HU191081B - Process for production of compositions consisting of izocyanurate-groups by means of cathalitic cyclotrimerization consisting of izocyanate aminosililgorups - Google Patents

Abstract

Monomeric or polymeric cpds. contg. isocyanurate gps. are prepd. by cyclotrimerisation of isocyanates in which the NCO gp. is not linked directly to a C atom forming part of an aromatic gp. Reaction is in presence of an aminosilyl catalyst of formula R(4-n)-Si-(NR'R")n, where R is a monovalent (un)satd. (cyclo)aliphatic, or aryl, aralkyl or alkalry hydrocarbon gp., opt. substd. by halogen or CN, or 2 R gps. may form a divalent hydrocarbon gp.; R' is R, SiR3, or -CO-N(R)-R", in which R"' is R or SiR3, or if R' is not an amide or SiR3 gp., it may form a divalent hydrocarbon gp. with R"; R" has the same meaning as R, or may be H if R' is not amide; and n=1 or 2; when n=2, R' is an R gp. Reaction is at moderate temp. and has no induction period. The catalyst is easily deactivated. Prods. obtd. from, e.g. hexamethylene diisocyanate, can be used in paints and varnishes.

Description

^{V 7} COMPOUNDS CONTAINING ISOCYANURATE GROUPS

FOR MANUFACTURING ISOCIANATES WITH AMINO-SILIL GROUP

BY CATALYTIC CYCLOTRIZERIZATION OF COMPOUNDS (57) EXTRACT

According to the present invention, a catalytic reaction is initiated using a compound comprising an amino-silyl group, namely monoamino silane, diaminosilane, silylurea or silazane.

This catalyst is suitable for the cyclotrimerization of aliphatic and cycloaliphatic isocyanates, and in particular allows for the preparation of polyisocyanate polyisocyanurate.

191,081

The present invention relates to a process for the preparation of compounds containing isocyanurate groups by catalytic cyclotrimerization of mono-isocyanates or polyisocyanates, with compounds containing amino-silyl groups, such as e.g. by initiating with an amino silane, silylcarboxide or silazane.

Numerous methods are known for the preparation of simple or polymeric compounds containing isocyanurate groups by catalytic cyclotrimerization of aliphatic, cycloaliphatic or aromatic isocyanates. The cyclotrimerization reaction may be complete or partial. Thus, monoisocyanurates can be obtained from monoisocyanates, while polyisocyanate polyisocyanurates by partial cyclotrimerization of polyisocyanates and polyisocyanurates without free isocyanate groups can be produced by total cyclotrimerization of polyisocyanates. Polyisocyanurates that do not contain free isocyanate groups are often used as polymeric substrates for cellular materials (polyisocyanurate foams).

In the preparation of isocyanurates or polyisocyanurates by complete trimerization of aliphatic, cycloaliphatic or aromatic monoisocyanates or polyisocyanates, the following chemical compounds may be used as catalysts: tertiary amines, phosphines, alcohols, alkali metal or alkaline earth metal such as e.g. oxides, hydroxides, carboxylates, or the like. These catalysts are, for example, the Journal of Cellular Plastics, January, 1965, pp. 85-90. and Macromolecular Chemistry (5/1), pp. 105-119 (1970). Some silicon and tin derivatives have also been described as catalysts for cyclotrimerization of phenyl isocyanates into isocyanurates. Thus, Itoh, Matsuzaki and Ishii presented the catalytic activity of bistrimethylsilyl sulfide [Journal Chemical Society (C), 2, 709-2, 712 (1968)], and the catalytic effect of N-silazane [Journal of Chemical Society (C)]. 2, 005-2007 (1969)]. It should be noted that trimethylsilamines make it possible to cyclotrimerize the phenyl isocyanate very slowly to the flavouranturate (experiments at 150 ° C for 42 hours). It therefore appears that silamines are very low-activity cyclotrimerization catalysts for aromatic isocyanates. The above-mentioned authors also describe that disilazanes (hexamethyldisilazane, heptamethyldisilazane and hexamethyl-N-ethyl-disilazane) do not catalyze the cyclotrimerization of phenyl isocyanate to triphenyl isocyanurate: on the contrary, these silazanes have proved to be reagents that are phenyl- with isocyanate gave imino-triphenylhexahydro-triazinone dione (e.g., 4 / methylimino / 1, 3,5-triphenylhexahydro-1,3,5-triazine-2,6-dione and 1.3, 5-triphen-1,2,4,6-tris / phenylimyl / lysalalid-1,3,5-triathine was formed with heptamethyldisilazane).

Polyisocyanate polyisocyanurates, which form the basis of varnishes and paints, can generally be prepared by cyclopolymerizing simple NCO groups of simple aliphatic or aromatic polyisocyanates using various catalysts such as tertiary amines (U.S. Patent No. 951,168), alkali metal or alkaline earth metal. derivatives, e.g. hydroxides, carbonates or alcoholates (French patent no. 1 190 065), quaternary ammonium hydroxides (French Patent Nos. 1 204 697 and 1 566 256 and European Patent Applications Nos 0/03 765 and 10 589), phosphines 2 (French Patent Nos. 1 510 342 and 2 023 423 and U.S. Patent No. 1,934,763), catalysts containing ethylene group (French Patent Nos. 1 401 513 and 2 230 642) and finally Mannichbases (French Patent Nos. 2 290 459 and 2 332 274). If necessary, these various catalysts are combinators with carbamic acid ester (tertiary amine + carbamate: French Patent No. 1,172,576, alkali metal or alkaline earth metal + carbamate. French Patent No. 1,304,301 or Mannich base + carbamate. 2) French Patent No. 290459).

Catalysts for the cleavage of the nc cloning site of the NCO groups should normally be deactivated when the desired ratio of free isocyanate groups is reached. This deactivation can be accomplished by the addition of an acidic compound (non-oxygenating acid, acid chloride or the like), an alkylating agent (methyl iodide or the like) or an acrylic scintillator. Finally, deactivation can be carried out by suitable heat treatment.

Various catalyst systems are therefore known to allow the trimerization of aliphatic or cycloaliphatic isocyanates to be isocyanurate compounds (simple isocyanurates or polyisocyanurates), but all of these catalysts have certain disadvantages. Catalysis with alkaline earth metal alkaline earth metal derivatives always takes place in an unpredictable manner, with some delay in time, and then suddenly, so it is generally difficult to control the excess activity of the catalysts. In the case of less reactive catalyst systems, no catalytic delay is observed, but catalysis is relatively less effective. Cyclotrimerization should be carried out at high temperatures, causing a significant amount of dimer formation. In addition, heating is usually required during the deactivation period, and this also favors dimer formation.

The problem was, therefore, to find a catalyst system that allows cyclotrimerization of aliphatic or cycloaliphatic isocyanates into compounds containing isocyanurate groups, where the catalytic reaction takes place without an induction period in a uniform manner at relatively low temperatures. It was also important for the catalyst to be easily deactivated.

We have developed a process for the preparation of monomer or polymer compounds containing isocyanurate groups by catalytic cyclotrimerization of isocyanates in which the isocyanate groups are directly attached to the carbon atom of the aromatic group. Cyclotrimerization is accomplished by treating the isocyanate with a compound that initiates the catalytic reaction. The catalytic reaction initiator used in the process is a compound having an amino-silyl group of the formula:

R ₍ 4_n ₎ Si (NR'R) _n (I)

N is 1 or 2,

R is C 1 -C 4 alkyl;

R 1 is C 1-9 alkyl, C 3-7 cycloalkyl, -Si R _3, or -CO- NRR ',

191 081 wherein R '' is hydrogen or C 1-5 alkyl, or

R and R 'together form a C 3-6 methylene chain,

R is hydrogen or C 1-5 alkyl;

R 'and R together form a C 3-6 methylene chain.

Cyclotrimerization initiating isocyanurate is very suitable for cyclotrimerization of aliphatic or cycloaliphatic isocyanates. This compound may be aminosilane, diaminosilane, silylurea or silazane, and its catalytic effect is immediate, even and not too high. These results are surprising. Knowing the low reactivity of aliphatic isocyanates [cf. eg. H. SAUNDERS and K.C. FR1SCH Polyurethanes, Chemistry and Technology, Part I, Chemistry, p. 64, Interscience Publieshers (1962)] were expected to obtain very low reactivity because of low reactivity in aromatic isocyanates. The opposite of what was expected was observed.

It has also been found that when using silazane as a catalyst, isocyanurates are obtained in the aliphatic or cycloaliphatic isocyanate line. This result is completely unexpected, as Itoh et al. Have reported that iminohexahydro-triazines have been added to the aromatic isocyanate line.

More particularly, the present invention relates to the preparation of compounds containing isocyanurate groups by catalytic action of compounds containing amino-silyl groups. Amino-silyl-containing compounds may be represented by formula (I), wherein the following may be used to illustrate each group:

Preferably R is methyl, ethyl, butyl, isobutyl, tert-butyl.

R is preferably C 1 -C 9 alkyl or C 3-7 cycloalkyl, or R 3, wherein R is preferably the same as listed above, and - CO (NR) -R 'wherein R' is is hydrogen or C 1-5 alkyl, ^or 'Un

R and R together may form a propylene butylene, pentylene or hexylene group.

Preferably R is hydrogen, methyl, ethyl, butyl, octyl, cyclohexyl, or

R 'and R together form a C 3-6 methylene chain.

As mentioned, the catalyst may be amino silane, diaminosilane, monosilylurea, disilylurea or silazane. Given the various meanings given above for the groups R, R ', R and R', it is easy to determine the compounds containing the amino-silyl groups that may be used. It should be noted that silylurea produced by the reaction of N-silyl isocyanates with a secondary amine is not applicable. These silyl ureas are not suitable in the process of the invention because the silyl isocyanate can only be released from them by heating.

More particularly, the present invention relates to a process for the preparation of monomeric or polymeric compounds containing isocyanurate groups by catalytic cyclotrimerization of isocyanates in which the isocyanate group is not directly attached to the carbon atom of the aromatic group and in which process the following compounds are used: monoaminosilane (n = 1 , R 'is R, and R and R' are as defined above, or R and

R ^h together form an alkylene chain);

diaminosilane (n is 2, R 'is R, and R and R' are R ')

R ¹ 'is as defined above, or R' and R together form an alkylene chain);

silylurea (n = 1, R 'is a carbonamide of formula -CO-NR-R', wherein R 'is R or SiR ₃ , wherein R and R are as defined above, or R' and R (R 'are at this time R) together form an alkylene chain) or silazane (n is I, R 'is S1R3).

Amino-silanes or diaminosilanes include methylamino-trimethylsilane, dimethylamino-trimethylsilane, diethylaminotrimethylsilane, dibutylamirrimethylsilane, diethylaminomethyldimethyl vinyl, and the like. silane, diethylamino-dimethylphenylsilane, bis (dimethylamino) dimethyl, ylane, bis (di-ethylamino) dimethylsilane, bis (dibutylamino) dimethylsilane and bis (dimethyl) amino) methyl fenilszilrn.

Examples of silylureas include N-methyl-N- (trimethylsilyl) -N'-methyl-N'-butylurea, N- (rimethylsilyl) -N-methyl-N ', N' -dimethylurea, N- (trimethylsilyl) -N-ethyl-N ', N'-dimethylurea and N (trimethylsilyl-N-butyl-N'-trimethylsilylcarbate).

The diazyls may be symmetrical or asymmetric in the process of the invention, preferably using symmetric disilazane, wherein the two SIR3 groups are the same.

Among the disilanes, hexamethyldisilazane, hcptamyldisilazane, 1,3-dictyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyl disilazane, hexaethyl may be used. -disilazane and 1,3-diphenyl-1,3,3,3-thiethyl disilazane.

Particularly preferred disilazanes are hexamethyldisilazane and heptamethyldisilazane.

The method according to the invention makes it possible to cyclotrimerize mono-isocyanates or polyisocyanates and polyisocyanate adducts (which are the polycondensation product of excess polyisocyanate and polyfunctional compounds) of a single aliphatic or cycloaliphatic type. The cyclotrimerization reaction may be partial or complete; it allows monoizocyanates, compounds containing a single isocyanurate group, such as e.g. alkyl or cycloalkyl isocyanurates and polyisocyanate polyisocyanurates from simple polyisocyanates or polyisocyanate adducts and polyisocyanurates having high molecular weight and no longer containing more free isocyanate groups.

Any simple aliphatic or cycloaliphatic type isocyanate or polyisocyanate or any isocyanate adduct or prepolymer is suitable provided that, as mentioned, the isocyanate group is not directly attached to the aromatic group.

Λ the following mono-cyanocyanates may be used: methitocyanate, butylzocyanate, n-hexyl isocyanate and cyclohexylisocyanate.

The diisocyanates include: tetramethylene diisocyanate, pentamethylene diisocyanate, hexa3

191 081 methylene diisocyanate, 1,2-diisocyanato-cyclohexane, 1,4-diisocyanato-cyclohexane, 1,2-bis (isocyanatomethyl) -cyclobutane, bis (4-isocyanato-cyclohexyl) -methane and 3,3,5- triinetil-5- (izocinnáto-inctil) -l-cyclohexane-Í7.ocianáto.

Of these, hexamethylene diisocyanate is particularly suitable.

Finally, among the polyisocyanate adducts or prepolymers that can be used, modified polyisocyanates are mentioned which are excess aliphatic or cycloaliphatic polyisocyanates and at least two isocyanate-reactive groups, e.g. can be obtained by reaction of diamine, diacid or the like. Modified polyisocyanates, which may be mixed with simple polyisocyanates, may also contain urea, biuret, ester, siloxane or the like.

Although the order of administration of the reagents is not essential, the process according to the invention is preferably carried out by adding a small portion of the catalyst to the isocyanate, which is from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight of the isocyanate used. further small amounts of catalyst may be added during the reaction.

The reaction is carried out by heating to a simple temperature of from 50 to 180 ° C, preferably from 80 to 130 ° C.

When the isocyanurate ratio reaches the desired value, the catalyst can be decomposed, for example, by the addition of an acid (a strong acid such as hydrochloric acid, acid chloride or the like). This type of process, which allows the preparation of polyisocyanate polyisocyanurate, is also a subject of the invention.

Optionally, the monomeric polyisocyanate can then be removed by any known method to obtain a polyisocyanate polyisocyanurate containing a low proportion of reduced monomeric isocyanate and a very small amount of dinine. Compounds of this type, such as e.g. compounds derived from hexamethylene diisocyanate, known compounds, which are very valuable lacquer and paint base materials.

If necessary, the cyclotrimerization reaction may also be carried out in a solvent. Suitable solvents include low polarity solvents such as e.g. aliphatic or aromatic hydrocarbons, esters or ethers. The process can then be carried out by dissolving the catalyst in the solvent and adding the isocyanate to this solution. Of course, it is also possible to add the catalyst solution to the isocyanate. However, the process is preferably carried out without a solvent.

The following examples illustrate the process of the invention.

Example 1

39.6 g (0.4 mole) of butylocyanate was added to a round-bottomed flask, followed by the addition of 4.7 g (0.04 mole) of N.Ndinicyl (triinctylsilyl) -ninite. The mixture was heated to 100-105 ° C in an oil bath and then heated to 100-110 ° C after 14 hours. 90% of NCO groups react.

Ációs distillation product 20.8 g tribulyl isocyanurate, boiling at 142 ° C / 1.3 mbar.

C, 60.4 (60.6 theoretical),

H, 99.14 (theoretical 9.1)

N, 14.5 (theoretical 14.15), ηθ = 1.474,

IR Spectrum Absorption at 1.460 and 1.690 cm '.

Example 2

Example 1 was used except that N, N-diethyl-trimethylsilylamine (5.8 g, 0.04 mol) was used instead of N, N-dimethyl-trimethylsilylamine. .

After reacting for 100 hours at 100-110 ° C, 88% of the NCO groups present are cloned. 20.8 g of tributyl isocyanate are isolated by distillation.

C, 60.82 (60.6, theoretical),

H, 9.17 (theoretical 9.1)

N, 14.03 (theory 14.15).

Example 3

537.6 g (3.2 moles) of hexamethylene diisocyanate were added to a round-bottomed flask and heated to 100 ° C. 7.5 g (0.063 mole of N, N-dimethyl (trimethylsilyl) amine) are added and 15% of the NCO groups present are reacted in 100 C at 1.5 ° C. The reaction is quenched by the addition of 7 ml of benzoyl chloride. most of it is distilled off at 130 ° C at 20 mbar.

184 products are retained and distilled in a film evaporator. 103 g of cyclotrim (0.546 NCO / 100 g) was obtained (theoretical 0.55 hexamethylene diisocyanate), having a Viscosity of 1.6 Pa at 25 ° C.

Example 4

29.7 g (0.3 mol) of butylisocyanate and 0.88 g (0.006 mol) of bis (dimethylamino) dimethylsilane are added to a round-bottomed flask. The mixture was heated to 105 ° C in an oil bath. 88% of the NCO groups present are reacted at 105 ° C for 14 hours. After distillation under a pressure of 0.67 mbar, 17.9 g of tributyl isocyanurate were obtained, distilling at 132-134 ° C.

Example 5

Example 4 shows the difference except that 29.7 g (0.3 mol) of butyl isocyanate and 0.87 g (trimethylsilyl) butylamine are charged. The reaction mixture was heated to 105 ° C. At 23 ° C for 23 hours, 67% of NCO groups react.

At a pressure of 0.67 mbar, 15.7 g of tributyl isocyanurate are distilled between 132 and 135 ° C.

Example 6

29.7 g (0.3 mol) of butylocyanate was added to a round-bottomed flask and 1.45 g (0.03 mol) of hexamethyldisilazane was added at room temperature over 10 minutes. The reaction mixture was heated to 100 ⁰ C and 110 ° C for 2 hours.

After 191,081 hours of reaction, only 7% of the isocyanate groups remain unreacted.

The reaction mixture was distilled off and 2.35 g of a volatile product was isolated. IR spectrum of the remaining 13.35 g tributyl isocyanurate: absorption at 1.465 and 1.690 cm ^-1 (urea, biuret or carbodiimide peaks not detectable). Microanalysis is the same as the theory.

found theoretical 60.76, 61.04 60.6 9.1 9.48 9.1 14.06 14,16 14.15 Example 7

EXAMPLE 6 EXCEPT THAN 2 MOL OF HEXAMETHYL DILILAZANE ABOUT 100 G OF BUTYLISOCIANATE. After completion of the reaction, only 10% of the isocyanate groups remain unreacted.

Tributyl isocyanurate (10.75 g) was obtained, which was refluxed at 125 ° C under a pressure of 0.27 mbar. M.p .: 9-10 ° C, ηθ = 1.4750.

The above shows that 1 mole of hexamethyldisilazane results in the reaction of 90 moles of butyl isocyanate.

Example 8

24.75 g (0.25 mol) of butyl isocyanate and 4.4 g (0.025 mol) of heptamethyldisilazane are added to a 100 mL magnetic stirrer and a three necked round bottom flask equipped with reflux and nitrogen inlet and the mixture is heated in an oil bath for 100 min. -110 ° C. Half of NCO groups react in 3 hours. After 16 hours of reaction, only 8% of the NCO groups remain unreacted, i.e. 1 mole of heptamethyldisilazane consumes 9.2 moles of butylisocyanate.

The resulting 22.2 g mixture was distilled off at 0.13 0.33 mbar to give tributylisocyanurate distilling 14.45 g at 112-132 ° C.

πθ = 1.4760, IR spectrum of the former.

Example 9

134.4 g (0.8 mol) of hexamethylene diisocyanate and 1.3 g (0.008 mol) of hexamethyldisilazane are added to a round-bottomed flask and the mixture is heated to 100 ° C for 7 hours. The ratio of NCO groups was 1.07 / 100 g.

The excess hexamethylene diisocyanate was distilled off and the residue was transferred to a fan evaporator equipped with stirrers. 19 g of product are obtained, containing 0.55 NCO groups per 100 g (theoretical tris (isocyanate hexamethylene) isocyanurate: 0.59).

The IR spectrum of the product shows the isodanurate trimer (1.645 and 1.690 cm ^-1 ) and the NCO groups (2.270 cm ^-1 ). Its viscosity at 25 ° C is 25 Pa · s, the tracer gas phase chromatogram shows that it consists essentially of trimers with a molecular weight of 504. The ratio of dimers is less than 5%. The free hexamethylene diisocyanate ratio is less than 0.1%.

The following reaction mixture was heated at 100 ° C for Example 10 hours:

isocyanate monomer: hexamethylene diisocyanate 100 g

catalyst: CH ₃ -NH-Si (CH ₃ ) ₃ l, 4g

The catalyst thus represents 1.4% by weight of the isocyanate. The reaction is stopped with 2 g of benzoic acid chloride, which deactivates the catalyst. The conversion rate of the isocyanate groups is 16%. After removal of the excess isocyanate monomer, the product obtained was tris (isocyanate hexamethyl n) -ocyanurate having a dlmcrl content of less than 5% and the content of the NCO group was 0.541 NCO / 100 g.

The following reaction mixture was heated to 100 ° C for Example 11:

- isocyanate monomer: hexamethylene diisocyanate 100 g catalyst: C ₈ H ₇ -NH-Si (CH ₃ ) ₃ 2.8 g

The catalyst thus represents 2.8% by weight of the isocyanate. The reaction is stopped by the addition of 2 g of benzoic acid chloride, which deactivates the catalyst. The conversion rate of the isocyanate groups is 14%. After removal of the excess isocyanate monomer, the product obtained was tris (isocyanate-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.560 NCO / 100 g.

Example 12

The reaction mixture was heated at 100 ° C for 2.5 hours.

Isocyanate monomer: hexamethylene diisocyanate 100 g catalyst: (trimethylsilyl) cyclohexylamine 2.5 g The catalyst thus represents 2.5% by weight of the isocyanate. The reaction is stopped by the addition of 2 g of benzoic acid chloride which deactivates the catalyst. The conversion rate of the isocyanate groups is 18%. After removal of the excess isocyanate monomer, the product was tris (isocyanato-6-hexyl) -1,3,5-flavorocyanurate having an NCO group content of 0.540 NCO / 100 g.

Example 13

The reaction mixture was heated at 100 ° C for 2.5 hours.

- isocyanate monomer: hexamethylene diisocyanate 100 g catalyst: (trimethylsilyl) dibutyl aniline 1.6 g

The catalyst thus represents 1.6% by weight of the isocyanate. The reaction is stopped by the addition of 0.6 g of hydrochloric acid gas which deactivates the catalyst. The conversion rate of the isocyanate groups is 20.5%. After removal of the excess isocyanate monomer, the product obtained was tris (isocyanato-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.529 NCO / 100g.

Example 14

The reaction mixture was heated at 110 ° C for 1.5 hours:

191,081

isocyanate monomer: hexamethylene diisocyanate 100 g

Catalyst: (trimethylsilyl) pentamethyleneamine 2.1 g The catalyst thus represents 2.1% by weight of the isocyanate. The reaction is stopped by the addition of 1.8 g of benzoic acid chloride which deactivates the catalyst. The conversion rate of the isocyanate groups is 19.5%. After removal of the excess isocyanate monomer, the product was obtained as lys (isoeyano-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.535 NCO / 100 g.

Example 15

The reaction mixture was heated at 90 ° C for 1.5 hours:

isocyanate monomer: hexamethylene diisocyanate 100 g

- catalyst: dimethyl bis (dibutylamino) silane 2.1 g The catalyst thus represents 2.1% by weight of the isocyanate. The reaction is stopped by the addition of 2.8 g of benzoic acid chloride which deactivates the catalyst. Λ the conversion rate of isocyanal powders is 21%. After removal of the excess isocyanate monomer, the product obtained was tris (isocyanato-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.524 NCO / 100 g.

Example 16

The reaction mixture was heated at 95 ° C for 1.1 h.

Isocyanate monomer: hexamethylene diisocyanate 100 g

catalyst: (CH ₂ ) ₅ N-Si (CH ₃ ) ₂ -N (CH ₂ ) ₅ 2.4 g

The catalyst thus constitutes 2.4% by weight of the isocyanate. The reaction is stopped by adding 1.6 g of acetic acid chloride, which deactivates the catalyst. The conversion rate of the isocyanate groups is 14%. Removal of the excess isocyanate monomer gave Tris (isocyanato-6-hexyl) -1,3,5-iso-azimate having an NCO content of 0.563 NCO / 100 g.

Example 17

The reaction mixture was heated at 105 ° C for 2.5 hours.

Isocyanate monomer: hexamethylene diisocyanate 100 g

- catalyst: (CH ₃ ) ₂ SiH-NH-HSi (CH ₃ ) ₂ lg

The catalyst thus represents 1% by weight of the isocyanate. The reaction is stopped by the addition of 0.9 g of propionic acid chloride which deactivates the catalyst. The conversion rate of the isocyanate groups is 12%. After removal of the excess isocyanate monomer, the product was tris (isocyanate-6-hexyl) -1,3,5-isocyanurate having a NCO content of 0.568 NCO / 100 g.

The following reaction mixture was heated at 105 ° C for 18 hours.

isocyanate monomer: hexamethylene diisocyanate 100 g

- catalyst. (C ₂ H _{s) 3} Si - NH-Si (C ₂ H _{5) 3} 3.8 g

The catalyst thus represents 3.8% by weight of the isocyanate. 6

The reaction is stopped by the addition of 2.1 g of benzoic acid chloride which deactivates the catalyst. The conversion rate of the isocyanate groups is 23%. Removal of the excess isocyanate monomer gave Tris (isocyanato-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.535 NCO / 100 g.

Example 19

The reaction mixture was heated at 110 ° C for 1.1 h.

Isocyanate monomer: hexamethylene diisocyanate 100 g

catalyst: (C ₂ H ₅ ) ₂ N-Si (C ₂ H _s ) ₃ l, 5g

The catalyst thus constitutes 1.5% by weight of the isocyanate. The reaction is stopped by the addition of 1.5 g of benzoic acid chloride which deactivates the catalyst. The conversion rate of isocyanate groups is 19%. After removal of the excess isocyanate monomer, the product obtained is tris (isocyanin-6-butyl) -1,3,5-isocyanirate having an NCO content of 0.535 NCO / 100 g.

The following reaction mixture was heated at 100 ° C for Example 20 hours:

- isocyanate monomer: butyl isocyanate 25 g - catalyst: (CH ₃ ) ₃ Si-N-CO-N-C ₄ H ₉ 4.5 g

I \ t

C ₄ H ₉ c ₄ h ₉

The catalyst thus represents 18% by weight of the isocyanate. The conversion rate of isocyanate groups is 94%. After removal of the excess isocyanate monomer, the product was obtained as tributyl-1,3,5-isocyanurate.

The following reaction mixture was heated at 105 ° C for Example 27 hours:

- isocyanate monomer: butyl isocyanate 25 g

catalyst: (CH ₃ ) ₃ Si-N-CO-NH-CH ₃ 2.5 g

I

CH ₃

The catalyst thus represents 10% of the isocyanate. The conversion rate of isocyanate groups is 94%. After removal of the excess isocyanate monomer, the product was obtained as tributyl-1,3,5-isocyanurate.

Example 22 was heated to 105-110 ° C for the following reaction:

- isocyanate monomer: butyl isocyanate 25 g - catalyst: (CH ₃ ) ₃ Si-N-CO-N (CH ₂ ) _S 3.5 g

I

Cll ₃

The catalyst thus represents 14% by weight of the isocyanate. The conversion rate of isocyanate groups is 91%. After removal of the excess isocyanate monomer, the product was obtained as tributyl-1,3,5-isocyanurate.

-6II

191,081

The following reaction mixture was heated at 105-110 ° C for an hour for example.

- isocyanate monomer: butyl isocyanate 25 g

- catalyst: (CH ₃ ) ₃ Si-N-CO-NH-C ₄ H ₉ 3.6 g

I c ₄ h ₉

The catalyst thus represents 14.4% by weight of the isocyanate. The conversion rate of isocyanate is 88%. After removal of the excess isocyanate monomer, the product was obtained as tribu tert-1,3,5-isocyanurate.

The following reaction mixture was heated at 110 ° C for 24 hours.

- isocyanate monomer: methyl isocyanate 28.5 g

catalyst: (CH ₃ ) ₂ N-Si (CH ₃ ) ₃ 2.6 g

Catalyst tylate represents 9.1% by weight of isocyanate. The conversion rate of isocyanate is 75%. The product obtained after removal of the isocyanate monomer was trimethyl-1,3,5-isocyanurate.

Example 25 was heated to 115 ° C for the following reaction:

Isocyanate monomer: octyl isocyanate 31 g

- catalyst: (C ₂ H _{s) 2} N-Si (CH3) ₃ 1.5 g

The catalyst has a total of 4.8% by weight of isocyanate. The conversion rate of isocyanate groups is 91%. After removal of the excess isocyanate monomer, the product was obtained as trioctyl-1,3,5-isocyanurate.

Example 26 was heated to 100 ° C for the following reaction:

Isocyanate monomer: tetramethylene diisocyanate 100 g

- catalyst: hexamethyldisilazane 1 g

The catalyst thus represents 1% by weight of the isocyanate. The reaction is stopped by the addition of 0.8 g of acetic acid chloride which deactivates the catalyst. The conversion rate of isocyanate groups is 19%. After removal of the excess isocyanate monomer, the product obtained is tris (isocyanato-4-butyl) -1,3,5-isocyanurate having an NCO content of 0.597 / 100 g.

The following reaction mixture was heated to 100 ° C for Example 27 hours:

Isocyanate monomer: bis (isocyanatomethyl) 1,2-cyclobutane 100 g

- catalyst: (CH ₃ ) ₃ Si-NH-Si (CH ₃ ) ₃ 2 g

The catalyst thus represents 2% by weight of the isocyanate. The reaction is stopped by adding 1.5 g of acetic acid chloride, which deactivates the catalyst. The conversion rate of the isocyanate group 1 is 16%. After removal of the excess isocyanate monomer, the product obtained is tris (isocyanomethyl-2-cyclobutyl) -1,3,5-isocyanurate having an NCO content of 0.540 / 100 g.

The following reaction mixture was heated at 130 ° C for Example 28 hours:

isocyanate monomer: trimethyl-3,5,5-isocyanatomethyl-5-isocyanato-1-cyclohexane 100 g catalyst. (CH ₃ ) ₃ Si-N (CH ₃ ) ₂ 1.4 g

The catalyst thus represents 1.4% by weight of the isocyanate. The reaction is stopped by the addition of 2 g of bczzoic acid chloride, which deactivates the catalyst. The conversion rate of the isocyanate groups is 14%. After removal of the excess isocyanite monomer, the product obtained was tris (trimethyl-3,5,5-isocyanomethylcyclohexyl) -1,3,5-isocyanurate having an NCO content of 0.410 NCO / 100 g.

The following reaction mixture was heated at 130 ° C for Example 29:

- isocyanate monomer; hexamethylene diisocyanate 100 g catalyst: hexamethyldisilazane 10 g

The catalyst thus represents 10% by weight of the isocyanate. Reaction A is stopped by adding 6 g of acetic acid chloride, which deactivates the catalyst. The conversion rate of isocyanate groups is over 90%. The product obtained is insoluble and fusible polyisocyanurate.

The following reaction mixture was heated at 100 ° C for 30 hours.

- isocyanate monomer: hexamethylene diisocyanate 100 g - catalyst: hexamethyldisilazane 3 g

The catalyst thus represents 3% by weight of the isocyanate. The reaction is stopped by the addition of 1 g of benzoic acid chloride, which deactivates the catalyst. The conversion rate of the isocyanate groups is 30%. After removal of the excess isocyanate monomer, the product was trisocyanate-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.490 NCO / 100 g.

Example 31

Heat the following reaction mixture for 1/4 hour at J50 ° C:

- isocyanate monomer: hexamethylene diisocyanate 200 g catalyst: hexamethyldisilazane 1 g

The catalyst thus constitutes 0.5% by weight of the isocyanate. The reaction is stopped by the addition of 1.5 g of methyl iodide, which deactivates the catalyst. The conversion rate of isocyanate groups is 6.1%. After removal of the excess isocyanate monomer, the product obtained is tris (isocyanato-hex-hexyl) -1,3,5-isocyanurate having an NCO content of 0.575 NCO / 100 g.

-713

191,081

Example 32 was heated to 80 ° C for the following reaction:

isocyanate monomer: hexamethylene diisocyanate 100 g

- catalyst: (CH ₃ ) ₃ Si-NH-Si (CH ₃ ) 3 1 g

The catalyst thus represents 1% by weight of the isocyanate. The reaction is stopped by the addition of 0.8 g of acetic acid chloride which deactivates the catalyst. The conversion rate of isocyanate groups is 5.2%. After removal of the excess isocyanate monomer, the product is tris-isocyanate-6-hexyl) -1,3,5-isocyanurate having an NCO content of 0.575 NCO / 100g.

Example 33

Heat the following reaction mixture at 100 ° C:

Isocyanate monomer: hexamethylene diisocyanate 100 g

catalyst: (CH ₃ ) ₃ Si-NH-Si (CH ₃ ) ₃ 2g

The reaction was continued for 6.5 hours, taking 3 hours, 4 hours, 40 minutes, and then after 6 hours 30 minutes. Upon sampling and removal of excess isocyanate monomer, polyisocyanate isocyanates having the following properties are obtained:

Sampling time Viscosity pas, At 25 ° C The ratio of the height of the peaks between the heptamer and the pentamer 3 hours 18 0.465 4 hours 40 minutes 28 .533 6 hours 30 minutes 56 .610

The pentamer is a polyisocyanate polyisocyanurate containing 2 molecules of cyclic isocyanurate prepared from 5 moles of bexamethylene diisocyanate.

The heptamer is a polyisocyanate polyisocyanurate containing 3 molecules of cyclic isocyanurate prepared from 7 mol of hexamethylene diisocyanate.

Claims (4)

PATIENT LETTERS are not directly attached to the aromatic carbon atom, ε cyclotrimerization is carried out in the presence of isocyanates and a catalytic reaction initiating compound, wherein 0.3 to 20% by weight of the amine of formula I is used as the initiator. a silyl-containing compound - where it is R ₍₄ _ _n> SilNR'R) _n (I) N is 1 or 2; R is C 1 -C 4 alkyl; R 'is a C 1-9 alkyl group, a C 3 -C 7 cycloalkyl group, a -SR ₃ or —CO — —NRR' group of needles wherein i: R is as defined above, · R 'is H or 1-5; atomic alkyl, or 2θR and R '' together form a C3-6 methylene chain, R is hydrogen or C 1-5 alkyl, or R 'and R together form a C 3-6 methylene chain 2g and cyclotrimerization is carried out at a temperature of 80 ° C to 150 ° C for 0.25-18 hours. 2. A process according to claim 1, wherein the isocyanate is hexamethylene diisocyanate, tetramethylenis diisocyanate, 1,2-bis (isocyanothiomethyl) -cyclobutate, 3,3,5-triinetyl-5- (isocyanate). -methyl) -1-isocyanato-cyclohexane or (C1-C10 alkyl) isocyanate. 3. The method of claim 1, wherein the initiator is one R ' R ₃ Si-N-C0-N ^x I ^R A compound of formula R wherein R, R and R 'are as defined in claim 1 is used. The method of claim 1, wherein the initiator is one of R ₃ Si -N-SiR ₃ 1. A process for the preparation of compounds containing isocyanurate groups by catalytic cyclotrimerization of isocyanates in which the isocyanate groups are present. The compound of formula R is used, R and R 'are as defined in claim 1. Without drawing Published by the National Inventory Office Λ publisher responsible: Zoltán Himer Head of Department Published by the Technical Publisher COPYLUX Printing and Reproductive Small Business