Method for preparing isocyanurate group-containing polyisocyanates

Abstract

The present invention relates to a method for preparing an isocyanurate group-containing polyisocyanate P by trimerizing A) at least one organic diisocyanate or polyisocyanate having isocyanate groups independently bonded to aliphatic groups, alicyclic groups and / or aromatic aliphatic groups, B) at least one trimerization catalyst selected from the group consisting of quaternary tetraalkylammonium hydroxide, quaternary trialkylarylammonium hydroxide and choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide, and C) at least one alcohol as a solvent.

Description

[Background technology]

[0001] The preparation of isocyanurate group-containing polyisocyanates by trimerizing monomeric diisocyanates and / or polyisocyanates has been known for many years.

[0002] Typically, trimerization catalysts, such as quaternary tetraalkylammonium hydroxides or trialkylarylammonium hydroxides like Triton B, and choline-type hydroxyalkyl-substituted quaternary ammonium hydroxides, such as choline acetate, are used.

[0003] In the prior art, known methods (e.g., Patent Document 1) are carried out by first supplying an alcoholic solution of the catalyst to the isocyanate component to be trimerized. As a result, an exothermic reaction is initiated, causing the temperature of the reaction mixture to rise. During further steps of the method, the exothermic reaction is controlled by adding an appropriate amount of catalyst solution. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] European Patent Application Publication No. 2700665

[0005] Surprisingly, it has now been discovered that the reaction behavior can be improved by first adding an alcoholic catalyst solution to initiate the reaction, and then subsequently adding only alcohol by metering without any further catalyst. This metering behavior allows for reduced catalyst consumption while maintaining the same reaction time, or, in semi-batch methods, faster reaction initiation and reduced reaction time while maintaining the same amount of catalyst, and in cascade methods, increased yield. In the former (first) case, less catalyst consumption means less termination agent is needed to stop the reaction, less catalyst is present in the product, and this also means improved product quality (less discoloration). Reduced reaction time means the method becomes more economically viable. In addition, since the amounts of catalyst and alcohol added can be controlled independently of each other, the reaction regime can be better adapted to the quality of the diisocyanate used (in relation to the acidic component).

[0006] The present invention A) At least one organic diisocyanate or polyisocyanate having isocyanate groups independently bonded to aliphatic groups, alicyclic groups and / or aromatic aliphatic groups, B) At least one trimerizing catalyst selected from the group consisting of quaternary tetraalkylammonium hydroxide, quaternary trialkylarylammonium hydroxide, and choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide, and C) At least one alcohol as a solvent, A method for preparing an isocyanurate group-containing polyisocyanate P by trimerization in the presence of I) The step of initially adding component A to the reactor, II) The total amount of catalyst component B, and the first portion of component C (C T1 ) is supplied, and the degree of trimerization T is in the range of 0.5% to 25%, preferably 0.5% to 20%. g This is a step of trimerizing component A until the desired result is obtained, where, Tg =(NCO0 - NCO t ) / NCO0, where in the formula NCO0 corresponds to the amount of free NCO groups originally present in the initially charged Component A, NCO t corresponds to the amount of free NCO groups in the reaction solution at time t, and these are each determined by NCO titration according to M105 - ISO 11909, the steps III) supplying a second partial amount (C T2 ) of Component C and continuing the trimerization of Component A, provide a method comprising or consisting only of these.

[0007] The above method is hereinafter referred to as Embodiment 1.

[0008] It is also possible to first add the alcoholic catalyst solution at a high concentration and then meteringly add the catalyst solution only at a low concentration after the start of the reaction.

[0009] Therefore, the present invention A’) at least one organic diisocyanate or polyisocyanate having isocyanate groups bonded to an aliphatic group, an alicyclic group, and / or an araliphatic group independently of each other, B’) at least one trimerization catalyst selected from the group consisting of quaternary tetraalkylammonium hydroxides, quaternary trialkylarylammonium hydroxides, and choline - type hydroxyalkyl - substituted quaternary ammonium hydroxides, and C’) at least one alcohol as a solvent, a method for preparing an isocyanurate - group - containing polyisocyanate P’ by trimerization in the presence of I’) a step of initially charging Component A’ into a reactor, II’) a first partial amount (B’ T1 ) of the catalyst component B’ and a first partial amount (C’ T1 ) of Component C’ are supplied, where the catalyst component B’ T1Based on the first partial amount (C' T1 ) of component C' used in step II', it is used in an amount of 0.6% by weight or more to 8% by weight or less, preferably 0.8% by weight or more to 5% by weight or less, particularly preferably 0.8% by weight or more to 2% by weight or less, a step of trimerizing component A' until a degree of trimerization T g ' in the range of 0.5% or more to 25% or less, preferably 0.5% or more to 20% or less is obtained, where T g ' = (NCO0 - NCO t ) / NCO0, In the formula, NCO0 corresponds to the amount of free NCO groups originally present in the initially charged component A', NCO t corresponds to the amount of free NCO groups in the reaction solution at time t, These are each determined by NCO titration according to M105-ISO 11909, the steps, III') supply the second partial amount (B' T2 ) of catalyst component B' and the second partial amount (C' T2 ) of component C', where the catalyst component B' T2 is used in an amount of more than 0% by weight to 0.5% by weight or less, preferably more than 0% by weight to 0.1% by weight or less based on the second partial amount (C' T2 ) of component C' used in step III', ​​​​​​​​​​​​​​To carry out the method according to the present invention, all organic diisocyanates or polyisocyanates with an average molecular weight of 154 g / mol to 600 g / mol, each independently having isocyanate groups bonded to aliphatic groups, alicyclic groups, and / or aromatic aliphatic groups, can be used in pure form or in any desired mixture. Examples include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2-methylpentane 1,5-diisocyanate (MPDI), 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane (1,3-H6-XDI and 1,4-H6-XDI), 1,3-bis(isocyanatomethyl)benzene and 1,4-bis(isocyanatomethyl)benzene (1,3-XDI and 1,4-XDI ), 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI); isophorone diisocyanate (IPDI), bis(isocyanatomethyl)norbornane (NBDI), 4-isocyanatomethyloctane 1,8-diisocyanate (triisocyanatononane, TIN), 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(2-isocyanatopropyl-2)benzene, and bis(4(2)-isocyanatocyclohexyl)methane (H 12 Examples include MDI, Desmodur® W (a product of Covestro AG). Here, it is not important which method is used to prepare the above (poly)isocyanates, i.e., whether or not phosgene is used.

[0013] Preferably, at least one organic diisocyanate or polyisocyanate is selected from the group consisting of PDI, HDI, MPDI, 1,3-H6XDI and 1,4-H6XDI, 1,3-XDI and 1,4-XDI, and NBDI. HDI, or a mixture of HDI and PDI, MPDI, 1,3-H6XDI and 1,4-H6XDI, 1,3-XDI and 1,4-XDI and / or NBDI is particularly preferred.

[0014] In step I of Embodiment 1, component A can be degassed under reduced pressure, optionally with heat supply. It is preferable to degass component A in step I. The same applies to component A' in step I' of Embodiment 2.

[0015] In the method according to the present invention, catalyst component B or catalyst component B' is preferably at least one quaternary trialkylarylammonium hydroxide and / or at least one choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide. Particularly preferably, at least one benzyltrialkylammonium hydroxide and / or at least one choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide is used. Particularly preferably, benzyltrimethylammonium hydroxide (Triton B) and / or 2-hydroxyethyl-trimethylammonium acetate (choline acetate) is used.

[0016] Preferably, any desired aliphatic alcohol and / or alicyclic alcohol, preferably an aliphatic alcohol, is used as solvent component C or solvent component C', and a low molecular weight monool or diol is preferred. Examples include methanol, ethanol, isopropanol, n-butanol, 2-ethylhexanol, 2-ethylhexane-1,3-diol, 1,2-dihydroxyethane, 1,2-dihydroxypropane, 1,3-dihydroxybutane and 1,4-dihydroxybutane, 1,6-dihydroxyhexane and 2,5-dihydroxyhexane, or 2,2,4-trimethyl-1,3-dihydroxypentane, or any desired mixture of these alcohols. Alcohols having at least one primary alcohol group are particularly preferred. n-butanol, 2-ethylhexanol, 2-ethylhexane-1,3-diol, 1,2-dihydroxyethane, 1,2-dihydroxypropane, 1,3-dihydroxybutane and 1,4-dihydroxybutane, 1,6-dihydroxyhexane, or 2,2,4-trimethyl-1,3-dihydroxypentane, or any desired mixture of these alcohols, is particularly preferred.

[0017] In Embodiment 1, the at least one alcohol C used in step II may be the same as or different from the at least one alcohol used in step III. Similarly, in Embodiment 2, the at least one alcohol C' used in step II' may be the same as or different from the at least one alcohol used in step III'.

[0018] Embodiment 1: In step II, the entire amount of catalyst component B and the first portion of solvent component C (C T1 ) is supplied to the reactor, and the degree of trimerization T is in the range of 0.5% to 25%, preferably 0.5% to 20%. g Component A is trimerized until the desired result is obtained.

[0019] The supply of components B and C is preferably carried out such that at least a portion of the total amount of catalyst component B dissolves in at least a portion of the first portion of solvent component C. In this case, the following embodiments are preferred.

[0020] The entire amount of component B is dissolved in the entire first portion of component C and supplied to the reactor (Embodiment a), and the supply can be continuous or discontinuous.

[0021] The entire amount of component B can be dissolved in a first portion of a first portion of component C and supplied to the reactor, and the remaining portion of the first portion of component C can be supplied to the reactor as pure component C (Embodiment b). Both of these processes can be carried out independently, continuously or discontinuously. In this context, the expression "pure component C" means that C does not contain any catalyst of component B.

[0022] Catalyst component B is calculated based on the total amount of solvent component C used in step II, i.e., C T1 Based on this, it is preferably used in an amount of 0.3% by weight or more to 8% by weight or less, particularly preferably 0.5% by weight or more to 5% by weight or less, and very particularly preferably 0.8% by weight or more to 2% by weight or less.

[0023] Catalyst component B is generally used in an amount of 0.001% to 2% by weight, preferably 0.001% to 1% by weight, and particularly preferably 0.001% to 0.2% by weight, based on the amount of isocyanate component A used.

[0024] Step II can be carried out such that trimerization begins either during or after the supply of component B. This may be thermally affected. The first option is preferred.

[0025] The trimerization in step II is preferably carried out at a reaction temperature of 50°C to 120°C, and particularly preferably 55°C to 90°C. When HDI is used as component A, the trimerization in step II is very preferably carried out at a temperature of 57°C to 65°C.

[0026] In step III, the second portion of solvent component C (C T2 The ) is supplied to the reactor. This can be done continuously or discontinuously.

[0027] The total amount of solvent component C supplied is the sum of the two portions from steps II and III (C T1 +C T2 This corresponds to ). The total amount of supplied solvent component C is preferably 0.3% to 5% by weight, and particularly preferably 1% to 2% by weight, based on the amount of isocyanate component A used.

[0028] The trimerization in step III is preferably carried out at a reaction temperature of 50°C to 120°C, and particularly preferably 55°C to 90°C. When HDI is used as component A, the trimerization in step III is very preferably carried out at a temperature of 60°C to 65°C.

[0029] The reaction temperatures in steps II and III may be the same or different.

[0030] In step III, the trimerization of component A is continued until the desired degree of trimerization is achieved.

[0031] Embodiment 2: In step II', the first portion of catalyst component B' (B' T1 ), and the first portion of solvent component C' (C' T1 ) is supplied to the reactor, and the degree of trimerization T is in the range of 0.5% to 25%, preferably 0.5% to 20%. g Trimerize component A' until ' is obtained.

[0032] In this case, the supply of components B' and C' is preferably carried out such that at least a portion of the first portion of catalyst component B' dissolves in at least a portion of the first portion of solvent component C'. In this case, the following embodiments are preferred.

[0033] The entire first portion of component B' is dissolved in the entire first portion of component C' and supplied to the reactor (Embodiment a'), and the supply can be continuous or discontinuous.

[0034] The entire first portion of component B' is dissolved in the first portion of the first portion of component C' and supplied to the reactor, and the remaining portion of the first portion of component C' is supplied to the reactor as pure component C' (Embodiment b'). Both methods can be carried out independently, continuously or discontinuously. In this context, the expression "pure component C'" means that C' does not contain any catalyst of component B'.

[0035] B' T1 This is based on the entire first portion of component C' used in step II' (i.e., C' T1 It is used in an amount of 0.6% to 8% by weight, preferably 0.8% to 5% by weight, and particularly preferably 0.8% to 2% by weight, based on the total amount.

[0036] Step II' can be carried out so that trimerization begins either during or after the supply of component B'. This may be thermally affected. The first option is preferred.

[0037] The trimerization in step II' is preferably carried out at a reaction temperature of 50°C to 120°C, and particularly preferably 55°C to 90°C. When HDI is used as component A', the trimerization in step II' is very preferably carried out at a temperature of 57°C to 65°C.

[0038] In step III', the second portion of catalyst component B' (B' T2 ) and the second portion of solvent component C' (C' T2 ) is supplied to the reactor.

[0039] Regarding the method of supplying components B' and C', the description made with respect to step II' (paragraphs 2 to 4 of "Embodiment 2") is applied similarly here.

[0040] B' T2 This is based on the entire second portion of component C' used in step III' (i.e., C' T2 It is used in an amount greater than 0% by weight and less than or equal to 0.5% by weight, preferably greater than 0% by weight and less than or equal to 0.1% by weight, based on the total amount.

[0041] The total amount of catalyst component B' supplied is the sum of the two portions from steps II' and III' (B' T1 +B' T2 This corresponds to ). The total amount of the supplied catalyst component B' is generally 0.001% by weight or more to 2% by weight or less, preferably 0.001% by weight or more to 1% by weight or less, and particularly preferably 0.001% by weight or more to 0.2% by weight or less, based on the amount of the isocyanate component A' used.

[0042] The total amount of solvent component C' supplied is the sum of the two portions from steps II' and III' (C' T1 +C' T2This corresponds to ). The total amount of the supplied solvent component C' is preferably 0.3% to 5% by weight, and particularly preferably 1% to 2% by weight, based on the amount of the isocyanate component A' used.

[0043] The trimerization in step III' is preferably carried out at a reaction temperature of 50°C to 120°C, and particularly preferably 55°C to 90°C. When HDI is used as component A', the trimerization in step III' is very preferably carried out at a temperature of 57°C to 65°C.

[0044] The reaction temperatures in steps II' and III' may be the same or different.

[0045] In step III', the trimerization of component A' is continued until the desired degree of trimerization is achieved.

[0046] Once the desired degree of trimerization is achieved in Embodiment 1 or Embodiment 2, the reaction can be stopped immediately, either chemically or thermally. Thermal stopping is preferred. In the case of chemical stopping, the reaction solution is stopped by adding an acidic compound, an acid, and / or an alkylating agent. Preferred thermal stopping is carried out by simply continuing stirring at the selected reaction temperature after the reaction has subsided, or by further raising the temperature by up to 50°C and continuing stirring at this temperature. Preferably, the stopping temperature is raised only slightly by up to 20°C compared to the reaction temperature. Particularly preferred, thermal stopping is carried out at the reaction temperature.

[0047] The method according to the present invention can be carried out in one or more stirred tanks as a batch method, a semi-batch method, or continuously.

[0048] When the trimerization reaction is terminated by optional termination, the reaction products present are a solution of isocyanurate group-containing polyisocyanate P in the diisocyanate and / or polyisocyanate of the monomer of component A in excess (reaction mixture R), or a solution of isocyanurate group-containing polyisocyanate P' in the diisocyanate and / or polyisocyanate of the monomer of component A' in excess (reaction mixture R').

[0049] In a preferred embodiment of the present invention, in a later step, any remaining monomer diisocyanates and / or polyisocyanates of component A or component A' are removed from the reaction mixture R or reaction mixture R' by distillation. This is preferably done under very mild conditions, for example, by thin-film distillation under reduced pressure, for example, less than 1.0 mbar, preferably less than 0.5 mbar, and particularly preferably less than 0.2 mbar, at a temperature of, for example, 100°C to 200°C, preferably 120°C to 180°C. The monomer diisocyanates and / or polyisocyanates can be removed in a single stage, but preferably in multiple stages. For example, a drop film evaporator is used as a pre-evaporator to remove most of the monomer diisocyanates and / or polyisocyanates. Further starting isocyanates are removed in a downstream thin-film evaporator. In this way, a high-quality isocyanurate group-containing polyisocyanate is obtained, with a free monomer diisocyanate and / or polyisocyanate content of up to 0.5% by weight, preferably up to 0.1% by weight. The resulting distillate is reused for trimerization.

[0050] In further embodiments, the monomer diisocyanate and / or polyisocyanate are removed from the reaction product by extraction with a suitable solvent inert to the isocyanate group, such as an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, cyclopentane, or cyclohexane. This method is less preferred.

[0051] The low-monomer isocyanurate group-containing polyisocyanates obtained in this manner can be used as is, or further dissolved in a suitable solvent inert to the NCO group to form a polyisocyanate solution. Polyisocyanates prepared by the method according to the present invention are used in known applications such as two-component polyurethane coatings or in adhesive applications. As is known, the polyisocyanates obtained in this manner also serve as starting materials for further derivatives prepared therefrom, such as blocked polyisocyanates or hydrophilic polyisocyanates. [Modes for carrying out the invention]

[0052] Examples: Unless otherwise noted, the reactants used were used without further purification. Hexamethylene diisocyanate and Desmodur LD were obtained from Covestro Deutschland AG. All other reactants were ordered from Sigma Aldrich (Merck AG): Triton B 40% in methanol, 2-ethylhexanol, n-butanol, 2-ethylhexane-1,3-diol, 4-heptanol, and choline acetate.

[0053] The following standard method was used: The NCO value was determined by NCO titration according to M105-ISO 11909. Viscosity was determined according to M014-ISO 3219 / A.3. The free monomer content was determined according to M106-ISO 10283.

[0054] Online reaction monitoring was performed using Raman spectroscopy. For this purpose, a Kaiser Optics RAMAN RXN2 device was used, with the attached measurement sensor introduced into the reaction vessel and spectra recorded every two minutes. The C=O band of isocyanurate was observed at wavenumber 1760 cm⁻¹. -1It can be uniquely assigned to the band. Signal calibration was performed by combining the determination of NCO by titration with the assumption that all reacted NCO groups become isocyanurates.

[0055] Device configuration The apparatus consists of a 0.5-liter jacketed glass reactor (Buechi, Type 2), which is capable of operating at a pressure of 6 bar and a temperature of up to 200°C. The inside of the reactor is heated via a thermostat (Huber, Ministat 240) connected to the jacket. Temperature control within the thermostat is based on the temperature measured inside the reactor using a thermocouple. A stirrer inserted through the reactor lid is used to ensure the most uniform mixing possible inside the reactor. A Raman probe can be inserted into the reactor through the lid and used for online reaction monitoring. For offline analysis, it is also possible to take a sample from the reactor using a syringe.

[0056] Batch reaction Example 1: Reference test using conventional weighing and addition (not the present invention) 350 g of hexamethylene diisocyanate (HDI) was initially added to a 0.5 L stirred reactor and heated to 70°C. The diisocyanate was degassed at this temperature and 20 mbar for 60 minutes. After venting the reaction vessel and cooling the diisocyanate to 60°C, 4.6 g of 0.5 wt% Triton B solution in 2-ethylhexanol was weighed and added to the vessel as quickly as possible while stirring (1000 rpm). After a short waiting period, the reaction commenced, resulting in a decrease in the free NCO value. A degree of trimerization of 10% was rapidly achieved. The NCO value continued to decrease for a further 3 hours, but at a slower rate than before.

[0057] Example 2: Use of the method described (the present invention) The experiment described in Example 1 was repeated in the same manner until a degree of trimerization of 20% was reached. Then, 1.16 g of 2-ethylhexanol was added all at once. After a short waiting time, the NCO value decreased more sharply than in the reference experiment (Example 1). The decrease in the NCO value was beyond the range that could be explained by the reaction between the free NCO groups and the added alcohol to form urethanes and allophanates. The increase in the number of isocyanurate units compared to Example 1 could be confirmed using Raman spectroscopy.

[0058] Similar experiments were conducted with n-butanol, 2-ethylhexane-1,3-diol, and 4-heptanol. The combination of choline acetate / 2-ethylhexanol was also confirmed experimentally.

[0059] Example 3: Specific role of alcohol in comparative experiments (not the present invention) The experiment described in Example 1 was repeated in the same manner until a degree of trimerization of 20% was reached. Then, 5 g of Desmodur LD (Covestro's trade name: 2-ethylhexyl (6-isocyanatohexyl) carbamate) was added all at once. Because the added component Desmodur LD contains free isocyanate groups, the NCO value increased slightly compared to reference Example 1. Otherwise, the reaction course remained unchanged, and the number of isocyanurate units did not increase.

[0060] Figure 1 shows a comparison of the reaction processes in Examples 1 to 3. [Brief explanation of the drawing]

[0061] Explanation of Figure 1: Example 1 = solid line; Example 2 = dotted line; Example 3 = dashed line. Comparison of three trimerization reactions at 60°C using Triton B as a catalyst and 2-ethylhexanol as an alcohol. Arrows indicate the time for additional metering and addition for Examples 2 and 3.

[0062] Semi-batch testing (reduction of reaction time) Example 4: Semi-batch test using conventional weighing and adding (not the present invention) 350 g of hexamethylene diisocyanate (HDI) was initially added to a 0.5 L stirred reactor and heated to 70°C. The diisocyanate was degassed at this temperature and 1 mbar for 60 minutes. After venting the reaction vessel and cooling the diisocyanate to 65°C, the 1.5 wt% Triton B solution in 2-ethylhexanol was added to the vessel at a rate of 0.18 ml / min while stirring (500 rpm). After 10 minutes, the addition of the catalyst solution was stopped. After another 30 minutes, the addition of the catalyst solution was resumed at a rate of 0.017 ml / min until a total of 1.85 g of catalyst solution had been added to the vessel. The reaction was continued until a degree of trimerization of 11.2% was reached. The reaction was then stopped by adding DBP (dibutyl phosphate; 120 wt% relative to the amount of Triton B used).

[0063] Example 5: Semi-batch test using the method described (the present invention) 350 g of hexamethylene diisocyanate (HDI) was initially added to a 0.5 L stirred reactor and heated to 70°C. The diisocyanate was degassed at this temperature and 1 mbar for 60 minutes. After venting the reaction vessel and cooling the diisocyanate to 65°C, the 1.9 wt% Triton B solution in 2-ethylhexanol was added to the vessel at a rate of 0.18 ml / min while stirring (500 rpm). After 10 minutes, the addition of the catalyst solution was stopped. After another 30 minutes, T g At a concentration of 7.6%, the addition of pure alcohol was resumed at a rate of 0.017 ml / min until a total of 1.85 g of catalyst solution and the added alcohol was weighed into the container. The reaction was continued until a degree of trimerization of 11.2% was reached. The reaction was then stopped by adding DBP (dibutyl phosphate; 120 wt% relative to the amount of Triton B used).

[0064] TIFF2026522009000001.tif49170

[0065] As can be seen from Table 1, in the present invention, the reaction starts faster and the reaction time is shortened.

[0066] The raw materials produced in Examples 4 and 5 were distilled in the same manner to remove excess free HDI monomers. As shown in Table 2, the quality of the resulting products was identical (as expected when using the same amounts of catalyst and alcohol).

[0067] TIFF2026522009000002.tif56170

Claims

1. A) At least one organic diisocyanate or polyisocyanate having isocyanate groups bonded independently to aliphatic groups, alicyclic groups and / or aromatic aliphatic groups, B) At least one trimerizing catalyst selected from the group consisting of quaternary tetraalkylammonium hydroxide, quaternary trialkylarylammonium hydroxide, and choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide, and C) At least one alcohol as a solvent, A method for preparing an isocyanurate group-containing polyisocyanate P by trimerization in the presence of I) The step of initially adding component A to the reactor, II) The total amount of catalyst component B and the first partial amount of component C (C Ｔ１ ) is supplied, and the degree of trimerization T is in the range of 0.5% to 25%, preferably 0.5% to 20%. ｇ This is a step of trimerizing component A until the desired result is obtained, where, T ｇ = (NCO ０ - NCO ｔ ) / NCO ０ And, During the ceremony, NCO ０ This corresponds to the amount of free NCO groups originally present in component A that was initially added. NCO ｔ This corresponds to the amount of free NCO groups in the reaction solution at time t, These are steps determined by NCO titration according to M105-ISO 11909, respectively. III) A step of supplying a second partial amount (C Ｔ２ ) of component C and continuing the trimerization of component A A method that includes or consists solely of these.

2. A') At least one organic diisocyanate or polyisocyanate having isocyanate groups bonded independently to aliphatic groups, alicyclic groups and / or aromatic aliphatic groups, B') At least one trimerizing catalyst selected from the group consisting of quaternary tetraalkylammonium hydroxide, quaternary trialkylarylammonium hydroxide, and choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide, and C') At least one alcohol as a solvent, A method for preparing an isocyanurate group-containing polyisocyanate P' by trimerization in the presence of I') The step of initially adding component A' to the reactor, II') First partial amount of catalyst component B' (B' Ｔ１ ), and the first portion of component C' (C' Ｔ１ ) to supply, Here, catalyst component B' Ｔ１ The first portion (C') of component C' used in step II'. Ｔ１ Based on the above, it is used in an amount of 0.6% by weight or more to 8% by weight or less, preferably 0.8% by weight or more to 5% by weight or less, and particularly preferably 0.8% by weight or more to 2% by weight or less. Trimerization degree T in the range of 0.5% or more to 25% or less, preferably 0.5% or more to 20% or less. ｇ A process of trimerizing component A until ' is obtained, where, T ｇ '=(NCO ０ - NCO ｔ ) / NCO ０ And, During the ceremony, NCO ０ This corresponds to the amount of free NCO groups originally present in component A' that was initially added. NCO ｔ This corresponds to the amount of free NCO groups in the reaction solution at time t, These are steps determined by NCO titration according to M105-ISO 11909, respectively. III') Second portion of catalyst component B' (B' Ｔ２ ), and the second portion of component C' (C' Ｔ２ ) to supply, Here, catalyst component B' Ｔ２ The second portion (C') of component C' used in step III'. Ｔ２ Based on this standard, it is used in an amount greater than 0% by weight to 0.5% by weight or less, preferably greater than 0% by weight to 0.1% by weight or less. The process of continuing the trimerization of component A', A method that includes or consists solely of these.

3. At least one organic diisocyanate or polyisocyanate (A) is PDI, HDI, MPDI, 1,3-H ６ XDI and 1,4-H ６ The method according to claim 1, selected from the group consisting of XDI, 1,3-XDI and 1,4-XDI and NBDI, or at least one organic diisocyanate or polyisocyanate (A') is PDI, HDI, MPDI, 1,3-H ６ XDI and 1,4-H ６ The method according to claim 2, selected from the group consisting of XDI, 1,3-XDI and 1,4-XDI, and NBDI.

4. The method according to claim 1 or 3, wherein component B is at least one benzyltrialkylammonium hydroxide and / or at least one choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide, or the method according to claim 2 or 3, wherein component B' is at least one benzyltrialkylammonium hydroxide and / or at least one choline-type hydroxyalkyl-substituted quaternary ammonium hydroxide.

5. The method according to claim 4, wherein benzyltrimethylammonium hydroxide (Triton B) and / or 2-hydroxyethyl-trimethylammonium acetate (choline acetate) is used.

6. The method according to any one of claims 1 or 3 to 5, wherein component C is an aliphatic and / or alicyclic mono- or diol, preferably having at least one primary alcohol group, or the method according to any one of claims 2 to 5, wherein component C' is an aliphatic and / or alicyclic mono- or diol, preferably having at least one primary alcohol group.

7. The method according to any one of claims 1 or 3 to 6, wherein catalyst component B is used in an amount of 0.001% by weight or more to 2% by weight or less, preferably 0.001% by weight or more to 1% by weight or less, and particularly preferably 0.001% by weight or more to 0.2% by weight or less, based on the amount of isocyanate component A used, or the method according to any one of claims 2 to 6, wherein catalyst component B' is used in an amount of 0.001% by weight or more to 2% by weight or less, preferably 0.001% by weight or more to 1% by weight or less, and particularly preferably 0.001% by weight or more to 0.2% by weight or less, based on the amount of isocyanate component A' used.

8. Catalyst component B is used in step II in the first partial amount of component C (C Ｔ１ The method according to any one of claims 1 or 3 to 7, wherein the amount used is 0.3% by weight or more to 8% by weight or less, preferably 0.5% by weight or more to 5% by weight or less, and particularly preferably 0.8% by weight or more to 2% by weight or less, based on ).

9. The method according to any one of claims 1 or 3 to 8, wherein the trimerization in step II is carried out at a reaction temperature of 50°C to 120°C, preferably 55°C to 90°C, or the method according to any one of claims 2 to 7, wherein the trimerization in step II' is carried out at a reaction temperature of 50°C to 120°C, preferably 55°C to 90°C.

10. Total amount of solvent component C supplied in steps II and III (C Ｔ１ +C Ｔ２ ) is 0.3% by weight or more to 5% by weight or less, preferably 1% by weight or more to 2% by weight or less, based on the amount of isocyanate component A used, according to the method of claim 1 or any one of claims 3 to 9, or the total amount of solvent component C' supplied in steps II' and III' (C' Ｔ１ +C' Ｔ２ The method according to claims 2 to 7 or 9, wherein the amount of each isocyanate component A' used is 0.3% by weight or more to 5% by weight or less, preferably 1% by weight or more to 2% by weight or less.

11. The method according to any one of claims 1 or 3 to 10, wherein the trimerization in step III is carried out at a reaction temperature of 50°C to 120°C, preferably 55°C to 90°C, or the method according to any one of claims 2 to 7, 9, or 10, wherein the trimerization in step III' is carried out at a reaction temperature of 50°C to 120°C, preferably 55°C to 90°C.

12. The method according to any one of claims 1 to 11, which is carried out in one or more stirred tanks as a batch process, a semi-batch process, or continuously.

13. The method according to any one of claims 1 or 3 to 12, wherein the trimerization of component A is stopped chemically or thermally, preferably thermally, when a desired degree of trimerization is reached, or the method according to any one of claims 2 to 7 or 9 to 12, wherein the trimerization of component A' is stopped chemically or thermally, preferably thermally, when a desired degree of trimerization is reached.

14. The method according to any one of claims 1 or 3 to 13, characterized in that in a later step, either the diisocyanate and / or polyisocyanate of the monomer of component A that is still present is removed from the reaction product by distillation, or the method according to any one of claims 2 to 7 or 9 to 13, characterized in that in a later step, either the diisocyanate and / or polyisocyanate of the monomer of component A' that is still present is removed from the reaction product by distillation.

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