WO2001044333A1

WO2001044333A1 - Thermosetting resin obtained by reaction of a triazine compound with an aldehyde and an activated olefinic compound

Info

Publication number: WO2001044333A1
Application number: PCT/NL2000/000845
Authority: WO
Inventors: Wouter Heinen; Bartholomeus Johannes Margretha Plum; Patricia Hubertina Cornelis Grolleman; Rudolfus Antonius Theodorus Maria Van Benthem
Original assignee: Dsm N.V.
Priority date: 1999-12-15
Filing date: 2000-11-17
Publication date: 2001-06-21
Also published as: AU2237101A; NL1013851C2

Abstract

Thermosetting resin obtained by condensing a triazine compound, an aldehyde and an activated olefinic compound, this condensation taking place in the presence of a catalyst that is capable of effecting alkylolation of a double bond and as triazine compound use preferably being made of melamine, melamine-formaldehyde resin, hydroxyalkyl melamines or a mixture of these compounds.

Description

THERMOSETTING RESIN OBTAINED BY REACTION OF A TRIAZINE COMPOUND WITH AN ALDEHYDE AND AN ACTIVATED

OLEFINIC COMPOUND

The invention relates to a thermosetting resin obtained by reaction of a triazine compound with an aldehyde and an activated olefinic compound. The invention further relates to a process for the preparation of this thermosetting resin.

A thermosetting resin obtained by reaction of a triazine compound with formaldehyde and an activated olefinic compound in the presence of a catalyst is described in EP-A-514792. In said patent a methacrylate prepolymer is prepared from a triazine compound, formaldehyde and a hydroxy- functional methacrylate. The catalysed reaction of the triazine compound melamine with formaldehyde yields melamine-formaldehyde-containing resins. The methylol groups that are present in the melamine- formaldehyde-containing resins can etherify with hydroxy-functional acrylates, so that acrylate- functionalised melamine-formaldehyde resins are obtained. The formation of the resin is catalysed by using acid or alkaline compounds.

Each of the catalysts mentioned in EP- A-514792 is capable only of effecting etherification of hydroxyl groups already present in the acrylate with hydroxymethyl melamine compounds. This has the disadvantage that resin formation proceeds slowly in many cases or is not possible at all.

Surprisingly, it has been found that new thermosetting resins are obtained by condensing a triazine compound, an aldehyde and an activated olefinic compound, this condensation taking place in the presence of a catalyst capable of effecting alkylolation of a double bond.

An alkylolation catalyst is a catalyst that is capable of introducing a -CRH-OH group at a double bond, but for instance also at an amine group or at a hydroxyl group, with R representing hydrogen, an alkyl group or an alkoxy group that may or may not contain one or more functional groups . Suitable triazine compounds for use in the present invention are 1, 3 , 5-triazines that carry one or more amino substituents at the ring. Examples are melamine, melam, benzoguanamine, acetoguanamine, cyclohexane guanamine, cyclohexene guanamine, norbornane carboguanamine and norbornene carboguana ine . Substituted melamines can also be used. Examples of substituted melamines are alkyl melamines and hydroxyalkyl melamines . Examples of alkyl melamines are trimethyl melamine, dimethyl melamine, monomethyl melamine, triethyl melamine and tribenzyl melamine. Examples of hydroxyalkyl melamines include hydroxymethyl melamines formed by the reaction of one to nine formaldehyde molecules with for instance melamine, melamine-formaldehyde resins and trishydroxyethyl melamine. In addition, condensation products of one or more of the above- mentioned hydroxyalkyl melamines can be used. Preferably, melamine, melamine-formaldehyde resin, hydroxyalkyl melamines or mixtures of these are used.

Suitable aldehydes are aldehydes that are capable of alkylolation of melamine and activated double bonds. Alkylolation is the reaction in which an aldehyde reacts to form a hydroxyalkyl group. Methylolation, for instance, is the reaction in which formaldehyde reacts to form a hydroxymethyl group . Examples of such aldehydes are formaldehyde, acetaldehyde, propanal, butanal, benzaldehyde, 1, 4-butaandial, chloral, furfuraldehyde, esters of glyoxylic acid and derivatives from esters of glyoxylic acid such as hemi-acetals . Preferably, formaldehyde is used. Formaldehyde can be used as gaseous formaldehyde, as formaldehyde dissolved in water (formalin) or as paraformaldehyde . Paraformaldehyde is the polymeric or oligomeric form of formaldehyde that splits off formaldehyde upon depolymerisation. Paraformaldehyde with a degree of polymerisation equal to n can thus produce n molecules of formaldehyde and thus contains n formaldehyde equivalents. Preferably, use is made of paraformaldehyde or formalin, and in particular paraformaldehyde .

It has further been found that the formaldehyde component or part thereof, of the resin according to the invention can also be introduced by using compounds that contain methylol groups, such as for instance melamine-formaldehyde resins with methylolated double bonds and compounds with oxymethylene or polyoxymethylene. In melamine- for aldehyde resin both the triazine component and the formaldehyde component are present. When use is made of melamine-formaldehyde resin, a part of the formaldehyde equivalents present as methylol groups in the melamine-formaldehyde resin, which have reacted reversibly with melamine, can be released and react with the activated olefinic compound under the influence of the alkylolation catalyst. The terms hydroxymethyl and methylol are synonyms, as are the terms methylolation and hydroxymethylation and as are the terms alkylolation and hydroxyalkylation.

Activated olefinic compounds are compounds with an activated double carbon-carbon bond. These are compounds in which an electron- withdrawing group is present directly adjacent to the double carbon-carbon bond. Examples of electron-withdrawing groups in which a carbonyl group is present are the aldehyde group, the ketone group, the ester group and the amide group. In the present invention the proximity of the carbonyl group activates the double carbon- carbon bond in such a way that it can first react with an alkylolation catalyst and subsequently with the aldehyde. Examples of activated olefinic compounds are acrylates, crotonates, acrylamides, crotylamides, enones and acrylonitriles or mixtures of these.

Examples of acrylates that are suitable for the present invention are methyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3- hydroxypropyl acrylate, 4-hydroxy-butyl acrylate, oligoethylene glycol acrylate, the ethylether of oligoethylene acrylate, 2-ethoxyethyl acrylate, N,N, -dimethyl-aminoethyl acrylate, N,N, -diethyl- aminoethyl acrylate. Preferably, use is made of hydroxyethyl acrylate, the hydroxypropyl acrylates and the hydroxybutyl acrylate, in particular hydroxyethyl acrylate. If non-volatile acrylates are required, use is preferably made of oligoethyl acrylate or its methylether. Examples of crotonates are hydroxyethylcrotonate and 2- hydroxypropylcrotonate . Examples of suitable acrylamides are N-methylacrylamide, N-(2- hydroxyethyl) acrylamide and N,N'-(1,2- dihydroxyethylene) -bisacrylamide . Examples of suitable enones are acrolein, fumaraldehyde, 2- cyclohexenone, crotonaldehyde, 4-methylpent-3-en-2- one and coniferaldehyde . Examples of active acrylonitriles are 4-hydroxybut-2-en-l-nitrile, 5- aminopent-2-en-l-nitrile and fumaronitrile . The alkylolation catalyst can also promote other reactions. Examples of such reactions are etherifications, trans-etherifications, esterifications and trans-esterificiations . When use is made of an alkylolation catalyst and hydroxy-functional activated olefinic compounds, such as for instance 2-hydroxyethyl acrylate, esterification and trans-esterification reactions may occur in which one activated diolefinic compound is formed from two hydroxy-functional activated olefinic compounds, with an alcohol compound being split off. A favourable effect of this reaction is that the amount of monomeric activated olefinic compound is reduced. Monomeric activated olefinic compounds generally have a low molecular weight and are volatile, as a result of which they can easily give rise to undesirable emission of organic compounds. In addition, two hydroxy-functional activated olefinic compounds can undergo an etherification reaction, which also yields an activated diolefinic compound, with the advantage outlined above.

It is also possible to use mixtures of various activated olefinic compounds. Applicant has found, however, that methacrylates, methacrylo- nitriles and methacrylamides are not suitable. The methyl substituent at the alpha position of the double bond in these compounds prevents methylolation of this position.

Suitable alkylolation catalysts are compounds in which a strongly activated nitrogen atom is present. Examples of strongly activated nitrogen atoms are nitrogen atoms to which electron-donating substituents, such as alkyl substituents, are attached. The activation of the nitrogen atoms can be reinforced through a fixed orientation of the electron-donating substituents around the nitrogen atom, so that the substituents cannot move freely around the nitrogen atom. Examples of alkylolation catalysts are pyrrocoline, quinoldine, 1, 4-diaza [2.2.2 jbicyclooctane (DABCO) , 1-aza [ 2 . 2 .2]bicyclooctane (quinuclidine) , 3- quinuclidinone, 3-quinuclidinol, 1,5-diaza- bicyclo [4.3.0]non-5-ene (DBN) , 1, 8-diazabicyclo- [5.4.0]undec-7-ene (DBU) and aza [2.2. ljbicyclo- heptane. Preferably, use is made of DABCO, quinuclidine, 3-quinuclidinone or aza [2.2. l]bicycloheptane . In particular, use is made of DABCO and/or quinuclidine. Besides straightforward alkylolation catalysts use can also be made of mixtures of two different catalysts. It has been found that alkaline catalysts are more suitable than acid catalysts. Acid catalysts, such as for instance paratoluene sulphonic acid, are not capable of effecting the alkylolation. Moreover, the condensation rate of melamine-formaldehyde resin is higher under acid conditions than under basic conditions and this has the disadvantage that it may lead to premature gelling of the composition during resin preparation. The invention also relates to a process for the preparation of a thermosetting resin by converting a triazine compound with an aldehyde and an activated olefinic compound using a catalyst, a catalyst being used that is capable of effecting alkylolation of a double bond.

The resin can be prepared by combining and stirring the components at an elevated temperature and optionally reduced pressure. The temperature preferably lies between room temperature and the boiling point of the activated olefinic compound at the prevailing pressure. If the temperature is too low, resin preparation will proceed at an undesirable slow rate. If the temperature is too high, radicals may spontaneously be formed, which may cause spontaneous polymerisation of the activated olefinic compound. Preferably, resin preparation takes place at between 40°C and 150°C. Most preferably, resin preparation takes place at between 60°C and 130°C. A reduced pressure is advantageous since this makes it easier to remove products of the various condensation reactions, in most cases water. Use of a reduced pressure and removal of water is not necessary for preparation of the resin. In general, use of a reduced pressure and the removal of products of the various condensation reactions that are possible will lead to faster resin preparation. The resin is preferably prepared at a pressure between 0.005 MPa and atmospheric pressure. More preferably, the resin will then be prepared at a pressure of between 0,02 MPa and atmospheric pressure. The type of atmosphere under which the resin preparation takes place may be an inert gas, such as for instance nitrogen, or air.

During the preparation of the resin according to the invention, structures will be formed that are typical of the resin. An example of a typical structure that will occur in the resin is the methylol group attached to a double bond as represented by -CH₂OR₄ and -CH₂OR. in formulae 1 and 2.

Formula 1

Formula 2

Substituents R₁ up to and including R₇ can be chosen as desired and independently of one another and follow from the choice of the activated olefinic compound. R up to and including R₇ may be hydrogen and/or alkyl substituents and/or alkoxy substituents that may or may not contain one or more functionalities. X may be 0, S or NH.

During and after the preparation the resin may still contain a certain amount of free, unbound activated olefinic compound. At a later stage, during curing of the resin, this fraction will be incorporated in the polymer structure and as such will not give rise to emission of volatile organic components. The amount of free, unbound activated olefinic compound can, if desired, be reduced by prolonging the condensation reaction or by removing the water that is released during resin preparation as a consequence of the condensation reaction. This removal may for instance be effected by preparing the resin at a higher temperature or a lower pressure or for instance by allowing the free, unbound activated olefinic compound to react with a suitable reagent after the condensation reaction. Preferably, the amount of free acrylates, such as hydroxyethyl acrylate, is reduced by reaction with isocyanates such as propylisocyanate or butylisocyanate or reaction with anhydrides such as methacrylic anhydride . The composition of the resin can be varied depending on the desired properties of the resin and the cured resin in its final application. Preferably, the ratio of triazine : formaldehyde (equivalents) : activated olefinic compound lies between 1 : 1 : 1 and 1 : 12 : 12. More preferably, the ratio of melamine : formaldehyde (equivalents) : activated olefinic compound lies between 1 : 1 : 1 and 1 : 8 : 8.

The amount of alkylolation catalyst can be chosen freely, but too small an amount of catalyst will result in undesirable slow resin formation, while the reaction may proceed too fast and is difficult to control when the amount of catalyst is too large. The amount of alkylolation catalyst can be chosen between 0.01 and 8 moles relative to the total of 100 moles of triazine compound together with activated olefinic compound and formaldehyde or formaldehyde equivalents .

The resin according to the invention can be prepared in the presence of a solvent such as, for instance, water or non-reactive acrylates. It is also possible to prepare the resin by dispersing the activated olefinic compound in for instance water and adding this dispersion to the other resin components. The reagents can be fed to the reactor together or in a random sequence. In a special embodiment the activated olefinic compound and the aldehyde, preferably formaldehyde or a compound supplying formaldehyde equivalents, are converted in the presence of an alkylolation catalyst into a reactive solvent (essentially water-free) and later the triazine compound is added. At elevated temperature the alkylolation catalyst causes formaldehyde and the activated olefinic compound to react to form a clear, colourless and homogeneous mixture of compounds. The reactive solvent can be prepared at another temperature than that at which the triazine compound is reactively dissolved. The reactive solvent can be stored at, for instance, room temperature before the triazine compound is dissolved. After dissolving of the triazine compound in the reactive solvent, the composition and the characteristics of the resin will essentially be the same as when the components are dosed simultaneously. The resins can be prepared in the presence of radical stabilisers such as for instance phenothiazines, methylhydroquinone , di-t.butyl- hydroquinone and nitrostyrene .

It is possible to prepare resins that have a different viscosity and that differ in the degree to which the reagents have reacted with one another. These parameters can be controlled as desired by the choice of the catalyst, the type of triazine compound, the type of activated olefinic compound, the reaction temperature and the pressure during the reaction. Depending on the application of the resin the viscosity can be varied over a wide area. Resins according to the invention can have a viscosity in excess of 40 mPa.s, a value between 40 mPa.s and 100 Pa . s being preferred.

Before the resin is used for processing in its final application, the resin can be modified. The modified resin can contain all customary additives. Examples of customary additives are mould release agents, antistatic agents, adhesion improvers, plasticisers, flame retardants, fillers, flow promoters, colourants, thinning agents, polymerisation initiators, UV- stabilisers and heat stabilisers. Examples of fillers are glass fibres, mica, carbon fibres, metal fibres, clay, aramide fibres and strong polyethylene fibres.

The resin, optionally processed in an application and optionally modified, is usually cured prior to of the end product in which the resin is processed. Curing of the resin can take place in various ways. The resin can for instance be cured thermally. In thermal curing free radicals are formed spontaneously at a higher temperature, and these initiate the addition polymerisation of the activated double bonds in the resin. It is also possible for condensation polymerisation to occur as a consequence of the condensation of the methylol groups present in the resin (so-called dual-cure) . To promote the formation of radicals, radical initiators can be added. When curing takes place at a lower temperature use can be made for instance of cobalt-methylethylketone peroxide or benzoylperoxide-dimethylaniline. For curing at moderate temperatures use can for instance be made of diisopropyl peroxydicarbonate, benzoylperoxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy neodicanate or azi-bis-diethylvaleronitrile . For curing at higher temperatures use can be made for instance of t-butylhydroperoxide, cumene hydroperoxide or t-butylperbenzoate.

The resin can also be cured under the influence of UV light. Radiation with UV light causes the formation of radicals in the resin. The radicals can start the addition polymerisation. For more efficient formation of radicals a UV initiator can be added. Examples of UV initiators are Norrish type-I initiators, Norrish type-II initiators and type-II amine initiators. Examples of Norrish type- I initiators are Irgacure® 184, Derocure® 1137, Irgacure® 369 and Irgacure® 907 (all from Ciba) . Examples of Norrish type-II initiators are benzophenone, thioxanthone, camphorquinone and anthraquinone . Examples of Type-II amines are tertiary aliphatic and aromatic amines. Curing by radiation with UN light and thermal curing can be combined by radiating the resin with UN light at elevated temperature. The elevated temperature can for instance be obtained by radiation with infrared light.

Curing of the resin can also be effected by treating the resin with an electron beam. As a result of the radiation with an electron beam, free radicals are formed in the resin that bring about the addition polymerisation of the activated double bonds in the resin. The resin can also be cured by combining two or more of the above-mentioned techniques .

The resin or the modified resin can be used in numerous areas. To obtain moulded articles, the resin can for instance be used as casting resin. This for instance involves pouring the resin into a mould and curing it, following which a moulded article of a desired design is obtained.

The resin is also suitable for use as impregnation resin. A carrier material can be passed through a bath with resin of a suitable viscosity, or the resin can be applied to the carrier material in a different way. Examples of suitable carrier materials are woven or non-woven materials on the basis of fibres, yarns or bundles made of, for instance, cellulose, cellulose acetates, artificial silk, cotton, wool, glass, rock wool, thermoplastic polymers or mixtures of different materials .

The resin according to the invention is also eminently suitable for use as coating. The resin can readily be applied in a thin layer to surfaces and then be cured to form a coating according to one of the methods described above. As substrate for the coating many materials can be used, for instance glass and wood or wood-based materials such as, for instance, medium density fibreboard (MDF) , high density fibreboard (HDF) , chipboard and oriented strand board (OSB) , and plastics such as, for instance, polyethylene and polypropylene, and metals such as, for instance, aluminium, steel and iron and paper-based or cellulose-fibre-based materials such as LPL laminates, HPL laminates, Trespa Athlon®, Trespa Meteon® and Trespa Toplab® from Trespa B.V. The coatings obtained are very hard, have an excellent solvent resistance, and are clear, colourless and scratch resistant.

The resin according to the invention can further be used as glue to glue components together. The resin is particularly suitable for gluing wooden parts, in which case part of the melamine may be replaced by urea.

The resin can suitably be used as crosslinking agent for other resins. The resin can for instance be mixed with styrene, 2-hydroxy- methacrylate, methylmethacrylate, hexane diol dimethacrylate, hexane diol diacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylol propane triacrylate, acrylonitrile, vinylester resin, urethane (meth) acrylate, polyester acrylate, diallylphthalate, unsaturated polyester resin, methylmethacrylate resin or mixtures of two or more of the said components. In addition, the resin can be mixed with prepolymers that are capable of reacting with hydroxy groups or amino groups. Examples of such prepolymers are isocyanate monomers, diisocyanate monomers such as, for instance, isophorone diisocyanate and methylene diisocyanate, allophanate-containing prepolymers, biuret-containing prepolymers and isocyanurate- containing prepolymers .

Moulded articles made of or with thermally cured melamine-formaldehyde resin (MF) generally possess a number of very favourable properties. Examples of articles made of or with thermally cured melamine-formaldehyde resin are MF laminate floors, desk tops with a cured MF-laminate top layer, dinnerware on the basis of melamine- formaldehyde resin and a filler originating from wood and structural moulded articles on the basis of MF and an inorganic filler. Examples of the favourable properties are surface hardness, flame retardancy, good colouring properties and high scratch resistance. A disadvantage of thermal curing is its slowness and the high pressure at which it takes place. The introduction of radically curable groups into melamine-formaldehyde resin makes it possible to obtain materials which after curing, for instance in another way than the thermal curing which is customary for melamine- formaldehyde resins, have almost all favourable properties of thermally cured MF resin and moreover this method is fast and simple to use.

The invention will be elucidated on the basis of the following examples:

Examples 1-1 up to and including 1-27 and comparative examples A, B and C See Table 1. A reactor is charged with an activated olefinic compound (AOC, columns 2 en 3), melamine, paraformaldehyde and an alkylolation catalyst (column 8) . The molar ratios of the reagents and the alkylolation catalyst, as well as the amount of activated olefinic compound added, are presented in the table (columns 4, 5, 6, and 7, respectively) . Then the reactor is externally heated up to the temperature indicated in column 9 and the pressure in the reactor is adjusted to the value indicated in column 10. The point of time at which the (cooled) prepared resin stays clear and homogeneous at 25°C is given in column 11. The preparation time of the resin is presented in column 12, while column 13 gives the viscosity of the resin after the preparation time (measured at

25°C in a Brookfield viscosimeter) . Column 14 gives the value, calculated by means of interpolation or extrapolation, for the time at which the resin has a viscosity of 1000 mPa . s (at 25°C) .

Examples 2-1 up to and including 2-12 and comparative examples D and E

See Table 2. 1 wt . % Irgacure 184® is added to an amount of the resin as prepared according to one of the preparation ways described in Table 1 (see column 2), following which a layer of approximately 100 μm is applied to a glass plate, and optionally to an MDF and an aluminium plate. The plates with the coating are transported under UV lamps at a speed of 10 .s^"1. Above the glass plates a nitrogen atmosphere is provided. The UN lamps have the following intensities: UV-A 1.6 to 1.7 W/cm², UV-B 1.3 to 1.5 W/cm² and UV-C 0.16 to 0.18 W/cm². The hardness of the coatings on the plates is measured using a Kδnigs hardness meter (pendulum hardness) and is expressed in seconds

(columns 3, 4 and 5) . With the same Kδnigs hardness meter the following reference values were measured: glass: 248 s, MDF : 60 s, aluminium: 182 s. The solvent resistance of the coatings is determined by performing at least a hundred double rub movements with an acetone-soaked wad of cotton wool over the coating surface (acetone double rubs) . The number of "acetone double rubs" that can be performed without causing visual damage to the coating is indicated (column 6) .

Examples 2-13

85 mg Irganox 184® is added to 8.5 g of the resin described in Examples 1-13, which has a viscosity of 2525 mPa.s. At the bottom of a round mould a layer of the resin is applied, the thickness varying from 2 to 5 mm. The mould with the resin is transported under UV lamps at a speed of 10 m.s^"1. Above the glass plate a nitrogen atmosphere is provided. The UV lamps have the following intensities: UV-A 1.58 W/cm², UV-B 1.41 W/cm² and UV-C 0.18 W/cm². A crystal-clear lens- shaped object is obtained.

Example 3-1

50 g of the reactive solvent as prepared in Example 1-20 is heated to 90°C and 10.8 g melamine is added, so that the melamine : formaldehyde equivalent : hydroxyethylacrylate ratio is 1 : 4 : 4. Within an hour the resin is clear and homogeneous. After 150 minutes a resin having a viscosity of 22 Pa.s is obtained.

Example 3-2

29.4 g tris (hydroxyethyl)melamine is added to 50.7 g of the reactive solvent described in Example 26, which has a viscosity of 44 mPa.s. Within twenty minutes a clear and homogeneous resin mixture has formed and after 60 minutes the resin has a viscosity of 5300 mPa . s .

Example 3-3

26.6 g hydroxyethyl acrylate, 6.80 g paraformaldehyde and 0.66 g DABCO (1 : 1 : 0.026) are fed to a reactor and subsequently heated to 90°C and stirred. The mixture is clear within a reaction time of 30 minutes. The resulting reactive solvent is cooled, kept at room temperature for 48 hours, and subsequently again heated to 90°C. Melamine is then added in portions so that after 4 hours a clear and homogeneous reaction mixture is obtained in which the melamine : hydroxyethyl acrylate : formaldehyde equivalent ratio is 1 : 3 : 3.

Example 3-4

A reactor is charged with: 12.6 g melamine, 68.4 g hydroxyethyl acrylate, 18.9 g paraformaldehyde and 3.4 g DABCO (molar ratio 1 : 6 : 6 : 0.3). The reactor is heated from 25°C to 90°C in 40 minutes, and is then kept at 90°C. Seventy minutes after the start of heating the resin is clear, homogeneous and colourless. The resin is kept for 16 months at 8°C and after that is still clear, homogeneous, colourless and liquid.

Examples 3-5 up to and including 3-7 See Table 3. A reactor is charged with an amount of Madurit 909® (a solid, spray-dried melamine-formaldehyde resin with a melamine : formaldehyde ratio of 1 : 1.7; column 2), an amount of 95% paraformaldehyde (column 3), an amount of hydroxyethyl acrylate (column 4) and an amount of DABCO (column 5) . The hydroxyethyl acrylate : melamine : formaldehyde equivalent : DABCO ratio is presented in columns 6, 7, 8 and 9. The reactor is heated to 90°C. After a certain time (column 11) a clear and homogeneous mixture is obtained. After the reaction time (column 12) the resin has a certain viscosity (column 13) .

Table 1. Evaluation of the resins - part 1: Examples A up to and including 1-12, columns 1 up to and including 10.

1 2 3 4 5 6 7 8 9 10 activated amount molar component olefinic of AOC ratios reaction compound T at pressure example (AOC) ⁽g⁾ AOC M Fe cat . cat . (°C) (hPa)

A HPA 132 5 1 5 0.08 pTSA.H₂0 90 500

B HEA 116 5 1 5 0.08 TEA 90 500

C HEA 93.2 4 1 4 0.08 TEA 90 500 co

1-1 HPA 132 5 1 5 0.08 DABCO 90 500

1-2 HEA 116 5 1 5 0.04 DABCO 90 1000

1-3 HEA 92. g ) 4 1 4 0.04 DABCO 90 1000

1-4 HEA 116. 1 5 1 5 0.04 DABCO 90 1000

1-5 HEA 139. 3 6 1 6 0.04 DABCO 90 1000

1-6 HEA 93.2 4 1 6 0.08 DABCO 90 1000

1-7 HEA 116. 1 5 1 6 0.08 DABCO 90 1000

1-8 HEA 139. .3 6 1 6 0.08 DABCO 90 1000

1-9 HEA 116. 1 5 1 5 0.04 DABCO 90 500

1-10 HEA 139. .3 6 1 6 0.16 DABCO 90 1000

1-11 HEA 139. .3 6 1 6 0.3 DABCO 90 1000

1-12 HEA 553 4 1 4 0.08 DABCO 90 500

Table 1. Evaluation of the resins part 2: examples 1-13 up to and including 1-27, columns 1 up to and including 10.

2 3 4 5 6 7 8 10 activated amount molar component olefinic ratios reaction compound AOC T at pressure example (AOC) ⁽g⁾ AOC M Fe cat . cat . (°C) (hPa)

1-13 HPA 619 4 1 4 0.08 DABCO 90 500 1-14 HEA 139.3 6 1 6* 0.04 DABCO 90 1000 1-15 HEA 116.1 5 1 5* 0.04 DABCO 90 1000 r 1-16 HEA 27.9 3 1 3 0.08 DABCO 90 500 o 1-17 HBA 25.0 4 1 4 0.04 DABCO 90 500 1-18 HEA 116 5 1 5 0.08 DABCO 90 500 1-19 HEA 552 6 1 6 0.08 DABCO 90 500 1-20 HEA 350 6 0 6 0.16 DABCO 75 1000 1-21 HEA 139.3 6 1 6* 0.04 DABCO 90 1000 1-22 HEA 116.1 5 1 5* 0.04 DABCO 90 1000 1-23 HEA 18.4 4 1 4 0.08 Qui 70 500 1-24 HEA 18.4 4 1 4 0.08 Qui 100 500 1-25 HEA 9.22 4 1 4 0.08 Qui 85 500 1-26 HEA 36.9 4 1 4 0.08 Qol 85 500 1-27 Con \ 10.0 4 1 4 0.08 DABCO 85 500

HEA / 6.6

Table 1. Evaluation of the resins - part 3: examples A up to and including 1-12, columns 1 and 11 up to and including 14. 1 11 12 13 14 the cooled resin reaction viscosity at (calculated) time needed is clear at t ( in) time(min) end of reaction to reach a viscosity of 1

Pa.s

A not 40 premature gelling premature gelling

B >90 320 310 990

C <85 150 1670 110 IX)

1-1 <60 225 1450 155

1-2 <55 285 580 490

1-3 <60 140 1800 950

1-4 <60 285 580 500

1-5 <90 285 250 2260

1-6 <30 150 3910 40

1-7 <30 300 1250 235

1-8 <30 265 570 510

1-9 <50 300 1400 245

1-12 <30 90 1774 58

Table 1. Evaluation of the resins - part 4: examples 1-13 up to and including 1-27, columns 1 and 11 up to and including 14.

1 11 12 13 14 the cooled resin reaction viscosity at the (calculated) time needed to is clear at t (min) time (min) end of reaction reach a viscosity of 1 Pa.s

1-13 <30 100 2525 n.d.

1-14 <60** 120** 230 n.d.

1-15 <60** 120** 600 n.d.

1-16 <75 90 8150 n.d.

1-17 <120 190 390 n.d. ro

1-18 <60 165 830 195

1-19 <60 660 1780 560

1-20 <60 360 44 n.d.

1-21 <60** 60** 230 n.d.

1-22 <60** 120** 600 n.d.

1-23 180 240 825 n.d.

1-24 25 25 35 n.d.

Table 2. Evaluation of the coatings - examples D up to and including 2-12 1 2 3 4 5 6 hardness hardness hardness "acetone resin of on glass on MDF on aluminium double rubs" example example (s) (s) (s) (number)

D 1-20 28 n.d.

E B 63 >100

2-1 1-14 76 >100

2-2 1-15 97 >100

2-3 1-3 109 50 110 >100 ro ω

2-4 1-4 112 56 117 >100

2-5 1-9 130 67 133 >100

2-6 1-5 91 66 90 >100

2-7 3-1 130 >100

2-8 1-18 119 >100

2-9 1-16 119 >100

2-10 1-19 118 >100

2-11 1-12 126 >100

2-12 1-13 99 >100

Table 3. Various examples 1 2 3 4 5 6 7 8 9 10 11 12 13 amounts of molar component cooled viscosity reagents (g) ratios resin is reaction at end of example T clear at t time reaction

Mad F HEA DABCO HEA M Fe DABCO (°C) (min) (min) (mPa.s)

3-5 19.7 7.7 52 1. .5 4 1 3.9 0.1 90 9 60 1650

3-6 3.0 0 11.9 0, .15 6 1 1.7 0.08 90 3 48 190

3-7 18.0 0 11.9 0, .9 1 1 1.7 0.08 90 40 40 34000*** r =

Explanation for the Tables ;

M: melamine

F : paraformaldehyde

HEA : hydroxyethyl acrylate

Fe : formaldehyde equivalents cat.: alkylolation catalyst

HBA: hydroxybutyl acrylate

TEA: triethyl acrylate

HPA: hydroxypropyl acrylate; mixture of isomers

DABCO: l,4-diaza[2.2.2]bicyclooctane p-TSA.H₂0: para-toluene sulphonic acid hydrate

Qui . : quinuclidine

Qol . : quinuclidinol

Con. : coniferaldehyde

Mad. : Madurit® 909 n.d.: not determined

* dosed 1 hour after the other ingredients ** after addition of the last ingredient *** measured at 60°C

Claims

C L A I M S

1. Thermosetting resin obtained by condensing a triazine compound, an aldehyde and an activated olefinic compound, characterised in that this condensation takes place in the presence of a catalyst that is capable of effecting alkylolation of a double bond.

2. Thermosetting resin according to claim 1, characterised in that the triazine compound is chosen from melamine, melamine-formaldehyde resin, hydroxyalkyl melamines or a mixture of these compounds .

3. Thermosetting resin according to claims 1 -2, characterised in that the aldehyde compound is formaldehyde in the form of gaseous formaldehyde, formalin or paraformaldehyde.

4. Thermosetting resin according to claims 1-3, characterised in that as activated olefinic compound use is made of an acrylate, crotonate, acrylamide, crotylamide, enone, acrylonitrile or a mixture of two or more of these components.

5. Thermosetting resin according to claims 1-4, characterised in that as activated olefinic compound use is made of hydroxyalkyl acrylate.

6. Thermosetting resin according to claims 1-5, characterised in that as alkylolation catalyst use is made of a compound with a strongly activated nitrogen atom.

7. Thermosetting resin according to claim 6, characterised in that as alkylolation catalyst a choice is made from 1, 4-diaza [2 , 2 , 2] - bicyclooctane, quinuclidine, 3-quinuclidinone, aza [2.2.1] cycloheptane or a mixture of two or more of these compounds.

8. Process for the preparation of a thermosetting resin by converting a triazine compound with an aldehyde and an activated olefinic compound with the aid of a catalyst, characterised in that use is made of a catalyst that is capable of effecting alkylolation of a double bond.

9. Process according to claim 8, characterised in that the thermosetting resin is prepared by first preparing a reactive solvent on the basis of an activated olefinic compound and an aldehyde in the presence of an alkylolation catalyst, and at a later stage adding the triazine compound.

10. Process according to claims 8-9, characterised in that the triazine compound is chosen from melamine, melamine-formaldehyde resin, hydroxyalkyl melamines or a mixture of these compounds .

11. Process according to claims 8-10, characterised in that the aldehyde compound is formaldehyde and in that formaldehyde is chosen in the form of gaseous formaldehyde, formalin, paraformaldehyde or hydroxymethyl groups .

12. Process according to claims 8-11, characterised in that as activated olefinic compound use is made of an acrylate, crotonate, acrylamide, crotylamide, enone, acrylonitrile or a mixture of two or more of these components.

13. Process according to claims 8-12, characterised in that hydroxyalkyl acrylate is chosen as activated olefinic compound.

14. Process according to claims 8-13, characterised in that the alkylolation catalyst is chosen from 1, 4-diaza [2 , 2 , 2]bicyclooctane, quinuclidine, 3- quinuclidinone, aza [2.2.1] cycloheptane or a mixture of two or more of these compounds.

15. Process according to claims 8-14, characterised in that the resin is prepared in the presence of

0.01 to 8 mole parts of alkylolation catalyst on the total of the 100 mole parts of triazine compound, activated olefinic compound and formaldehyde or formaldehyde equivalents.

16. Use of the resin according to claims 1-7 as impregnation resin.

17. Use of the resin according to claims 1-7 as coating.

18. Use of the resin according to claims 1-7 as glue.

19. Use of the resin according to claims 1-7 as crosslinking agent.

20. Moulded articles prepared from or with the resin according to claims 1-7.

21. Thermosetting resin, process for the preparation of this resin and use of this resin as substantially described in the description and the examples .