WO2004029017A1 - Nouveaux composes d'ammonium quaternaire - Google Patents

Nouveaux composes d'ammonium quaternaire Download PDF

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WO2004029017A1
WO2004029017A1 PCT/AU2003/001260 AU0301260W WO2004029017A1 WO 2004029017 A1 WO2004029017 A1 WO 2004029017A1 AU 0301260 W AU0301260 W AU 0301260W WO 2004029017 A1 WO2004029017 A1 WO 2004029017A1
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Prior art keywords
lignosulfonate
benzalkonium
quaternary ammonium
alkyl
sulfate
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PCT/AU2003/001260
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English (en)
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Michael Susic
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Cooee Biosciences Limited
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Priority claimed from AU2002951785A external-priority patent/AU2002951785A0/en
Priority claimed from AU2003900463A external-priority patent/AU2003900463A0/en
Priority claimed from AU2003902377A external-priority patent/AU2003902377A0/en
Application filed by Cooee Biosciences Limited filed Critical Cooee Biosciences Limited
Priority to AU2003264174A priority Critical patent/AU2003264174A1/en
Publication of WO2004029017A1 publication Critical patent/WO2004029017A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl

Definitions

  • Quaternary ammonium compounds are widely used in the home, industry, and on the land as safe, powerful disinfectants and germicides.
  • the quaternary ammonium ion acts as a non-specific biocide by attaching to cell walls, and generally becomes active in the 1-3 ppm range.
  • the compounds are considered to be non-toxic to humans and animals.
  • Lignosulfonates are by-products from wood lignin, produced in the pulping processes in the manufacture of paper. Lignosulfonates are used in a variety of commercial applications as dispersants, sequestrants, emulsifiers, resin co-reactants and more commonly as binders or strengtheners. Lignins are highly complex amorphous natural polymers and as such the exact structure has not been ascertained to date.
  • Lignosulfonates are formed from the sulfonation of lignins, and are thought to be a combination of non-random two-dimensional polymers and random three-dimensional polymers of p-hydoxyphenylpropane.
  • the common counter-ions for lignosulfonates include sodium, ammonium, calcium, potassium and magnesium.
  • Calcium lignosulfonate is commonly used as a binder for particulate materials such as aggregate in the formation of road base.
  • the disadvantage with the use of calcium lignosulfonate as a binder in road construction is that calcium lignosulfonate is water soluble and tends to be leached away from road bases during episodes of rain, thus removing its binding effect and reducing the stability of the road base. Furthermore, the lignosulfonates when leached are an unsightly red-brown color.
  • US patent 4,666,522 describes the use of lignosulfonates in emulsion with a hydrophobe such as wax, oil, fat, asphalt or mixture thereof for use as a binding agent, and in particular the binding of particulate materials such as coal. US patent 4,666,522 teaches the presence of a hydrophobe to increase the strength of the binding effect but does not appear to address the leaching problem.
  • a hydrophobe such as wax, oil, fat, asphalt or mixture thereof
  • US patent 5,486,296 discloses the use of quaternary ammonium compounds as powerful antimicrobial agents, but they are very toxic to aquatic and marine life. US patent 5,486,296 teaches the use of lignosulfonates to neutralize the toxicity of alkyl quaternary ammonium compounds to aquatic organisms. To date there has been little or no investigations into water insoluble quaternary ammonium compounds, in particular quaternary ammonium lignosulfonates and dodecyl (lauryl) sulfates, their methods of production or their various applications such as binders, waterproofing agents, antifouling agents, antimicrobial agents or termite repelling agents or even determining how the toxicity is neutralized.
  • Ri is selected from alkyl; substituted alkyl; substituted phenyl alkyl; substituted phenoxy alkoxy alkyl; aryl; substituted aryl;
  • X- is selected from lignosulfonate; alkyl sulfate; alkyl sulfonate; fatty acid anions; naphthylacetate; naphthalene sulfonate; naphthyloxyacetate naphthalene disulfonate and aminonapthalenesulfonate.
  • alkyl refers to linear, branched or cyclic structures and combinations thereof, having 1 to 32 carbon atoms.
  • alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s- and t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cyclopropyl, cyclobutyl, cylcopentyl, cyclohexyl, and the like.
  • substituted alkyl refers to linear, branched or cyclic structures and combinations thereof, having 1 to 32 carbon atoms, as described above, substituted with one or more of the following: halogen, hydroxy, amine, carboxyl, carbonyl, ether, ester and the like.
  • substituted alkyl is selected from amine talloate or amine palmate.
  • Alkoxy means alkoxy groups of a straight, branched or cyclic configuration having 1-6 carbon atoms. Preferably alkoxy is selected from methoxy, ethoxy, propoxy, isopropoxy, and the like.
  • Heterocyclic refers to a non-aromatic ring having 1 to 4 heteroatoms said ring being isolated or fused to a second ring selected from 3- to 7- membered alicyclic ring containing 0 to 4 heteroatoms, aryl and heteroaryl, wherein said heteroatoms are independently selected from O, N and S.
  • Non- limiting examples of heterocyclyl include oxetanyl, 1 ,3-dithiacyclopentane, dihydrobenzofuran, and the like.
  • Aryl means a 6-14 membered carbocyclic aromatic ring system comprising 1-3 benzene rings. If two or more aromatic rings are present, then the rings are fused together, so that adjacent rings share a common bond. Examples include phenyl and naphthyl.
  • the aryl group may be substituted with one or more substituents independently selected from halogen, such as chlorine, fluorine or bromine; hydroxy; alkyl and alkoxy, as described above.
  • heteroaryl as used herein represents a 5-10 membered aromatic ring system containing one ring, 1-2 heteroatoms, selected from O, S and N.
  • Heteroaryl includes, but is not limited to, furanyl, diazinyl, imidazolyl, isooxazolyl, isothiazolyl, pyridyl, pyrrolyl, thiazolyl, triazinyl.
  • the heteroaryl group may be substituted with halogen, amino, hydroxy and alkyl.
  • fatty acid anions as used herein represents a fatty acid of high molecular weight having a 12- to 14- carbon chain. Non-limiting examples of fatty acid anions include but are not limited to myristate, palmitate and stearate.
  • R-i is a substituted phenoxy alkoxy alkyl it is a 2-(p- (1 ,1 ,3,3-teteramethylbutyl)phenoxy) ethoxy ethyl.
  • Ri is selected butyl; 2-(p-(1 ,1 ,3,3-teteramethylbutyl)phenoxy) ethoxy ethyl; benzyl; alkylbenzyl, wherein alkyl is C4 - C32; talloate; and palmate;
  • R 2 and R 3 are selected from hydrogen; methyl; ethyl; or butyl;
  • R 4 is selected from hydrogen; methyl; ethyl; butyl; C4 - C32 alkyl; or
  • Ri, R 2 & R 3 together form a pyridinium ion with the nitrogen; and
  • X " is selected from lignosulfonate; dodecyl (lauryl) sulfate; tetradecyl sulfate; fatty acid anions are selected from stearate, myristate or palmitate; naphthylacetate; naphthyloxyacetate; aminonapthalenesulfonate; naphthalene disulfonate, and aminonaphtholsulfonate.
  • the quaternary ammonium compounds of formula (I) are selected from; benzalkonium lignosulfonate; mixed alkyl (C12-C16) benzyl dimethyl ammonium lignosulfonate; benzethonium lignosulfonate; tetrabutyl ammonium lignosulfonate; cetylpyridinium lignosulfonate; tallow diammonium lignosulfonate; benzyl ammonium lignosulfonate; trimethyldodecylammonium lignosulfonate; benzalkonium dodecyl (lauryl) sulfate; cetylpyridinium dodecyl (lauryl) sulfate; tetra butylammonium dodecyl (lauryl) sulfate; dequalinium dilauryl (didodecyl) sulfate; triclobi
  • benzalkonium 8-amino-2-naphthalene sulfonate benzalkonium 1-amino-2-naphthol-4-sulfonate; or benzalkonium 6-amino-1 -naphthol-3-sulfonate.
  • More preferably quaternary ammonium compounds of formula (I) are selected from; benzalkonium lignosulfonate; benzalkonium dodecyl (lauryl) sulfate; benzalkonium 5-amino-2-naphtalene sulfonate; or cetylpyridinium dodecyl (lauryl) sulfate.
  • the invention provides a method of producing the quaternary ammonium compounds of formula (I), comprising the steps of; adding a solution of X " to an aqueous solution of an ammonium compound having a formula (II), defined below;
  • n, m, R-i, R 2 , R 3 , R 4 and X are as defined for formula (I) above;
  • Y " is selected from chlorine, bromine and phosphate. stirring the solution until a precipitate of quaternary ammonium lignosulfonate of formula (I) is formed; separating and drying the compound of formula (I).
  • the method of producing compounds of formula (I) may further comprise the step of acidifying an amine precursor in order to protonate the amine to form the ammonium ion of formula (II) prior to addition of the aqueous lignosulfonate solution.
  • the aqueous solutions of X " and ammonium of formula (II), or its amine precusor are formed by addition of the respective reagents to hot water or adding the respective reactants to cold water and heating till dissolved.
  • the invention provides the use of quaternary ammonium compounds of formula (I) as waterproofing agents; binders; strengtheners; antifouling agents; antimicrobial agents; anti-termite agents and/or biocides.
  • quaternary ammonium compounds of formula (1) are used as anti-termite agents they are mixed with or co-applied with emulsions of bitumen or high molecular weight esters, such as wool grease.
  • lignosulfonate is taken to mean any source of lignosulfonate obtained either commercially or as a by-product of paper pulping processes and may include but is not limited to calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, potassium lignosulfonate, iron lignosulfonate or chrome lignosulfonate.
  • FIG 1 is a graph showing a comparison of dry and wet shock strengths of calcium lignosulfonates and benzalkonium lignosulfonates.
  • lignosulfonate such as benzalkonium lignosulfonate, benzethonium lignosulfonate, tetrabutyl ammonium lignosulfonate, mixed C12-16 alkyl benzyl dimethyl ammonium lignosulfonate and cetylpyridinium lignosulfonate are all produced by the process described below.
  • the lignosulfonate source may be selected from calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, potassium lignosulfonate, iron lignosulfonate, chrome lignosulfonate and the like.
  • the quaternary ammonium compound, or amine precursor is dissolved in hot water to give a 50-80% solution.
  • the solution also has acid added to it in order to protonate the amine, thus forming an ammonium ion source.
  • lignosulfonate solution Approximately 2 parts by weight of lignosulfonate solution are mixed with approximately 1 part by weight of quaternary ammonium solution and reacted whilst stirring thoroughly and rapidly for 10-15 min with a blade stirrer or similar device.
  • concentration of lignosulfonate to be reacted is 10-50%.
  • concentration of ammonium compound to be reacted is preferably 10-80%.
  • Benzalkonium lignosulfonate was formed by reacting 0.5-0.55 g of benzalkonium chloride with 1 g of calcium lignosulfonate. Formation of other quaternary ammonium lignosulfonates may require slightly different ratios but will be of a similar order of magnitude.
  • the resultant quaternary ammonium lignosulfonate precipitate is allowed to settle, usually taking about 15 min, prior to decantation of the liquid and washing the precipitate 3-5 times with a volume of water equal to the decanted liquid.
  • the precipitated quaternary ammonium lignosulfonate is generally a sticky precipitate that requires agitation during the washing step to ensure removal of solvents and unreacted ingredients. Drying can be done at ambient temperature or with the aid of heat, air currents, or similar.
  • a convenient manner to store and transport the quaternary ammonium lignosulfonates is to dissolve them in a polar solvent such as ethanol, methanol, propanol, pentanol, butanol, methoxy propoxy propanol and the like, or aqueous mixtures with an alcohol having up to 60% water.
  • a polar solvent such as ethanol, methanol, propanol, pentanol, butanol, methoxy propoxy propanol and the like
  • an alcohol having up to 60% water aqueous mixtures with an alcohol having up to 60% water.
  • the quaternary ammonium lignosulfonates are dissolved in hot alcohol with vigorous stirring, preferably by mechanical means, in order to break up the sticky quaternary ammonium lignosulfonate mass and encourage dissolution.
  • the quaternary ammonium lignosulfonates dissolved in ethanol may have a concentration of up to about 85% (w/v) quaternary ammonium lignosulfonate, depending on which quaternary ammonium lignosulfonate is being prepared.
  • Some quaternary ammonium lignosulfonates for example cetyl pyridinium lignosulfonate, are insoluble in ethanol. Whilst cetylpyridinium lignosulfonate as a product is insoluble it is produced in a similar manner to the process outlined above.
  • an aqueous solution of amine is protonated by the addition of hydrochloric acid (HCI).
  • HCI hydrochloric acid
  • tallow amine is protonated by adding hydrochloric acid to the aqueous solution of tallow amine to give a pH of 1 , prior to mixing with the lignosulfonate solution.
  • benzalkonium lignosulfonate formed by the above process found 2.18% (w/w) nitrogen, from the quaternary ammonium portion, and 2.34% (w/w) sulfur, from the lignosulfonate portion, which may be used as a means of defining the amounts of each ingredient to use. Alternatively, it may be calculated that there are on average 3 quaternary ammonium groups to 1 lignosulfonate, although this method is not very accurate.
  • the compounds are very soluble in alcohols, but poorly soluble in other solvents, with the exception of cetylpyridinium lignosulfonate, which is not soluble in water or alcohols.
  • a trace amount of quaternary ammonium lignosulfonate dissolves in water to form a low concentration surfactant and biocide.
  • the quaternary ammonium lignosulfonates typically absorb water (43% (w/v) for benzalkonium lignosulfonate) to form an extremely sticky, reddish-black mass. On complete drying they are hard, brittle, reddish-brown solids. It has been found that mixed alkyl benzyl dimethyl ammonium lignosulfonate remains a soft material even after thorough drying.
  • EXAMPLE 2 QUATERNARY AMMONIUM COMPOUNDS MANUFACTURE:-
  • the quaternary ammonium raw material is dissolved in water, generally at a 50% (w/v) solution.
  • This type of solution is commonly available as an inexpensive commercial product (e.g. from APS Chemicals) and can be used without further treatment.
  • the compound with the counter- ion is also dissolved in water, or purchased as such.
  • Calcium lignosulfonate is readily purchased as a 72% (w/v) solution (e.g. from Dustex Australia Pty Ltd).
  • Benzalkonium lauryl sulfate is prepared by adding 1.05 times the weight of benzalkonium chloride in a 50% (w/v) solution to a given weight of sodium lauryl sulfate in a 10% (w/v) solution.
  • the benzalkonium chloride 50% (w/v) solution is used as purchased.
  • the sodium lauryl sulfate is dissolved in hot water with an electric mixer or similar means and allowed to cool.
  • the benzalkonium chloride and sodium lauryl sulfate are mixed with an electric mixer or similar means.
  • the white precipitate is allowed to settle (several days), is filtered, or is centrifuged out. The supernatant is removed and discarded.
  • the insoluble product is washed several times with water, the supernatant being removed and discarded, and the product is finally dried at ambient conditions or more commonly at about 100°C.
  • Benzalkonium 5-amino-2-naphthalene sulfonate is prepared in a similar way to benzalkonium lauryl sulfate. However, 1.4 times the benzalkonium chloride to sodium 5-amino-2-naphthalene sulfonate must be used, and the initial product is a pink oil. This oil forms a layer below the water and can be readily washed. It was found after the first washing that the oil formed a solid of low melting point. Final drying is done at about 60°C.
  • All other compounds are formed in a similar manner to benzalkonium lauryl sulfate. However, some compounds are difficult to isolate and/ or purify and may for example require centrifugation in order to separate oily layers.
  • Some of the quaternary ammonium compounds of the invention may be prepared in-situ and used successfully if the by-products that are formed are compatible with intended application. For example, addition with high speed mixing of equimolar amounts of commercial 50% (w/v) benzalkonium chloride to 10% (w/v) sodium lauryl sulfate gives a 17% (w/v) emulsion of benzalkonium lauryl sulfate that also contains about 1.7% (w/v) dissolved sodium chloride.
  • the mixture formed from in-situ production can be applied without isolating and purifying the benzalkonium lauryl sulfate.
  • BLS benzalkon um lignosulfonate
  • BzLS benzethonium lignosulfonate
  • CPLS cetylpyridinium lignosulfonate
  • TMDALS trimethyldodecylammonium lignosulfonate
  • BDS benzalkonium dodecyl (lauryl) sulfate
  • CPDS cetylpyridinium dodecyl (lauryl) sulfate
  • TBADS tetrabutylammonium dodecyl (lauryl) sulfate
  • BSt benzalkonium stearate
  • BNA benzalkonium naphthylacetate
  • BNOA benzalkonium naphthyloxyacetate
  • BANS benzalkonium 5-amino-2-naphthalene sulfonate
  • DDS dequalinium dilauryl (didodecyl) sulfate
  • Fatty acid derivatives form thick gels, and other products are oils or compounds that are readily soluble in an excess of one of the ingredients.
  • the compounds are soluble in only a narrow range of solvents, primarily in alcohols such as methanol, ethanol, and n-butanol. They are only slightly soluble in solvents such as acetone and ethyl acetate, and are insoluble in more hydrophobic solvents such as chloroform. Cetylpyridinium lignosulfonate is insoluble in all common solvents. MODE OF ACTION
  • Compounds of formula (I), particularly when they are quaternary ammonium lignosulfonates, may be used as strengtheners and binders on a range of materials, including particulate materials which may be used in road base, including crusher dust, aggregate, crushed coral, laterite and the like, or on cellulose materials such as cardboard and paper.
  • an ethanol solution of the quaternary ammonium lignosulfonate compound of formula (I) or an emulsion in water/ ⁇ -butanol (9:1) can be applied to road base materials by spraying or similar means either at the mill and pugged, or on site, with or without further mixing, and allowed to dry.
  • Application of the quaternary ammonium lignosulfonate solution or emulsion to other materials such as paper, cardboard, etc. may be carried out in a similar manner to the application to road base.
  • water/alcohol emulsions of quaternary ammonium lignosulfonate may be also be formed with other alcohols, such as sec-butanol, tert-butanol and the like.
  • the ratio of water to alcohol preferably ⁇ -butanol is from 2:1 to 12:1. Most preferably the ratio of water to alcohol is 9:1, especially in the case of water to ⁇ -butanol.
  • These water/alcohol emulsions of quaternary ammonium lignosulfonate may be used in a range of applications as outlined in more detail below.
  • the quaternary ammonium compounds of formula (I) have been found to be effective antimicrobial agents.
  • the compounds of formula (I) are lignosulfonates they may be formulated into an ethanol solution (preferably 5-10% w/v), can be readily painted or sprayed onto all surfaces, including wood, glass, plastic, painted surfaces, and metals.
  • the quaternary ammonium lignosulfonate solutions dry into a thin, hard, light brown, homogeneous film that becomes soft if placed under water, but does not dissolve.
  • the quaternary ammonium lignosulfonate solutions by themselves may be used as coatings or varnishes, or may be mixed with other materials such as paints, and used as antimicrobials. .
  • Quaternary ammonium ions at 1-3 ppm in water, are known to be powerful antimicrobial agents. It is therefore hypothesized that these novel compounds of the invention will be useful in providing slow-release, water- insoluble antimicrobial agents.
  • the quaternary ammonium compounds of formula (I), including the lignosulfonate containing compounds, may be used in diverse applications such as commercial air conditioning systems, paints and varnishes on walls, floors, and equipment in areas requiring a high degree of disinfection.
  • the quaternary ammonium compounds of formula (I) have been found to be effective antifouling agents.
  • quaternary ammonium compounds of foumula (I) may be used as antimicrobial agents, for example the quaternary ammonium lignosulfonate compounds of formula (I) may be used as coating or varnishes, or mixed with other materials, such as paints, and may also be used as antifouling agents.
  • Antifouling agents work by releasing minute quantities of toxic materials from a matrix. In the case of coatings or films of quaternary ammonium lignosulfonates when water runs over a surface coating small amounts of quaternary ammonium ion are released.
  • the advantage of the quaternary ammonium ions as an antifouling agent is that they are known to be non-toxic to humans and animals.
  • EXAMPLE 3A BINDING STRENGTH TESTS
  • the quaternary ammonium lignosulfonates of formula (I) stick strongly and are excellent binders for materials such as road bases, cardboard, paper, etc. When totally dry most are brittle and poor binders. By adding a small amount of calcium chloride the quaternary ammonium lignosulfonates remain stickier and less brittle. However, calcium chloride in roads causes corrosion of vehicles and may not be useful. However, the mixed C12-C16 alkyl benzyl dimethyl ammonium lignosulfonate retains its stickiness even when totally dry, and is therefore a superior binder.
  • FIG 1 demonstrates the dry and wet shock strengths of crusher dust with added binder.
  • Wet shock strength of calcium lignosulfonate is less than its dry shock strength, whereas for benzalkonium lignosulfonate the opposite is true.
  • Another strength test is to submerse the molds in water and measure the time for complete disintegration.
  • EXAMPLE 3B ANTIBACTERIAL PROPERTIES A 10% (w/v) solution of benzalkonium lignosulfonate was tested against six common bacteria, namely Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Bacillus cereus, Salmonella typhimu um, and Klebsiella pneumoniae. The organisms were transferred from plate cultures and inoculated into nutrient broths, then incubated at 37°C overnight to establish viability. The cultures were reinoculated into fresh broths and then transferred to nutrient agar plates while in log growth phase. Oxoid blank susceptibility disks were soaked in the 10% solution for 15 minutes and then dried overnight in the 37°C incubator.
  • Disks were also soaked in ethanol to determine any effect the solution solvent was contributing. Sterilised blank disks were used as a negative control and Chloramphenicol 30 ⁇ g (Cm 30) as a positive control. The disks were added to the agar plates and incubated overnight in the 37°C incubator.
  • Ethanol did not contribute to growth inhibition.
  • Benzalkonium lauryl sulfate was tested in the same manner and found to be strongly effective against S. aureus, B. subtilis, and B. cereus, and moderately effective against E. coli. In contrast to benzalkonium lignosulfonate, it was found to be ineffective against K. pneumoniae and S. typhimurium.
  • a 10% (w/v) solution of benzalkonium lignosulfonate in ethanol was mixed with a water-based acrylic paint to give various concentrations of the benzalkonium lignosulfonate.
  • the mixture was applied evenly onto pieces of plywood at the rate of 1 U 5 m 2 , allowed to dry, and placed into a damp shower recess for 2 weeks. Mold growth was measured by the amount of black matter that covered the rear of the plywood.
  • the control (no benzalkonium lignosulfonate) had 85% mold cover, a 0.1% (w/v) concentration had 4% mold cover, a 0.25% (w/v) concentration had 1% mold cover, but 0.5% and 1% (w/v) concentrations were totally free of mold.
  • the high molecular weight ester timber treatment comprises wool grease dissolved in D60 (a heavy hydrocarbon solvent) and stearic acid and emulsified in water, in a manner similar to that described in PCT/AU03/00963.
  • the wool grease emulsion contains greater than 7.5% (w/v) of wool grease, a hydrocarbon solvent, a carboxylic acid, such as stearic acid in an oil-in-water emulsion.
  • Benzalkonium lignosulfonate and benzalkonium lauryl sulfate were also tested for efficacy against wood rot fungi. Growth of a white-rot fungus Perenniporia tephropora (7904) and a brown-rot fungus Coniophora olivacea (1779) was monitored on each of three filter papers treated with 10% ethanol solutions of benzalkonium lignosulfonate and benzalkonium lauryl sulfate, respectively. Growth was compared to control filter papers treated with ethanol and water, respectively. Ethanol was allowed to evaporate from all filter papers prior to inoculation.
  • novel quaternary ammonium compounds are non-toxic to humans and animals, are water-insoluble, have excellent antibacterial activity, and some have high heat resistance, but become soft above about 150°C. This makes them excellent compounds for incorporating into many types of plastics because many plastics are extruded at temperatures between 160- 220°C. Therefore, these compounds could be incorporated into plastics used for packaging films, food containers, drinking water reservoirs, air conditioners, washing machines, refrigerators, toys, dolls, milk containers, toothbrushes, and the like.
  • the quaternary ammonium compounds of the invention may act as preservatives of timber and in the prevention of termite infestation, either alone or in combination with wool grease emulsions.
  • the quaternary ammonium compounds may be painted or sprayed onto timber surfaces or applied under cycles of vacuum and pressure. After application of the quaternary ammonium compounds the timber may be further coated with one or more coats of a wool grease emulsion, such as described in Example 3C. Alternatively, the antimicrobials may be mixed with the wool grease emulsion and applied simultaneously onto timber surfaces or applied under cycles of vacuum and pressure.
  • the wool grease emulsion contains greater than 7.5% (w/v) of wool grease, a hydrocarbon solvent, a carboxylic acid, such as stearic acid in an oil-in-water emulsion.
  • the mixture contains in addition to the ingredients above 2% (w/v) of benzalkonium lauryl sulfate, or 1.2% (w/v) of benzalkonium lignosulfonate, or 3% (w/v) of benzalkonium 5-amino-2- naphthalene sulfonate.
  • Wood blocks of Pinus radiata (50 x 40 x 40 mm, with the grain in the 50 mm direction) were treated with the quaternary ammonium lignosulfonates of formula (I) with and without wool grease emulsion treatment (as described above), and solvent controls of both ethanol and water were similarly treated. Controls were soaked for 15 min consecutively in ethanol and water. All samples were dried at ambient conditions for 3 days.
  • Base Wood block nearest cap with wire-vent hole.
  • Table 5 outlines the assessment criteria used in these qualitative assessments.
  • the scale offers an indication of the palatability of treated timber specimens in test, and is not a definitive quantitative assessment scale.
  • Timber treatments refer to any materials added onto or into untreated wood specimens. This includes solvent controls, such as ethanol or water, which have no other additive or toxin.
  • Base Wood block nearest cap with wire-vent hole.
  • Randomized treated wood blocks were placed within each of five tube containers (300 x 90 mm), and inserted into aboveground mound colonies of C. lacteus. Termites were allowed to forage into the tube containers for 28 days. After this period, all the tube containers were withdrawn from the mound colonies and the feeding response of the natural populations of C. lacteus towards the various treated wood blocks was measured using a simple objective rating system of attack and damage, as outlined in Table 4, above).
  • Table 8 Termite feeding response to treated wood blocks in the C. lacteus above-ground mound colonies in the field experiment as measured by visual ratings after a 28-day test period.
  • Base Wood block nearest cap with wire-vent hole.
  • Top Wood block nearest poly pipe into tube container from termite mound.
  • Blocks treated with the highest loadings of anti-microbial and one coat of wool grease emulsion showed mostly termite visits and only a single termite nibble.
  • the anomalous responses of the termites to the 0.5 and 1.0% anti-microbial blocks are considered to be due to differences in application rates.
  • the wood blocks treated with 1.5% solution of anti-microbial and wool grease emulsion showed the lowest feeding response after the 28 day test period. TABLE 9. Summary of results applying wool grease emulsions and/ or benzalkonium lauryl sulfate solutions
  • TV Termite visit
  • TN Termite nibble
  • SA Slight attack
  • MA Moderate attack
  • SV Severe attack.
  • Example 4A The process of Example 4A was repeated using benzalkonium stearate (BSt), benzalkonium dodecyl (lauryl) sulfate (BDS) and benzalkonium lignosulfonate (BLS) but where they were used in combination with wool grease emulsions they were mixed with the emulsion rather than applied separately. Results are summarised below in Table 10.
  • Wool grease emulsion is an O ⁇ /V emulsion containing wool grease.
  • Softwood timber pieces were allowed to soak overnight in solutions of wool grease emulsions containing 2% (w/v) benzalkonium lignosulfonate, 2% (w/v) benzalkonium lauryl sulfate, and 2% (w/v) benzalkonium 5-amino-2- naphthalene sulfonate as described in Example 4 above, and allowed to dry for 3 days.
  • the treated softwood timber samples were placed on concrete blocks covered in mold and exposed to the weather. In this accelerated mold test, after 4 weeks the control was almost totally covered with black mold, but the treated samples were totally free of mold.
  • Cationic, but preferably anionic, bitumen emulsions may be added to the water insoluble quaternary ammonium compounds when such compounds form an emulsion (refer to "In situ preparation" above).
  • Examples of compounds that give an emulsion are benzalkonium lauryl sulfate and cetylpyridinium lauryl sulfate.
  • Bitumen is slowly added to and mixed with these emulsions in ratios ranging from 1 part bitumen to 5 parts quaternary ammonium compound to 10 parts bitumen to 1 part quaternary ammonium compound.
  • the product is used for "enveloping" timber by painting, spraying, or dipping.
  • the benzalkonium lauryl sulfate/ bitmen mixture has also been shown to be effective against marine borers in tropical and sub-tropical coastal waters.
  • Timber was enveloped with an emulsion containing 6% (w/v) benzalkonium lauryl sulfate + 32% (w/v) bitumen at the rate of 1 L/ 10 m 2 .
  • the product was painted onto the timber and allowed to dry for two days prior to being placed into sea water. After 3 months no marine borers had attacked the timber either above or below the water line, and there were no signs of any degradation, while controls were severely attacked. Under laboratory conditions a softwood block submerged in sea water for 6 months showed no signs of peeling, flaking, or any other signs of degradation. In fact, the benzalkonium lauryl sulfate and bitumen on drying forms a soft, plastic-like material that appears to be an excellent coating for timber.
  • Benzalkonium lignosulfonate was found to be a better antibacterial than benzalkonium lauryl sulfate, correlating with their respective amounts leached into water. Since quaternary ammonium compounds are known to be non-specific antimicrobial by targeting cell walls, our data are consistent with the notion that efficacy of the novel quaternary ammonium compounds is due to the amount of free quaternary ammonium ion in water. This means that compounds can be designed to deliver specific amounts of quaternary ammonium ion concentrations into their surrounding water to achieve a desired efficacy. Therefore toxicity levels in aquatic and marine environments can be better controlled than by the use of current very soluble compounds such as benzalkonium chloride. This is well illustrated in the experiment with aquatic snails described above.
  • novel quaternary ammonium compounds of the invention are water resistant, antimicrobial and anti-termite compounds, they can be used for timber treatment.
  • they When prepared as an O/W emulsion prior to any isolation or purification, they can be added as a surface product to timber or injected under vacuum or pressure or both sequentially into timber.
  • After isolation, purification and dissolution of the compounds in ethanol or similar solvents they can be added as a surface product to timber or injected under vacuum or pressure or both sequentially into timber. They protect against water ingression, termites, rot, mold, algae, and fungi.
  • quaternary ammonium compounds of the invention mix well with high molecular weight ester O/W emulsions, such as the wool grease emulsions described above, used for timber treatment.
  • Benzalkonium lignosulfonate can be added up to a concentration of 1.2% (w/v) without compromising emulsion stability. At this concentration, together with 7% (w/v) of the high molecular weight esters, the mixture becomes an effective anti-termite/ antifungal product, and retards mold and algal growth.
  • Benzalkonium lauryl sulfate is an antimicrobial, water resistant, wax- like compound that forms an emulsion and can be added at higher concentrations (up to about 10% (w/v)) to the high molecular weight ester O ⁇ /V emulsions used for timber treatment.
  • the benzalkonium lauryl sulfate enhances the water repelling properties of the high molecular weight esters, and at 2% (w/v) provides antimicrobial properties, and the mixture strongly repels termites and prevents rot and mould from attacking timber.
  • the quaternary ammonium compounds of the invention may be designed to deliver target levels of quaternary ammonium ions and to incorporate properties of the counter-ion, providing flexibility in the properties available that is not provided by the currently known quaternary ammonium compounds which generally have chloride, bromide, or phosphate as their counter ions.
  • lignosulfonate in the quaternary ammonium compound results in an extremely sticky substance that can be utilised in applications that require surface adhesion of a thin coat.
  • Lauryl sulfates form wax like compounds that can be applied to timber to repel water, thereby helping to preserve timber from cracking and splitting and from rot fungi that require high moisture contents, as well as delivering the antimicrobial effect.
  • Amino naphthalene sulfonates contain the naphthalene group that is a powerful insect repellent. Whilst, stearates are gels like soaps, so form an antimicrobial soap that does not readily dissolve in water.
  • the compounds of this invention are insoluble in water and therefore more readily persist at their application site. Since they leach into water up to about 300 ppm, they are still powerful biocides, but their toxicity to aquatic and marine life is dramatically reduced. Further, the quaternary ammonium compounds of this invention have been designed to take advantage of special properties that the counter ion may have. For example, the lignosulfonates adhere strongly to all surfaces, thereby keeping the compound indefinitely at its application site, and the lauryl sulfates are water repelling wax-like compounds that are excellent for waterproofing timber. It will be appreciated by the person skilled in the art that variations in the invention may be made without departing from the essence of the invention.

Abstract

L'invention concerne un composé d'ammonium quaternaire insoluble dans l'eau, représenté par la formule (I), dans laquelle n égale 1 ou 2 ; m égale 0 ou 1 ; R1 est sélectionné dans le groupe comprenant alkyle, alkyle substitué, phénylalkyle substitué ; alcoxy alkyle phénoxy substitué ; aryle ; aryle substitué ; R2 et R3 sont sélectionnés indépendamment entre hydrogène et alkyle ; R4 est sélectionné indépendamment dans le groupe comprenant hydrogène, alkyle et aryle ; ou R1, R2 et R3 forment ensemble avec l'azote un noyau hétérocyclique ou hétéroaryle éventuellement substitué ; et X est sélectionné dans le groupe comprenant lignosulfonate, sulfate d'alkyle, sulfonate d'alkyle, anions d'acides gras, acétate de naphtyle, sulfonate de naphtalène, disulfonate de naphtyloxyacétate naphtalène et sulfonate d'aminonaphtalène. L'invention concerne aussi un procédé de production de ces composés et leur utilisation comme agents imperméabilisants, liants, renforçateurs, agents antisalissures, agents antimicrobiens, agents antitermites et/ou biocides.
PCT/AU2003/001260 2002-09-26 2003-09-24 Nouveaux composes d'ammonium quaternaire WO2004029017A1 (fr)

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AU2002951785 2002-09-26
AU2002951785A AU2002951785A0 (en) 2002-09-26 2002-09-26 Novel quaternary ammonium lignosulfonates
AU2003900463 2003-02-04
AU2003900463A AU2003900463A0 (en) 2003-02-04 2003-02-04 Novel quaternary ammonium lignosulfonates
AU2003902377 2003-05-16
AU2003902377A AU2003902377A0 (en) 2003-05-16 2003-05-16 Novel quaternary ammonium compounds

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WO2013024486A1 (fr) 2011-08-18 2013-02-21 Director General, Defence Research & Development Corporation Formulation biologique anti-termite et procédé pour la préparation de celle-ci
WO2018191331A1 (fr) * 2017-04-11 2018-10-18 Stepan Company Composition pour désinfecter des surfaces contenant des bactéries provoquant la tuberculose
US11261389B2 (en) 2019-05-15 2022-03-01 Innospec Limited Compositions and methods and uses relating thereto
CN116283751A (zh) * 2023-03-17 2023-06-23 胜利油田物华化工厂 一种用于污水处理的杀菌剂及合成方法

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WO2013024486A1 (fr) 2011-08-18 2013-02-21 Director General, Defence Research & Development Corporation Formulation biologique anti-termite et procédé pour la préparation de celle-ci
WO2018191331A1 (fr) * 2017-04-11 2018-10-18 Stepan Company Composition pour désinfecter des surfaces contenant des bactéries provoquant la tuberculose
US11089779B2 (en) 2017-04-11 2021-08-17 Stepan Company Composition for disinfecting surfaces containing tuberculosis causing bacteria
US11261389B2 (en) 2019-05-15 2022-03-01 Innospec Limited Compositions and methods and uses relating thereto
CN116283751A (zh) * 2023-03-17 2023-06-23 胜利油田物华化工厂 一种用于污水处理的杀菌剂及合成方法

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