Patent Application: US-80749497-A

Abstract:
an organometallic polymer having the following moiety : ## str1 ## is disclosed . r 1 and r 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 1 and r 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 .

Description:
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 &# 39 ; s molybdenum alkylidene ( 1 ) ( fig1 ) has been our catalyst of choice for producing such macromolecules ; however , grubbs &# 39 ; 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 ) ( fig2 ) in admet polymerizations with a well - defined metathesis catalyst ( 1 ) ( fig1 ) and with complexes ( 2 ) and ( 3 ) ( fig1 ) in a classical type metathesis catalytic system . schrock &# 39 ; 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 &# 39 ; s well - defined catalyst ( 1 ). mo ( chcme 2 ph ) ( n - 2 , 6 - c 6 h 3 - i - pr 2 ) ( oc ( me ) 2 cf 3 ) 2 . sup . ( 7 ) ( 1 ), w ( o ) cl 2 ( o - 2 , 6 - c 6 h 3 - br 2 ) 2 . sup . ( 2 ) ( 2 ), and wcl 4 ( o - 2 , 6 - c 6 h 3 - ph 2 ) 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 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 å molecular sieves in an inert atmosphere of argon . 1 h ( 300 mhz ) , 13 c ( 75 mhz ) , and 119 sn ( 112 mhz ) nmr was performed on a varian vxr - 300 mhz superconducting spectrophotometric system . 1 h and 13 c nmr are referenced to an internal 0 . 05 % w / w tms standard whereas 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 å , 5 , 000 å , 500 å ) 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 . 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 4 ci solution . the organic layer was separated , washed with di h 2 o , dried over mgso 4 , and vacuum distilled under full schlenk vacuum . the product was then dried over cah 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 : 1 h nmr : δ ( 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 ). 13 c nmr : δ ( ppm )= 138 . 7 , 114 . 4 , 38 . 6 , 29 . 3 , 27 . 4 , 26 . 6 , 13 . 7 , 8 . 8 , 8 . 6 . 119 sn nmr : δ ( ppm )=- 13 . 1 . elemental analysis calculated for c 18 h 36 sn . calculated : c ( 58 . 25 %), h ( 9 . 78 %). found : c ( 58 . 35 %), h ( 9 . 80 %). 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 ° c . in the case of complexes ( 2 ) and ( 3 ), the reaction is carried out at 90 ° 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 : 1 h nmr : δ ( 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 ) . 13 c nmr ; δ ( 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 . 119 sn nmr : δ ( 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 %). 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 &# 39 ; 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 1 h and 13 c nmr . end group analysis of the quantitative 13 c nmr ( see fig3 ) of polymer ( 5 ) ( fig2 ) 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 fig4 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 1 h and quantitative 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 119 sn nmr spectrum of polymer ( 5 ) produced using catalyst ( 1 ) ( see fig6 ), 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 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 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 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 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 13 c nmr is 26 : 74 . 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 1 and r 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 1 and / or r 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 ≠ 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 . 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