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Publication numberUS3651107 A
Publication typeGrant
Publication dateMar 21, 1972
Filing dateOct 14, 1969
Priority dateOct 14, 1969
Also published asCA969967A1, DE2048354A1
Publication numberUS 3651107 A, US 3651107A, US-A-3651107, US3651107 A, US3651107A
InventorsMaggio Thomas E, Stanback Robert J
Original AssigneeTenneco Chem
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Organotin salts of monoalkyl alkenylsuccinates
US 3651107 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

U nitcd States Patent 3,651,107 ORGANOTIN SALTS 0F MONOALKYL ALKENYLSUCCINATES Robert J. Stanback, Gladstone, and Thomas E. Maggio, Somerville, N.J., assignors to Tenneco Chemicals, Inc. No Drawing. Filed Oct. 14, 1969, Ser. No. 866,366

Int. Cl. C07f 7/22 U.S. Cl. 260429.7 7 Claims ABSTRACT THE DISCLOSURE Organotin compounds that have the structural formula wherein each R represents phenyl or an alkyl group having from 4 to 12 carbon atoms; one R represents an alkenyl group having from 8 to 22 carbon atoms; the other R represents hydrogen; and R" represents an alkyl group having from 1 to 16 carbon atoms are used to protect surface-coating compositions from attack by microorganisms. Among the most effective of these biocidal compounds is (tri-n-butyltin)-n butyldodecenylsuccinate.

This invention relates to novel bioeidal compounds and to their use in the control of the growth of fungi, bacteria, and other microorganisms. More particularly, it relates to organotin salts of monoalkyl alkenylsuccinates and to surface-coating compositions containing these compounds that have improved resistance to deterioration resulting from attack by microorganisms.

It is well known in the art that paints and varnishes often have inadequate resistance to the action of micro organisms. Some of these coating compositions, such as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyd resins, which are subject to attack by fungi and bacteria. Others, for example, aqueous dispersions of water-insolube synthetic linear polymers, generally contain as plasticizers and thickeners materials that have their origin in animal or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full scale utilization, particularly in those areas and in those applications that are conducive to such attack.

Various biocidal materials have been suggested for use in surface-coating compositions, but none have been suggested for use in surface-coating compositions, but none has proven entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, While others undergo sulfide staining and still others hydrolyze in alkaline aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching once the coating has been spread in a thin layer over the surface to be protected.

This invention relates to biocides that are of particular value in surface-coating compositions. These biocides, which are thoroughly compatible with the resinous binders that commonly are used in surface-coating compositions and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by fungi and other microorganisms without adversely affecting the color, pH, viscosity, and other physical properties of the surface-coating compositions.

3,651,107 Patented Mar. 21, 1972 The bioeidal compounds of this invention are organotin salts of monoalkyl alkenylsuccinates. These compounds may be represented by the structural formula wherein each R represents phenyl or an alkyl group having from 4 to 12 carbon atoms; one R represents a straight-chain or branched-chain alkenyl group having from 8 to 22 carbon atoms; the other R' represents hydrogen; and R" represents an alkyl group having from 1 to 16 carbon atoms. Illustrative of these compounds are the following:

(tri-n-butyltin)-methyl-n-octenylsuccinate,

( tri-n-butyltin) -n-hexyldo decenylsuccinate, (tri-n-hexyltin)-n-octyl-n-octadecenylsuccinate, (trin-octyltin)-n-decyl-n-dodecenylsuccinate, (tridodecyltin)-isooctyleicosenylsuccinate, (triphenyltin)-hexadecylisododecenylsuccinate,

and the like. A single organotin salt of a monoalkyl alkenylsuccinate or a mixture of two or more of these compounds may be present in the surface-coating compositions of this invention. Particularly advantageous results have been obtained using tri-n-butyltin salts of monoalkyl alkenylsuccinates.

In addition to being useful in the preservation of surface-coating compositions, the organotin compounds of this invention can also be used as agricultural fungicides because they can be applied to plants, to plant seeds, or to the soil in which plants are growing to control the growth of a number of plant pathogens.

The organotin salts of monoalkyl alkenylsuccinates may be prepared by any suitable and convenient procedure. F or example, they may be prepared by the reaction of a trialkyltin oxide with the appropriate monoalkyl ester of an alkenylsuccinic acid.

The organotin compounds of this invention can be used to impart fungal and bacterial resistance to a wide variety of surface-coating compositions including both organic solvent-based and water-based coating systems. They are particularly valuable as biocides in water-based coatings that contain as their resinous binder a water-insoluble synthetic linear addition polymer.

In a preferred embodiment of the invention, the novel organotin compounds are used in aqueous dispersions that contain about 10 percent to 60 percent by Weight of a water-insoluble resinous binder that is an oleoresinous hinder or a synthetic linear addition binder. Suitable oleoresinous binders include drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safllower oil, or fish oil; bodied drying oils; blends of drying oils or bodied drying oils with a resin component, such as limed rosin, an ester gum, or a phenolic resin; oleoresinous varnishes formed by heating one of the afore-mentioned resins with one or more drying oils or bodied drying oils; and alkyd resins, which are resinous products resulting from the reaction of a polyhydric alcohol, such as pentaerythritol or glycerol, with a dicarboylic acid, such as phthalic anhydride, and fatty acids.

The useful aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenically unsaturated compounds, especially those of monoethylenically unsaturated character, although butadiene, chlorobutadiene, and isoprene may be used to some extent. Illustrative of the synthetic linear addition polymers that can be used as the resinous binder in the aqueous dispersions are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with vinyl chloride; copolymers of vinyl acetate with acrylonitrile; copolymers of vinyl chloride with acrylonitrile; copolymers of vinyl chloride with vinylidene chloride; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acids esters of alcohols having 1 to 8 carbon atoms with vinyl acetate; vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of the aforementioned acrylic acid esters, the aforementioned methacrylic acid esters, and acrylic acid; and copolymers of styrene with maleic anhydride.

In another preferred embodiment of the invention, an organotin salt of a monoalkyl alkenylsuccinate is used as the biocide in a solvent-based system that contains an oleoresinous binder as hereinbefore defined.

Only a small concentration of the organotin compound need be present in the surface-coating compositions of this invention. It has been found that as little as 0.10 percent of one or more of these compounds, based on the weight of the composition, will bring about an appreciable improvement in the resistance of the composition to attack by microorganisms. Three percent or more of the biocidal compounds can be used, but these larger amounts generally do not provide further improvement in the properties of the surface-coating compositions and for this reason are not ordinarily used. While the amount of the biocidal compound that will provide optimum protection for a surface-coating composition depends upon such factors as the choice of biocidal compound, the choice of resinous binder and other components of the surfacecoating composition and the amount of each that is used, and the application for which the coating composition is intended, in most cases about 1 percent to 2 percent of theorganotin compound, based on the weight of the surface-coating composition, is used.

-In addition to the resinous binder and the organotin compound, the surface-coating compositions of this invention may contain various auxiliary materials, such as pigments, extenders, solvents, dyes, deforming agents, driers, emulsifiers, plasticizers, and the like in the amounts ordinarily used for these purposes.

The organotin compound that is used as the biocide may be incorporated into the surface-coating composition by any convenient procedure. For example, it can be combined with the pigments and other components to form a pigment phase that is mixed with the resinous binder and water or organic solvent to form the surface-coating composition. Alternatively, it can be added to a composition that contains the resinous binder, pigment, and water or organic solvent. The organotin compound can be added as such to the other components, or it can be added as a solution of the organotin compound in, for example, an alcohol, ether, or ketone.

The invention is further illustrated by the examples that follow.

EXAMPLE 1 A mixture of 13.3 grams (0.050 mole) of dodecenylsuccinic anhydride and 4.0 grams (0.054 mole) of n-butyl alcohol was heated with stirring at 100 C. for one hour. It was then heated to 100 C. under vacuum (15 mm.) for one hour. Fifteen grams of bis-(tri-n-butyltin)-oxide was added to the half ester at 50 C., and the reaction mixture was heated with stirring at 1l0120 C. for two hours. The tri-n-butyltin salt of mono-n-butyldodecenylsuccinate obtained was a pale yellow oil that contained 18.5% Sn (calculated, 18.8% Sn). Its structure was confirmed by infrared analysis.

- 4 EXAMPLE 2 The following organotin compounds were prepared by the procedure described in Example 1:

(Tri-n-butyltin)-isodecyloctenylsuccinate (Tri-n-butyltin)-isodecylcaprylenylsuccinate (Tri-n-butyltin)-isodecyl-n-dodecenylsuccinate (Tri-n-butyltin)-isodecyl-n-octadecenylsuccinate (Tri-n-butyltin)-methyl dodecenylsuccinate (Tri-n-butyltin)-ethyl isododecenylsuccinate (Tri-n-butyltin) -n-hexyl isododecenylsuccinate Analysis of these compounds indicated that each contained approximately the calculated amount of tin and had the indicated structure.

EXAMPLE 3 v (A) A polyvinyl acetate emulsion paint was prepared by mixing together the following materials:

Parts by weight Water 280 Potassium pyrophosphate 3 Calcium metasilicate 135 Titanium dioxide (rutile) 220 2% aqueous solution of methylcellulose 200 Diethyl ether of diethylene glycol 37 55% aqueous solution of polyvinyl acetate 350 To samples of this paint was added either 2 percent by weight of one of the organotin compounds of this invention or 2 percent by weight of a comparative biocide.

(B) An acrylic paint was prepared by mixing together the following materials:

Parts by weight Water 250 Acrylic acid resin solids) (Acryloid B-66) 385 Monoethyl ether of ethylene glycol 259 .Titanium dioxide 143 Aluminum silicate 45 Magnesium silicate 98 To samples of this paint was added either 2 percent by weight of one of the organotin compounds of this invention or 2 percent by weight of a comparative biocide.

'(C) An exterior house paint was prepared by mixing together the following materials:

To samples of this paint was added 2 percent by weight of either one of the organotin compounds of this invention or a comparative biocide.

EXAMPLE 4 Samples of the acrylic paint, the polyvinyl acetate paint, and the oil-based paint whose preparation was described in Example 3 where evaluated by the following procedure: Pieces of drawndown paper were dipped into the paint, dried for 24 hours, and again dipped into the paint. After a 24-hour drying period, the coated paper samples were cut into 1% inch squares. Each of the coated paper squares was placed on a plate ofmalt and mycophil agar, which had been inoculated with 1 ml. of a suspension of the test organism. The plates, prepared in triplicate, were incubated at 28 C. and observed weekly. The growth was estimated according to the following key, and theresults 5 of the triplicate plates were averaged. In the tables that follow ZO=Zone of inhibition in mm.

=No zone of inhibition Tr=Trace zone 1-9=Increasing amounts of growth on specimen.

The biocidal compounds tested and the results obtained are set forth in Tables I, H, and III.

TABLE I.RESISTANCE 0F ACRYLIC PAINT FILMS TO ATTACK BY MICROORGANISMS Bacteria Fungi Aero- Pseudo- Pullu- Pembacter 'mmuzs laria cillium Aspar- Bacz'llus new aerupullucmsgillus Biocide subtilis genes ainosa lane tosum niger (Tri-n-butyltin) -isodeeyl-n-octenylsuccinate ZO- 0 0 0 0 0 (Tri-n-butyltin)isodeey1capry1eny1succinate ZO-5 0 0 0 0 0 (Tri-n-butyltin)-isodeeyl-n-dodecenylsuecinate. ZO-l 0 0 0 0 0 (Tri-n-butyltin)-lsodeeyl-n-octadecenylsuecinate ZO-5 0 0 0 0 0 (Tri-n-butyltin)-methyldodeeenylsuccinate Z 0-1 0 0 Z O-2 0 Z O-l (Tri-n-butyltin)ethyl-isododecenylsuccinate. Z0-1 0 0 ZO-l 0 Tr (Tri-n-butyltin)-n-butyldodecenylsuccinate do 20-3 0 0 20-1 0 ZO-l (Tri-n-butyltin(-n-hexyl-isododecenylsucciriatedo ZO-3 0 Tr 0 0 0 Comparative biocides: Bis-(phenylmereury)-dodeceny1sueeinate 9.4 do 20-9 ZO-7 ZO-8 ZO-lO 20-1 20-11 (Super Ad-it). 2,3,5,6-tertachloro-4-(methylsulfonyl)- 9. 4 do- Z O-9 0 0 Z 0-10 Z O-9 Z 07 pyridine (Dow 1013).

TABLE II.RESISTAN CE 015 POLYVIN YL ACETATE PAINT FILMS TO ATTACK BY MIOROO RGANISMS Bacteria Fungi Paint on A. P. P. P. paint B. ueroaerupullucrus- A. Biocide pH color subtillis genes ginosa lans toxum 'm'ger (Tri n-butyltin)-isodecyl-n-oetenylsuceinate 7. 2 None- ZO-3 0 0 Tr 0 0 (Tri-n-butyltin)-isodeeylcaprylenylsuccinate 7. do-... 20-3 0 0 20-1 0 Tr (Tri-n-butyltin)-isodecyl-n-dodecenylsuccinate.-.. Z 0 0 0 0 0 (Tri-n-butyltin)-isodeeyl-n-octadecenylsucernate 0 0 0 0 0 (Tri-n-butyltin)ethyl-isododeceuylsuecinate. 0 0 Tr 0 Tr (Tri-n-butyltin)-n-butyldodecenylsuccinate. 0 0 Z02 0 Z0-2 (Tri-n-butyltin)-n-hexyl-isodedoeenylsuecina 0 0 20-1 0 ZO-2 Comparative biocides:

Bisphengngcury) -do deoenylsucemate 7. 1 -do.. Z O-ll Z O-9 Z O-10 Z O12 Z O-lO Z O-S uper -r 7.4 -do.- ZO-9 0 0 -12 20-7 ZO-8 2,3,5,6-tetrachloioA-(rnethylsulionyl)- pyridine (D ow 1013).

TABLE BIL-RESISTANCE 0F OIL-BASED PAINT FILM TO ATTACK BY MICROORGANISMS Microorganisms P. pul- P. cruslulam tosum pyridlne.

DQOOO OOOOOQ From the data in Tables I-lII it will be seen that the organotin compounds of this invention are effective biocides for paint systems, and'particularly for acrylic and polyvinyl acetate paint systems. They impart to the paints alkaline conditions and loses its effectiveness on aging in acrylic paint systems and other alkaline paint systems.

The terms and expressions which have been employed are used as terms of description and not of limitation. There is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recog nized that various modifications are possible within the scope of the invention claimed.

What is claimed is:

1. An organotin compound having the structural formula wherein each R represents phenyl or an alkyl group having from 4 to 12 carbon atoms; one R represents an alkenyl group having from 8 to 22 carbon atoms; the other R represents hydrogen; and R" represents an alkyl group having from 1 to 16 carbon atoms.

8 2. An organotin compound as set forth in claim 1 wherein each R represents n-butyl. References Clted 3. The organotin compound as set forth in claim 1 that UNITED STATES PATENTS is (tri-n-butyltin)-n-buty1-dodccenylsuccinate. 3 019 247 1/1962 M t 1 I e ack et a1. 260-429.7 4. The organotm compound as set forth 1n 01am 1 that 5 3,236,793 2/1966 Robins at a]. 26 9 is (tri-n-butyltin)-methyl-dodecenylsuccinate.

5. The or anotin com und as set forth in claim 1 that 1 is (tri-n-butgltin)-isodecdodecenylsuccinate. JAMES POER Pnmary Exammer 6. The organotin compound as set forth in claim 1 that BELLAMY, s ist E m n is (tri-n-butyltin)-isodecyl-n-octenylsuccinate. 10 a 7. The organotin compound as set forth in claim 1 that is (tri-n-butyltin)-isodccyl-n-octadecenylsuccinate. 260 537; 424 288 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,651,107 Dated March 21, 1972 Inventor(s) Robert J. Stanaback and Thomas E. Maggio It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column. 1, line 4, change "Stanback" to Stanaback Column 1, lines 53 and 54, delete "have been suggested use in surface-coating compositions, but none".

for

Column 2, line 8, in the Structural formula change R!: to n I Column 3, line 45, change "deforming" to defoaming Column 4, line 66, change "where" to were Column 5, last item in Table I, change "tertach1oro-" to tetrachloro- Signed and sealed this 25th day of July 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTI'SCHALK Commissioner of Patents Attesting Officer USCOMM-DC 60376-P69 a us GOVERNMENT PRINTING OFFICE: \969 0-366-334 F ORM PO-IOSO (10-69)

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4055581 *Nov 14, 1975Oct 25, 1977Hooker Chemicals & Plastics CorporationHeat and light stabilizers for halogen containing polymeric resins
US4231949 *Jul 28, 1978Nov 4, 1980Albright & Wilson LimitedProcess for preparing organotin esters
US4261914 *Feb 9, 1979Apr 14, 1981Shakhtakhtinsky Togrul N OBis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids, method for producing same and compositions for antifouling coatings
Classifications
U.S. Classification556/94, 562/590
International ClassificationC07F7/00, C07F7/22
Cooperative ClassificationC07F7/2244
European ClassificationC07F7/22D5
Legal Events
DateCodeEventDescription
Aug 21, 1985AS17Release by secured party
Owner name: CHASE COMMERCIAL CORPORATION
Owner name: NUODEX INC., TURNER PLACE, PO BOX 365, A CORP. OF
Effective date: 19850801
Aug 21, 1985ASAssignment
Owner name: NUODEX INC., TURNER PLACE, PO BOX 365, A CORP. OF
Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE COMMERCIAL CORPORATION;REEL/FRAME:004444/0624
Effective date: 19850801
Mar 28, 1983ASAssignment
Owner name: NUODEX INC.; TURNER PLACE, PISCATAWAY, NJ. 08854
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TENNECO CHEMICALS, INC.;REEL/FRAME:004120/0362
Effective date: 19821222
Dec 30, 1982ASAssignment
Owner name: CHASE COMMERCIAL CORPORATION, 560 SYLVAN AVE., ENG
Free format text: SECURITY INTEREST;ASSIGNOR:NUODEX, INC.;REEL/FRAME:004080/0833
Effective date: 19821222