MODIFIED HYBRIDE RESIN BASED ON NATURAL FATTY ACIDS AND METHOD FOR THE MANUFACTURE THEREOF

Field of the invention

The invention relates to natural fatty acid based hybride resin, modified with reactive monomers, and to a method for the manufacture thereof. The invention also relates to the use of modified natural fatty acid based hybride resin as binding agent particularly in aqueous coatings and adhesives, and also as environmentally friendly impregnating agent for wood.

State of the art

The use of water based coatings and especially latex based coatings has increased continuously because of for example the positive environmental effects of these coatings and easy water cleanability of the equipment used for application. The popularity of solvent-based alkyd paints has decreased mainly because of the volatile organic components (VOC) contained therein. Solvent-based alkyd paints have anyhow some remarkable advantages compared to latex paints, such as compatibility especially with wood and modified wooden materials, such as thermo-wood and impregnated wooden products, and good surface gloss and hardness

Use of products, manufactured from renewable raw materials or biomaterials is con- tinuously increasing. This is because of many good properties of these products, which are among other things biodegradability, recyclability and low toxicity. In order to reach as high proportion of raw materials derived from natural materials in biocomposites as possible it is generally desirable that also the auxiliary agents used in the preparation are biobased.

Methods for producing water based modified alkyd resins particularly for coating applications are known e.g. from US 4,436,849, US 4,346,044 and JP 85-170952 publications. A semidrying alkyd resin according JP 85-170952 or an alkyd resin according to US 4,436,849 prepared from linen seed oil and containing cyanuronic groups, is allowed to react with maleic anhydride to provide a modified alkyd resin product. In the publication US 4,346,044 an alkyd resin prepared from soybean oil is modified with hexahydrophthalic anhydride.

A major problem of tall oil based wood impregnating products of the state of the art is the leaking out of the tall oil from the product, which requires further treatment and increases the amount of waste formed in the method.

Based on the above it can be seen that there exists an obvious need to provide alkyd resin based water-soluble alkyd resin products having improved properties, as well as methods for the manufacture thereof.

Object of the invention

The object of the invention is to provide modified natural fatty acid based hybride resins.

Another object of the invention is to provide maleic acid modified natural fatty acid based hybride resins.

Another object of the invention is a method for the manufacture of modified natural fatty acid based hybride resins.

Another object of the invention is the use of modified natural fatty acid based hybride resins as binding agents (binders) in coatings, paints and adhesives and as compo- nents in impregnation agents of wood products.

The characteristic features of the modified natural fatty acid based hybride resins, of the method for their manufacture and their use are presented in the patent claims.

Hybride resin refers here to a condensation product of a modified natural fatty acid mixture and an alkyd resin.

Summary of the invention

The invention relates to modified natural fatty acid based hybride resins, to a method method for their preparation and to their use.

The modified natural fatty acid based hybride resins according to the invention comprise condensation products of natural fatty acid mixtures or natural fatty acid ester mixtures, modified with di- and/or oligo-carboxylic acids or di- and/or oligo- carboxylic anhydrides or di- and/or oligo-carboxylic acid half esters, and natural fatty acid based alkyd resins.

The method according to the invention for the manufacture of modified natural fatty acid based hybride resins comprises the steps, wherein in step 1) natural fatty acid mixture or natural fatty acid ester mixture, selected from fatty acid mixtures and fatty acid ester mixtures obtained from natural oils and fats, plant based fatty acid mixtures and natural oils containing fatty acid esters, is modified with a di- and/or oligo- carboxylic acid or di- and/or oligo-carboxylic anhydride or di- and/or oligo- carboxylic acid half ester, and in step 2) the product obtained from step 1 and natural fatty acid based alkyd resin are condensed, whereby modified natural fatty acid based hybride resin is obtained as product, which is optionally dispersed in water.

Fatty acid mixtures and fatty acid ester mixtures, which may also be oligomeric and polymeric products, can be obtained from natural oils and fats with any known method, e.g. by hydrolysing directly or via intermediate steps.

The modified natural fatty acid based hybride resins according to the invention can be used as binding agents (binders) particularly in aqueous coatings, adhesives and as components in environmentally friendly impregnation agents of wood products.

Detailed description of the invention

It was surprisingly found that modified natural fatty acid based hybride resins can be produced from natural fatty acid mixtures or natural fatty acid ester mixtures, modified with di- and/or oligo-carboxylic acid or di- and/or oligo-carboxylic anhydride or di- and/or oligo-carboxylic acid half ester, by condensing them with natural fatty acid based alkyd resins, and the hybride resins thus obtained can optionally further be dispersed in water whereby they form a stable emulsion.

The properties of the thus obtained modified natural fatty acid based hybride resin products, such as water dispersibility, adhesive properties and penetrability especially to natural materials such as e.g. into wood, hemp and linen, are excellent.

Natural fatty acid mixtures and natural fatty acid ester mixtures exist e.g. in plants, trees and especially in natural oils, tall oil fatty acid mixtures and in fatty acid mix- tures of suberin and cutin. Natural oils refer here to natural oils containing conjugated or non-conjugated double bonds, such as a plant oils, preferably linen seed oil, soybean oil, rapeseed oil, rape oil, sunflower oil etc.

Tall oil fatty acid mixture refers especially to fatty acid mixture separated from tall oil side product of wood processing industry, the typical fatty acid composition of which is presented in the following. The fatty acid mixture of tall oil contains about 50 % (45-55 %) of linolic acid and other diunsubstituted Cis fatty acids, including conjugated acids, about 35 % (30-45 %) of oleic acid, about 7 % (2-10 %) of polyunsaturated fatty acids, about 2 % (0.5-3 %) of saturated fatty acids and at most 3 % (0.5-3 %) of rosin acids as weight percents.

Natural fatty acid mixture and natural fatty acid ester mixture refer in this connection to a mixture comprising unsaturated and saturated fatty acids or corresponding fatty acid esters having the carbon number in the range between Ci ₂ and C ₂₀ .

The suggested fatty acid compositions of some natural acids are presented in the following Table 1 :

Table 1.

The modified natural fatty acid based hybride resin according to the invention, is a condensation product of natural fatty acid mixture or natural fatty acid ester mixture, modified with di- and/or oligo-carboxylic acid or anhydride or half ester, and natural fatty acid based alkyd resin. The natural fatty acid mixture or natural fatty acid ester mixture comprises a fatty acid mixture or fatty acid ester mixture selected from the group consisting of tall oil fatty acids, suberin fatty acids, cutin fatty acids and plant

oils, preferably tall oil fatty acids, suberin fatty acids, linen seed, soy, rapeseed, rape, sunflower and olive oil and their mixtures.

Natural fatty acid based alkyd resin refers here to alkyd resin, which is prepared by condensing from 20-80, preferably 40-75 % by weight of natural fatty acid starting materials or a mixture thereof, in which the proportion of conjugated fatty acids can be 0-70 % by weight, from 1 -45, preferably 5-30 % by weight of one or more polyols, from 5-45, preferably 10-39 % by weight of one or more polybasic acids and optionally from 0-15 % by weight of one or more monobasic acids. The fatty acid starting material comprises natural fatty acid mixture or natural fatty acid ester mixture selected from the group consisting of tall oil fatty acids, suberin fatty acids, cutin fatty acids, plant oils and their mixtures, preferably tall oil fatty acids, suberin fatty acids, linen seed, soy, rapeseed, rape, sunflower and olive oil. The polyol is selected from the group consisting of glycerol, pentaerythritol, trimethylolpropane, neopentyl glycol and their mixtures . The polybasic acid is selected from the group consisting of di- and polyacids and their anhydrides, preferably the polybasic acid is phthalic anhydride, isophthalic acid or terephthalic acid. The monobasic acid is selected from the group consisting of aromatic monoacids and aliphatic C ₄ -C ₂₀ carboxylic acids, preferably from valeric acid (n-pentanoic acid) and benzoic acid.

The alkyd resin is prepared by condensing the polyol(s), mono-, di- and/or polya- cid(s) or anhydride and the free fatty acid starting material(s) together under an inert gas at a temperature of 200-270°C, preferably 220-260 ⁰ C.

When fatty acid esters such as plant oils are used in the preparation of the alkyd resin, the fatty acid esters are first allowed to react at a temperature of 150-240°C, preferably 180-200°C, with an excess of a polyol in an ester exchange reaction called alco- holysis, whereby to the equilibrium mixture free hydroxyl groups are obtained which can react further under an inert gas with mono-, di- and/or polyacids or anhydrides at a temperature of 200-270°C, preferably 220-260 ⁰ C. Commonly used alcoholysis cata-

lysts are lithium hydroxide, calcium oxide and sodium hydroxide. In the alcohoiysis, the polyol is typically used twice the molar amount of the oil; the oihpolyol molar ratio is typically 1.0:1.2-1.0:3.0, preferably 1.0:1.5-1.0:2.0.

The molar mass of the alkyd resins thus obtained is typically <20,000 g/mol, preferably 2,000-10,000 g/mol and the acid number is typically <25, preferably <15.

In the method according to the invention also natural fatty acid based alkyd resin can be used which is modified with maleic anhydride or C ₁ -C ₂₀ alkyl/alkenyl derivatives of maleic anhydride or di- and half esters of maleic anhydride. The fatty acid based alkyd resin is warmed to a temperature of 100-200, preferably 150-180°C, then maleic anhydride or its derivative (5-35 mol %, preferably 10-20 mol % of the fatty acid content of the alkyd) is added in small portions during 0.5-2 hours, after which the reaction mixture is warmed to 150-220, preferably 180-200 ⁰ C and agitated for a further 1-5 hours. As a final product a modified alkyd resin is obtained having a higher acid functionality as the alkyd resin starting material.

A method according to one embodiment, for the preparation of modified natural fatty acid based hybride resins, comprises the steps, where in step 1) natural fatty acid mix- ture or natural fatty acid ester mixture selected from the group consisting of fatty acid mixtures obtained from natural oils, plant based fatty acid mixtures and natural oils containing fatty acid esters, such as triglyceride esters, is modified with a di- and/or oligo-carboxylic acid or anhydride or half ester containing free acid groups of maleic anhydride, and in step 2) the product obtained from step 1 and natural fatty acid based alkyd resin are condensed, whereby a modified natural fatty acid based hybride resin is obtained as product, which is optionally dispersed in water.

In the following Scheme 1 the first step of the method is presented as an example of the invention, wherein di- and/or oligo-carboxylic acid or anhydride or half ester, in S cheme 1 maleic anhydride ( 1 ) or maleic acid (2) reacts with the double bond of con-

jugated (3) or non-conjugated (4) natural fatty acid forming as products (5), (6) and (7) according to Scheme 1 ,

Scheme 1. _j

-CH ₂ -CH=CH-CH=CH-CH ₂ -

In the method according to the invention, in step 1) natural fatty acid mixture or natu- ral fatty acid ester mixture, which can be non-conjugated or conjugated, is modified with reactive monomers. The modified natural fatty acid mixture or ester mixture is condensed to an alkyd structure through reacting via transesterification or via double bond addition wherein the desired hybride resin is formed. The modified hybride resin thus obtained may optionally be dispersed further in water.

As suitable reactive monomers to the method according to the invention, di- and/or oligo-carboxylic acids and anhydrides and half esters are selected from the group consisting of itaconic anhydride, fumaric anhydride, C2-C18 alkylene maleic anhydrides, C2-C18 alkylene maleic acids, maleic acid, maleic anhydride, fumaric acid, itaconic acid as well as half esters of above mentioned acids, including oligo- carboxylic acid derivatives such as suberic acid derivatives containing a reactive double bond. The reactive monomer is preferably maleic anhydride.

In the method according to the invention, in the first step the modifying is accomplished by treating the natural fatty acid mixture or natural fatty acid ester mixture with 1 -50, preferably 5-30 mol % (calculated from the fatty acid/ester) of a di- and/or oligo-carboxylic acid or anhydride or half ester at a temperature of 80-230, preferably 120-200°C for 1-10, preferably 2-6 hours to give the desired modified non- conjugated or conjugated natural fatty acid mixture or natural fatty acid ester mixture.

The modified natural fatty acid mixture or natural fatty acid ester mixture, obtained in the method according to the invention, in the first step, is condensed in the second step of the method to an alkyd structure by allowing 15-50 % by weight (calculated from the amount of alkyd resin) of the modified natural fatty acid mixture or natural fatty acid ester mixture to react with natural fatty acid based alkyd resin at a temperature of 50-150, preferably 80-120°C for 1-8, preferably 2-6 hours, to give the desired modified hybride resin. The acid number of the modified hybride resin may vaiy be- tween 15-95, preferably 35-85.

The hybride resins according to the invention may optionally be dispersed or emulsified in water, whereby water based alkyd emulsion according to the invention is obtained having dry matter content of 10-50, preferably 25-45 % by weight. The pH of the hybride resin is adjusted with base between 6-10, preferably between 6,5-9 and suitable bases are e.g. KOH as well as ammonia as water solutions and 2- dimethylaminoethanol. The neutralised hybride resin solution so obtained is dispersed/emulsified in water at temperature of 15- 80 ⁰ C, preferably 25-65 ⁰ C. Optionally 0-30 % by weight of co-solvents selected from the group consisting of isopropa- ' nol, 2-butoxyethanol, methoxypropanol and propylene glycol butyl ether etc. can be used. Additionally, dispersing agents known in the art can also be used when required. The dispersing/emulsifying is preferably carried out with known mixers and/- or homogenisers, which provide speeds of rotation of 100-50,000 rpm, preferably 100-25,000 rpm. Stable aqueous emulsions of the hybride resins are thus obtained. The stable aqueous emulsions of hybride resins according to the invention are well

suited as binding agents in coating and adhesive compositions as well as in tackyfier compositions as pressure sensitive adhesives.

Typical components used in coating and adhesive compositions are in addition to the binding agent, 0.2-1.2% of fungicides, 0.2-0.5% of bactericides, 0.1-2% of surfactants, 10-30% of pigments and extenders (inert fillers), 0.2-2% of thickeners (thickener agents), and water.

The hybride resins according to the invention may also be used as hot melt glues as such or, as desired, with known adjuvants.

The hybride resin according to the invention can be used as such for wood impregnating applications by mixing 1 -30%, preferably 5-15% of the product to a tall oil fatty acid mixture or plant oils, such as linen seed, soy or rapeseed oil or by using the water based emulsion, if required, with known additives for impregnating wood-derived products.

The modified hybride resin according to the invention can additionally be used as a binding agent and coating agent with known additives.

The modified natural fatty acid based hybride resins according to the invention bring several advances. In coating applications, such as paints the dry matter content of the coating can be increased with aid of them to even 40 - 60 % by weight which is considerably higher than 18 % by weight dry matter content, which is typically used with a product produced by direct emulsifying from an alkyd resin. Additionally, the amount of emulsifiers and surfactants, which impair the properties of paints, can be reduced considerably in paint compositions. These surfactants typically migrate to the surface of the paint film where they act like plastisizers, as a result of which the paint film becomes softer and sticky, additionally water resistance and chemical resistance are impaired. The hybride resins according to the invention are so called self-

emulsifying products and no external emulsifiers or co-solvents are required.

The use of the hybride resins according to the invention in coatings reduces substantially emissions of volatile organic substances from the products in question, because the need for using other solvents and additives is substantially reduced when compared to conventional alkyd resins.

Because the hybride resin also contains components originating from natural fatty acids or natural fatty acid esters containing double bonds, the compositions contain- ing hybride resins dry quickly and conjugation enhances the drying. The coatings have excellent gloss and hardness and the coatings are also remarkably well suited for treatment of modified wood such as thermo-wood because the hybride resins are compatible with natural materials such as the own components of wood. Additionally the penetrability of the product into the material to be treated is excellent.

The use of the hybride resin according to the invention as binding agent will promote the natural features, biodegradability and non-toxicity of the product. Additionally, the hybride resin according to the invention is a reactive binding agent improving physical properties of the product, such as strength, water resistance and solvent re- sistance as well as the fixation and even distribution of the matrix material in the product.

When using the reactive hybride resin according to the invention either as such or together with plant oils for impregnation of wood, the leaking out of the impregnating agent from wood decreases and adhesion to the wood is facilitated.

The invention is described in more detail with the following examples, to which it is anyhow not meant to be restricted.

EXAMPLES

Example 1: Modifying of fatty acid mixture with maleic anhydride

Tall oil fatty acid mixture (400 g, 1.423 mol) containing a fewpercents of conjugated fatty acids was warmed to 18O ⁰ C. Maleic anhydride (27.9 g, 0.285 mol, 20 mol %) was added in small portions during 2 hours, after which the reaction mixture was warmed to 200°C and stirred for further 3 hours. According to NMR analysis no un- reacted maleic anhydride was left in the reaction product (414 g).

Example 2: Modifying of fatty acid mixture with maleic anhydride

Tall oil fatty acid mixture (2000 g, 7.114 mol) containing a few percents of conjugated fatty acids was warmed to 18O ⁰ C. Maleic anhydride (139.5 g, 1.423 mol, 20 mol %) was added in small portions during 2 hours, after which the reaction mixture was warmed to 200°C and stirred for further 3 hours. According to NMR analysis the reaction product (2119.8 g) didn't contain unreacted maleic anhydride.

Example 3: Modifying of conjugated fatty acid mixture with maleic anhydride

Conjugated tall oil fatty acid mixture (100 g, 0.356 mol) was wanned to 12O ⁰ C. Maleic anhydride (10.5 g, 0.107 mol, 30 mol %) was added in small portions during 15 min, then the reaction mixture was warmed and agitated for 3 hours. According to NMR analysis the product (96.4 g) didn't contain unreacted maleic anhydride.

Example 4: Preparation of tall oil based alkyd resin

Alkyd resin was prepared from tall oil fatty acids (1484.4 g), isophthalic acid (222.4 g) and trimethylolpropane (375.5 g). The starting materials were mixed and warmed at 250-260 ⁰ C. The progress of reaction was followed with samples, from which acid number and when the reaction mixture became clear also viscosity (R.E.L. rotating

cone/plate viscometer) were determined. The reaction was boiled for 11 hours. Acid number of the cooled product (1875.2 g) was 10.3 mgKOH/g and viscosity 2.4 Poise/50°C.

Example 5: Preparation of tall oil based alkyd resin

Alkyd resin was prepared from tall oil fatty acids (372.6 g), isophthalic acid (55.9 g) and pentaerythritol (71.5 g). The starting materials were mixed and warmed at 240- 26O ⁰ C with bubbling nitrogen into the reaction mixture. The progress of the reaction was followed with acid number, and when the reaction mixture became clear, also with viscosity (R.E.L.). The reaction was boiled for 11 hours. From the cooled product (420.3 g) acid number (5) and viscosity (8.7 Poise/ 50°C and 10305 cP/ RT (= room temperature) (Brookfield) were determined.

Example 6: Modifying of tall oil fatty acid based alkyd resin with maleic anhydride

Tthe alkyd prepared in example 4 (400 g, acid number 10.3 mgKOH/g, viscosity 2.4 Poise/50°C) was warmed to 18O ⁰ C. Maleic anhydride (8.0 g, 0.163 mol, 15 mol % of the fatty acid content of the alkyd) was added in small portions during one hour, then the reaction mixture was warmed to 200 ⁰ C and stirred for a further 3 hours. 396.9 g of the product was obtained, acid number was 19.7 mgKOH/g and viscosity 4.7 Poise/50°C.

Example 7: Preparation of linen seed oil based alkyd resin

Alkyd resin was prepared from linen seed oil (865.7 g), trimethylolpropane (402.0 g), isophthalic acid (300.0 g) and benzoic acid (294.3 g). Linen seed oil was warmed to a temperature of 150°C with agitating (450 rpm) under nitrogen atmosphere, then lith- ium hydroxide monohydrate (0.758 g) was added. The warming was continued to

200°C and trimethylolpropane was added. The alcoholysis reaction was followed with aid of a solubility test and when the reaction mixture was fully soluble in methanol (about 2 hours), isophthalic acid was added to the reaction vessel, and after mixing the benzoic acid was added. The wanning of the reaction mixture was continued at 200-220 ⁰ C and the progress of the reaction was followed with acid number, and when the reaction mixture became clear, also with viscosity. The reaction was boiled for 4 hours from the acid addition. From the cooled product (1713.6 g) acid number (21) and viscosity (5.2 Poise/50 ⁰ C, R.E.L.) were determined.

Example 8: Preparation of alkyd resin with conjugated tall oil fatty acid mixture

Alkyd resin was prepared from tall oil fatty acid mixture (205.9 g), conjugated tall oil fatty acid mixture (52.85 g), isophthalic acid (74.8 g), benzoic acid (73.2 g), pentae- rythritol (65.3 g) and trimethylolpropane (28. Ig). The starting materials were agitated and warmed at about 220-240 ⁰ C while bubbling nitrogen below the surface of the reaction mixture. The progress of the reaction was followed with acid number, and when the reaction mixture became clear, also with viscosity (R.E.L.). The reaction was boiled for 7 hours. From the cooled product (400.Ig) acid number (13,5) and viscosity (4.6 Poise/75°C, R.E.L. and RT/ 47500 cP (Brookfield) were determined.

Example 9: Condensation of maleic anhydride-modified tall oil fatty acid mixture to linen seed oil based alkyd structure

A mixture of linen seed oil based alkyd of example 7 (1600 g, acid number 21 and viscosity 5.2 Poise/50°C) and maleic modified tall oil fatty acid mixture of example 2 (800 g, acid number 23) was mixed and warmed for 3 hours at 120 ⁰ C. The addition/condensation product of alkyd resin and maleated oil obtained as product had an acid number of 83.5 and viscosity of 2.5 Poise/50°C.

Example 10: Modifying of soybean oil with nialeic anhydride

Soybean oil (300 g, 0.340 mol) was weighed into a reaction vessel and warmed at 150-170°C. Maleic anhydride (20 g, 0.204 mol, 20 mol % of the fatty acid equivalent) was added in small portions during 2 hours, then the reaction mixture was warmed to 200 ⁰ C, at which it was agitated for further 3 hours. The acid number of the reaction product (314 g) was 33.

Example 11: Preparation of soybean oil based alkyd resin

Alkyd resin was prepared from soybean oil (300 g), trimethylolpropane (114 g) and isophthalic acid (109.8 g). The reaction mixture was warmed to a temperature of 180°C with stirring under nitrogen atmosphere, and then lithium hydroxide monohy- drate (0.3 g) was added. The warming was continued to 240 ⁰ C, at which the reaction mixture was kept for 2 hours. The reaction mixture was cooled to 180°C and the isophthalic acid was added. The reaction mixture was warmed again to 240-250°C and the progress of the reaction was followed with acid number and viscosity. The reaction time after addition of the isophthalic acid was 2 hours. The acid number of the product (446.8 g) was 5 and viscosity 3.0 Poise/75°C (R.E.L.).

Example 12: Condensation of maleic modified soybean oil to soybean oil based alkyd and preparation of emulsion

A mixture of the soybean oil based alkyd resin prepared in example 11 (100 g) and the maleic modified soybean oil prepared in example 10 (50 g) was mixed and warmed at 120 ⁰ C for 3 hours. The mixture was allowed to cool to 100 ⁰ C and water (2.5 g) was added and heating and mixing were continued for 2 hours at 100 ⁰ C, whereby the acid number was 15. Then isopropyl alcohol (42 g) was added and the mixture was allowed to cool to a temperature of 5O ⁰ C. The pH of the solution was

adjusted to 7 with an aqueous ammonia solution. Water was added during 3 hours into the resin mixture, and emulsifying was carried out after each addition of water with Ultra Turrax homogeniser. The dry matter content of the emulsion was 40 %.

Example 13: Modifying of linen seed oil with maleic anhydride

Linen seed oil (400 g, 0.459 mol) was warmed to 18O ⁰ C. Maleic anhydride (27.0 g, 0,275 mol, 20 mole%) was added in small portions during 2 hours, then the reaction mixture was warmed to 200 ⁰ C and agitated for a further 3 hours. No unreacted maleic anhydride was observed in the NMR analysis of the reaction product (419 g).

Example 14: Preparation of linen seed oil based alkyd resin

Alkyd resin was prepared from linen seed oil (300 g), trimethylolpropane (93.5 g) and isophthalic acid (130.0 g). The reaction mixture of linen seed oil and trimethylolpropane was warmed to a temperature of 200 ⁰ C with stirring under nitrogen atmosphere, after which lithium hydroxide monohydrate (0.304 g) was added. The warming was continued to 250 ⁰ C, at which the reaction mixture was kept for 2 hours. The reaction mixture was cooled to 170 ⁰ C and isophthalic acid was added. The reaction mixture was warmed again to 240-260 ⁰ C and the progress of the reaction was followed with acid number and viscosity. The reaction time after addition of the isophthalic acid was 3.5 hours. From the cooled product (430.3 g) acid number (17) and viscosity (6.0 Poise/100 ⁰ C, R.E.L.) were determined.

Example 15: Condensation of maleic anhydride-modified linen seed oil to linen seed oil based alkyd structure and preparation of emulsion

A mixture of the linen seed oil based alkyd prepared according to example 14 (350 g, acid number 16 and viscosity 6.0 Poise at 100 ⁰ C) and the maleic modified linen seed oil prepared in example 13 (175 g) was agitated for 3 hours at 120 ⁰ C. Water (8.75 g)

was added and agitating was continued for 2 hours at 100 ⁰ C, whereby the acid number was 20. Then isopropyl alcohol (182 g) was added and the mixture was allowed to cool to a temperature of 5O ⁰ C. The pH of the solution was adjusted to 7 with an aqueous ammonia solution. Emulsifying was carried out by adding water in small portions during 3 hours into the resin mixture which was stirred vigorously and warmed at 50 ⁰ C. Emulsifying was carried out after each addition of water with Ultra Turrax homogeniser. The dry matter content of the emulsion was 42 % and pH 6.8.

Example 16: Condensation of nialeic anhydride-modified tall oil fatty acid mix- ture to alkyd resin based on tall oil fatty acid and preparation of emulsion

A mixture of the alkyd of example 5 (400 g) and the maleic modified tall oil fatty acid mixture of example 1 (200 g) was warmed for 3 hours at 12O ⁰ C. Water (10 g) was added and warming and agitating were continued for 2 hours at 100°C:ssa, whereby acid number was 89. Then isopropyl alcohol (182 g) was added and the mixture was allowed to cool to room temperature. The pH of the solution was adjusted to about 7 with an aqueous NH ₃ solution. Emulsifying was carried out by adding water in small portions during 3 hours into the resin mixture, which was stirred vigorously and warmed at 50 ⁰ C, after each addition of water the mixture was emulsified with Ultra Turrax homogeniser. The dry matter content of the final emulsion was 42 % and pH 7.

Example 17: Condensation of maleic anhydride-modified tall oil fatty acid mixture to alkyd resin based on tall oil fatty acid/conjugated tall oil fatty acid and preparation of emulsion

A mixture of the alkyd prepared in example 8 (100 g,) and the maleic modified tall oil fatty acid mixture of example 1 (50 g) was heated for 3 hours at 12O ⁰ C (Ar bubbling). Water (2.5 ml) was added and the agitating was continued for 2 hours at 100 ⁰ C ₅ whereby the acid number was 85. Then isopropanol (45.5 g) was added and

the mixture was allowed to cool to 5O ⁰ C. The pH of the product was adjusted to about 7 with an aqueous NH ₃ solution (about 28-30 % NH ₃ ). Emulsifying was carried out by adding water (80 g) in small portions during 3 hours into the resin mixture (100 g), which was agitated vigorously and warmed at 5O ⁰ C. Emulsifying was carried out after each addition of water with Ultra Turrax homogeniser. The pH of the emulsion was 7.8 and dry matter content 42 %.

Example 18: Preparation of emulsion from maleic anhydride-modified tall oil based alkyd resin

The maleic modified alkyd of example 6 (acid number 19.7 mgKOH/g and viscosity 4.7 Poise at 50°C, 200 g) was warmed to 100 ⁰ C and 3.5 g of water was added to it and agitating was continued for further 2 hours at 100°C. Acid number of the reaction mixture was determined (21.6 mgKOH/g). 60 g of isopropanol was added and the mixture was allowed to cool, the pH was adjusted to a value of about 7 with an aqueous NH ₃ solution. Emulsifying was carried out by adding water (21O g altogether) in small portions during 3 hours while stirring and warming the product mixture at 50 ⁰ C. After each addition of water homogenisation was carried out with Ultra Turrax homogeniser. The pH of the to room temperature cooled emulsion was 6.5.

Example 19: Preparation of tall oil based alkyd resin

Alkyd resin was prepared from tall oil fatty acids (372.6 g), isophthalic acid (55.9 g) and pentaerythπtol (71.5 g). AU starting materials were weighed into a reaction vessel and the reaction mixture was mixed and warmed at 240-260 ⁰ C with bubbling nitrogen below the surface of the reaction mixture. The progress of the reaction was followed with acid number, and when the reaction mixture became clear, also with viscosity. The reaction was boiled for 7 hours. The acid number of the cooled product (421.3 g) was 5 and viscosity 5.6 Poise/50°C, R.E.L. and 10305 cP/RT, Brookfield.

Example 20: Condensation of maleic anhydride-modified tall oil fatty acid mixture to alkyd resin based on tall oil fatty acid and preparation of emulsion

A mixture of the alkyd of example 19 (100 g) and the maleic modified tall oil fatty acid mixture of example 2 (50 g) was agitated (250-370 rpm) and heated for 3 hours at 120°C. Water (2.5 g) was added and the heating and mixing were continued for 2 hours at 100 ⁰ C, after which the mixture was allowed to cool to room temperature, whereby the acid number was 84. The pH of the solution was adjusted to 7 with a 25 % aqueous NH ₃ solution. Emulsifying was carried out by adding water drop wise during one hour to the resin mixture, which was stirred (450 rpm) and warmed at 50 ⁰ C. Finally, homogenisation was carried with Ultra Turrax homogeniser (1 min/13500 rpm). The dry matter content of the emulsion was 45 % and pH 7.

Example 21: Condensation of maleic anhydride-modified tall oil fatty acid mixture to alkyd resin based on tall oil fatty acid/conjugated tall oil fatty acid and preparation of emulsion

A mixture of the alkyd of example 8 (10Og) and the maleic modified tall oil fatty acid mixture of example 2 (50g) was agitated (250-600 rpm) and heated for 3 hours at

12O ⁰ C. Water (2.5g) was added and the heating and agitating were continued for 2 hours at 100 ⁰ C, after which the mixture was allowed to cool to room temperature, whereby the acid number was 93. The pH of the solution was adjusted to 7 with 25% aqueous NH ₃ solution. Emulsifying was carried out by adding water drop wise during one hour into the resin mixture, which was stirred (350 rpm) and warmed at 5O ⁰ C.

Finally homogenisation was carried out with an Ultra Turrax homogeniser (1 min/13,500 rpm). The dry matter content of the emulsion was 45% and pH 7.

Example 22: Modifying of linen seed oil with nialeic anhydride

Linen seed oil (2000 g) was warmed to 180 ⁰ C. Maleic anhydride ( 134.9 g) was added in small portions during 2 hours, then the reaction mixture was warmed to 200 ⁰ C and agitated (600 rpm) for further 3 hours. No unreacted maleic anhydride was observed in the NMR analysis of the product (1666 g). The acid number of the product was 35 and viscosity 1.0 Poise/25°C, R.E.L.

Example 23: Preparation of linen seed oil based alkyd resin

Alkyd resin was prepared from linen seed oil (450 g), trimethylolpropane (140.3 g) and isophthalic acid (195.0 g). A mixture of linen seed oil and trimethylolpropane was warmed to 200 ⁰ C with agitating under N ₂ atmosphere and then lithium hydroxide monohydrate (0.752 g) was added. The warming was continued to 250 ⁰ C, at which the reaction mixture was kept for 3 hours, then the mixture was cooled to 17O ⁰ C and isophthalic acid was added. The reaction mixture was rewarmed to about 220-250 ⁰ C and the progress of the reaction was followed with acid number and viscosity. The reaction time after addition of isophthalic acid was 4 hours. The acid number of the cooled product (703.3 g) was 15 and viscosity 4.0 Poise/100 ⁰ C, R.E.L.

Example 24: Condensation of maleic anhydride-modified linen seed oil to alkyd based on linen seed oil and preparation of emulsion

A mixture of linen seed oil based alkyd of example 23 (400 g) and maleic modified linen seed oil of example 25 (200 g) was agitated for 3 hours at 12O ⁰ C. Water (10 g) was added and agitating was continued for 2 hours at 100 ⁰ C. The mixture was allowed to cool to room temperature (acid number 23, viscosity 3.2 Poise/100 ⁰ C). The pH of the solution was adjusted to about 7 with a 25 % aqueous NH ₃ solution. Emulsifying was carried out in a 2000 ml glass reactor by slowly adding water. The resin product (500 g) was added into the reactor and warmed agitating (300 rpm) to 5O ⁰ C,

then water (5O ⁰ C) (900 g) was pumped slowly during 2.5 hours into the resin mixture. After addition of the water the mixture was allowed to cool to room temperature still stirring. The dry matter content of the ready emulsion was 3 5% and pH 7.7.