A Novel Glycol-Silicone Polymer*

MICHAEL A. BROOK: CHRISTINA H. KREMERS, THOMAS

SEBASTIAN, and WEIFENG YU, Department of Chemistry,
McMaster University, 1280 Main St. W.,Hamilton, Ontario,
Canada U S 4Ml

INTRODUCTION
Chlorosilanes readily react with molecules bearing hydroxyl groups to form Si-0
bonds and HCl. Perhaps the most important example of this process is the reaction of
water with chlorosilanes, one of the fundamental reactions in the commercial prepara-
tion of organosilicones.’ Other polyhydroxylated molecules such as diols, however,
react equally well to form “glycol-silicones”2 in which the silicon atoms are separated
by a dioxaalkyl moiety rather than an oxygen atom (Scheme 1).
Materials of the latter type were synthesized and examined for potential utility
particularly during the 1950s and early 1960s“: the diols used include glycerol, 4,4‘-
dihydroxybenzophenone, 4,4’-dihydroxydiphenylmethane,etc. According to N ~ l l the ,~
hydrolytic instability of these polymers precluded their use in applications which are
usually well served by silicones (e.g., coatings), and little activity has been reported in
this area since that time?p6
During the course of work directed toward the synthesis of small molecules, the
reaction between ethylene glycol and Me,SiCl, was examined. Under the conditions
used, the dimeric ring 1 was obtained in addition to traces of the monomeric species z7
(Scheme 2). In contrast, the reaction under identical conditions between MeHSiCl,
and ethylene glycol led to a gel, clearly a polymer. We report herein our synthetic and
structural studies of this polymer which show it to be a crosslinked glycol-silicone
polymer 3 containing both disiloxane and glycol-siloxane components.

R
HO- ’OH -- R‘ZSiCI,
R
Scheme 1.
.o ,
R; ,R‘
S i .
R‘\ / R’
o, R o, s i o, R o, SL
R;
.
p’

MezSiClz \ ono
,si: ‘sic +
HO 0 0’ ’ 0
U
(only traces)
1 2
Scheme 2.

*Presented at the XXI Organosilicon Sympasium, Montreal, June 1988, Abstract P-20.
‘Natural Sciences and Engineering Research Council of Canada University Research Fellow,
1985-1990. Author to whom correspondence should be addressed.

Journal of Polymer Science: Part C: Polymer Letters, Vol. 27, 229-234 (1989)
0 1989 John Wiley & Sons, Inc. CCC 0360-6384/89/07029~-06$04.00
230 BROOK ET AL.
K I?
0’
I
..0I I
CI
I
0 - SI- l l - SI- C1- Si- 0-Si-
/ I I I / I
R R II
OXR OXR 0,
R

5 6 7

14.9 -27.7 - 3.1

CI
I
0-Si-
/ I
R CI

n 9 10 11

6 (*9sinmr) -9.4 -49.g4 -57.8‘ -67.1 lo

R = CH2CH20-
Scheme 3.

RESULTS AND DISCUSSION

The polymeric gel 3 described above is simply made by the addition at room
temperature of methyldichlorosilane to an equimolar amount of ethylene glycol in
CH,Cl,: a rapid evolution of gases accompanied this addition? In addition to the
normal production of HC1 in such reactions, concomitant H, formation was also
observed and could be shown to be taking place by, among other things, the high
flammability of the gases. The latter observation facilitated the understanding of the
process which was occurring.
The structure of the polymer was determined primarily using solid state, MAS
(magic angle spinning) ”Si-NMR; other spectroscopic and “ wet chemical” techniques
were also utilized.
Several functionally different silicon species could be envisaged to arise from the
reaction described. To aid in distinguishing between them, a variety of structurally
related, monomeric model compounds were synthesized (Scheme 3), and the silicon
chemical shifts of each were determined. From this information and the known
chemical shifts of other polymeric methylsubstituted silicon species6 { PDMS [poly(di-
methylsiloxane)]? lo PMHS [poly(methylhydr~siloxane)]~~}, it was possible to assign
all the peaks in the ”Si-NMR (Fig. 1). Thus, the polymer is composed primarily of
pseudo T units, 4. Additionally, there are chloroalkoxysilane units present, 6 (compo-
nents related to 7 and 8 were not observed), pseudo DH units 5, mixed alkoxy-
silane/disiloxane units, 9, lo6 presumably resulting from hydrolytic processes, and T
units, 119 (Fig. 1, Scheme 3).
Qualitative examination of materials prepared with different reaction times showed
a correlation between the “hardness” and reaction time: short reaction times led to a
compressible ge112 3a, longer times led to brittle resins 3b. These could be further
correlated with the Si-H content of the polymer: gradual loss of the Si-H with
increased reaction times could be directly seen in the infrared (IR).I3 Subsequently, the
 A NOVEL GLYCOL-SILICONE POLYMER 231

I I I I I I I I I I
-16 -2E -38 -48 -50 -60 -70 -RE -90
eem
Fig. 1. "Si-NMR (solid state, MAS) of 3a.

Si-H content of 3 was quantified. The polymer readily decolorized iodine, and,
therefore, by backtitrating an excess of iodine with thiosulfate, it was possible to assay
the total Si-H content in the sample quantitatively. Table I shows the relationship
between reaction time and Si-H content. Clearly, longer reaction times resulted in a
lower Si-H content, more crosslinking, and harder materials.
The results outlined above clearly show that material 3 (Scheme 4) consists of the
linear glycol-silicone which would be expected to be formed from the reaction of the
diol with the Sic1 bonds (Scheme 4A, type 5). However, in addition, glycol-silicone
crosslinks arise from the reaction of the hydroxyl groups with the Si-H bond to liberate
H, (Scheme 4B, type 4). For some time, this latter reaction has been known to occur

TABLE I
Relationship Between Si-H Content and Reaction Time
~~~~ ~

Temperature Si-H Reaction

Entry ("C) mEq/g)' time (h)

1 20 27.46b 14
2 - 78 -c -
3 0 1.40 48
4 20 6.04 48
5 20 5.00 50.5
6 20 0.18d 68

a Determined by iodometric methods.

bCompound 3a,a hard, compressible gel.
No reaction was observed to take place.
dCompound 3b, a brittle resin.
232 BROOK ET AL.

0
‘siJ\r
3’21
Scheme 4.

under acidic conditions which are present in the reaction mi~ture.’~ In a formal sense,
the Si-H bond is “reducing” the alcohol. This is a very favorable process thermody-
namically, ’with an overall energy difference of approximately 37 kcal/mol (Si-H 90.3
kcal/mol, Si-0 127 kcal/m01).’~ Finally, because the reaction of the chlorosilane is not
complete (leaving type 6 units), disiloxane formation occurs when the reaction mixture
is exposed to atmospheric moisture leading to components of types 9,10,and 11.
The relationship between Si-H content and reaction time is straightforward. Unless
the HC1 produced in the reaction is stripped from the mixture, the acid can react to
convert &functional silane units to trifunctional units (Scheme 5) at the expense of the
Si-H functionality. Eventually, in the presence of moisture, these chloroalkoxy units
(e.g., 6) crosslink to form disiloxane components (e.g., types 9,10,11),with a corre-
sponding increase in “hardness” of the polymeric species.

6 9
Scheme 5.
 A NOVEL GLYCOL-SILICONE POLYMER 233

CONCLUSION
A novel glycol-silicone 3 can be readily formed by the reaction of gl.ycols with
MeHSiCl,. The structure of this material has been determined by ,'Si-NMR and other
techniques t o consist of a crosslinked polymer containing glycol-silicone and silicone
components. The degree of crosslinking can be conveniently controlled by changing the
reaction time. An evaluation of the potential utility of this material is currently under
way.

EXPERIMENTAL

Apparatus, Materials, and Methods

The 'H-NMR spectra were recorded on a Bruker AM 500 (500 MHz) spectrometer.
The samples were dissolved in chloroform-d using tetramethylsilane (TMS) as internal
standard. Chemical shifts, quoted as 6 valuq, were measured in relation to TMS.
,'Si-NMR spectra were recorded on a Bruker MSL 100 (100 MHz) spectrometer (solid
spectra) operating with a spinning rate of 4 kHz or a Bruker WM 250 (250 MHz)
spectrometer (solution spectra).
Infrared spectra were run on a Perkin-Elmer 283 spectrometer in CHCl, solution,
CHCl, film, neat film, or as a KBr pellet.
All reactions were carried out in dry apparatus under a nitrogen atmosphere using
septa and syringes for the transfer of reagents.
MeHSiCl, (Dow Coming) was purified by distillation from CaH,. Ethylene glycol
(Fisher) was distilled prior t o use. CH,Cl, was purified by distillation from P,O, under
a nitrogen atmosphere just prior to use.

General Procedure
T o a solution of ethylene glycol (6.27 g, 0.1 mmol) in CH,Cl, (100 mL) was slowly
added' MeHSiC1, (10.5 mL, 0.1 mmol). The complete addition normally took between
5 and 30 min. The mixture was allowed to stir at ambient temperature for 14-68 h, at
which time the solvents were removed under vacuum first at 15 Torr and finally at 0.1
Torr. Typical recoveries were > 90%.

3a (Reaction Time 14 h)
I R (film on NaC1): 3360,2970,2880,2160,1271,1118,1079,1030,901,760; 'H-NMR
(CD,OD), note: the polymer undergoes solvolytic decomposition in alcoholic solvents)
6: 0.06-0.08 ( m ,3H), 3.59 (s,4H); ,'Si-NMR (MAS, peak height given in parentheses)
6: - 14.9 [6, MeHSi(OCH,CH,O-),I, - 27.1 [2, MeClSi(OCH,CH,O-),I, - 42.08
[60, MeSi(OCH,CH,O-),I, - 50.16 [35, MeSi(0Si-)(OCH,CH,O-),I; - 58.57
[17, MeSi(0Si-),(OCH,CH,O-)], - 67.93 [4, MeSi(0Si-),I.

3b (Reaction Time 68 h)
I R (film on NaCl): 3360,2955,2880,1264,1078,1030,874,758; ,'Si-NMR (MAS, peak
height given in parentheses) 6: - 42.08 [60, MeSi(OCH,CH,O-),I, - 50.16 [48, MeSi
(OSi-)(OCH,CH,O-),I; - 58.57 [24, MeSi(0Si-),(OCH,CH,O-)], - 67.93
[5, MeSi(0Si-),I.

The running of solid state NMR samples (Mr. Brian Sayer) and solution samples (Mr. Carol
Dallaire) is gratefully acknowledged. We thank the Deutscher Akademischer Austauschdienst
(DAAD) for awarding a McMaster University: Universitat Duisburg Exchange Fellowship to
 BROOK ET AL.

CHK and Jiangxi University for awarding an overseas visiting scholarship to WY. The gift of
chlorosilanes from Dow Corning Corporation, Canada, is greatly appreciated. This work was
supported by the Natural Sciences and Engineering Research Council of Canada.

References
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68-120; W. Noll, Chemistry and Technology of Silicones, Academic Press, New York, 1968, pp.
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2. The term glycol-silicone is used to indicate polymeric alkoxysilanes derived from a glycol
(or polyol) and a difunctional or trifunctional silicon moiety.
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Received July 27, 1988
Accepted January 18, 1989