WO2008131918A1

WO2008131918A1 - Reactive surfactants and their use

Info

Publication number: WO2008131918A1
Application number: PCT/EP2008/003349
Authority: WO
Inventors: Janne Hulkko; Salme Koskimies; Reetta KYLÄKOSKI; Aki Laine; Hendrik Luttikhedde; Pia WILLBERG-KEYRILÄINEN
Original assignee: Ciba Holding AG; BASF SE
Current assignee: BASF Schweiz AG; BASF SE
Priority date: 2007-04-25
Filing date: 2008-04-25
Publication date: 2008-11-06
Anticipated expiration: 2009-10-25

Abstract

The present invention relates to polymerizable anionic surfactants, to manufacture thereof, to preparation of emulsion polymers by using the surfactants and to uses of these polymers.

Description

REACTIVE SURFACTANTS AND THEIR USE

Field of the Invention

The present invention relates to polymerizable surfactants, to manufacture thereof, to preparation of emulsion polymers by using the surfactants and to uses of these polymers.

Prior Art

With increasing environmental concern, there has been severe pressure to remove volatile organic compounds from coatings, inks and adhesives. As a consequence, alternative coating technologies, which minimise or eliminate the role of organic solvents in formulations, are being aggressively pursued. Nowadays water-borne polymer dispersions (latexes) are widely used e.g. in paints, inks, adhesives and paper coatings.

Surfactants have an important role in the production of polymer dispersions, but they can also have unfavourable effects on the properties of prepared polymer films. The surfactants can desorb from the polymer particles surface, which may cause flocculation. Also migration of the unbounded surfactant through the film can cause lack of adhesion upon the substrate, modify water sensitivity and have adverse effects on the optical properties. These disadvantages are due to the mobility of the surfactant.

The use of polymerizable surfactants in emulsion polymerization has been studied and in optimal cases they can minimize the defects caused by the traditional surfactants. However, industrial manufacturing of the polymerizable surfactants is generally complicated and more expensive than the preparation of conventional unreactive surfactants thus limiting their application areas. Besides, the structure of the polymerizable surfactant and its reactivity during polymerization processes are of vital importance in obtaining stable polymer dispersions with the desired

CONRRMATION COPY properties. Too high reactivity of the reactive surfactant leads to its too early co- polymerization, burying surfactants inside the growing polymer particles leading to the incomplete surface coverage and decreased stability. On the other hand, if the reactivity is very low, the reactive surfactant behaves like a nonreactive surfactant and it does not incorporate into the polymers. The polymerizable groups can be either in the hydrophilic or hydrophobic part of the surfactants. As the monomers of the emulsion polymerization are usually hydrophobic and the polymerization takes places mainly inside the polymer particles, the polymerizable groups should be preferably located in the hydrophobic part of the polymerizable surfactant.

This invention teaches that novel polymerizable surfactants with optimal co- polymerization behaviour in emulsion polymerizations can be economically derived from cashew nutshell liquid (CNSL) or cardanol. Numerous publications and patents describe surface active alkyl phenols derived from CNSL and cardanol, but those surfactants haven't been used for emulsion polymerizations and the reactivity of the unsaturated double bonds haven't been exploited at all. In the most of the publications, the double bonds of cardanol have appeared as unwanted functionalities, which have complicated the derivatisation processes and impaired the end use properties. Therefore the reactive double bonds have been usually removed by hydrogenation of cardanol to 3-n-pentadecylphenol or by other modifications prior conversion to surface active derivatives.

Publication Indian J. Technol. 1 (1963) 348-355 discloses preparation of sulphonates from cardanol, tetrahydrocardanol and their ethers and esters, having surface active effects.

GB-A-2262525, US-B1-7084103, WO-A 1-2004/020554 and WO-A 1-92/21741 describe non-ionic ethoxylated cardanol derivatives and their use in cleaning compositions, fuel emulsifiers and lubricating fluids. Publication Tyman, J. H. P., Bruce, I.E., Biodegradable Surfactants Derived from Phenolic Lipids in Surfactants in lipid chemistry: Recent synthetic, physical and biodegradative studies, ed. J. H. P. Tyman, Royal Society of Chemistry, Cambridge, 1992, pp. 159-177 describes preparation of non-ionic surfactants like cardol, saturated cardol and 3-pentadecylphenol polyethoxylates.

This invention, different from prior art, concerns phosphate and sulphate esters of cardanol, cardol, CNSL or cardanol (poly)alkoxylates and use of these anionic cardanol, cardol, CNSL or cardanol (poly)alkoxylate derivatives as polymerizable surfactants.

Some phosphorylated derivatives of CNSL and cardanol have already been reported, but those lack the surface active and highly unsaturated character and are not applicable as polymerizable surfactants.

A process for the preparation of phosphorylated prepolymers of CNSL and cardanol has been described in Indian patent specification 176069. The phosphorylation and oligomerization reactions are simultaneously initiated by heating cardanol with orthophosphoric acid to yield resinous oligomeric products.

GB-A-997165 describes the preparation of phosphate esters of 3- pentadecylphenol (i.e. hydrogenated cardanol). Corrosion inhibiting compositions containing the phosphate esters are also claimed. Similar triphosphate esters of cardanol and sulphurized cardanol are also described in US 2414263, but the cardanyl phosphates therein are non-ionic, water insoluble and not applicable as polymerizable surfactants.

Object of the Invention

The object of the invention are novel compounds derived from cashew nutshell liquid (CNSL) and especially from cardanol, which is obtained from CNSL. The disclosed compounds are especially anionic surface active agents like phosphate and sulfate derivatives of cardanol, CNSL or their (poly)alkoxy ethers.

Another object of the invention is the use of novel anionic surface active agents like phosphate and sulfate derivatives of cardanol, CNSL or their (poly)alkoxy ethers as reactive (polymerizable) surfactants, stabilizers and/or dispersing agents in the preparation of styrene-acrylic, styrene-butadiene, polyvinyl acetate and - alcohol polymer dispersions.

The object of the invention is also coatings and binder compositions containing anionic surface active agents like phosphate and/or sulfate derivatives of cardanol, CNSL or their (poly)alkoxy ethers.

Further, the object of the invention is to provide a method for improvement of coating and binder compositions' mechanical stability, high solids content and also water resistance and adhesive properties of polymer films.

Characteristic features of the novel anionic compounds, preferably phosphates and sulfates, which are derived from cashew nutshell liquid (CNSL), cardanol or their (poly)alkoxy ethers, the use of above mentioned anionic derivatives as reactive (polymerizable) surfactants, stabilizers and/or dispersing agents in the preparation of polymer dispersions and a method for improvement of coating and binder compositions' mechanical stability, high solids content and also water resistance and adhesive properties of polymer films are presented in the examples.

Summary of the Invention

According to the invention, anionic surfactants like phosphate and sulfate derivatives of cardanol, CNSL or their (poly)alkoxy ethers, are used as reactive (polymerizable) emulsifiers and/or stabilizers in surfactant-mediated heterophase polymerization processes, especially in emulsion polymerization for the preparation of polymer dispersions. Preferably in aqueous coating and binder compositions, reactive surfactants derived from CNSL and preferably from cardanol are used for the improvement of coating and binder compositions' mechanical stability and reduced surfactant migration thereby improving water resistance and adhesive properties of polymer films, coatings and binders according to the invention.

Detailed Description of the Invention

The disclosed novel surface active compounds are derived from cardanol (See Fig. 1), which is a product obtained by treating cashew nutshell liquid (CNSL).

CNSL is a unique alternative to petrochemically derived phenols and it is traditionally obtained as a by-product of cashew industry. Natural (cold, solvent extracted) CNSL contains approximately 70 % anacardic acid, 18 % cardol (See

Fig. 2), and 5 % cardanol and the remainder consists of other phenols and less polar substances. In technical (heat extracted) CNSL, the heating process leads to decarboxylation of the anacardic acid to form cardanol. Distilled technical CNSL contains generally approx. 78 % cardanol and 8 % cardol, but highly purified grades may consist solely of cardanol. Both cardanol and cardol are mixtures containing the mono-, di- and triene side chains. The average number of double bonds is approximately 2.

wherein n = 0, 1, 2, 3

Fig 1. Cardanol.

wherein n = 0, 1, 2, 3

Fig 2. Cardol.

It was surprisingly found that the problems of the known solutions of prior art may be eliminated or at least substantially reduced by the procedure of the invention. The invention is based on the finding that anionic polymerizable surfactants, particularly phosphate and sulfate derivatives can be produced selectively from inexpensive renewable waste material, cardanol and its (poly)alkoxy ethers with straightforward and economical methods.

Further, according to the invention CNSL based anionic polymerizable surfactants may totally or partly substitute traditional surfactants in heterophase polymerization processes, particularly in the preparation of polymer dispersions, and provide coatings and binder compositions with better storage stability, improved water resistance and also excellent adhesive properties and optical properties. This is due to high surface active character of disclosed compounds and their optimal co-polymerizability in emulsion polymerizations thanks to the abundance of reactive double bonds in the lipophilic part of the compounds.

The invention is now illustrated in more detail with the following description and finally by means of some examples.

According to the invention, anionic polymerizable surfactants derived from cardanol, cardol or cashew nutshell liquid are used as surfactants in emulsion polymers based on water or other solvents. The general formula below (Fig 3) shows the structure of the anionic polymerizable surfactants.

(CH₃),

Fig 3. Structure of novel anionic polymerizable surfactants.

wherein

A) and A₂ independently represent anionic group PO(OMi)(OM₂), wherein Mi and M₂ independently represent either H, Li, Na, K, NH₄, NH(CH₂CH₃)₃, NH₃CH₂CH₃OH, NH₂(CH₂CH₃OH)₂, NH(CH₂CH₃OH)₃ or C₆H₄-m-C i₅H₃i_-2n, wherein n being from O to 3, or anionic groups SO₂OM₃, CH₂-CH₂-SO₂-OM₄, CH₂-CO₂M₅, CO-CH=CH-CO₂M₆, CO-CH₂-CH₂-CO₂M₇ or CO-[C₂H₃(SO₃H)]- CO₂M₈, wherein M₃, M₄, Ms, M₆, M₇ and M₈ independently represent either H, Li, Na, K, NH₄, NH(CH₂CH₃)₃, NH₃CH₂CH₃OH, NH₂(CH₂CH₃OH)₂ or NH(CH₂CH₃OH)₃, i and y being independently from O to 30, preferably from O to 16, j and z being independently 1 or 2, k and x being independently from O to 30, preferably from O to 16, m being O or 1 , n being from 0.1 to 3, preferably from 1.2 to 1.5.

According to the invention, the lipophilic part (alkenylphenoxy) of anionic polymerizable surfactants is derived from cardanol, cardol or cashew nutshell liquid, which is mainly a mixture of aforementioned components. Further, their alkenyl groups consists of mono-, di- and triene sidechains, whose proportions depend on the starting material. The average number of double bonds is preferably between 1.0 and 3.0 per molecule and most preferably between 1.6 and 2.4. In the alkenyl groups of natural CNSL, multiple double bonds are separated by single methylene units, but the reactivity of the invented polymerizable surfactants can be further improved by conjugation of these double bonds.

The (poly)oxyalkylene groups may consist of oxyethylene residues alone, of oxypropylene residues alone, or they may include both oxyethylene and oxypropylene residues to give a random or block copolymer chain. Particularly, the chain is homopolymeric polyoxyethylene chain. The anionic functionality can be provided by a phosphorus acid group, a sulphur acid group or a carboxylic acid group. Suitable phosphorus acid groups include phosphate, and monoester phosphate (phosphoric acid dicardanyl ester). Suitable sulphur acid groups include sulphate, sulphonate and isethionate and suitable carboxylic acid groups include carboxymethoxy, maleate, succinate and sulphosuccinate. The salt forming moiety can be alkali metal, particularly Li, Na, K, ammonium, including amine or hydroxy-substituted amines like triethylamine and mono-, di- and triethanolamines.

Exemplary anionic polymerizable surfactants derived from cashew nutshell liquid or cardanol include sodium, potassium and ammonium salts of phosphoric acid monocardanyl ester, sodium salt of conjugated cardanyl monophosphate ester, sodium salt of hydroxyethylcardanyl ether monophosphate ester, sodium and potassium salts of cardanyl sulphate and sodium salt of conjugated cardanyl sulphate.

Anionic polymerizable surfactants of the invention may be produced using the following synthesis method comprising one to three steps, depending on the desired product. The first two optional steps comprising (poly)ethoxylation or (poly)propoxylation and/or conjugation followed by addition of anionic group into molecule including phosphation, sulphation, sulphonation, etherification or esterification in the third step and neutralization in the last step. In (poly)ethoxylation/(poly)propoxylation known in the art, cardanol, cardol or CNSL is allowed to react with 1 to 30, preferably with 1 to 20 molar equivalents of ethylene oxide or propylene oxide with acid or base catalysis at a temperature of 110 to 230 °C and preferably 150 to 220 °C under a pressure of 0.9 to 10 bar and preferably 1.0 to 5.0 bar. The product is suitably recovered by purging the reaction mixture with nitrogen and by washing the free alkali off. Generally the reaction time is 1 to 7 hours, preferably 2 to 5 hours and as catalyst, sodium methoxide, sodium hydroxide, potassium hydroxide or Lewis acids such as BF₃, SbCl₅ or SnCL_t is used at an amount of 0.05 -5 %, preferably 0.5-2 % by weight.

Alternatively, cardanol, cardol, or CNSL may be hydroxyalkylated with cyclic organic carbonates like ethylene and propylene carbonates in the presence of organic or inorganic catalysts like sodium or potassium hydroxide, sodium or potassium carbonate, triethylamine or imidazole with prior art processes. Preferably the reaction is carried out at a temperature of 140 to 180 °C for 0.5 to 5 hours. The amount of catalyst is preferably 0.2 to 5 % based on the total reactant weight and the preferred molar ratio of cardanol: cyclic organic carbonate is 1 :1.2 to 1 :3. The product may be recovered by distillation or filtration.

Isomerisation or conjugation reaction is carried out in an alkali-solvent solution, whereby cardanol, cardol or CNSL containing interrupted diene and triene systems are isomerised into conjugated systems. The isomerisation reaction is carried out in a solution of potassium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate, sodium methoxide and potassium t-butoxide in (poly)ethylene glycol, propylene glycol or glycerol under a stream of nitrogen. The amount of solvent is generally from 0.1 to 10 times, preferably from 0.2 to 5 times the weight of the starting material and typically about 5 % to 100 % of stoichiometric alkali excess provides a good working range and preferably 10-70 % of stoichiometric alkali excess is used. The reaction temperature is generally from 110 to 190° C, preferably from 130 to 180° C. The reaction time is generally from 1 to 6 hours, preferably from 2 to 3.5 hours. Typically, conversion level of 85 % or more is achieved when the reaction is carried out under the above- described preferable reaction conditions. The product is suitably recovered by washing the reaction mixture with aqueous solution of mineral acid, preferably phosphoric acid or hydrochloric acid and by separating the organic layer to obtain the yield of at least over 85 %, and typically at least 90 %. The product can be also isolated by extracting the mixture after acidification with organic solvent such as hexane and by evaporation. Optionally, the product may be isolated by distillation under diminished pressure.

Aforementioned alkoxylation and isomerization reactions may be also performed as a one-step reaction.

Cardanol, cardol, CNSL or their (poly)alkoxylates including conjugated derivatives may be phosphated with 1 to 4 molar equivalents, preferably with 1 to 1.4 molar equivalents of phosphorus oxychloride (POCl₃). A solvent can be used in the reaction. Examples of appropriate solvents include organic non-reactive solvents like hydrocarbons including toluene and hexane, ethers like diethyl ether, isopropyl ether, methyl tert-butyl ether, chlorinated hydrocarbons like dichloromethane and esters like ethyl acetate. The phosphation is generally conducted at a temperature of -10 to 50 °C, preferably at 10 to 30 °C. Triethylamine, pyridine or inorganic carbonates like potassium and sodium carbonates may be added as a deacidification agent in order to trap hydrogen chloride, which is formed during the reaction. Alternatively, AlCl₃ or KCl may be used as a catalyst. The base may be used in an amount of 1 to 4 molar equivalents, preferably 1 to 2 molar equivalents and particularly preferably 1 to 1.3 molar equivalents in order to ensure the high proportion of monophosphate ester in final product. If AlCl₃ or KCl is used as a catalyst, the suitable amount is 0.1 to 5 mol- % and preferably 0.5 to 3 mol-%. The reaction time is generally from 0.5 to 6 hours, preferably from 0.5 to 2 hours. The formed aryl- or alkyl phosphorodichloridate intermediate can be converted to corresponding monophosphate ester by treatment with water, preferably at elevated temperature. The monophosphate ester can be recovered after washing with water, phase separation and evaporation of solvent(s). Salt can generally be made from free acid by direct reaction with an appropriate base such as lithium, potassium or sodium hydroxide or carbonate, ammonia, triethylamine, ethanolamine, diethanolamine or triethanolamine, preferably with sodium or potassium hydroxide, ammonia or triethanolamine. The neutralization is typically performed in an aqueous mixture by adjusting the final pH of solution to range 5-10, preferably to range 6-8. As a product after neutralization, typically aqueous solution having pH value of 5 to 10, preferably 6 to 8, solids content of 50 % or more is obtained. Alternatively, the salt in solid form can be prepared by dissolving the phosphate ester in suitable solvent such as isopropanol before neutralization, decanting the liquid off after neutralization and by drying the jelly residue in vacuum, preferably at elevated temperature. The yield is generally over 80 % and more usually over 90 %. The product contains a high proportion of phosphoric acid monoester, generally over 70 % and more usually over 80 %.

Alternatively cardanol, cardol, CNSL or their (poly)alkoxylates including conjugated derivatives may be phosphated with 0.3 to 0.7 molar equivalents (calculated as phosphorus pentoxide), preferably with 0.4 to 0.6 molar equivalents of phosphoric acid, polyphosphoric acid, phosphorus pentoxide or their mixture at a temperature of 40 to 140 °C, preferably at 60 to 90 °C for 0.5-24 hours, preferably for 2-10 hours. The phosphate salts are prepared by stirring the phosphate esters high in monophosphate ester content, into a solution of an appropriate base. As examples of suitable base materials for producing the salts may be mentioned lithium, potassium or sodium hydroxide or carbonate, ammonia, triethylamine, ethanolamine, diethanolamine or triethanolamine, preferably sodium or potassium hydroxide, ammonia or triethanolamine. As a product after neutralization, typically aqueous solution having pH value of 5 to 10, preferably 6 to 8 and solids content of 50 % or more is obtained. The product contains a high proportion of phosphoric acid monoester, generally over 50 % and more usually over 65 %.

Cardanol, cardol, CNSL or their (poly)alkoxylates including conjugated derivatives may be sulphated with 1 to 4 molar equivalents, preferably with 1.3 to 2.5 molar equivalents of chlorosulfonic acid (ClSO₃H). An inert solvent for example toluene can be used in the reaction. The sulphonation is generally conducted at a temperature of -10 to 50 °C, preferably at 0 to 30 ⁰C. Triethyl amine, pyridine or inorganic carbonates like potassium and sodium carbonates may be added as a deacidification agent in order to trap hydrogen chloride, which is formed during the reaction. Pyridine or triethylamine may be also used as solvent. The reaction time is generally from 0.5 to 4 hours, preferably from 0.5 to 2 hours. The salt of sulphate ester can be recovered after neutralization with an aqueous solution of an appropriate base such as lithium, potassium or sodium hydroxide or carbonate, ammonia, triethylamine, ethanolamine, diethanolamine or triethanolamine, preferably with sodium or potassium hydroxide, ammonia or triethanolamine. Optionally, the product may be isolated by extracting the product from the reaction mixture with organic solvent such as butanol and by evaporating the solvent off after phase separation. The yield is generally over 80 %.

Sulphonation may be also performed by reacting cardanol, cardol, CNSL or their (poly)alkoxylates with sulphuric acid or oleum. Sulphonate end group may be also provided by reaction with isethionic acid.

Moreover, carboxymethoxy end groups can be introduced by reaction with chloroacetic acid or an acrylic ester under appropriate conditions. Maleate and succinate end groups can be provided by esterification reactions with maleic anhydride and succinic anhydride, correspondingly. Sulphosuccinate may be further provided by reaction of succinate ester with sodium bisulphite.

According to the invention polymerizable surfactants derived from CNSL, cardanol, cardol or their (poly)alkoxylates may be used for producing of various compositions. They may for instance be used for production of aqueous or solvent-based dispersions containing binders, as well as additives and adjuvants known as such. It is particularly preferable to produce aqueous dispersions. Binders known for latex paints, paper coatings, inks and adhesives such as polyvinyl acetate and -alcohol, polyacrylic, styrene-acrylic, styrene-butadiene and copolymers thereof may serve as binders.

Generally, polyvinyl acetate and -alcohol, polyacrylic, styrene-acrylic, styrene- butadiene consist of polymers of ethylenically unsaturated monomelic units preferably produced using emulsion polymerization technique. Said monomers are typically selected from a group consisting of vinyl acetate, vinyl alcohol, ethylene, propylene, butadiene, styrene, acrylonitrile, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic and methacrylic acids, and branched or linear Q-C₉ esters, particularly Ci-C₈ esters thereof. Typical useful esters of (meth)acrylic acid include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate. The polymer may also comprise monomers having several reactive groups. Typical reactive groups present in the monomers include di- or polyfunctional (meth)acrylates like ethyleneglycol-, 1 ,2-propanediol-, 1,3- and 1,4-butanediol-, 1 ,4-neopentylglycol- and 1,6-hexanediol dimethacrylates, trimethylolpropane trimethacrylate and pentaerythritol tetramethacrylate, hydroxyl groups (e.g. hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate), amine groups, carbonyl groups (e.g. diacetone acrylate, diacetone acrylamide, acrolein, acetoacetoxyethyl methacrylate), urea groups, and epoxide groups (e. g. glycidyl methacrylate). It is also possible to use other monomers, typical examples of which include acrylamide and derivatives thereof (e.g. N- methylol acrylamide and N-isobutoxymethyl acrylamide, and various compounds having more than one double bond, such as divinyl benzene.

In addition to abovementioned polymers, also alkyd-acrylic hybrids, which are normally prepared by polymerizing (meth)acrylic monomers described above in the presence of colloidal alkyd droplets, may be used as binders. Generally, alkyd is a synthetic resin (polyester) produced by the reaction of fatty acid or oil such as tall, linseed, soy, sunflower, rapeseed or olive oil(s), polyol(s) such as trimethylolpropane, pentaerythritol neopentyl glycol or glycerol and polyacid(s) or their anhydrides such as isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride or trimellitic anhydride.

The anionic polymerizable surfactants of the invention may be used in coating compositions including paint, varnish, joint mortar, filler mortar, mortar, ink, paper coatings and adhesive compositions, preferably in aqueous compositions, and particularly preferably in compositions based on latexes, for instance in paints and paper coatings containing binders that forms films or discrete binding polymer particles after the coating has dried. The amount of the polymer dispersion serving as a binder in the coating composition typically varies between 20 % and 80 %. Suitable binders include for example polyacrylate or styrene- acrylic latexes wherein styrene is polymerized with one or more acrylate or methacrylate monomer(s). Examples of preferable monomer combinations include styrene-butyl (meth)acrylate-(meth)acrylic acid, methyl (meth)acrylate-butyl (meth)acrylate- (meth)acrylic acid, styrene-2-ethylhexyl (meth)acrylate- (meth)acrylic acid and methyl (meth)acrylate-butyl (meth) acrylate-hydroxyethyl (meth)acrylate. Suitable binders include also styrene-butadiene latexes wherein styrene is polymerized with butadiene and preferably carboxylated by the use of such acids as maleic, fumaric, itaconic, acrylic or methacrylic.

The polymer typically comprises from 20 to 80 %, preferably from 40 to 60 % of the dispersion. In addition to the polymer and water, the polymer dispersions typically contain chain transfer agents, preserving agents, antifoam agents, and buffering agents. Dispersing and thickening agents may be mentioned as other possible additives and adjuvants.

According to the invention the amount of the novel anionic polymerizable surfactants in the emulsion polymers varies between 0.1 and 20 % by weight, preferably from 1 to 5 % by weight. The surfactant in the coating composition may consist of the novel anionic polymerizable compound of the invention alone, a mixture of such anionic polymerizable compounds, or a mixture of the anionic polymerizable compound(s) and conventional surfactant(s). Preferably the anionic polymerizable surfactants comprise at least 20 % by weight, and more preferably at least 50 % of the total amount of the surfactants present.

Considerable advantages are attained with the present invention. The latexes with CNSL or cardanyl based anionic reactive surfactants have lower levels of free surfactants, their mechanical and freeze-thaw stabilities are improved and they have a reduced foaming tendency. The water resistance and binding power of the applied latexes are improved together with better optical properties and water resistances. Latexes with cardanol based reactive surfactants are suitable for paper and board manufacturing, especially as binders for coating colors and as barrier coatings. Especially, the barrier performances of latex and talc containing water based barrier and sizing formulations described in WO-A 1-98/54409, EP-Bl- 1490549 and US-B2-7214728 are significantly improved with latexes containing cardanol based surfmers. In coating colours, cardanol surfmer containing latexes provide enhanced printability, which is the result of higher wet and dry strengths of coatings and the reduced amount of latex hydrosolubles. Cardanol based surfactants also improve the performance of water borne coatings and paints particularly in the protection of wood, metal and architectural structures. In addition, these new latex based binders offer benefits for the binding of non- woven fabrics and building materials.

EXAMPLES

The following examples illustrate the present invention but are not intended to limit it.

Example 1.

Isomerization of cardanol

To 180 g of polyethylene glycol (PEG 300) was added cardanol (Cardolite NX4708, 180 g, 596 mmol) and aqueous KOH (45 % w/w, 96.6 g, 775 mmol) under N₂. The resulting brown mixture was stirred vigorously at 140 °C for 3 hours. During heating vigorous boiling occurred as water was lost from the system. After cooling to 90 °C the reaction mixture was acidified with H₃PO₄ (85 % w/w, 100 ml) and the mixture was stirred for 30 minutes at 90 °C. The organic phase was washed three times with H₃PO₄ (60 % w/w, 60 ml) at 90 °C for 30 minutes to remove excess PEG and water. The organic layer was separated to yield 175 g (97 %) of conjugated cardanol as brown liquid. The conversion, determined from the proton nuclear magnetic resonance spectrum, was 99 %. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Examples 2 to 7.

Isomerization of cardanol

The procedure of example 1 was repeated with different cardanol/alkali ratios, which were 1.5 (KOH) (example 2), 1 :1.25 (KOH) (example 3), 1 :1.15 (KOH) (example 4) and 1 :1.15 (NaOH) (example 5). The procedure of example 1 was also repeated with different solvent/cardanol ratios, which were 1 :6 (example 6) and 1 :3 (example 7). These results are shown in table 1.

TABLE 1.

Solvent/ Cardanol/

Cardanol alkali ratio Temperature Reaction Conversion Yield Double Ex. Solvent ratio [g/g] [mol/mol] [⁰C] time [h] [%] [%] bonds *

1 PEG 300 1 :1 1:1.3 (KOH) 140 3 99 97 1.9

2 PEG 300 1 :1 1:1.5 (KOH) 140 3 99 87 2.0

3 PEG 300 1 :1 1:1.25 (KOH) 140 3 99 96 2.1

4 PEG 300 1 :1 1:1.15 (KOH) 140 3 91 85 2.1

5 PEG 300 1 :1 1:1.15 (NaOH) 140 3 86 85 1.9

6 PEG 300 1 :3 1:1.3 (KOH) 140 3 90 1.7

7 PEG 300 1 :6 1:1.3 (KOH) 140 3 85 1.9

* The average number of double bonds per alkyl chain according to NMR studies. Example 8.

Isomerization ofcardanol

8.6 g of solid potassium hydroxide (86 %, 133 mmol) was dissolved in 30 g of ethylene glycol under N₂ and the temperature of the solution was raised to 100 °C. Thereafter, 30 g cardanol (Cardolite NX4708, 100 mmol) was added to the solution, and this mixture allowed to react at 180 °C for 3 hours. After reaction time, reaction mixture was cooled to room temperature and made neutral by the addition of H₃PO₄ (85% w/w). The mixture was stirred for 15 minutes. Subsequently, the pH of the reaction mixture was adjusted to 3. The reaction mixture was extracted with hexane (50 ml) three times. Thereafter, the hexane was evaporated under reduced pressure to yield 27.2 g (90 %) of conjugated cardanol as brown liquid. The conversion, determined from the proton nuclear magnetic resonance spectrum, was 99 %. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Examples 9 to 14.

Isomerization ofcardanol

The procedure of Example 8 was repeated with different reaction temperatures, which were 170 ⁰C (example 9), 160 °C (example 10) and 150 °C (example 11). Example 12 was prepared according to example 1 except that the solvent was changed to ethylene glycol. The procedure of example 8 was repeated except that the solvent was changed to propylene glycol and the temperature was 165 °C (example 13) and 150 °C (example 14). These results are shown in table 2. TABLE 2.

Solvent/ Cardanol/

Cardanol alkali ratio Temperature Reaction Conversion Double Ex. Solvent ratio [g/g] [mol/mol] [⁰C] time [h] [%] bonds *

8 ethylene glycol 1: I 1: 1.3 (KOH) 180 3 99 1.9

9 ethylene glycol 1 : I 1: 1.3 (KOH) 170 3 93 1.8

10 ethylene glycol 1 : I 1: 1.3 (KOH) 160 3 83 1.8

11 ethylene glycol 1 : I 1: 1.3 (KOH) 150 3 80 1.7

12 ethylene glycol 1 : I 1: 1.3 (KOH) 140 3 50 1.8

13 propylene glycol 1: I 1: 1.3 (KOH) 165 3 99 1.7

14 propylene glycol 1: I 1 : 1.3 (KOH) 150 3 85 1.7

* The average number of double bonds per alkyl chain according to NMR studies.

Example 15.

Preparation of sodium salt of cardanyl phosphate

744.5 g of cardanol (Cardolite NX-4708, 2.47 mol) was dissolved in 4.0 L of ethyl acetate under N₂ and the solution was cooled to 8 °C. 416.3 g (2.71 mol) of phosphorus oxychloride was added cautiously during 5 minutes to the solution. To the stirred and cooled solution 274.6 g (2.71 mol) of triethylamine was added during 40 minutes. After addition was complete, the solution was stirred efficiently for 100 minutes at 20-22 °C. The solution was cooled to 10 °C during 35 minutes and the reaction was quenched cautiously with 1.6 L of cold water. The mixture was stirred for 15 minutes and the layers were allowed to separate. The water layer was discarded and the organic layer was washed three times with 2 L of water. Finally, the organic layer was separated and evaporated to dryness under vacuum to produce 859 g (91 %) of cardanyl phosphate as brown low- viscous oil. The residual cardanol content, determined from the proton nuclear magnetic resonance spectrum, was <0.5 mole percent. The molar ratio of phosphate esters, determined from quantitative phosphorous-31 nuclear magnetic resonance data, were 83.6 % phosphoric acid monocardanyl ester, 2.7 % phosphoric acid dicardanyl ester and 0.9 % phosphoric acid tricardanyl ester. 450.1 g (1.18 mol) of cardanyl phosphate was dissolved in 900 ml of isopropyl alcohol and the solution was heated to 50 °C. Then the pH of mixture was adjusted to 8.5 with 5 M aqueous solution of NaOH with vigorous stirring. The mixture was stirred for 1 hour and allowed to cool to room temperature. The supernatant clear liquid was decanted off and the remaining brown gel was evaporated to dryness in vacuum and powdered to yield 467.8 g (98 %) of sodium salt of cardanyl phosphate as light beige powder. The molar ratio of phosphate esters, determined from phosphorous-31 nuclear magnetic resonance data, were 96.7 % sodium salt of phosphoric acid monocardanyl ester, 2.5 % phosphoric acid dicardanyl ester and 0.8 % phosphoric acid tricardanyl ester. The average number of double bonds per alkyl chain was 1.8 according to NMR studies.

Example 16.

Preparation of sodium salt of phosphoric acid monocardanyl ester

95.2 g of cardanol (NC 700, 315 mmol) was dissolved in 500 ml of anhydrous CH₂Cl₂ and 53.2 g (347 mmol) of phosphorus oxychloride was added cautiously to the solution under N₂. While stirring the solution 35.1 g (347 mmol) of triethylamine was added during 25 minutes to maintain gentle reflux. After addition was complete, the solution was stirred 80 minutes and extracted twice with 200 ml of water. The solution was dried, filtered and evaporated to dryness to give brown liquid. The residue was stirred with the mixture of 400 ml of THF and 140 ml of water at 50 °C for 60 minutes. To this solution, 500 ml of ethyl acetate was added and the water layer was discarded. The organic layer was washed twice with 200 ml of water, dried, filtered and evaporated to dryness under vacuum to produce 113.8 g (95 %) of phosphoric acid monocardanyl ester as reddish brown low-viscous oil. The residual cardanol content, determined from the proton nuclear magnetic resonance spectrum, was <5 mole percent.

The sodium salt of phosphoric acid monocardanyl ester was prepared according to example 15. As a starting material 20 g (52.4 mmol) of phosphoric acid monocardanyl ester was used. pH of mixture was adjusted to 8.5 with 5 M aqueous solution of NaOH. 20.8 g (98 %) yield of sodium salt of phosphoric acid monocardanyl ester as light brown powder was achieved. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Example 17.

Preparation of potassium salt of phosphoric acid monocardanyl ester

The potassium salt of phosphoric acid monocardanyl ester was prepared according to example 15. As a starting material 20 g (52.4 mmol) of cardanyl phosphate was used. pH of mixture was adjusted to 8.5 with 5 M aqueous solution of KOH 22.7 g (99 %) yield of potassium salt of phosphoric acid monocardanyl ester as light brown powder was achieved. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Example 18.

Preparation of ammonium salt of phosphoric acid monocardanyl ester

The ammonium salt of phosphoric acid monocardanyl ester was prepared according to example 15. As a starting material 20 g (52.4 mmol) of cardanyl phosphate was used. pH of mixture was adjusted to 8.5 with 5 M aqueous solution ofNH₃. 19.9 g (95 %) yield of ammonium salt of phosphoric acid monocardanyl ester as light brown powder was achieved. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Example 19.

Preparation of sodium salt of conjugated cardanyl phosphate The conjugated cardanyl phosphate was prepared according to example 16. 125.5 g (415 mmol) of conjugated cardanol, which was prepared according to example 1 was used as a starting material. Other reagents were phosphorus oxychloride (70.1 g, 457 mmol) and triethylamine (46.3 g, 457 mmol). 157 g (98 %) yield of conjugated cardanyl phosphate as brown low-viscous oil was achieved. The residual content of conjugated cardanol, determined from the proton nuclear magnetic resonance spectrum, was <0.5 mole percent.

The sodium salt of conjugated cardanyl phosphate was prepared according to example 15. As a starting material 157 g (555 mmol) of conjugated cardanyl phosphate was used. pH of mixture was adjusted to 8.5 with 5 M aqueous solution of NaOH. 162 g (98 %) yield of sodium salt of conjugated cardanyl phosphate as light brown powder was achieved. The molar ratios of phosphate esters, determined from phosphorous-31 nuclear magnetic resonance data, were 84.2 % salt of phosphoric acid monocardanyl ester, 7.3 % phosphoric acid dicardanyl ester and 8.5 % phosphoric acid tricardanyl ester. The average number of double bonds per alkyl chain was 1.2 according to NMR studies.

Example 20.

Preparation of phosphate ester of hydroxyethylated cardanol and its sodium salt

The phosphate ester of hydroxyethylated cardanol was prepared according to example 16. As a starting material 114.6 g (331 mmol) of monohydroxyethylcardanyl ether (Cardolite Lite 2020) was used. Other reagents were phosphorus oxychloride (56.3 g, 367 mmol) and triethylamine (37.1 g, 367 mmol). 115 g (81 %) yield of monohydroxyethylcardanyl ether phosphate ester as brown solid was achieved. The residual content of monohydroxyethylcardanyl ether, determined from the proton nuclear magnetic resonance spectrum, was <1.0 mole percent. The monophosphate ester content, determined from phosphorous-31 nuclear magnetic resonance data, was 87.2 %. The sodium salt of phosphate ester of hydroxyethylated cardanol was prepared according to example 15. As a starting material 114.7 g (269 mmol) of ester of hydroxyethylated cardanol was used. pH of mixture was adjusted to 8.5 with 5 M aqueous solution of NaOH. 128 g (98 %) yield of sodium salt of monohydroxyethylcardanyl ether monophosphate ester as light powder was achieved. The content of monohydroxyethylcardanyl ether monophosphate ester sodium salt, determined from phosphorous-31 nuclear magnetic resonance data, was 72.0 %. The average number of double bonds per alkyl chain was 2.0 according to NMR studies.

Example 21.

Preparation of sodium salt of cardanyl sulphate

Chlorosulfonic acid (20.4 ml, 304 mmol) was added dropwise to anhydrous pyridine (140 ml) in a flask at 0 ⁰C. Then 40 g (132 mmol) of cardanol (Cardolite NX4708) was mixed into 60 ml of anhydrous pyridine in another flask, and this mixture was added gradually with vigorous stirring to the reaction flask. The reaction mixture was stirred for 1.5 hours at room temperature and added dropwise to a cooled saturated solution of sodium carbonate (400 ml) with vigorous stirring. The product was extracted with butyl alcohol (3x200 ml) and the organic layers were combined. Finally, the solvent was evaporated under reduced pressure to yield sodium cardanol sulfate (55 g, 99 %) as light brown powder. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Example 22.

Preparation of potassium salt of cardanyl sulphate

The potassium salt of cardanyl sulphate was prepared according to example 22 except that the reaction mixture was neutralized with aqueous solution Of K₂CO₃. As a starting material 10.0 g (33 mmol) of cardanol (Cardolite NC-700) and 5.1 ml (76 mmol) of chlorosulfonic acid as a reagent were used. 10.2 g (81 %) yield of potassium salt of cardanyl sulphate as light brown powder was achieved. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Example 23.

Sodium salt of conjugated cardanyl sulphate

The sodium salt of conjugated cardanyl sulphate was prepared according to example 22. 10.1 g (33 mmol) of conjugated cardanol, which was prepared according to example 1 was used as a starting material and 5.1 g (76 mmol) of chlorosulfonic acid was used as a reagent. 10.3 g (77 %) yield of sodium salt of conjugated cardanyl sulphate as light brown powder was achieved. The average number of double bonds per alkyl chain was 1.9 according to NMR studies.

Comparative example 25. Styrene acrylate latex with a conventional surfactant to be used preferably for paper coatings.

A 1 dm3 polymerization reactor was charged with 72.7 g of water, 1.45 g of Emcol K8300 (alkanolamide sulfosuccinate; 38% solids) and 0.70 g of sodium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 142.2 g of butyl acrylate, 87.3 g of styrene and 9.55 g of metacrylic acid and 13.7 g of Emcol K83OO in 109.6 g of water, together with 0.47 g of sodium persulfate in 29.1 g of water, were introduced continuosly over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 1.07 g of tert-butyl hydroperoxide in 8.73 g of water and 0.48 g of sodium metabisulphite in 9.70 g of water at 65 °C for 1 hour. Finally 3.98 g of fatty alcohol polyglycolether in 9.21 g of water was added. Examples 26. Styrene acrylate latex with 25% of the conventional surfactant replaced with sodium salt of cardanyl phosphate to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 169.9 g of water, 2.25 g of Emcol K8300 (alkanolamide sulfosuccinate; 38% solids), 0.90 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 and 1.46 g of sodium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid, 21.53 g of Emcol K8300 and 8.61 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 in 213. I g of water, together with 0.98 g of sodium persulfate in 60.0 g of water, were introduced continuously over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 8.20 g of fatty alcohol polyglycolether in 19.0 g of water was added.

Examples 27. Styrene acrylate latex with 50% of the conventional surfactant replaced with sodium salt of cardanyl phosphate to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 169.7 g of water, 1.50 g of Emcol K8300 (alkanolamide sulfosuccinate; 38% solids), 1.80 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 and 1.46 g of sodium persulfate. The mixture was heated to 80 ⁰C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid, 14.35 g of Emcol K8300 and 17.22 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 in 211.6 g of water, together with 0.98 g of sodium persulfate in 60.0 g of water, were introduced continuosly over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 8.20 g of fatty alcohol polyglycolether in 19.0 g of water was added.

Examples 28. Styrene acrylate latex with 75% of the conventional surfactant replaced with sodium salt of cardanyl phosphate to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 169.4 g of water, 0.75 g of Emcol K8300 (alkanolamide sulfosuccinate; 38% solids), 2.70 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 and 1.46 g of sodium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid, 7.17 g of Emcol K8300 and 25.83 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 in 210.2 g of water, together with 0.98 g of sodium persulfate in 60.0 g of water, were introduced continuously over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 8.20 g of fatty alcohol polyglycolether in 19.0 g of water was added.

Examples 29. Styrene acrylate latex with all of the conventional surfactant replaced with sodium salt of cardanyl phosphate to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 169.4 g of water, 3.60 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 and 1.46 g of sodium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid and 34.4 g of 25% aqueous solution of sodium salt of cardanyl phosphate of example 15 in 208.8 g of water, together with 0.98 g of sodium persulfate in 60.0 g of water, were introduced continuosly over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 8.20 g of fatty alcohol polyglycolether in 19.0 g of water was added. According to NMR analysis of latex, the conversion of double bonds of cardanyl phosphate was 65% and no free cardanyl phosphate was detected in the aqueous phase of latex.

Following table summarizes the properties of latexes from examples 25-29. According to the contact angles with water, the replacement of conventional surfactant with sodium cardanyl phosphate greatly improves hydrophobicity and water resistance of latexes. Films of latexes from examples 25 and 29 were dried at room temperature and then immersed in water for 30 minutes. The cardanyl phosphate containing latex film from example 29 remained clear, whereas the reference latex film from example 25 turned whitish and cloudy due to the absorption of water.

Examples 30. Styrene acrylate latex with sodium salt of conjugated cardanyl phosphate to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 169.4 g of water, 3.60 g of 25% aqueous solution of sodium salt of conjugated cardanyl phosphate of example 19 and 1.46 g of sodium persulfate. The mixture was heated to 80 ⁰C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid and 34.4 g of 25% aqueous solution of sodium salt of conjugated cardanyl phosphate of example 19 in 208.8 g of water, together with 0.98 g of sodium persulfate in 60.0 g of water, were introduced continuously over the course of 4 hours. The mixture was agitated for 1 hour before stripping chemical with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 8.20 g of fatty alcohol polyglycolether in 19.0 g of water was added. According to NMR analysis of latex, the conversion of the double bonds of conjugated cardanyl phosphate was 78 %. The resulting acrylate polymer dispersion had a Brookfield 20rpm viscosity of 112 mPas, a solid content of 46.0 %, particle size by intensity of 138.8 nm and particle size by number of 116.4 nm. The grit formation was 0.08 % of total amount of latex. The contact angles with water, ethylene glycol and diiodomethane were 69.43°, 61.71° and 45.20° respectively.

Examples 31. Styrene acrylate latex with phosphate ester of hydroxyethylated cardanyl phosphate sodium salt to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 169.4 g of water, 3.60 g of 25% aqueous solution of cardanol derivative of example 20 and 1.46 g of sodium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid and 34.4 g of 25% aqueous solution of cardanol derivative of example 20 in 208.8 g of water, together with 0.98 g of sodium persulfate in 60.0 g of water, were introduced continuously over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 8.20 g of fatty alcohol polyglycolether in 19.0 g of water was added. According to NMR analysis of latex, the conversion of the double bonds of the cardanol derivative was 45 %. The resulting acrylate polymer dispersion then had a Brookfield 20rpm viscosity of 112 mPas, a solid content of 46.9 %, particle size by intensity of 154.3 nm and particle size by number of 130.9 nm. The grit formation was 0.07 % of total amount of latex. The contact angles with water, ethylene glycol and diiodomethane were 71.08°, 59.37° and 45.69° respectively.

Examples 32. Styrene acrylate latex with sodium salt of cardanyl sulphate to be used preferably for paper coatings.

A 2 dm3 polymerization reactor was charged with 151.0 g of water, 1.08 g of sodium salt of cardanyl sulphate of example 21 and 1.66 g of potassium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 293.4 g of butyl acrylate, 180.1 g of styrene and 19.7 g of metacrylic acid and 8.74 g of cardanyl sulphate of example 21 and 235.0 g of water, together with 1.11 g of sodium persulfate in 60.0 g of water, were introduced continuously over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 2.20 g of tert-butyl hydroperoxide in 20.0 g of water and 1.00 g of sodium metabisulphite in 20 g of water at 65 °C for 1 hour. Finally 20.0 g of water was added and the pH was adjusted with 3.4 g of 25 % ammonia in 5.1 g of water. According to NMR analysis of latex, the conversion of the double bonds of the cardanol derivative was 35 %. The resulting polymer dispersion then had a Brookfield 20rpm viscosity of 22 mPas, a solid content of 46.2 %, particle size by intensity of 359.8 nm and particle size by number of 316.6 nm. The grit formation was 0.21 % of the total amount of latex of latex.

Examples 33. Styrene acrylate latex with sodium salt of conjugated cardanyl sulphate to be used preferably for paper coatings.

A 1 dm3 polymerization reactor was charged with 75.5 g of water, 0.54 g of sodium salt of conjugated cardanyl sulphate of example 23 and 0.83 g of potassium persulfate. The mixture was heated to 80 °C under nitrogen atmosphere. The monomer emulsion consisting of 146.7 g of butyl acrylate, 90.1 g of styrene and 9.9 g of metacrylic acid and 4.37 g of conjugated cardanol derivative of example 23 and 117.5 g of water, together with 0.56 g of potassium persulfate in 30.0 g of water, were introduced continuously over the course of 4 hours. The mixture was agitated for 1 hour before chemical stripping with 1.10 g of tert-butyl hydroperoxide in 10.0 g of water and 0.5 g of sodium metabisulphite in 10 g of water at 65 °C for 1 hour. Finally 10.0 g of water was added and the pH was adjusted with 1.7 g of 25% ammonia in 2.55 g of water. According to NMR analysis of latex, the conversion of the double bonds of the cardanol derivative was 70 %. The resulting polymer dispersion then had a Brookfield 20rpm viscosity of 40 mPas, a solid content of 46.2 %, particle size by intensity of 349.2 ran and particle size by number of 309.7 ran. The grit formation was 0.08 % of the total amount of latex.

Example 34. Acrylate latex with all of the conventional surfactant replaced with ammonium salt of cardanyl phosphate to be used preferably in a outdoor paint for wooden surfaces.

Into a 3 1, four neck cylindrical reactor equipped with a stirring means, thermometer and reflux condenser, was charged 789.0 g of water, 2.6 g of Sokalan CPlO from BASF (modified Na polyacrylate of low molecular weight) and 0.1 g of ammonium salt of phosphoric acid monocardanyl ester of example 18. The reactor was heated up to the polymerization temperature 80 °C. In separate vessels, a monomersolution consisting of 648.0 g of BA and 509.6 g of MMA and an initiatorsolution consisting of 5.6 g potassiumpersulfate diluted in 200 g water, were prepared. 15 g of the initiatorsolution was charged into the reactor and 5 minutes later 58 g of the monomersolution. A surfactant solution consisting of 16.8 g of ammonium salt of phosphoric acid monocardanyl ester of example 18 in 200.0 g water, was prepared. Feeding of remaining monomersolution, initiatorsolution and surfactant solution were commenced simultaneously. Monomer and surfactant solutions were fed during 195 minutes, while initiator solution was fed during 225 minutes. After the continuous charging has been completed, the temperature 80 °C was maintained for one more hour. The dispersion was allowed to cool to room temperature and the pH was neutralised with ammonia. The resulting acrylate polymer dispersion then had a Brookfield 20rpm viscosity of 65 mPas, a solid content of 49.6%, and particle size of 133 nm. Grit formation was 0.03% of total amount of latex

Example 35. Styrene-acrylate latex with all of the conventional surfactant replaced with sodium salt of cardanyl phosphate to be used preferably in a outdoor paint for wooden surfaces.

Into a 3 1, four neck cylindrical reactor equipped with a stirring means, thermometer and reflux condenser, was charged 789.0 g of water, 2.6 g of Sokalan CPlO from BASF (modified Na polyacrylate of low molecular weight) and 0.3 g of sodium salt of phosphoric acid monocardanyl ester of example 16. The reactor was heated up to the polymerization temperature 80 °C. In separate vessels, a monomer solution consisting of 648.0 g of butyl acrylate and 329.3 g of methyl methacrylate and 180.0 g of styrene and an initiator solution consisting of 5.6 g potassiumpersulfate diluted in 200 g water were prepared. 15 g of the initiator solution was charged into the reactor and 5 minutes later 58 g of the monomer solution. A surfactant solution consisting of 28 g of of sodium salt of phosphoric acid monocardanyl ester of example 16 in 200.0 g water was prepared. Feeding of remaining monomer solution, initiator solution and surfactant solution were commenced simultaneously. Monomer and surfactant solutions were fed during 195 minutes, while initiator solution was fed during 225 minutes. After the continuous charging has been completed, the temperature 80 °C was maintained for one more hour. The dispersion was allowed to cool to room temperature and the pH was neutralised with ammonia. The resulting acrylate polymer dispersion then had a Brookfield 20rpm viscosity of 39 mPas, a solid content of 48.2%, and particle size of 162 nm. Grit formation was 0.01% of total amount of latex.

Comparative example 36. Polyvinylacetate-acrylate latex with conventional surfactants A 2 dm3 polymerization reactor was charged with 247.6 g of water, 3.00 g of Geropon ACR/4 (a sulfosuccinate surfactant; 31% solids) and 1.27 g of sodium persulfate. An addition funnel was charged with an emulsion consisting of 24.0 g of Geropon ACR/4, 4.82 g of Ufapol EPL25, 425,4 g of vinyl acetate, 48.2 g of butyl acrylate, 5.77 g of methacrylic acid and 126.7 g of water. 10% of the monomer emulsion was added to the reactor, which was heated to 75 °C. 9.6 g of 50% aqueous solution of AMD was mixed to the monomer emulsion, which was added to the reactor during 5.5 hours. An initiator feed consisting of 0.44 g of sodium persulfate in 19.6 g of water was started 1 hour after the beginning of the monomer addition. The feeding time was 5 hours. When the monomer and initiator feed were completed, the reaction temperature was raised to 80 ⁰C for 1.5 hours. Finally, the dispersion was allowed to cool to room temperature, 14.7 g of Genapol X-407 in 71.3 g of water was added and the pH was neutralised with ammonia. The resulting polymer dispersion then had a Brookfield 20rpm viscosity of 130 mPas, a solid content of 47.6 %, particle size by by number of 130.4 nm. The grit formation was 0.14 % of total amount of latex. The mechanical stability of the latex was inadequate.

Example 37. Polyvinylacetate-acrylate latex with 50% of the conventional surfactant replaced with sodium salt of cardanyl phosphate.

The polymerization of the comparative example 36 was repeated, but 50% of Geropon ACR/4 (sulfosuccinate type surfactant) was replaced with an equivalent aqeuous solution of sodium salt cardanyl phosphate of example 15. The resulting polymer dispersion then had a Brookfield 20rpm viscosity of 115 mPas, a solid content of 45.2 %, particle size by by number of 102.6 nm. The grit formation was 0.13 % of total amount of latex. The mechanical stability of the latex was good.

Claims

1. Polymerizable anionic surfactant based on chemically modified cardanol or cashew nutshell liquid and possessing the formula:

(CH₃)_V

wherein

A) and A₂ independently represent anionic group PO(OMi)(OM₂), wherein Mi and M₂ independently represent either H, Li, Na, K, NH₄, NH(CH₂CH₃)₃,

NH₃CH₂CH₃OH, NH₂(CH₂CH₃OH)₂, NH(CH₂CH₃OH)₃ or C₆H₄-m-Ci₅H₃i_-2n, wherein n being from O to 3, or anionic groups SO₂OM₃, CH₂-CH₂-SO₂-OM₄,

CH₂-CO₂M₅, CO-CH=CH-CO₂M₆, CO-CH₂-CH₂-CO₂M₇ or CO-[C₂H₃(SO₃H)]-

CO₂M₈₁ wherein M_3? M₄, M₅, M₆, M₇ and M₈ independently represent either H, Li, Na, K, NH₄, NH(CH₂CH₃)₃, NH₃CH₂CH₃OH, NH₂(CH₂CH₃OH)₂ or

NH(CH₂CH₃OH)₃, i and y being independently from O to 30, preferably from O to 16, j and z being independently 1 or 2, k and x being independently from O to 30, preferably from O to 16, m being O or 1 , and n being from 0.1 to 3, preferably from 1.2 to 2.5.

2. Polymerizable surfactant according to claim 1, wherein the double bonds of cardanol or cashew nutshell liquid are conjugated.

3. Polymerizable surfactant according to claim 1 or 2, wherein phosphate esters of cardanol or cashew nutshell liquid are produced with phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, phosphorus pentoxide, sodium trimetaphosphate, phosphoric acid or polyphosphoric acid.

4. Polymerizable surfactant according to claim 1 or 2, wherein sulphate esters of cardanol or cashew nutshell liquid are produced with sulphuric acid or chlorosulphonic acid.

5. Aqueous formulation of the polymerizable surfactant according to any of claims 1 to 4.

6. Process for the preparation of an emulsion polymer comprising polymerization of monomers with the reactive surfactant according to any of claims 1 to 4 in an aqueous medium, or addition of the reactive surfactant according to any of claims 1 to 4 or the aqueous formulation according to claim 5 to a polymer after the polymerization of the monomers.

7. Process according to claim 6, wherein the amount of the reactive surfactant is from 0.1 to 20 %, preferably from 1 to 5 %, of the weight of the monomers.

8. Emulsion polymer comprising the reactive surfactant according to any of claims 1 to 4 in amount of from 0.1 to 20 %, preferably from 1 to 5 %, of the weight of the monomers in an aqueous medium.

9. Process according to claim 6 or 7 or emulsion polymer according to claim 8, wherein the monomers comprise ethylenically unsaturated monomers.

10. Process according to claim 6 or 7 or emulsion polymer according to claim 8, wherein the monomers comprise ethylenically unsaturated monomers selected from the group consisting of: styrene, alpha-methylstyrene, vinyltoluene; dienes; (meth)acrylic esters comprising esters of acrylic acid and meth acrylic acid with hydrogenated or fluorinated Cl -C 12; vinyl nitriles having from 3 to 12 carbon atoms; carboxylic acid vinyl esters; vinyl halides; di- and tri-(meth)acrylic esters of diols and triols; glycidyl methacrylate or allyl glycidyl ether;

N-(hydroxymethyl)acrylamide or diacetone acrylamide;

2-acrylamido-2-methylpropane-sulphonic acid; unsaturated ethylenic mono- and dicarboxylic acids; monoalkyl esters of the abovementioned dicarboxylic acids with alkanols and their N-substituted derivatives; amides of unsaturated carboxylic acids; ethylenic monomers comprising sulphonic acid group and its alkali metal and ammonium salts; unsaturated ethylenic monomers comprising a secondary, tertiary or quaternary amino group or a heterocyclic group comprising nitrogen; zwitterionic monomers;

11. Use of the emulsion polymer according to any of claims 8 to 10 in the manufacture of paper or paperboard, paints, non-woven fabrics and building materials.

12. Pigmented coating composition for paper or paperboard containing the emulsion polymer according to any of claims 8 to 10.

13. Water based barrier coating containing the emulsion polymer according to any of claims 8 to 10 and plate-like pigment particles, preferably talc.

14. Barrier coating according to claim 11 wherein the proportion of the emulsion polymer in the coating is between 20 and 80 % and the proportion of the pigment particles in the coating is between 20 and 80 %, calculated as dry matter.