Skip to main content

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

See other formats


AD-A063 075 


UNCLASSIFIED 


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 


/ OF | 
^3075 



MICROCOPY RESOLUTION TEST CHA&T 

NATIONAL BUREAU OF STANDARDS -1963-^ 


I 










nnn file copr 





/)o±o 32 7 


>•?. A J »' N ST ? 0’ C T LG ’« j 

REFo.^ ccv?l : : r,\.o kosm 


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' 


3. CONTRACT OR GRANT SUM* 



performing organization name ano aodress 


Union Carbide Corporation/ 
Tarrytown, New York 


10. PROGRAM element, project, task 
AREA * WORK UNIT NUMBERS 


14. MONITORING AGENCY NAME $ AOORESSf/* dUirrent from Controlling Otltce) 15. SECURITY CLASS. ( of this report) 


I 


II. CONTROLLING OFFICE NAME ANO ADDRESS 

Chemistry Branch f // j 

Office of Naval Research - 

Arlington, Virginia 22217 


(5? 


NUMBER OF PAGES 


„ I L-i 


Unclassified 


15*. OECL ASSIrl CATION/ DO rfNGRAOING 
SCHEDULE 


I IS. OISTHI9UTIOM STATEMENT fof Ml* R.por:; 


Technical Report Distribution List 

This docum^t has boon approved 
{or public re’ c.vd sclo; iis 


PJ 


Vwil^W v 


17. DISTRIBUTION STATE 


inHrM'atsck : 


M hem Ropon 


I 18. SUPPLEMENTARY NOTES 


Submitted to J. Polymer Science 


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 


472 :GAN : 716 : cam 
78u472-608 


TECHNICAL REPORT DISTRIBUTION LIST, GEN 


NO . 

Copies 

Office of Naval Research 

800 North Quincy Street 

Arlington, Virginia 22217 

Attn: Code 472 2 

ONK Branch Office 

536 S. Clark Street 

Chicago, Illinois 60605 

Attn: Dr. George Sandoz 1 

ONR Branch Office 
715 Broadway 

New York, New York 10003 

Attn: Scientific Dept. 1 

ONR Branch Office 

1030 East Green Street 

Pasadena, California 91106 

Attn: Dr. R. J. Marcus 1 

ONR Area Office 

One Hallidie Plaza, Suite 601 

San Francisco, California 94102 

Attn: Dr. P. A. Miller 1 

ONR Branch Office 

Building 114, Section D 

666 Summer Street 

Boston, Massachusetts 02210 

Attn: Dr. L. H. Peebles 1 

Director, Naval Research Laboratory 

Washington, D.C. 20390 

Attn: Code 6100 1 

The Assistant Secretary 
of the Navy (R.E&S) 

Department of the Navy 
Room 4E736, Pentagon 

Washington, D.C. 20350 1 

Commander, Naval Air Systems Command 
Department of the Navy 
Washington, D.C. 20360 

Attn: Code 310C (H. Ro^enwasser) 1 


No. 

Copies 

Defense Documentation Center 

Building 5, Camexcn Station 

Alexandria, ViAini^ 22314 12 

U.S. Army Research Office 
P.0. Box 1211 

Research Triangle Park, N.C. 27709 
Attn: CRD-AA- IP 1 

Naval Ocean Systems Center 

San Diego, California 92152 

Attn: Mr. Joe McCartney 1 

Naval Weapons Center 

China Lake, California 93555 

Attn: Dr. A. B. Amster 

Chemistry Division i 

Naval Civil Engineering Laboratory 

Port Hueneme, California 93401 

Attn: Dr. R. W. Drisko 1 

Professor K. E. Woehler 
Department of Physics & Chemistry 
Naval Postgraduate School 
Monterey, California 93940 1 

Dr. A. L. Slafkosky 
Scientific Advisor 
Commandant of the Marine Corps 
(Code RD-1) 

Washington, D.C. 20380 1 

Office of Naval Research 

800 N. Quincy Street 

Arlington, Virginia 22217 

Attn: Dr. Richard S. Miller 1 

Naval Ship Research and Development 
Center 

Annapolis, Maryland 21401 
Attn: Dr. G. Bosmajian 

Applied Chemistry Division 1 

Naval Ocean Systems Center 
San Diego, California 91232 
Attn: Dr. S. Yamamoto, Marine 
Sciences Division 


I 

f 


l 


472 :CAN: 716 :tan 
78u472-608 


TECHNICAL REPORT DISTRIBUTION LIST, 356B 


No. 

Copies 


No. 

Copies 


Dr. TSX. Will^rfms 
Union Caht»id<r Corporation 
Chemical ariasPlas tics 
Tarrytoyn Technical Center 
Tarry^wn, New York 

Dr. R. Soulen 

Contract Research Department 
Pennwalt Corportion 
900 First Avenue 

King of Prussia, Pennsylvania 19406 

Dr. A. G. MacDiarmid 
University of Pennsylvania 
Department of Chemistry 
Philadelphia, Pennsylvania 19174 

Dr. C. Pittman 
University of Alabama 
Department of Chemistry 
University, Alabama 35486 

Dr. K. Allcock 

Pennsylvania State University 
Department of Chemistry 
University Park, Pennsylvania 16802 

Dr. K. Kenney 
Case-Western University 
Department of Chemistry 
Cleveland, Ohio 44106 

Dr. R. Lenz 

University of Massachusetts 
Department of Chemistry 
Amherst, Massachusetts 01002 

Dr. K. David Curtis 
University of Michigan 
Department of Chemistry 
Ann Arbor, Michigan 48105 

Dr. M. Good 

Uni. :rs ity of New Orleans 
D»-p..r:ment of Chemistry 
Lake f root 

New Orleans, Louisiana 70122 


Douglas Aircraft Company 
3855 Lakewood Boulevard 
Long Beach, California 90846 
Attn: Technical Library 

Cl 290/36-84 
AUTO-Sutton 

NASA-Lewis Research Center 

21000 Brookpark Road 

Cleveland, Ohio 44135 

Attn: Dr. T. T. Serafini, MS 49-1 

Dr. J. Griffith 
Naval Research Laboratory 
Chemistry Section, Code 6120 
Washington, D.C. 20375 

Dr. G. Goodman 
Globe-Union Incorporated 
5757 North Green Bay Avenue 
Milwaukee, Wisconsin 53201 

Dr. E. Fischer, Code 2853 
Naval Ship Research and 
Development Center 
Annapolis Division 
Annapolis, Maryland 21402 

Dr. Martin H. Kaufman, Head 
Materials Research Branch (Code 4542) 
Naval Weapons Center 
China Lake, California 93555 

Dr. J. Magill 
University of Pittsburg 
Metallurgical and Materials 
Engineering 

Pittsburg, Pennsylvania 22230 

Dr. C. Allen 
University of Vermont 
Department of Chemistry 
Burlington, Vermont 05401 

Dr. D. Bergbreiter 
Texas A&M University 
Department of Chemistry 
College Station, Texas 77843 



Professor R. Drago 


Department of Chemistry 
University of Illinois 
Urbana, Illinois 61801 

Dr. r. Brinkman 

Chemical Stability & Corrosion 
Division 

Department of Commerce 
National Bureau of Standards 
Washington, D.C. 20234