An organometallic polymer having the following moiety: ##STR1## is disclosed. R.sub.1 and R.sub.2 are independently selected from the group of H, alkyl having 30 or fewer carbons, alkenyl having 30 or fewer carbons, and aromatic having one to ten rings; n=0-30; p=0-30; and M is a metal selected from the group consisting of Sn, Ge, Pb, Hg, Ni, Pd, Pt, Cr, Fe, Co, Cu, and Zn. Most preferably, M is Sn, R.sub.1 and R.sub.2 are n-butyl, n is 3, and p is 3. A preferred antibacterial/antifungal composition may be formed by combining the polymer with a suitable carrier.

CROSS REFERENCE TO RELATED APPLICATIONS 
Not applicable. 
BACKGROUND OF THE INVENTION 
1. Field Of The Invention 
This invention relates generally to polymers having antibacterial and 
antifungal properties. More particularly, it relates to 
polycarbometallanes and methods of making them. 
2. Background of the Art 
Previously, Basset and coworkers demonstrated that tungsten aryloxo 
complexes (i.e. (3) in FIG. 1) could efficiently catalyze the metathesis 
of cis-2-pentene in the presence of tetralkyltin or tetraalkyllead 
cocatalysts..sup.(1) These observations were followed by the synthesis of 
cycloolefins by Feldman and coworkers utilizing the aryloxo tungsten 
complex (i.e. (2) in FIG. 1) in the presence of tetraethyllead..sup.(2) 
Recently, Nubel and coworkers have shown that polybutadiene can be 
produced via acyclic diene metathesis ADMET condensation chemistry using 
WCl.sub.6 /Me.sub.4 Sn in the presence of propyl acetate..sup.(3) The 
disclosure of all the above articles, and of all other articles and 
patents cited herein, are incorporated by reference as if fully set forth 
herein. 
SUMMARY OF THE INVENTION 
We have discovered a new class of organometallic polymers which have 
antifungal and antibacterial properties. These polymers can be mixed with 
suitable carriers to make useful and economical compositions. 
In one aspect, the invention provides an organometallic polymer having the 
following moiety: 
##STR2## 
wherein n=0-30; p=0-30; R.sub.1 and R.sub.2 are independently selected from 
the group of H, alkyl having 30 or fewer carbons, alkenyl having 30 or 
fewer carbons, and aromatic having one to ten rings; and M is a metal 
selected from the group consisting of Sn, Ge, Pb, Hg, Ni, Pd, Pt, Cr, Fe, 
Co, Cu, and Zn. Most preferably, M is Sn, R.sub.1 and R.sub.2 are n-butyl, 
n is 3, and p is 3. 
Another aspect of the invention provides an antibacterial, antifungal 
composition comprising polymers of the above kind and a suitable carrier. 
A still further aspect of the invention provides a method of making an 
organometallic polymer comprising the steps of adding a bis(alkenyl) metal 
monomer to a suitable catalyst, but without the presence of co-catalyst; 
reacting the monomer under vacuum at a temperature between room 
temperature and 90.degree. C. to form a crude mixture of a polymer having 
the moiety 
##STR3## 
and purifying the polymer from the crude mixture; wherein n=0-30; p=0-30; 
R.sub.1 and R.sub.2 are independently selected from the group of H, alkyl 
having 30 or fewer carbons, alkenyl having 30 or fewer carbons, and 
aromatic having one to ten rings; and M is a metal selected from the group 
consisting of Sn, Ge, Pb, Hg, Ni, Pd, Pt, Cr, Fe, Co, Cu, and Zn. 
Preferably, the catalyst is selected from the group of molybdenum 
alkylidene and tungsten aryloxo complexes. It is also most preferred that 
M is Sn, R.sub.1 and R.sub.2 are n-butyl, n is 3, and p is 3. 
Still another aspect of the invention provides a method of controlling the 
growth of organisms comprising contacting the organisms with compounds and 
compositions of the above kind in an amount effective for the control of 
the growth of the organisms. 
These polymers (particularly those containing tin) are useful in 
antibacterial and antifungal coatings/compositions that can be used on the 
linings of ship hulls. Such coatings suppress the formation of barnacles 
and decrease hull drag. 
The objects of the invention, therefore, include providing polymers and 
compositions of the above kind: 
(a) which possess useful antibacterial and antifungal properties; 
(b) which can be synthesized efficiently and at relatively low cost; and 
(c) which can be mixed with inexpensive carriers. 
These and still other objects and advantages of the present invention will 
be apparent from the description below. However, this description is only 
of the preferred embodiments. The claims should, therefore, be looked to 
in order to assess the whole scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION 
Since the first successful ADMET polymerization,.sup.(4) we have actively 
made efforts to produce novel unsaturated polymers containing a variety of 
functional groups within the primary structure via metathesis condensation 
chemistry. To date, Schrock's molybdenum alkylidene (1) (FIG. 1) has been 
our catalyst of choice for producing such macromolecules; however, Grubbs' 
ruthenium alkylidene is also capable of producing high molecular weight 
polymers..sup.(5) The key to both catalysts well-defined nature is their 
inherit ability to perform metathesis chemistry without the presence of a 
Lewis acid cocatalyst, thus vinyl addition chemistry is 
eliminated..sup.(6) 
Thus, we chose to evaluate the reactivity of 
bis(4-penten-1-yl)di-n-butylstannane (4) (FIG. 2) in ADMET polymerizations 
with a well-defined metathesis catalyst (1) (FIG. 1) and with complexes 
(2) and (3) (FIG. 1) in a classical type metathesis catalytic system. 
Schrock's molybdenum alkylidene catalyst (1) was chosen for preliminary 
experiments due to its high reactivity, but we have found that if compound 
(4) is used in a presence of either complexes (2) or (3), the monomer 
itself functions as a cocatalyst and produces polymers identical to those 
obtained from Schrock's well-defined catalyst (1). 
Materials. 
Mo(CHCMe.sub.2 Ph) (N-2,6-C.sub.6 H.sub.3 -i-Pr.sub.2) (OC(Me).sub.2 
CF.sub.3).sub.2.sup.(7) (1), W(O)Cl.sub.2 (O-2,6-C.sub.6 H.sub.3 
-Br.sub.2).sub.2.sup.(2) (2), and WCl.sub.4 (O-2,6-C.sub.6 H.sub.3 
-Ph.sub.2).sub.2.sup.(8) (3) were synthesized according to published 
procedures. 5-Bromo-1-pentene was purchased from either Aldrich Chemical 
Company or Acros Organics and distilled from CaH.sub.2 immediately before 
use. Di-n-butyltin dichloride was purchased form Acros Organics and used 
as received. Diethyl ether was distilled from sodium benzophenone ketyl 
and stored over 4 .ANG. molecular sieves in an inert atmosphere of argon. 
.sup.1 H (300 MHz) , .sup.13 C (75 MHz) , and .sup.119 Sn (112 MHz) NMR was 
performed on a Varian VXR-300 MHz superconducting spectrophotometric 
system. .sup.1 H and .sup.13 C NMR are referenced to an internal 0.05% w/w 
TMS standard whereas .sup.119 Sn NMR are referenced to an internal 1% w/w 
tetramethyltin sample. Elemental analysis was performed by either 
Robertson Microlit Laboratories, Madison, N.J., or Atlantic Microlab Inc., 
Norcross, Ga. Gel permeation chromatography (GPC) was performed on a 
Waters Associates Model 590, chromatograph with three Phenomenex Phenogel 
columns in series (50,000 .ANG., 5,000 .ANG., 500 .ANG.) using both a UV 
and an RI detector. THF was used as the eluent at a flow rate of 1.0 
mL/min, and the instrument was calibrated using polystyrene standards. 
Experimental. 
Synthesis of Bis(4-penten-1-yl)di-n-butylstannane (4). 
The synthesis of bis(4-penten-1-yl)di-n-butylstannane was performed as 
follows. To 3 equivalents of preformed 4-penten-1-yl magnesium bromide in 
diethyl ether (1.0M) was charged one equivalent of di-n-bytyltin 
dichloride in diethyl ether (1.0M) at room temperature over a period of 2 
hours and then refluxed for 20 hours. The reaction mixture was then poured 
into an ice-cold 1M NH.sub.4 CI solution. The organic layer was separated, 
washed with DI H.sub.2 O, dried over MgSO.sub.4, and vacuum distilled 
under full Schlenk vacuum. The product was then dried over CaH.sub.2 for 
48 hours under full Schlenk vacuum before being fractionally distilled 
again yielding bis(4-penten-1-yl)di-n-butylstannane in 83% yield with the 
following spectral characteristics: .sup.1 H NMR: .delta. (ppm)=5.8 (m, 2 
H); 4.9 (m, 4H); 2.1 (q, 4 H); 1.6 (m, 4 H): 1.5 (m, 4 H); 1.3 (m, 4 H); 
0.9 (m, 14 H). .sup.13 C NMR: .delta. (ppm)=138.7, 114.4, 38.6, 29.3, 
27.4, 26.6, 13.7, 8.8, 8.6. .sup.119 Sn NMR: .delta. (ppm)=-13.1. 
Elemental analysis calculated for C.sub.18 H.sub.36 Sn. Calculated: 
C(58.25%), H(9.78%). Found: C(58.35%), H(9.80%). 
ADMET Polymerization of (4). 
In an argon purged dry box, the catalyst ((1), (2) or (3), 1 eq) was 
weighed and placed in a 50 mL round bottomed flask adapted with a Rotoflow 
valve. The monomer (4) (250 or 500 eq.) was then added to the flask which 
was in turn sealed and taken to a high vacuum Schlenk line. Vigorous 
ethylene evolution can be evidenced at room temperature in the case of 
catalyst (1) during the first 12 h of reaction. After this time, the 
system is heated to 60.degree. C. In the case of complexes (2) and (3), 
the reaction is carried out at 90.degree. C. The reaction is stopped by 
removal of the heat when magnetic agitation becomes impossible. The crude 
polymer is purified by dissolution in chloroform and subsequent 
precipitation into methanol or pentane. Anhydrous solvents must be used in 
the case of the polymer produced with catalysts (2) and (3). All three 
samples were viscous liquids with the following spectral properties: 
.sup.1 H NMR: .delta. (ppm)=5.4 (m, br, 2 H); 1.9 (m, br, 4 H); 1.5 (m, 8 
H); 1.3 (m, 4 H); 0.9 (m, 14 H) . .sup.13 C NMR; .delta. (ppm)=103.3 
(trans); 129.7 (cis); 37.4 (allylic, trans); 32.2 (allylic, cis); 29.3; 
27.4; 27.2; 13.7; 8.8; 8.7. .sup.119 Sn NMR: .delta. (ppm)=-12.8 (trans, 
trans); -13.0 (trans, cis); -13.2 (cis, cis). Elemental analysis. 
Calculated: C(56.00%), H(9.40%) . Found: C(56.23%), H(9.54%). 
Results and Discussion. 
Polymers containing tin within their structure, either as substituents or 
within the backbone, are well known, and several methods can be used to 
produce such macromolecules..sup.(9) Results reported by the authors 
mentioned above prompted us to investigate the activity of acyclic dienes 
containing tin moieties within a metathesis polymerization system. 
Based on the well-known activity exhibited by tin compounds as cocatalysts 
for classical metathesis systems, we chose to investigate the aryloxo 
tungsten (VI) complexes (2), utilized by Feldman et al. in ring closing 
metathesis (RCM) reactions,.sup.(2) and (3), developed by Basset and 
coworkers,.sup.(8) to attempt ADMET condensation chemistry in a classical 
type system. Preliminary results obtained in our laboratories show that 
these classical systems can also efficiently catalyze the ADMET 
polymerization of hydrocarbon dienes. Since the above systems involve 
either tetraalkyltin or tetralkyllead compounds as cocatalysts, we 
envisioned the possible reactivity of the bis(alkenyl)tin compound (4) as 
both the monomer and the cocatalyst. This represents the first metathesis 
polymerization in which the monomer participates as both the propagating 
species and the cocatalyst. Due to the highly reactive, well-defined 
nature of Schrock's alkylidene (1), we synthesized unsaturated 
polycarbostannanes of a well-defined structure and compared the results 
obtained from each polymerization system. 
The evolution of ethylene is apparent upon contact of monomer (4) with (1). 
Within 12 hours of reaction, the viscosity reaches a point to which heat 
must be applied to facilitate the production of high molecular weight 
polymer. Upon completion of the reaction, the crude polymer was 
characterized by .sup.1 H and .sup.13 C NMR. End group analysis of the 
quantitative .sup.13 C NMR (see FIG. 3) of polymer (5) (FIG. 2) 
illustrates that high molecular weight polymer has indeed formed with a 
number average molecular weight of 17,000 g/mol. Integration of the cis 
(129.7 ppm) and trans (130.8 ppm) olefin resonances yields a cis:trans 
ratio of 21:79 which is typical of ADMET polymerizations. GPC analysis 
computes a molecular weight of approximately 36,000 g/mol; however, this 
number is a direct reflection of the difference in hydrodynamic volume 
between the polycarbostannane sample and the polystyrene standard. 
The polymerization of (4) with either complex (2) or (3) also produces high 
molecular weight polymer (5) (see FIGS. 4 and 5). The reaction requires 
higher temperatures to facilitate the transmetallation-elimination 
reaction that occurs between the tin monomer and complex (2), leading to 
the formation of the active metathetic species..sup.(1) Our observation 
that gelation occurs upon contact of the product polymers with moisture, 
supports the work of Basset in that the hydrolysis of a Sn-Cl bond (which 
is formed in the initial transmetallation step between the tin monomer and 
complex (2) or (3)) must be occurring to produce a crosslinked polymer 
while no gelation is observed with (5) produced from (1), or when the 
polymer is synthesized via the complexes (2) or (3) and are worked up 
under anhydrous conditions. The number average molecular weights obtained 
from .sup.1 H and quantitative .sup.13 C NMR analysis is about 9,300 g/mol 
for the polymerization catalyzed by (2) and about 16,0900 g/mol for the 
polymer synthesized using complex (3), while GPC reveals Mn=17,000 and 
Mn=30,000 g/mol respectively. 
The incorporation of the metal is clearly evidenced by the three resonances 
observed in the .sup.119 Sn NMR spectrum of polymer (5) produced using 
catalyst (1) (see FIG. 6), assigned to the metal in three different 
environments arising from the geometry of the double bonds by which it is 
surrounded (trans-trans, trans-cis and cis-cis). Based on the intensity of 
the corresponding signals in the quantitative .sup.13 C NMR, the cis:trans 
ratio was determined to be 21:79 for polymer (5) synthesized using 
catalyst(1), while the intensity of the three signals in the .sup.119 Sn 
NMR was found to be 65:30:5, a value in good agreement with a distribution 
of 64:32:4 calculated from the .sup.13 C NMR data. Polymer (5) synthesized 
using catalyst (2) displayed a cis:trans ratio of 19:81 with a 
trans-trans:trans-cis:cis-cis ratio from .sup.119 Sn NMR of 64:32:5. 
Catalyst (3) produced polymer (5) with a trans-trans:trans-cis:cis-cis 
ratio of 59:35:6, and the total cis:trans ratio as determined by 
quantitative .sup.13 C NMR is 26:74. 
CONCLUSIONS 
We have shown that the synthesis of an unsaturated polycarbostannane from 
bis(4-penten-1-yl)di-n-butylstannane via ADMET polymerization can be 
accomplished by the use of either a well-defined alkylidene or classical 
catalytic systems based on tungsten aryloxo complexes. In the latter case, 
these complexes are converted into an active catalyst by activation with 
the monomer itself. 
Thus, it can be seen that the present invention provides unsaturated 
polycarbostannanes via metathesis chemistry. It should be understood that 
unsaturated polymers containing a variety of metals along the polymer 
backbone can also be synthesized using the method of the present invention 
and various bis(alkenyl) metal monomers. 
For example, metals such as Ge, Pb, Hg, Ni, Pd, Pt, Cr, Fe, Co, Cu, and Zn 
can be substituted for tin in the bis(alkenyl) monomer. Further, other 
bis(alkenyl)di-alkylstannanes may be used as monomers to make other 
unsaturated polycarbostannanes according to the present invention. 
Preferably, the alkenyl group of the bis(alkenyl) metal monomer has 2-30 
carbons, more preferably 3-6 carbons. 
With regard to R.sub.1 and R.sub.2, when alkyl is selected the alkyl 
preferably has one to six carbons, when aromatic is selected the aromatic 
preferably has one to three rings, and when alkenyl is selected the 
alkenyl preferably has two to six carbons. It should be noted that when 
R.sub.1 and/or R.sub.2 are/is an alkenyl group, the polymer would assume 
interesting characteristics due to branching and cross-linking. Such 
branched and cross-linked polymers would have advantageous applications as 
coatings for use in paints, for example. 
It should also be understood that the present invention includes polymers 
made from unbalanced acyclic dienes (where n.noteq.p). Such polymers would 
be especially useful as coatings because of their enhanced durability. 
It should be further understood that a suitable carrier for the polymer of 
the present invention in antibacterial, antifungal compositions of the 
above kind can include solvents or other polymers. Also, the carrier can 
include solids such as titanium dioxide. It will also be appreciated that 
the polymer of the present invention could be applied to a surface (e.g., 
a ship hull) by combining the monomer and catalyst via a spray/mixing 
nozzle. The polymer would then be formed and cured in situ. 
The ADMET chemical synthesis of the polymers of the present invention would 
follow directly from that shown for the exemplary polymer above. The 
synthesis of the starting monomers would be according to standard organic 
techniques. 
The claims should therefore be looked to in order to assess the full scope 
of the invention. 
(1) Quignard, F.; Leconte, M.; Basset, J. M. J. Mol. Cat. 1986, 36, 13. 
(2) Nugent, W. A.; Feldman, J.; Calabrese, J. C. J. Am. Chem. Soc. 1995, 
117, 8992. 
(3) Nubel, P. O.; Lutman, C. A.; Yokelson, H. B. Macromolecules. 1994, 27, 
7000. 
(4) Wagener, K. B.; Boncella, J. M.; Nel, J. G. Macromolecules. 1991, 24, 
1991. 
(5) Brzezinska, K.; Wolfe, P. S.; Watson, M.D.; Wagener, K. B.; Macromol. 
Chem. Phys. 1996, 197, 2065. 
(6) Wagener, K. B.; Boncella, J. M.; Nel, J. G.; Duttweiler, R. P.; 
Hillmyer, M. A. Makromol. Chem. 1990, 191, 365. 
(7) Schrock, R. R.; Murdzek, G. C.; Bazan, J. R.; DiMare, M.; O'Regan, M. 
J. Am. Chem. Soc. 1990, 112, 3875. 
(8) Quignard, Francoise; Leconte, Michel; Basset, Jean-Marie; Hsu, Leh-Yeh; 
Alexander, John J.; Shore, Sheldon G. Inorg. Chem. 1987, 26, 4272. 
(9) Pomogailo, Anatoly D.; Savost'yanov, Vladimir S. "Synthesis and 
Polymerization of Metal-Containing Polymers". CRC Press, Inc.; Boca Raton, 
Fla. 1994. 164 p.