the present invention is directed to liquid pesticides and allied formulations that are suitable for application as a spray or paint that dries at the infested site to allow the controlled release of the desired agent for a predetermined period of time without being compromised by prevailing environmental factors . the components of the liquid formulation are selected to ( 1 ) be compatible with the application method , such as spraying or painting ; ( 2 ) allow a timely formation of an amphiphilic pesticide - loaded film that adheres well to the different application sites infested with at least one damaging form of pest during at least one phase of the pest &# 39 ; s life cycle ; ( 3 ) form a pesticide - loaded film that is capable of releasing the agent at a fast rate shortly after contacting the site and maintaining a steady release for at least two days thereafter , by virtue of the composition of the film , which undergoes controlled dissolution upon exposure to water leading to a decrease in thickness and hence , compensating for the decrease in the net concentration of the agent in the film ; and ( 4 ) provide a film that has a finite life that terminates shortly after releasing most , if not all , of its active agent — as the film continues to dissolve and becomes more water soluble , it peels off the site and creates a limited mass of partially degraded polymer that has minimum impact on the surrounding environment . the design of the polymer molecular chain of the film material , subject of this invention , is based on ( 1 ) using at least two monomers to yield , simultaneously , hydrophilic repeat units that are randomly placed with hydrophobic repeat units or present as short - or long - segments in a segmented form , thus producing random or segmented chains that are amphiphilic — typical examples of the hydrophilic repeat precursors are hydroxyethyl methacrylate , acrylamide , methacrylic acid , n - vinyl pyridine , n - vinyl pyrrolidone , n - vinyl ε - caprolactam , while the precursor of the hydrophobic repeat units include methyl methacrylate , ethyl methacrylate , propyl methacrylate , n - butyl methacrylate , isobutyl methacrylate , n - hexyl methacrylate , octyl methacrylate , and styrene ; ( 2 ) ensuring that part of the hydrophobic component has a glass transition temperature close to room temperature to impart film flexibility and mechanical compliance at different application sites — typical examples of the monomeric precursors of such chain sequence include n - hexyl and n - octyl methacrylate ; ( 3 ) selecting at least one of the precursors of the hydrophobic sequence to be susceptible to ester hydrolysis , thus forming carboxylic groups to allow for increased solubility of the film and hence , its propensity to wash away from the application site following the release of its pesticide payload — a typical example of this monomeric precursor is an alkyl methacrylate ; ( 4 ) using a combination of hydrophilic and hydrophobic comonomers having a comparable or substantially different reactivity ratio to permit the formation of random or segmented copolymers at will — typical combinations include n - vinyl pyrrolidone and one or more alkyl acrylate ( s ); ( 5 ) using combinations of comonomers having different reactivity ratios as well as controlling the monomer feed to allow intermittent formation of one or more type ( s ) of continuous sequence of repeat units — this is to produce amphiphilic chains having hydrophilic and / or hydrophobic segments ; and ( 6 ) controlling the polymer chain composition and polarity to allow its solubility in a liquid solvent that is also a good solvent for most effective pesticides disclosed in this invention — a typical polymer - solvent combination is a copolymer containing about 20 weight percent of n - vinyl pyrrolidone - based repeat units and about 80 weight percent of a methacrylate - based sequence dissolved in 2 - propanol mixed with less than about 3 percent water . the selection of the solvent component of the formulation is based on ( 1 ) its ability to dissolve both the pesticide to yield the desired range of concentrations ; ( 2 ) its ability to mix freely with water and to allow the presence of certain amounts of the water in the film immediately after formation , which , in turn , allows the film to remain swollen and release the initial fraction of the of agent at a fast rate , if so needed ; having a boiling temperature and solubility to allow its timely evaporation during film formation without being highly susceptible to ignition ; ( 4 ) being harmless to the environment about the infested site ; and ( 5 ) being suitable to dispense through conventional equipment , such as a compression sprayer and trigger spray bottle . typical examples of desirable solvents include one or mixed alkanol selected from the group represented by 2 - propanol , t - butyl alcohol , ethanol , and n - butanol , with or without further mixing with an aliphatic ketone such as acetone , 2 - butanone , and 3 - pentanone . the selection of the pesticide or combination thereof is based on ( 1 ) exhibiting no chemical reaction with the solvent or the polymer component of the formulation ; ( 2 ) having a reasonable shelf - life in the liquid formulation ; ( 3 ) having sufficient solubility in the solvent to allow achieving the needed concentration ; ( 4 ) being stable in the alkanol or aqueous alkanol solvent ; and ( 5 ) exhibiting a broad spectrum and effect on more than one pest during at least one phase of their life cycles . typical examples of these pesticides that can be used individually or in combination ( without interacting chemically ) are : acephate , bifenthrin , carbaryl , chlorpyrifos , cypermethrin , diflubenzuron , imidacloprid , lindane , malathion , methoxychlor , permethrin , phosmet , and trichlorfon . this invention also deals with methods of applying the pesticide - containing and other allied formulation , which entails using a compression sprayer , trigger spray bottle , spray pump , and brush as well as similar modifications thereof . for the fire ant mounds , the formulation is sprayed on the entire area and preferably 10 percent beyond the visible perimeter . it is also preferable that the mounds are mechanically disturbed prior to spraying . for treating the gypsy moth and tent caterpillar , a complete band of film is formed around the tree trunk about 30 cm from the ground . the width of the band should exceed 3 cm and preferably more than 15 cm . more than one band along the tree trunk is also preferred . further illustrations of the present invention are provided by the following examples : synthesis of a typical amphiphilic polymer using n - vinyl pyrrolidone ( nvp ), n - butyl methacrylate ( bma ), and n - hexyl methacrylate ( hma ) a mixture of nvp ( 45 . 3 g - 0 . 4075 mole ), bma ( 115 . 9 g - 0 . 8150 mole ) and hma ( 138 . 8 g - 0 . 8150 mole ) was transferred to a predried 3 - neck flask equipped for mechanical stirring , an inlet for introducing nitrogen , and a reflex condenser . the charge was sparged with nitrogen . an aliquot of an azo initiator , namely 2 , 2 ′- bis - isobutyronitrile ( 2 . 25 g - 0 . 0137 mole ) was added to the comonomers . to this was transferred an aliquot of 2 - propanol ( 300 ml ) and the charge was sparged with nitrogen . the reactor components were rearranged to proceed with the polymerization while stirring under a nitrogen atmosphere . the azo initiator dissolved and the reaction mixture was heated to 65 ° c . while stirring for about 24 hours , until practically all the monomers were polymerized . this was achieved through periodic analysis of the reaction mixture by gel permeation chromatography ( gpc ) to determine the extent of monomer conversion . after cooling to room temperature , an aliquot of the polymer solution in 2 - propanol was withdrawn and heated at 40 ° c . under reduced pressure to yield a dry polymer which was used to ( 1 ) confirm its composition using ir , nmr spectroscopy , and elemental analysis for nitrogen ; ( 2 ) determine its molecular weight using gpc ; ( 3 ) determine its thermal properties in terms of thermal transitions using differential scanning calorimetry ; and ( 4 ) assess the polymer film - forming quality by casing on teflon paper and qualitatively assessing the film flexibility , affinity to water , and resistance to dissolve in water . preparation of a typical film - forming pesticidal formulation using the reaction product from example 1 and acephate prior to preparing the active formulation , about 1 , 000 ml of 2 - propanol was transferred to the reaction product from example 1 , stirred to homogenize at 65 ° c ., and cool to room temperature . an aliquot of this diluted polymer solution was mixed with an aliquot of acephate granules and a sufficient amount of 2 - propanol as well as a small amount of water to yield a solution containing 3 percent weight / volume of acephate , 3 percent weight volume of the polymer , and about 2 percent by volume of water . the resulting formulation was evaluated qualitatively for ease of application using a trigger spray bottle or compression sprayer and film formation by casing on a teflon sheet . application of the acephate controlled release film - forming solution from example 2 to fire ant mounds the acephate solution from example 2 was applied using a compression sprayer to the fire ant mounds using three protocols , namely , ( a ) through spraying undisturbed mounds , ( b ) spraying disturbed mounds , and ( c ) spraying undisturbed mound which then was disturbed and resprayed . all mounds were checked over a period of 5 days for fire ant vitality . all types of mounds were shown to be free of viable ants at 4 days post - treatment . however , the effectiveness of the treatment increased from protocol ( a ) to ( c ) with the protocol revealing no signs of vitality in less than 2 days . application of the acephate controlled release film - forming solution from example 2 to a tree infested with tent caterpillars using a compression sprayer as described in example 3 , a 15 cm wide film was formed around the trunk of a cherry tree infested with tent caterpillar . the film was formed at the base of the trunk about 30 cm from the ground . the tree was monitored over a 2 - week period and the film was shown to prevent the caterpillars from migrating from the tree base to areas of the trunk above the film location . although the present invention has been described in connection with the preferred embodiments , it is to be understood that modifications and variations may be utilized without departing from the principles and scope of the invention , as those skilled in the art will readily understand . accordingly , such modifications may be practiced within the scope of the following claims . moreover , applicant hereby discloses all subranges of all ranges disclosed herein . these subranges are also useful in carrying out the present invention .
a controlled pesticide delivery system includes a film - forming alkanol solution of at least one amphiphilic polymer and at least one pesticide composition for the treatment of at least one pest in gardens , landscapes , forests , and wooden structures , targeting at least one pest selected from fire ants , tent caterpillars , gypsy moths , wood - boring beetles , and bark beetles during at least one phase of their life cycles .