above and also shown in Table 11 (see Recently, new synthetic routes to cages and poly-
also Table 2 in Section 2). Most of them are poorly silsesquioxanes have been investigated using tetra-
soluble in organic solvents and have no melting point, alkylammonium salt as a catalyst: hydrolytic
but sublime or decompose at elevated temperature. As condensation of alkyl(triethoxy)silane in the presence
shown in Table 12, there are few reports on the of tetrabutylammonium fluoride provides octasilses-
physical properties of cubes, and the reported data are quioxane cage and higher homologues with short
sometimes inconsistent among different authors. reaction times and in very high yield (90%) [53]. The
Cubes of tetraammonium salt are prepared as hydrates redistribution reaction of oligohydridosilsesquioxane
with tens of molecules of water, and are soluble in using tetraalkylammonium hydroxide yields polyhy-
water, methanol, and ethanol. The synthesis must be dridosilsesquioxanes. Hydrolytic condensation of
improved in order to apply the cubes as a precursor for TEOS using a stoichiometric amount of water to
the preparation of silicon-based new materials. TEOS using tetraalkylammonium hydroxide also
ARTICLE IN PRESS
Table 10
Spectral and analytical data of linear oligosiloxanes 2–6 and 8
Compd Bp (8C/mm Hg) NMRa (ppm) IRb (cm1) MS/m=z

1 13 29
H C Si
2 128.1–129.9/13 0.50 (6H, s, CH3 –Si) 20.50 (C H3 –Si) 259.4 1099 ðnSiOSi Þ 255 (Mþ-15)
123 (NCO) 1280 ðdSiCH3 Þ
1457 ðdCH3 Þ
2310 ðnNCO Þ
3 111.3–112.1/1.0 0.389 (6H, s, CH3 –Si) 21.90 (CH3 –Si) 261.3 1079–1115 ðnSiOSi Þ 457 (Mþ-15)
0.474 (6H, s, CH3 –Si) 20.60 (CH3 –Si) 259.8 1274 ðdSiCH3 Þ
123 (Si–NCO) 1457 ðdCH3 Þ
2275 ðnNCO Þ
20.52 (CH3 –Si) 1455 ðdCH3 Þ
5 68.1–71.6/0.45– 0.50 0.389 (9H, s, CH3 –Si) 21.97 (CH3 –Si) 261.8 1063–1109 ðnSiOSi Þ 559 (Mþ-15)
20.52 (CH3 –Si) 1455 ðdCH3 Þ
0.484 (6H, s, CH3 –Si) 20.49 (CH3 –Si) 1454 ðdCH3 Þ
123 (Si–NCO) 1455 ðdCH3 Þ
2285 ðnNCO Þ
Mp: 73.6–75.5 8C.

a
Solv. CDCl3. Ref.: TMS.
b
CCl4 soln. method.
provides polyethoxysiloxanes [54].
ð7:1Þ
ð7:3Þ
ð7:2Þ ð7:4Þ
ARTICLE IN PRESS
Table 11
Syntheses of cube siloxanes
No. Reagent Substituent (R) Yield (%) References
1 HSiCl3, hexane, toulene, MeOH, FeCl3, HCl –H 23 [48–50,58–61]

2 No. 1, Cl2, CCl4, hn – Cl .95 [62–67]
3 No. 2, HC(OMe)3, heptane – OCH3 68 [62,63,68,69]
4 MeSiCl3 – CH3 37 [70–72]
5 TEOS, Me4NOH 5H20 – ONME4 76 [61,73–77]
6 No. 5, Me3SiCl – OSiMe3 72 [51,73,78]
7 No. 5, HMe2SiCl – OSiMe2H 83 [61,78,79,80]
8 No. 5, CH2yCHMe2SiCl – OSiMe2CHyCH2 61 [78,81–84]
9 No. 5, (Allyl)Me2SiCl – OSiMe2CH2 –CHyCH2 [85]
10 No. 5, C6H5Me2SiCl – OSiMe2C6H5 54 [83]
11 No. 5, ClCH2Me2SiCl – OSiMe2CH2Cl 53 [83,86]
12 EtSiCl3 – Et 37 [72]
13 PrSiCl3 – Pr 44 [72]
14 BuSiCl3 – Bu 38 [72]
15 PhSiCl3, C6H5NMe3OH – C6H5 [72,87,88]
16 p-MeC6H4SiCl3 – C6H4Me 19 [88]
17 (1-naphthyl)Si(OMe)3 – C10H7 60 [88]
18 ViSiCl3 – CHyCH2 21 [61,81,89–91]
19 (Allyl)SiCl3 – CH2CHyCH2 13 [92]
20 HS(CH2)3Si(OMe) – (CH2)3SH [93]
21 No. 1, 1-hexane – C6H13 90 [59]
22 No. 1, 1-octane – C8H17 [60]
23 No. 1, dec-1-ene – C10H21 [59]
24 No. 1, tetradec-1-ene – C14H29 [59]
25 No. 1, octadec-1-ene – C18H37 [59]
26 No. 1, CH2yCH6H9 – (CH2)2C6H9 [60]
27 No. 1, hydrosilylation – (CH2)3C6H4OCH3 [93]
28 No. 1, hydrosilylation – (CH2)3C6H5 [93]
29 No. 1, hydrosilylation – (CH2)3CN [93]
30 No. 1, hydrosilylation – (CH2)3 –O–CH2CH(O)CH2 [93]
31 No. 1, hydrosilylation – (CH2)3C6F5 [93]
32 No. 1, hydrosilylation – (CH2)3OC6H5 [93]
33 No. 1, hydrosilylation – (CH2)3Si(CH3)3 [93]
34 CH2yCHMe2CH(O)CH2 – (CH2)3CH(O)CH2 [60]
35 CH2yCHOMe2CHOCH2C6H9 – (CH2)3 –O–(CH2)2 –O–CH2C6H9 [60]
36 No. 48, (vinyl)MgCl – (CH2)3Si(CHyCH2)3 [91]
37 No. 7, CH2yCHCH2OH – OSiMe2(CH2)3OH 86 [80]
38 No. 7, 2-allyloxyethanol – OSiMe2(CH2)3OCH2CH2OH 87 [80]
39 No. 15, HNO3 – C6H4NO2 [88]
40 (3-ClC3H6)8Si8O12, NaI – (CH2)3I [93]
41 (3-ClC3H6)8Si8O12, NaSCN – (CH2)3SCN [93]
42 (3-ClC3H6)8Si8O12, KP(C6H5)2 – (CH2)3P(C6H5)2 [93]
43 (3-ClC3H6)8Si8O12, CH3SNa – (CH2)3SCH3 [93]
44 No. 35, m-CPBA – (CH2) –O–(CH3)2 –O–CH2C6H8(O) [60]
45 No. 18, m-CPBA – CH(O)CH2 50 [81]
46 No. 8, m-CPBA – OSi(CH3)2CH(O)CH2 80 [81]
47 No. 26, oxone, acetone, CH2Cl2 – (CH2)C6H8(O) [60]
48 No. 18, HSiCl3 – (CH2)2SiCl3 [91]
49 No. 8, HSiCl3 – OSi(CH3)2CH2CH2SiCl3 95 [84]
50 No. 7, Rh(acac)3 – OSi(CH3)2Br 99 [61]
51 No. 7, Co2(CO)8 – OSi(CH3)2Co(CO)4 99 [61]
Continued on next page
ARTICLE IN PRESS
Table 11 (continued)
No. Reagent Substituent (R) Yield (%) References
52 No. 7, CH2yCH(CH2)4O(C6H4)2CN – OSi(CH3)2(CH2)4O(C6H4)2CN 85 [79]

53 No. 7, CH2yCH(CH2)6O(C6H4)2CN – OSi(CH3)2(CH2)6O(C6H4)2CN [79]
54 No. 7, CH2yCH(CH2)11O(C6H4)2CN – OSi(CH3)2(CH2)11O(C6H4)2CN [79]
55 No. 1, CH2yCH(CH2)3OSiMe3(OSiMe3)2 – (CH2)5OSiCH3(OSiMe3)2 [94]
56 Me3SnCl – OSnMe3 [95]
57 Me4SbCl – OSbMe4 [95]
58 No. 7 – OSiMe2(CH2)17CH3 [96]
59 No. 7 – OSiMe2(CH2)2C6H5 [96]
60 No. 7 – OSiMe2CH2CH(CH3)C(O)OMe [96]
61 No. 7 – OSiMe2(CH2)2Si(C2H5)3 [97]
62 No. 7 – OSiMe2(CH2)2SiMe(OSiMe3)2 [97]
63 No. 7 – OSiMe2CHyCH–C6H5 [98]
64 No. 7 – OSiMe2CHyCH–C3H7 [98]
65 C6H11Si(OH)2OSi(OH)2C6H11 – C6H11 13 [43]
ð7:7Þ
ð7:5Þ
8. Application of oligo- and polysiloxanes
In another class of cubes, one pendant group differs
from the others. These are prepared by the reaction of The sila-functional oligosiloxanes described so far
various trichlorosilanes with the silane triols are potential candidates for surface modifier, coupling
T7R5(OH)3 (Eq. (7.6)), where most of the organic agents, additives, and building blocks for ladder and
substituents are cyclopentyl or cyclohexyl groups. An cube oligosiloxanes, polysiloxanes with well-con-
appreciable numbers of derivatives have been syn- trolled structure and silicon-based materials. It should
thesized as summarized in Table 13. The silane triol be noted that they are a potential precursor as well for
[55] and diol [56] are obtained as intermediates during the synthesis of silicon-based organic – inorganic
the preparation of cubes, but only in fairly low yields, hybrids, closely related to the polysiloxanes discussed
around 30%. Recently, It was a preparation of the triol above as additives and binders in combination with
as the sodium silanolate was reported, with almost organic polymers and inorganic materials such as
quantitative yields by the hydrolysis or the trichlor- glasses, oxides, and ceramics.
osilane with a stoichiometric amount of water and
sodium hydroxide (Eq. (7.7)) [56]. 8.1. Ceramic precursors
As discussed in the preceding, the sol –gel process

with TEOS forms polysiloxanes with sufficient
spinnability to form fibers that are transformed to
silica fibers by a subsequent pyrolysis. This is an
effective process to obtain silica fibers at an
appreciable low temperature although there are the
ð7:6Þ problems to be improved such as the stability of sols
ARTICLE IN PRESS
Table 12
Spectral and analytical data of cube siloxanes T8R8
R in T8R8
–H –Cl –OMe –CHyCH2 –ONMe4 – OSiMe2H
1
NMR [d/ppm] H 4.20 – 3.36 – 4.80 (H2O), 4.7 (Si H),
3.19 (CH3)4 N 0.2 (SiCH3)
13
C – – 51.3 128.1 (SiC HyCH2), – –
137.7 (CHyC H2)
29
Si 284.4 291.1 2101.4 280.2 299.0 0.5 (SiMeH)
– 108.8Si(O)4
IR (cm21) (nSi – O – Si 2290(s) 1142(s) 1155(s) 3064(vw) 3420 2961(w)

is shown in bold)
1140(vs) 1090(sh) 1090(vs) 3025(vw) 3019 2920(w)
918(w) 795(vw) 848(m) 2982(vw) 1643 2140(m), 1245(m)
885(sh) 712(s) 795(w) 2959(vw) 1489 1169(m)
870(s) 515(s) 720(w) 1601(w) 1404 1093(s)
500(sh) 450(m) 570(vs) 1404(w) 1019 897(s)
470(w) 335(m) 470(w) 1273(w) 949 744(w)
395(m) 395(m) 1144(m) 725(w)
1105(s) 644(w)
1000(w) 550(w)
965(w)
774(w)
579(m)
MS 423 (M–H)þ 665 (M–Cl)þ 664 (Mþ) – – –
Mp (8C) 250 173 (decomp.) 161 (decomp.) 278
Sublim. p. (8C/Torr) 130/0.5 135/0.5
Yield (%) 23 .95 68 20.5 75.6 82.6
Elemental analysis H: 2.0 (1.9) Cl: 40.75 C: 14.37 (14.45); C: 29.19 (30.35); – C: 18.74 (18.88);
found (calcd) (40.50) H: 3.64 (3.64) H: 3.88 (3.83) H: 5.04 (5.54)
to condensation regardless of the optical properties of [110]. A mixture of the two components of
silica fibers. On the other hand, esterification of silicic (RSiO3/2)n (R ¼ Me, Pr, Ph) provides silicon
acid provides spinnable polysiloxanes [13,14], for oxycarbide fibers on heating the precursor fibers
which the stability and/or self-condensation are in N2 or argon [111]. Black glasses, silicon
dependent on the degree of esterification (DE) and oxycarbide, are formed by heat-treatment of
the alkyl group, so that the esters with appropriate polysilsesquioxane gels prepared by hydrolytic
DEs can be used as a good precursor for the polycondensation. They are also obtained by
preparation of silica fibers. Thus, esters with DE less heating the polysiloxanes prepared by hydrolytic
than around 60% undergo further condensation which, polycondensation of TEOS/a,v-polydimethylsiloxa-
on precipitation with a solvent such as hexane, form nediol [112] or TEOS/Me2Si(OEt)2 [113].
insoluble powders which are the precursors for the As described in Section 6, controlled hydrolytic
preparation of submicrometer-sized silica particles polycondensation of methyl- and vinyltrimethoxy-
[108]. Silicic acid itself is also used as a precursor for silane yields polymethyl- and vinylsilsesquioxanes,
the preparation of bulk silica glasses, which are providing access to bulk gels and flexible free
prepared by aging a concentrated silicic acid in standing films. Black glasses are formed on
organic solvents, followed by gradual evaporation of pyrolysis of the precursor films at 1400 8C under
the solvent at room temperatures [15,109]. N2 atmosphere [114].
Polysilsesquioxanes can be a precursor for the Pyrolysis of polymethylsilsesquioxane films
preparation of silicon oxycarbide SiOC or SiC forms broken pieces of black glass. However,
ARTICLE IN PRESS
polyvinylsilsesquioxane films provides ceramic films molecules and also between the molecules and
without cracks, though they shrink about 15% both in substrate in the coating are of central importance.
length and width. In addition, a little weight loss These interactions depend on the molecular structure
(about 10%) is observed for both films. The ceramics and molecular weight: the silanol groups as a pendant
are identified to be silicon oxycarbide with the afford an intermolecular force and an interaction with
composition of SiOxCy ðx ¼ 0:71 , 2:0; y ¼ 1:40 , substrates, and in some cases, forms a chemical
1:60Þ: The black glass ceramic films have a free bonding. As it is well known, polysiloxane sols
carbon content up to 90%, in contrast to the free prepared by a sol – gel process with TEOS provide
carbon content of only several wt% into silica glasses good precursors for coatings, although they produce
by the usual melt method. This may result from the silica thin films. Correspondingly, polysilicic acid
fact that the structure of the precursor films is well- esters (polyalkoxysiloxanes) [11 – 14] and polysilses-
controlled, and subsequently converted into ceramics quioxanes [22 – 24] can be the potential candidates
via an organic – inorganic hybrid in which the vinyl because they forms fibers and flexible free-standing
groups are incorporated into silica matrices through films.
addition polymerization. In general, the chemical coating process is
conveniently performed by dip or spin coating
8.2. High performance coatings methods using rather simple apparatuses (Fig. 12)
Here, the results on coatings with PMSQ and PVSQ
Among the various shapes of materials, thin films will be described [115]. The coating solutions are
have found wide applications, especially as functional 20 wt% PMSQ or PVSQ acetone – methanol (v/v)
materials for protectors, optics, electronics and solutions, and organic or inorganic substrates are
membranes for separation or gas permeation. Thus, used: high density polyethylene (HDPE), polypro-
high performance coatings having excellent proper- pylene (PP), polycarbonate (PC), polyethylene
ties are possible with polysiloxanes if they show film terephthalate (PET), 6-nylon, Aluminum, stainless
formation. The interactions between polysiloxane steel (SUS304), soda-lime glass, quartz glass, and
Fig. 12. Apparatus for dip-coating (a) and spin-coating (b).

ARTICLE IN PRESS
Table 13 PC , PET , 6-Nylon, but the coatings do not

Mono-substituted cubes adhere to HDPE or PP. Strong adherence to the
No. Substituent (R0 ) References inorganic substrates may be due to the formation
of metallasiloxane bonds, in addition to physical
66 –H [99] interaction with the surfaces, while the different
67 –Cl [92] adhesion among the organic substrates is associated
68 –OH [92] with the solubility parameter ðdÞ of coatings and
69 –CHyCH2 [100–104]
70 –CH2CHyCH2 [105]
substrates. Table 15 gives the solubility parameter
71 –CH2CH(O)CH2 [105] of PMSQ and some of the substrates. A high
72 –(CH2)6CHyCH2 [100–104] adhesive strength is observed when the solubility
73 –CHyCH(CH2)8CHyCH2 [100–104] parameters of polymer and substrate are close in
74 –(CH2)2C6H4CHyCH2 [100–104] value. Adhesive strength by the crosscut tape test
75 –(CH2)2Si(CH3)Cl2 [100–104]
76 –(CH2)2SiC6H4Cl2 [100–104]
based on JIS K5400 is a qualitative test. The
77 –(CH2)3OCOCH–CH2 [106] adhesive strength shown in Fig. 13 was evaluated
78 –(CH2)3OCOC(CH3)yCH2 [107] quantitatively by the stud-pull method, commonly
known as the Sevastian method. Values in the
silicon wafers. Films are prepared by dipping the ranges 50 , 100 and 80 , 130 kg/cm2 for PMSQ
substrates into the solution and pulling up followed and PVSQ, respectively, correspond to values in
by heating at 80 8C for 24 h and then 100 8C for Table 14. The pencil hardness of PMSQ, which
several hours. was measured using the Japanese Industrial
Dip-coating of 1 – 10 times provides films of Standard K5400 protocol, also depends on the
thickness 0.25 , 0.85 mm (PMSQ) and heating time and molecular weight of the PMSQ,
0.40 , 0.95 mm (PVSQ). The film thickness depends as is shown in Table 16. Similar, but lower, results
on the molecular weight of the polymer. Higher the were observed for the adherence and hardness of
molecular weight lead to thicker the films, and PVSQ PVSQ. (Fig. 14)
provides thicker films than PMSQ. Thin films are highly transparent, with transmit-
The adhesive strength of PMSQ was measured tance of more than 98% at 500 nm. As shown in
using the Japanese Industrial Standard K5400 Fig. 13, both PMSQ and PVSQ are thermally stable up
protocol, with results given in Table 14. to 450 , 500 8C, as evaluated by measuring the
Obviously, the properties depend on heating time adherence at various temperatures. The adhesive
and the PMSQ molecular weight. Polysilsesquiox- strength increases with the increasing temperature
anes adhere more strongly to the inorganic up to 800 8C, indicating that a film still remains. The
substrates than to the organics. Different degrees unexpected thermal stability may be due to the fact
of adhesion are observed for the organic substrates: that polysilsesquioxanes are converted into ceramics
adhesive strength increases in the order: films via an organic –inorganic hybrid.
Table 14
Adhesive strength of PMS coating films
Mw (H2O/MTS) 5500 (1.10) 21,000 (1.23) 55,000 (1.30)
Heating timea (h) 0 3 6 12 0 3 6 12 0 3 6 12

PC 2 6 6 6 4 8 8 8 6 8 8 8
PET 4 6 8 8 8 10 10 10 10 10 10 10
6-Nylon 6 8 8 10 10 10 10 10 10 10 10 10
Aluminum 8 10 10 10 10 10 10 10 10 10 10 10
SUS304 10 10 10 10 10 10 10 10 10 10 10 10
Glass 10 10 10 10 10 10 10 10 10 10 10 10
Coating conditions: the number of dipping, one time; winding speed, 80 mm/min. No adhesions to PP and HDPR.
a
At 100 8C after drying at 80 8C for 24 h.
ARTICLE IN PRESS
8.3. Interlayer low dielectrics for electronic devices
One research target for silicon-based materials is

the development of interlayer low dielectrics for
semiconductor electronic devices. In the near future,
dielectric materials with the k values lower than 2.0
will be needed for practical uses in very large scale
integrated circuits. Despite their being low dielec-
trics, organic compounds can not be applied to the
present device preparation process at high tempera-
tures around 400 , 450 8C. A candidate to over-
come this limitation is offered by polysiloxanes,
Fig. 13. The variation of tensile strength of polymethyl silsequiox-
with their excellent chemical, physical, and elec-
ane (PMSQ) and polyvinylsilsesquioxane (PVSQ) coating films by
stud-pull method, commonly known as the Sevastian method, as a trical properties, but only if they are capable of
function of heating temperature. Coating films were prepared on forming thin films. Suitable polysiloxanes could
silicon wafer by dip coating and then heated at 808C for 24 h under include sols by sol – gel process with TEOS,
nitrogen atmosphere followed by further heating at various copolymers of TEOS and Me42nSi(OMe)n (n ¼ 2
temperatures for 1 h.
or 3), and polysilsesquioxanes. The sols from TEOS
provide films with k around 4. At present,
copolymers are used in the spin-on-glass (SOG)
Table 15 process to provide films with the k values in the
Solubility parameters ðdÞ range 2.9 , 3.0. On the other hand, polysilsesquiox-
Substrate d (calcd)a Note anes are expected to be a potential candidate as
mentioned in Section 8.2, for they provide high
PP 8.01 Non-polar/crystalline performance coatings. At present, no investigations
HDPE 8.56 have been made to evaluate dielectric constant k of
PC 10.5 Polar/non-crystalline
polysilsesquioxanes for correlation with the molecu-
PET 11.7 Polar/crystalline
6-Nylon 11.9–12.5 lar structure [115,116].
PMS ðMw ¼ 5500Þ 12.01 13.14b Table 17 shows the results on the measurement
(Mw ¼ 55,000) 12.17 13.17b of dielectric constant of polymethylsilsesquioxanes,
PVS ðMw ¼ 2600Þ 12.09 13.15b consisting of T3 units of 47 , 58%, with various
(Mw ¼ 21,000) 12.71 13.28b
P P
molecular weights. The dielectric constants appear
a
d (cal/cm3)1/2 ¼ ðDE=DVÞ1=2 ¼ ð Dei = Dvi Þ1=2 ; Dei and Dvi : to be fairly low, around 2.5, compared with those
the additive atomic and group contribution for the energy of of practical films, which are in the range
vaporization and volume, respectively. Fedors RF. Polym Engng
Sci 1974;14:147. 2.9 , 3.0.
b
SP value of PMS (or PVS) 20 wt% acetone– methanol solution.
Table 16
Pencil-hardness of PMS coating films on soda-lime glass
Mw 5500 21,000 55,000
Heating timea (h) 0 3 6 12 0 3 6 12 0 3 6 12

Pencil-hardness 5H 5H 6H 9H 5H 5H 6H 9H 6H 6H 7H 9H
Coating conditions: number of dipping, one time; winding speed, 80 mm/min.

a
At 100 8C after drying at 80 8C for 24 h.
ARTICLE IN PRESS
tional silanes from 3-chloropropyltrialkoxysilane. Przemysl

Chemiczny 1998;77:288 – 90. (b) Abe Y. Synthesis of
isocyanatosilanes and their uses as versatile reagents 1995;
40. (c) Abe Y. Fac Sci Technol (Senryo to Yakuhin) 1995;
40:141–7.
[3] Sakurai H. Application of organosilicon compounds to organic
synthesis. In: Nozaki H, Yamamoto S, Tsuji J, Noyori R,
editors. Kagaku Zokan, vol. 105. Kagaku Dojin. 1985. p.
33– 40.
[4] (a) Iler RK, Pinkney PS. Polysilicic acid esters-preparation
from sodium silicate. Ind Engng Chem 1947;39:1379. (b) Iler
RK. The chemistry of silica. New York: Wiley; 1979. p. 140.
(c) Lentz CW. Silicate structures extracted intact. Chem
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Prog. Polym. Sci. xx (2004) xxx–xxx

Oligo- and polysilo xanes

* Corresponding author. Tel.: þ 81-4-7124-1501x3608; fax: þ 81-4-7123-9890.

2 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

1. Introduction versatile as starting materials. The synthesis and

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 3

Nomenclature Mw/Mn polydispersity

4 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

insoluble products, because base catalysis promotes

3.1. Various oligo- and polysiloxanes

Bifunctional silanes are used as starting materials

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 5

Siloxane bond formation reactions are represented 4. Polysiloxanes

6 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 7

hexane. Especially, gelation of ester was favored

4.2. Polysiloxanes capable of forming fibers and films

8 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 9

10 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

1 1.50 7 17.4 1700 1.3 8 37 45 10 0

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 11

4.4. Flexible free-standing films from RSi(OMe)3

Much attention has been paid to hydrolytic

12 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

Fig. 5. Free-standing films prepared by casting a 20 wt% acetone–

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 13

Molar ratio H2O/TEOS Spinnability (cm) Mw £ 103 Mw =Mn State

As prepared After 30 min

PMSQ 1.28 2 40 31.0 9.2 Viscous liquid

14 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

convenient and selective synthesis routes of sila-

5.1. Facile synthesis routes

5.1.1. Vapor phase hydrolysis

Fig. 7. 29Si NMR spectra of poly(3-methacryloxypropyl)siloxanes

importance to investigate the reaction mechanisms as

5. Linear and cyclic sila-functional oligosiloxanes

Sila-functional oligosiloxanes, as well as silanes,

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 15

16 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

Cat./MAS H2O/MAS Mn Mw =Mn Polysiloxane Powder

1 HCl 1.05 £ 1021 1.5 70 2200 1.6

5 NH3 1.0 £ 1021 3.0 70 620 1.9 9.39 –

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 17

Compound Bp (8C/mm Hg) NMRa (ppm) IRb (cm1) MS/m=z

18 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

in good yields, for they easily undergo condensation

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 19

Ladder polyphenylsilsesquioxane has excellent

then subjected to base-catalyzed equilibration reac-

20 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

synthesized and isolated as one component of several

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 21

22 Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx

Y. Abe, T. Gunji / Prog. Polym. Sci. xx (2004) xxx–xxx 23

Compd Bp (8C/mm Hg) NMRa (ppm) IRb (cm1) MS/m=z

Mp: 73.6–75.5 8C.

provides polyethoxysiloxanes [54].