A process for the preparation of polytriazines from aromatic polycyanates

This invention relates to a process for the preparation of polytriazine from aromatic knequannates of the formula Ar (fOCN), wherein n - in the formula Ar is an aromatic group and n is 1-7. It is prepared by reacting aromatic polycyanates at a temperature of 20 to 200 ° C using C as a catalyst.₆_₂cobalt salt of g-carboxylic acid.

For example, upstream of the aromatic polycyanate form of ar- (OCN)_of, vari Ar är en aromatic group och n är 1-7. Framställningen sker genom att aromatic polycyanat fAr reagera at a temperature of 20-200 ° C under an atmosphere of cobalt to C₆__2Q-carbons with a catalyst.

Process for the preparation of polytriazines from aromatic polycyanates

This invention relates to a process for the preparation of polytriazines using catalysts suitable for the preparation of polytriazines from aromatic polycyanates.

It is known from U.S. Patent 4,094,852 (Sundermann et al., September 13, 1978) that aromatic cyanates can be polymerized to give polytriazine polymers. Such polymers are prepared by contacting aromatic cyanates with suitable catalysts at an elevated temperature. According to said patent, suitable catalysts include acids, bases, salts and nitrogen and phosphorus compounds, for example Lewis acids such as A1C1.₃, BF₃, FeCl₃, TiCl₄, TiCl₄, ZnCl₂ and SnCl₄; protic acids such as HCl and H₃PO₄; aromatic hydroxy compounds such as phenol, p-nitrophenol, pyrocatechol and dihydroxynaphthalene; sodium hydroxide, sodium methylate, sodium phenolate, trimethylamine, triethylamine, tributylamine, diazobicyclo [2.2.2] octane, quinoline, isoquinoline, tetrahydroisoquinoline, tetraethylammonium chloride, pyridine N-oxide, tributylphosphine³-oxa-1-phenyl, zinc octoate, tin octoate, zinc naphthenate and mixtures thereof.

According to U.S. Patent 3,694,410 (Demke, September 26, 1972), chelates of metal ions, which may be of the nonionic or ionic type and contain 16 chelate rings (or more chelate rings), are capable of catalyzing the production of polytriazines from aromatic polycyanates.

When preparing polytriazines from aromatic polycyanates, it is desirable to use a catalyst which achieves a short polymerization time.

The invention relates to a process for the preparation of polytriazine by contacting an aromatic polycyanate with a catalytic amount of a metal salt of a carboxylic acid at a temperature of 20 to 200 ° C. The process is characterized in that C is used as the catalyst₆_₂₀cobalt salt of carboxylic acid and that the aromatic polycyanate is a polyaromatic cyanate of the formula

<img file="FI89934C_D0001.tif" />

—E ---- (0CN)_g (IV) where

E is an aromatic radical;

B is a polycyclic aliphatic group having 7 to 20 carbon atoms;

D at each occurrence is independently any substituent that does not contain an active hydrogen atom; q, r and s are independently at each occurrence 0,1, 2 or 3, provided that the sum of q + r + s is at least 2; t is independently an integer from 0 to 4 at each occurrence; and x is any number from 0 to 5.

The polytriazines of this invention can be used as in-situ curable resins, or can be formed into moldings when thermal stability, chemical inertness, and solvent resistance are desired or required.

Catalysts have been found which are suitable for the preparation of polytriazines from aromatic polycyanates and which achieve shorter polymerization times.

934 than hitherto known catalysts. These catalysts are C₆_₂₀cobalt salts of carboxylic acids. Preferred catalysts are C₆_₁₀cobalt salts of carboxylic acids, with cobalt octoate and cobalt naphthenate being most preferred. Cobalt naphthenate is prepared by treating cobalt (II) hydroxide or acetate with naphthenic acid. Naphthenic acid consists of saturated fatty acids obtained from a petroleum gas fraction by extraction with sodium hydroxide solution and then addition of acid.

The amount of catalyst suitable for this use is the amount that catalyzes the preparation of polytriazines from aromatic polycyanates to the desired extent. A suitable amount of catalyst is 0.001 to 5% by weight of the amount of aromatic polycyanates. The preferred amount is 0.01 to 1% by weight of the amount of aromatic polycyanates. An even more preferred amount is 0.01 to 0.1% by weight of the amount of aromatic polycyanates.

Aromatic polycyanates corresponding to general formula II, (NC0) are known

<img file="FI89934C_D0002.tif" />

(OCN) (II) wherein each R, which may be the same or different from each other, is hydrogen, halogen or a straight-chain or branched C 1-4 alkyl, phenyl, C 1-4 alkoxy or 1-4 C atom containing in its alkyl moiety an alkoxycarbonyl group or two adjacent R groups of the same ring may together form a carbocyclic 5- or 6-membered ring or two adjacent R groups may together form a 5- or 6-atom heteroatom (0, S, N)

39934 rosycyclic ring; R 'has the same meaning as R or is of formula III

<img file="FI89934C_D0003.tif" />

corresponding group;

A means direct bond, C₁_₂₀-alkylene group optionally substituted by C₁_₄~ alkyl or phenyl, a cycloaliphatic or aromatic, 5- or 6-atom ring optionally cleaved by oxygen, a sulfonyl group (-SO₂~), carbonyl dioxide group (-0C0-)

II o or a carbonyl group;

a is a number from 1 to 5 when e 1, and a number from 2 to 5 when e = 0;

b is 5 - a when e £ 1, and 6- (a + d) when e = 0;

c is 5 - d;

d is a number from 0 to 5; and e is 0, 1, 2 or 3;

provided that the sum of a and d is always 2 to

5.

Preferably, the symbols appearing in general formula II have the following meanings:

R is hydrogen, fluorine, chlorine, bromine, C_x_₄-alkyl, methoxyl, ethoxyl, methoxycarbonyl, ethoxycarbonyl or butoxycarbonyl; A is a direct bond, oxygen or sulfonyl, carbonyl, carbonyl dioxide, methylene, ethylene, 2,2-propyleneS9934

CH

I ³ (-C-) ch₃ or a cyclohexylene group;

<td>a</td><td>is</td><td> 1,</td><td colspan="2">when e</td><td>$ 1, and 2 when e = 0;</td>

<td>b</td><td>is</td><td> 1</td><td>or</td><td> 2,</td><td>more preferably 1;</td>

<td>c</td><td>is</td><td> 1</td><td>or</td><td> 2,</td><td>most preferably 1;</td>

<td>d</td><td>is</td><td> 0</td><td>or</td><td> 1;</td><td>And</td>

<td>e</td><td>is</td><td> 0,</td><td> 1,</td><td> 2</td><td>or 3; provided that</td>

As examples of compounds corresponding to one or more of the above formulas, the following compounds may be mentioned in particular: 1,3- and 1,4-dicyanatebenzene, 2-t-butyl-1,4-dicyanatebenzene, 2,4-dimethyl-1,3-dicyanatebenzene, 2,5-di-t-butyl-1,4-dicyanatebenzene , tetramethyl-1,4-dicyanatebenzene, 2,4,6-trimethyl-1,3-dicyanatebenzene, 4-chloro-1,3-dicyanatebenzene, 1,3-, 1,4-, 1,5-, 1,6- , 1,7-, 1,8-, 2,6- and 2,7-dicyanate naphthalene, 1,3,5-tricyanatebenzene, 4,4'-dicyanate biphenyl, 2,2'-dicyanate biphenyl, 3,3 ', 5 , 5'-tetramethyl-4,4'-dicyanate biphenyl, 3,3 ', 5,5'-tetrachloro-4,4'-dicyanate biphenyl, 3,3 ', 5,5'-tetrachloro-2,2'-dicyanate biphenyl, 2,2', 6,6'-tetrachloro-4,4'- dicyanate biphenyl, 4,4'-bis (3-cyanate phenoxy) biphenyl, 4,4'-bis (4-cyanate phenoxy) biphenyl, 2,2'-dicyanate-1,1'-binaphthyl, 4,4'-dicyanate diphenyl ether, 3.3 ', 5,5'-tetramethyl-4,4'-dicyanate diphenyl ether, 3,3', 5,5'-tetrachloro-4,4'-dicyanate diphenyl ether, 4,4'-bis (p-cyanate phenoxy) diphenyl ether, 4,4'-bis (p-cyanatephenyl isopropyl) diphenyl ether, 4,4'-bis (p-cyanate phenoxy) benzene, 4,4'-bis (m-cyanate phenoxy) diphenyl ether, 4,4'-bis [4 - (4-cyanatephenoxy) phenylsulfone] -diphenyl ether, 4,4'-dicyanatediphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-dicyanatediphenylsulfone, 3,3', 5,5'-tetrachloro-4, 4'-dicyanate diphenylsulfone, 4,4'-bis (p3 9 9 3 4 cyanatephenylisopropyl) diphenylsulfone, 4,4'-bis (4-cyanatephenoxy) diphenylsulfone, 4,4'-bis (3-cyanatephenoxy) diphenylsulfone, 4,4'-bis [4- (4-cyanatephenylisopropyl) phenoxy] diphenylsulfone, 4,4'-bis [(4-cyanatephenylsulfone) phenoxy] diphenylsulfone, 4 , 4'-bis [4- (4-cyanate) diphenoxy] diphenylsulfone, 4,4'-dicyanate diphenylmethane, 4,4'-bis (p-cyanatephenyl) diphenylmethane, 2,2, bis (p-cyanatephenyl) propane, 2 , 2bis (3,5-dimethyl-4-cyanatephenyl) propane, 2,2-bis (3,5-dichloro-4-cyanatephenyl) propane, 1,1-bis (p-cyanatephenyl) cyclohexane, bis (2-cyanate-1-naphthyl) methane, 1,2-bis (p-cyanatephenyl) -1,1,2,2-tetramethylethane, 4,4'-dicyanatebenzophenone, 4,4-bis (4-cyanatephenoxy) benzophenone, 1,4-bis (p-cyanatephenylisopropyl) benzene, 2,2 ', 5,5, -tetrazyanate diphenylsulfone and polycyanic acid esters of novolaks (products obtained by reacting phenol or alkyl- or halogen-substituted phenols with formaldehyde in acid solution) 5 OCN groups.

Aromatic polycyanates are known compounds and can be prepared by the method described in U.S. Patent 4,094,852 (Sundermann et al.).

According to the invention, the aromatic cyanates are polyaromatic cyanates corresponding to the formula IV, ⁽?&gt; t (NCO -) ---- E - q

<img file="FI89934C_D0004.tif" />

⁽?^}t —E ----- (- OCN)

O (IV) wherein B is a polycyclic aliphatic group having 7 to 20 carbon atoms, D is any substituent that does not contain an active hydrogen atom;

E is an aromatic radical;

q, r and s are independently at each occurrence

9 9 3 4

0, 1, 2 or 3, provided that the sum q + r + s is at least 2; t is independently an integer from 0 to 4 at each occurrence; and x is any number from 0 to 5.

Aromatic radical as used herein means any radical containing an aromatic group. Examples of aromatic radicals are radicals derived from benzene, naphthalene, phenanthracene, anthracene or biaryls, or radicals containing two or more aromatic groups joined together via alkylene bridges. Preferred aromatic radicals are those derived from benzene, naphthalene, biphenyl, binaphthyl and diphenylalkylene. A particularly preferred aromatic radical is a benzene radical.

Polycyclic aliphatic group as used herein means any aliphatic group containing at least two rings. Polycyclic aliphatic groups may contain one or more double or triple bonds. Preferred polycyclic aliphatic groups are those corresponding to formulas V-XVI

<img file="FI89934C_D0005.tif" />

<img file="FI89934C_D0006.tif" />

<img file="FI89934C_D0007.tif" />

XII,

39934

<img file="FI89934C_D0008.tif" />

<td>in which formulas</td><td> 0</td><td> 0</td>

<td></td><td>II</td><td>II</td>

<td>Y is -CH₂-, -S-,</td><td>-S-</td><td>or -S- and II 0</td>

<td>D¹ is C 1-6 alkyl</td><td> •</td><td></td>

B is particularly preferably a group corresponding to formula V, VI, VII, VIII, IX, X, XI or XVI, with groups corresponding to formulas V, VI, VII, VIII and XVI being even more preferred and groups corresponding to formula V being most preferred.

D is any substituent attachable to an organic hydrocarbon radical, except that it must not contain an active hydrogen atom. Substituents within the scope of this invention are known to those skilled in the art. An active hydrogen atom as used herein means a hydrogen atom attached to an oxygen, sulfur or nitrogen atom. Examples of the substituents referred to in D are alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl, alkoxyl, nitro, carboxylate, sulfone, sulfide and carbonate groups and halogens. Preferred substituents are C₁_₁₀-alkyl, C 1-4 alkenyl and nitro and halogens, with C 1-3 alkyl and C 1-4 alkynyl and bromine and chlorine being most preferred.

Preferably each of the symbols q, r and s is independently 1 or 2, most preferably 1. Preferably each t is Independently 0, 1 or 2, even more preferably 0 or 1 and most preferably O. x is preferably between 0 and 2, said values, and more preferably between 0 and 1, inclusive.

The polyaromatic cyanates of this invention usually exist as a mixture of several isomers.

In addition, these polyaromatic cyanates are usually present as a mixture of compounds in which x ranges from 0 to 5. For each particular mixture, the numerical value assigned to x is usually an average number.

In a preferred embodiment, the polyaromatic cyanates correspond to the formula

<img file="FI89934C_D0009.tif" />

OCN where x is any real number from 0 to 5.

Polyaromatic cyanate esters are generally prepared by reacting a suitable polyaromatic phenol with cyanogen chloride in the presence of a tertiary amine. It is preferred to prepare the cyanogen chloride in situ by contacting a solution containing chlorine in a chlorinated hydrocarbon with an aqueous solution of an alkali metal cyanide. The reaction mixture is divided into an organic layer consisting of a chlorinated hydrocarbon containing cyanogen chloride and an aqueous layer containing an alkali metal chloride salt. In general, the alkali metal cyanide and chlorine are reacted in a molar ratio of 1.0: 1.0 to 1.0: 1.15, preferably in a molar ratio of 1.0: 1.0 to 1.0: 1.05, and most preferably in a molar ratio of 1.0: 1.0. An excess of either may lead to adverse consequences, i. excess chloro may react later with phenol and excess alkali metal cyanide may lead to a decrease in product purity. This reaction is carried out at a temperature of 0 ° C or lower, preferably below -15 ° C. Above 0 ° C the cyanogen chloride trimerizes. Preferred solvents for chlorine are aliphatic chlorinated hydrocarbons such as methylene chloride, chloroform and trichloroethane. The preferred alkali metal cyanide is sodium cyanide.

The aqueous layer and the organic layer are then separated. Separation of the organic layer from the aqueous layer is advantageous because the presence of the aqueous layer at a later stage of the process lowers the purity of the polyaromatic cyanates finally obtained.

The organic layer containing the cyanogen chloride is then reacted with a polycyclic hydroxy-substituted polyaromatic bridging compound dissolved in a suitable solvent in the presence of a tertiary amine.

The polycyclic hydroxy-substituted polyaromatic bridging compounds useful in this process correspond to the formula

<img file="FI89934C_D0010.tif" />

wherein E, B, D, q, r, s, t and x are as defined above.

In a preferred embodiment, the polycyclic hydroxy-substituted polyaromatic bridging compounds correspond to the formula

39934

<img file="FI89934C_D0011.tif" />

where x is a number as defined above. The polycyclic hydroxy-substituted polyaromatic bridging compounds used usually exist as a mixture of isomers. In addition, these polycyclic hydroxy-substituted polyaromatic bridging compounds usually exist as a mixture of compounds in which x ranges from 0 to 5. Usually, the numerical value assigned to x is an average number. Secondary or tertiary alcohols or chlorinated hydrocarbons are used to dissolve polycyclic hydroxy-substituted polyaromatic bridging compounds. Preferred solvents are secondary alcohols and aliphatic chlorinated hydrocarbons, with isopropyl alcohol and methylene chloride being most preferred.

This reaction is preferably carried out at a temperature of 0 ° C or lower, more preferably at a temperature of -15 ° C or lower.

Complete conversion of hydroxyl groups attached to aromatic groups to cyanate groups requires at least 1 mole of cyanogen chloride for each hydroxyl equivalent. To ensure complete conversion, it is preferred to use a 10 mol% excess of cyanogen chloride relative to the hydroxyl equivalent.

The tertiary amine acts as a recipient of the hydrogen chloride, and the hydrochloride salt of the tertiary amine is thus a by-product of the process. In general, at least 1 mole of tertiary amine is used for each hydroxyl equivalent. Hydroxyl equivalent herein means the average molecular weight of a polycyclic hydroxy-substituted polyaromatic bridging compound divided by the average number of hydroxyl groups contained in one molecule.

Polyaromatic cyanates can be isolated from the reaction solution as follows. The reaction mixture is first treated with a dilute aqueous solution of a base, for example bicarbonate, to remove excess cyanogen chloride. The reaction mixture is then treated with water to remove the hydrochloride salt of the tertiary amine. The reaction solution is then treated with a dilute aqueous acid solution to neutralize any base contained in the solution. A 1 to 20% by weight solution of hydrochloric, phosphoric or sulfuric acid, preferably 5 to 10% by weight, may be used. The reaction solution is then washed with water to remove any impurities in the solution. To remove water, the reaction solution is dried with a desiccant, and the solvent is removed.

The isolated polyaromatic cyanate has a surprisingly high degree of purity and can be used directly for the preparation of polytriazines.

Polycyclic hydroxy-substituted polyaromatic bridging compounds useful in the present invention can be prepared by reacting an aromatic compound containing at least one hydroxy-substituted aromatic group and at least one alkylatable position in the aromatic ring with an unsaturated polycyclic aliphatic compound under such a condition. that a polycyclic hydroxy-substituted polyaromatic bridging compound useful in this invention is formed.

Suitable substituted aromatic hydroxy compounds for use herein include all compounds containing one or two aromatic rings, at least one phenol hydroxyl group, and at least one alkylatable ring on the ring.

II

39934 a position ortho or para to the hydroxyl group.

Hydroxy-substituted aromatic compounds 5 which are particularly suitable for use herein include, for example, phenol, chlorophenol, bromophenol, methylphenol, hydroquinone, catechol, resorcinol, quaiacol, pyrogallol, phloroglucinol, octophenol, isopropylphenol, ethylphenol, propylphenol, t-phenylphenol, propylphenol, p-phenylphenyl , o-phenylphenol, m-phenylphenol, bisphenol A, dihydroxydiphenylsulfone and mixtures thereof.

The hydroxy-substituted polyaromatic compound can be reacted with an unsaturated polycyclic aliphatic compound in a solvent. Preferred solvents are chlorinated hydrocarbons, aliphatic and aromatic hydrocarbons and nitro-substituted hydrocarbons. In general, the hydroxy-substituted polyaromatic compound is reacted with an unsaturated polycyclic aliphatic compound in a molar ratio of 20.0: 1.0 to 1.0: 1.0, preferably in a molar ratio of 10.0: 1.0 to 1.5: 1.0.

This reaction is preferably carried out in the presence of a catalyst.

Acid catalysts useful in this reaction include, for example, Lewis acids, alkyl, aryl and aralkyl sulfonic acids, diphenyl oxide and alkylated diphenyloxide, disulfonic acids, sulfuric acid and mixtures thereof. Preferred catalysts are Lewis acids such as BF₃gas and organic boron trifluoride complexes, such as those formed with boron trifluoride with phenol, cresol, ethanol and acetic acid. Lewis acids include, for example, aluminum chloride, zinc chloride and stannous chloride. Other catalysts include, for example, activated clays, silica and silica-alumina complexes.

In the preparation of compounds containing on average more than one phenol hydroxyl group and

39934 more than one aromatic ring per molecule, the reaction between phenolic hydroxyl-containing compounds and unsaturated hydrocarbons can be carried out at a temperature of 33 to 270 ° C, preferably 33 to 210 ° C.

The products prepared by the process presented here are polytriazines, which in their simplest form can be described by the formula

<img file="FI89934C_D0012.tif" />

through. When a polyaromatic cyanate has one cyanate group, the product is a trimer formed from aromatic cyanates. When there are two or more cyanate groups, a crosslinked polymer is formed in which the basic unit is a triazine, for example a triazine as described above.

The polymers prepared in accordance with this invention may be as well homopolymers as copolymers of two or more aromatic polycyanates. It is possible to use one or more monocyanates, together with one or more polycyanates, to produce polytriazines with modified properties. Such modified properties may include solubility, glass transition temperature, moisture resistance, and impact resistance.

This method can be used to prepare fully cured polytriazines that do not contain substantially cyanate functional groups and partially cured prepolymers. Such prepolymers are cyanate-containing, liquid

39934 waxy or solid polytriazines soluble in organic solvents. These prepolymers withstand storage very well. These prepolymers can be subsequently converted to high molecular weight polytriazines by exposing them to conditions leading to polymerization. Prepolymers are prepared to facilitate processing of the resin prior to final use. In addition, these prepolymers are useful in coating substrates such as metallic and ceramic materials (both porous and other) as well as impregnating varnishes and laminate resins.

In the preparation of polytriazines, the aromatic polycyanates are reacted in the presence of a catalytic amount of the catalyst already indicated at a temperature of 20 to 200 ° C, optionally in the presence of a solvent. The preferred temperature range is 80 to 180 ° C.

Prepolymers are prepared by the same method with the exception that either a lower temperature or a lower amount of catalyst is used so that the aromatic polycyanates do not polymerize completely.

The rate of polymerization depends on the temperature and the amount of catalyst. As either, or both, the rate of polymerization increases. At higher temperatures, a smaller amount of catalyst is required to achieve the desired degree of polymerization than at lower temperatures.

The solvent may be any compound in which the aromatic polycyanates are soluble and which does not interfere with the reaction. Suitable solvents include aromatic hydrocarbons, alcohols and ketones.

The polyfunctional aromatic polycyanates can be combined with powdered or fibrous fillers or reinforcing agents either before or after the heat treatment of the aromatic polycyanates and in principle by any method. For example, it is possible to impregnate powdered or fibrous fillers or waxes

39934 twisting agents, such as quartz sand or glass cloths, with aromatic cyanates which may be used as solutions. Examples of solvents which can be used for this purpose and which generally have to be removed later are inert solvents such as methylene chloride, acetone, methyl ethyl ketone, xylene, ethyl acetate, benzene, toluene, tetrahydrofuran, chlorobenzene, dibutyl ether, dimethylformamide and tetramethylamide.

Suitable fillers or reinforcing agents are generally in some powder form and / or fibrous products, for example of the type commonly used in the manufacture of castings based on unsaturated polyester resins or epoxy resins. Examples of such products are, in particular, granular fillers such as quartz powder, ground clay stone, asbestos powder, ground corundum, chalk, iron powder, aluminum powder, sand, gravel and the like, as well as inorganic and organic fibers, especially glass fibers, in the form of fibers, filaments, pre - spun yarns, yarns, nonwovens or nonwovens. Aminosilane-based finishes have proven to be particularly effective in this context. It is also possible to use similar textile structures formed by organic, preferably synthetic, fibers (polyamides, polyesters) or based on quartz, carbon, metals, etc., as well as single crystals (fibrous crystals).

The end products combined with fillers or reinforcements can be used in particular in the manufacture of containers and pipes for their coating, in electrical engineering, in the manufacture of molds, in the manufacture of tools, in the manufacture of high-stress parts and in aerospace construction in light ships.

The following examples are presented to illustrate the invention in more detail and are not intended to limit the scope of the invention or the claims.

Method

Aromatic polycyanate samples (2-4 g) were poured into aluminum weighing bowls, and the weight of each sample was accurately determined. Methyl ethyl ketone (5-10 ml) was added to dissolve the aromatic polycyanate. A weighed amount of catalyst was added to each plate and the excess solvent was allowed to evaporate into air.

Samples of approximately 1 g of the mixtures described above were removed from the plates and placed on a gel plate set at 177 ° C. The gel time of each mixture was then determined. The actual gel time was defined as the time required for the aromatic polycyanate to polymerize to the point where it could no longer be remelted on the gel plate. The shorter the gel time, the higher the catalytic activity.

Example 1

A dicyclopentadiene bisphenol cyanate compound having the structure

<img file="FI89934C_D0013.tif" />

gel times using different catalysts. The results are summarized in Table I.

Table I

<td>Catalyst</td><td>Catalyst concentration (pmm)</td><td>Catalyst concentration (wt%)</td><td>Gel time (min.)</td>

<td>Nothing</td><td> -</td><td> -</td><td> 60,0</td>

<td>Kobolttioktaatti</td><td> 800</td><td> 0,08</td><td> 0,5</td>

<td></td><td> 400</td><td> 0,04</td><td> 2,75</td>

<td></td><td> 200</td><td> 0,02</td><td> 8,25</td>

<td></td><td> 120</td><td> 0,012</td><td> 21,0</td>

<td>cobalt</td><td> 800</td><td> 0,08</td><td> 2,2</td>

<td></td><td> 400</td><td> 0,04</td><td> 6,7</td>

<td></td><td> 200</td><td> 0,02</td><td> 20,0</td>

<td>Sinkkioktaatti</td><td> 400</td><td> 0,04</td><td> 12,5</td>

<td>tin octoate</td><td> 800</td><td> 0,08</td><td> 40,0</td>

<td>Lyijyoktaatti</td><td> 800</td><td> 0,08</td><td> 5,5</td>

<td>Kobolttiasetyyli-</td><td> 800</td><td> 0,08</td><td> 13,25</td>

<td>acetate</td><td> 400</td><td> 0,04</td><td> 24,25</td>

<td></td><td> 200</td><td> 0,02</td><td> 45,0</td>

<td>Sinkkiasetyyli-</td><td> 800</td><td> 0,08</td><td> 5,5</td>

<td>acetate</td><td> 400</td><td> 0,04</td><td> 19,0</td>

<td>Nikkeliasetyyli-</td><td></td><td></td><td></td>

<td>acetate</td><td> 1,600</td><td> 1,06</td><td> 25,0</td>

<td>novolak</td><td> 70,000</td><td> 70,0</td><td> 4,5</td>

Example 2

Gelling times of an aromatic polycyanate compound having the structure of the formula were determined

<img file="FI89934C_D0014.tif" />

polymerization using various catalysts. The results are summarized in Table II.

Table II

<td></td><td>the catalyst</td><td>the catalyst</td><td>The gel time</td>

<td>Catalyst</td><td>(Ppm)</td><td>(Wt%)</td><td>(Min.)</td>

<td></td><td>El nothing</td><td> -</td><td> -</td><td> 120,0</td>

<td></td><td>Kobolttinafte-</td><td></td><td></td><td></td>

<td></td><td>top</td><td> 40</td><td> 0,004</td><td> 5,65</td>

<td></td><td>Kobolttiasetyyli-</td><td></td><td></td><td></td>

<td> 15</td><td>asebonaatti</td><td> 100</td><td> 0,010</td><td> 35,0</td>

<td></td><td>cobalt chloride</td><td> 540</td><td> 0,054</td><td> 16,1</td>

<td></td><td>Example 3</td><td colspan="2">(Comparative Example)</td><td></td>

<td> 20</td><td>determined</td><td colspan="2">gel times bisphenol A</td><td>A: sta</td>

dicyanate of the formula

<img file="FI89934C_D0015.tif" />

structure, for polymerization using various catalysts. The results are summarized in Table III.

Table III

<td></td><td>Catalyst</td><td>Catalyst-</td><td>gelling</td>

<td></td><td>content</td><td>content</td><td>of notice</td>

<td>Catalyst</td><td>(Ppm)</td><td>(Wt%)</td><td>(Min.)</td>

<td colspan="4">Cobalt-</td>

<td>octoate</td><td> 100</td><td> 0,01</td><td> 14,2</td>

<td>Kobolttinafte-</td><td></td><td></td><td></td>

<td>top</td><td> 100</td><td> 0,01</td><td> 12,5</td>

<td>Sinkkioktaatti</td><td> 100</td><td> 0,01</td><td> 29,8</td>

<td>Kobolttiasetyyli-</td><td></td><td></td><td></td>

<td>acetate</td><td> 100</td><td> 0,01</td><td> 46,8</td>

<td>cobalt chloride</td><td> 2,133</td><td> 2,0133</td><td> 2, 16</td>

<td>The above</td><td>examples</td><td>show</td><td>that cobalt</td>

octoate and cobalt naphthenate are better catalysts for this process than the catalysts reported in the above sources. In fact, the catalytic activity of cobalt octate and cobalt naphthenate is 3-10. times the activity of the catalysts described in the above sources.