DTIC ADA063075: Organosilane Polymers. II. Copolymers of Ethylmethyl- and Methylpropylsilylenes with Dimethylsilylene.

AD-A063 075

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UNION CARBIDE CORP TARRYTOWN N Y F/G 11/9

ORGANOSILANE POLYMERS. II. COPOLYMERS OF ETHYLMETHYL- AND METHY— ETC<U)
DEC 78 JP WESSON. T C WILLIAMS N00014-75-C-1024

TR-78-1 NL

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MICROCOPY RESOLUTION TEST CHA&T

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5. TYPE OF P£PO«T 4 ? P Pj 33 COVER ED

Organosilane Polymers*

XI* Copolymers of Ethylmetby 1- and
Methylpropylsilylenes jfith
Dimethylsilylene —

Technical

8. PEfl^OHMIHG OKG. Rs?OST HUMiCR

J . P . /Wesson -rtT.C . / Williams X /Cl [ n0^014-75-C- 1024'

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I is. KEY WORDS (Contlmio on roeetae mldm It nmcoooery end Identify hr block ntmtbmr)

Silanes
Polysilanes
Organopolysi lanes

Ethylmethylsilylene

Methylpropylsilylene

Dimethylsilylene

' ABSTRACT (Continue on revere* old* it nmcoosory ond Identify 5/ block number)

Random copolymers of ethylmethyl- and methylpropylsilylenes with
dimethylsilylene prepared by alkali metal coupling of chloro-
silanes were found to have improved solvent solubilities. Some
copolymers soluble at ambient temperatures in common solvents
were obtained but crystallization behavior was not substantially
altered.

DO ijAN^l 1473 EOitKoj* o* I NOV »J IS 0350LE2

S/N 0102-014- «60t I

SI 6 ^ 78 12 20 02 0

SECURITY CLASSIFICATION 0 F TMIS PAGE *Smn Def Snter^i)

Office of Naval Research

Contract N-00014-75-C-1024
Technical Report No. 78-1

Organosilane Polymers, II: Copolymers of
Ethylmethyl- and Methylpropylsilylenes With Dimethylsily leue

by

J.P. Wesson and T.C. Williams

Union Carbide Corporation
Tarrytown, New York 10591

December 1978

?6 iz Z0 uZO

INTRODUCTION

Poly(diorganosilylene) higher polymers have received

previous attention only as by-product poly(dimethylsilylene)

which was found useful as an intermediate in the preparation of

( i 2 3 )

cyclic dimethylsilylenes ’ ’ and more recently as linear
higher polymers of dimethylsily lene v . The poly (dimethyl-
silylene) higher polymers are high melting and largely
crystalline. They are only soluble at temperatures above about
200°C and are not thermoformable below their decomposition
temperatures .

Since one of our goals has been to obtain tractable
silylene polymers that are conveniently soluble or thermo-
formable, we have examined various kinds of copolymers of
dimethylsily lene with other diorganosilylenes . This approach
stemmed in part from the observation that in some crystalline
or crystallizable polymers, the introduction of a few bulky side
groups can interfere with chain packing processes thereby
depressing crystallization rates and enhancing solubility and
thermoforming qualities^ - ^ ^ . We report here on the effects
of replacing methyl groups with ethyl and propyl groups in
random copolymers of dimethylsilylene with ethyl methyl- and
raethylpropylsilylenes .

EXPERIMENTAL

Monomers

Dimethyldichlorosilane (DMDCS) monomer was purified

by treatment with diethyl ether and distillation as described
Ml

earlier v . Ethylmethyldichlorosilane (EMDCS) and methyl-

propyldichlorosilane (MPDCS) were fractionally distilled under
dry nitrogen through a vacuum jacketed column (2.0 x 45. cm)
packed with perforated lime glass beads (0.4 cm diam.).
Distillation rate was 60 mL hr -1 with about 20:1 reflux ratio.
Foreruns up to 100°C for EMDCS and up to 125°C for MPDCS were
discarded. Product cuts distilling at 100-100. 5°C (EMDCS) and
125-125. 5°C (MPDCS) were collected and stored under dry
nitrogen. After distillation the EMDCS and MPDCS monomers were
found to be chromatographically pure.

Copolymers

Random copolymers were prepared by sodium metal

dechlorination of mixtures of DMDCS with EMDCS or MPDCS using

( 4 )

the methods and precautions previously described ’ . Monomer
charges and copolymer yields for typical polymerizations are
given in Table I. Copolymers of DMDCS and EMDCS were insoluble
in the octane reaction solvent and were recovered directly by
filtration. Copolymers of DMDCS and MPDCS ranged from
partially to completely soluble in the reaction solvent and
were recovered in three fractions:

a)

copolymer insoluble in the octane reaction
solvent was isolated by filtration,

b) copolymer soluble in octane was stripped of
solvent, taken up in THF (lOOmL) and
precipitated by dropwise addition to acetone
(300 mL) and dried,

c) copolymer which remained soluble in THF-
acetone was solvent stripped to yield viscous
oil .

Analytical Methods

Infra-red absorption spectra on the various polymers

( 4 )

were obtained with equipment and methods described earlier .

Spectra for ethylmethyl- and methylpropylsilylene homopolymers

are given for reference in Figures 1 and 2, and absorption band

assignments are shown in Tables 2 and 3. Copolymer spectra

appeared as typical combinations of the spectra for dimethyl-,

ethylmethyl- and methylpropylsilylene homopolymers. Copolymer

compositions were calculated from infra-red spectra using

absorbances of the 1245cm -1 (CHgSi), 1455cm - ' 1 ' (CgH^Si) and

1460cm -1 (n-CgHgSi) bands *' 1 ^ ’ 14 . Solubilization and

precipitation temperatures of the copolymers in perhydro-

r 4 )

fluorene were determined as described earlier' . Molecular
weights of polymers insoluble at moderate temperatures were

(4 )

obtained by infra-red methods . Molecular weights of
conveniently soluble copolymers were obtained on toluene
solutions with a Knauer Vapor Pressure Osmometer at 35 and 65°C;
toluene solutions of dodecamethylcyclohexasilane were used as
molecular weight references.

j

II

RESULTS AND DISCUSSION

Copolymerizations were done by adding chlorosilane

monomer mixtures dropwise to sodium metal dispersed in hot,

stirred n-octane. The reactions are fast and very exothermic.

Suitable precautions are essential to maintain a controlled

( 4 )

reaction sequence . The two series of copolymers behave
differently during the reaction period. DMS-EMS copolymers were all
readily recovered by filtration and worked up to finely divided
white powders. With the DMS-MPS system, copolymer solubility
in the reaction solvent increased with MPS concentration and it

became necessary to recover the products in fractions as
described in the Experimental Section. As EMDCS concentration
in the monomer mixture is increased, the total yield of
copolymer drops steadily to a minimum at about 80 mole-% and
then increases somewhat thereafter, Figure 3. In contrast,
DMS-MPS copolymer yields are relatively steady at about 65-75%
across the composition range. Increased reaction times do not
significantly increase yields and nart of the sodium metal
remains unreacted. Visual inspection of the residual metal
suggests that some part of the copolymer coats the metal
surface and may then inhibit further reaction. High shear
agitation that could scour the metal surface might alter this
situation but has not yet been tried. Plots of monomer vs
copolymer composition (Figures 4 and 5) indicate that both
EMDCS and MPDCS react more slowly than DMDCS particularly at
concentrations above about 20 mole %.

^

Molecular weights were measured as described on the
various total polymers and fractions but no significant trends
against composition or other experimental variables were noted.

In general, for the higher polymers varied over the range of
25,000 to 50,000 except for the EMS homopolymer which appeared to
be in excess of 100,000.

Solubilization tests were made on octane insoluble

copolymers in which the temperatures for complete solution (T )

s

and precipitation (T ) were measured for 2 wt % solutions of

copolymer in perhydrof luorene , one of the best solvents for the

parent DMS homopolymer so far encountered. Solution and

precipitation of the copolymers occurs rather sharply and is

generally reproducible within two or three degrees. In the

DMS-EMS system, solution temperature (T ) (Figure 6) decreases

rapidly as EMS in the copolymer increases up to about 25 mole %

and thereafter decreases slowly to a minimum at about 65 mole %.

With DMS-MPS copolymers, the decrease in T is also initially

s

very rapid and the extent of depression even more pronounced.

At MPS concentrations above about 10 mole %, the copolymers

become soluble at ambient temperatures and below and these

compositions also become quite soluble in common solvents such

as toluene, Figure 7. Thus, silylene copolymers that are

soluble at convenient temperatures can be obtained by modifying

the parent poly(dimethylsilylene) with relatively small

proportions of EMS or MPS units. However, the lack of any

significant increase in the solution-precipitation temperature

difference (T -T ) suggests that neither the ethyl or propyl
s p

group has had any substantial effect on crystallization of the
copolymers. This is further borne out in the observation that
the copolymers precipitate abruptly from the cooling solution
as fine powders with no appreciable tendency for coherent film
formation .

To obtain further insight on the effects of
structural modifications on copolymer solubility and
crystallization a number of block copolymers and short chain
branched copolymers are being examined and will be described in
future reports.

This work was supported in part by the Office of Naval

Research .

REFERENCES

1

1 .

2 .

3.

4.

5.

6 .

7.

8 .

9 .

10 .

11 .

12 .

H. Gilman, R.A. Tomasi, J. Org. Chem. , 2j3, 1651 (1963)

M. Kumada, K. Tames, Adv. Organometal. Chem., 6, 49, 65
(1968)

E. Carberry, R. West, J. Amer. Chem. Soc . , 9_1, 5440
(1969)

J.P. Wesson, T.C. Williams, J. Polym. Sci., Polym.

Chem. Ed. , in press

D.J. Fischer, J. Appl. Polym. Sci., 5, 436 (1961)

M. J. Richardson, P.J. Flory, J.B. Jackson, Polymer, 4,
221 (1963)

J.B. Jackson, P.J. Flory, Polymer, 5, 159 (1964)

S.N. Borisov, V.A. Marei , Kauchuk i Rezina, 23, 1 (1964)

N. Ueda, Kobunshi Kagaku, 22, 1 (1965)

S.N. Borisov, Kauchuk i Rezina, 25, 3 (1966)

Godovskii, Y.K., Vyskomol. Soedin., Ser. A, 1J., 2129
(1969)

Marei, A. I., Petrova, G.P., Novikova, G.E., Kuryland,
S.K., Fiz. Svoistva Elastomerov, 77, 132 (1975)

CA 84: 75376v

13.

A.L. Smith, Spectrochim. Acta, 87 (I960)

14.

L.J. Bellamy, Infra-Red Spectra of Complex Molecules,
3rd. Ed., Chapman and Hall, London (1975)

Table 1 Dimethy lsilylene Copolymers

Table 2 Infra-Red Absorptions of Poly(ethylmethylsilyene)

Table 3 Infra-Red Absorptions of Poly(propylmethylsilylene)

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Infra-Red Absorption Spectrum Poly (dimethyl-co-
ethylmethy lsilylene )

Infra-Red Absorption Spectrum Poly (dimethyl-co-
met hylpropy lsilylene)

Poly ( dime thy 1-co-e thy lmethy lsilylene ) Copolymer
Yields

Monomer-Copolymer Composition Poly ( dimethyl-co-
ethy lmethy lsilylene )

Monomer-Copolymer Composition Poly(dimethyl-co-
propy lmethy lsilylene )

Solution and Precipitation Temperatures of
Poly ( dime thy 1-co-e thy lmethy lsilylene ) in
Perhydrof luorene (2 wt % Solutions)

Solution and Precipitation Temperatures of
Poly (dimethyl -co-met hylpropy lsilylene ) in
Perhydrof luorene (2 wt % Solutions)

TABLE 1

DIMETHYLS I LYLENE COPOLYMERS

Monomer

Charged

(Mole-%)

Copolymer

Yield

(wt-%)

Copolymer

Composition

(Mole-%)

EMDCS :

EMS:

20

74

17

30

67

22

45

48

24

60

44

27

80

23

66

100

74

100

MPDCS :

MPS:

10

73

8

30

66

20

50

67

41

80

46 (1)

58

100

7S

100

1. Accidental

Losses in Work-Up

I

TABLE 2

INFRA-RED ABSORPTIONS OF

POLY ( ETHYLMETHYLS I LYENE ]

(3450)
2950 '

(HgO Stretch)

2930 |
2890 j
2870 ,

CH Stretch

1455

CHg— f-C) Deformation

(a)

1420

CH 3 (Si) Deformation

(a)

1375

CH 3 (C) Deformation

(s)

1245

CH 3 ISi) Deformation

(s)

1065

SiOSi

1005

SiCH 2 CH 3

935

SiCH 2 CH 3

775 j
740 t

SiC Stretch

690 j
670 *

! 0H o Rocking

1 2

650

610

EtMeSi Rocking

■P 1 'nf

TABLE 3

INFRA-RED ABSORPTIONS OF
POLY ( PROPYLMETHYLS I LYLENE )

Absorption

Assignment

(3450)

(H 2 0 Stretch)

2950

2920 |

CH Stretch

2890 |

2870 ,

(1630)

(H 2 0 Overtone)

1460

-CE 9 t 4C) Deformation

(a)

1450

CH 2 ~(C) Deformation

(a)

1415

CHg— fSi) Deformation

(a)

1375

CHg (C) Deformation

(s)

1325

CH 2 ~(C) Deformation

(s)

1245

CH 3 (Si) Deformation

(s)

1065

(s)

SiCSi

1060

CH 3 CH 2 CH 2 Si

985

CH 3 CH 2 CH 2 Si

790)

SiC Stretch

745 j

710

CH 2 Rocking

660

MePrSi Rocking

*

(s) Shoulder

0

2000 1800 1400

WAVELENGTH (cm -1 )

1000 800 600 400

Figure 2.

INFRA-RED ABSORPTION SPECTRUM
POLY (DIMETHYL-Co-METHYLPROPYLSILYLENE)

T

1

200

1

[ i

1 ! ! t

i t p

150

1

°C)

l

1 ►

T| COPOLYMERS WITH
|| MPS ABOVE 10%

l SOLUBLE AT ROOM

100

I TEMPERATURE

1

1

1

1

50

1

1

1

? 1

1 1 1 1 ►

0 10 20
MPS in COPOLYMER (mole %)

Figure 7.

SOLUTION AND PRECIPITATION TEMPERATURES
OF POLY (DIMETHYL-Co-METHYLPROPYLSILYLENE)
IN PERHYDROFLUORENE (2 WT % SOLUTIONS)

t

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