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(12) United States Patent (10) Patent No.: US 8,058,382 B2 Richter Et Al

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(12) United States Patent (10) Patent No.: US 8,058,382 B2 Richter Et Al USOO8058382B2 (12) United States Patent (10) Patent No.: US 8,058,382 B2 Richter et al. (45) Date of Patent: Nov. 15, 2011 (54) URETDIONE FORMATION IN SOLUTION (56) References Cited (75) Inventors: Frank Richter, Leverkusen (DE); U.S. PATENT DOCUMENTS Hans-Josef Laas, Odenthal (DE); 3,496,234. A 2, 1970 van Leeuwen .................... 568/9 Reinhard Halpaap, Odenthal (DE): 4476,054 A 10, 1984 Disteldorf et al. 260,239 A 4,912,210 A 3, 1990 Disteldorf et al. ... 540,202 Andreas Hecking, Langenfeld (DE) 4,929,724. A 5/1990 Engbert et al. ..... ... 540,202 2002/002893.0 A1 3/2002 Laas et al. ...... ... 540,202 (73) Assignee: Bayer MaterialScience AG, Leverkusen 2004/0049028 A1 3/2004 Laas et al. ... ... 540,202 (DE) 2004/0059082 A1 3/2004 Laas et al. ....................... 528.65 2004/0106789 A1 6/2004 Richter et al. ................ 540,202 ( c ) Notice: Subject tO any distic the t FOREIGN PATENT DOCUMENTS patent 1s extended or adjusted under EP O 780377 A1 6, 1997 U.S.C. 154(b) by 1441 days. GB 1153815 5, 1969 JP 11-228524 8, 1999 (21) Appl. No.: 11/333,575 OTHER PUBLICATIONS (22) Filed: Jan. 17, 2006 Database WPI Section Ch, Week 199944 Derwent Publication Ltd., London, GB: AN 1999-522662 XP002382268 & JP 11 228524 A (65) Prior Publication Data (Nippon Polyurethane Kogyo KK) Aug. 24, 1999. US 2006/O173152 A1 Aug. 3, 2006 Laas H J et al: “Zur Synthese Aliphatischer Polyisocyanate— Lackpolyisocyanate Mit Biuret-, Isocyanurat-Oder Uretdionstruktur the Synthesis of Aliphatic Polyisocyanates Containing Biuret, (30) Foreign Application Priority Data Isocyanurate or Uretdione Backbones for Use in Coatings' Jan. 1994, Journal Fur Praktische Chemie, Chemiker Zeitung, Wiley VCH, Jan. 21, 2005 (DE) ......................... 102005 002867 Weinheim, DE, pp. 185-200, XP000441642. (51) Int. Cl. * cited by examiner O 18, 388 Primary Examiner — Rabon Sergent CD7C 263/6 (2006.01) (74) Attorney, Agent, or Firm — Connolly Bove Lodge & CD7C 265/00 (2006.01) Huitz LLP C07D 229/00 (2006.01) (57) ABSTRACT (52) U.S. Cl. ......... 528/73; 252/1822:528/45; 540/202; 548/951 : 548/952: 5607330: 5607336 The invention relates to a process for preparing polyisocyan (58) Field of Classification search s s 528/45 ates having a high uretdione group content by phosphine catalysed isocyanate oligomerization in the presence of 528/73; 540/202: 548/951, 952 655. organic carbonates and/or nitriles. See application file for complete search history. 11 Claims, 2 Drawing Sheets U.S. Patent Sheet 1 of 2 US 8,058,382 B2 N S. N U U.S. Patent US 8,058,382 B2 N S. 'N U US 8,058,382 B2 1. 2 URETOONE FORMATION IN SOLUTION done, NMP, Hildebrand parameter 11.3 cal' cm'). Con sequently, a person skilled in the art cannot derive any general CROSS-REFERENCE TO RELATED teaching as to which solvents are reliably suitable for increas APPLICATION ing the uretdione selectivity and reducing by-product forma tion and which are not from JP 11228524. This application claims priority under 35 U.S.C. S 119 (a)- In addition, numerous publications disclose carrying out (d) to German application DE 10 2005 002867, filed Jan. 21, isocyanate oligomerizations in the presence of solvents in 2005. general terms without, however, naming individual com pounds and/or specifically indicating compounds which lead FIELD OF THE INVENTION 10 to an improvement in the uretdione selectivity and a reduction in by-product formation. This invention relates to a process for preparing polyiso It has now been found that the paired use of phosphines and cyanates having a high uretdione group content by phos organic carbonates and/or organic nitriles as catalyst system phine-catalysed isocyanate oligomerization in the presence has a particularly advantageous effect on the selectivity of of organic carbonates or nitriles. 15 uretdione formation. BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION Aliphatic isocyanates having uretdione groups are valuable The invention therefore provides for the use of organic raw materials for, interalia, producing polyurethane coatings. carbonates and/or organic nitriles in the phosphine-catalysed Products based on optionally branched, linear-aliphatic diiso oligomerization of monoisocyanates and/or polyisocyanates cyanates have a particularly low viscosity. Products based on to form uretdiones in order to achieve an increase in selectiv cycloaliphatic diisocyanates are generally highly viscous to ity in the oligomerization. Solid Substances which can be used as elimination product The invention further provides a process for preparing free, internally blocked crosslinkers in coating systems. A 25 polyisocyanates containing uretdione groups, in which poly summary is provided in J. Prakt. Chem./Chem. Ztg. 1994, isocyanates are oligomerized in the presence of a catalyst 336, 185-200. system comprising phosphines and organic carbonates and/or Tris(dialkylamino)phosphines (DE-A3 030513), if appro organic nitriles. priate in combination with cocatalysts (DE-A 3 437 635), display good selectivity for the formation ofuretdione groups 30 BRIEF DESCRIPTION OF THE DRAWINGS (uretdione selectivity). However, the serious problem of the high carcinogenic potential of their phosphorus oxides, e.g. The invention is further illustrated by the following non hexamethylphosphoramide, stands in the way of their indus limiting drawings in which: trial use. FIG. 1 is a calibration curve as described in Example 1; and DE-A3739549 discloses the catalytic NCO dimerization 35 FIG. 2 is a graph showing the relationship between uretdi using 4-dialkylamino-pyridines, e.g. 4-dimethylaminopyri one structures and trimer structures. dine (DMAP), although uretdione formation proceeds selec tively only in the case of specific cycloaliphatic isocyanates DETAILED DESCRIPTION OF PREFERRED Such as isophorone diisocyanate (IPDI). Linear-aliphatic iso EMBODIMENTS cyanates Such as hexamethylene diisocyanate (HDI) and also 40 branched, linear-aliphatic isocyanates such as trimethylhex As used herein in all sections of this document, including ane diisocyanate (TMDI) and methylpentane diisocyanate as used in the examples and unless otherwise expressly speci (MPDI) give mainly strongly coloured, heterogeneous reac fied, all numbers may be read as if prefaced by the word tion products when DMAP and related compounds are used. "about’, even if the term does not expressly appear. Also, any DE-A 1 670 720 discloses the preparation of aliphatic 45 numerical range recited herein is intended to include all Sub polyisocyanates having uretdione groups, with tertiary phos ranges Subsumed therein. phines having at least one aliphatic Substituent and also boron As polyisocyanates, it is possible to use all aliphatic, trifluoride and its adducts being used as catalysts. The uret cycloaliphatic and/or araliphatic polyisocyanates having an dione selectivity here is temperature-dependent, and appre NCO functionality of preferably 22 which are known perse ciable amounts of Viscosity-increasing isocyanate trimers 50 to those skilled in the art. It is unimportant whether these have (isocyanurates and iminooxadiazinediones) and, particularly been prepared by means of phosgene or by phosgene-free at temperatures of >80° C., other undesirable by-products processes. If desired, Small amounts of monoisocyanates can Such as carbodiimides or uretonimines are always formed. also be used concomitantly, but this is not preferred. One way of increasing the uretdione selectivity and Preference is given to using aliphatic and/or cycloaliphatic decreasing the by-product formation is the use of specific, 55 polyisocyanates, either individually or in any mixtures with bulky phosphines having P-bonded cycloalkyl groups (EP-A one another. 1 422 223, unpublished German Patent Application DE Examples of suitable polyisocyanates are the isomeric pen 10354544). The fact that the uretdione selectivity for a given tane diisocyanates, hexane diisocyanates, heptane diisocyan phosphine catalyst can be improved by addition of additives ates, octane diisocyanates, nonane diisocyanates, decane or solvents has been examined in JP 11228524. According to 60 diisocyanates, undecane diisocyanates and dodecane diisocy this, nonaromatic solvents having a Hildebrand solubility anates and also isophorone diisocyanate (IPDI), bis(isocy parameter of greater than 7 cal' cm' are suitable for pre anatocyclohexyl)-methane (HMDI), bis(isocyanatom paring polyisocyanates rich in uretdione groups in the pres ethyl)benzene (xylylene diisocyanate, XDI) and bis(2- ence of phosphine catalysts. However, as has been able to be isocyanatoprop-2-yl)benzene (tetramethylxylylene shown in the examples of the present patent application, this 65 diisocyanate, TMXDI). is not always reliably the case (cf. chloroform; Hildebrand Particular preference is given to using hexamethylene parameter 9.3 cal' cm, compared to N-methylpyrroli diisocyanate (HDI), methylpentane diisocyanate (MPDI), tri US 8,058,382 B2 3 4 methylhexane diisocyanate (TMDI), bis(isocyanatomethyl) hept-3-yl)phosphine, methylbis(2,6,6-trimethylbicyclo cyclohexane (HXDI) and norbornane diisocyanate (NBDI), 3.1.1 hept-3-yl)phosphine, ethylbis(2,6,6-trimethylbicyclo either individually or in any mixtures with one another, as 3.1.1 hept-3-yl)phosphine, propylbis(2,6,6-trimethyl-bicy polyisocyanates. clo3.1.1 hept-3-yl)phosphine, butylbis(2,6,6- Of course, the higher molecular weight NCO-functional trimethylbicyclo[3.1.1 hept-3-yl)phosphine, hexylbis(2,6,6- reaction products based on the abovementioned polyisocyan trimethylbicyclo3.1.1 ept-3-yl)phosphine and octylbis(2,6, ates and containing isocyanurate, uretdione, iminooxadiaZin 6-trimethylbicyclo[3.1.1]hept-3-yl)phosphine. etrione, urethane, allophanate and/or biuret structures can These can be used either individually, in any mixtures with also be used as polyisocyanates in the process of the inven one another or in mixtures with other primary, secondary tion. 10 and/or tertiary alkyl phosphines, aralkyl phosphines and/or As phosphines, use is made of tertiary phosphines having aryl phosphines as catalyst for uretdione formation. alkyl and/oraryl groups as Substituents, with these also being The amount of the catalyst to be used in the process of the able to be substituted.
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