NL8302643A - FUNGICIDE COMPOSITION AND METHODS FOR USE THEREOF. - Google Patents

Description

* * N.0. 31947 1

Fungicidal composition and methods of using it

The present invention relates to new urethanes, fungicidal compositions containing these urethanes as well as their uses.

U.S. Pat. No. 3,923,870 describes the synthesis of urethanes from position 1 halogen-substituted alkynes and their fungicidal activity and use in compositions and various matrices as fungicides.

U.S. Patent 4,276,211 describes the use of urethanes from 1-halogen-substituted alkynes and combinations of these compounds with epoxides to provide color stabilized fungicides for use in coatings.

Certain carbamates have been used as insecticides in herbicides.

The insecticide Sevin (carbamyl or naphthylmethyl carbamate) is known as an algicide in the range of 1 to 100 ppm (yg / ml). However, when tested at 100 ppm, it reduced the population of an ash-like culture of Chlorella pyrenoidosa by 30% (Christie, 1969, "Pesticide Microbiology").

"Zectran", a mexacarbate formulation, would prevent photosynthesis in 20 blue-green algae (bacteria). However, it does not pose a threat to aquatic algae in "normal" spray applications (Snyder and Sharidan, 1974). This formulation, Zectran, was not intended to be used as an algicide and is therefore not particularly suitable for that purpose.

Phenyl carbamates, often used as herbicides, have shown activity against blue-green algae (bacteria). Propham, Cloropropam and Barban (trade names) caused a 50% reduction in the growth of blue-green algae in the range between 0.73 ppm (data from Hill and Wright, 1978). Barban did not inhibit all tested algae-30 species. Like Sevin and Zectran, the phenyl carbamates are not structural urethanes of 1-halogen-substituted alkynes.

It is also known in the past to use mercury compounds which have limited efficacy and toxicity deficiencies. Copper compounds have activity and can be used, "but have the drawback of being colored for many applications.

Tributyltin oxide has been used, but it is relatively expensive for these purposes and it exhibits unsatisfactory outdoor lighting stability.

Although some different compounds have been used for limited use in lakes, ponds and still water areas, there has been no comprehensive understanding of the need for algicides in coatings until recently. It has been found possible to "load" certain compositions with products such as zinc oxide, but this causes problems in pigmented paints and coatings, has low algicidal activity, and gives stability problems in coatings.

For special applications in water towers such as cooling and storage towers, products such as chlorine and sodium hypochlorite have been used. However, these products are currently unacceptable from an environmental health point of view and, if used as such, are dangerous to the environment.

The present invention relates to the preparation of new, selected urethanes from halogenated substituted alkyls. These new compounds are generally substituted with aralkyl and substituted aryl groups.

The invention further relates to the general use of the urethanes of 1-halogen-substituted alkynes as algicides for the destruction and control of algae and algal microorganisms, including, but not limited to, certain protozoa, which are classified with algae.

The invention also relates to compositions such as coating compositions, protective compositions, decorative compositions and the like for algae control.

The invention furthermore relates to methods using such compositions which combat algae in paints, coatings, caulked seams, seals, spray liquids, lacquers, finishing preparations, polishes, wood, mortar, concrete, cement, fillers, molding compounds, waxes, resins , polymers, fibers and the like.

The present invention involves the use of urethanes of halogen-substituted alkynes to control and prevent algae growth and to kill preexisting algae growth. These compounds, which have been found to have extraordinary algicidal activity, are derivatives of 1-iodine-substituted alkynes of the general formula 1, wherein R is selected from substituted and unsubstituted alkyl, aryl-40 and alkylaryl groups having one up to no more than 20 carbon atoms and with 8302643 * * 3 one to three bonds corresponding to m, and m and n being integers between 1 and 3, which may be the same or different.

These compounds have been found to have many benefits as algicides for controlling and destroying many different types of algae and algal microorganisms. They are very stable even when incorporated into water-containing and non-water-containing compositions and are deactivated and / or destroyed only by continued exposure to high temperatures.

They have only a low toxicity to animals, birds and other game and pets and to humans. Consequently, their use in the algicidal compositions requires only the usual good practice and handling methods and such precautions are established and in use for the handling of commercial and household biocides.

Laboratory tests have indicated that the urethane compounds of the invention may optionally be combined with other biocides to broaden and increase their activity and expand the areas of their utility.

The compositions in which they are used can contain a relatively wide variety of components as known in the art.

The compounds of the invention can generally be used as algicides in concentrations of 0.01 to 12.0% by weight, in some cases depending on their stability in the compositions used, especially whether or not they are water-containing . In some cases, the compounds can be used as premixed dispersions. The compounds can also be prepared as solutions or dispersions and then added to the final protective compositions. For example, 3-iodo-2-propynyl-N-butyltyl carbamate (Polyphase) has been found to be soluble in water at a level of about 150-200 parts per million.

In all cases, it is necessary to use an effective amount (concentration) of the urethanes to effect control and / or destruction of the algae (s) or similar species to be controlled or destroyed. In some cases, it may be necessary to use up to about 40% by weight of the compounds to control and / or destroy certain algae and algal microorganisms and, for example, under certain conditions of good growth.

40 For their use as algicides, urethanes can be relied on on 8302643

* M

4 place 1 halogen substituted alkynes, dissolved or solubilized in water and for various organic solvents, are included in a wide variety of compositions, which protect and freedom from algae growth, including wood and mortar, and 5 moist paints, coatings, caulk seams , fillers and the like. When used as algicides, the urethanes of halogen-substituted alkynes are active as algicides and to combat algae found in seawater, fresh water, and land and airborne situations. They are also effective against species found in cooling water towers, clogging irrigation channels and growth on mortar and wood and find use as special valuable agents when applied to these objects.

For example, the compositions may include all types of water-based latex paints, including acrylic and PVA latex paints and chlorinated rubber vinyl paints, oil-alkyd paints, oil-based stains, pigmented paints and protective and decorative compositions, rubber and / or asphalt-containing roofing materials , inorganic and polymeric caulk compounds, molding materials, sealants, silicone compositions, liquid compositions, both aqueous and non-aqueous, adapted for dyeing, dipping or spraying, as well as other types of protective compositions for the many widely used applications of such materials to be.

These algicidal compounds have also been found to be particularly valuable for applications in clogging problems in irrigation ditches, channels, conduits and the like, the Batrachospermun (red algae) being particularly difficult.

It is also possible to use these algicidal compounds to combat the so-called "red tidal" problem, which is generally caused by one or more algae species of the class Dinophyceae.

The compounds can also be used to prevent odors by controlling, limiting and / or destroying the algae population in water, such as in irrigation towers, water towers, sewage recirculation systems and similar water storage and transport systems.

In particular, of this group, the urethane compound 3-iodo-2-propynyl-N-butyl carbamate (known as Polyphase, a trade name of Troy Chemical Corporation) has been found to be very effective and suitable as an algicide.

According to another feature of the invention, the group of new u-8302643 * 5 rethanes of 1-iodohydroxyalkynes of the formula 1 wherein R are selected from the group of the aralkyl and substituted aryl groups, and m and n are integers between 1 and 3, which may be the same or different, have been found to be very effective as algicides.

The groups of algae that can be effectively treated with the compounds and compositions of the present invention include algae in the subgroups Clorophyta (green algae), Chrysophyta (yellow-green algae), Cyanophyta (blue-green algae or bacteria), Euglenophyta ( euglenoxden), Phaeophyta (brown algae) and Rhodophyta (red algae); The algae against which the compounds and compositions are active are in no way limited to these groups or the species included therein.

The algae used for testing the algae control compounds and compositions and algicide activity were obtained from Ward's Natural Science Establishment of Rochester, N.Y.

The individual algae tested were more fully reported and described in the examples, as can be seen from the data where the compounds were very effective in fighting the growth of the algae under investigation.

The examples set out below are for illustrative purposes only. The data of the tables and the test results are given to illustrate the use of the compounds and the various coating compositions containing them, but are not intended to limit the invention specifically thereto or the compounds and compositions in the algicide limit their activity or to any particular algae class or species or to the specific amounts or concentrations of the algicides used to control the algae species under investigation. It is known in the art that it is usually easier to control or prevent growth than to kill an already grown algae population. It is also known that it is easier to control a small population rather than a large population of algae. The examples are particularly intended to demonstrate the algicidal properties of the compounds and compositions containing these compounds, and in particular to illustrate data on the efficacy of the compositions for such species, when are protected by thick hairstyles, as well as those that grow and multiply rapidly as thick colonies, such as Scytonema species, which have thick hairstyles and Nostoc species, which grow as thick colonies.

8302643 j ί 6

Example I

Preparation of the p-chlorophenyl urethane from hydroxyiodopropyne (compound of formula 2).

0.2 mol of hydroxyiodopropyne (10 = 0-0¾OH) as a 70% solution in ether, which has been dried with anhydrous sodium sulfate, is mixed with 0.2 ml of p-chlorophenyl isocyanate and a few drops of dibutyltin dilaurate are used as catalyst added. An exothermic reaction takes place. The mixture is refluxed until the reaction is complete. 21 g of a light cream-colored precipitate with a melting point. about 95 ° -100 ° C is filtered from the transparent filtrate and partial evaporation gives 22 grams of additional precipitate with a melting point. from 93 ° -95 ° C. Iodine content = 36.8%; theoretical »37.8%.

Example II

Preparation of the 3-methylphenyl urethane from hydroxyiodopropyne (compound of formula 3).

The reaction for the preparation of the product of Example I is followed, except that m-tolyl isocyanate is used instead of p-chlorophenyl isocyanate. The product is separated from the reaction mixture after overnight storage in the freezer after an initial filtration to remove a small amount of sediment. The yield is 37 grams of slightly creamy crystals with a melting point of 93 ° C. Jew content »39.97%; theoretically »40.2%.

Example III

Preparation of mixed diurethanes of hydroxyiodopropyne and toluene diisocyanate (compound of formula 4).

Hydroxy iodopropyne and a commercial isomer of mixed isomers of tolylene diisocyanate known as Mondur TD-30 (trademark), a product of Mobay Chemical Co., consisting of 80% 2.4 and 20% 2.6 iso-30mers are combined converted in the molar ratio of 2.15 mol HIP (hydroxyiodopropyne) to 1 mol diisocyanate. 60 g of a 72 percent solution of HIP in ether are mixed with 200 g of dichloromethane, 1/3 cm3 of dibutyltin dilaurate and 19.2 g of Mondur TD-30 are added slowly over a period of 50 minutes. When all the reagents have been added, the mixture is heated to reflux and a total of 250 g of dichloromethane are added, if required, to disperse the precipitate formed. The reaction mixture is refluxed for 2.5 hours and left overnight. The next morning, the reaction mixture is filtered to form 51 g of 40 a creamy colored powder, which melts at 174 ° -177 ° C.

8302643 6 Λ 7

Example IV

Preparation of the diurethane from dihydroxyiodopropyne and 4,4'-methylenediphenylisocyanate (compound of formula 5).

The reaction for the preparation of the product of Example III 5 is followed, except that the isocyanate used is 4,4'-methyl diphenyl isocyanate obtained as Mondur M (trademark) from Mobay Chemical.

The yield of the reaction of 39 g of HIP and 25 g of Mondur M was 55.5 g of a cream-colored powder with a melting point. of 165 ° C-168 ° C and an iodine content of 40% (theoretical = 41.4%).

10 Example V

Preparation of the diurethane of hydroxyiodopropyne and 2,4-toluene-diisocyanate (compound of formula 6).

This product was prepared according to the procedure of Example III, but using 2,4-tolylene diisocyanate (Mondus TDS, trademark 15, Mobay Chemical). The yield is 52 g of cream colored powder with a melting point. 181 ° -184 ° C and an iodine content of 47% (theoretical * 47.2).

Example VI

Preparation of the benzyl urethane from hydroxyiodopropyne (compound 20 of formula 7).

14.6 g of HIP are dissolved in 20 cm 2 of ether and 0.1 cm 2 of dibutyltin dilaurate is added. 16.7 g of benzyl isocyanate are added to this for 0.5 hour. An exotherm brings the temperature to 39 ° C and precipitation takes place. Mixing is continued for another 0.5 hour and the reaction mixture is filtered and washed with ether to give 20.5 g of cream-colored powder with a melting point. from 107 ° -110 ° C.

This product is resuspended with ether and filtered again to yield 17.5 g of pale yellow creamy crystals; m.p. 112 ° C-113 ° C. Jew content = 39.4%; theoretical = 40.3%.

Example VII

Several known nutrient solutions, such as Bristol solution, Erdschreiber solution, dirty water medium and other liquid media, were combined with appropriate amounts of an aqueous solution containing 100 µg / ml 1-iodo-2-propy-35nyl N -butynyl carbamate (Polyphase, a trademark of Troy Chemical Corp.) in screw-sealed tubes. The tubes were inoculated with an active culture of Carteria sp., Chlamydomonas sp.,

Eudorina sp., Haematococcus sp., Pandorina sp., Volvox sp., Or other algae species that want to grow well on the environment. Control tests 40 were prepared by combining the mediums with water and inoculated with an 8302643 * s δ algae species. For example, the following mixtures were prepared, inoculated with Prorocentrum and controlled with Polyphase.

TABLE A

5 Preparation of test solutions.

* Solution vol- H2O Polyphase ** Inoculum concentration gene Erdscheiber (ml) (1-iodo-2- (ml) polyphase (ml) propynyl-N- (yg / ml) butyl-carbamate) _ solution (ml) _ ______________ 7.00 0.00 0.00 3.00 0.00 6.50 0.00 0.50 3.00 5.00 6.00 0.00 1.00 3.00 10.0 15 5.50 0.00 1.50 3.00 15.0 5.00 0.00 2.00 3.00 20.0 4.50 0.00 2.50 3.00 25.0 4.00 0.00 3.00 3.00 30.0 3.50 0.00 3 50 3.00 35.0 20 3.00 0.00 4.00 3.00, 40.0 2.50 0.00 4.50 3.00 45.0 2.00 0.00 5.00 3.00 50, 0 2.00 5.00 0.00 3.00 0.00 25 * Standard sea salt solution used by algalogists as a growth medium.

** 100 yg Polyphase per ml

The tubes inoculated with Prorocentrum were incubated under cold white fluorescent light (40W) at about 20 ° C for 2 days and examined microscopically. Viable (motile) cells were observed both in the control tubes without Polyphase and in the tubes containing 5 µg polyphase with ml. Viable cells were not observed in the tubes containing concentrations of 10 µg / ml and above Polyphase.

When green algae species were used as the inoculum, chlorosis (the fading or disappearance of the green color) could often be used to determine the toxic level of polyphase to the algae. Microscopic examination, chlorosis or both were used to study these species. These techniques were applied to all unicellular and / or microscopic algae species tested, 8302643-9, with the test results reported in Table B.

Example VIII

Solutions were prepared as described in Example VII, except that the final volume in any case without the inoculum was ten milli-5 liters. The inoculum consisted of threads of algae species, such as Spi-rogyra and Scytonema, cut-pieces of large seawater algae, such as UIva, and marble-sized colonies of species, such as Nostoc. The small amount of water that adhered to the threads, pieces and colonies was neglected. Chlorose was used to determine the algicidal activity of Polyphase.

Both fresh water and sea water were tested as described in Examples VII and VIII and summarized in Table B. It appears that Polyphase shows excellent algicidal activity against both groups of organisms. Seawater algae are reported separately in Table C-15. Polyphase and analogs of Polyphase may find applications in the treatment of seawater algae blossoms, such as "red tides".

Since Polyphase is water soluble to a degree of about 175 ppm (pg / ml) and analogs of various water solubilities are available, it has been determined that saturated water solutions will contain enough biocide to combat the hardest algae.

8302643 1. ^ 10

Table B

Toxicity of 3-iodo-propynyl-n-butyl carbamate (Polyphase) to algae in aquatic environments - toxic level of 5 Organism Polyphase (yg / ml)

Subgroup Chlorophyta (green algae) 5-40

Class Chlorophyceae

Order Volvocales 10 - 20 I. Carteria sp. 10 10 2. Chamydomanas rhinhardtii 15 3. Eudorina sp. 20 4. Haematoccus sp. 10 5. Pandorina sp. 20 6. Platymonas sp. 10 15 7. Volvox sp. 20

Order Ulotrichales 8. ülothrix sp. 40

Order Ulvales 9. Ulva sp. 30 20 Order Oedogoniales 10. Oedogonium sp. 15

Order Cladophorales II. Cladophora sp. 25 12. Pithophora sp. 25 25 Order Chlorococcales 5-20 13. Ankistrodesmus sp. 10 14. Chlorella pyreniodosa 20 15. Hydrodictyon sp. 5 16. Protosiphon sp. 10 30 17. Scenedesmus sp. 5

Order Zygnematales 15 - 30 18. Closterium sp. 30 19. Mougeotia sp. 20 20. Spirogyra sp. 15 35 Class Charophyceae

Order Charales 21. Nitella sp. 5

Subgroup Chrysophyta (yellow-green algae) 15 - 35

Class Xanthophyceae 40 8302643 • f £ ^ 11 toxic level of

Organism Polyphase (yg / ml)

Order Heterotrichales 22. Botrudiopsis sp. 30 5 23. Tribonema sp. 15

Order Heterosiphonales 24. Botrydium sp. 20 25. Vaucheria sp. 10

Class Ghrysophyceae 10 Order Chrusomonadales 26. Synnra sp. 15

Class Bacillariophyceae

Order Pennales 27. Navicula sp. 35 15 Euglenophyta subgroup

Order Eugleniales 28. Astasia sp. 15 29. Euglena gracilis (green form) 35 30. Phacus sp. 15 20 31. Trachelomonas sp. 5

Subgroup Pyrrophyta (Desmokonten and Dinoflagellates)

Klassa Desmokontae

Order Desmonadales 25 32. Prorocentrum sp. 10

Class Dinophyceae Order Perdiniales 33. Perldinium sp. 15

Subgroup Rhodophyta (red algae) 30 Under class Bangiodeae 34. Porphyridium sp. 15

Under class Florideae 35. Batrachospermun sp. 35 indefinite systematic place 35 36. Rhodochorton sp. 30 indefinite systematic place Class Cryotophyceae Order Cryptomonodales 37. Chilomonas sp. 25 40 8302643 * <12 toxic level of

Organism Polyphase (yg / ml)

Subgroup Cyanophyta (Cyanobacteria)

Class Myxophyceae (Myxohacteria) 5 [(blue-green algae (bacteria)] 15-75

Order Chroococcales 40 - 60 38. Anacystis sp. 60 39. Gloeocapsa sp. 40 40. Merismopedia sp. 55 10 Order Oscillatoriales 15 - 75 41. Anabaena sp. 35 42. Cylindrospermum sp. 15 43. Gloeotrichia sp. 40 44. Lyngbya sp. 65 15 45. Nostoc sp. 55 46. Oscillatoria sp. 60 47. Phormidium sp. 75 48. Scytonema sp. 60 49. Spirulina sp. 25 20 50. Tolypothrix sp. 40

TABLE C

1 'r "o toxic level of

Organism Polyphase (pg / ml 25 Subgroup Chlorophyta (green algae)

Order Volvocales 1. Platymonas sp. 20

Order Ulvales 2. Ulva sp. 30 30 Subgroup Chrysophyta (yellow-green algae)

Order Chrysomonadales 3. Synura sp. 15

Subgroup Pyrrophyta

Order Desmonadales 35 4. Prorocentrum sp. 10

Subgroup Rhodophyta Order Bangiales 5. Phosphridium sp. 15 8302643 f r * * '13 toxic level of

Organism Polyphase (yg / ml)

Unspecified systematic place 6. Bhodochorton sp. 30 5 Subgroup Cyanobacteria 7. Spirulina 25

Subgroup Phaeophyta (brown algae) 8. Fuscus 65

Example IX

Disks of analytical paper from Schleicher and Schnell (No. 740-E, diameter 12 mm) were dipped 1 to 40 percent solutions of the test compounds dissolved in acetone. A T * pen, pressed through the center of each disc, was used to hold the disc in place during dipping and subsequent drying. The treated disks were air dried by pressing them onto the 'T' pins in a cork plate.

Protease agar plates were prepared and seeded with a "field" of Chlorella pyrenoidosa from an ash-like culture. Treated air-dried discs containing Polyphase or analogs thereof as identified in Table D were placed in the center of each plate. The Petri dishes were incubated under cold white fluorescent light (40W) at ambient temperature (about 20 ° C) until algae growth was obtained (about 6 days). The size of the inhibition zone 25 was measured from the edge of the disc to the edge of the algae growth (in mm). The data obtained are shown in Table E.

The urethanes of iodine-substituted alkynes, the compounds of the invention, were observed to show high toxicity against Chlorella pyrenoidosa. Thus, it appears that these compounds, including polyphase, exhibit toxicity to a wide range of algae species in each major subgroup at a wide range of growth sites occupying a wide range in the known algae classes.

8302643 «14

TABLE D

Chemical compounds tested including the Polyphase compound ** Polyphase (compound of Formula 8) 5 A (compound of Formula 9) B (compound of Formula 10) C (compound of Formula 11) D (compound of Formula 12) E ( compound of formula 13) 10 F (compound of formula 14) G (compound of formula 15) * H (compound of formula 2) * 1 (compound of formula 3) * J (compound of formula 4) 15 * K (compound with formula 5) * L (compound of formula 6) * M (compound of formula 7) * These compounds are new compounds of the invention.

20 ** Trade name of Troy Chemical Corporation.

e 8302643 »* 15

TABLE E

Sensitivity of Chorella pyrenoidosa to the investigated compounds plus Polyphase

Sample (compound) Solvent Concentration zone concentration (mm) 5 ___ (%) __

Polyphase acetone 1.0 10

Polyphase acetone 2.0 11

Polyphase acetone 5.0 12

Polyphase acetone 40.0 13 10 A acetone 1.0 10 B acetone 1.0 14 C acetone 1.0 9 D acetone 1.0 14 E acetone 0.5 10 15 F acetone 1.0 8 G acetone 1.0 7 * H acetone 1.0 13 acetone 1.0 9 * 1 acetone 1.0 20 20 * J acetone 1.0 6 * K acetone 1.0 5 * L acetone 1.0 5 * M acetone 1.0 42 8302643

¥ Q

16

Example X.

Formulations of latex paint, oil-alkyd paint and oil-based stain (details of the formulation are given in Tables G, H and I below) were prepared from commercially available products. Poly-5 phase was added in amounts of 2.4, 4.8 and 7.2 g / dm 2. Sheets of filter paper were coated or treated with the formulations and the control, which did not contain a Polyphase, dried, and 12 mm diameter disks were cut from the sheets. These discs were placed on plates containing protease agar inoculated with a field of Chorella pyrenoidosa and incubated as described in Example IX. Inhibition zones were measured as described in Example IX. The test results are shown in Table F.

It was observed that a narrow inhibition zone was obtained in control tests containing no Polyphase. This irregularity is caused by the solvents and biocides normally added to paints and other coatings to protect them from bacterial growth. However, after application as coatings, these toxic agents are removed by weathering, leaving the coatings unprotected. Larger zones of inhibition were observed in Polyphase protected coatings. These results clearly demonstrate the added and extended protection of Polyphase use.

8302643 t f * •>.

17

TABLE F

Algae protection of Polyphase containing coatings

Sample Polyphase inhibition zone No. (g / dm3) (mm) 5 Alkyd paints (oil-alkyd paint) la. (control) 0 4 lb. 2.4 6 lc. 4.8 10 10 ld. 7.2 13 stains (oil-based stain) 2a. (control) 0 6 2b. 2.4 8 15 2c. 4.8 10 2d. 7.2 13

Latices (alkyd latex paint) 3a. (control) 0 0 20 3b. 7.2 4/8302643 .. »* ▼ 18

TABLE G

oil-alkyd paint (1-a, b, c & d) formulate dry weight (non-volatile) 5 material kg 1 _ (kg) _ boiled linseed oil 102 106 102 alkali-purified linseed oil 34 37.8 34

Beckosol, P296-6010 (trademark

Reichhold Chem.) 34 37.8 20.4 White spirit 88.5 113.5 - Cobalt dryer 6% 1.14 1.14 Calcium dryer 6% 2.27 2.27 - 15 Antifog 0.91 0.76 - Non-chalk tend titanium dioxide 136 33.3 136 talc 136 47.7 136 suspending agent 3.27 1.14 2.27 20 536.89 381.37 430.67 1-a none Polyphase --------- 1-b 2.4 g / dm ^ --------------- 0.84 g active PP / 1 kg dry weight 1-c 4.8 g / dm ^ ------- ------- 1.68 g active PP / 1 kg dry weight 25 1-d 7.2 g / dm ^ ------------- 2.52 g active PP / 1 kg dry weight 8302643 '♦ ·', s · 19 TABLE Η oil-based stain (2- a, b, c, & d) white stain or alkyd oil base 5 Material kg _! dry weight / kg titanium dioxide 22.68 5.51 22.68 suspending agent 1.36 1.14 1.36

Beckosol P296-60 (Trademark 10 Kechhold Chem.) 63.96 68.89 38.37 Crude linseed oil 38.56 41.45 38.56 White spirit 204.57 261.60 - Cobalt dryer 6% 0.50 0.45 - Calcium dryer 6% 1.27 1.32 - 15 antifoil 0.45 0.49 - 333.35 400.85 100.97 2, a none Polyphase --- 2, b 2.4 g PP / dm ^ - 3, 59 g / kg dry weight 20 2, c 4.8 g PP / dm3 ---- 7.14 g / kg dry weight 2. d 7.2 g PP / dm3 - 10.6 g / kg dry weight 8302643, , t

»V

20

TABLE I

Acrylic latex paint (3 - a and b) _composition_ 5 Material kg 1 dry weight / kg water 160.57 42.5

Cellosize QP-15000 (Union trademark

Carbide) 1.69 1.14 1.72 10 Tamol 731 (trademark Rohm &

Haas) 4.54 1.1 1.13 lecithin 0.91 0.76 0.91 ethylene glycol 6.80 1.6 15 Carbotil (Union Carbide trademark) 4.54 1.2 -

Defoamer-999 (trademark, Troy

Chemical Corp.) 0.91 1.3 20 titanium dioxide 124.74 8.1 123.74 talc 38.56 3.6 38.56 mica 22.68 2.1 22.68

Rhoplex, AC35 (Trademark, Rohm & 25 Haas) 165.10 40.3 75.75 531.04 102.3 274.49 3, a no Polyphase -------- 3, b 7.2 g * / dm3 ------------ 4.1 g PP / kg dry weight 30 * Polyphase 8302643 * <- * 5 21

Example XI

Polyphase was added to a roofing material at levels between 0.1 and 1.0% (approximately equal to 1.2 to 12 g / dm 2). The roofing material called Traycote (trademark) (the composition of which is shown in Table J with and without Polyphase) was applied to standard 2.5 x 7.5 cm microscope slides, dried for two days and for three days leached with distilled water. The coatings were cut from the slides using a razor and plated on protease ager covered with a field of Chlorel-10 la pyrenoidosa cells. The plates were incubated and examined under cold white fluorescent light (4OW) for 2 days.

A green "field" of algae cells was observed growing to the edge of the control coat without Polyphase. The observation included growth below the surface of the control coating (as seen in reflected light); however, no growth was observed among coating samples containing more than or as much as 0.4% Polyphase. In addition, zones of inhibition between 0.5 and 4.0 mm in width were observed around the protected coatings.

20 TABLE J

Composition of roofing material Traycote (trademark of Traycote, Inc. Columbia, S.C.) is a protective roofing material with the following composition (g / dm- *): 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 8302643

Material g / dm ^ 2 ethylene glycol 27.96 3

Natrasol 250HR (trademark, 4

Hercules Ine.) 4.80 5 water 237.36 6

Nopco NXZ (trademark, 7

Diamond Shamrock) 109.84 8

Tamol 250 (trademark, 9

Rohm & Haas) 5.64 10 calcium carbonate 109.84 11 titanium dioxide 78.36 12 talc 335.40 13 acrylic latex resin 531.12 14 water-containing ammonia 15 (26 Baume) 2.28 16 * Troysan 174 (trademark -

Troy Chemical Corp.) 3.50 22 4 («* ^ 9 * Troysan 174 is a volatile bactericide used for" canned "preservation

Example 12 A commercially available rubber-containing asphalt roofing material of the composition as listed in Table K was combined with Troysan (trademark of Troy Chemical Corp.) Polyphase AF-1 formulation. The active polyphase content of this formulation is 40% and the remaining inert ingredients are solvents. The mixture 10 contained 0.0, 0.5, 1.0, 1.5 and 2.0 percent Polyphase AF-1 and 0.0, 0.2, 0.4, 0.6 and 0.8 wt. percent active Polyphase.

These samples were applied to glass slides with a wooden tongue-shaped presser and dried for 3 days. The samples were razor-plated and plated on the surface of protease-ager plates inoculated with Chlorella pyrenoidosa with the smooth surface down. The samples were incubated under ambient 40W white fluorescent light at ambient temperature (about 22 ° C) for 7 days.

Chlorella pyrenoidosa grew on and below the surface of the control sample, which did not contain Polyphase. Its growth was inhibited and dropped below the surface of samples containing polyphase at all concentration levels. Zones of inhibition were observed at 0.6 and 0.8 percent active Polyphase.

25 TABLE K

Rubber-containing asphalt roofing composition

Material% _ asphalt 50 30 Attagel (trademark Engelhardt

Industries) (thickener) 15

Kraton rubber (trademark - Shell Oil) <5 lecithin and surfactants <1 aromatic processing oil <5 35 high flash point naphtha 24-25 8302643 *% * '23

Example XIII

Polyphase solutions in ethanol were prepared at levels of 0.0, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0 grams per 100 ml. The solutions were transferred to an "Omit" air delivery device and sprayed onto the surface of protease ager in Petri dishes. The protease ager was pre-inoculated with chlorella pyrenoidosa, which will grow to form a field of cells on the surface. The Petri dishes were incubated under cold white fluorescent light of 40W for one week at ambient temperature (about 22 ° C).

Chlorella pyrinoidosa grew to cover the surface of the ager sprayed with ethanol containing no Polyphase. Some spot-like growth occurred at levels of 0.1 and 0.2 g / 100 ml polyphase. No growth at all was observed on plates sprayed 0.4 g per 10 ml and higher levels of Polyphase.

8302643

Claims (33)

Urethanes of 1-iodohydroxyalkynes of formula 1, wherein R is selected from the group consisting of aralkyl groups and substituted aryl groups and m and n are integers between 1 and 3, which may be the same or 5 different. Urethanes according to claim 1 of formula 1, characterized in that m is 1. Urethanes according to claim 1 of formula 1, characterized in that m is 2. Urethanes according to claim 1 of formula 1, characterized in that m is 3. Urethanes according to claim 1 of formula 1, characterized in that η is 1. Urethanes according to claim 1 of formula 1, characterized in that n is 2. Urethanes according to claim 1 of formula 1, characterized in that n is 3. 8. Compound of formula 2. 9. Compound of formula 3. 10. Compound of formula 4. 11. Compound of formula 5. 12. Compound of formula 6. 13. Compound of formula 7. 14. Protective coatings adapted to control the growth of algae and algal microorganisms, characterized in that effective concentrations of urethanes of 1-iodohydroxyalkynes of formula 1 are present, in which formula R is selected from the group consisting of aralkyl groups and substituted aryl groups and m and n are integers between 1 and 3, which may be the same or different. Decorative compositions adapted to control the growth of algae and algal microorganisms, characterized in that effective concentrations of urethanes of 1-iodohydroxyalkynes of formula 1 are present, wherein R is selected from the group consisting of 35 from aralkyl groups and substituted aryl groups and m and n are integers between 1 and 3, which may be the same or different. 16. Coating compositions adapted to control the growth of algae and algal microorganisms, characterized in that effective concentrations of urethanes of 1-iodohydroxy-8302643 * 1 w alkynes of formula 1 are present, In which formula R is selected from the group consisting of aralkyl groups and substituted aryl groups and m and n are integers between 1 and 3, which may be the same or different. Process for controlling the growth of algae and algal microorganisms, characterized in that in protective coatings effective amounts of at least one compound selected from the group consisting of the urethanes of iodine-substituted alkynes of formula 1 wherein R is selected from the group consisting of substituted or unsubstituted alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl and cycloalkenyl groups of one to no more than 20 carbon atoms and of one to three bonds corresponding to m and n, and m and n are integers between 1 and 3, which may be the same or different. 18. Process according to claim 17, characterized in that compounds of formula 1 are used, in which m is 1. Process according to claim 17, characterized in that compounds of formula 1 are used, in which m is 2. 20. Process according to claim 17, characterized in that 20 compounds of formula 1 are used, in which m is 3. Process according to claim 17, characterized in that compounds of formula 1 are used, wherein η is 1. Process according to claim 17, characterized in that compounds of formula 1 are used in which n is 2. 23. Process according to claim 17, characterized in that compounds of formula 1 are used, wherein n is 3. 23. A method of controlling the growth of algae and algal microorganisms, characterized in that effective coatings of at least one compound selected from the group consisting of 1-iodohydroxyalkynes of the formula 1, wherein R is selected, are incorporated in protective coatings. from the group consisting of aralkyl groups and substituted aryl groups and m and n are integers between 1 and 3, which may be the same or different. 25. Process according to claim 24, characterized in that 35 compounds of formula 1 are used, in which m is 1. 26. Process according to claim 24, characterized in that compounds of formula 1 are used, in which m is 2. 27. Process according to claim 24, characterized in that compounds of formula 1 are used, in which m is 3. 28. Process according to claim 24, characterized in that 8302643 I 4 T 2 * compounds of formula 1 are used, wherein η is 1. 29. Process according to claim 24, characterized in that compounds of formula 1 are used, in which n is 2. 30. Process according to claim 24, characterized in that 5 compounds of formula 1 are used, wherein n is 3. 31. Process according to claim 24, characterized in that 3-iodo-2-propynyl-N-butyl carbamate is used as the compound of formula 1. 32. A method of controlling the growth of algae and algal microorganisms, characterized in that the microorganisms are contacted with effective amounts of at least one compound selected from the group consisting of urethanes of iodine-substituted alkynes of Formula 1, wherein R is selected from the group consisting of substituted or unsubstituted alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl and cyclalkenyl groups having one to no more than 20 carbon atoms and having one to three bonds that correspond to m and n, and m and n are integers between 1 and 3, which can be the same or different. 33. Process according to claim 32, characterized in that the urethane compound used is 3-iodo-2-propynyl-N-butyl carbamate. --- ooo --- 8302643