Note: Descriptions are shown in the official language in which they were submitted.
1~59~
BACKGROUND OF THE INVENTION
U.S. Patent 3~923~870 describes the synthesis of
urethanes of l-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
of l-halogen substituted alkynes and combinations of these
compounds with epoxides to provide color stabilized
fungicides for use in coatingsO
Certain carbamates have been employed as insect-
icides and herbicides. The insecticide SevinTM (carbamyl
or naphthyl methyl carbamate) is known to be algacidal in
the range between 1 and 100 ppm ~g./ml.). However, even
when tested at 100 ppm, it only reduced the population of
an axenic culture of Chlorella pyrenoidosa by 30% (Christie,
1969, "Pesticide Microbiology").
"ZectranTM," a mexacarbate formulation has been
claimed to prevent photosynthesis in blue green algae
(bacteria). However, in "normal" spray applications it did
not pose a threat to aquatic algae (Snyder and Sharidan, 197~)~
This formulation, ZectranTM, was not intended to be used as
an algacide and is, therefore, not particularly useful for
that purpose.
Phenylcarbamates, fre~uently employed as herbicides,
have demonstrated activity against blue green algae (bacteria).
Propham, Chloropropham and Barban (tradenames) caused a 50
reduction in the growth of blue green algae in the range
between 0.3 and 70 ppm (data from Hill and Wright, 1978)o
Barban did not inhibit all of the algae species tested. Like
Sevin and Zectran, the phenyl carbamates are not structurally
urethanes of l-halogen substituted alkynes.
~259~
It has also been known in the past to use mercury compound~
which have limited effectiveness and toxicity shortcomings.
Copper compounds have activity and can be used but have the
disadvantage for many applications that they are colored.
Tribut~1 tin oxide has been used but it is relatively
expensive for these purposes and shows unsatisfactory s~abi-lity
for exterior exposure.
Although some various compounds have been employed for
limited use in lakesl ponds and areas of stagnant water~ there
has not been a wide recognition of the need for algacides in
coatings until recently. It has been found possible to "load"
certain compositions with such materials as zinc oxide but this
causes problems in pigmented paints and coatings, has low
algacidal activity and gives stability problems with coatings.
For the special application of use in water towers such as
cooling and holding towers, such materials as chlorine and
sodium hypochlorite have been used. However, these materials
are presently unacce~table by the Environmental Protection
Agency and are possible environmentally hazardous when so used.
SUMMARY OF THE INVENTION
An object of the invention is the production of novel,
selected urethanes of halogenated substituted alkynes. These
25 1 novel compounds are generally substituted by aralkyl and
sustituted aryl groups.
Another object of the invention is to employ enerally the
urethanes if l-halogen substituted alkynes as alg~acides for
i destruction and control of algae and algae-like microorganisms
including but not limited thereto certain protozoa which may be
classified with algae.
~25~
Another object is to describe compositions includinq but
not limited thereto, coating compositions, protective
compositions, decorative compositions and the like bu~ not
limited thereto for the control of algae.
A further object is the description of methods using such
various compositions which control algae in paints, coatings,
caulkings, linings, sealants, sprays, lacquers, finishin~
compositions, polishes, wood, mortar, concrete, cement,fillers,
molding compounds, waxes, resins, polymers, fibers and the like~
DETAILED DESCRIPTIO~ OF THE I~7ENTION
This invention involves the use of urethanes of 1-halogen
I substituted alkynes to control and prevent~the growth of algae
l and to kill already existing algal growths. These com~ounds
15 ¦ have been found to have outstanding alqacidal activity are
derivatives of l-iodo-substituted alkynes having the generic
formula:
[ I-C=C-(CH2)n~-~-N-]mR
,~,.
where R is selected from substituted and unsubstituted alkyl,
aryl and alkyl aryl groups having from one to not more than 20
carbon atoms and having from one to three linkages corxesponding
to m, and m and n are whole number inte~ers between 1 and 3,
l and may be the same cr different.
These compounds have been shown to have many advantages as
algacides for controlling and destroying many different species
of algae and algae-like microorganisms, They are very stable
even when incorporated into aqueous and non-aqueous compositions.
and are deactivated and/or destroyed only by prolonged
exposures to high temperatures.
~259~ 6
They possess only low toxicity towards anim~ls,
birds and other wildlife and domestic animals and toward man.
Consequently, their use in the algacidal compositions require
only the usual good practice and procedures in handling and
such precautions as are well established and in use for handling
commercial and household biocides.
Laboratory tests have indicated that the ure~hane compounds
of the invention can be combined with other biocides as
desired to both broaden and enhance their activity and extend
the areas of their usefulness. .
The compositions in which they are used may contain a
relative wide variety of componen-ts such as are well known in
the art.
The compounds useful in the invention may be used when
generally employed as algacides in concentrations from 0.01
percent up to 12.0 percent by weight, in some cases depending
on their stabilities in the compositions employed including
whether they are aqueous or non-aqueous. In some instances, the
compounds may be employed as premixed dispersions, They may
also be prepared as solutions or dispersions and therea~ter
added to the final protective compositions. For examples,
3-iodo-2-propynyl-N-butyl carbamate (Polyphase) is found to be
.
soluble in water at a level of about 150-200 parts per million.
In all instances it is necessary to employ an effective
amount (concentration) of the urethanes to accomplish control
and/or destruction of the algae specie(s), or similar species
which are to be controlled or destroyed~ For instance, in some
cases, it may be necessary to employ up to approximatelv 40 perce~ It
by weight of the compounds to control and~or destroy certain
algae and algae-like microorganisms and, for instance und~r
certain conditions of well-established growth.
1.
,.:1
~59
For their use as algacldes, the urethanes of l~halogen
substituted alkynes, dissolved or solubilized in water and for a
variety of organic solvents, can be incor~orated into a wide
variety of compositions which require protection and freedom
from algal growth, including wood and mortar, and most paints,
coatings, caulkings, fillers and the like. ~hen emploved as
algacides, urethanes of l-halogen substituted alkynes are
active as algacides and for control against algal species found
growing in marine, fresh water, terrestrial and aerial
situations. They are also active against species found in
water cooling towers, clogging irrigation canals and growing
on mortar and wood and find use as especiallv valuable agents
when used for these objectives.
The compositions may be for example, all types of water-
based latex paints including acrylic ~nd pva latex Paints and
chlorinated rubber-vinyl paints, oil alkyl paints, oil based
stains, pigmented paints and protective and decorative
compositions, rubber and/or asphalt containing roof coatings,
inorganic and polymeric caulkings, molding materials, sealants,
; 20 silicone compositions, liquid compositions,
both aqueous and non-aqueous adapted for painting, dipping or
spraying as well as other types of protective compositions for
the many widely used applications of such materials.
It has also been found that these algicidal compounds are
particularly valuable for applications in clogging problems in
irrigation ditches, canals, conduits and the like where the
Batrachospermun (red algae) are particularly troublesome.
1~ i
~ ~ ~59~2~ .
It is also possible to use these algacidal compounds for
control of the so-called "red tide" problem which is generally
caused by one or more algal species from the class Dinophxceae.
The compounds ma~ also be used to prevent odors by
controlling, limiting, and/or destroying the algae population
in water, such as in irrigation systems, water towers,
recirculating sewage water systems and similar water holding and
transporting systems.
: In particular, and of this group, the urethane compound
3-iodo-2-propynyl-N-butyl carbamate 5known as Polyphase, a
tradename o Troy Chemical Corporation) has been found highly
effeotive and useful as an algacide.
In another featl.lre of the invention, the group of novel
urethanes of l-iodohydroxy alkynes having the formula
[I-C~C-(C~2)n-0-~-NH]mR in which R is selected from the group of
aralkyl and substituted aryl groups, and m and n are whole
number integers between 1 and 3 and may be the same or diferent
have been found highly effective as algacides.
The algal groups which can be treated effecti~ely by ~he
ZO. compounds and compositions of this invention include algae in
the Divisions Chlorophyta (green algae), Chr~so~hyta (yellow-
green algae), Cyano~hyta tblue-green algae or bacteria),
Euglenophyta (euglenoides), Phaeophyta (brown algae), and
Rhodophyta (red algae); the algae against which the compounds
2~ and compositions are effective are in no way limlted to these
groups r to the species er~raced thereby.
-
~ 9~ 6
The algae used for testing the compounds and compositionsfor algae contxol and algacidal activity were obtained from
Ward's Natural Science Establishment of Rochester, N.Y.
The individual algae which were tested are shown and
described more completely in the Examples, as shown by the data,
the compound5 were highly effective in controlli~g the qrow~h
of algae tested.
Examples which are set forth below are intended for
illustrative purposes only. The data of the tables and the test
results are presented to exemplify the use of the compounds and
various coating compositions containing them but are not intended
to limit the invention specifically thereto or to limit the
compounds and compositions in their algacidal activity or to any
particular algal classes or species or to the specific amounts .
or concentrations of the algacides employed to control the
algal species tested. It is well known in the art that it is
usually easier to control or prevent growth than it is to kill
an already growing algal population. It is also known to be
easier to control a small rather than a large population of
algal organisms. The Examples are especially intended to show
the algacidal properties of the compounds and compositions
containing them and particularly to show illustra~ive data on
the effectiveness of the compositions for such species as are
protected by thick capsules as well as those which grow and
multiply rapidly as thick colonies, such as Scytonema species
which have thick capsules and Nostoc species which grow as thick
colon s.
-
11 ~2~9~26
Exa~p:e 1
Preparation of p-chlorophenyl urethane of hydroxy-icdo~propyne
cl--~NH-~-o-cH2-c-c-I
0.2 Moles of hydroxyiodopropyne (IC=C-CH2OH~ as a 70%
solution in ether, dried with anhydrous sodium sulfate, is
mixed with 0.2 moles of ~-chlorophenyl isocyanate and a few
drops of dibutyl tin dilaurate ~s added as catalyst~ An
exothermic reaction occurs~ The mixture is refluxed until
reaction is complete, A yield of 21g of pale cream precipitate
with an approximate m.p. of 95a- 100C is filtered from the
clear filtrate and partial evaporation yields 22 grams,of
additional precipitate with a m.p. of 93- 95 .
~ Iodine= 36,8; theoretical = 37.8~.
Example 2
Preparation of 3-methylphenylurethane of hydroxy-iodo-propyne
NH-~-O~CH2-C--C-I
The reaction for preparation of the product of Example 1,
is followed, except that m-tolyl isocyanate is used instead of
p-chlorophenyl isocyanate. The product is isolated from the
reaction mixture after standing in the freezer overnight after
an initial filtration to remove a small amount of sediment.
The yield is 37 gramS of pale cream crystals with a melting
point of 93~C.
% Iodine = 39.97; theoretical - 40.2~.
.-ll -`
~;~5
Example 3
Preparation of mixed diurethanes of hydroxy-iodopropyne and
toluene diisocyanate
lI-C_~-C~2-0-~-NH-]2- [80% 2,4- and 20~ 2,6-tolyl]
S Hydroxyiodopropyne and a commercial preparation of mixed
isomers of toluene diisocyanate known as Mondur TD-30 (Trademark3
a product produced by Mobay Chemical Co., and consisting of
80% 2, 4- and 20% 2, 6- isomers are reacted together in the
molar ratio of 2.15 m HIP thydroxyiodopropyne) to 1 mole
dis~cyanate. 6~g of a 72% solution of HIP in e~her is mixed
with 200g methylene chloride, 1/3 cc dibutyl tin dilaurate,
and 19.2g Mondur TD-30 is added slowly over a period of 50
minutes. When all reactant has been added, the mixture is
heated to reflux and methylene chloride is added as required,
about'250g in all to keep the precipitate that forms dispersed~
The reaction mixture is held at reflux 2 1/2 hours and allowed
to stand overnight.. The following morning, it is filtered to
obtain 51g of a cream colored powder melting at 174~- 177~C. .
xamp~e 4
Preparation of diurethane of hydroxy-iodopropyne and 4,4'-
methylene diphenyl isocyanate.
I-C-C-CH2-0-~-NH- ~ CH2 ~ -NH-~-O~H2-C-C-I~
~rhe reaction for preparing the pro of Example 3 is
followed except that the isocyanate used is 4,4i methylene
diphenyl isocyanate, obtained as Mondur M tTrademark) from
Mobay Chemical~ The yield reaction of 39g HIP and 25g Mondur M
was 55.5g of a cream colored powder having a m.p~ of 165 - 168~C
and an iodine content of 40% (theoretical = 41.4~).
~ 5~
Example 5
Preparation of diurethane of hydroxy-iodopropyne and toluene
. 2,4- diisocyanate
-......... ~I-C-C-C-CH2-0-~-NH-~2- [2,4-tolyl]
This product was made according to the procedure of .
Example 3, but using toluene 2,4 diisocyanate (~ondur TDS~
Trademark, Mobay Chemical~.. The yield ~s 52g cream colored
powder with an approximate mO p. of 181 - 184 C and an iodine
content of 47~ (theoretical = 47.2%1.
Example 6
Preparation of benzyl urethane of hydroxy-iodopropyne
CH2-NH-~-o-cH2-c-c I
14.6 g HIP is dissolved in 20 cc ether and 0.1 cc dibutyl
tin dilaurate is added. To this is added during 1~2 hour,
: 16.7g benzyl isocyanate. An exotherm brings the temperature
up to 3~C and preoipitation occurs~ Mixing is continued for
: an additional 1/2 hour and the reaction mixture filtered and
washed with ether t~ yield 20.5g cream colored powder with a
20 ~ m.p. of 107 - llO~Co This product is reslurried with ether and
refiltration yields 17.5g of very pale cream crysta~s;
m.p, = 112~- 113`'
. % Iodine = 39.4; theoretical = 40.36.
~ i9~f~
Example 7
Various well-known nutrient solutions, such as Bri~stol's
solution, Erdschreiber solution, soil-water medium and other
liquid media were combined with appropriate quantities of an
aqueous solution containing 100~3./ml, of 1-iodo-2-propynyl
~-butyl carbamate (Polyphase, a trademark of Troy Chemi~al
Corp.~ in screw capped tu~es. The tubes were inoculated with
an active culture of Carteria sp., Chlamydomonas sp.,
Eudorina sp., Haematococcus sp., Pandorina sp., Volvox sp.,
or other algal species which would grow well on the medium.
Controls were prepared by co~bining the media wi~h H20 and
inoculated with an algal species. For example, the following
mixtures were prepared and inoculated wlkh Prorocentrum and
challenged with Polyphase.
TABLE 1
Preparation of Test Solutions.
* Erdscheibers H2O Polyphase** Inoculum Concentration
Solution (ml.) (ml.) (l-iodo-2-(ml.) Pol~phase
propynyl-N-(~3./ml~)
butyl-
carbamate)
Solution (ml )
. . __
7.00 0.00 o.oo 3.00 0.00
6.50 o.oo 0.50 3.00 5.00
6.00 0.00 1.00 3.00 10.0
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
3.00 0.00 4.00 3.no 40.0
~.50 0.00 4.50 3.00 45.0
2.00 0.00 5.00 3.~0 50~0 _
2.00 5.00 0.00 3.0~ 0.00
* Standard marine salt used by algalogists as a growth medium.
~* 100 ~. Polyphase per ml.
12
~i~59~
The tubes inoculated with Prorocentrum were ~ncubated
under cool white fluorescent light (40W~ at about 20for 2
days and examined microsoopically. Viahle (motile~ cells were
observed both in control tubes without Polyphase and in the
tubes containing 5 ~'g. o Polyphase per ml. ~la~le cells were
not observed in the tubes containing concentrations of ~0 ~g./ml~
and higher Polyphase.
When species of green algae were employed as the inoculum,
chlorosis ~the bleaching or disappearance of the green color~
could often be employed to detect the toxic level of PolYphase
to the algae, Either micxoscopic examination, chlorosis or
both were employed to study these species. These techniques
were employed with all unicellular and~or microscopic algal
species tested, the test results being shown in Table 2 below.
Example 8
Solutions were prepared as described in Example 7, except
that the final volume in each instance without the inoculum
was ten milliliters. The inoculum consisted of filaments of
algal species, such as Spiro~yra and Scytonema, cut piec~s
20 ¦ of large marine a}gae, such as Ulva, and marble size colonies
of species, such as Nostoc. The small amount of water adhering
to the filaments, pieces and colonies was ignored, Chlorosis
was employed to detect khe algacidal activity of Polyphase.
Both fresh-water and marine species were tested as
described in Examples 7 and 8 summarized in Table 2. It was
shown that Pol~phase demonstrated excellent algacidal activity
against both groups of organisms. Marine algae are separated
in Table 3. Polyphase and analogs of Polyphase could have
applications in the treatment of marine al~al b1oomsr such
as "red tides."
Since Polyphase is soluble in water ~o the extent of about _
175 ppm. (~g./ml.) and analogs of varying solubilities in water
~;~59~
are available, it was concluded that saturated solutions in
water would contain sufficient biocide to control the hardiest
algae.
TABLE 2
Toxicity of 3-iodo-propynyl-n-butyl carbamate ~Pol~phase~
Towards_Alqae in Aqueous Media
Toxic Level of
Or~anism PolyE~ase-~ ml.3
Division Chlorophyta ~Green Algae) S - 40
Class Chloroph~cea.e
Order Volvocales 10 - 20
1. Carteria sp. 10
2. Chlamydomonas rhinhardtii 15
3. Eudorina sp. 20
4. Haematoccus sp. 10
5. Pandorina sp. 20
6. Plat~monas sp. 10
7. Volvox sp. 2a
Order Ulotrichales
8. Ulothrix sp. 40
Order Ulvales
9. Ul~la sp. 30
Order Oedogoniales
lQ. Oedogonium sp. 15
Order Cladophorales
~ 11. Cladophora sp. 25
12. Pithophora sp. 25
: Order Chlorococcales . 5 - 23
13. Ankistrodesm~s sp. 10
¦~ To~ic Level of
Organism ~L~S~;2f:; ~ol~phase ~ /ml . )
14. Chlorella pyreniodosa 2Q
15. Hydrodi~yon sp. 5
16, Protosiphon sp. lQ
17. Scenedesmus spp 5
Order Zygnematales 15 - 3Q
18. Closterium sp. 30
19. ~ougeotia sp~ 20
20, Spiro~yra sp. 15
Class Charoph~ceae
Order Charales
21. Nitella sp.
Division ChrysoPhyta (Yellow Green Algae) 15 - 35
Class Xanthoph~ceae
Order Heterotrichales
22. Botrydiopsis sp. 30
23. Tribonema sp. 15
Oxder Heterosiphonales
24. Botrydium sp. 20
25. Vaucheria sp. 10
Class Chrysophyceae
Order Chrysomonadales
26. Synnra sp. 15
Class ~acillariophyceae
Order Pennales
27. Navicula sp. 35
Division Euglenophyta
Order Eugleniales
28. Astasia sp. 15 .
29. Euglena gracilis l~reen form) 35
30. Phacus sp. 15
31. Trachelomonas sp. 5
Division Pyrrophyta (Desmokontes and
Dinoflagellates)
Class _e mokontae
3. Order Desmonadales
32. Prorocentrum sp~ 10
1~
I Toxia Level of
Organism ~59~6 Poly~ha-se (~1,/ml~?
Class Dinophyceae
Order Perdini~les
33. Peridinium sp. 15
Division Rho~ophyta (Red Algae)
Subclass Bangiodeae
34. Porphyridium sp. 15
Subclass Florideae
35. Batrachospermun sp. 35
Uncertain Systematic Position
36. Khodochorton sp. 30
~ncertain Systematic Position
Class Cryptophyceae
Order Cryptomonodales
37. Chilomonas sp. 25
Division Cyanophyta (Cyanobacteria)
Class Myxophyceae (Myxobacteria~
: lBlue Green Algae (Bacteria)] 15 - 75
Order Chroococcales 40 - 60
38. Anacystis sp. 60
39. Gloeocapsa sp. 40
40~ Merismopedia sp. 55 ~ .
~rder Oscillatoriales l5 - 75
41. Anabaena sp. 35
42. Cyli~drospermum sp. 15
43. Gloeotrichia sp. ~ --- 40
44. Lyngbya sp. 65
45. Nostoc sp. 55 O
46. Oscillatoria sp. 60
47. Phormidium sp. 75
48. Scytonema sp. 60
49. Spirulina sp. 25
50~ Tolypothrix sp. 40 '
16
59~2~-` .
TABLE 3
Toxic Level of
Organism Polyphase (~./ml.)
Division Chlorophyta (Green Algae)
Order Volvocales
l. Platymonas sp. 20
Order Ulvales
. 2. Ulva sp. 30
Division Chr~sophyta (Yellow Green Algae~
: Order Chrysomonadales
3. Synura sp. 15.
Division P~rrophyta
Order Desmonadales
4. Prorocentrum sp. 10
Division Rhodophyta
Order Bangiales
lS 5. Posphridium sp. 15
. Uncertain Systematic Position .
6. Rhodochorton sp. 30
Division Cyanobacteria
7. Spirulina 25
Division Phaeophyta (Brown Algae)
8. Fuscus 65
S~6-
Example 5
Schleicher and Schnell Analytical Paper (#740-E, ~"
Diam. - 12 mm~ discs were dipped ~nto 1% - 40% solutions of
the compound(s) tested which were dissolved in acetone. A 'T'
pin pushed through the center of each disc was employed to
hold it during dipping and subsequent drying, The treated
discs were air-dr~ed by holding them on the ~T' pins pushed
into corkboard.
Protease agar plates were prep~red and seeded with a "lawn"
of hlorella pyrenoidosa from an axenic culture. Treated air
dried discs, containing Polyphase or its analogs as identified
in Table 4 were placed in the center of each plate. The petri
dishes were incubated under a cool whi~e fluorescent light (40W)
at am~ient temp. (about 20U) until algal growth was obtained
(about 6 days). The size of the zone of inhibition was
measured from the edge of the disc to the edge of the algal
growth (in mm.). The data obtained in reported in Table 5
below.
It was observed that the urethanes of l-iodo substituted
alkynes, the compounds of the invention, demonstrated high
toxicity towards Chlorella pyrenoidosa. Thus it ~as been shown
that these compounds including Polyphase exhibit toxicity
towards a large range of algal species in every major division
from a wide range of habitats and occupying a wide range of
niches in the known classes of algae.
I ..
l 18
- 1~59~i2~6~
TABLE 4
Che~ical Structures of Compounds Tested Includin~ P~ly~hase
Compound
** Polyphase
I-c-c-cH2 - o - c-NH-cH2cH2cH2cH3
I-C~C-CH2-0-C-NH-Butyl(n)
B .
I-c-c-cH2-cH2-o-c-NH--cx3
,~ C O -NH-C-O-CH2-C_C-I
I-C~C-CH2-0 t~-NH-CH2CH3
E O
\ -NH-C-O-CH2-C-C-I `
I-C-C-CH2-0-~-NH-Hexyl(n)
I-C~-C-C'.2- 0 ~ `.i;i-Oc
~H Cl ~ -NH-c-o-cH
*I ~ -NH-C-O-CH2-C-C-I
5~3~ `; .
[I ~C-CH2-0-C-NH-]2-[80% 2,4- and 20~ 2,6-tolYl~
I-CSC-FH2-0-C-NH- <~3-CH~-NH-C-o-CEr2-C$-]
*L O
[I-C-C-CH2-0-C-NH-]2 [2,4-tolyl~
*M ~ CH2-NH-C-O-CH2-C_C-I
* These compounds are new compositions of matter and are
: claimed herein as such.
** Tradename - Troy Chemical Corporation
59~ i
TAsLE 5
Sensitivity of Chlorella pyrenoidosa to Com~ounds Tested
Includina PQ1YPhaSe
.. . __
Sample tCompound) Solvent Concentration Inhibitory Zone (mm.)
Polyphase Acetone 1.0 10
Polyphase " 2.0 11
Polyphase " 5.0 12
Polyphase " 40.0 13
A " 1.0 10
B " 1.0 14
C " 1.0 ` 9
D " 1.0 14
E " 0.5 10
F " 1.0 8
G " 1.0 7
*H " 1,0 13
" 1.0 9
*I " 1.0 20
*J " 1.0 6 .
*K " 1.0 5
*L " 1.0 5
*M " 1.0 42
- ~-
1~36
Example 10
Formulations of latex paint~ oil alkyd paint, and oil
based st~In (details of formulations shown herein after in
Ta~les 7, 8 and 9) were prepared from commercially available
materials. Polyphase was added at levels of 2,4 and 6
lbs.flOO gallons. Filter paper sheets were coated or treated
with the formulations and control containing no Pol~hase,dried an d
discs 12 mm~ in diameter cut from the sheets. These discs
were placed on plates containing proteose agar which had been
seeded with a lawn of Chlorella pyrenoidosa and incubated as
described in Example 9. Zones of inhibition were measured
as described in Example 9. The test results are recorded in
Table 6.
It was observed that a small zone of inhibition was
obtained on controls which did not contain Polyphase. This
anomaly is caused by the solvents and biocides which are
normally added to paints and other coatings to protect them
from bacterial growth. However, after applica~ion 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 prolonged protection of Polyphase use.
5~ 6
T~BLE 6
Algal Protect-Ion of Coatings ContaXnin~ Poly~hase
S~mple Polyphase Zone of
No-. (l~s.!100. gal.)Inhibition (mm.)
Alkyds
(oil alkyd paint)
la. (.control). ~ 4
1~. 2 6
lc. 4 10
ld. 6 13
Stains
(oil based stain)
2a. (control~ O 6
2b. 2 8
2c. 4 10
2d. 6 13
Latices
(alkyd latex paintl
3a~ (.control~ O 0
3b. 6 4
TA~LE 7
Qil ~lkyd Paint (l-a, b, c & dl Composltion
Dry Wt.
(.non-volatile)
Material lbs. ~ls. Clbs~)
. , ~
Heat-bodied
linseed oil 225 28.0 225
Alkali-refined
linseed oll 75 10.0 75
Beo~osol, P296-60
CTrademark,
Reichhold Chem.) 75 10.0 45
Mineral Spirits 195 30.0 : --
Cobalt drier 6% 2.5 0.3 --
Calcium drier 6% 5 a . 6 --
Anti-skinning agent 2 0.2
Non-chalking
titanium dioxide 300 8.8 300
Talc 3Q0 12.6 300
Suspending agent 5 _ 0.3 5
1184.510Ø8 950
l-a No Polyphase ----- ---
l-b 2 lbs/100 gal. ~ - 0.8 lbs. active PP/950 lbs. dry wt~
l-c 4 I- _______ 1.6 lbs. "
l-d 6 " ------- 2.4 lbs. "
24
Il ~25~6~
TABLE 8
Oil Based Stain (2~ a,b,c, & d)
White Alk~d Oil Stain
Mat~r~al lbs. Gal. Dry W~.~lbs.
Titanium dioxide 50 1.46 50
Suspension agent 3 0.3 3
Bec.kosol P296-60
~Trademark
Reichhold Chem.2 141 18.2 84.6
Raw linseed oil8510.95 85
Mineral spirits45168.85
Cobalt drier 6~1.10.12
~alcium drier 6% 2.8 0.35
Anti-skimming agent 1 0;13
734.9106.36 222.6
2,a No Polyphase -------
2,b 2 lbs. PP/100 gal. ---- 0.8 lbs. PP/223 lbs, dry
2,c 4 " ---- 1.6 lbs. PP/224
2,d 6 " . ---- 2.4 lbs. PP/225
5~ 6` -``
TABLE 9
Acrylic Latex Paint (3 - a and bl
Composition
Material lbs.yals. Dry wt./lbs.
Water 354 42.5
Cellosize QP-15~00
(Trade~ark Union
Carbide2 3.750,3 3,8
Tamol 731
CTrademark Rohm ~
Haas) lO.Q1,1 2~5
Lecithin 2.00Q.2 2~0.
Ethylene glycol 15~01.6
Carbitol (Trademark
Union Carbide) 10.~1~2
Defoamer~999 _ .
-(Tradename, Troy
Chemical Corp.) 2.001.3
Titanium dioxide 275 8.1 275
Talc 85.Q3.6 85
~ica 50~02.1 50
Rhoplex, AC35
(Trademark, Rohm &
Haas) 364 40.3 167 _
1170.75lQ2.3 585
3,a No Polyphase
3,b 6#PP*/10.0 gal. ---~ - 2.4 lbs. PP~585 # dr~
*Poly~hase
26
~;259~.
Example ll
Polyphase was added at levels between 0~1 and 1,0%
~approximately equal to between 1 and 10 lbs~ n gallonsl to
a roof coating material~ The roof coating material called
Traycote (trademark) (the composition of w~ich is shown in
Table 10, with and without Polyphase) was caated onto standard
1" x 3" glass microscope slides, allowed to dry for 2 days, and
leached with distilled water for 3 days. The coatinqs were
cut from the slides using a razor blade and plated onto proteose
agar covered with a lawn of Chlorella pyrenoidosa cells. The
plates were incubated under cool white fluorescent light (40W)
for 2 days and examined. A green "lawn" of algal cells was
observed growing to the edge of the control coating without
Polyphase. The observation included growth under the surface
of the control coating (as viewed in reflec~ed light); however,
no growth whatever was observed under coa~ing samples cont~ining
greater than or equal to 0.4% Polyphase. In addition, zones
of inhibition between 0.5 and 4.0 mm. wide were observed
around the protected coatings.
9G~
TABLE 10
Com~Fosition of Roof Coatin~Material
Traycote (Tradem~rk - Traycote, Inc~ of Col~m~iap 5,C,~ is a
protectiye ro~fing coating ha~ing the following c~mposition
(.lbs./l~0 gallons);
Mater~al Lbs./10~ gal.
Ethylene ~lycol 23,3
Natrasol 25QHR (Trademark,
Hercules ~nc.) 4.0
Water 197.8
Nopco NXZ (Trademark,
Diamond Shamrock) 93.2
Tamol 250 (Trademark,
Rohm ~ Haas~ 4-7
Calcium Carbonate 93.2
Titanium dioxide 65.3
Talc 279.5
Acrylic Latex Resin442.6
Aqueous ~mmonia (26 Baume~ 1.9
*Troysan 174 (Trademark -
Troy Chemical Corp.)2.5
* Troysan 174 is a volatile bactericide employed for "in-can"
preservation.
;~
~5~
Exam~le 12
A commerci~lly ay~ hle rubber~zed asphalt roof coating
materi~l haYing t~e composition shown in Table 1~ was combined
with Troysan ~rrademark of Troy Chemical Corp.~ Polyphase AF-l
foxmulation. The ~ctive Polyphase con~ent of this formulation
is 40 percen~ and the remaining ine~t ingredients are solvents.
The mxxture contained ~.0, Q,5, 1.0, 1.5 ~nd 2~0 percent
Polyphase AF-l and 0~0, 0.2, 0.4, 0.6 and 0,8 percent active
Polyphase by weight.
These samples were applied to glass slides with a wooden
tongue depressor and dried or three days. They were removed
from the slides with a razor blade and placed, smooth surface
down, on the surface of proteose agar plates seeded with
Chlorella pyrenoidosa. The samples were incubated for 7 days
under 40W white fluorescent light at ambient temperature
(about 22~).
Chlorella pyrenoidosa grew up to and under ~he surface
of the control sample not containing Polyphase. Its growth
was inhibited and it ~ailed to grow under the surface of samples
containing Polyphase at all concentration levels. Zones of
inhibition were observed at G.6 and 0.8 percent active
Polyphase.
TABLE 11
Composition of Rubberized Asphalt
Roo~ Coatinq
Material
Asphalt 50.
Attagel(Tradename Engelhaxdt
Industries) (thickenerl 15
~raton rubber (Trademark - Shell Oil) ~5
Lecithin and surfactants ~l
Aromatic process oil ~ 5
High flash naphtha 24-25
-
59~ `
Example 13
Solutions of Polyphase in ethanol were prepared at levels
of 0.0, O.lr 0,-2, 0.4, 0.6, 0,8 and 1.0 grams per 100 ml.
The solutions were transferred to an "Omit" air dispenser
a~d sprayed onto the surface of proteose agar in petri dishes.
The proteose agar had previously been inoculated with
Chlorella pyrenoidosa which would grow producing a "lawn" of
cells upon the surface. The petri dishes were incubated under
40W cool white fluorescent light for one week at ambient
temperature ~about 22~).
Chlorella pyrenoidosa grew covering the surface of the
agar sprayed with ethanol which did not contain Polyphase.
Some spotty growth occurred at 0.1 and 0.2 grams/100 ml. levels
of Polyphase. No growth at all was observed on plates sprayed
with 0.4g per 100 ml. and higher levels of Polyphase.
