EP2445945A1

EP2445945A1 - Low-catalyst carbodiimide groups and/or isocyanate mixtures comprising uretonimine groups

Info

Publication number: EP2445945A1
Application number: EP10719296A
Authority: EP
Inventors: Emmanouil Spyrou; Evelyn Albrecht; Annegret Lilienthal; Iris Brückner; Andrea VÖCKER
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2009-06-26
Filing date: 2010-04-21
Publication date: 2012-05-02
Also published as: CN102803326A; DE102009027246A1; US20120065424A1; WO2010149406A1; AU2010265038A1; JP2012530743A

Abstract

The invention relates to low-catalyst carbodiimide groups and/or isocyanate mixtures comprising uretonimine groups, to a method for the production, and to the use thereof.

Description

Katalvsatorarme Carbodiimidqruppen and / or Uretoniminqruppen containing Isocvanatmischungen

The invention relates to low-catalyst carbodiimide groups and / or uretonimine containing isocyanate mixtures, a process for the preparation and their use.

The carbodiimidization of isocyanates is a known process and described in many patent applications. Thus, processes for the preparation of carbodiimide and / or uretonimine containing isocyanate mixtures with the very effective for this reaction catalysts of the phospholene series z. B. from US 2,853,473 and EP 515 933 known.

The use of the phosphole oxides as catalysts for the carbodiimidization reaction requires that the catalyst remaining in the product must be effectively stopped (deactivated) if storage-stable, low-carbodiimide and / or uretonimine-containing isocyanate mixtures with a defined NCO content are to be prepared. Otherwise carbodiimidized isocyanate mixtures tend to post-reaction and continue to split CO ₂ . It comes to changes in the product during storage and pressure build-up in closed containers.

Several writings deal with the possibilities for stopping the carbodiimidization reaction:

Suitable deactivators for the phospholene carbodiimide catalyst are, for. As mentioned in the patents EP 515 933, EP 609 698 and US 6,120,699 and include z. As acid, acid chlorides, chloroformates and silylated acids.

EP 1 616 858 also discloses a process for preparing organic isocyanates containing carbodiimide and / or uretonimine groups by partial carbodiimidization of isocyanate groups using phospholene-type catalysts. Here, the carbodiimidization reaction by the addition of a silylated acid and the additional addition of a non-silylated acid and / or an acid chloride and / or a sulfonic ester stopped. EP 1 616 858 thus describes the preparation of liquid storage-stable isocyanate mixtures with low color numbers by deactivating the phospholene catalyst.

No. 4,068,055 and US Pat. No. 4,068,065 describe polymer-bound phospholene catalysts which can be separated off again by filtration after the carbodiimide reaction. On the one hand, such polymeric catalysts are difficult to prepare and on the other hand they can be separated from highly viscous or solid carbodiimide mixtures only with great technical effort or not at all.

DE-OS-102 06 112 describes aqueous dispersions composed of polycarbodiimides. Here, residues of unreacted TMXDI are distilled off from a tetramethylenexylylene diisocyanato-TMXDIJ polycarbodiimide mixture after preparation, there is thus hardly any monomeric diisocyanate remaining in the end product and then reacted with an alcohol to give a carbodiimide-containing polycarbodiimide urethane. A separation of the catalyst is not mentioned, and as can be seen on page 3, line 68, it is usually deactivated when using phospholene oxides as a catalyst for the preparation of carbodiimides by blocking with acid chlorides. The catalyst content was also determined neither in the residue nor in the distillate.

The complete separation of other monomeric diisocyanates

Polycarbodiimide mixtures have not hitherto been described because they are difficult to obtain either because of excessively high boiling points (for example dicyclohexylmethylene diisocyanate (Hi ₂ MDI) and / or because of the reaction of aliphatic isocyanates with carbodiimides (uretonimine formation)) (for example US Pat Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),

Thmethylhexamethylene diisocyanate (TMDI)). The Uretoniminbildung ensures that a significant proportion (usually 1-15 wt .-%) of monomeric diisocyanates remains in the residue. The practice shows that a carbodiimide and / or uretonimine containing isocyanate having on the one hand by the remaining in the product phosphorus-containing catalyst is not storage stable and on the other hand tends to undesirable discoloration. State of the art are therefore a variety of complex efforts to deactivate the catalyst. However, the substances added to the deactivation in carbodiimide and / or uretonimine groups-containing isocyanate mixtures are in part hazardous and expensive secondary components and are therefore undesirable. The phosphorus-containing catalysts are harmful to health and even very expensive.

It is an object of the present invention to provide a process for the preparation of storage-stable isocyanate mixtures containing carbodiimide and / or uretonimine groups, which does not have the abovementioned deficiencies and leads to storage-stable carbodiimide-containing products with a low color number.

Surprisingly, it has been found that low-catalyst carbodiimide groups and / or uretonimine groups-containing isocyanate mixtures can be prepared by simultaneous distillative removal of a proportion of monomeric diisocyanates and catalysts. Although the content of monomeric diisocyanates is not lowered to the usual level (<0.5 wt .-%), but reduced the proportion of the catalyst to a maximum of 0 - 20% of the original concentration.

The invention relates to a catalyst-poor carbodiimide groups and / or uretonimine containing isocyanate mixture prepared by reacting

I)

A) at least one diisocyanate, in the presence of

B) phosphorus-containing catalysts for carbodiimide formation, wherein the reaction does not take place until complete conversion of the diisocyanate and 1 to 80 wt .-% of the diisocyanate used remain in the reaction mixture; with subsequent simultaneous removal by distillation of a portion of the excess monomeric diisocyanate A) and the phosphorus-containing catalyst B);

with a content of the isocyanate mixture of monomeric diisocyanate A) of 0.5 to 20 wt .-%, based on the diisocyanate A) used and a content of catalyst B) from 0 to 20 wt .-%, based on the catalyst B used ).

The content of carbodiimides in the catalyst-poor

Carbodiimide groups and / or uretonimine containing isocyanate mixture (residue) is between 0.1 wt .-% and 50 wt .-%.

The invention also relates to a process for the preparation of a catalyst-poor carbodiimide and / or uretonimine containing isocyanate mixture by partial carbodiimidization of isocyanate groups with phosphorus catalysts and subsequent distillative separation of a portion of the monomeric diisocyanate used and simultaneously the catalyst. The catalyst may also be partially but also completely separated.

The catalyst-poor carbodiimide groups and / or uretonimine groups-containing isocyanate mixtures according to the invention are particularly colorable and storage-stable. The majority of the separated phosphorus-containing catalyst is present in the separated monomeric diisocyanate and can be reused directly for re carbodiimidization.

The diisocyanates A) used according to the invention may consist of any desired aliphatic, cycloaliphatic and / or (cyclo) aliphatic or aromatic diisocyanates.

Suitable aliphatic diisocyanates advantageously have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic Diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical. Under (cyclo) aliphatic diisocyanates, the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z. B. isophorone diisocyanate is the case. In contrast, is meant by cycloaliphatic diisocyanates those which have only directly attached to the cycloaliphatic ring NCO groups, for. B. Hi ₂ MDI. Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate and / or dodecane diisocyanates.

Also suitable are methyldiphenyl diisocyanate (MDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 4-methylcyclohexane-1,3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylene-bis (cyclohexyl) diisocyanate, 1,4-diisocyanato-4-methyl-pentane.

As aliphatic, (cyclo) aliphatic and / or cycloaliphatic diisocyanates A) are particularly suitable: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicylcohexylmethane (Hi ₂ MDI) 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate ^ ^^ - trimethylhexamethylene diisocyanate (TMDI), and norbornane diisocyanate (NBDI). Very particular preference is given to IPDI, HDI and Hi ₂ MDI.

Of course, it is also possible to use mixtures of the diisocyanates.

The inventive carbodiimide groups and / or uretonimine-containing isocyanate mixture is prepared in the presence of the highly effective catalysts B).

A detailed description of suitable catalysts and production methods can be found, for. In Houben-Weyl, Methods of Organic Chemistry, Volume E4, carbonic acid derivatives, Georg-Thieme-Verlag, Stuttgart, 1983, p. 897 to 900 and 910, and in Chemical Reviews, Volume 67, Number 2, 1967, pp. 107-113, or in Angew. Chem., 1962, No. 21, 801-806. Carbodiimidization catalysts are also described in US 2,941,966, US 2,853,518, US 2,853,473 or DE 35 12 918. Preferred catalysts are phospholens and phospholanes and also their oxides and sulfides, particularly preferably of the phospholene oxide type. Examples of commonly used catalysts are 1-methyl-2-phospholene-1-oxide, 1-methyl-3-phospholene-1-oxide, 3-methyl-1-phenyl-3-phospholene-1-oxide and 3-methyl-1 - phenyl-2-phospholene-1-oxide and the corresponding phospholane types. Preference is given to using 3-methyl-1-phenyl-2-phospholene-1-oxide. Also suitable are phosphine oxides. The amount of catalyst based on the diisocyanate A) is 0.1 to 3 wt .-%, preferably 0.5 -1, 5 wt .-%.

The isocyanate mixture according to the invention having carbodiimide groups and / or uretonimine groups is preferably prepared according to a process wherein at least one isocyanate mentioned under A) with addition of at least one of the catalysts listed under B) by heating to temperatures of 30 - 200 ⁰ C with elimination of Carbon dioxide to be implemented. The temperature is preferably 80-200 ^° C., the time duration preferably between 30 minutes and 24 hours. Depending on the catalyst content, temperature and time, smaller or larger amounts of monomeric diisocyanate remain in the reaction mixture, preferably from 1 to 80% by weight, based on the amount of A) used.

The distillative simultaneous separation II) of a proportion of monomeric diisocyanate and phosphorus catalyst is carried out in suitable distillation units, for. B. in short path evaporators, thin film evaporators or falling film evaporators. The temperature is dependent on the boiling point of the diisocyanate used at 100 to 240 ⁰ C preferably 130 to 200 ⁰ C. It may be advantageous, the mixture to be distilled before the actual distillation to a temperature between 100 and 200 ⁰ C, preferably between 120 and 160 ⁰ C preheat. The pressure is maintained between 0.001 mbar and 50 mbar, preferably between 0.01 and 10 mbar. The monomeric content of diisocyanate in the residue, that is to say in the catalyst-poor isocyanate mixture having carbodiimide groups and / or uretonimine groups according to the invention, is 0.5 to 20% by weight, preferably 3, after the distillation to 10% by weight. The catalyst used is after distillation to about 80 - 100% in the distillate before, and about 0 - 20% in the residue, based on the amount of catalyst used. Preferably, it is 95-99% in the distillate before and 1-5% in the residue. Smaller amounts of catalysts (0 - 10% based on the total amount used) can also in the cold trap or on the

Distillation apparatus remain. The content of carbodiimides in the residue is between 0.1 wt .-% and 50 wt .-%.

The invention also provides a process for the preparation of a catalyst-poor carbodiimide groups and / or uretonimine containing isocyanate mixture, by reacting

I)

A) at least one diisocyanate in the presence of B) phosporous catalysts for carbodiimide formation, wherein the reaction does not take place until the complete conversion of the diisocyanate and 1 to 80 wt .-% of the diisocyanate used remain in the reaction mixture;

II) with subsequent simultaneous removal by distillation of a portion of the excess monomeric diisocyanate A) and the phosphorus-containing catalyst B);

Carbodiimide-containing compounds are used in the paint and adhesives industry and in the plastics industry in general as stabilizers, or / and as crosslinkers. Examples

General determination methods:

The NCO content is determined titrimetrically by reaction of the NCO groups with dibutylamine and subsequent back-titration of the excess of dibutylamine with hydrochloric acid. The hot value is determined after 30 minutes of heating the sample to 180 ⁰ C and sudden cooling. The carbodiimide content is determined after two hours of boiling with butanol under copper (I) chlod catalysis and then reaction with dibutylamine and subsequent back-titration of the excess of dibutylamine with hydrochloric acid.

1a) Preparation of the carbodiimides from IPDI

1581, 4g IPDI (Evonik-Degussa) with 18.6 g of 3-methyl-1-phenyl-2-phospholene-1 - oxide (Alfa Aesar) under permanent N ₂ stream in 3.5 h at 110 ⁰ C under CO ₂ Removal proportionately converted to carbodiimide. Part of the carbodiimide further reacts in a reversible reaction with free isocyanate to uretonimine. The following data was determined from the reaction product:

NCO content cold: 27.66% by weight - NCO content hot: 30.46% by weight - carbodiimide content: 3.55% by weight - color Hazen: 96, viscosity 23 ^° C.: 691 mPas

1b) separation of the phosphorus-containing catalysts by distillation and preparation of the catalyst-poor carbodiimide groups and / or uretonimine-containing isocyanate mixture

539 g of the carbodiimide prepared under 1 a) of IPDI is at 155 ⁰ C and 0.2 mbar with about 200 g / h of a short-path chromatography (KDL4, UIC). 145.6 g are collected as a residue. This residue contains 8.2% by weight of monomeric IPDI and 110 ppm of phosphorus. This corresponds to approximately 1.4% of the catalyst used. The distillate (375.4 g) contains 2800 ppm of phosphorus, which corresponds to 95.5% of the catalyst used. NCO content cold: 10.95 wt.% NCO content hot: 14.11 wt.% Carbodiimide content: 10.4 wt.% Color Hazen (30% in toluene): 115 M.p. 64 ⁰ C 2a) Renewed Preparation of Carbodiimide from IPDI Distillate from 1b)

350 g of IPDI distillate from 1b) are diluted with 221 g of IPDI (Evonik-Degussa). The reaction takes place under permanent N ₂ current within ₃ h at 110 ⁰ C and CO ₂ elimination proportionately to carbodiimide. The following data is determined from the reaction product:

NCO content cold: 28.24% - NCO content hot: 30.87% - carbodiimide content: 3.54% - color Hazen: 91 - color Gardner: 0.2 - viscosity 23 ⁰ C: 629 mPas

2b) renewed separation of the phosphorus-containing catalyst by distillation and preparation of the catalyst-poor carbodiimide groups and / or uretonimine-containing isocyanate mixture

400.6 g of the carbodiimide prepared under 2a) of IPDI is at 155 ⁰ C and 0.2 mbar with about 200 g / h of a short-path chromatography (KDL4, UIC). 85.2 g are collected as a residue. This residue contains 8.4% monomeric IPDI and 180 ppm phosphorus. This corresponds to about 2.1% of the catalyst used. The distillate (297.5 g) contains 2500 ppm of phosphorus, which corresponds to 95.6% of the catalyst used. NCO content cold: 9.85% by weight - NCO content hot: 12.60% by weight - carbodiimide content: 10.8% by weight - color Hazen (30% in toluene): 107 - M.p. 78 ⁰ C

From these examples, it can be seen that most of the phosphorus-containing catalyst remains in the distillate. This can be used again without any restrictions, while the residue is largely low in catalyst.

storage stability

To determine the storage stability, the products 1 a) (before distillation), 1 b) (after distillation) and 1 b) + 1 wt .-% catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) Stored for 7 days at 50 ⁰ C and the found NCO content (hot) compared with the starting NCO content (hot).

^* comparative experiments not according to the invention

From these examples, it can be seen that only the catalyst-poor product 1 b) is storage-stable (decrease in the hot NCO number after 7 days at 50 ^° C. is less than 5%). The two comparative products 1 a) and 1 b) + 1% catalyst show after storage at 50 ⁰ C, a post-reaction, formation of further carbodiimide with elimination of carbon dioxide, which after one week, the decrease in the NCO number is greater than 5%.

Claims

claims:

1. Catalyst-poor carbodiimide groups and / or uretonimine groups-containing isocyanate mixture, prepared by reaction of I)

A) at least one diisocyanate in the presence of

B) phosphorus-containing catalysts for carbodiimide formation, wherein the reaction does not take place until complete conversion of the diisocyanate and 1 to 80 wt .-% of the diisocyanate used remain in the reaction mixture;

2. Catalyst-poor carbodiimide groups and / or uretonimine-containing isocyanate mixture according to claim 1, characterized in that diisocyanates selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicylcohexylmethane (Hi ₂ MDI)

2-methylpentane diisocyanate (MPDI), 2,2,4-thmethylhexamethylene diisocyanate / 2,4,4-thmethylhexamethylene diisocyanate (TMDI), and norbornane diisocyanate (NBDI), used alone or in mixtures.

3. Catalyst-poor carbodiimide groups and / or uretonimine-containing isocyanate mixture according to at least one of the preceding claims, characterized in that IPDI, HDI and Hi ₂ MDI are used.

4. Catalyst-poor carbodiimide groups and / or uretonimine containing isocyanate mixture according to at least one of the preceding claims, characterized in that as catalysts phospholene and phospholanes and their oxides and

Sulfides, especially of the phospholene oxide type can be used.

5. Catalyst-poor carbodiimide groups and / or uretonimine groups having isocyanate mixture according to at least one of the preceding claims, characterized in that as catalysts 1-methyl-2-phospholene-1-oxide, 1-methyl-3-phospholene-1 - oxide, 3-methyl 1-phenyl-3-phospholene-1-oxide and 3-methyl-1-phenyl-2-phospholene-1-oxide and the corresponding phospholane types are used.

6. Catalyst-poor carbodiimide groups and / or uretonimine containing isocyanate mixture according to at least one of the preceding claims, characterized in that the amount of catalyst based on the diisocyanate A) 0.1 to 3 wt .-%, preferably 0.5 to 1, 5 wt .-%, is.

7. Catalyst-poor carbodiimide groups and / or uretonimine-containing isocyanate mixture according to at least one of the preceding claims, prepared by a process, wherein the isocyanates mentioned under A) with the addition of the catalysts listed under B) by heating to temperatures of 30 - 200 ⁰ C with elimination of Carbon dioxide to be implemented.

8. Catalyst-poor carbodiimide groups and / or uretonimine groups having isocyanate mixture according to at least one of the preceding claims, characterized in that the distillative simultaneous separation II. A proportion of monomeric diisocyanates and phosphorus catalysts in short path evaporators, thin film evaporators or falling film evaporators.

9. Low-catalyst carbodiimide groups and / or uretonimine containing isocyanate mixture according to claim 8, wherein the temperature at 100 to 240 ⁰ C, preferably at 130 to 200 ⁰ C, is.

10. Catalyst-poor carbodiimide groups and / or uretonimine containing isocyanate mixture according to claim 8 or 9, characterized in that the mixture to be distilled before the actual distillation to a temperature between 100 and 200 ⁰ C, preferably between 120 and

160 ⁰ C, preheated.

11. Low-catalyst carbodiimide groups and / or uretonimine-containing isocyanate mixture according to claim 8 to 10, characterized in that the distillation at a pressure between 0.001 mbar and 50 mbar, preferably between 0.01 and 10 mbar, is performed.

12. Catalyst-poor carbodiimide groups and / or uretonimine containing isocyanate mixtures according to at least one of the preceding claims, characterized in that the part of the separated phosphorus-containing catalyst present in the separated monomeric diisocyanate is reused directly for re carbodiimidization.

13. Catalyst-poor carbodiimide groups and / or uretonimine groups-containing isocyanate mixture according to at least one of the preceding claims with a content of the isocyanate mixture of monomeric diisocyanate A) of 3 to 10 wt .-%, based on the diisocyanate A) and a content of catalyst B) of 1 to 5 wt .-%, based on the catalyst B) used.

14. Catalyst-poor carbodiimide groups and / or uretonimine-containing isocyanate mixtures according to at least one of the preceding claims, characterized in that the content of carbodiimides in the catalyst-poor carbodiimide and / or uretonimine containing isocyanate mixture (residue) is between 0.1 wt .-% and 50 wt .-%.

15. A process for the preparation of a low-carbodiimide carbodiimide and / or uretonimine containing isocyanate mixture by partial carbodiimidization of isocyanate groups with phosphorus-containing catalysts and subsequent distillative separation of a portion of the monomeric diisocyanate used and simultaneously the catalyst.

16. A process for the preparation of a low-catalyst carbodiimide groups and / or uretonimine containing isocyanate mixture, by reacting

I) A) at least one diisocyanate in the presence of

B) phosporous catalysts for carbodiimide formation, wherein the reaction does not take place until complete conversion of the diisocyanate and 1 to 80% by weight of the diisocyanate used remain in the reaction mixture; II) with subsequent simultaneous removal by distillation of a portion of the excess monomeric diisocyanate A) and the phosphorus-containing catalyst B);

with a content of the isocyanate mixture of monomeric diisocyanate A) of 0.5

- 20 wt .-%, based on the diisocyanate A) used and a content of catalyst B) from 0 to 20 wt .-%, based on the catalyst used B).

17. The method according to claim 15 or 16, characterized in that the content of carbodiimides in the residue between 0.1 wt .-% and 50 wt .-% is.