U.S. patent number 3,575,123 [Application Number 04/838,269] was granted by the patent office on 1971-04-13 for marine structure coated with an acrylic insoluble water-swellable polymer.
This patent grant is currently assigned to National Patent Development Corporation. Invention is credited to Francis E. Gould, Thomas H. Shepherd.
United States Patent |
3,575,123 |
Shepherd , et al. |
April 13, 1971 |
MARINE STRUCTURE COATED WITH AN ACRYLIC INSOLUBLE WATER-SWELLABLE
POLYMER
Abstract
Hydrophilic acrylic resins are applied to the underwater portion
of boats to reduce the drag on moving the boats through water. The
resins are useful in antifoulant compositions.
Inventors: |
Shepherd; Thomas H. (Hopewell,
NJ), Gould; Francis E. (Princeton, NJ) |
Assignee: |
National Patent Development
Corporation (New York, NY)
|
Family
ID: |
27416030 |
Appl.
No.: |
04/838,269 |
Filed: |
July 1, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
654044 |
Jul 5, 1967 |
|
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|
|
650259 |
Jun 30, 1967 |
|
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|
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567856 |
Jul 26, 1966 |
3520949 |
Jul 21, 1970 |
|
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Current U.S.
Class: |
114/67R;
106/18.31; 114/20.1; 428/907; 106/18.35; 416/241A; 416/224;
138/145 |
Current CPC
Class: |
C08K
5/0058 (20130101); C09D 4/00 (20130101); C08K
5/56 (20130101); C08F 20/62 (20130101); C09D
5/1668 (20130101); C09D 4/00 (20130101); C08F
220/26 (20130101); Y02T 70/10 (20130101); Y10S
428/907 (20130101); Y02T 70/121 (20130101); Y02T
70/123 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/81 (20060101); A61K
8/19 (20060101); A61K 8/24 (20060101); C09D
4/00 (20060101); C09D 5/16 (20060101); C08F
20/00 (20060101); C08F 20/62 (20060101); C08K
5/00 (20060101); C08K 5/56 (20060101); C03c
017/00 () |
Field of
Search: |
;260/41 ;106/15 (AF)/
;424/81 ;117/161,(P),(N),148,130,138.8 (A)/ ;117/124 (C)/ ;117/123
(D)/ ;106/15 ;260/29.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Liebman; Morris
Assistant Examiner: Morris; T.
Parent Case Text
The present application is a continuation-in-part of application
Ser. No. 654,044 filed Jul. 5, 1967 and application Ser. No.
650,259, filed Jun. 30, 1967 now abandoned and application Ser. No.
567,856 filed Jul. 26, 1966 now U.S. Pat. No. 3,520,949 issued Jul.
21, 1970.
Claims
I claim:
1. A marine structure which is a watercraft having an adherent
coating consisting essentially of either (1) a water-insoluble
hydrophilic acrylic polymer which is swellable to an extent of at
least 20 percent in water wherein the coating is sufficient to
reduce the drag of the watercraft when in water or (2) said
hydrophilic acrylic polymer having encapsulated therein at least
one member of the group consisting of antifouling agents and
pigment.
2. A marine structure having a coating film consisting essentially
of a water-insoluble hydrophilic acrylic resin which is swellable
to an extent of at least 20 percent in water and containing in the
coating film an antifouling agent.
3. A marine structure according to claim 1 wherein the coating
polymer is a polymer of a hydrophilic hydroxyalkyl or
hydroxyalkoxyalkyl acrylate or methacrylate or acrylamide, alkyl
acrylamide, methacrylamide, alkyl methacrylamide or diacetone
acrylamide.
4. A marine structure according to claim 3 wherein the coating
polymer is a polymer of hydroxyethyl acrylate, hydroxypropyl
acrylate, hydroxyethyl methacrylate or hydroxypropyl
methacrylate.
5. A marine structure according to claim 4 wherein the polymer is a
linear polymer.
6. A marine structure according to claim 5 wherein the polymer is a
homopolymer.
7. A marine structure according to claim 4 wherein the polymer is a
copolymer of said acrylate or methacrylate with a minor amount up
to 20 percent of a cross-linking agent.
8. A marine structure according to claim 2 wherein the antifouling
agent is an organolead compound.
9. A marine structure according to claim 2 wherein the coating
polymer is a polymer of hydroxyethyl acrylate, hydroxypropyl
acrylate, hydroxyethyl methacrylate or hydroxypropyl
methacrylate.
10. A method of increasing the speed of watercraft comprising
moving said watercraft through water while having on the watercraft
below the waterline the coating set forth in claim 1.
11. A method according to claim 10 wherein the coating polymer is a
polymer of a hydrophilic hydroxyalkyl or hydroxyalkoxyalkyl
acrylate or methacrylate or acrylamide, alkyl acrylamide,
methacrylamide, alkyl methacrylamide or diacetone acrylamide.
12. A method according to claim 11 wherein the coating is a linear
polymer.
13. A method according to claim 11 wherein the coating is a
homopolymer of hydroxyethyl acrylate, hydroxyethyl methacrylate,
hydroxypropyl acrylate or hydroxypropyl methacrylate.
14. A method providing continuous availability of an antifouling
agent comprising placing in water a marine structure having the
coating composition of claim 2 applied thereto, the swelling of the
hydrophilic acrylic resin in water rendering the antifouling agent
readily available for its intended purpose.
15. A marine structure according to claim 2 wherein the
swellability of the polymer is not over 120 percent.
16. A marine structure according to claim 1, wherein the
swellability of the polymer is not over 120 percent.
17. A marine structure according to claim 2 including a
pigment.
18. A marine structure which is a watercraft having an adherent
coating film of a water-insoluble hydrophilic acrylic resin which
is swellable to an extent of at least 20 percent in water wherein
the film is sufficient to reduce the drag of the watercraft when in
water,
19. A marine structure according to claim 18 wherein the film has a
thickness of 0.3 to 5 mils and the resin is a polymer of
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl
acrylate or hydroxypropyl methacrylate.
20. A marine structure according to claim 19 wherein the film
consists essentially of said polymer having releasably encapsulated
therein an organometallic antifoulant, said film being
characterized by the fact that said antifoulant is still effective
after at least 6 months of use of the marine structure in
water.
21. A marine structure according to claim 19 wherein the polymer is
a linear polymer.
22. A marine structure according to claim 1 wherein the adherent
coating consists essentially of (1) and the hydrophilic acrylic
polymer is linear polymer of hydroxyethyl acrylate, hydroxyethyl
methadcrylate, hydroxypropyl acrylate or hydroxypropyl
methacrylate.
Description
The present invention relates to the use of water-insoluble
hydrophilic acrylic resins.
It is an object of the present invention to reduce the resistance
developed on moving watercraft through water.
Another object is to develop novel antifoulant compositions.
A further object is to provide watercraft and underwater static
structures with an improved antifoulant coating.
Still further objects and the entire scope of applicability of the
present invention will become apparent from the detailed
description given hereinafter; it should be understood, however,
that the detailed description and specific examples, while
indicating preferred embodiment of the invention, are given by way
of illustration only, since various changes and modifications
within the spirit and scope of the invention will become apparent
to those skilled in the art from this detailed description.
It has now been found that these objects can be attained by the use
of water-insoluble hydrophilic acrylate and methacrylate polymers
(hydrophilic acrylic resins) as coatings at least for the
underwater portion of watercraft and underwater static
structures.
The term marine coating is used in the present application and
claims to cover both coatings for watercraft and underwater static
structures. The term watercraft includes movable boats of all
kinds, including but not limited to sailboats, yachts, inboard and
outboard motor boats, rowboats, motor launches, canoes, kayaks,
water skis, surfboards, ocean liners, tugboats, tankers and other
cargo ships, submarines both of the atomic and conventional
varieties, aircraft carriers, destroyers, etc. Underwater static
structures include but are not limited to wharves, piers,
permanently moored watercraft, pilings, bridge substructures, etc.
The underwater surface can be made of wood, metal, plastic,
fiberglass, concrete or other material.
The antifoulant compositions are useful as marine coatings to
render the structure (moving or static) resistant to fouling by
marine organisms such as barnacles, algae, slime, acorn-shells
(Balanidae), goose mussels (Lepadoids), tube-worms, sea moss,
oysters, brozoans, tunicates, etc.
It is critical that the hydrophilic acrylic resins be water
insoluble since otherwise they cannot be permanently applied to the
underwater surface. The hydrophilic acrylic resin should be capable
of absorbing at least 20 percent of its weight of water and
preferably does not absorb more than about 120 percent of its
weight of water. It has been found that linear polymers which are
usually alcohol soluble are preferable although cross-linked
polymers can also be used providing they are applied while still in
a workable condition. These coatings effectively reduce the "drag"
or resistance developed on moving the coated surface through
water.
If it is desired to employ the coating solely to effect friction
reduction on racing or pleasure craft, for example, which do not
remain static in water for extended periods, it is not necessary to
incorporate an antifouling agent.
While not being bound by any theory it is believed that the
mechanism of friction reduction is twofold. The coating absorbs a
substantial percentage of water and the water-swollen coating
exhibits a low contact angle with the water. In addition, the
swollen coatings are soft, (particularly if a linear polymer is
employed) and the softness can provide a hydrodynamic damping
effect and reduce turbulence of the flow.
Preferably the hydrophilic monomer employed is a hydroxy lower
alkyl acrylate or methacrylate or hydroxy lower alkoxy lower alkyl
acrylate or methacrylate, e.g. 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, diethylene glycol monoacrylate,
diethylene glycol monomethacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,
3-hydroxypropyl methacrylate, dipropylene glycol monomethacrylate
and dipropylene glycol monoacrylate. The most preferred monomers
are the hydroxyalkyl acrylates and methacrylates, particularly
2-hydroxyethyl methacrylate.
There can also be employed polymers of acrylamide, methacrylamide,
N-alkyl substituted acrylamide and methacrylamide such as
N-propylacrylamide, N-isopropyl acrylamide, N-isopropyl
methacrylamide, N-propyl methacrylamide, N-butyl acrylamide,
N-methyl acrylamide and N-methyl methacrylamide, diacetone
acrylamide, N-(2-hydroxyethyl) acrylamide and N-(2-hydroxyethyl)
methacrylamide.
Likewise, there can be employed copolymers of these monomers with
each other or with other copolymerizable monomers. In fact, if the
hydrophilic monomer gives a product which is water soluble, e.g.
polyacrylamide, it is necessary to employ a copolymerizable monomer
to render it only water swellable rather than water soluble. The
copolymerizable monomer can be used in an amount of 0.05 to 50
percent. Preferably, comonomers include methyl acrylate, ethyl
acrylate, isopropyl acrylate, propyl acrylate, butyl acrylate, sec.
butyl acrylate, pentyl acrylate, 2-ethylhexyl acrylate, methyl
methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl
methacrylate, butyl methacrylate, sec. butyl methacrylate, pentyl
methacrylate, lower alkoxyethyl acrylates and methacrylates, e.g.
methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl
acrylate and ethoxyethyl methacrylate, triethylene glycol acrylate,
triethylene glycol methacrylate, glycerol monoacrylate and glycerol
monomethacrylate.
There can also be used unsaturated amines, p -aminostyrene,
o-aminostyrene, 2-amino- 4-vinyltoluene, alkylamino alkyl acrylates
and methacrylates, e.g. diethylaminoethyl acrylate,
diethylaminoethyl methacrylate, dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, t-butylaminoethyl acrylate,
t-butylaminoethyl methacrylate, piperidinoethyl acrylate,
piperidinoethyl methacrylate, morpholinoethyl acrylate,
morpholinoethyl methacrylate, 2-vinylpyridine, 3-vinyl pyridine,
4-vinyl pyridine, 2-ethyl-5-vinylpyridine, dimethylamino propyl
acrylate, dimethylamino propyl methacrylate, dipropylaminoethyl
acrylate, dipropylaminoethyl methacrylate, di-n-butylaminoethyl
acrylate, di-n-butyl aminoethyl methacrylate, di-sec.
butylaminoethyl acrylate, di-sec. methacrylate, dimethylaminoethyl
vinyl ether, diethylaminoethyl vinyl ether, diethyl-aminoethyl
vinyl sulfide, aminoethyl vinyl ether, aminoethyl vinyl sulfide,
monomethylaminoethyl vinyl sulfide, monomethylaminoethyl vinyl
ether, N-(gamma-monomethylamino) propyl acrylamide,
N-(beta-monomethylamino) ethyl acrylamide, N-(beta-monomethylamino)
ethyl methacrylamide, 10-aminodecyl vinyl ether, 8-aminoctyl vinyl
ether, 5-aminopentyl vinyl ether, 3-aminopropyl vinyl ether,
4-aminobutyl vinyl ether, 2-aminobutyl vinyl ether,
monoethylaminoethyl methacrylate, N-(3,5,5 -trimethylhexyl)
aminoethyl vinyl ether, N-cyclohexylaminoethyl vinyl ether,
2-(1,1,3,3 -tetramethylbutylamino) ethyl methacrylate,
N-t-butylamino-ethyl vinyl ether, N-methylamino-ethyl vinyl ether,
N2-ethylhexylaminoethyl vinyl ether, N-t-butylaminoethyl vinyl
ether, N-t-octylaminoethyl vinyl ether, 2-pyrrolidinoethyl
acrylate, 2-pyrrolidinoethyl methacrylate,
3-(dimethylaminoethyl)-2-hydroxypropyl acrylate,
3-(dimethylaminoethyl)-2-hydroxypropyl methacrylate, 2-aminoethyl
acrylate, 2-aminoethyl methacrylate. The presently preferred amino
compounds are alkylaminoethyl acrylates and methacrylates, most
preferably t-butyl aminoethyl methacrylate.
While linear polymers (including both homo- and copolymers) are
preferred when the hydrophilic resins are used only to reduce the
resistance on moving a coated watercraft surface through water
there can also be employed cross-linked hydrophilic copolymers.
Such cross-linked copolymers are frequently advantageously employed
when antifouling agents are included in the composition to insure
more permanent adherence to the underwater structure.
Preferably, the cross-linking agent is present in an amount of 0.1
to 2.5 percent, most preferably not over 2.0 percent, although from
0.05 to 15 percent, or even 20 percent, of cross-linking agents can
be used. Of course, care should be taken that cross-linking agents
are not used in an amount which renders the product incapable of
absorbing at least 20 percent of water.
Typical examples of cross-linking agents include ethylene glycol
diacrylate, ethylene glycol dimethacrylate, 1,2-butylene
dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene
dimethacrylate, propylene glycol diacrylate, propylene glycol
dimethacrylate, diethylene glycol dimethacrylate, dipropylene
glycol dimethacrylate, diethylene glycol diacrylate, dipropylene
glycol diacrylate, divinyl benzene, divinyl toluene, diallyl
tartrate, allyl pyruvate, allyl maleate, divinyl tartrate, triallyl
malamine, N,N'-methylene bis-acrylamide, glycerine trimethacrylate,
diallyl maleate, divinyl ether, diallyl monoethylene glycol
citrate, ethylene glycol vinyl allyl citrate, allyl vinyl maleate,
diallyl itaconate, ethylene glycol diester of itaconic acid,
divinyl sulfone, hexahydro- 1,3,5-triacryltriazine, triallyl
phosphite, diallyl ester of benzene phosphonic acid, polyester of
maleic anhydride with triethylene glycol, polyallyl glucose, e.g.
triallyl glucose, polyallyl sucrose, e.g. pentaallyl sucrose,
sucrose diacrylate, glucose dimethacrylate, pentaerythritol
tetraacrylate, sorbitol dimethacrylate, diallyl aconitate, divinyl
citraconate, diallyl fumarate.
There can be included ethylenically unsaturated acids or salts
thereof such as acrylic acid, cinnamic acid, carotonic acid,
methacrylic acid, itaconic acid, aconitic acid, maleic acid,
fumaric acid, mesaconic acid and citraconic acid. Also, as
previously indicated there can be used partial esters such as mono
2-hydroxypropyl itaconate, mono 2-hydroxyethyl itaconate, mono
2-hydroxyethyl citraconate, mono 2-hydroxypropyl aconitate, mono
2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, monomethyl
itaconate, monoethyl itaconate, mono Methyl Cellosolve ester of
itaconic acid (Methyl Cellosolve is the monomethyl ether of
diethylene glycol), Mono Methyl Cellosolve ester of maleic
acid.
The polymers can be prepared as casting syrups, e.g. as prepared in
applicants' parent application, as aqueous dispersions, by aqueous
suspension polymerization or as solutions in organic solvents such
as ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl
alcohol, formamide, dimethyl sulfoxide or other appropriate
solvent.
Polymerization can be carried out at 20.degree. to 150.degree. C.,
frequently 35.degree. or 40.degree. C. to 90.degree. C. and can be
completed after applying as a marine coating. The polymerization
can be carried out employing a free radical catalyst in the range
of 0.05 to 1 percent of the polymerizable monomers. Typical
catalysts include t -butyl peroctoate, benzoyl peroxide, isopropyl
percarbonate, 2, 4-dichlorobenzoyl peroxide, methyl ethyl ketone
peroxide, cumene hydroperoxide and dicumyl peroxide. Irradiation,
e.g. by ultraviolet light or gamma rays, also can be employed to
catalyze the polymerization.
In addition to the examples of polymerzation set forth in the
parent applications there can be employed polymers prepared, for
example, as in examples A--G below. Unless otherwise indicated in
the specification and claims all parts and percentages are by
weight.
EXAMPLE A
One thousand grams of silicone oil (polydimethyl siloxane, 100
grams of 2-hydroxyethyl methacrylate and 0.33 grams of isopropyl
percarbonate were charged to a flask equipped with an agitator and
heating mantle. The flask was rapidly agitated at 100.degree. C.
under a nitrogen atmosphere. After 15 minutes the slurry was
filtered not to isolate the polymer. The polymer powder was
reslurried in b 300 ml. of xylene, filtered and dried. A 98 percent
yield of 2 to 5-micron particle size alcohol soluble powder was
obtained.
EXAMPLE B
Example A was repeated using xylene in place of the silicone oil
and employing 300 grams of 2-hydroxyethyl methacrylate and the
quantity of isopropyl percarbonate increased to 0.99 gram. An 85
percent yield of polymer beads was obtained.
EXAMPLE C
The procedure of example A was repeated replacing the
2-hydroxyethyl methacrylate by 100 grams of 2-hydroxypropyl
methacrylate to produce a thermoplastic solvent soluble hydrophilic
finely divided bead polymer.
EXAMPLE D
Eight hundred grams of ethylene glycol monomethyl ether, 180 grams
of 2-hydroxyethyl methacrylate, 20 grams of acrylic acid and 2
grams of t-butyl peroctoate were charged into a flask. The solution
was heated and stirred under a carbon dioxide atmosphere for 6
hours. The product of this example while thermoplastic and solvent
soluble has the capability of curing to cross-linked solvent
insoluble polymer by further heating, particularly if additional
catalyst is added.
EXAMPLE E
A casting syrup was made from 100 parts of 2-hydroxyethyl acrylate,
0.2 parts of ethylene glycol dimethacrylate and 0.4 parts t-butyl
peroctoate.
EXAMPLE F
Ten kilograms of 2-hydroxyethyl methacrylate, 150 grams of ethylene
glycol dimethacrylate and 4.0 grams of t-butyl peroctoate were
heated with stirring for 50 minutes at 95.degree. C. to yield a
syrup having a viscosity of 420 centipoises at 30.degree. C. To
this syrup was added 20 grams of ethylene glycol dimethacrylate and
20 grams of t-butyl peroctoate and the syrup stirred until a
homogeneous solution was obtained.
Similar results were obtained when replacing the ethylene glycol
dimethacrylate by divinyl benzene.
EXAMPLE G
Seventy-five liters of ethanol, 1 kilogram of t-butylaminoethyl
methacrylate, 1.5 kilograms of N-isopropyl acrylamide and 22.5
kilograms of hydroxyethyl methacrylate (containing 0.3 percent of
ethylene glycol dimethacrylate) together with 100 grams of t-butyl
peroctoate were charged into a vessel and the solution heated at
85.degree. C. for 7 hours to effect polymerization to a 90 percent
conversion level.
There can be incorporated with the hydrophilic polymers of the
invention to provide coatings to prevent fouling by marine
organisms any of the conventional inorganic or organic antifoulants
including cuprous oxide, copper powder, mercuric oxide, cuprous
oxide-mercuric oxide (e.g. 3:1 mercurous chloride), organotin
compounds including triphenyltin chloride, triphenyltin bromide,
tri p-cresyltin chloride, triethyltin chloride, tributyltin
chloride, phenyl diethyltin fluoride, tri (p-chlorophenyltin)
chloride, tri (m-chlorophenyltin) chloride, dibutyl ethyltin
bromide, dibutyloctyltin bromide, tricyclohexyltin chloride,
triethyltin stearate, tributyltin stearate, triethyltin fluoride,
tributyltin fluoride, diphenyl ethyltin, chloride, diphenyl
ethyltin fluoride, triphenytin hydroxide, triphenyltin thiocyanate,
triphenyltin trichloroacetate, tributyltin acetate, tributyltin
neodecanoate, tributyltin neopentanoate, trioctyltin neodecanoate,
tributyltin oxide, trioctyltin oxide, triphenyltin fluoride,
tripropyltin oleate, tripropytlin neodecanoate, tributyltin
laurate, tributyltin octanoate, tributyltin dimethyl carbomate,
tributyltin resinate, tributyltin chromate, amyldiethyltin
neodecanoate, tributyltin naphthenate tributyltin
isooctylmercaptoacetate, bis-(tributyltin) oxalate,
bis-(tributyltin) malonate, bis-(tributyltin) adipate,
bis-(tributyltin) carbonate; organo lead compounds, e.g. triphenyl
lead acetate, triphenyl lead stearate, triphenyl lead neodecanoate,
triphenyl lead oleate, triphenyl lead chloride, triphenyl lead
laurate, triethyl lead oleate, triethyl lead acetate, triethyl lead
stearate, trimethyl lead stearate, triphenyl lead bromide,
triphenyl lead fluoride, organic compounds including
10,10'-oxybisphenoxazine (SA-546), 1, 2,
3-trichloro-4,6-dinitrobenzene, hexachlorophene, dichlorodiphenyl
trichloroethane (DDT), phenol mercuric acetate,
tetrachloroisophthalonitrile, bis-(n-propylsulfonyl) ethylene,
etc.
The quantity of antifouling agent required in the coating as would
be expected varies with the particular agent used and the severity
of fouling tendency encountered in the particular service to which
the coated vessel or static structure is to be used. In general,
the amount of antifouling agent employed will range from 2 to 50
percent of the resin, although as little as 0.1 percent of
antifoulant can be used based on the resin.
Of course, there can be included in the formulations conventional
pigments and fillers such as titanium dioxide, red lead, bone
black, red iron oxide, talc, aluminum silicate, fullers earth,
pumice, zinc oxide, calcium carbonate, etc.
The coatings of the present invention can be applied to the
surfaces to be subjected to underwater conditions from solution in
organic solvents or from aqueous dispersions. Suitable solvents
include lower aliphatic alcohols such as methanol, ethanol,
propanol and isopropanol or mixtures of these solvents with higher
boiling alcohols such as ethylene glycol, diethylene glycol,
propylene glycol, dipropylene glycol, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, diacetone alcohol,
n-butanol, sec. butanol, isobutanol and mixtures of these solvents
with water.
The coatings of the present invention generally exhibit adequate
adhesion to marine surfaces protected by corrosion resistant
finishes such as epoxy or vinyl-based paints, to previously applied
antifouling finishes and to polyester-fiberglass laminates. Typical
of such finishes are those shown in Sparmann U.S. Pat. No.
2,970,923, Scott U.S. Pat. No. 3,214,279 and Robins U.S. Pat. No.
3,236,793.
The thickness of the coating applied will vary with the particular
formulation employed and the method of application. It can be from
0.1 mil to 250 mils or more in thickness. Usually it will be
between 0.3 mil, and 5 mils. The coatings can be applied to the
marine surface, e.g. boat bottom or hull or wharf piling by any
conventional procedure such as brushing, dipping, spraying, roller
coating etc.
Coating applied at boat yards, marinas or similar locations will
normally be placed in water soon after drying. These coatings if
made from linear, alcohol soluble polymers will remain alcohol
soluble. However, as pointed out supra it is also possible to
provide cured or cross-linked coatings which exhibit improved
mechanical durability. There can be used the peroxide catalysts
referred to supra alone or as part of a two-component catalyst
system which is mixed into the coating solution immediately prior
to application. Alternatively, the coating can be cured by
incorporating a free radical initiator and heating the coated
surface after drying.
Two-component catalyst systems for effecting cure at ambient
conditions, e.g. 20.degree. C., include peroxides of the type
referred to supra together with such amine accelerators as
N,N-dimethylaminoethyl acetate, N,N-dimethyl aniline, N,N-dimethyl
aminoethanol, N,N-dimethyl toluidine. The accelerator can be used
in an amount of 0.05 to 1 part per part of peroxide, e.g. a mixture
of 89 percent benzoyl peroxide and 11 percent dimethylaniline can
be employed.
The invention will be understood best in connection with the
drawings wherein:
FIG. 1 shows a boat having a coating according to the invention;
and
FIG. 2 is a sectional view along the line 2-2 of FIG. 1.
Referring more specifically to the drawings, the boat 2 in water 4
has a coating 6 of hydroxyethyl methacrylate polymer below the
water line 8. If desired, the entire boat can be coated with the
polymer. The thickness of the coating 6 is greatly exaggerated for
illustrative purposes.
EXAMPLE 1
2-hydroxyethyl methacrylate (50 parts) and Ti0.sub.2 (30 parts) are
ground in a pebble mill to a fine powder (Hegeman 7--8). Additional
2-hydroxyethyl methacrylate (50 parts) is added along with ethylene
glycol dimethyacrylate (0.2 part), cobalt naphthenate a
conventional metallic paint dryer or catalyst (0.1 part) and
t-butyl peroctoate (0.4 part). The resulting viscous syrup is
painted onto a wooden boat hull and cured at 20.degree. to
35.degree. C. The resulting protective marine coating is
characterized by its ability to discourage barnacle and algae
growth and corrosion on prolonged underwater exposure.
Additionally, it reduces the drag on moving the coated hull through
water.
EXAMPLE 2
The procedure of example 1 is repeated with the modification that
the coating syrup is cast onto a steel hull and cured at
100.degree. C. in the absence of cobalt naphthenate. The drag on
moving the coated hull through water was reduced compared to an
uncoated hull.
EXAMPLE 3
The procedure of example 1 is repeated employing an isomeric
mixture of hydroxy isopropyl methacrylate isomer is place of the
hydroxyethyl methacrylate.
EXAMPLE 4
To a glass-lined reactor was charged 800 lbs. of ethanol, 200 lbs.
of hydroxyethyl methacrylate and 0.5 lb. of t-butyl peroctoate. The
reactor was flushed with nitrogen and heated to 80.degree. C. over
a period of 1 hour. The reactor was stirred at 80.degree. C. for 7
hours, wherein 90 percent conversion of hydroxyethyl methacrylate
to polymer was attained.
The resulting solution, containing 18 percent polymer by weight was
used for the formulation of coatings for sailboats and motorboats
below the waterline. The boats were made of wood, metal and
fiberglass (i.e. polyester impregnated fiberglass).
EXAMPLE 5
Example 4 was repeated using 20 lbs. of methyl methacrylate and 180
lbs. of hydroxyethyl methacrylate as the monomer charge. A
conversion of 95 percent was attained in 7 hours. The resulting
solution was used for the formulation of marine coatings in a
similar fashion to example 4.
EXAMPLE 6
Example 4 was repeated using 80 lbs. of methyl methacrylate and 120
lbs. of hydroxyethyl methacrylate as the monomer charge. A
conversion of 90 percent was attained in 6 hours. The resulting
solution was used for the formulation of marine coatings in a
similar fashion to example 4.
EXAMPLE 7
A 22-foot polyester fiberglass boat (Aqua Sport) equipped with a
100-horsepower outboard engine was operated at two different
throttle settings between two buoys approximately 1 mile apart.
Average times required to travel between buoys going in both
directions were determined at each throttle setting. The boat was
then removed from the water, the bottom was washed with fresh water
and dried. The polymer solution of example 4 was applied with a
roller to provide a dry coating thickness of 0.75 to 1.0 mil.
The boat was replaced in the water and the speed at the same
throttle settings between the buoys was determined. The following
results were obtained. ##SPC1##
The results show a 13 percent reduction in drag resistance at a
speed of about 10 knots and a 15 percent reduction at the higher
speed.
EXAMPLE 8
The "apparent viscosity" of water at 23.degree. C. was measured
using a Brookfield RVT Syncroelectric viscosimeter employing a -1
spindle at 100 r.p.m. The value obtained was 11.1 centipoises. The
spindle was removed, dried, and was coated with the solution
prepared in example 4 by dipping and allowing the spindle to drain
and dry. The coating thickness was approximately 0.5 mil. The
"apparent viscosity" of water at 23.degree. C. was again measured
at 100 r.p.m. using the coated spindle. A value of 10.7 centipoises
was obtained. The peripheral speed of the -1 spindle at 100 r.p.m.
is approximately 0.6 mile per hour. At this speed approximately 4
percent reduction in frictional resistance or drag was
obtained.
EXAMPLE 9
A 9-foot polyester-fiberglass dinghy was towed behind a motor
launch with a rope attached to a spring scale having a capacity of
10 kilograms. The dinghy was towed at 25 knots. An average force of
8 kilograms was noted on the scale. The dinghy was then removed
from the water, rinsed with fresh water and dried. The dinghy was
then brush coated with the polymer solution of example 4 to provide
a 1.5 mil coating, after drying, the dinghy was again towed at 25
knots. An average force of 6.5 kilograms was recorded on the scale.
Thus, at 25 knots approximately 18 percent reduction in drag
resistance was obtained.
EXAMPLE 10
Using a high-shear mixer, 200 grams of triphenyl lead acetate and
50 grams of titanium dioxide were dispersed in 8 kilograms of the
polymer solution prepared in example 4. To the dispersion was added
2 kilograms of sec-butyl alcohol. A -1 spindle of a Brookfield
viscosimeter was coated with the dispersion by dipping and allowing
to dry. An average coating thickness of 0.6 mil was obtained. The
"apparent viscosity" of water was measured as in example 8. A value
of 10.5 centipoises was obtained. The coating was removed from the
spindle and the "apparent viscosity" was again determined. A value
of 11.0 centipoises was obtained.
The coating composition prepared in example 10 was employed on
sailing craft, both of the wood hull type and polyester-fiberglass
laminate type to provide a fouling resistant drag-reducing
coating.
EXAMPLE 11
Example 4 was repeated using a monomer charge of 40 lbs. of
hydroxypropyl acrylate and 160 lbs. of hydroxyethyl methacrylate. A
conversion of 85 percent was achieved after 7 hours. The procedure
of example 8 was repeated using this solution. Similar results were
obtained. The solution of example 11 was also coated on the bottom
of a metal-bottomed motor launch to provide a drag-reducing
coating.
EXAMPLE 12
The procedure of example 11 was repeated replacing the
hydroxypropyl acrylate by 40 lbs. of acrylamide. Similar results
were obtained.
EXAMPLE 13
To 500 grams of the coating dispersion of example 10 was added 2
grams of ethylene dimethacrylate (ethylene glycol dimethacrylate),
1 gram of benzoyl peroxide and 0.4 gram of N,N-dimethyl aniline.
The coating was immediately applied to a polyester-fiberglass
laminated boat hull surface. After drying and standing at
75.degree. F. (about 24.degree. C.) for 2 hours the coating merely
swelled but did not dissolve in alcohol. The resulting coating was
tougher when water swollen than the coating of example 10. It was
also effective as a fouling-resistant drag-reducing coating for the
boat bottom.
A number of antifouling experiments were carried out using the
hydrophilic polymers of the present invention. After 6 months of
testing on polyester resin panels the best results were obtained
using triphenyl lead acetate as the active antifouling ingredient.
The results were also superior to using the antifouling agent in
formulations which did not include the hydrophilic polymer.
Most antifouling compositions now used on oceangoing vessels are
based on the use of cuprous oxide pigment, a relatively inert
material. A large proportion of the cuprous oxide is not
effectively used because it is encapsulated in the resin and is
unavailable unless the resin itself breaks down. A second
disadvantage of cuprous oxide is that it can induce galvanic
corrosion. In addition, because of its dark color, it is
unsatisfactory as an antifouling ingredient for decorative
finishes.
The U.S. Navy is, of course, interested in antifouling finishes. It
would like to have a 21/2 year minimum, but finds that cuprous
oxide coatings last from 12--18 months. Another market for
effective systems is on tankers and large freighters. The operators
are constantly seeking ways to decrease fouling because even a
small amount of extra drag on the hull makes an appreciable
difference to the efficiency of the vessel, which has an important
effect on the economics, particularly in tanker operations. In
addition, there is a need for periodic removal from service for
bottom cleaning.
During the past decade a number of organometallic and organic
pesticides have been found to exhibit high activity against a broad
spectrum of marine fouling organisms. Economic utilization of these
chemical antifoulants in shipbottom formulations has not been
successfully accomplished, however, primarily because of the
encapsulation problem. The new antifoulants are all several time
more potent than cuprous oxide, but their relatively high cost
dictates that they be employed at a fraction of the normal
concentration of the latter cuprous oxide. Continuous contact
between toxicant particles in the paint film is not maintained at
these relatively low concentrations, so that the toxicants are not
even utilized as efficiently as cuprous oxide, which in turn is
also partially inactivated by encapsulation. Modification of the
paints with inert extender pigments or water-soluble resin
constituents improves the efficiency of toxicant utilization, but
degrades the physical integrity of the paint films to an
intolerable degree. To date, the most successful comprise is
represented by blends of organometallic antifoulants with cuprous
oxide to obtain durability and high potency. However, such blends
eliminate the two major benefits offered by organic and
organometallic antifoulants: freedom from the galvanic corrosion
hazard of cuprous oxide, and flexibility of decorative
pigmentation.
The use of hydrophilic water insoluble polymers of the present
invention reduces the problem of encapsulation of active
antifoulants in impermeable resin systems due to the
water-swellable nature of the hydrophilic film. In other acrylic
resins and in other types of resin systems, solid organic and
organometallic antifoulants do not demonstrate any significant
activity unless their concentration in the film exceeds a threshold
of about 25 percent by weight of the resin. In the systems of the
present invention activity at much lower concentrations is noticed
indicating that the hydrophilic resin does not impermeably
encapsulate the toxicant particles.
In the following examples, Hydron-S is hydroxyethyl methacrylate
homopolymer. Hema is an abbreviation for hydroxyethyl
methacrylate.
EXAMPLE 14
This series of experiments was designed as an attempt to determine
whether or not one of a variety of toxicants showed any activity
against marine organisms when incorporated into unmodified Hydron-S
films. Accordingly, ethanol solutions of Hydron-S containing
concentrations of 2--32 percent of the active ingredients were
applied to panels and immersed at a Miami Beach test facility.
Three toxicants of different chemical type were selected;
hexachlorophene (G11), tetrachloroisophthalonitrile (DAC-2787) and
triphenyl lead acetate (TPLA). These solutions, which contained 14
percent Hydron, were applied by brush to panels of glass-reinforced
polyester laminate which has been sanded to give a clean surface.
The details of the formulations are given in Table 1.
These panels were observed at monthly intervals. After the first
period, all three of the formulations showed some activity against
marine organisms. The resin itself was inactive, as demonstrated by
the control sample which rapidly became fouled. The G11-containing
series showed good protection with the exception of the panel
containing the 2 percent active ingredient (the lowest level).
DAC-2787 was described as moderately active while TPLA exhibited a
degree of control described as "startling." The films were
completely free of slimes and silt, as well as macrofouling. In all
cases, the physical integrity of the film was good. This was highly
encouraging, since organolead compounds have not demonstrated
useful levels of protection in coatings even though they are known
to have broad-spectrum activity in sea water when leached out of
porous blocks.
After five months' immersion, the G11 and DAC-2787 panels were
removed because all had fouled extensively. However, the TPLA
series was still performing well, and after 6 months the two films
containing the most concentrated quantity of active ingredient (16
to 32 percent) were still rated as 100 percent effective at this
time, the film containing 8 percent TPLA was rated 92 percent, the
4 percent film 84 percent, and the 2 percent coating, 36 percent.
Complete results are summarized in Table 2. ##SPC2## ##SPC3##
EXAMPLE 15
Triphenyl lead acetate (TPLA) tests were also carried out at four
concentrations from 2 to 16 percent by weight in Hydron-S and also
in two copolymers (90 percent Hema-10 percent methyl methacrylate
and 60 percent Hema-40 percent methyl methacrylate). The copolymers
have lower levels of sea water permeability than Hydron-S. These
coatings were applied by both brush and doctor-blade techniques.
8inches .times. 10 inches aluminum alloy panels were employed in
the testing of effectiveness against fouling. After one month the
Hydron-S formulations performed better than the copolymers.
Pigmentation of the Hydron-S did not detract from its performance.
##SPC4## ##SPC5## ##SPC6##
EXAMPLE 16
In another series of experiments, aluminum panels were prepared
from Hydron-S solutions containing the following antifoulants:
##SPC7##
The formulations containing these antifoulants are shown in Table
5, and the results after one months's immersion in Table 6. Again,
these results are from tests in sea water at Miami, Florida.
Panels K4 and K16, each with cast and brushed films containing
cuprous oxide on aluminum, were expected to show galvanic
corrosion. Since cuprous oxide is of importance for comparison,
additional K4 and K16 films were applied to glass-reinforced
polyester panels. K4 replicates were brushed, and K16 cast because
only the latter panels were flat enough to permit accurate film
draw-down.
A number of the formulations show considerable interest, not only
because of the protection afforded, but also because of the
sizeable content of pigments. ##SPC8## ##SPC9## ##SPC10## ##SPC11##
##SPC12##
In example 14 through 16, the formulations containing pigments were
prepared on a paint mill. All were applied (with the few exceptions
indicated) to 6061-T6 anodized aluminum alloy by doctor-blade
coating or brushing.
* * * * *