United States Patent 19 11 Patent Number: 4,554,155 Allan et al. (45) Date of Patent: Nov. 19, 1985 54 CONTROLLED RELEASE COMPOSITIONS Phytotoxicity of Some Systemic Insecticides to Spanish (75) Inventors: George G. Allan, Seattle, Wash.; Cedar. Amar N. Neogi, Greenville, N.C. Pree et al., J. Econ. Entomol., 65(4):1081–1085, Aug. 1972, Chemical Control of the European Pine Shoot 73 Assignee: Washington Research Foundation, Moth. Seattle, Wash. Guilbaud et al., Chem. Abstr. 50, #9667D (1956) of Fr. (21) Appi. No.: 640,428 Patents 991,694-5-6-7. G. G. Allan et al., Turrialba, 2004): 478-487, Oct. Dec. (22 Filed: Dec. 15, 1975 1970. G. G. Allan et al., Int, Pest. Contr., pp. 4-11, Jul/Aug. Related U.S. Application Data 1974. 63 Continuation of Ser. No. 434,083, Jan. 17, 1975, aban U.S.P.T.O. Translation of FR. 991694, Guilbaud et al. doned. U.S.P.T.O. Translation of FR. 991.695, Guilbaud et al. 51 Int. Cl.' ...... A01N 25/08; A01N 25/34 U.S. P.T.O. Translation of FR. 991696, Guibaud et al. 52 U.S.C...... 424/22; 424/19; U.S.P..T.O. Translation of FR. 991697, Guilbaud et al. 424/78; 71/DIG. 1; 514/777 CG Primary Examiner-Shep K. Rose 58) Field of Search ...... 71/DIG. 1; Attorney, Agent, or Firm-Seed and Berry 424/358-365 57 ABSTRACT 56) References Cited Controlled release compositions releasing an effective U.S. PATENT DOCUMENTS amount of biologically active material such as Re. 29,238 5/1977 Dimitri et al...... 7/DIG. into the environment over an extended period of time 2,714,553 8/1955 Bibb et al...... 7/64 are disclosed. The compositions comprise an intimate 3,657,446 4/1972 Blackmore. ... 424/274 admixture of an organic polymer and a component 3,705,467 12/1972 McKnight ...... 47A9 3,737,551 6/1973 Karsten et al. . 71/DIG. 1 incorporating a biologically active material wherein the 3,813,236 5/1974 Allan ...... 71/92 biologically active material is released by molecular 3,920,442 11/1975 Albert et al...... 71/92 diffusion through the matrix of the polymer at the sur 3,929,453 12/1975 Dimitri et al...... 71/10 faces exposed to the environment. The component in 4,144,050 3/1979 Frensch et al. ... . 71/DIG. I. cluding the biologically active material is incorporated 4,244,728 1/1981 DelliOolli et al...... 7/DIG. 1 in the polymer in amounts sufficient that diffusion of the FOREIGN PATENT DOCUMENTS component at the surfaces exposed to the environment results in loss of structural integrity and/or fraction of 991694 10/1951 France . 99.695. 10/1951 France the polymer to thereby expose new surfaces to decom 991696 10/1951 France . position for further release of the biologically active 99.1697. Ov1951 France material resulting in a rate of release over an extended 1164709 9/1969 United Kingdom ...... 7/DIG. period of time in proportion to that necessary to offer protection. OTHER PUBLICATIONS Graham-Allan et al., Int. Pest. Contr; 15(1):4-7 (1973) 15 Claims, 2 Drawing Figures U.S. Patent Nov. 19, 1985 4,554,155

2OO CUMULATIVE RELEASE (MGS) OO

O O 4. 8 2 6 -> t (days) FIG. I.

8OO

6OO

CUMULATIVE RELEASE (MGS) 4OO

O 5O OO 5O 2OO t (hrs) FIG 2 4,554,155 1. 2 CONTROLLED RELEASE COMPOSITIONS SUMMARY OF THE INVENTION The compositions described herein comprise an inti This is a continuation of application Ser. No. 434,083 mate mixture of an organic polymer and a component filed Jan. 17, 1975, now abandoned. incorporating a biologically active mixture with or without a carrier material wherein the biologically ac BACKGROUND OF THE INVENTION tive material is released to the environment by molecu 1. Prior Art Relating to the Disclosure lar diffusion through the lattice of the polymer at the A great deal of work has been carried out to increase surfaces exposed to the environment. A sufficient the protection period of biologically active material O amount of the component is incorporated in the poly mer so that diffusion of the component including the such as which have relatively short lives biologically active material at the surfaces exposed to while, at the same time, diminishing the residual waste the environment results in loss of structural integrity of of such pesticides which are the major cause of serious the polymer and/or fracture thereof to thereby expose pollution problems and damage to wildlife. Systems 15 new surfaces of the biologically active material have been developed which utilize the concept of "con polymer to the environment for further release of the trolled release' to release the pesticide at a controlled component. rate effective to control the pest while minimizing the The objects of this invention are to provide con undesired contamination of water sources with subse trolled release compositions: (1) which have release quent damage to aquatic and wildlife. One method of 20 rates effective for purposes desired over an extended accomplishing controlled release is by providing solid period of time; (2) where loss of biologically active solutions of pesticides in polymers. U.S. Pat. No. material in the composition at the surfaces of the com 3,076,744 discloses a urea-formaldehyde resin incorpo position exposed to the environment results in fracture rating up to 10 percent of an organic insecticide and an and/or disintegration of the polymer at those surfaces edible material attractive to insects. U.S. Pat. No. 25 to expose new surfaces to the environment for further 3,269,900 discloses an intimate admixture of a polyure diffusion of the biologically active material; (3) which in thane foam with a nonvolatile organic pesticide, the the case of pesticides, require much less pesticide for the polyurethane foam forming a protective cover around same period of activity, are easier to handle, less toxic, the pesticide with release of the pesticide occurring provide lower risk of damage to plants, reduce toxicity gradually. U.S. Pat. No. 3,343,941 discloses physically 30 to other organisms such as wildlife, reduce costs due to admixing herbicidally active alkyd resins with other less frequent application and have minimal pollution herbicides for slow release both by hydrolysis of the hazard. chemically incorporated herbicide as well as by physi BRIEF DESCRIPTION OF THE DRAWINGS cal release of the admixed herbicide. Canadian Pat. No. 35 FIG. 1 is a graph of release rate vs. time of a composi 846,785 discloses the incorporation of a pesticide in a tion made in accordance with this invention, and one thermoplastic polymer having desired permeability to prepared as described in Canadian Pat. No. 846,785; the pesticide with release of the pesticide by diffusion of FIG. 2 is a graph of release rate vs. time for composi the pesticide through the polymer lattice. tions, prepared as described in Canadian Pat. No. The rate of release and length of protection afforded 40 846,785, compared with those of the present invention. by the pesticide compositions disclosed in the above patents has not been commercially advantageous in DETAILED DESCRIPTION OF THE many instances. The pesticide compositions disclosed in INVENTION Canadian Pat. No. 846,785 release the pesticide rapidly The following are definitions of terms as used herein at first and then too slowly to be effective for the pur 45 in the specification: poses desired. Up to as much as 80 percent of the pesti Polymer-Natural or synthetic compounds having a cide remains in the polymer after a reasonable period of multiple of their molecular weight which are water time. Thereafter, the pesticide is released at too slow a insoluble, inert with respect to the biologically active rate to be effective. The rate of release of compositions material incorporated therewith and permeable to the disclosed in Canadian Pat. No. 846,785 is determined by 50 biologically active material incorporated therewith, the difference in pesticide concentration in the soil adja i.e. the biologically active material is diffusible cent the polymer and that in the polymer surfaces ex through the polymer lattice. The polymer may be a posed to the environment. Pesticide concentration partial solvent for the biologically active material or sharply falls over a period of time, slowing the rate of the biologically active material a solvent for the poly 55 re. release of the pesticide. Biologically active material-Those compounds used It has remained a problem to devise controlled re to inhibit, repel, exterminate or alter the activities of lease biologically active material compositions provid insects, moles, fungi, bacteria, protozoa, viruses, ing a release of a biologically active material over ex plants, invertebrates, worms and the like and includ tended periods of time at effective rates for control. 60 ing medicinals, herbicides, insecticides, miticides, This application is directed to means providing release , fungicides and the like which are non of the biologically active materials over an extended reactive with the polymer used in conjunction there period of time and preventing the reduction of the re with but soluble or dispersible therein; not thermally lease rate of the biologically active material from a degraded at the temperatures used in formulating the biologically active material-polymer admixture below 65 admixture, and which may be water-soluble or insolu that necessary to be effective by continually exposing be. fresh surfaces of the polymer-biologically active mate Carrier-A material which enhances fracture of the rial mixture to the environment. composition by dissolution, degradation, etc. which 4,554,155 3 4 may be monomeric or polymeric and which is com -continued patible with the biologically active material and poly pyrophosphate mer used, inert with respect thereto, and preferably Methy-4-aminobenzene sulfonyl Asulox water soluble. carbanate Pesticide Component-The pesticide alone or in admix 5 S-2,3-Dichloroallyl diisopro Avadex pylthiocarbamate ture with a carrier. S-2,3,3-Trichloroallyl-diiso Avadex BW Polymers used in preparation of the controlled re propylthiocarbamate lease compositions of this invention may include: (1) 2,6-di-tert-Butyl-p-tolylmethyl Azak synthetic polymers such as polyethylene, polypropyl carbamate 10 Dimethyl phosphate of 3-hydroxy Azodrin ene, polystry rene, polyacrylates, polymethacrylates, N-methyl-cis-crotonamide polyamides, polyureas, ethylene-vinylacetate copoly Benzoyl chloride (2,4,6-tri Banamite mers, ethylene-acrylic acid copolymers, polyvinylchlo chlorophenyl)-hydrazone ride, polyvinylidene chloride, polyesters, polyvinyl 3,6-Dichloro-o-anisic acid Banvel 4-Chloro-2-butynyl-m-chloro Barban alcohols, cellulose acetate, cellulose triacetate, polyan carbanitate hydrides, polyacetals, polyepoxides, polyethers, 15 2-Isopropoxyphenyl N-methyl Baygon acrylonitrile-butadiene copolymers and styrenemaleic carbamate anhydride copolymers; (2) natural thermoplastic poly 2,5-Dichloro-4'-nitro Bayluscide salicylanilide ethanolamine mers such as natural gums and "Vinsol'-type resins N-Butyl-N-ethyl-a,a,a-trifluoro Benefin (high melting, thermoplastic polymers derived from 2,6-dinitro-p-toluidine southern pine stump wood); (3) bitumens such as as 20 Methyl-1-(butylcarbamoyl)-2 Benomy phalt, asphaltites, asphaltic pyrobitumens and uintaite benzimidazole carbamate Ethy 0-benzoyl-3-chloro-2, Benzomate (Gilsonite); (4) rosins such as wood rosins, hydroge 6-dimethoxybenzohydroximate nated rosin, heat treated rosin, polymerized rosins and Methyl m-hydroxycarbanilate Betanal esterified rosins; and lignin or lignin derivatives. Pre m-methylcarbanilate ferred polymers include polyvinylacetate, Gilsonite and 25 S-(0,0-Diisopropyl phosphoro Betasan dithioate) ester of N-(2-mer kraft lignin. The polymer should be of such type as to captoethyl)benzene disintegrate after the active and/or inactive component sulfonamide leaves the composition. Dimethyl phosphate of 3-hydroxy Bidrin Where the biologically active material is a pesticide N,N-dimethyl-cis-crotonamide 30 2-sec-Butyl-4,6-dinitrophenyl Binapacryl selected for use in the controlled release compositions 3-methyl-2-butenoate may be from those commercial pesticides now available 2-(4-Chloro-6-ethylamino-s- Bladex including the following: triazin -2-ylamino)-2-methyl propionitrile S-(4-Chlorobenzyl)-N.N- Bolero N-sec-Butyl-4-tert-butyl- A-820 35 diethylthiocarbamate 2,6-dinitroaniline Triphenyltinacetate Brestan 2-Chloro-4-ethylamino-6- AAtrex 5-Bromo-3-sec-butyl-6- Bromacil isopropylamino-s-triazine methyluracil 0,0,0,0'-Tetramethyl 0, Abate 3,5-Dibromo-4-hydroxybenzo Bromoxynil 0'-thiodi-p-phenylene nitrile phosphorothioate 40 3,5-Dibromo-4-octanoyloxy Bromoxynil Isopropyl 4,4'-dichloro Acaralate benzonitrile Octiidate benzilate m-(1-Methylbutyl)phenyl methyl Bux Ten Isopropyl 4,4'-dibromo Acarol carbarnate -- m-(1-ethylpro benzilate pyl)phenyl methylcarbamate 2-Diethylamino-6-methyl Actellic Dimethyl arsinic acid Cacodylic acid pyrinidin-4-yl dimethyl 1-(p-tert-Butylphenoxy)-2- Calamite phosphorothionate 45 butyl 1-(2-butynyl)sulfite 2-(0,0-Diethyl thionophos Afugan N-Tridecyl-2,6-dimethyl Calixin phoryl)-5-methyl-6-car morpholine bethoxypyrazolo-(l.5a) cis-N-((trichloromethyl)thio)- Captain pyrimidine 4-cyclohexene-1,2-dicarboximide 2-2-chloro-1-(2,5-dichloro Akton 1-Naphthyl methylcarbamate Carbaryl phenyl)-vinyl)0,0-diethyl 50 2,3-Dihydro-2,2-dimethyl-7- Carbofuran phosphorothioate benzofuranyl methylcarbamate n-Octanol 28% plus n-Decanol 38% Alcohol C8, C10 m(Dimethylamino)methylene Carzol n-Decanol Alcohol C10 amino)phenyl methylcarbamate 1, 2, 3, 4, 10, 10-Hexachloro- Aldrin hydrochloride 1, 4, 4a, 5, 8, 8a-hexahydro N-n-propyl-N-cyclopropylmethyl CGA-10832 l, 4 endo-exo-5, 8-dimethano 55 4-trifluoromethyl-2,6- naphthalene dinitroaniline DL-2-Allyl-4-Hydroxy-3-methyl- Alethrin 0-(Methyl-2-propinylamino) CGA-3608 2-cyclopenten-1-one esterified phenyl N-methylcarbamate with a mixture of cis and trans Isopropyl N-phenylcarbamate Chen Hoe DL-chrysanthemum monocarboxylic 3-(4-Bromo-3-chlorophenyl)-1- Chlorbromuron acid 60 methoxy-1-methylurea 2-Propene-l-ol Ally alcohol Mixture of 60% octachloro-4,7- Chlordane 3-Amino-2,5-dichlorobenzoic Amiben methanotetrahydroindance and acid 40% related compounds 3-Amino-1,2,4-triazole Amit role N'-(4-Chloro-o-tolyl)-N,N- Chlordimeform 2-Propenal Aqualin dimethylformamidine 3-(4-Chlorophenyl)-1-methoxy- A resin 65 Ethyl 4,4'-dichlorobenzilate Chlorobenzilate 1-methylurea 1,4-Dichloro-2,5-dimethoxy Chloroneb 4,6-Dinitro-2-sec-butylphenyl Aretit benzene acetate Trichloronitromethane Chloropicrin 0,0,0,0-Tetrapropyl dithio- Aspon 3-(p-(p-chlorophenoxy)phenyl Chloroxuron 4,554,155 5 6 -continued -continued 1,1-dimethylurea Triphenyltin hydroxide Du-Ter Isopropyl m,-chlorocarbanilate Chlorpropham 0-Ethyl-S-phenyl-ethylphos- Dyfonate Dimethyl phosphate of a-methyl Ciodrin phonodithioate benzyl 3-hydroxy-cis-crotonate 0,0-Dimethyi (2,2,2-trichloro- Dylox N,N-Diethyl-2,4-dinitro-6- Cobex 1-hydroxyethyl)phosphonate trifluoromethyl-m-phenylene 2,4-Dichloro-6-(o-chloroaniline)- Dyrene diamine s-triazine 0,0-Diethyl 0-3-chloro-4- Co-Ral 6,7,8,9,10,10-Hexachloro-1,5.5a, Endosulfan methyl-2-oxo-2H-1-benzopyran 6,9,9a-hexahydro-6.9-methano 7-yl-phosphorothioate 10 2,4,3-benzodioxathiepin-3-oxide 0-p-Cyanophenyi Cyanox 7-Oxabicyclo(2.2.1)heptane-2,3- Endothall 0,0-dimethyl phosphorothioate dicarboxylic acid 3-2-(3,5-Dimethyl-2-oxocyclo Cycloheximide 1,2,3,4,10,10-Hexachloro-6,7- hexyl)-2-hydroxyethyl-glutar epoxy-1,4,4a,5,6,7,8,8a imide octahydro-1,4-endo-endo-5,8- 2-(Diethoxyphosphinylimino)- Cyolane 15 dimethanonaphthalene 1,3-dithiolane Ethyl 3,7,11-trimethyl Entocon ZR-512 Dodecylguanidine acetate Cyprex dodeca-2,4-dienoate 2-(Diethoxyphosphinylimino) Cytrolane Isopropyl 11-methoxy-3,7,1 1 Entocon ZR-515 4-methyl-1,3-dithiolane trimethyldodeca-2,4-dienoate 2,4-Dichlorophenoxyacetic acid: 2,4-D 0-Ethyl-0-p-nitrophenyl EPN also used as amine salts and esters 20 phenylphosphonothioate 2,4,5,6-Tetrachloroisophthalo Daconi 2787 S-Ethyl dipropylthiocarbamate Eptam nitrile 2-(2,4,5-Trichlorophenoxy) ethyl Erbon Dimethyl-2,3,5,6-tetrachloro Dacthal 2,2-dichloropropionate terephthalate 0,0,0,0'-Tetraethyl S.S'-methyl- Ethion 2.2 Dichloropropionic acid Dalapon ene bisphosphorodithioate 0,0-Diethyl 0-(p-(methylsulfinyl)- Dasanit (2-Chloroethyl) phosphonic acid Ethel phenylphosphorothioate 25 2-Ethyl-1,3-hexanedioi Ethylhexanediol 4-(2,4-Dichlorophenoxy)butyric acid: 2,4-DB 2-(Ethylamino)-4-(isopropylamino) = EVIK also salt, amine salt and ester 6-(methylthio)-s-triazine formulations 2,3,6-Trichlorophenylacetic acid Fenac 1,2-Dibromo-3-chloropropane DBCP or sodium salt 2,6-Dichloro-4-nitroaniline DCNA 0,0-Dimethyl-0-4-(methylthio)-m- Fenthion 1,1,1-Trichloro-2,2-bis(p-chloro DDT 30 tolyl-phosphorothioate phenyl)ethane 1,1-Dimethyl-3-(a.a.a-trifluoro- Fluometuron S.S.S-Tributyl phosphoro def m-tolyl)urea trithioate p-Nitriphenyl a,a,a,-trifluoro- Fluorodifen 0,0-Diethyl 0-(2-isopropyl-6-methyl Diazinon 2-nitro-p-tolyl ether 4-pyrimidinyl)phosphorothioate S.S.S-Tributyl phosphoro- Folex 2,6-Dichlorobenzonitrile Dichlobenil 35 trithioite 2,3-Dichloro-1, 4-naphthoquinone Dichlone N-(Trichloromethylthio)- Folpet 2-(2,4-Dichlorophenoxy)- Dichlorprop phthalimide propionic acid Isomers of Benzene Fortified Benzene 2,2-Dichlorovinyl dimethyl phosphate Dichlorvos hexachloride containing 40% Hexachloride 1,1-bis(p-Chlorophenyl)-2,2,2- Dicofol (by weight) of gamma isomer trichloroethanoi 40 Contains 7.9%. 2-(n-chlorophenoxy)- Fruitone CPA I,2,3,4,10,10a, or all,2,3,4,10, Dieldrin propionamide and 0.4% free acid 10-hexachloro-6,7-epoxy-1,4,4a, 3-(a-Acetonyl furfuryl)-4- Fumarin 5,6,7,8,8a-octahydro-1,4-endo hydroxycoumarin exo-5,8-dimethanonaphthalene 2-Chloro-1-(2,4,5-trichlorophenyl) Gardona cis-N-(1,1,2,2-Tetrachloroethyl)- Difolatan vinyl dimethyl phosphate thio)-4-cyclohexene-1,2- 45 2,4a,7-Trihydroxy-1-methyl-8- Gibberellic acid dicarboximide methylenegibb-3-ene-1,10 0,0-Dimethyl S-(N-methylcarbamoyl Dimethoate carboxylic acid-l - 4 lactone methyl) phosphorodithioate Ethyleneglycol bis (trichloro- Glytac 2,4-Dimethylbenzyl 2,2-dimethyl-3-(2- Dimethrin acetate) methylpropenyl)cyclopropane 0,0-bis (p-Chlorophenyl)aceti- Gophacide carboxylate 50 midoylphosphoramidothioate 2-Dimethylcarbamyl-3-methyl-5- Dimetilan 0,0-Diethyl-s-4-oxo-1,2,3- Guthion pyrazolyl dimethylcarbamate benzotriazin-3(4H)-ylmethyl)- 2-(sec-Butyl)-4,6-dinitrophenol Dinoseb phosphorodithioate 2,3-p-Dioxanedithiol-S, S-bis Dioxathion 74%. 1,4,5,6,7,8,8a-Heptachloro- Heptachlor (0,0-diethyl phosphorodithioate) 3a,4,7a-tetrahydro-4,7-methano 2-Methoxy-4H-1,3,2-benzodioxa Salithion indene phosphorin-2-sulfide 55 3-(Hexahydro-4,7-methanoinden- Herban 2-Diphenylacetyl-1,3-indandione Diphacin 5-yl)-1,1-dimethylurea N,N-Dimethyl-2,2-diphenyl Diphenamid Indole-3-butyric acid Hormodin acetamide 1-Phenyl-3-(0,0-diethylthio- Hostathion Diphenylanine Diphenylamine nophosphoryl)-1,2,4-triazol 0,0-Diethyl-S-2-(ethylthio)- Disulfoton N-(Mercaptomethyl)phthalimide Inidan ethylphosphorodithioate 60 S-(0,0-dimethyl phosphoro 3-(3,4-Dichlorophenyl)-1,1- Diuron dithioate) dimethylurea Butyl 3,4-dihydro-2,2-dimethyl- Indalone 2-Methyl-4,6-dinitrophenol DNOC 4-oxo-l-2H-pyran-6-carboxylate sodium salt 2,6-Dinitro-N,N-dipropyl Isopropalin DL-2-Allyl-4-hydroxy-3-methyl D-trans Alethrin cumidine 2-cyclopenten-1-one esterified 65 2-(1-Methylheptyl)-4,6-dinitro- Karathane with D-trans chrysanthemum phenyl crotonate monocarboxylic acid 3,5-Dichloro-N-(1,1-dimethyl-2- Kerb SOW 0,0-Diethyl 0-(3,5,6-trichloro Dursban propynyl) benzamide 2-pyridyl) phosphorothioate 3-Trifluoromethyl-4-nitrophenol, Lamprecid 4,554,155 7 8 -continued -continued sodium salt diamidate Mixture of about 20%. 2,3,5-Tri Landrin Ethyl 4-(methylthio)-m-tolyl Nemacur methylphenyl methylcarbamate; and isopropylphosphoramidate 80% 3,4,5-trimethylphenyl 2,2-Dimethyl-3-(2-methylpropenyl) Neo-Pynamin methylcarbamate cyclopropanecarboxylic acid 2-Chloro-2',6'-diethyl-N- Lasso ester of N-(hydroxymethyl)-1- (methoxymethyl)acetanilide cyclohexane-1,2-dicarboximide 3-Cyclohexyl-6,7-dihydro-1H Lenacil Ethyl hydrogen 1-propyl phosphonate Ni 10637 cyclopentapyrimidine-2.4 1-Propylphosphonic acid Nia 10656 (3H,5H)-dione 10 6-tert-Butyl-3-isopropylisothia Nia 19873 g-Butoxy-g'-thiocyanodiethyl Lethane 384 Zolo-(3,4-d)pyrimidin-4(5H)- ether Oile 1,2,3,4,5,6-Hexachlorocyclo Lindane 6-tert-Butyl-3-isopropylisoxazo Nia 21844 hexane containing at least lo-(5,4-d)pyrimidin-4 (5H)-one 99% gamma isomer 6-tert-Butyl-3-propylisoxazolo Nia 21861 3-(3,4-Dichlorophenyl)-1-methoxy Linuron 15 (5,4-d)pyrimidin-4(5H)-one i-methylurea 6-tert-Butyl-3-isopropylisoxazolo Nia 234.86 Phenyl 5,6-dichloro-2-trifluoro Lovozal (3,4-d)pyrimidin-4(5H)-one methylbenzinidazole-l-carboxylate 3-(1-Methyl-2-pyrrolidyl)pyridine Nicotine 2-Chloro-2',6'-diethyl-N- Machete 2,4-Dichlorophenyl p-Nitrophenyl Nitrofen (butoxymethyl)-acetanilide ether 0,0-Dimethyl phosphorodithioate of Malathion 2,-Chloro-6-(trichloromethyl) N-Serve diethyl mercaptosuccinate 20 pyridine 1,2-Dihydro-3, 6-pyridazinedione Maleic hydrazide N-(3,5-Dichlorophenyl)succimide Ohric 4-(Dimethylamino)-m-tolyl meth Matacil 2-(p-tert-Butylphenoxy) cyclohexyl Omite ylcarbamate 2-propynyl sulfite 2-Methyl-4-chlorophenoxyacetic MCPA S-Ethylhexahydro-lh-azepine-1- Ordram acid carbothioate 4-(2-Methyl-4-chlorophenoxy) MCPB 25 O.S.-Dimethyl acetylphosphorami Orthene butyric acid dothioate 2-(2-Methyl-4-chlorophenoxy) MCPP 2-sec Butyl phenyl-N-methyl car Osbac propionic acid bamate S-(4,6-Diamino-s-triazin-2-yl Menazon 2-Chioro-4-(cyclopropylamino)- Outfox methyl) 0,0-dimethyl 6-(isopropylamino)-s-triazine 3,4-Dimethylphenyl-N-methyl Meobal 30 0,0-Diethyl 0-p-nitrophenyl phos Parathion carbamate phorothioate 2-(4-Thiazolyl)benzimidazole Mertect a,a-bis(p-Chlorophenyl)-3-pyri Parino 4-(Methylthio)-3, 5-xylylmethyl Mesurol dine methanol carbarnate Pentachloronitrobenzene PCNB 3-Methylphenyl-N-methyl carbamate Metacrate Pentachlorophenol PCP S-(2-(Ethylsulfinyl)ethyl Meta-Systox R 35 Decachlorobis(2,4-cyclopen tadiene Pentac 0,0-dimethyl phosphorothioate 1-yl) S-Methyl N-(methylcarbamoyl)- Methomy i. 1-Dichloro-2.2-bis(p-ethylphenyl) Perthane oxylthioacetimidate ethane (88%) plus related com 2,2-bis (p-Methoxyphenyl)-1,1, Methoxychlor pounds, 12% 1-trichloroethane Dibenzo 1,4-thiazine Phenothiazine Methyl nonyl ketone Methyl nonyl ketone 40 0,0-Dimethyl S-(a-ethoxycarbon Phenthoate 0,0-Dimethyl 0-p-nitrophenyl Methyl parathion ylbenzyl)-phosphorodithioate phosphorothioate 0,0-Diethyl S-(ethylthio)-methyl Phorate 3-(p-Bromophenyl)-1-methoxy-1- Metrobromuron phosphorodithioate methylurea Tributyl 2,4-dichlorobenzylphos Phosfon 2-Carbomethoxy-1-methylvinyl Mevinphos phonium chloride dimethyl phosphate, cisomer 45 2-Chloro-N,N-diethyl-3-(dimethox Phosphamidon N-(2-Ethylhexyl) bicyclo[2.2.1- MGK. 264 yphosphinyloxy)crotonamide 5-heptene-2,3-dicarboximide 0-(4-Bromo-2,5-dichlorophenyl) Phosvel 2,3,4,5-bis(2-Butenylene) tetra MGK Repellent 11 0-methyl phenylphosphonothioate hydrofurfural 4-Amino-3,5,6-trichloropicolinic Picloram Dipropyl isochinchomeronate MGK Repellent 326 acid Piperalin 2-Hydroxyethyl-n-octyl sulfide MGK Repellent 874 50 3-(2-Methylpiperidino)propyl Scilliroside glycoside MGK. 3,4-dichlorobenzoate 5-Butyl-2-dimethylamino-4-hydroxy Milcurb 2-Dimethylamino-5, 6-dimethylpy Primor 6-methylpyrimidine rimidin-4-yl dimethylcarbamate 5-Butyl-2-ethylamino-4-hydroxy Milstem 4-(Methylsulfonyl)-2, 6-dinitro Planavin 6-methylpyrimidine N,N-dipropylaniline Dodecachlorooctahydro-1,3,4- Mirex 5,6-Dihydro-2-methyl-1,4-oxathin Plantvax metheno-1H-cyclobutacd)-pentalene 55 3-carboxanilide-4,4-dioxide 4-Benzothienyl-N-methylcarbamate Moban Tricyclohexyltin hydroxide Pictran 0-Ethyl S, S-dipropyl phosphoro Mocap 2-Diethylamino-6-methylpyrimidin Princid dithioate 4-yl diethyl phosphorothioate 0,S-Dimethyl phosphoroamidothioate Monitor 2-Chloro-4,6-bis (ethylamino)- Princep 3-(p-Chlorophenyl)-1,1-dimethylurea Monuron s-triazine 3-(4-Chlorophenyl)-1, 1-dimeth Monuron TCA 60 2-(3,4-Dichlorophenyl)-4-methyl Probe ylurea trichloroacetate 1,2,4-oxadiazolidine-3,5-dione 6-Methyl-2,3-quinoxalinedithiol Morestan 2,4-bis(isopropylamino)-6-meth Prometone cyclic-S, S-dithiocarbonate oxy-s-triazine 1,2-Dibromo-2,2-dichloroethyl Naled 2,4-bis(isopropylamino)-6- Prometryme dimethyl phosphate (methylthio)-s-triazine i-Naphthalene acetamide Naphthalene acetamide 65 3,4-Dichloropropiomanilide Propanil l-Naphthaleneacetic acid Naphthalene acetic acid 2-Chloro-4,6-bis(isopropylamino)- Propazine 1-n-Butyl-3(3,4-dichlorophenyl)- Neburon s-triazine i-methylurea Di-n-propyl 6,7-methylenedioxy Propyl isome O-Phenyl, N,N'-dimethylphosphoro Nellite 3-methyl-1,2,3,4-tetrahydrona 4,554,155 9 10 -continued -continued phthalene-1,2-dicarboxylate (3-thioallophanate) 1,8-Naphthalic anhydride Protect Dimethyl 4,4'-o-phenylene-bis Thiophanate M 5-Amino-4-chloro-2-phenyl-3(2H)- Pyramin (3-thioallophanate) pyridazinone bis(Dimethylthiocarbamoyl)disul- Thiram 2-Chloro-N-isopropylacetanilide Ramrod fide N,N-Diallyl-2-chloroacetamide Randox 1,4-Dithiaanthra- Thynon (5-Benzyl-3-furyl)methyl-2,2-di Resmethrin quinone-2,3-di-carbonitrile methyl-3-(2-methyi-propenyl) 2,3,5-Triiodobenzoic acid Tiba cyclopropanecarboxylate S-Propyl butylethylthiocarbamate Tiam S-Ethyl N-ethyl-N-cyclohexylthio Ro-Neet 10 S-(2-Chloro-1-phthalimido-ethyl)- Torak carbamate 0 0-diethyl phosohorodithioate 0,0-Dimethyl-O-(2,4,5-trichloro Ronnel N,N-bis(2-chloroethyl)-2,6- Torpedo phenyl) phosphorothioate dinitro-p-toluidine 2-tert-Butyl-4-(2,4-dichloro-5- Ronstar Chlorinated camphene with 67- Toxaphene isopropyloxyphenyl)-5-oxo-1, 69% chlorine 3,4-oxadiazoline 5 a.a.a-Trifluoro-2,6-dinitro- Trifluralin Rotenone Rotenone N,N-dipropyl-p-toluidine 2,5 Dimethyl-1-pyrrolidinecarbo Rowtate S-(((p-Chlorophenyl)thiomethyl) Trithion xanilide 0,0-diethyl phosphorodithioate 4-tert-Butyl-2-chlorophenyl Ruelene Piperonal bis 2-(2'-n-butoxy- Tropital 0-methyl methylphosphoroamidate ethoxy)ethyl)acetal Succinic acid 2,2-dimethylhydra SADH 3-Phenyl-1, 1-dimethylurea Urab zide trichloroacetate 2-Methoxy-4H-1,3,2-benzo Salithion 0-2,4-Dichlorophenyl 0, 0-di- VC-13 dioxaphosphorin-2-sulfide ethyl phosphorothioate 2-Ethylthio-4,6-bis-isopropyla Sancap 2-Chloroallyl diethyldithio- Vegadex mino-s-triazine carbamate 4-Amino-6-t-butyl-3-(methylthio)- Sencor S-Propyl dipropylthiocarbamate Vernan 1,2,4-triazin-5(4H)-one 25 5,6-Dihydro-2-methyl-1,4-oxa- Vitavax 2-Methyl-5,6-dihydro-4-H-pyran Sicarol thiin-3-carboxanilide 3-carboxylic acid anilide 4-Dimethylamino 3,5-xylyl methyl- Zectran 1-(2-Methylcyclohexyl)-3-pheny Siduron carbamate lurea 0,0-Diethyl-2-(2-pyrazinyl) Zinophos 2-(2,4,5-Trichlorophenoxy)-pro Silvex phosphorothioate pionic acid 30 0,0-Diethyl S(6-chloro-2-oxo- Zolone 6-Ethoxy-1,2-dihydro-2,2,4- Stop Scald benzoxazolin-3-yl)methyl trimethylguinoline phosphorodithioate 2,4-Diguanidino-3,5,6-trihydroxy Streptomycin cyclohexyl 5-deoxy-2-0-(2-deoxy 2-methyl-amino-a-glucophyranosyl)- Preferred are pesticides which act through the root 3-formyl pentanofuranoside 35 system of the plant, such as organophosphorus, carba l-Methyl-2-(3,4-methylenedioxy Sulfoxide mate and phenoxyacid pesticides and particularly the phenyl)ethyl octyl sulfoxide following pesticides: 2,4-dichlorophenoxyacetic acid 0,0-Dimethyl 0-(4-nitro-m-tolyl)- Sumithion phosphorothioate (2,4-D) and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl 2-sec-Butylamino-4-ethylamino Sumitol methylcarbamate (Carbofuran). 6-methoxy-s-triazine The polymer and pesticide or pesticide and carrier 0,0-Dimethyl S-(2-methoxy-1,3,4- Supracide are physically admixed generally by heating the solid thiadiazol-5(4H) onyl-4-methyl phosphorodithioate polymer to the liquid state and then thoroughly admix 0-p-Cyanophenyl 0-ethylphenyl Surecide ing, at that temperature, the desired pesticide or pesti phosphonothioate cide and carrier until a uniform distribution is obtained. S-13 Ethyl diisobutylthiocarbamate Sutan 45 The choice of a particular polymer with a particular A 2:1 mixture of 0,0-diethyl Systox 0-2-(ethylthio)ethylphospho pesticide is determined by a number of factors. One of rothioate (thiono isomer) I and the most important is the ability of the pesticide to dif 0,0-diethyl-S-2-(ethylthio)ethyl fuse through the polymer lattice. In general, the pesti phosphorothioate (thiolisoner) II cide and polymer must be mutually compatible. The 2,4,5-Trichlorophenoxyacetic acid 2,4,5-T 50 m-(3,3-Dimethyiureido)phenyl Tandex amount of pesticide or pesticide and carrier incorpo tert-butylcarbamate rated in the polymer, in the case of a substantially non Dimethylamine salt of 2,3,6-tri 2,3,6-TBA biodegradable polymer must be sufficient to induce chlorobenzoic acid and other stresses within the structure of the composition of diffu trichlorinated benzoic acids Trichloroacetic acid, sodium salt TCA sion of the pesticide from the polymer at those surfaces Trichlorobenzylchloride TCBC 55 exposed to the environment so that the polymer-pesti Tetrachlorothiophene TCTP cide or polymer-pesticide-carrier combination will lose 2-Methyl-2-(methylthio)propio Tennik naldehyde 0-(methylcarbamoyl)- its structural integrity at those surfaces exposed to the oxime environment to expose fresh surfaces to the soil envi Tetraethyl purophosphate TEPP ronment. If the pesticide component is used alone, it 3-tert-Butyl-5-chloro-6-methyl Terbacil 60 must generally be incorporated within the polymer in uracil amounts greater than 50 percent by weight so that the 2-tert-Butylamino-4-ethylamino Terbutry in 6-methylthio-s-triazine pesticide forms the matrix of the composition although 5-Ethoxy-3-trichloromethyl Terrazole lower percentages can be used with kraft lignin because 1,2,4-thiadiazole of the low cohesivity of this polymer. As the pesticide 4'-Chlorophenyl2,4,5-trichloro Tetradifon 65 diffuses into the environment at the exposed surfaces of phenyl sulfone Isobornyl thiocycanoacetate Thanite the composition, the polymer left behind loses its struc (82%) and related compounds tural integrity and fractures or disintegrates exposing Diethyl 4,4'-o-phenylene-bis Thiophanate E new surfaces of the composition to the environment for 4,554,155 1. 12 further diffusion thereof. When the pesticide is admixed with a carrier and incorporated into the polymer, the EXAMPLE 3 amount of pesticide-carrier should usually be greater Molten Gilsonite was mixed with varying amounts of than 50 percent by weight. Carbofuran to prepare pesticide-polymer compositions The carrier may be a water-soluble monomeric or containing 10%, 20%, 30% and 50% by wt., respec polymeric material which is compatible with the poly tively, of Carbofuran. Each of the homogeneous com mer and the pesticide, nontoxic for the desired use and positions was cast into plate form. The release rate of diffusable through the polymer lattice. The carrier may each of the compositions was determined by dipping the also be a polymeric material which is biodegradable in plates of the respective compositions in water (25 ml.) the environment in which the composition is to be used, 10 and withdrawing the plates from the water at varying such as cellulosic fibers, urea-formaldehyde polymers, time intervals for analysis by total UV determination. etc. Examples of water soluble carriers which may be The release rates of the compositions containing 10% to used include polyethylene glycols having molecular 40% by wt. of Carbofuran were insignificant while the weights ranging from 600 to 6000, biodegradable mono compositions containing 50% by wt. of Carbofuran meric materials such as maleic anhydride, tartaric acid, 15 showed significant release rates. The release rates of the etc. 50% by wt. Carbofuran composition remained substan In the case of a biodegradable polymer such as kraft tially constant over an extended period of time. lignin the amount of pesticide or pesticide-carrier incor EXAMPLE 4 porated in the polymer should be at least the amount, 20 Kraft lignin (10 gm.) was dissolved in dry dioxane when released, to effectively control the pest. The (500 ml.) after which dioxane (350 ml.) was evaporated amount may range from 15 wt. 76 to 50 wt. % or off. Carbofuran (5 gm.) in dioxane (50 ml.) was then greater. The biodegradable polymer-pesticide composi added and most of the solvent removed under reduced tion peels away at the soil-composition interface after pressure. The viscous mixture was poured into a War release of the pesticide incorporated therewith to ex 25 ing blender containing hexane (500 ml.). The mixture pose new surfaces of polymer-pesticide to the environ was filtered, air-dried and pelletized. The pellets con ent, tained about 25 wt. percent of Carbofuran. The relative amounts of carrier and pesticide used in the controlled release composition may range from 0 to EXAMPLE 5 80 percent carrier to 100 to 20 percent pesticide. 30 Kraft-lignin-Carbofuran mixtures were prepared sim The controlled release compositions may be and are ilar to that of Example 4 with varying concentrations of generally cast in pellet form of any desired shape for Carbofuran. The mixtures were pressed into wafers or ease of use and transportation. The pellets, when incor cast into cylinders and used in field tests by placing porating a pesticide, are either incorporated in the soil them in the soil around young trees (Sweitenia macro around the area desired to be treated or spread on the 35 phylla) in Costa Rica. A randomized block approach surface of the soil with release of the pesticide occur was employed with 15 blocks of 16 trees each for a total ring over an extended period of time by diffusion from of 240 trees. Within each block of trees was one repli the composition into the soil environment surrounding cate each of three formulations in three levels each. In the pellets. seven blocks three additional formulations in one level The following examples are illustrative of the inven 40 each were included. The formulations and treatment tion but are not intended to be limiting in any manner. levels were as follows: EXAMPLE 1. Treatment Pesticide-polymer prepared according to Canadian Level Desig Pat. No. 846,785. 45 Formulation (per tree) nation One part of 2,4-dichlorophenoxyacetic acid was A. Kraft-lignin-Carbofuran wafers 2 pellets Ll 59.3% Carbofuran 3 pellets L2 blended with one part of molten polyvinyl acetate and 9.8 cm/pellet (avg. area) 4 pellets L3 cast into a block having a surface area of 20 square 1.28 g/pellet centimeters. The block was immersed in 500 ml. of 50 B. Kraft-lignin-Carbofuran cylinders 3 pellets Cl water and the release rate of the pesticide into the water 57.6 Carbofuran 4 pellets C2 4.35 cm/pellet (avg. area) 6 pellets C3 determined over a period of time. The results illustrated 0.73 g/pellet by FIG. 1 (Curve A) clearly show that the rate of re C. Kraft-lignin-Carbofuran cylinders lease of the pesticide is initially rapid and then dimin 79.9% Carbofuran ishes with time. 4.86cm/pellet (avg. area) 4 pellets C4 55 0.439 g/pellet EXAMPLE 2 D. Kraft-lignin-Carbofuran cylinders 89.2% Carbofuran A mixture of one part 2,4-dichlorophenoxyacetic acid 2.92 cmpellet (avg. area) 4 pellets C5 was admixed with one part of a 1:1 mixture of molten 0.42 g/pellet polyvinyl acetate and a water soluble polyoxyethylene 60 glycol polymer having a molecular weight of about A block of trees was selected at random after each 6000. The molten composition was cast into a block two week period, infested with 20 eggs/tree of the having a surface area of 20 square centimeters and im Hypsipyla grandella shootborer pest and observed for mersed in 500 ml. of water. The release rate of the pesti survival of larvae and damage. Additionally, samples of cide was measured at various time intervals. Curve B in 65 fresh leaves from the trees were selected and bioassayed FIG. i clearly shows that the amount of pesticide re in the laboratory with first instar Hypsipyla larvae. To leased does not diminish with passage of time but is be considered "toxic', as indicated in Table I, a tree had substantially constant. to both withstand the field infestation with an intact 4,554,155 13 14 terminal and complete larvae mortality and also kill the material, escapes from the composition, resulting in larvae in the laboratory bioassay. Trees which exhibited loss of the structural integrity and disintegration of poor growth or died were eliminated from the results. the outer surfaces only of the composition to ex As Table I indicates, about 27% of the trees on the pose new, undisintegrated surfaces of the composi alloted site were eliminated due to the poor conditions 5 tion containing the diffusible component for fur of the site. The blocks were only able to be monitored ther release thereof. for six months in the manner set out before drought 2. The composition of claim 1 wherein the solid solu conditions set in and prematurely aborted the experi- tion is formed by heating the biologically active pesti net. cide material to the liquid state and thoroughly admix In Table I those marked with zeros are those tree 10 ing the polymer and diffusible component with the eliminated from the results due to poor growth or biologically active pesticide material in the liquid state death. The "control' (an average of 60 untreated trees) until the polymer and component are uniformly distrib had a "percentage effectiveness' of 11.9% compared uted throughout the biologically active pesticide mate with the most successful test (C3) of 80%. Tests L1, L2 rial. and L3, releasing, on the average, about 40% of the 15 3. The composition of claim 1 wherein the diffusible available Carbofuran in six months were not too effec- component is present in the composition in an amount tive in controlling the pest, probably because of inade- equal to or greater than 50 percent by weight relative to quate-active released Carbofuran to cover the root sys- the water-insoluble biodegradable organic polymer so ten of the trees. that the diffusible component forms the matrix of the Tests C1 to C3 released, on the average, about 50% 20 composition and wherein the diffusible component con of their available Carbofuran in six months. Test C3 (6 tains a major amount of the biologically active pesticide pellets/tree) was about 80% effective in controlling the material. pest. 4. The solid, control release, biologically active pesti Tests C4 and C5, employing more concentrated mix- cide material delivery composition of claim 1 wherein tures of Carbofuran released, on the average, about 25 the diffusible component includes a major amount of a 49% of the available Carbofuran in six months. The low biologically active pesticide material and a minor percentage effectiveness was apparently due to inade- amount of a water-soluble substance inert with respect quate active Carbofuran in the soil over an area suffi- to the biologically active pesticide material, the diffus cient to cover the root system of the tree. ible component present in an amount equal to or greater TABLE I Amount of Active Ingredient Elapsed Time (days) 30 43 61 76 91 107 125 138 153 169 183 Applied Released Percentage Block No. 8 14 S 12 3 4. 2 10 6 13 9 (g) in 6 months Effectiveness Treatments L ------1.3 0.56 54% L2 - - 0 ------2.2 0.85 30 L3 -- -- 3.1 13 27 C1 O vow na 2 0.63 O C2 - O - O ------17 0.84 33 C3 ------0 -- - - 2.7 1.26 80 C4 0 0 - O -- - - O - - O 0 1.7 0.88 20 C5 0 0 - O - - O - - 0 0 15 0.72 O Control 0.0 0.0 11.9 *Average of 60 trees. - c toxic - c not toxic 0 is not treated, tree dead or unhealthy The embodiments of the invention in which a particu- than 50 percent by weight relative to the organic poly lar property or privilege is claimed are defined as fol- mer and wherein the water-soluble substance diffuses lows: 50 simultaneously with the biologically active pesticide 1. A solid, controlled release, biologically active pes- material. ticide material delivery composition for release of the 5. A method of protecting plants from pests over an biologically active pesticide material over an extended extended period of time, comprising: period of time into the surrounding environment by applying to the environment in which the plant to be molecular diffusion of the biologically active pesticide 55 protected is located an amount of a pesticide com material through the matrix of the composition from the position effective to control the pest, the composi surfaces of the composition exposed to the environ- tion consisting essentially of kraft lignin as a biode ment, the composition consisting essentially of: gradable solid solution of a water-insoluble, solid a solid solution of kraft lignin and a biodegradable organic polymer which is soluble in the pesticide in water-insoluble organic polymer which is soluble 60 a diffusible component, including a pesticide which in the biologically active pesticide material in a is non-reactive with the organic polymer, the dif diffusible component which includes a biologically fusible component present in the composition at active pesticide material non-reactive with the least at 15 wt.% a concentration that when the organic polymer, the diffusible component present outer surfaces of the composition are exposed to at least a 15 wt.% concentration in the composition 65 the environment, the diffusible component, includ that when the outer surfaces of the composition are ing the pesticide, escapes from the composition, exposed to the environment, the diffusible compo resulting in loss of the structural integrity and disin nent, including the biologically active pesticide tegration of the outer surfaces only of the composi 4,554,155 15 16 tion to expose new, undisintegrated surfaces of the mer exposed to the soil, the component present in composition containing the diffusible component the composition in an amount sufficient such that for further release thereof over an extended period diffusion of the component into the soil at the sur of time until the component and the organic poly faces of the composition exposed to the soil results mer are substantially dissipated. in loss of the structural integrity and disintegration 6. A solid, controlled release pesticide composition of the kraft lignin polymer at the exposed surfaces from which the pesticide is released by molecular diffu to thereby expose new surfaces of the composition sion through the matrix of a solid polymer from the to the soil for further diffusion of the component to surface of the composition, the composition consisting the soil over an extended period of time until the essentially of kraft lignin a biodegradable solid solution 10 component including the organic, systemic pesti of a water-insoluble polymer which is soluble in the cide is substantially dissipated. pesticide in a diffusible component, including a pesti 10. A shaped, controlled release pesticide composi cide which is non-reactive with the organic polymer, tion for application in or on the soil wherein the pesti the diffusible component present in an amount equal to cide is released to the soil by molecular diffusion or greater than 50 percent by weight relative to the 5 through the matrix of kraft lignin at the surfaces of the weight of the organic polymer so that when the outer composition exposed to the soil, the composition con surfaces of the composition are exposed to the environ sisting of an intimate mixture of kraft lignin and Car ment, the diffusible component, including the pesticide, bofuran, with the Carbofuran present in the composi escapes from the composition, resulting in loss of struc tion in an amount at least 50 percent by weight, relative tural integrity and disintegration of the outer surfaces to the weight of the kraft lignin, the composition, when only of the composition to expose new, undisintegrated exposed to the soil, resulting in diffusion of the Carbofu surfaces of the composition containing a diffusible com ran into the soil and disintegration of the kraft lignin at ponent for further release thereof over an extended the outer surfaces of the composition exposed to the period of time. soil, with resulting exposure of new surfaces of the 7. The solid, controlled release pesticide composition 25 of claim 6 wherein the pesticide is Carbofuran. composition to the soil for sustained release of the Car 8. A shaped, solid, controlled release pesticide com bofuran over an extended period of time. position for application in or on the soil wherein the 11. The composition of claim 1 wherein the diffusible pesticide is released to the soil by molecular diffusion component is a pesticide present in the composition in through the matrix of the solid polymer at the surfaces 30 an amount equal to or greater than 50 percent by weight of the composition exposed to the soil, the composition relative to the organic polymer so that the pesticide consisting essentially of forms the matrix of the composition. an intimate mixture of kraft lignin and a component 12. The composition of claim 1 wherein the diffusible containing Carbofuran present in the composition component includes a pesticide and a water-soluble in an amount such that when the outer surfaces of 35 substance inert with respect to the pesticide, the compo the shaped composition are exposed to the soil, the nent present in an amount equal to or greater than 50 component present in the outer surfaces of the percent by weight relative to the organic polymer and shaped composition diffuses into the soil, resulting wherein the water-soluble substance diffuses simulta in loss of the structural integrity and disintegration neously with the pesticide. of the kraft lignin at those outer surfaces to expose 40 13. The composition of claim 1 wherein the diffusible new surfaces of the composition to the soil for component includes a substantially water-insoluble pes further release of the component over an extended ticide and a water-soluble material inert with respect to period of time until the component and kraft lignin the pesticide, the diffusible component present in the are substantially dissipated. composition in an amount equal to or greater than 50 9. A method of protecting plants from pests over an 45 percent by weight relative to the organic polymer and extended period of time, comprising: wherein the water-soluble material diffuses into the applying to the soil in which the plant to be protected environment on exposure thereto, carrying the insolu is located, an amount of a shaped composition ef ble pesticide therewith. fective to control the pest, the composition consist 14. The method of claim 5 wherein the pesticide is an ing essentially of an intimate mixture of kraft lignin 50 organic, systemic pesticide. and a component containing an organic, systemic 15. The method of claim 9 wherein the pesticide is pesticide, wherein the pesticide is released to the Carbofuran present in an amount greater than 50 per soil by molecular diffusion through the matrix of cent by weight relative to the kraft lignin. the kraft lignin polymer at the surfaces of the poly 2k xk k >k k 55

65. UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4,554,155 DATED November 19, 1985 INVENTOR(S) : George G. Allan et al. it is certified that error appears in the above-identified patent and that said Letters Patent is hereby Corrected as shown below: On the cover sheet, item 63, please change "Jan. 17, 1975" to --Jan. 17, 1974--. Col. 13, line 59, "and a biodegradable" should be -- as a biodegradable -- .

Signed and Sealed this Twenty-eighth Day of April, 1987

Attest:

DONALD J. QUIGG Attesting Officer Commissioner of Patents and Trademarks