Improved Polymeric Mdi Color Polymeres MDI Mit Verbesserter Farbe MDI Polymériques Avec Une Couleur Améliorée

Europäisches Patentamt *EP000918052B1* (19) European Patent Office

Office européen des brevets (11) EP 0 918 052 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: C07C 263/10, C07C 263/20, of the grant of the patent: C08G 18/76 28.05.2003 Bulletin 2003/22

(21) Application number: 98121255.8

(22) Date of filing: 07.11.1998

(54) Improved polymeric mdi color Polymeres MDI mit verbesserter Farbe MDI polymériques avec une couleur améliorée

(84) Designated Contracting States: • Blue, Clarence D. BE DE ES FR GB IT NL PT New Martinsville, Wv 26155 (US)

(30) Priority: 20.11.1997 US 975434 (74) Representative: Steiling, Lothar, Dr. et al Bayer AG (43) Date of publication of application: Konzernbereich RP 26.05.1999 Bulletin 1999/21 Patente und Lizenzen 51368 Leverkusen (DE) (73) Proprietor: Bayer Corporation Pittsburgh, PA 15205-9741 (US) (56) References cited: EP-A- 0 581 100 (72) Inventors: • Adkins, Rick L. New Martinsville, Wv 26155 (US)

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 918 052 B1

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Description

[0001] Processes for the production of polymethylene polyphenyl polyamines (PMDA) and phosgenation of such polyamines to produce the corresponding polyisocyanates are well known in the art (see, e.g., U.S. Patents 3,253,031, 5 3,260,751, 3,277,139, 3,277,173, 3,362,979, 3,496,229, 3,517,062, 3,641,094, 3,912,600 and 4,259,526). [0002] In general, the process of producing the polyisocyanates includes the steps of phosgenating the polyamines in solution in an organic solvent, removing excess phosgene and then stripping the inert solvent. Some effort has been expended in reducing the color of resultant polyisocyanates. U.S. Patent 4,465,639 describes the addition of water prior to the solvent stripping step to reduce the color. U.S. Patent 4,792,624 describes a specific polyamine recycling 10 step during the aniline/formaldehyde reaction to cause a reduction in color of the corresponding polyisocyanate. [0003] Czechoslovakian Patent 154,431 describes a method of isolating isomers of diaminodiphenylmethane using a water extraction process. The reference describes the use of deoxygenated water in the extraction and suggests that reducing agents should be added to the water in order to minimize staining of the isolated diamine. [0004] U.S. Patent 5,312,971 describes a process whereby a reducing agent such as borane-tetrahydrofuran added 15 to the polyamines can result in reduction of color of the corresponding isocyanate.

SUMMARY OF THE INVENTION

[0005] A process for the production of polymethylene polyphenyl polyisocyanates (PMDI) is disclosed. The process 20 comprises phosgenating the corresponding polyamines in solution in an inert organic solvent, for example monochlo- robenzene (MCB), removing excess phosgene, and stripping the solvent, the improvement wherein at least 0.00015 percent by weight of hydrazine or a hydrazine derivative is added to the polyamines at any time prior to the stripping step.

DESCRIPTION OF THE INVENTION 25 [0006] The present invention is directed to the discovery that a relatively small amount of hydrazine and/or its derivatives added to the polyamines can result in a significant reduction in the color of the corresponding polyisocyanate. More particularly, the present invention is directed to a process for the production of polymethylene polyphenyl polyisocyanates comprising phosgenating the corresponding polyamines in solution in an inert organic solvent, removing 30 excess phosgene, and stripping said solvent, the improvement wherein at least 0.00015 % by weight of the hydrazine and/or its derivatives is added to said polyamines at any time prior to said stripping step. [0007] As is well known in the art, the polymethylene polyphenyl polyamines are prepared by reacting aniline and formaldehyde in the presence of an aqueous acid catalyst (generally hydrochloric acid). The polyamines are isolated from the reaction mixture by first adding an excess of a neutralizing agent (generally sodium hydroxide), and then 35 removing any excess neutralizing agent, water and aniline. The hydrazine and/or derivatives of the present invention have been found to be effective in reducing the color of the corresponding polyisocyanate if they are added at any time following the addition of the neutralizing agent and before the stripping of the solvent used for phosgenation. Most effective results have been found where the addition of the hydrazine occurs prior to phosgenation of the polyamine. [0008] The details of the production of the polymethylene polyphenyl polyamines and the phosgenation to the cor- 40 responding polyisocyanates are known and described, for example, in U.S. Patents 3,253,031, 3,260,751, 3,277,139, 3,277,173, 3,362,979, 3,496,229, 3,517,062, 3,641,094, 3,912,600, 4,259,526, 4,465,639 and 4,792,624. [0009] Substantially any hydrazine and/or its derivatives can be used herein. Useful additives include hydrazine, hydrazine hydrate, hydrazine hydro-chlorides, hydrazine and its salts, carbohydrazides and carbohydrazide derivatives. Specific additives include 4-Nitrophenylhydrazine, acetyl-hydrazine, acetyl phenyl hydrazine, 1-acetyl-2-phenyl 45 hydrazine, benzoyl-hydrazine, benzylhydrazine dihydrochloride, 2-bromophenylhydrazine hydrochloride, 3-bromophe- nyl-hydrazine, 4-bromophenylhydrazine-hydrochloride, tert-butylphenylhydrazine, 4-n-butylphenylhydrazine hydrochloride, 4-tert-butylphenylhydrazine hydrochloride, N-a-(chloro-benzoyl)-p-methoxy-phenylhydrazine, 2-chlorophenylhydrazine hydrochloride, 3-chloro-phenylhydrazine hydrochloride, 4-chlorophenyl-hydrazine hydrochloride, cyclohexyl methylhydrazine, symdibenzoyl-hydrazine, 2,3-dichloro-phenylhydrazine, 2,4-dichlorophenyl-hydrazine hy- 50 drochloride, 2,3-dichlorophenylhydrazine, 2,5-dichlorophenyl-hydrazine hydrochloride, 2,6-dichlorophenylhydrazine hydrochloride, 3,4-dichlorophenyl-hydrazine hydrochloride, 3,5-dichlorophenylhydrazine hydrochloride, 2,4-difluoro- phenylhydrazine hydrochloride, dihydrazine sulfate, 1,2-dimethyl-hydrazine dihydrochloride, 1,1-dimethylhydrazine (unsymmetrical), 2,3-dimethyl-phenylhydrazine hydrochloride, 2,4-dimethylphenylhydrazine hydrochloride, 2,5 dimethylphenylhydrazine hydrochloride, 2,6 dimethyl-phenylhydrazine hydrochloride, 3,4-dimethylphenylhydrazine 55 hydrochloride, 3,5-dimethylphenylhydrazine hydrochloride, 2,4-dinitrophenylhydrazine,1,1-diphenylhydrazine hydrochloride,(2-ethylphenyl)hydrazine hydrochloride, 4-ethylphenylhydrazine hydrochloride, 2-fluorophenylhydrazine hydrochloride, p-fluorophenyl hydrazine hydrochloride, 4-fluorophenyl hydrazine hydrochloride, anhydrous hydrazine, hydrazine base, hydrazine dihydrobromide, hydrazine dihydrochloride, hydrazine hydrate, hydrazine monoacetate,

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hydrazine monohydrobromide, hydrazine monohydrochloride, hydrazine mononitrate, hydrazine oxygen scavenger, hydrazine solution, carbohydrazide, 1,5-diphenylcarbazide, and 4-phenylsemicarbazide. The presently preferred additive is hydrazine hydrate. [0010] The amount of additive added can vary over a wide range. In general, at least 0.00015% by weight of additive 5 per 100% by weight of the polyamine should be added. The upper limit is dictated by economics. In general, amounts in excess of 10% by weight of additive per 100% of polyamine do not show any increased advantage. [0011] The color of polymethylene polyphenyl polyisocyanates can be broken down into two main absorptions in the UV-Visible spectrum - 430 nm and 520 nm. A color improvement is herein defined as an increase in the color number of a standard PMDI. A color number is defined as the ratio of the 430 nm to 520 nm absorbances. 10 [0012] The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.

EXAMPLES

15 Example 1 (PMDI Laboratory Standard)

[0013] PMDA (100 g) was dissolved in 500 ml MCB and purged with nitrogen. MCB (1.5 liters) was cooled to 0°C and phosgene added at 2 mole/h for 1.5 hours. The phosgene flow was then reduced to 0.5 mole/h. The PMDA/MCB solution was added to the phosgene solution at 0°C. After complete addition, the phosgenation solution was slowly 20 heated to 130°C and maintained at this temperature for 1h with phosgene. The PMDI/MCB solution was purged with nitrogen for 20 minutes and then the solvent was vacuum distilled to give the final PMDI product.

Example 2

25 [0014] PMDA (100 g) and 64% hydrazine hydrate (0.1 g) were stirred at 100°C under nitrogen for 24 hours. The PMDA was then water washed and dried of water to remove residual hydrazine hydrate. The hydrazine level was measured at 1.5 ppm. The PMDA was then phosgenated as shown above.

Example 3 30 [0015] PMDA (100 g) and 64% hydrazine hydrate (0.1 g) were stirred at 100°C under nitrogen for 24 hours. The PMDA was then phosgenated as shown in Example 1 above.

Examples 4-6 35 [0016] These examples were identical to Example 2 except for the hydrazine level.

Example 7

40 [0017] PMDA (100 g) and anhydrous hydrazine (0.9 g) were stirred at 100°C under nitrogen for 24 hours. The PMDA was then phosgenated as shown in Example 1 above.

Example 8

45 [0018] PMDA (100 g) was dissolved in 500 ml MCB and purged with nitrogen. Hydrazine hydrate (0.7 g) was added to this solution and stirred for 5 minutes. This solution was then phosgenated as shown in Example 1 above.

Example 9

50 [0019] PMDA (100 g) was dissolved in 500 ml MCB and purged with nitrogen. MCB (1.5 liters) was cooled to 0°C and phosgene added at 2 mole/h for 1.5 hours. The phosgene flow was then reduced to 0.5 mole/h. The PMDA/MCB solution was added to the phosgene solution at 0°C. After complete addition, the phosgenation solution was slowly heated to reflux (about 128°C). At this point 0.4 g of anhydrous hydrazine was added, and the reaction mixture was maintained at this temperature for 1h with phosgene. The PMDI/MACB solution was purged with nitrogen for 20 minutes 55 and then the solvent was vacuum distilled to give the final PMDI product.

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Example 10 (Example using reducing agent from U.S. 5,312,971)

[0020] Borane-tetrahydrofuran complex (0.011 mole, 0.9 wt. %) was added to PMDA (100 g) and heated at 100°C for 1 hour. Methanol (2 ml) was slowly added to neutralize residual complex, and the solution was heated to 100°C 5 under vacuum to remove low boilers. This PMDA was then phosgenated as shown in Example 1 above.

Table I. Effect of Hydrazine on PMDI Color

10 Product Hydrazine (wt. %) Color Number Example 1 0.0 2.2 Example 2 0.00015 3.5 Example 3 0.06 6.7 15 Example 4 0.45 8.2 Example 5 0.9 8.5 Example 6 2.6 9.1

20 Example 7 0.9 7.1 Example 8 0.45 8.1 Example 9 0.4 4.3 Example 10 0.9 borane-THF 5.3 25 1) Examples 1 - 6 illustrate that color improves with increasing hydrazine concentration. 2) Example 7 illustrates that the color improvement is due to the presence of hydrazine, not from the water as suggested by U.S. Patent No. 4,465,639. 3) Example 8 illustrates that hydrazine can be added to the PMDA/MCB solution immediately prior to phosgenation, rather than to an MDA storage vessel for 24 hr. 30 4) Example 9 illustrates that the hydrazine can be added during the phosgenation. 5) Example 10 illustrates that the preferred reducing agent from U.S. Patent No. 5,312,971 is not as effective as hydrazine. For instance, the molar ratio of Example 10 vs. Example 3 is 5.8, which indicates that the concentration of borane-tetrahydrofuran is much higher. The color number ratio of Example 10 vs. Example 3, however, is 0.79.

35 Therefore, at a much lower concentration, hydrazine hydrate gives better and improved color numbers when com- pared with borane-tetrahydrofuran.

Claims

40 1. In a process for the production of polymethylene polyphenyl polyisocyanates comprising phosgenating the corresponding polyamines in solution in an inert organic solvent, removing excess phosgene, and stripping said solvent, the improvement wherein at least 0.00015 percent by weight of an additive per 100 percent by weight of polyamine are added to said polyamines at any time prior to said stripping step, wherein said additive is hydrazine or a hydrazine derivative. 45

2. The process of Claim 1, wherein said hydrazine derivative is selected from the group consisting of hydrazine hydrate, hydrazine hydrochlorides, hydrazine and its salts, carbohydrazides and carbohydrazide derivatives.

3. The process of Claim 2, wherein said hydrazine derivative is selected from the group consisting of 4-Nitrophenyl- 50 hydrazine, acetyl-hydrazine, acetyl phenyl hydrazine, 1-acetyl-2-phenyl hydrazine, benzoylhydrazine, benzylhydrazine dihydrochloride, 2-bromophenylhydrazine hydrochloride, 3-bromophenylhydrazine, 4-bromophenylhydra- zinehydro-chloride, tert-butylphenylhydrazine, 4-n-butylphenylhydrazine hydrochloride, 4-tert-butylphenylhydrazine hydrochloride, N-a-(chlorobenzoyl)-p-methoxy-phenylhydrazine, 2-chlorophenylhydrazine hydrochloride, 3-chlorophenyl-hydrazine hydrochloride, 4-chlorophenylhydrazine hydrochloride, cyclohexyl methylhydrazine, 55 symdibenzoylhydrazine, 2,3-dichlorophenylhydrazine, 2,4-dichlorophenylhydrazine hydrochloride, 2,3-dichlorophenylhydrazine, 2,5-dichlorophenylhydrazine hydrochloride, 2,6-dichlorophenylhydrazine hydrochloride, 3,4-dichlorophenylhydrazine hydrochloride, 3,5-dichlorophenylhydrazine hydrochloride, 2,4-difluorophenylhydra-

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zine hydrochloride, dihydrazine sulfate, 1,2-dimethylhydrazine dihydrochloride, 1,1-dimethylhydrazine (unsymmetrical), 2,3-dimethylphenylhydrazine hydrochloride, 2,4-dimethylphenylhydrazine hydrochloride, 2,5 dimethylphenylhydrazine hydrochloride, 2,6 dimethylphenylhydrazine hydrochloride, 3,4-dimethylphenylhydrazine hydrochloride, 3,5-dimethylphenylhydrazine hydrochloride, 2,4-dinitrophenylhydrazine,1,1-diphenylhydrazine hydrochlo- 5 ride,(2-ethylphenyl)hydrazine hydrochloride, 4-ethylphenylhydrazine hydrochloride, 2-fluorophenylhydrazine hydrochloride, p-fluorophenyl hydrazine hydrochloride, 4-fluorophenyl hydrazine hydrochloride, anhydrous hydrazine, hydrazine base, hydrazine dihydrobromide, hydrazine dihydrochloride, hydrazine hydrate, hydrazine monoacetate, hydrazine monohydrobromide, hydrazine monohydrochloride, hydrazine mononitrate, hydrazine oxygen scavenger, hydrazine solution, carbohydrazide, 1,5-diphenylcarbazide and 4-phenylsemicarbazide. 10 4. The process of Claim 1, wherein said additive is hydrazine hydrate.

Patentansprüche 15 1. Verfahren zur Herstellung von Polymethylenpolyphenylpolyisocyanaten, das das Phosgenieren der entsprechen- den Polyamine in Lösung in einem inerten organischen Lösungsmittel, das Entfernen des überschüssigen Phos- gens und das Abziehen des Lösungsmittels umfasst, dadurch gekennzeichnet, dass zu einem beliebigen Zeit- punkt vor dem Schritt des Abziehens wenigstens 0,00015 Gew.-% eines Additivs pro 100 Gew.-% Polyamin zu 20 den Polyaminen gegeben werden, wobei es sich bei dem Additiv um Hydrazin oder ein Hydrazinderivat handelt.

2. Verfahren gemäß Anspruch 1, wobei das Hydrazinderivat aus der Gruppe ausgewählt ist, die aus Hydrazinhydrat, Hydrazin-Hydrochloriden, Hydrazin und seinen Salzen, Carbohydraziden und Carbohydrazid-Derivaten besteht.

25 3. Verfahren gemäß Anspruch 2, wobei das Hydrazinderivat aus der Gruppe ausgewählt ist, die aus 4-Nitrophenyl- hydrazin, Acetylhydrazin, Acetylphenylhydrazin, 1-Acetyl-2-phenylhydrazin, Benzoylhydrazin, Benzylhydrazin-Di- hydrochlorid, 2-Bromphenylhydrazin-Hydrochlorid, 3-Bromphenylhydrazin, 4-Bromphenylhydrazin-Hydrochlorid, tert-Butylphenylhydrazin, 4-n-Butylphenylhydrazin-Hydrochlorid, 4-tert-Butylphenylhydrazin-Hydrochlorid, N- α-(Chlorbenzoyl)-p-methoxyphenylhydrazin, 2-Chlorphenylhydrazin-Hydrochlorid, 3-Chlorphenylhydrazin-Hydro- 30 chlorid, 4-Chlorphenylhydrazin-Hydrochlorid, Cyclohexylmethylhydrazin, sym-Dibenzoylhydrazin, 2,3-Dichlorphe- nylhydrazin, 2,4-Dichlorphenylhydra:zin-Hydrochlorid, 2,3-Dichlorphenylhydrazin, 2,5-Dichlorphenylhydrazin-Hy- drochlorid, 2,6-Dichlorphenylhydrazin-Hydrochlorid, 3,4-Dichlorphenylhydrazin-Hydrochlorid, 3,5-Dichlorphenyl- hydrazin-Hydrochlorid, 2,4-Difluorphenylhydrazin-Hydrochlorid, Dihydrazinsulfat, 1,2-Dimethylhydrazin-Dihydro- chlorid, 1,1-Dimethylhydrazin (unsymmetrisch), 2,3-Dimethylphenylhydrazin-Hydrochlorid, 2,4-Dimethylphenylhy- 35 drazin-Hydrochlorid, 2,5-Dimethylphenylhydrazin-Hydrochlorid, 2,6-Dimethylphenylhydrazin-Hydrochlorid, 3,4-Dimethylphenylhydrazin-Hydrochlorid, 3,5-Dimethylphenylhydrazin-Hydrochlorid, 2,4-Dinitrophenylhydrazin, 1,1-Diphenylhydrazin-Hydrochlorid, (2-Ethylphenyl)hydrazin-Hydrochlorid, 4-Ethylphenylhydrazin-Hydrochlorid, 2-Fluorphenylhydrazin-Hydrochlorid, p-Fluorphenylhydrazin-Hydrochlorid, 4-Fluorphenylhydrazin-Hydrochlorid, wasserfreies Hydrazin, Hydrazin-Base, Hydrazin-Dihydrobromid, Hydrazin-Dihydrochlorid, Hydrazinhydrat, Hy- 40 drazinmonoacetat, Hydrazin-Monohydrobromid, Hydrazin-Monohydrochlorid, Hydrazinmononitrat, Hydrazin-Sau- erstofffänger, Hydrazin-Lösung, Carbohydrazid, 1,5-Diphenylcarbazid und 4-Phenylsemicarbazid besteht.

4. Verfahren gemäß Anspruch 1, wobei es sich bei dem Additiv um Hydrazinhydrat handelt.

45 Revendications

1. Dans un procédé de production de polyméthylène polyphényle polyisocyanates comprenant le traitement au phos- gène des polyamines correspondantes en solution dans un solvant organique inerte, l'élimination du phosgène 50 en excès, et l'appauvrissement en ledit solvant, l'amélioration dans laquelle on ajoute au moins 0,00015 pourcent en poids d'un additif pour 100 pourcent en poids de polyamine auxdites polyamines à un quelconque moment avant ladite étape d'appauvrissement, dans lequel ledit additif est de l'hydrazine ou un dérivé d'hydrazine.

2. Procédé suivant la revendication 1, dans lequel ledit dérivé d'hydrazine est sélectionné parmi le groupe comprenant 55 de l'hydrate d'hydrazine, des chlorhydrates d'hydrazine, de l'hydrazine et ses sels, des carbohydrazides et des dérivés de carbohydrazide.

3. Procédé suivant la revendication 2, dans lequel ledit dérivé d'hydrazine est sélectionné parmi le groupe comprenant

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de la 4-nitrophénylhydrazine, de l'acétylhydrazine, de l'acétylphénylhydrazine, de la 1-acétyl-2-phénylhydrazine, de la benzoylhydrazine, du dichlorhydrate de benzylhydrazine, du chlorhydrate de 2-bromophénylhydrazine, de la 3-bromophénylhydrazine, du chlorhydrate de 4-bromophénylhydrazine, de la t-butylphénylhydrazine, du chlorhydrate de 4-n-butylphénylhydrazine, du chlorhydrate de 4-t-butylphénylhydrazine, de la N-a-(chlorobenzoyl)-p- 5 méthoxyphénylhydrazine, du chlorhydrate de 2-chlorophénylhydrazine, du chlorhydrate de 3-chlorophénylhydra- zine, du chlorhydrate de 4-chlorophénylhydrazine, de la cyclohexylméthylhydrazine, de la symdibenzoylhydrazine, de la 2,3-dichlorophénylhydrazine, du chlorhydrate de 2,4-dichlorophénylhydrazine, de la 2,3-dichlorophénylhy- drazine, du chlorhydrate de 2,5-dichlorophénylhydrazine, du chlorhydrate de 2,6-dichlorophénylhydrazine, du chlorhydrate de 3,4-dichlorophénylhydrazine, du chlorhydrate de 3,5-dichlorophénylhydrazine, du chlorhydrate de 10 2,4-difluorophénylhydrazine, du sulfate de dihydrazine, du dichlorhydrate de 1,2-diméthylhydrazine, de la 1,1-di- méthylhydrazine (asymétrique), du chlorhydrate de 2,3-diméthylphénylhydrazine, du chlorhydrate de 2,4-dimé- thylphénylhydrazine, du chlorhydrate de 2,5-diméthylphénylhydrazine, du chlorhydrate de 2,6-diméthylphénylhy- drazine, du chlorhydrate de 3,4-diméthylphénylhydrazine, du chlorhydrate de 3,5-diméthylphénylhydrazine, du 2,4-dinitrophénylhydrazine, du chlorhydrate de 1,1-diphénylhydrazine, du chlorhydrate de (2-éthylphényl)hydra- 15 zine, du chlorhydrate 4-éthylphénylhydrazine, du chlorhydrate de 2-fluorophénylhydrazine du chlorhydrate de p- fluorophénylhydrazine, du chlorhydrate de 4-fluorophénylhydrazine, de l'hydrazine anhydre, de l'hydrazine forme basique, du dibromhydrate d'hydrazine, du dichlorhydrate d'hydrazine, de l'hydrate d'hydrazine, du monoacétate d'hydrazine, du monobromhydrate d'hydrazine, du monochlorhydrate d'hydrazine, du mononitrate d'hydrazine, un piégeur d'oxygène hydrazine, une solution d'hydrazine, du carbohydrazide, du 1,5-diphénylcarbazide et du 4-phé- 20 nylsemicarbazide.

4. Procédé suivant la revendication 1, dans lequel ledit additif est de l'hydrate d'hydrazine.