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(12) United States Patent (10) Patent No.: US 9,127,098 B2 Nesvadba Et Al

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(12) United States Patent (10) Patent No.: US 9,127,098 B2 Nesvadba Et Al US009 127098B2 (12) United States Patent (10) Patent No.: US 9,127,098 B2 Nesvadba et al. (45) Date of Patent: Sep. 8, 2015 (54) O-IMINO-ISO-UREACOMPOUNDS AND (56) References Cited POLYMERIZABLE COMPOSITIONS THEREOF U.S. PATENT DOCUMENTS 2,654,725 A * 10/1953 Price ............................. 526,302 (71) Applicant: BASFSE, Ludwigshafen (DE) 5,166.394 A * 1 1/1992 Breipohl et al. .............. 558,301 2006.0128903 A1 6/2006 Roth et al. (72) Inventors: Peter Nesvadba, Marly (CH); Lucienne 2006/0172080 A1 8, 2006 Wolfetal. Bugnon Folger, Pfeffingen (CH): 2008/O132600 A1 6/2008 Nesvadba et al. Antoine Carroy, Limburgerhof (DE); Marc Faller, Hegenheim (FR); Bruno FOREIGN PATENT DOCUMENTS Spony, Wahlbach (FR) WO O1901.13 11, 2001 WO 2004 081100 9, 2004 (73) Assignee: BASFSE, Ludwigshafen (DE) WO 2006 05104.7 5, 2006 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS past lSo G adjusted under 35 Radau et al . Addition von Oximen an Carbodiimide unter M YW- y yS. Tetrafluorborsaure-Katalyse, Sep. 24, 1971, Arch. Phamarz., 702 707): (21) Appl. No.: 14/135,788 Office Action issued Jan. 9, 2014 in Japanese Patent Application No. 2012-509020 (English translation only). (22) Filed: Dec. 20, 2013 Radau, M. et al., “Addition von Oximen an Carbodiimide unter O O Tetrafluorborsaure-Katalyse'. Archiv Der Pharmazie, vol. 305, pp. (65) Prior Publication Data 702-707, XP-002547647, (1972). Schmidt, E. et al., “Zur Kenntnis Aliphatischer Carbodiimide'. US 2014/O113987 A1 Apr. 24, 2014 Justus Liebigs Annalen Der Chemie, vol. 639, pp. 24-31, XP-002547648, (1961). Related U.S. Application Data International Search Report Issued Aug. 11, 2010 in PCT/EP10/ - - - 056063 filed May 5, 2010. (62) Division of application No. 13/319.244, filed as Office Action issued Dec. 9, 2014, in Russian Patent Application No. application No. PCT/EP2010/056063 on May 5, 2010, 2011 149550/04(074356). now Pat. No. 8,664,288. STN database, registration No. RN408532-87-6, entry date Apr. 29. 2002. (30) Foreign Application Priority Data * cited by examiner May 7, 2009 (EP) ..................................... O91596O4 May 7, 2009 (EP) ..................................... O9159664 Primary Examiner — Ling Choi Assistant Examiner — Jessica E. Whiteley (51) Int. Cl. (74) Attorney, Agent, or Firm — Oblon, McClelland, Of 5.% 3.08: Maier & Neustadt, L.L.P. B29C 7L/04 (2006.01) (57) ABSTRACT A6IL 2/08 (2006.01) - - - A6IL 24/00 (2006.01) The invention relates to the use of O-limino-iso-urea com C08G 6L/04 (2006.01) pounds as Source of radicals to polymerizable compositions CSF I2O/8 (2006.015 comprising these O-imino-iso-urea and to new O-imino-iso C07C 275/70 (2006.01) urea compounds. The O-Imino-isoureas compounds are com CSF 4/00 (2006.01) pounds of the formula (I) C07C 251/58 (2006.01) CSF 8/32 (2006.01) (I) C09D 35/02 (2006.01) R101 R103 (52) U.S. Cl. R Y. CPC ............. C08F 120/18 (2013.01); C07C 251/58 100 (2013.01); C07C 275/70 (2013.01); C08F 4/00 N-O-( (2013.01); C08F8/32 (2013.01); C09D 135/02 N-R104 (2013.01); C07C 2101/14 (2013.01); C07C / " 2101/20 (2013.01) R102 (58) Field of Classification Search CPC ....... C08F 120/18: C08F 8/32: C07C 251/58; wherein CO9D 135/O2 and salts thereof. USPC ................................................. 522/28: 520/1 See application file for complete search history. 6 Claims, No Drawings US 9,127,098 B2 1. 2 O-MINO-ISO-UREACOMPOUNDS AND The object of the invention is the use of O-imino-isoureas POLYMERIZABLE COMPOSITIONS compounds of the general formula (I) as source of radicals, THEREOF particular as polymerization initiators CROSS REFERENCE TO RELATED APPLICATION(S) (I) This application is a divisional of U.S. application Ser. No. 13/319.244, filed on Jan. 13, 2012, which is a 35 U.S.C. S371 national stage patent application of international patent appli 10 cation PCT/EP10/056063, filed on May 5, 2010, the text of which is incorporated by reference, and claims foreign prior ity to EPO 09 159664.3 filed on May 7, 2009 and EPO 09159604.9 filed on May 7, 2009, the entire content of which is incorporated herein by reference. 15 wherein The invention relates to the use of O-limino-iso-urea com n is 1, 2, 3 or 4. pounds as source of radicals in particular as polymerization Roo and Rio are independently H, C is alkyl, initiators, to polymerizable compositions comprising these C-C cycloalkyl, Co-Caryl, C-Cheteroaryl, O-imino-iso-urea and to new O-imino-iso-urea compounds. C7-Cisaralkyl, C-Claheteroaralkyl, cyano, or Roo and Free-radical polymerization belongs to the most important Rio form together with the carbon to which they are polymerization methods. It is used for preparing many com attached a mono or polycyclic C-C carbocyclic or mercially important polymers such as polystyrene, PVC, C-Cls heterocyclic ring; polyacrylates, polymethacrylates, PAN and other polymers. Ro and Ros are independently C-C salkyl, For technical details, reference may be made to the still rel C-C2cycloalkyl, Co-Caryl, Co-Caryl once or more evant standard work G. Odian, Principles of Polymerization, 25 than once Substituted by C-C alkyl, C7-Caralkyl, McGraw-Hill New York 1991. (CH)-Si-; or Free-radical polymerizations are started using initiators. Ro and Rios are C1-Cisalkyl, Ca-Cacycloalkyl, Examples of initiators which have become established in Co-Caryl, C7-Cisaralkyl or Ro and Ros are polymer technology are azo compounds, dialkyl peroxides, C-C salkyl, C-C cycloalkyl which are interrupted or diacyl peroxides, hydroperoxides, thermolabile C C 30 substituted by O or by N containing groups selected dimers, redox systems and photoinitiators. Reference is made from C-C salkylamino, bis(C-C salkyl)amino or tris to the “Handbook of Free Radical Initiators', (E.T. Denisov, (C-C alkyl)ammonium; T. G. Denisova, T. S. Pokidova, J. Wiley & Sons, Inc. Hobo Roa if n is 1 is H. C-C alkyl, C-Cacycloalkyl, ken, N.J., 2003). C7-Caralkyl, Co-Caryl or acyl selected from the group Despite their widespread use, the known polymerization 35 consisting of the following acyls initiators have various disadvantages. Thus, for example, per —C(=O)—H. —C(=O)—C-C salkyl, -C(=O)—C- oxides are extremely readily ignitable and Sustain fire and Cisalkenyl, —C(=O)—C-Caryl, —C(=O)—C- present thus potential explosion hazards, so that their manu Cisalkenyl-C-Caryl. —C(=O)—O-C-Cisalkyl, facture, storage, transport and use has to involve costly safety —C(=O)—O—C-Caryl, —C(=O) NH C precautions. Some initiators further generate toxic products, 40 Cisalkyl, —C(=O) NH-C-Caryl and as e.g. AIBN. —C(=O)—N(C-C salkyl); or There is therefore a general need for new initiators for Ro and Roa if n is 1 form together with the nitrogenatom to free-radical polymerization processes which have a satisfac which they are attached a 5 to 12 membered ring which my tory safety profile. contain additional heteroatoms, M. Radau and K. Hartke describe in “Archiv der Pharma 45 Roa if n is more than 1 is di-, tri-, tetra-C-Cisalkylidene, zie' Vol. 305, 1972, pages 702-707 the addition of oximes to diacyls, triacyls or tetraacyls carbodiimide. The use as polymerization initiator is not and salts thereof. described. Examples of Such rings Ro-Roa are: pyrrolidine, piperi Erich Schmidt etal describe in “Justus Liebigs Annalender dine, morpholine, piperazine, N-methyl-piperazine, hexam Chemie' Vol. 639, 1961, pages 24-31 O-imino-isourea com 50 ethyleneimine. pounds prepared by reacting methyl tert. butyl-carbodiimide The structure of (I) can be such (e.g. dimeric, trimeric, or diisopropyl carbodiimide with methylisopropylketoxim. oligomeric or polymeric) that the molecule (I) contains the The use as polymerization initiator is not described. isourea fragment more than once, for example 2 to 10 times. WO 2001/901 13 and WO 2004/081100 describe sterically Preferred is a monomeric structure (n is 1); a dimeric hindered N-acyloxyamines as a new class of polymerization 55 structure (n=2), or a trimeric structure n=3. initiators. The compounds (I) are Suitable as polymerization initiators Further new polymerization initiators N-substituted imides of free radical polymerization, particularly for use in poly are described in WO 2006/051047 O-dialkylamino-isoureas merization processes to prepare coatings. Thermal curing and PCT/EP200906794 (filed Dec. 28, 2009) and aryltriaZenes dual curing processes are encompassed, especially those in EP 09 156625.7 (filed Mar. 30, 2009). 60 which the second curing process is triggered by electromag We have now discovered that O-limino-isoureas available netic or actinic radiation, for example by light, near infrared for example via reaction of carbodiimides with oximes are radiation or electron beam. very efficient initiators of free radical polymerization or of Furthermore, these compounds (I) are suitable for other other processes which are triggered off by free radicals, for processes which are triggered off by free radicals, for example controlled degradation of polyolefines or for 65 example, controlled degradation of polyolefines. crosslinking processes. Furthermore, many of these O-limino Furthermore these compounds (I) are suitable for isoureas are novel compounds. crosslinking unsaturated polymer resins. US 9,127,098 B2 3 4 The crosslinking process comprises heating the unsatur Non limiting examples of the resulting cycloalkylidenes ated polymer resin together with the compounds (I). RoRoC— are: 3-azacyclopentylidene, 3-oxacyclopentyl The term polymer encompasses oligomers, cooligomers, idene, 2-methyl-3-oxacyclopentylidene, 4-azacyclohexy polymers and copolymers, for example, random block, multi lidene, 3,3,5,5-tetramethyl-4-azacyclohexylidene, 4-thiacy block, Star or gradient copolymers.
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