DK153497B - STABLE TIXOTROP DISPERSION OF A TRIALKYLTIN INFLUORIDE IN ONE OR MORE ORGANIC SOLVENTS AND ANTI-DISPOSAL COATING MATERIALS INCLUDING SUCH DISPERSION - Google Patents
STABLE TIXOTROP DISPERSION OF A TRIALKYLTIN INFLUORIDE IN ONE OR MORE ORGANIC SOLVENTS AND ANTI-DISPOSAL COATING MATERIALS INCLUDING SUCH DISPERSION Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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Description
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Den foreliggende opfindelse angår en stabil tixo-trop dispersion af et trialkyltinfluorid i et eller flere organiske opløsningsmidler. Disse stabile dispersioner af trialkyltinfluorid kan oplagres i længere tid uden 5 nogen signifikant forøgelse af viskositeten. Desuden angår opfindelsen et antibegroningsovertræksmateriale indeholdende en sådan dispersion.The present invention relates to a stable thixotropic dispersion of a trialkyltin fluoride in one or more organic solvents. These stable dispersions of trialkyltin fluoride can be stored for a long time without any significant increase in viscosity. In addition, the invention relates to an antifouling coating material containing such dispersion.
En række trialkyltinfluorider, især tri-n-butyltin-fluorid, hæmmer fastgørelse og vækst af Cirripedia og 10 andre organismer, der er ansvarligefor bevoksning af flader under vandoverfladen såsom søgående skibes skrog og piloteringen af dokker og andre faciliteter, der er udsat for saltvand. Trialkyltinfluoriderne er derfor værdifulde som giftmidler til antibegroningsovertræk. Et 15 typisk antibegroningsovertræksmateriale indeholder giftstoffet, et eller flere pigmenter og en filmdannende polymer. Alle disse bestanddele opløses eller disperge-res i et organisk opløsningsmiddel såsom xylen eller toluen, eventuelt kombineret med en keton såsom 2-butanon.A number of trialkyltin fluorides, notably tri-n-butyltin fluoride, inhibit the attachment and growth of Cirripedia and 10 other organisms responsible for underwater surface vegetation such as seagoing hulls and docking and other saltwater-exposed facilities. The trialkyltin fluorides are therefore valuable as toxicants for anti-fouling coatings. A typical antifouling coating material contains the toxin, one or more pigments and a film-forming polymer. All of these components are dissolved or dispersed in an organic solvent such as xylene or toluene, optionally combined with a ketone such as 2-butanone.
20 Hidtil har det været vanskeligt at fremstille ac ceptable overtræksmaterialer indeholdende trialkyltin-fluorider, da disse er faste materialer ved omgivelsernes temperatur. Dispersioner af trialkyltinfluorider i organiske opløsningsmidler udviser en stærk tendens til at 25 agglomerere i form af store partikler. Disse materialer kan derfor ikke dispergeres i overtræksmaterialer med organiske opløsningsmidler, som blandes med stor hastighed.Hitherto, it has been difficult to prepare acceptable coating materials containing trialkyltin fluorides, since these are solid materials at ambient temperature. Dispersions of trialkyltin fluorides in organic solvents show a strong tendency to agglomerate in the form of large particles. Therefore, these materials cannot be dispersed in high solvent organic solvent coating materials.
Denne usædvanlige opførsel kan forklares ved forskellen mellem tins og fluors elektronegativiteter. Denne for-30 skel resulterer i en forholdsvis svag tiltrækningskraft mellem tinatomet på ét molekyle og fluoratomet på et tilstødende molekyle, hvilket resulterer i en struktur, der ligner et lineært polymermolekyles. Uanset årsagen er agglomereringen uønsket, fordi den gør det vanske-35 ligt eller umuligt at fremstille gode overtræksmaterialer, 2This unusual behavior can be explained by the difference between the electronegativities of tins and fluorine. This difference results in a relatively weak attraction between the tin atom of one molecule and the fluorine atom of an adjacent molecule, resulting in a structure similar to a linear polymer molecule. Whatever the reason, the agglomeration is undesirable because it makes it difficult or impossible to produce good coating materials, 2
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idet sådannes maksimale partikelstørrelse skal være 45^u eller mindre. Denne_finhedsgrad kan ikke opnås uden at formale giftmidlet i en pebblesmølle eller en kuglemølle, hvilket er en langsommelig tidskrævende proces.such maximum particle size being 45 µm or less. This degree of fineness cannot be achieved without grinding the toxin into a pebbles mill or a ball mill, which is a slow time consuming process.
5 Selv efter en sådan formaling kan der stadig være et antal hårde agglomerater til stede i giftmidlet. Disse agglomerater må fjernes manuelt, for at giftmidlet skal kunne indgå i et egnet overtræksmateriale.Even after such grinding, a number of hard agglomerates may still be present in the toxin. These agglomerates must be removed manually in order for the toxin to form part of a suitable coating material.
Offentliggjort japansk patentansøgning nr.Published Japanese patent application no.
10 7.338.847 omtaler opvarmning af tri-n-butyltinfluorid ved 40-60°C i et flydende carbonhydrid eller halogeneret car-bonhydrid, der koger fra 50 til 200°C. Den fremkomne opslæmning størkner dog ved henstand i blot lidt længere tid og er derfor ikke egnet til inkorporering i antibe-15 groningsovertræksmaterialer. Selv efter formaling giver de fremkomne partikler ikke en dispersion med passende finhed.No. 10,338,847 discloses heating tri-n-butyltin fluoride at 40-60 ° C in a liquid hydrocarbon or halogenated hydrocarbon boiling from 50 to 200 ° C. However, the resulting slurry solidifies upon standing for just a little longer and is therefore not suitable for incorporation into antibody coating materials. Even after grinding, the resulting particles do not give a dispersion of appropriate fineness.
Det er således opfindelsens formål at angive en stabil tixotrop dispersion af et trialkyltinfluorid i 20 et eller flere organiske opløsningsmidler således, at trialkyltinfluoridet let kan dispergeres i overtræksmaterialer, uden at formaling er nødvendig for at opnå den ønskede partikelstørrelse i dispersionen.It is thus the object of the invention to provide a stable thixotropic dispersion of a trialkyltin fluoride in one or more organic solvents such that the trialkyltin fluoride can be easily dispersed in coating materials without grinding necessary to obtain the desired particle size in the dispersion.
Det har nu overraskende vist sig, at tilstedevæ-25 reisen af visse uorganiske forbindelser bevirker, at tri-alkyltinfluorider såsom tri-n-butyltinfluorid kan dispergeres i en specifik klasse af organiske opløsningsmidler uden agglomerering, så at der fås stabile dispersioner. De herved fremstillede dispersioner forbliver sta-30 bile i længere tid og kan let inkorporeres i overtræks^-materialer, herunder skibsmaling.Surprisingly, it has now been found that the presence of certain inorganic compounds causes tri-alkyltin fluorides such as tri-n-butyltin fluoride to be dispersed in a specific class of organic solvents without agglomeration to provide stable dispersions. The dispersions thus prepared remain stable for a long time and can easily be incorporated into coating materials, including ship paint.
Opfindelsen angår således en stabil, tixotrop dispersion af et trialkyltinfluorid i et eller flere organiske opløsningsmidler, som er ejendommelig ved, at den 35 i det væsentlige består afThe invention thus relates to a stable, thixotropic dispersion of a trialkyltin fluoride in one or more organic solvents, characterized in that it consists essentially of
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a) 40-70 vægtprocent af et trialkyltinfluorid med formlen R^SnF, hvor R er alkyl med 2-12, fortrinsvis 3-6, carbonatomer, b) 20-60 vægtprocent af et organisk flydende medium 5 valgt blandt alkoholer med 4-12 carbonatomer, aliphatiske carbonhydrider med 5-12 carbonatomer og aromatiske car-bonhydrider med en kauri-butanolværdi på 96 eller mindre eller blandinger heraf, idet en blanding eventuelt yderligere indeholder enten 1) n-butylacetat og isobutylacetat eller 10 2) amylacetat, og c) 0,5-10 vægtprocent af en forbindelse valgt blandt 1) lithium- og natriumsalte af p-toluensulfon-syre, phenylphosphonsyre og kiselsyre, 15 2) salpetersyresalte af calcium, magnesium, na trium, lithium, jern og zink, 3) salte af p-toluensulfonsyre eller phenylphosphonsyre og et grundstof valgt blandt magnesium, calcium, strontium og barium, 20 4) magnesium-, calcium-, mangano-, ferro-, ferri-, cupri-, stanno- og bismuthchlorid og 5) carboxylsyresalte af bly, mangan[II], zirconium, barium og strontium, hvor carboxylsyren indeholder 2-12 carbonatomer.a) 40-70% by weight of a trialkyltin fluoride of formula R 1 SnF, wherein R is alkyl of 2-12, preferably 3-6, carbon atoms, b) 20-60% by weight of an organic liquid medium selected from alcohols of 4-12 carbon atoms, aliphatic hydrocarbons having 5-12 carbon atoms, and aromatic hydrocarbons having a kauri-butanol value of 96 or less or mixtures thereof, a mixture optionally further containing either 1) n-butyl acetate and isobutyl acetate or 2) amyl acetate, and c) 0.5-10% by weight of a compound selected from 1) lithium and sodium salts of p-toluenesulfonic acid, phenylphosphonic acid and silicic acid, 2) nitric acid salts of calcium, magnesium, sodium, lithium, iron and zinc, 3) salts of p-toluenesulfonic acid or phenylphosphonic acid and an element selected from magnesium, calcium, strontium and barium; 4) magnesium, calcium, manganese, ferrous, ferric, cupri, stannous and bismuth chloride and 5) carboxylic acid salts of lead, manganese [II], zirconium, barium and strontium, where the carboxylic acid contains 2-12 carbon atoms.
25 Det karakteristiske træk ved de omhandlede disper sioner ligger i tilstedeværelsen af forholdsvis små mængder af forbindelser, der indeholder et af de metalliske grundstoffer. Disse forbindelser stabiliserer dispersionen ved at forhindre agglomerering af trialkyltin-30 fluoridpartiklerne. Nedenstående eksempler belyser, at mange lignende typer forbindelser ikke er egnede stabilisatorer. Det er derfor umuligt(uden eksperimente-ring) på forhånd at sige, hvilke forbindelser der er egnede. Medens således natriumforbindelser i reglen er an-35 vendelige, er den eneste effektive kaliumforbindelse hy-droxidet. Den organiske væske er ligeledes en kritisk faktor for dispersionens stabilitet.The characteristic feature of the present dispersions lies in the presence of relatively small amounts of compounds containing one of the metallic elements. These compounds stabilize the dispersion by preventing agglomeration of the trialkyltin fluoride particles. The following examples illustrate that many similar types of compounds are not suitable stabilizers. It is therefore impossible (without experimentation) to say in advance which compounds are suitable. Thus, while sodium compounds are generally useful, the only effective potassium compound is the hydroxide. The organic liquid is also a critical factor for the stability of the dispersion.
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Den kationiske del af disse forbindelser, der har vist sig at være effektive dispersionsstabilisatorer, udgøres af de anførte metalliske grundstoffer fra grupperne I-A, I-B, II-A, II-B, IV-A, IV-B, V-A, VII-B og VIII i det 5 periodiske system. Den anioniske del af molekylet er en rest af en uorganisk syre såsom salpetersyre eller kisel-syre eller en organisk syre såsom p-toluensulfonsyre, phenylphosphonsyre eller en carboxylsyre med 2-12 carbon-atomer. Eksempler på carboxylsyrer omfatter eddikesyre, 10 propionsyre, smørsyre, hexansyre, heptansyre, cyclohexan- -carboxylsyre og benzoesyre.The cationic portion of these compounds, which have been found to be effective dispersion stabilizers, is constituted by the metallic elements listed from groups IA, IB, II-A, II-B, IV-A, IV-B, VA, VII-B and VIII of the 5 periodic system. The anionic portion of the molecule is a residue of an inorganic acid such as nitric or silicic acid or an organic acid such as p-toluenesulfonic acid, phenylphosphonic acid or a carboxylic acid having 2 to 12 carbon atoms. Examples of carboxylic acids include acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, cyclohexane-carboxylic acid and benzoic acid.
Chlorider af nogle af de anførte polyvalente metalliske grundstoffer er ligeledes effektive dispersionsstabilisatorer. Som sammenligning skal nævnes, at en 15 dispersion, der indeholder natriumchlorid, størkner ved henstand. Med undtagelse af kaliumhydroxid gælder dette også for dispersioner indeholdende kaliumanaloge af de natriumforbindelser, der er nærmere omtalt nedenfor.Chlorides of some of the listed polyvalent metallic elements are also effective dispersion stabilizers. By comparison, a dispersion containing sodium chloride solidifies upon standing. With the exception of potassium hydroxide, this also applies to dispersions containing potassium analogs of the sodium compounds, which are discussed further below.
Ud over valg af en passende uorganisk dispersions- 20 o stabilisator er også det organiske medium, der anvendes som dispersionsbærer, kritisk for opnåelsen af en ikke-koagulerende dispersion af et trialkyltinfluorid. Egnede organiske medier omfatter som nævnt aliphatiske carbonhydrider med 5-12 carbonatomer og aromatiske carbonhy- nc drider méd en kauri-butanolværdi på 96 eller mindre. Et" carbonhydridopløsningsmiddels kauri-butanolværdi er lig med det volumen i kubikcentimeter (målt ved 25°C) af et givet opløsningsmiddel, der giver en angivet grad af uklarhed, når det sættes til 20 g af en standardopløsning af 30 kauriharpiks i normal butanol. Prøvemetoden er offentliggjort af American Society for Testing and Materials som ASTM prøve nr. 01133-61 (atter godkendt i 1973).In addition to selecting an appropriate inorganic dispersion stabilizer, the organic medium used as a dispersion carrier is also critical for obtaining a non-coagulant dispersion of a trialkyltin fluoride. Suitable organic media, as mentioned, include aliphatic hydrocarbons having 5-12 carbon atoms and aromatic hydrocarbons having a kauri-butanol value of 96 or less. The kauri-butanol value of a hydrocarbon solvent is equal to the volume in cubic centimeters (measured at 25 ° C) of a given solvent that gives a specified degree of turbidity when added to 20 g of a standard solution of 30 kauri resin in normal butanol. is published by the American Society for Testing and Materials as ASTM Sample No. 01133-61 (re-approved in 1973).
Som eksempler på anvendelige flydende carbonhydrider kan nævnes aliphatiske carbonhydrider med 5-12 carbonatomer.Examples of useful liquid hydrocarbons include aliphatic hydrocarbons having 5-12 carbon atoms.
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Disse carbonhydrider kan anvendes individuelt eller i blandinger, der fås i handelen som mineralsk terpentin, pe-troleumsether og nafta. Toluen har en kauri-butanolværdi på 105 og er derfor ikke et egnet medium til de her om-5 talte dispersioner. Andre egnede flydende medier omfatter alkoholer med 4-12 carbonatomer. Overraskende nok kan der ikke fremstilles en stabil dispersion i n-propanol.These hydrocarbons can be used individually or in commercially available mixtures such as mineral turpentine, petroleum ether and naphtha. Toluene has a kauri-butanol value of 105 and is therefore not a suitable medium for the dispersions referred to herein. Other suitable liquid media include alcohols having 4-12 carbon atoms. Surprisingly, a stable dispersion in n-propanol cannot be prepared.
De trialkyltinfluorider, der kan anvendes i de stabile dispersioner ifølge opfindelsen, har formlen R^SnF, 10 hvor R er alkyl med 2-12, men især 3-6 carbonatomer. Dersom dispersionen skal inkorporeres i et overtræksmateriale, der skal forhindre begroning med Cirripedia og andre organismer på skibsskrog og andre strukturer, der normalt befinder sig under vandoverfladen, er R fortrinsvis n-butyl, 15 da dette giftmiddel er det mest effektive over for marine organismer.The trialkyltin fluorides which can be used in the stable dispersions of the invention have the formula R If the dispersion is to be incorporated into a coating material to prevent fouling with Cirripedia and other ship hull organisms and other structures normally beneath the water surface, R is preferably n-butyl, as this toxin is most effective against marine organisms.
Ved fremstillingen af den omhandlede stabile tixo-trope dispersion med de organiske væsker, der er omtalt nærmere nedenfor, er det muligt at inkorporere 40 til 20 70 vægtprocent af et trialkyltinfluorid i dispersionen.In the preparation of the present stable thixotropic dispersion with the organic liquids discussed further below, it is possible to incorporate 40 to 70% by weight of a trialkyltin fluoride in the dispersion.
Det har hidtil ikke været muligt at inkorporere mere end ca.So far, it has not been possible to incorporate more than approx.
40 vægtprocent af et trialkyltinfluorid såsom tri-n-butyl-tinfluorid i en dispersion. Den maksimale mængde fluorid, der kan dispergeres, vil naturligvis afhænge af den sær-25 lige dispersionsstabilisator og den valgte organiske væske.40% by weight of a trialkyltin fluoride such as tri-n-butyltin fluoride in a dispersion. The maximum amount of dispersible fluoride will, of course, depend on the particular dispersion stabilizer and the organic liquid selected.
Den fysiske form af de omhandlede dispersioner varierer fra viskose væsker til halvfaste pastaer afhængigt af koncentrationen af trialkyltinfluoridet. En vigtig fordel ved disse dispersioner består i deres tixotropi, som 30 gør, at de let kan blandes ved simpel omrøring med andre materialer, der normalt anvendes i overtræksmaterialer.The physical form of the present dispersions varies from viscous liquids to semi-solid pastes depending on the concentration of the trialkyltin fluoride. An important advantage of these dispersions lies in their thixotropy, which allows them to be readily mixed by simple stirring with other materials normally used in coating materials.
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Disse yderligere bestanddele er naturharpiks, vinyl-chloridhomopolymere og copolymere af vinylchlorid med en eller flere ethylenisk umættede monomere såsom vinylacetat, pigmenter såsom titaniumdioxid og jernoxid, 5 bentonitlerarter samt et eller flere organiske opløs ningsmidler.These additional constituents are natural resin, vinyl chloride homopolymers and copolymers of vinyl chloride with one or more ethylenically unsaturated monomers such as vinyl acetate, pigments such as titanium dioxide and iron oxide, 5 bentonite clays, and one or more organic solvents.
Opfindelsen angår også et antibegroningsover-træksmateriale, der i det væsentlige består af 1,0 til 20,0 vægtprocent af en dispersion af et trialkyltinfluor id, 10 til 50 vægtprocent af mindst ét pigment, (i reglen titaniumoxid eller zinkoxid alene eller kombineret med farvede pigmenter såsom jernoxid), 10 til 50 vægtprocent af mindst ét filmdannende materiale valgt blandt vinylchloridhomopolymere og -copolymere, 15 naturharpiks og chloreret naturlig eller syntetisk gummi (såsom polychloropren), og 20 til 60 vægtprocent af mindst et organisk opløsningsmiddel, (herunder xylen, cyclohexanon, 2-butanon og blandinger af carbonhydrider, der i reglen- omtales som "aliphatisk nafta" og "nafta 20 med højt flammepunkt") samt eventuelt op til 5 vægt% af en bentonitlerart (medtages i reglen som viskositets-modifikator) for at gøre det færdige materiale tixo-tropt. Antibegroningsovertræksmaterialet er ejendommeligt ved, at dispersionen er som ovenfor defineret.The invention also relates to an anti-fouling coating material consisting essentially of 1.0 to 20.0% by weight of a dispersion of a trialkyltin fluoride, 10 to 50% by weight of at least one pigment, (usually titanium oxide or zinc oxide alone or in combination with colored pigments such as iron oxide), 10 to 50% by weight of at least one film-forming material selected from vinyl chloride homopolymers and copolymers, 15 resin and chlorinated natural or synthetic rubber (such as polychloroprene), and 20 to 60% by weight of at least one organic solvent (including xylene, cyclohexanone) , 2-butanone and mixtures of hydrocarbons commonly referred to as "aliphatic naphtha" and "high flash point naphtha 20"), and optionally up to 5% by weight of a bentonite clay species (generally included as viscosity modifier) to make the finished material tixo-tropt. The anti-fouling coating material is peculiar in that the dispersion is as defined above.
25 Fremstillingen af et særlig foretrukket antibe- groningsovertræksmateriale beskrives i eksempel 5 nedenfor.The preparation of a particularly preferred antibody coating material is described in Example 5 below.
Inkorporering af tri-n-butyltinfluorid i overtræks- materialer såsom skibsmaling har hidtil været en lang-30 vang og tidskrævende proces på grund af fluoridets tendens til at agglomerere. Det derved fremkomne overtræks-materiale skal i reglen formales i flere timer i en småstens- eller sandmølle for at opnå en finhed på blot 4-5 efter Hegman N.S.-skalaen, hvor 0 betyder ingen formaling og oc 10 betyder udmærket formaling. En bedømmelse på 4-5 7Incorporation of tri-n-butyltin fluoride in coating materials such as ship paint has heretofore been a lengthy and time consuming process due to the tendency of the fluoride to agglomerate. The resulting coating material is usually ground for several hours in a pebble or sand mill to achieve a fineness of just 4-5 according to the Hegman N.S. scale, where 0 means no grinding and 10 means excellent grinding. A rating of 4-5 7
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på denne skala svarer til en gennemsnitlig partikelstørrelse på 40-70 μ. Lignende problemer, der stammer fra ag-glomerering, opstår, hvis man prøver at dispergere tri-alkyltinfluoridet i et organisk opløsningsmiddel, før det 5 inkorporeres i overtræksmaterialet. Hertil kommer, at selv om man har opnået en dispersion af den ønskede partikelstørrelse, kan den ikke opbevares, fordi den hurtigt størkner til et voksagtigt fast stof.on this scale corresponds to an average particle size of 40-70 μ. Similar problems arising from agglomeration arise when trying to disperse the trialkyltin fluoride in an organic solvent before incorporating it into the coating material. In addition, although a dispersion of the desired particle size has been obtained, it cannot be stored because it solidifies rapidly to a waxy solid.
Nedenstående eksempler 1-3 tjener til ved gennemgang 10 af foretrukne udførelsesformer nærmere at belyse dispersionen og overtræksmaterialet ifølge opfindelsen. Alle dele og procentdele er efter vægt, medmindre andet er angivet.Examples 1-3 below serve to elucidate, in review 10 of preferred embodiments, the dispersion and coating material of the invention. All parts and percentages are by weight unless otherwise stated.
Eksempel 1 15 Der fremstilles dispersioner af tri-n-butyltinfluorid ved at blande 60 dele af denne forbindelse, 5 dele af den uorganiske stabilisator og 35 dele af en blanding indeholdende 64% specialnaphthalit (en blanding af flydende carbon-hydrider, der indeholder mindre end 8% aromatiske carbonhy-20 drider), 12% ethylbenzen, 9% n-butylacetat (fortyndingsmiddel) , 5% isobutylacetat (fortyndingsmiddel) og 10% n-buta-nol. Blandingens flammepunkt er 14,4°C, kauri-butanolværdien er 36, og den koger mellem 123 og 145°C. 100 g af den herved fremkomne blanding anbringes i en cylindrisk beholder, der 25 måler 5,1 cm i diameter og 11,4 cm i højden. I denne beholder anbringes ligeledes 250 g rustfri stålkugler, der måler 4,7 mm i diameter. Beholderen lukkes og rystes kraftigt i 20 minutter, hvorefter beholderens indhold tømmes ud på en stålsigte med store masker. Dispersioner, der størkner 30 under formaling og smuldrer, når de prikkes med en spatel, anses som uacceptable og afprøves ikke yderligere. Acceptable materialer er enten viskose væsker eller homogene sammenhængende halvfaste stoffer, der kan tvinges gennem sigtens åbninger med en spatel. De materialer, der kan passere gen-35 nem sigten, opsamles og holdes ved omgivelsernes temperatur i to dage. Ved slutningen af denne periode undersøges de tilExample 1 Dispersions of tri-n-butyltin fluoride are prepared by mixing 60 parts of this compound, 5 parts of the inorganic stabilizer and 35 parts of a mixture containing 64% special naphthalite (a mixture of liquid hydrocarbons containing less than 8% aromatic hydrocarbons), 12% ethylbenzene, 9% n-butyl acetate (diluent), 5% isobutyl acetate (diluent) and 10% n-butanol. The flash point of the mixture is 14.4 ° C, the kauri-butanol value is 36, and it boils between 123 and 145 ° C. 100 g of the resulting mixture is placed in a cylindrical container measuring 25 inches in diameter and 11.4 cm in height. 250 g stainless steel balls measuring 4.7 mm in diameter are also placed in this container. The container is closed and shaken vigorously for 20 minutes, after which the contents of the container are emptied onto a large mesh screen. Dispersions that solidify 30 during grinding and crumble when dotted with a spatula are considered unacceptable and are not tested further. Acceptable materials are either viscous liquids or homogeneous cohesive semi-solids which can be forced through the openings of the screen with a spatula. The materials that can pass through the screen are collected and kept at ambient temperature for two days. At the end of this period, they are being investigated for
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bestemmelse af, hvorvidt der er indtruffet forandringer i deres fysiske form i løbet af dette tidsrum. De materialer, der er størknet og ikke længere kan omrøres med en spatel, anses for uacceptable. Alle acceptable materialer er tixo-5 trope halvfaste stoffer eller viskose væsker, der udviser en betydelig viskositetsreduktion under forskydning. Nogle af materialerne, der fremtræder som sammenhængende faste stoffer, kan alligevel let omrøres med hånden med en spatel under anvendelse af kun ringe kraft.determining whether changes have occurred in their physical form during this time. The materials that are solidified and can no longer be stirred with a spatula are considered unacceptable. All acceptable materials are tixo-tropic semi-solids or viscous liquids which exhibit a significant reduction in viscosity during shear. Nevertheless, some of the materials which appear as cohesive solids can be easily stirred by hand with a spatula using only little force.
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Uorganiske forbindelser, der giver acceptable disdispersioner omfatter:Inorganic compounds which give acceptable dispersions include:
Natrium-p-toluensulfonat Calcium-di-(p-toluensulfonat)Sodium p-toluenesulfonate Calcium di- (p-toluenesulfonate)
Natriumphenylphosphonat Calciumphenylphosphonat Bariumacetat Strontiumacetat Z irconiumacetat Mangan (II)acetat Blyacetat Calciumnitrat Ferronitrat FerrinitratSodium Phenyl Phosphonate Calcium Phenyl Phosphonate Barium Acetate Strontium Acetate Z Zirconium Acetate Manganese (II) Acetate Lead Acetate Calcium Nitrate Ferronitrate Ferrin Nitrate
Zinknitrat 25Zinc nitrate 25
Natriumsilicatsodium silicate
Magnes iumchloridMagnesum chloride
Calciumchloridcalcium chloride
Mangan (II)chloridManganese (II) chloride
Ferrochlorid 30Ferrochloride 30
Ferrichloridferric chloride
Cuprichloridcupric chloride
StannochloridStannous chloride
Bismuthchlorid 35Bismuth Chloride 35
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Forbindelser, der ikke giver acceptable dispersioner, omfatter:Compounds which do not give acceptable dispersions include:
Kalium-p-toluensulfonat Kaliumphenylphosphonat 5 KaliumacetatPotassium p-toluenesulfonate Potassium phenylphosphonate Potassium acetate
Nikkel (II)acetat Cuproacetat Cupriacetat C admiumacetat 10 KaliumnitratNickel (II) acetate Cuproacetate Cupriacetate C admium acetate 10 Potassium nitrate
Bariumnitrat Nikkel (II)nitrat Magnesiumsilicat Chlorider af natrium, kalium og 15 monovalent kobberBarium nitrate Nickel (II) nitrate Magnesium silicate Chlorides of sodium, potassium and 15 monovalent copper
Ca1c iumfluor idCa1c iumfluoro id
Man mener, at en effektiv stabilisator griber ind i dannelsen af stærke bindinger mellem fluoratomerne på ét 20 molekyle og tinatomer på tilstødende molekyler. Denne bindingsdannelse mener man er ansvarlig for agglomereringen, der næsten altid indtræffer, når et trialkyltinfluorid dis-pergeres i et organisk opløsningsmiddel uden tilstedeværelse af en af de omhandlede uorganiske forbindelser.It is believed that an effective stabilizer interferes with the formation of strong bonds between the fluorine atoms of one 20 molecule and the tin atoms of adjacent molecules. This bond formation is believed to be responsible for the agglomeration that almost always occurs when a trialkyltin fluoride is dispersed in an organic solvent without the presence of one of the inorganic compounds.
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Eksempel 2Example 2
Virkningen af forskellige organiske væsker eller fortyndingsmidler på en sådan dispersions; stabilitet, der indeholder 60 vægtprocent tri-n-butyltinfluorid, 30 5% calciumchlorid· og 35% af den organiske væske, bestem mes ved at fremstille en dispersion som beskrevet i det foregående eksempel. Sådanne dispersioner, der kan klassificeres som viskose væsker eller sammenhængende halvfaste stoffer efter den indledende formalingsproces, 35The effect of various organic liquids or diluents on such dispersions; stability containing 60% by weight of tri-n-butyltin fluoride, 30% of calcium chloride and 35% of the organic liquid is determined by preparing a dispersion as described in the previous example. Such dispersions which may be classified as viscous liquids or cohesive semi-solids after the initial grinding process, 35
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opbevares i én uge under omgivelsernes betingelser og undersøges så til afgørelse af, om den oprindelige tixotrope karakter er blevet bibeholdt.stored for one week under ambient conditions and then examined to determine if the original thixotropic character has been retained.
De organiske væsker, der bedømmes, omfatter en blan-5 ding af aromatiske carbonhydrider, der fås under navnet "Solvesso1® 150 fra Exxon Company og har et typisk flammepunkt på 63-65°C og en kauri-butanolværdi på 92, VM&P nafta (en blanding af aliphatiske carbonhydrider, der har et typisk flammepunkt på 6,7°C (bæger lukket med strop) og som 10 koger fra 118-139°C og har en kauri-butanolværdi på 32), mineralsk terpentin (en blanding af aliphatiske carbonhydrider, der har et typisk flammepunkt på 42,2°C (bæger lukket med strop) og koger mellem 160 og 196°C og har en kauri--butanolværdi på 37), ethylbenzen med en kauri-butanolværdi 15 på 94, amylacetat (fortyndingsmiddel), en blanding (A), der indeholder 33,3% VM&P nafta (kauri-butanolværdi 32), 28,9% cyclohexan (kauri-butanolværdi 50) og 37,8% amylacetat (fortyndingsmiddel), og en anden blanding (B), der indeholder 34,4% mineralsk terpentin (kauri-butanolværdi 37), 4,4% 20 "Solvesso1® 150 (kauri-butanolværdi 92), 12,2% ethylbenzen (kauri-butanolværdi 94) og 49,2% amylacetat (fortyndingsmiddel) .The organic liquids evaluated include a mixture of aromatic hydrocarbons obtained under the name "Solvesso1® 150 from Exxon Company and having a typical flash point of 63-65 ° C and a kauri-butanol value of 92, VM&P naphtha ( a mixture of aliphatic hydrocarbons having a typical flash point of 6.7 ° C (cup closed with a strap) and boiling from 118-139 ° C and having a kauri-butanol value of 32), mineral turpentine (a mixture of aliphatic hydrocarbons having a typical flash point of 42.2 ° C (beaker closed with a strap) and boiling between 160 and 196 ° C and having a kauri-butanol value of 37), ethylbenzene having a kauri-butanol value of 94, amyl acetate ( diluent), a mixture (A) containing 33.3% VM&P naphtha (kauri-butanol value 32), 28.9% cyclohexane (kauri-butanol value 50) and 37.8% amyl acetate (diluent), and another mixture ( B) containing 34.4% mineral turpentine (kauri-butanol value 37), 4.4% 20 "Solvesso1® 150 (kauri-butanol value 92), 12.2% ethylbenzene (kauri butanol value 94) and 49.2% amyl acetate (diluent).
Ligeledes bedømmes cyclohexan (kauri-butanolværdi 50), xylen (98), 2-butanon, n-butylacetat, isobutylacetat, n-bu-25 tanol, ethylenglycol, n-propanol, octanol, "Cellosolve'®--acetat (ethylenglycolmonomethylethermonoacetat) og toluen (105). Af de opløsningsmidler, der bedømmes, er de to blandinger (A & B), VM&P-nafta (32), "Solvesso1® 150 (92), mineralsk terpentin (37), ethylbenzen, cyclohexan, n-butanol 30 og octanol dem, der giver acceptable dispersioner. Dispersioner fremstillet under anvendelse af de andre opløsningsmidler hærdner i løbet af en opbevaringstid på en uge eller er for stive og gummi-agtige til anvendelse i overtræksmaterialer.Also evaluated are cyclohexane (kauri-butanol value 50), xylene (98), 2-butanone, n-butyl acetate, isobutyl acetate, n-butanol, ethylene glycol, n-propanol, octanol, Cellosolve® acetate (ethylene glycol monomethyl ether monoacetate) and toluene (105). Of the solvents evaluated, the two mixtures (A & B), VM & P-naphtha (32), "Solvesso1® 150 (92), mineral turpentine (37), ethylbenzene, cyclohexane, butanol 30 and octanol those which give acceptable dispersions. Dispersions made using the other solvents cure over a one-week storage period or are too rigid and rubbery to be used in coating materials.
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11 DK 153497B11 DK 153497B
Eksempel 3Example 3
En dispersion indeholdende 60 vægtprocent tri-n--butyltinfluorid (TBTF) fremstillet som beskrevet i eksempel 1 ved anvendelse af calciumchlorid som stabili-5 sator kan inkorporeres i et gængstovertræksmateriale med følgende sammensætning:A dispersion containing 60% by weight of tri-n-butyltin fluoride (TBTF) prepared as described in Example 1 using calcium chloride as a stabilizer can be incorporated into a thread coating material of the following composition:
DeleParts
Titaniumdioxid 15,12Titanium Dioxide 15.12
Talkum (magnesiumsilicat) 11,22Talc (magnesium silicate) 11.22
Zinkoxid 7,08Zinc oxide 7.08
En vinylchlorid-vinyl-acetatpolymer (VAGH) 11,16A vinyl chloride vinyl acetate polymer (VAGH) 11.16
Naturharpiks 3,73 2-butanon 20,31 15 Xylen 18,84Natural Resin 3.73 2-Butanone 20.31 Xylene 18.84
Bentonitler 0,51Bentonites 0.51
Methanol (95%) 0,15 TBTFx-dispersion efter behov 20 x) - tri-n-butyltinfluoridMethanol (95%) 0.15 TBTFx dispersion as needed 20x) - tri-n-butyltin fluoride
Opløsningsmidlet, der anvendes til fremstilling af dispersionerne, er en blanding indeholdende 64% special-naftalit, 12% ethylbenzen, 9% n-butylacetat (fortyndings-25 middel), 5% isobutylacetat (fortyndingsmiddel) og 10% n-butanol. Specialnaftalit er beskrevet i eksempel 1.The solvent used to prepare the dispersions is a mixture containing 64% special naphthalite, 12% ethylbenzene, 9% n-butyl acetate (diluent), 5% isobutyl acetate (diluent) and 10% n-butanol. Special naphthalite is described in Example 1.
Den mængde tri-n-butyltinfluoriddispersion, der anvendes, svarer til 12 vægtprocent, beregnet på hele overtræksmaterialet. Dispersionen blandes sammen med de andre 30 komponenter, til der fås en homogen blanding.The amount of tri-n-butyltin fluoride dispersion used corresponds to 12% by weight, based on the entire coating material. The dispersion is mixed with the other 30 components until a homogeneous mixture is obtained.
Overtræksmaterialet bedømmes ved hjælp af en Heg-man N.S.-måler til bestemmelse af formalingens "finhed".The coating material is evaluated by a Heg-man N.S. meter to determine the "fineness" of the grinding.
Der påføres en 0,0076 cm tyk film på en metalflade ved hjælp af en aftrækker-klinge, og den fremkomne films teks-35 tur bedømmes ved hjælp af følgende skala:A 0.0076 cm thick film is applied to a metal surface by means of a trigger blade, and the texture of the resulting film is judged by the following scale:
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1. Ru overflade, der let kan konstateres ved at gnide en hånd over malingens overflade.1. Rough surface which can be easily identified by rubbing a hand over the surface of the paint.
5 2. 10-20 klumper, der ses ensartet fordelt på malingens overflade.5 2. 10-20 lumps that are seen to be evenly distributed on the surface of the paint.
3. Adskillige synlige klumper.3. Several visible lumps.
4. Glat.4. Smooth.
Data fra en typisk bedømmelse af et overtræksmateriale er anført i den følgende tabel. En Hegman-finhed 10 på 4 eller 5 betragtes som acceptabel.Data from a typical rating of a coating material is given in the following table. A Hegman fineness 10 of 4 or 5 is considered acceptable.
Bedømmelse % CaCl2 Hegman-formaling nr. af film 10 - 4 15 5 - 4 2,5 4 4 1 4-5 3-4 0,5 4-5 1-2 20 Den film, der frembringes ved påførelse af et overtræksmateriale baseret på en dispersion, der indeholder 0,5 vægtprocent calciumchlorid og 60% tri-n--butyltinfluorid, kan have en tekstur, der er for ru til at kunne betragtes som acceptabel, men denne mængde 25 calciumchlorid ville være tilstrækkeligt til at stabili sere dispersioner, der indeholder mindre end 60% tri-alkyltinforbindelse, f.eks. ca. 50 vægtprocent.Rating% CaCl2 Hegman Grinding No. of Film 10 - 4 15 5 - 4 2.5 4 4 1 4-5 3-4 0.5 4-5 1-2 20 The film produced by applying a coating material based on a dispersion containing 0.5% by weight calcium chloride and 60% tri-n-butyltin fluoride may have a texture too rough to be considered acceptable, but this amount of calcium chloride would be sufficient to stabilize dispersions containing less than 60% tri-alkyltin compound, e.g. ca. 50% by weight.
Eksempel 4 30 En typisk rød skibsmaling egnet til anvendelse sammen med den foreliggende dispersion indeholdende tri-n-butyltinfluorid kan fremstilles på følgende måde: 35Example 4 A typical red ship paint suitable for use with the present dispersion containing tri-n-butyltin fluoride can be prepared as follows:
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1. Følgende ingredienser blandes let på en hur-tigtløbende omrører til en ensartet dispersion:1. The following ingredients are easily mixed on a fast-running stirrer for a uniform dispersion:
Na turharpik s (70 vægtproc ent i xylen) 4,89 dele 5 En blanding indeholdende ben- tonitler 0,47 dele og methanol 0,14 dele 2. Blanding (1) forties med cyclohexan 12,00 dele 10 3. Tilsæt pigmenterne Rødt jernoxid 13,90 deleNa tur resin s (70% by weight in xylene) 4.89 parts 5 A mixture containing benzene titles 0.47 parts and methanol 0.14 parts 2. Mixture (1) is diluted with cyclohexane 12.00 parts 10 3. Add the pigments Red iron oxide 13.90 parts
Talkum 10,30 deleTalc 10.30 parts
Zinkoxid 6,05 dele 4. Tilsæt den filmdannende polymer- vinylchlorid/delvis hydrolyseret 15 vinylacetatcopolymer (fås som VAGH fra Union Carbide Corporation) som en 3 vægtprocents opløsning i en 2-butanon/xylen-blanding 34,13 dele 5. Tilsæt en stabil dispersion af 20 tri-n-butyltinfluorid som beskrevet i eksempel 1 17,65 dele 6. Omrør blandingen ved stor hastighed, indtil den udviser en finhed på 4-5 efter Hegman N.S.- 25 skalaen.Zinc oxide 6.05 parts 4. Add the film-forming polymer vinyl chloride / partially hydrolyzed 15 vinyl acetate copolymer (available as VAGH from Union Carbide Corporation) as a 3% by weight solution in a 2-butanone / xylene mixture 34.13 parts 5. Add a stable dispersion of 20 tri-n-butyltin fluoride as described in Example 1 17.65 parts 6. Stir the mixture at high speed until it shows a fineness of 4-5 according to the Hegman NS scale.
Eksempel 5Example 5
En dispersion, der indeholder 50 vægtprocent TBTF, fremstillet som beskrevet i eksempel 1 ved an-30 vendelse af calciumchlorid som stabilisator, kan inkorporeres i et antibegroningsovertræksmateriale, hvis filmdannende komponent er en chloreret gummi.A dispersion containing 50% by weight of TBTF prepared as described in Example 1 using calcium chloride as a stabilizer may be incorporated into an anti-fouling coating material whose film-forming component is a chlorinated rubber.
35 1435 14
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DK 153497BDK 153497B
Ingrediens Dele Rød jernoxid 17,24Ingredient Parts Red iron oxide 17.24
Zinkoxid 8,09Zinc oxide 8.09
Talkum (magnesiumsilikat} 7,30 5 Bentonitler 0,59Talc (magnesium silicate} 7.30 Bentonitles 0.59
Methanol 0,18Methanol 0.18
Chloreret naturlig gummixx^ 8,9Chlorinated natural rubber mixx ^ 8.9
Naturharpiks 8,9Natural resin 8.9
Xylen 21,9 10 TBTF-dispersion 26,9 100,00 x) "Bentone27 fra NL Industries xx) 64-65 vægtprocent chlor, viskositet = 17-25 cps, målt i en 20 vægtprocents op- 15 løsning i toluen ved 25°C.Xylene 21.9 10 TBTF dispersion 26.9 100.00 x) "Bentone27 from NL Industries xx) 64-65 wt% chlorine, viscosity = 17-25 cps, measured in a 20 wt% solution in toluene at 25 ° C.
Overtræksmaterialet fremstilles på følgende måde: 1. Foren bentonitler og methanol, bland omhyggeligt og foren med naturharpiks, bland indtil homogenitet.The coating material is prepared as follows: 1. Combine bentonite clay and methanol, mix thoroughly and combine with natural resin, mix until homogeneous.
20 2. Tilsæt opløsningsmiddel (xylen) med pigmen terne indtil ønsket viskositet i hele dispersionen.2. Add solvent (xylene) with the pigments until desired viscosity throughout the dispersion.
3. Tilsæt pigmenterne i den anførte rækkefølge og disperger til 5-formaling på Hegman N.S.- 25 skalaen: Rød jernoxid 17,243. Add the pigments in the order listed and disperse for 5 grinding on the Hegman N.S.- 25 scale: Red Iron Oxide 17.24
Zinkoxid 8,09Zinc oxide 8.09
Talkum 7,03 4. Tilsæt langsomt det chlorerede gummi under om- 30 røring, indtil det er opløst, og 5. Tilsæt TBTF-dispersionen og bland indtil 4-5 formaling på Hegman N.S.-skalaen.Talc 7.03 4. Slowly add the chlorinated rubber with stirring until dissolved, and 5. Add the TBTF dispersion and mix until 4-5 milling on the Hegman N.S. scale.
3535
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87423278 | 1978-02-01 | ||
| US05/874,232 US4191580A (en) | 1977-01-28 | 1978-02-01 | Stable dispersions containing trialkyltin fluorides |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK40379A DK40379A (en) | 1979-08-02 |
| DK153497B true DK153497B (en) | 1988-07-18 |
| DK153497C DK153497C (en) | 1988-12-12 |
Family
ID=25363273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK040379A DK153497C (en) | 1978-02-01 | 1979-01-31 | STABLE TIXOTROP DISPERSION OF A TRIALKYLTIN INFLUORIDE IN ONE OR MORE ORGANIC SOLVENTS AND ANTI-DISPOSAL COATING MATERIALS INCLUDING SUCH DISPERSION |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS608064B2 (en) |
| AR (1) | AR222031A1 (en) |
| AU (1) | AU523113B2 (en) |
| CA (1) | CA1115460A (en) |
| CH (1) | CH637525A5 (en) |
| DE (1) | DE2902653C2 (en) |
| DK (1) | DK153497C (en) |
| FR (1) | FR2416250B2 (en) |
| GB (1) | GB2016018B (en) |
| IL (1) | IL56371A (en) |
| IT (1) | IT1165930B (en) |
| NL (1) | NL183333C (en) |
| NO (1) | NO151667C (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4012503A (en) * | 1973-04-30 | 1977-03-15 | M & T Chemicals Inc. | Coating compositions used to control barnacles |
-
1979
- 1979-01-04 IL IL56371A patent/IL56371A/en unknown
- 1979-01-15 FR FR7900885A patent/FR2416250B2/en not_active Expired
- 1979-01-24 DE DE2902653A patent/DE2902653C2/en not_active Expired
- 1979-01-25 JP JP54006608A patent/JPS608064B2/en not_active Expired
- 1979-01-26 GB GB7902890A patent/GB2016018B/en not_active Expired
- 1979-01-26 NL NLAANVRAGE7900620,A patent/NL183333C/en not_active IP Right Cessation
- 1979-01-29 NO NO790287A patent/NO151667C/en unknown
- 1979-01-31 AU AU43801/79A patent/AU523113B2/en not_active Ceased
- 1979-01-31 IT IT09331/79A patent/IT1165930B/en active
- 1979-01-31 DK DK040379A patent/DK153497C/en active
- 1979-02-01 CA CA320,730A patent/CA1115460A/en not_active Expired
- 1979-02-01 CH CH99979A patent/CH637525A5/en not_active IP Right Cessation
- 1979-02-10 AR AR275367A patent/AR222031A1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE2902653A1 (en) | 1979-08-02 |
| NL7900620A (en) | 1979-08-03 |
| DK40379A (en) | 1979-08-02 |
| IL56371A (en) | 1984-02-29 |
| FR2416250A2 (en) | 1979-08-31 |
| NL183333B (en) | 1988-05-02 |
| FR2416250B2 (en) | 1986-05-09 |
| NO151667C (en) | 1985-05-22 |
| AU4380179A (en) | 1979-08-09 |
| IT1165930B (en) | 1987-04-29 |
| IT7909331A0 (en) | 1979-01-31 |
| CA1115460A (en) | 1982-01-05 |
| NO151667B (en) | 1985-02-04 |
| NL183333C (en) | 1988-10-03 |
| DK153497C (en) | 1988-12-12 |
| IL56371A0 (en) | 1979-03-12 |
| DE2902653C2 (en) | 1983-11-10 |
| GB2016018B (en) | 1983-01-12 |
| JPS54113430A (en) | 1979-09-05 |
| GB2016018A (en) | 1979-09-19 |
| AU523113B2 (en) | 1982-07-15 |
| CH637525A5 (en) | 1983-08-15 |
| JPS608064B2 (en) | 1985-02-28 |
| AR222031A1 (en) | 1981-04-15 |
| NO790287L (en) | 1979-08-02 |
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