DE2615881A1 - POLYMERS FILM-FORMING MASS - Google Patents

Description

FROM KREISLER SCHÖNWALD MEYER EISHOLD FUES FROM KREISLER KELLER SELTING

PATENT LAWYERS Dr.-Ing. by Kreisler "t" 1973

Dr.-Ing. K. Schönwald, Cologne Dr.-Ing. Th. Meyer, Cologne Dr.-Ing. K. W. Eishold, Bad Soden Dr. J. F. Fues, Cologne Dipl.-Chem. Alek von Kreisler, Cologne Dipl.-Chem. Carola Keller, Cologne Dipl.-Ing. G. Selling, Cologne

Ke / Ax

5 COLOGNE 1, a. April

DEICHMANNHAUS AT THE MAIN RAILWAY STATION

The British Petroleum Company Limited,

Britannic House, Moor Lane, London, EC2Y 9BU (England)

Polymeric film-forming compositions

The invention relates to the treatment of ship's bottom and underwater structures for protection against corrosion and Growth by marine organisms.

Surfaces intended for underwater use are usually coated with a number of coats of paint Mistake. In order to combat the growth of marine organisms, an antifouling paint is usually used Top layer applied. The antifouling paint contains toxins, e.g. copper (I) oxide. The copper (I) oxide slowly reacts with the seawater to form a water-soluble salt that leaches from the paint layer will. The leaching process cannot be directed and regulated uniformly and is undesirable quickly as soon as a ship is put into service or put back into service. As a result, higher Toxic concentrations are present around the ship as necessary to begin with. This results in waste and contamination, and the later lower concentrations allow the fouling organisms to adhere.

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Telephone: (02 21) 2345 41-4 Telex: 888 2307 dopa d - Telegram: Dompolenl Cologne

261588

Further, the coating becomes rough by leaching with time, so that a surface is formed, fouling organisms easier to attach to the <. As long as enough toxins are released, growth is prevented. If this is no longer the case, however, the growth is favored.

If growth is formed by marine organisms under these conditions, it adheres firmly to the ship _(body He is usually removed in dry dock by scraping and re-painting, a ^kostspie-:.. Liges and time-consuming process Alternatively, some limited improvement by hosing can be achieved with water under high pressure or mechanical scrubbing, but as the roots of the vegetation are not removed due to the porous nature of the paint, the improvement is only temporary.

The shipowner is faced with the problem to choose short but frequent or more seldom and longer periods in which his ship is not in service. '

One solution to the problem is to apply a so-called "self-polishing coating" to the surface of a usual antifouling paint. The self-polishing; Coating contains a polyester of an acrylic acid and an organotin compound, e.g. a tin trialkyl compound manure. The ester gradually hydrolyzes, with the organotin oxide being released into the water and in the process is steadily worn away.

According to the invention, salts of polyacrylic acids are used, ie the metals are as cations and not; present as organometallic radicals. These salts are less susceptible to hydrolysis and are therefore long lasting _; antifouling properties. i

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26158S1

The invention relates to a polymeric film-forming composition which can be used as an antifouling paint for Ship bottoms and underwater structures are suitable and made from a polymer or copolymer of an ethylenically unsaturated one Acid or its anhydride or said polymer or copolymer and one or contains several metal cations with antifouling properties.

The antifouling paint preferably contains copper, zinc, nickel, cobalt, manganese, tin as metal cations and / or mercury.

Polyacrylates are preferred as polymers, namely polyacrylates as such or alkyl acrylate polymers. Ethylene / maleic anhydride polymers are also suitable.

The metal polyacrylates have the following general structure:

CIi

C ι C

U = O

CiI-,

Ü = ü I

1-x

Here, R stands for a hydrogen atom or a

1
C.-C.-alkyl radical, R for a hydrogen atom or a C.-C-jQ hydrocarbon radical, M for a metal cation of the type mentioned above and χ for 0.05 to 1.0 molar. The two structures can be distributed randomly in the polymer. When M is a multivalent metal cation, there may be additional crosslinking across the metal cation.

The metal polyacrylate can be the main polymeric film-forming component of the composition as well as the antifouling agent be.

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Acrylic and methacrylic acid esters are known to have film-forming properties. In this embodiment, those carboxyl groups which do not contain any metal cations are preferably esterified, in particular with a C _{.. -C 4} alkyl radical.

The metal-containing part of the polymer itself is not film-forming, and in this embodiment it is Molar ratio of ester to salt at least 60:40, preferably 70:30 to 85:15. Preferably the maximum Amount of metal incorporated in line with the development of film-forming properties.

The ester-salt copolymer can by copolymerization an ester and an acid such as methyl acrylate and methacrylic acid, followed by ion exchange of the Acid part are prepared with a metal salt solution to form the polymeric salt. The lowest Molecular weight required to form a film-forming mass is similar to that of known ones non-metallic polyacrylates and can easily be determined experimentally.

The film-forming copolymer can be applied to the surfaces as a solution in a suitable solvent v / earth. The presence of a metal in the copolymer can reduce its solubility in common solvents worsen. However, an example of a suitable solvent is a 2-eutoxyethanol-isopropanol mixture, which is commercially available under the name "Butyl Cellosolve".

Other normal components of antifouling paints can also be present if the copolymer is the main film-forming component. On that is discussed in more detail below.

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The metal polyacrylate can also be in a conventional polymeric film-forming component, e.g. a common base for antifouling paints, dissolved or be dispersed. The carrier for the metal polyacrylate. for example, can be one or more of the following Components contain: polyester, polyurethane, epoxy resins, epoxy coal tar resins, chlorinated rubber, polyvinyl compounds, e.g. polyvinyl chloride, polyvinyl alcohol and polyvinyl acetate, polyethylene and polytetrafluoroethylene len. The carrier is preferably such that it can be applied to a surface by brushing or spraying, is possible at ambient temperature. For this purpose, the carrier can contain conventional solvents for film-forming Component, e.g. mineral spirits or similar petroleum derivatives, ketone solvents, e.g. methyl isobutyl ketone, or aromatic Solvents such as toluene. The paint can also be used in a known manner as thickeners, e.g. bentonite, pigments, e.g. titanium or iron oxides, fillers, e.g. aluminum silicates, and drying agents, e.g. cobalt or manganese naphthenate.

It is a feature of the invention that the metal poly < acrylate in the usual bases for antifouling paint

medium can be used that have a porosity |

show that it is used as an antifouling agent j

Metal polyacrylate enables its antifouling properties to maintain businesses over long periods of time.

«Hen the metal polyacrylate by itself is not a film! dend is another area of metal content and molecular weights possible. So can the amount of metal 1 to 50% by weight, preferably 10 to 40% by weight of the polymer and the molecular weight of the polymer 5000

up to 1,000,000. The amount of metal polyacrylate based on the weight of the dry film can be 1 to 1 90% by weight, preferably 5 to 70% by weight. Depending on the amount of polymer and its metal content

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9 R 1 L UI

the ketal weight in the dried film 1 to 30% by weight, preferably 5 to 25% by weight.

The preparation can be carried out in the manner described above, e.g. by forming a polymer or Copolymer containing acrylic acid groups, and subsequent Ion exchange with a metal salt solution, For example, aqueous polyacrylic acid solutions treated with an aqueous solution of an inorganic metal salt, the metal polyacrylate is precipitated. If desired, the acid can be converted to the alkali salt first and this salt then to the Be subjected to base exchange with a salt of the desired metal.

Another possible manufacturing process for film-forming or non-fUmbildende polymers consists in the fact that the metal acrylate monomers are formed and the Monomers then polymerized with an appropriate amount of metal-free acrylic acid or a metal-free ester or is copolymerized.

Besides antifouling properties, paintings should be used for Underwater structures and ship floors also expediently have a smooth surface with a low coefficient of friction to have. The presence of polyethylene and polytetrafluoroethylene in the carrier can therefore be particularly useful.

The following examples describe the production of metal polyacrylates.

example 1

120 g of an aqueous solution of polymethacrylic acid (20% polyacid) (manufacturer EDH Limited) were with distilled water diluted to a total volume of 500 ml. While stirring, 6 g of NaOH were added to 100 ml of water

by _t ; ;;. u i. ; , UD!

added. A solution of 21.5 g of ZnSO ₄ .7 HpO in 100 ml of water was added dropwise to the partially neutralized polyacid solution with stirring. The precipitate was centrifuged, filtered, washed several times with distilled water and placed in a vacuum oven ^! dried at 50 ° C. Yield 23.5 g (Zn = 12.1% by weight ).

Example 2

The experiment was carried out in the same way as the experiment described in Example 1, but with; the polyacid by adding 12.0 g of NaOH further new! was neutralized and then 43 g of ZnSO ₄ .7 HpO were used in the exchange reaction. Yield 40 g (Zn = 18.3% by weight ).

Example 3

The experiment was carried out in the manner described in Example 1, except that 5.5 g of NaOH in 200 ml of water and 16.6 g of Cu (NO ₃ ) .3H ₂ O in 100 ml of water were used instead of zinc sulfate. Yield 26 g (Cu = 12.06 wt%).

Example 4

The experiment was carried out in the manner described in Example 1, but using 11.0 g of NaOH in 200 ml of | Wa s.-: he and 33.2 g of Cu (NO ₃ ) ₂ · 3 H ₃ O in 200 ml of water were used. Yield 37 g (Cu = 18.04 wt%).

Example 5

25 g of an aqueous polyacrylic acid solution (25% polyacid, molecular weight of the polyacid 230,000) were further diluted with 200 ml of water. 3.4 g of NaOH in 100 ml of water were added to the solution with stirring. 10.24 g of copper nitrate Cu (NO ₃ ) ₂ · 3 H ₃ O in 100 ml of water were the; Solution added with stirring, whereby a colored precipitate formed «9.5 g of polycopper acrylate (Cu = 20.9%) were isolated«,

ß 0 9 H U ki 1 η 6 1

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The invention is further illustrated by the following examples: explained. !

Example 6 j

90 g of methyl methacrylate, 26 g of methacrylic acid and 1.0 g of azobisisobutyronitrxl (A.Z.B.N.) were added dropwise from a dropping funnel to 62 ml isopropanol, 37 ml; 2- ^ utoxyethanol and 1.0 g AZBN in one at 70 ° C

given 500 ml three-necked flask. After ' During the addition, the temperature was kept at 80 to 90 ° C. for a further 8 hours. The product was cooled and the ί Copolymer isolated by adding water. The copolymer had a mixture of petroleum obtained solvent with an epoxy resin thinner ("petroleum solvent-commercial epoxy thinner) (manufacturer Valspar Ltd.) has an intrinsic viscosity of 0.0213 m / kg. It was found that the intrinsic viscosity and thus the Molecular weight of the copolymer could be changed by the amount of initiator (AZBN) present. In another similar experiment in which the amount of AZBN was increased (4.0 g in total), the copoly-, merisat an intrinsic viscosity of 0.0187 m / kg.

Parts of the copolymer solution having an intrinsic viscosity of 0.0213 m / kg were mixed with metal salt solutions as follows treated:

a) 2.5 ml of an NaOH solution (6 g of NaOH in 100 ml of H 2 O) were added to 5 g of copolymer solution. Then 5 ml of a solution of ZnSO ₄ * 7 H ₃ O (21.5 g ZnSO ₄ «7H _? O) in 200 ml v / water) were added with stirring. The precipitated polymer was filtered off and washed. It had a zinc content of 305% by weight.

b) The experiment described under (a) was repeated,

however, 4.5 ml of the NaOH solution and 9 ml of the ZnSQ ₄ · 7H “0 solution were used. _o The precipitated one

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The polymer had a zinc content of 5.3% by weight.

c) 2.5 ml of NaOH solution (6 g of NaOH in 100 ml of water) were added to 5 g of copolymer solution. Then 5 ml of a solution of CuCl ₂ »2H ₂ O (12.78 g of CuCl ₂ » 2H ₂ O in 200 ml of water) were added with stirring. The excluded \ precipitated polymer contained 3, 6 wt .-% copper.

The metal-containing copolymers prepared in the manner described were in an eutoxyethanol-isopro-, Panol-water mixture soluble and in dimethylformamide I soluble to at least 20% by weight. Overlays were successful rich on mild steel sheets and already with a corro-; Mild steel sheets with anti-ionic coating: brings. Hard films that were very stable in sea water were formed.

Example 7

Commercially available two-component epoxy carbon tar resins with the trade name "Epotan" (manufacturer Goodlass Wall and Co.) were used to produce paints on ₍ metal. Polymetallic methacrylates, which were produced in the manner described in Examples 1 to 5)

These were added to the epoxy coal tar resin in different amounts so that paint films having different metal contents were obtained. The \ coats were applied mm Flußstahlbleche in size, 114.3 χ 38.1 who've been painted with a corrosion protection paint. The trays were kept in seawater near Singapore for 6 weeks and _; then assessed visually for growth on a scale from 1 (no growth) to 10 (strong growth).

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Sheet no. Metal content of
dry film,
Wt% Evaluation of the
Antifouling effect 1 5.2% zinc 2 2 1.8% zinc 4th 3 1.1% zinc 10 4th 6.3% copper 1 5 5.2% copper 2 6th 1.8% copper 5 7th 1.1% copper 10

The evaluation number 1 of the antifouling effect for the Elech 4 meant that the Elech was completely free of Overgrowth by mussels and algae was.

The results for the other sheets show a reduced growth proportional to the metal content of the Recognize paint films.

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Claims (11)

Claims; 1) Polymeric film-forming masses that act as anti-' fouling paints are suitable, characterized in that they consist of one of an ethylenically unsaturated Acid or its anhydride-derived polymer or copolymer, the one or more Contains metal cations with antifouling effect, exist or this polymer or Copoiymerisat contain. ! 2) polymeric film-forming compositions according to claim 1, characterized in that they are used as metal cations Contain copper, zinc, nickel, cobalt, manganese, tin and / or mercury. 3) polymeric film-forming compositions according to claim 1 or 2, characterized in that the polymer is a Is polyacrylate. 4) polymeric film-forming compositions according to claim 1 to 3, characterized in that the polyacrylate has the general structure [ - c - c ο IN THE = 0 CH. = O 1-x has, wherein R is a hydrogen atom or a C ₁ -C ,, - 1 -L 4 Alkyl radical, R a hydrogen atom or a C ₁ -C ^ _n -hydrocarbon radical, M is a metal cation of the type mentioned above and χ has a value of 0.05 to 1.0 mol. 5) polymeric film-forming compositions according to claim 1 to 4, characterized in that the metal-containing polymer 6 0 9 84 UI 1 0 6 1 Risat is at the same time the main polymeric film-forming component and the antifouling agent. 6) polymeric film-forming compositions according to claim 1 to 5, characterized in that the polymer is a Is a copolymer of an acrylic acid ester and an acrylic acid salt, the ratio being of Ester to salt is at least 60:40, preferably 70:30 to 85:15. 7) polymeric film-forming compositions according to claim 1 to 6, characterized in that the metal-containing polymer or the copolymer is dissolved or dispersed in a base which forms a polymeric film. 8) polymeric film-forming compositions according to claim 1 to 7, characterized in that they are 1 to 90 wt .-% of the metal-containing polymer or copolymer, based on the weight of the dry paint film, contain. 9) polymeric film-forming masses according to claims 1 to 8, characterized in that the metal-containing polymer or the copolymer is a metal polyacrylate which contains 1 to 50% by weight of metal. 10) polymeric film-forming compositions according to claim 7 to 9, characterized in that the metal-containing polymer or copolymer has a molecular weight of 5000 to 1,000,000. 11) polymeric film-forming compositions according to claim 1 to 10, characterized in that they are 5 to 25 wt .-% Metal based on the weight of the dried film. h (IH. I, UI 1 (J 6 1