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 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. clohexylidene, 4-oxacyclohexylidene, Definition of the Radicals The term “di, tri, or tetra C-C alkylidene' (when n is The residue alk’ or cycloalk is used in combination with greater than 1) refers to a straight or branched carbon chain standard IUPAC terminology. that may be fully saturated or have one or more units of alkene' is standing for residues comprising one or more unsaturation and has two points, three points or four points of double bonds as well as optionally single bonds however 10 attachment to the rest of the molecule. excluding aromatic residues and 'alkine standing for resi The term “diacyl, means having two carbonyl or thiocar dues comprising one or more triple bonds as well as option bonyl groups bonded to a radical selected from, for example, ally single and/or double bonds, the maximal number of alkylene, alkenylene, alkynylene, haloalkylene, alkoxyalky double and triple bonds in said residue alkene' or 'alkine 15 lene, aryl, heterocyclyl, heteroaryl, aralkyl, cycloalkyl, being totally no more than one half of the number of C atoms cycloalkylalkyl, and cycloalkenyl. Examples of “diacyl are in said residue alkene' or 'alkine'. phthaloyl, terephthaloyl, isophthaloyl, malonyl, Succinyl, C-C salkyl in the compound of formula I is, for example, adipoyl, and the like. C-Calkyl, e.g. methyl, ethyl, n-propyl or isopropyl or n-, Examples of “triacyl are residues derived from sec- or tert-butyl or straight-chain or branched pentyl or or from trimesic acid. hexyl, or C7-Coalkyl, e.g. straight-chain or branched heptyl, Examples of “tetracyls' are residues derived from naph octyl, isooctyl, nonyl, tert-nonyl, decylor undecyl, n-tridecyl thaleneteteacarboxylic acid, benzophenone-tetracarboxylic n-tetradecyl, n-hexadecyl or n-octadecyl. acid. The C-C salkyls and C-C cycloalkyls in the groups Salts of the O-limino-isoureas are for example HBF, per Ro-Roa of compound of formula I may also be substituted 25 chlorate, hydrochloride, Sulfate, hydrogensulfate, alkylsul by Suitable Substituents, e.g. C-C alkoxy, or halogen, e.g. fonate, arylsulfonate or carboxylate salts. chlorine or fluorine In one embodiment n is 1 resulting in the use of O-Imino C-C salkenyl is for example ethenyl, propenyl, butenyl, isoureas compounds of the general formula (I) as source of pentenyl, hexenyl, heptenyl, octenyl, dodecenyl and the like radicals including their isomers. 30 C-C-Aryl, C7-Caralkyl, C-Cheteroaryl and C-Cheteroaralkyl can be mono- or polycyclic, condensed (I) or conjugated, or two or more aromatic or heteroaromatic groups may be bridged with an alkylene group. Co-CalAryl, C7-Caralkyl, C-Cheteroaryl or C-Cheteroaralkyl are 35 for example phenyl, benzyl, naphthyl, indyl, indenyl, fluore nyl, acenaphthyl, biphenylyl, anthracyl, o-, m- orp-terphenyl. Co-Caryl is, for example, carbocyclic monoaryl or diaryl, preferably monoaryl, e.g. phenyl, which may be monosubsti tuted or disubstituted by suitable substituents, e.g. 40 C-C alkyl, e.g. methyl, ethyl or tert-butyl, C-C alkoxy, e.g. methoxy or ethoxy, or halogen, e.g. chlorine. In the case of disubstitution, the 2- and 6-positions are preferred. Co-Caryl once or more than once Substituted by wherein C-C salkyl is for example phenyl once or twice Substituted 45 Roo and Ro are independently H, C is alkyl, by C-C salkyl, especially twice Substituted, for example 2.6 C-C cycloalkyl, Co-Caryl, C-Cheteroaryl, diisopropylphenyl. C7-Cisaralkyl, C-Claheteroaralkyl, cyano, or Roo and C7-Coaralkyl is for example benzyl, phenylpropyl, O.C.- Rio form together with the carbon to which they are dimethylbenzyl or C.-methylbenzyl. attached a mono or polycyclic C-Cs carbocyclic or C-C salkyl interrupted by at least one O atom is for 50 C-Cls heterocyclic ring; example —CH2—CH2—O—CH2—CH, —CH2—CH2 Ro and Ros are independently C-C salkyl, O—CH or —CH2—CH2—O CH, CH, CH, O C-C2cycloalkyl, Co-Caryl, Co-Caryl once or more CH, CH. It is preferably derived from polyethylene gly than once Substituted by C-C alkyl, C7-Caralkyl, col. A general description is —((CH), O), H/CH, (CH)-Si-; or whereina is a number from 1 to 6 and b is a number from 2 to 55 Ro and Rios are C1-Cisalkyl, C-Cacycloalkyl, 10. Co-Caryl, C7-Cisaralkyl or Roo and Rio form together with the carbon to which they Ro and Rios are C-Cisalkyl, Cs-C12cycloalkyl which are attached a mono or polycyclic C3-C18 carboxylic ring. are interrupted or substituted by O or by N containing Non limiting examples of the resulting cycloalkylidenes groups selected from C-C salkylamino, bis(C- RoRoC— are cyclobutylidene, cyclopentylidene, cyclo 60 Cisalkyl)amino or tris(C-C alkyl)ammonium; hexylidene, cycloheptylidene, cyclooctylidene, Roa is H. C-Cacycloalkyl, C7-Caralkyl, Co-Caryl or cyclononylidene, cyclodecylidene, cycloundecylidene, acyl selected from the group consisting of the following cyclododecylidene, 4-methylcyclohexylidene, 3.3.5.5-tet acyls ramethylcyclohexylidene, 3,3,5-trimethylcyclohexylidene, —C(=O)—H. —C(=O)—C-C salkyl, -C(=O)—C- 2,3-benzocyclohexylidene, 3,4-benzocyclohexylidene. 65 Cisalkenyl, —C(=O)—C-Caryl, Roo and Rio form together with the carbon to which they —C(=O)—C-C salkenyl-C-Caryl, —C(=O)—O— are attached a mono or polycyclic or C-Cls heterocyclic ring. C-C salkyl, —C(=O)—O—C-Caryl, US 9,127,098 B2 5 6 —C(=O)—NH C-C alkyl, —C(=O)—NH C- Novel O-Imino-isourea compounds Caryl and —C(=O)—N(C-C alkyl); or The invention further relates to novel O-limino-isoureas of Ro and Rio form together with the nitrogen atom to which the formula I they are attached a 5 to 12 membered ring which my contain additional heteroatoms; 5 i and salts thereof. R101 R103 (I) Preferences v In one embodiment n of formula I is 1. R100 N In one embodiment n of formula I is greater than 1. N-O-( A preferred embodiment of the invention provides the use 10 N-Rod of compounds of the formula I wherein n is 1, as source of radicals, and wherein Roo and Rio are independently H, C is alkyl, wherein Cs-Cacycloalkyl, Co-Caryl, C-Claheteroaryl, is n is 1, 2, 3 or 4, C7-Caralkyl, or Roo and Rio form together with the Roo, Rio, Rio, Rios and Rio are as defined above, carbon to which they are attached a C-C carbocyclic and salts thereof; ring: with the proviso that the following compounds are excluded Ro and Rios are independently C1-C alkyl, Cs-C12cycloalkyl, Co-Caryl, Co-Caryl once or more 20 than once substituted by C-C alkyl, C7-Caralkyl: Ro is H. C-C salkyl, Cs-C12cycloalkyl, C7-Caralkyl, Co-Caryl or acyl selected from the group consisting of the following acyls —C(=O)—H. —C(=O)—C-C alkyl, —C(=O)—C- 25 Calkenyl, -C(=O)—C-Caryl; or H Ro and Rio form together with the nitrogen atom to which O they are attached a 5 to 6 membered ring: 1s Another preferred embodiment of the invention provides 30 HN -O) and the use of compounds of the formula I wherein n is 1, as Source of radicals, and wherein Roo and Ro are independently Cls alkyl, Cs-Cacycloalkyl, Co-Caryl, C-Cheteroaryl, C7-Caralkyl or Roo and Rio form together with the carbon to which they are attached a C-C carbocyclic 35 ring: Ro and Ros are independently C-C alkyl, cyclohexyl, OH C-Caryl; Co-Caryl once or more than once substituted bVy C-C calkVl:alkyl; 40 H N H Ro is H. C-C salkyl, Cs-Cacycloalkyl, —C(=O)—C- Calkyl, or Ro and Rio form together with the nitrogen O O atom to which they are attached a 5 to 6 membered ring, 1. and salts thereof { Exemplified is the use of O-limino-isoureas compounds of 45 I N-C(CH3) and HN N and the general formula (I) as source of radicals wherein C(CH3)3 Roo and Rio are independently C-1s alkyl, phenyl or Roo -N and Rio form together with the carbon to which they are isopropyl isopropyl attached a C-C cycloalkyl ring. 1. Roz and Rios are independently C1-C alkyl, C5-C1. " N CH3 N isopropyl cycloalkyl, Co-Caryl; Co-Caryl once or more than once substituted by C-Calkyl: h O Ro is hydrogen or —C(=O)—C-C alkyl. 1. 1. and salts thereof. 55 HN -(- and HN -(- and In one embodiment the invention provides the use of com CH3 CH3 pounds of formula I whereinn is 2, 3 or 4 as source of radicals, methyl and wherein Roo and Rio are independently C-1s alkyl, phenyl or Roo and Rio form together with the carbon to which they are 60 N isopropyl attached a C-C cycloalkyl ring. O Ro and Rios are independently C1-Calkyl, Cs-C2 cycloalkyl, C-Caryl; Co-Caryl once or more than once substituted by C-Calkyl: I N-isopropyl Ro is di-, tri-, tetra-C-Cisalkylidene, diacyls, triacyls or 65 isopropyl tetraacyls, and salts thereof US 9,127,098 B2 7 8 and the following O-Imino-isoureas derived from Ketoximes -continued NHB-t

N-O-CEN-B-t NHMe Me-C N=C-O-N=CMe -ve Me Me-C-Me -o-c-s-?-s and HBF4 salt Me NHMe Me 10 ? ).

N-O-CEN-C-Me M--

Me-C-CH-Me Me k

NHMe Me 15 N-O-CEN-C-Me Me Me-C-CH2-Et Me NHMe Me --vi Me Me Me N-O-CEN-C-Me N=C-O-N=C-CH2-C And HBF salt Me-CH-C-CH-Me Me M-- Me k MeC=N-O Me 25 N=C-NH-CH-Me And picrate salt MeC=N-O Me Me-CH-Me Me N=C-NH-C-Me And HBF salt 30 Me-CH-NH Me Me-C - Me Me

N-O-CEN-CH-Me Me Me-C-CH-Me 35 Me Concerning the novel compounds the compounds described by M. Radau and K. Hartke in Archiv der Phar Me-CH-NH Me mazie' Vol. 305, 1972, pages 702-707 and described by Erich Schmidt et al. in “Justus Liebigs Annalen der Chemie' Vol. N-O-CEN-CH-Me 639, 1961, pages 24-31 are disclaimed. 40 Me-C-CH-Et In one embodiment the invention further relates to novel Me O-limino-isoureas of the formula I" wherein n is 1

Me HCH-NH Me (I) N-O-CEN-CH-Me 45 R100 Me-CH-C-CH-Me 4. Me N R101 O Me-CH-NH Me 50 Me C=N-C-Me and HBF salt R102 1s N1 R103 Me R 104

55 Roo, Rio, Rio, Rios and Rio are as defined above, and y salts thereof; Me-C-NH with the proviso that the compounds listed above are Me excluded Me 60 Preferred novel O-imino-isoureas of the formula (I) cor N-O-C=N-C-Me And HBF salt respond to those preferred compounds of the formula (I) t-st Me listed above. Preparation of the Inventive Compounds (I) or (I) 65 The compounds (I) with Roa-H are conveniently pre pared via addition of aldoximes or ketoximes (II) to carbodi imides (III) according to the equation: US 9,127,098 B2

R100 R100 1. R101 + Rio-N=C=N-Rio - es R101 R101 OH (III) O O (II) R102 1. R103 R102n 1. - R103 1. N1 R104-X N R101 10 H R 104 O (I, R104 = H) (I, R104 not H) R102 1s R103 N1 The Suitable alkylation agents Rio X are well known 15 and comprise e.g. alkyl-, cycloalkyl- or aralkyl halides, Sul R 104 fonates, triflates or trialkyloxonium salts. The group Roa can be introduced also via Michael addi tion of compounds I (Ra-H) to a suitable activated Roo. Rio, Rio and Rios are as defined above. Michael acceptors such are e.g. acrylonitrile or alkyl acry Additions of this type are described in the literature, e.g. by lates. E. Schmidt, W. Carl. Liebigs. Ann. Chem. 24, (639), 1961. The suitable acylation agents Roa X are well known and The addition can be conveniently performed by stirring the comprise e.g. acyl halides or acyl anhydrides. Yet another Solution of (II) and (III) in an appropriate solvent Such as for possibility is the reaction of compounds I (Ro-H) with example ethyl acetate, , dichloromethane, acetoni 25 isocyanates. trile, tetrahydrofurane, hexane and the like. The reaction tem The alkylation or acylation of compound (I, Ro-H) is perature can be room temperature (rt) or below, say -78°C., optionally conducted in the presence of a base to neutralize or above, say rt to 150° C. the liberated acid H. X. Example of suitable bases are alkali Admixture of catalysts, for example Broensted acids such hydroxides or alkali carbonates or Such as triethy as HCl, p-TsOH, HBF or HSO or Lewis acids such as for 30 lamine or pyridine. example BF or Cu(OSCF) or bases, e.g. alkali metal Yet another possibility for synthesis of compounds (I) con hydroxides, alkoxides, amides or hydrides or amines such as sists of reacting the oximes (II) with trisubstituted forma e.g. triethylamine or DABCO or of amidines such as e.g. midines (IV). DBU or DBN may help improve the speed and yield of the addition of (II) to (Ill). Working under conditions of phase 35 transfer catalysis is an another option. Y R100 The oXimes (II) and their preparation, for example via reaction of carbonyl compounds with hydroxylamine, is well *s-s-s -- 4. R101 known and does not need to be discussed. Moreover, many of them are commercially available 40 R104 OH Also many carbodiimides (III) are commercially available, (IV) (II) R100 C.2. N,N'-Dicyclohexylcarbodiimide 1,3-Diisopropylcarbodiimide Bis-(o-tolyl)-carbodiimide 45 's R101 Bis-(p-tolyl)-carbodiimide O Bis-(2,6-diisopropylphenyl)-carbodiimide R102 1s R103 Bis-(trimethylsilyl)-carbodiimide s N1 1-sec-Butyl-3-ethyl carbodiimide 50 N-Cyclohexyl-N'-[4-(dimethylamino)-O-naphthyl-carbodi R104 (I, R104 not H) 1-Cyclohexyl-3-(2-morpholinoethyl)-carbodiimide 1,3-Di-tert-butyl carbodiimide Y=Halogen, S-Alkyl, O-Alkyl 1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide 55 1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide methio The formamidines (IV) are known compounds and are dide readily prepared from the corresponding trisubstituted ureas Bis-(2,4,6-triisopropylbenzene)-carbodiimide or thioureas. For example the preparation of chloroforma The carbodiimides Ill may be also of oligomeric or poly midines (IV.Y—Cl) is described by R. Appel, K. D. Ziehn, K. meric. 60 Warning.: Chemische Berichte 2093, 106(7), 1973. Methods for preparation of carbodiimides bearing another The alkylthioformamidines (IV. Y—S-Alkyl) are readily substituents are well-known and described for example in: obtained from trisubstituted thioureas as described by. e.g. Henri Ulrich, “Chemistry and technology of carbodiimides'. Lecher & Graf.: Chemische Berichte 1328, 56, 1923. Wiley 2007. Compounds of the formula (I) or (I) wherein n is greater The compounds (I) where Roa is not H are conveniently 65 than 1 are prepared by reacting a compound of formula (I) prepared via alkylation or acylation of compounds (I) with wherein n is 1 and Roa is hydrogen with a di-, or tri-, or tetra Roa-H; carboxylic acid. US 9,127,098 B2 11 12 Use Definition of the Ethylenically Unsaturated Compound: These compounds are suitable as polymerization initiators, The general radical-polymerizable compound is selected particularly for use in polymerization processes, since they from known radical-polymerizable compounds having at allow the formation of particularly pure polymers and copoly least one ethylenically unsaturated double bond. Included are mers. The compounds are also suitable as polymerisation 5 monomers, prepolymers, oligomers, a mixture thereof or a Initiators in dual cure processes where they are used in com copolymer thereof. bination with photoinitiators. Non-limiting examples of Such monomers include: ethyl The term polymer encompasses oligomers, cooligomers, enically unsaturated polymerizable monomers selected from polymers and copolymers, for example random block, multi the group consisting of alkenes, conjugated , styrenes, 10 acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, block, Star or gradient copolymers. maleic anhydride, acrylic acid, acrylic acid derivatives, vinyl A further advantageous property of the novel compounds halides and vinylidene halides. in process technology is their suit-ability as additives in pro Examples of alkenes and conjugated alkenes are ethylene, cesses for lowering the molecular weight of polymers, in isoprene, 1,3-butadiene and C-C-Cisalkenes. particular polypropylenes, and in processes for achieving a 15 Suitable styrenes may be substituted on the phenyl group controlled increase in the molecular weight in particular in by from one to three substituents selected from the group crosslinking of polyethylene. consisting of hydroxy, C-C alkoxy, e.g. methoxy or ethoxy, Composition halogen, e.g. chlorine, amino and C-C alkyl, e.g. methyl or The compounds of formula I or I" are present as polymer ethyl. ization auxiliaries or polymerization initiators in polymeriZ Unsaturated carboxylic acids such as (meth)acrylic acid, able compositions which comprise at least one ethylenically crotonic acid, (methylene Succinic acid), maleic unsaturated, polymerizable monomer or oligomer. acid, or fumaric acid and salts, esters and amides thereof. The polymerization process initiated by the O-imino Also mentioned are unsaturated fatty acids such as lino isoureas can be triggered by different stimuli, for example by lenic acid and oleic acid. Acrylic and methacrylic acid are heat but also by electromagnetic radiation Such as X-ray, 25 preferred. ultraviolet, visible or infrared light or by actinic radiation It is also possible, however, to use saturated di- or poly Such as for example B-radiation (electron beam). carboxylic acids in admixture with unsaturated carboxylic Preferably a coating is prepared. acids. Examples of Suitable Saturated di- or poly-carboxylic The invention therefore further provides a composition acids include, for example, malonic acid, Succinic acid, glu comprising 30 taric acid, adipic acid, sebacic acid, 1,4-cyclohexane dicar A) at least one ethylenically unsaturated, polymerizable boxylic acid, tetrachlorophthalic acid, tetrabromophthalic monomer or oligomer; and acid, phthalic anhydride, tetrahydrophthalic acid, isophthalic B) at least one compound of the formula I or I", acid, terepthalic acid, trimelitic acid, heptane-dicarboxylic C) optionally a photoinitiator. acid, dodecanedicarboxylic acid, hexahydrophthalic acid, In one embodiment the photoinitiator is present. Any 35 etc. known photoinitiator can be used. Examples can be found e.g. Esters of the above mentioned unsaturated acids are e.g. in Crivello J. V., Dietliker K. K., (1999): Chemistry & Tech alkyl esters such as methyl, ethyl, 2-chloroethyl, N-dimethy nology of UV & EB Formulation for Coatings, Inks & Paints, laminoethyl, n-butyl, isobutyl-, pentyl, hexyl, cyclohexyl, and in Bradley G. (ed.) Vol. 3: Photoinitiators for Free Radical 2-ethylhexyl, octyl, isobornyl 2-exobornyl esters; or phenyl, and Cationic Polymerisation 2nd Edition, John Wiley & Son 40 benzyl or o-, m- and p-hydroxyphenyl esters; or hydroxy Ltd. Such compounds and derivatives are derived, for alkyl esters e.g. 2-hydroxyethyl, 2-hydroxypropyl, 4-hy example, from the following classes of compounds: ben droxybutyl, 3,4-dihydroxy-butyl or glycerol 1,2,3-propan Zoins, benzil ketals, benzophenones, acetophenones, etriolesters, or epoxy alkyl esters e.g. glycidyl, 2,3-epoxy hydroxyalkylphenones, aminoalkylphenones, acylphosphine butyl, 3,4-epoxy butyl, 2,3-epoxycyclohexyl, 10.11 oxides, bisacylphosphine oxides, acylphosphine Sulfides, 45 epoxyundecyl esters, oramino alkyl or mercapto alkyl esters, bisacylphosphine Sulfides acyloxyiminoketones, alky or esters as described below. lamino-Substituted ketones, such as Michler's ketone, peroxy Amides of the above mentioned unsaturated acids are e.g. compounds, dinitrile compounds, halogenated acetophe (meth)acryl amides, N-Substituted (meth)acryl amides, e.g. nones, phenylglyoxylates, dimeric phenylglyoxalates, ben N-methylolacrylamide, N-methylolmethacrylamide, N-ethy Zophenones, oximes and oxime esters, thioxanthones, cou 50 lacryamide, N-ethylmethacrylamide, N-hexylacrylamide, marins, ferrocenes, titanocenes, onium salts, Sulfonium salts, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclo iodonium salts, diazonium salts, borates, triazines, bisimida hexylmethacrylamide-, N-hydroxyethylacrylamide, N-phe Zoles, polysilanes and dyes. It is also possible to use combi nylacrylamide, N-phenylmethacrylamide, N-benzylacryla nations of the compounds from the mentioned classes of mide, N-benzylmetacrylamide, N-nitrophenylacrylamide, compounds with one another and combinations with corre 55 N-nitrophenylmethacrylamide, N-ethyl-N-phenylacryla sponding coinitiator systems and/or sensitisers. mide, N-ethyl-N-phenylmethacrylamide, N-(4-hydroxyphe The photopolymerisable compositions comprise the pho nyl)acrylamide, and N-(4-hydroxyphenyl)methacrylamide, toinitiator advantageously in an amount from 0.05 to 15% by IBMAA (N-isobutoxy-methyl acrylamide, or amides with weight, preferably from 0.1 to 8% by weight, based on the aliphatic polyvalent amines. composition. 60 (Meth)acrylnitriles: Preferably the compound of formula I or I" is present in an Unsaturated acid anhydrides Such as itaconic anhydride, amount of from 0.01 to 10 weight-%, more preferably maleic anhydride, 2,3-dimethyl maleic anhydride, and between 0.1 to 6 weight-% based on the weight of the unsat 2-chloromaleic anhydride. urated polymer(s) and monomer(s). Styrenes, such as methyl styrene, chloromethyl styrene, The compound A is present in an amount that the total 65 and o-, m-, and p-hydroxystyrene. amount is compounds A and B or A, B and C is 100% by Vinyl ethers such as isobutyl vinyl ether, ethyl vinylether, weight. 2-chloroethyl vinylether, hydroxyethyl vinylether, propyl US 9,127,098 B2 13 14 vinylether, butyl vinylether, isobutyl vinyl ether, octyl polymethacrylic acid hydroxyalkyl esters or copolymers vinylether and phenyl vinylether. thereof. Further suitable polyols are oligoesters having Vinyl esters such as vinyl acetate, vinyl chloroacetate, hydroxyl terminal groups. vinylbutyrate and vinyl benzoate. Examples of aliphatic and cycloaliphatic polyols include vinyl chloride and vinylidene chloride alkylenediols having preferably from 2 to 12 carbon atoms, N-vinyl heterocyclic compounds, N-vinylpyrrolidone or Such as ethylene glycol, 1.2- or 1,3-propanediol. 1.2-, 1.3- or suitably substituted vinylpyrrolidones, N-vinylcarbazol, 1,4-butanediol, pentanediol, hexanediol, octanediol, dode 4-vinylpyridine, canediol, diethylene glycol, triethylene glycol, polyethylene Further examples of esters are: diacrylate esters such as glycols having molecular weights of preferably from 200 to 10 1500, 1,3-cyclo-pentanediol, 1.2-, 1.3- or 1,4-cyclohex 1,6-hexane diol diacrylate (HDDA), ethylene glycol diacry anediol. 1,4-dihydroxymethylcyclohexane, glycerol, tris(B- late, propylene glycol diacrylate, tripropylene glycol diacry hydroxyethyl), trimethylolethane, trimethylolpropane, late, neopentylglycol diacrylate, hexamethylene glycol dia pentaerythritol, dipentaerythritol and sorbitol. crylate and bisphenol A diacrylate, divinylbenzene, divinyl The polyols may be partially or fully esterified by one or by Succinate, diallyl phthalate, triallyl phosphate, triallyl isocya 15 different unsaturated carboxylic acid(s), it being possible for nurate and tris(2-acryloyl-ethyl) isocyanurate. trimethylol the free hydroxyl groups in partial esters to be modified, for propane triacrylate, trimethylolethane triacrylate, trimethy example etherified, or esterified by other carboxylic acids. lolpropane trimethacrylate, trimethylolethane Aminoacrylates trimethacrylate, tetramethylene glycol dimethacrylate, trieth A second oligomer used in combination with a monomer is ylene glycol dimethacrylate, tetraethylene glycol diacrylate, an acrylate which has been modified by reaction with primary pentaerythritol diacrylate, pentaerythritol triacrylate, pen or secondary amines, as described, for example, in U.S. Pat. taerythritol tetraacrylate, dipentaerythritol diacrylate, dipen No. 3,844,916 of Gaske, in EP280 222 of Weiss et al., in U.S. taerythritol triacrylate, dipentaerythritol tetraacrylate, dipen Pat. No. 5,482,649 of Meixner et al. or in U.S. Pat. No. taerythritol pentaacrylate, dipentaerythritol hexaacrylate, 5,734.002 of Reich et al. Such amine-modified acrylates are tripentaerythritol octaacrylate, pentaerythritol dimethacry 25 also termed aminoacrylates. Aminoacrylates are obtainable, late, pentaerythritol trimethacrylate, dipentaerythritol for example, under the name EBECRYL 80, EBECRYL 81, dimethacrylate, dipentaerythritol tetrameth-acrylate, tripen EBECRYL 83, EBECRYL P115, EBECRYL 7100 from taerythritol octamethacrylate, pentaerythritol diitaconate, UCB Chemicals, under the name Laromer PO 83F. Laromer dipentaerythritol trisitaconate, dipentaerythritol pentaitacon PO 84F, Laromer PO 94F from BASF, under the name PHO ate, dipentaerythritol hexaitaconate, ethylene glycol diacry 30 TOMER 4775 F, PHOTOMER 4967 F from Cognis or under late, 1,3-butanediol diacrylate, 1,3-butanediol dimethacry the name CN501, CN503, CN550 from Cray Valley. late, 1,4-butanediol ditaconate, sorbitol triacrylate, sorbitol The unsaturated polymer can be used alone or in any tetraacrylate, pentaerythritol-modified triacrylate, sorbitol desired mixtures. tetrameth-acrylate, Sorbitol pentaacrylate, Sorbitol hexaacry Preparation of the Coating late, oligoester acrylates and methacrylates, glycerol di- and 35 The components of the formulation and optionally further tri-acrylate, 1.4-cyclohexane diacrylate, bisacrylates and bis additives are applied uniformly to a substrate by means of methacrylates of polyethylene glycol having a molecular known coating techniques, for example by spin-coating, weight of from 200 to 1500, and mixtures thereof. immersion, knife coating, curtain pouring, brush application The following esters are also suitable: dipropylene glycol or spraying, especially by electrostatic spraying and reverse diacrylate, tripropylene glycol diacrylate, glycerol ethoxylate 40 roll coating, and also by electrophoretic deposition. The triacrylate, glycerol propoxylate triacrylate, trimethylolpro quantity applied (coat thickness) and the nature of the Sub pane ethoxylate triacrylate, trimethylolpropane propoxylate strate (layer support) are dependent on the desired field of triacrylate, pentaerythritol ethoxylate tetraacrylate, pen application. The range of coat thicknesses generally com taerythritol propoxylate triacrylate, pentaerythritol propoxy prises values from 0.1 um to more than 300 um. late tetraacrylate, neopentyl glycol ethoxylate diacrylate, 45 Substrates neopentylglycol propoxylate diacrylate. Suitable are substrates of all kinds, e.g. wood, textiles, Nonlimiting examples of higher molecular weight (oligo paper, ceramics, glass, glass fibres, plastics such as polyester, meric) polyunsaturated compounds (also known as prepoly polyethylene terephthalate, polyolefins or cellulose acetate, mers) are esters of ethylenically unsaturated mono- or poly especially in the form of films, and also for metals such as Al, functional carboxylic acids as described above and polyols or 50 Cu, Ni, Fe, Zn, Mg or Co and GaAs, Sior SiO, to which there polyepoxides, and polymers having ethylenically unsaturated is to be applied a protective layer or an image by image-wise groups in the chain or in side groups, e.g. unsaturated poly exposure. esters, polyamides and polyurethanes and copolymers Applications: thereof, alkyd resins; polybutadiene and butadiene copoly Liquid coating or powder coating or gelcoats. The coatings mers, polyisoprene and isoprene copolymers, polymers and 55 may be pigmented. copolymers having (meth)acrylic groups in side chains such Also possible is the use in printing inks. as methacrylated urethanes and also mixtures of one or more The above-described compositions may further comprise Such polymers. customary additives, which may, as an alternative, also be Suitable polyols are aromatic and, especially, aliphatic and added after the polymerization. Such additives can be added cycloaliphatic polyols. Examples of aromatic polyols are 60 in Small amounts, e.g. UV-absorbers or light stabilizers, e.g. benzyl alcohol, hydroquinone, 4,4'-dihydroxydiphenyl, 2.2- compounds selected from the group consisting of hydrox di(4-hydroxy-phenyl)propane, and novolaks and resols. yphenylbenzotriazoles, hydroxyphenylbenzophenones, Examples of polyepoxides are those based on the said poly oxalamides and hydroxyphenyl-s-triazines. Particularly Suit ols, especially the aromatic polyols and epichlorohydrin. able light stabilizers are those selected from the group con Also suitable as polyols are polymers and copolymers that 65 sisting of sterically hindered amines (HALS), e.g. of the contain hydroxyl groups in the polymer chain or in side 2-(2-hydroxyphenyl)-1,3,5-triazine or 2-hydroxyphenyl-2H groups, e.g. polyvinyl alcohol and copolymers thereof or benzotriazole type. Examples of light stabilizers of the 2-(2- US 9,127,098 B2 15 16 hydroxyphenyl)-1,3,5-triazine type are known from the PREPARATION EXAMPLES patent literature, e.g. U.S. Pat. No. 4,619,956, EP-A-434-608, U.S. Pat. Nos. 5,198,498, 5,322,868, 5,369,140, 5,298,067, The following Table 1 summarizes the prepared com WO-94/18278, EP-A-704437, GB-A-2,297,091 or WO-96/ pounds. 28431. 5 The compositions may further comprise other customary TABLE 1 additives, e.g. fillers such as calcium carbonate, silicates, glass or glass fibre material, talcum, kaolin, mica, barium Examples of synthesized compounds (1) sulphate, metal oxides and hydroxides, carbon black, graph ite, pulverized wood and pulverized or fibrous material from Nr Structure other natural products, synthetic fibres, plasticizers, lubri cants, emulsifiers, pigments, fluidizers, catalysts, optical brighteners, flame retardants, antistatics or blowing agents. The invention further provides a process for preparing the above-described oligomer, cooligomer, polymer or copoly- O N mer by free-radical polymerization using the above-de- Y scribed novel compounds of formula I or I". 2O NH Free radical polymerisation includes thermal polymerisa tion and/or UV polymerisation. Thermal polymerisation is thermal curing, IR-curing or NIR-curing 25

Thermal Curing: 2 Thermal curing refers to the application of convection heat or IR- or NIR-radiation after the mixture has been applied to Substrate. In case of powder coatings the adhered powder coating is first melted to form a surface layer preferably by 30 convection heat. Y NIR-curing NH The NIR radiation used in the process according to the invention is short-wave infrared radiation in the wavelength 35 range from about 750 nm to about 1500 nm, preferably 750 nm to 1200 nm. Radiation sources for NIR radiation include, for example, conventional NIR radiation emitters, which are available commercially (for example, from Adphos). 40 IR-curing 3 The IR radiation used in the process according to the inven- 1. tion is medium wave radiation in the wave length range from N about 1500 nm to about 3000 nm and/or longer-wave infra red radiation in the wave length range above 3000 nm. 45 O YN IR radiation emitters of this kind are available commer cially (for example, from Heraeus). NH In a dual cure system the UV radiation may be followed by IR or NIR radiation or vice versa. Preferably the UV radiation 50 follows the IR or NIR radiation. It is also possible that the UV radiation follows a convection heat exposure. 4 The invention further relates to a process for preparing an oligomer, a cooligomer, a polymer or a copolymer character- ss ized in that the composition is subjected to the reaction con ditions of free radical polymerization. N The invention further relates to a process for lowering the O molecular weight of polypropylene, propylene copolymers or polypropylene blends characterized in defined in claim 1 or in HN N claim 7 is added to the polypropylene, propylene copolymers or polypropylene blend and the mixture is heated. The invention further relates to the use of the compounds of formula I or I' to prepare a coating. 65 The invention further relates to the use of the compounds of formula I or I' for crosslinking US 9,127,098 B2 17 18 TABLE 1-continued TABLE 1-continued

Examples of synthesized compounds (1) Examples of synthesized compounds (1)

Nr Structure Nr Structure

10

15

10

25

30

35 11

40

45

12 50

55

60

65 US 9,127,098 B2 19 20 TABLE 1-continued then stirred 5 hat room temperature under argon. The turbid mixture is thereafter filtered and evaporated under reduced Examples of synthesized compounds (1 pressure to afford 11.75 g of a liquid which solidifies on standing to give the title compound as a slightly yellow solid, Nr Structure mp. 45-48° C. 13 ESI-MS for CHNO (239.36) found M+1=239.8 'H-NMR (CDC1,300 MHz): 5.1-4.9 (bs, 1H, NH), 3.85 ) / 3.75 (m,2H, CH-Me), 2.58-2.54 (m,2H), 2.28-2.24 (m. 2H), 1.80-1.55 (m, 6H), 1.25-1.05 (m. 12H, CH-Me). -O Example 2 1,3-Dicyclohexyl-O-(N-2-butylideneamino)- isourea (Cmpd. 2) To a solution of methylethylketone oxime (4.6 g., 0.053 mol) in dry THF (30 ml) is added finely powdered NaOH -( ) OY N -() (0.15 g) and dicyclohexylcarbodiimide (10.3 g, 0.05 mol). O A The mixture is then stirred 5 hat room temperature under N argon. The turbid mixture is thereafter filtered and evaporated under reduced pressure. The residue is stirred 10 minutes with ( ) 2O acetonitrile (30 ml), the acetonitrile phase is then discarded, the oily residue is dissolved in dichloromethane (30 ml), filtered and evaporated to afford 11.24 g of the title compound as a slightly yellow liquid. ESI-MS for CHNO (293.5) found M+1'=294.0 'H-NMR (CDC1, 300 MHz): 5.4-5.1 (bs, 1H, NH), 3.6- D.C. 25 3.4 (m. 2H), 2.5-1.1 (m. 28H, residual aliphatic H). Example 3 1,3-Dicyclohexyl-O-(N-isopropylideneamino)- isourea (Cmpd. 3) To a solution of oxime (3.65 g, 0.05 mol) in dry THF (35 ml) is added finely powdered NaOH (0.2 g) and 35 dicyclohexylcarbodiimide (10.3 g, 0.05 mol). The mixture is then stirred 5 hat room temperature under argon. The turbid mixture is thereafter diluted with hexane (30 ml) filtered and 15 D. evaporated under reduced pressure to afford 13.8g of the title N compound as a slightly yellow liquid. 40 ESI-MS for CHNO (279.4) found M+1=280.1 'H-NMR (CDC1, 300 MHz): 5.4-5.1 (bs, 1H, NH), 3.6- 3.4 (m. 2H), 2.1-1.1 (m. 26 H, residual aliphatic H). N Example 4 45 1,3-Bis(2,6-diisopropylphenyl)-O-(N-cyclohexy lideneamino)-isourea (Cmpd. 4) 16 To a solution of cyclohexanone oxime (1.13 g, 0.01 mol) in dry THF (25 ml) is added finely powdered NaOH (0.04 g) and 50 bis(2,6-diisopropylphenyl)carbodiimide (3.65 g, 0.01 mol). The mixture is then stirred 4 hat room temperature under argon. The turbid mixture is thereafter filtered and evaporated under reduced pressure. The solid residue is crystallized from N dichloromethane-hexane to afford 3.9 g of the title compound as a colorless solid, mp. 150-152°C. Infusions-MS for OHNO (475.5) found M+1=476 C 55 H-NMR (CDC1, 300 MHz): 7.4-6.8 (m, 6H, ArH), 3.6- 3.4 (m. 2H), 3.2-3.0 (m. 2H), 2.3-2.1 (m, 4H), 1.8-1.1 (m, 3OH, residual aliphatic H). Example 1 60 Example 5 1,3-Diisopropyl-O-(N-cyclohexylideneamino)- isourea (Cmpd. 1) 1,3-Dicyclohexyl-O-(N-diphenylmethylidene amino)-isourea (Cmpd. 5) To a solution of cyclohexanone oxime (5.65 g, 0.05 mol) in 65 dry THF (40 ml) is added finely powdered NaOH (0.2 g) and To a solution of benzophenone oxime (3.94 g., 0.02 mol) in diisopropylcarbodiimide (7.57 g., 0.06 mol). The mixture is dry THF (40ml) is added finely powdered NaOH (0.08 g) and US 9,127,098 B2 21 22 dicyclohexylcarbodiimide (4.25 g, 0.0206 mol). The mixture Example 9 is then stirred 22 h at room temperature under argon. The turbid mixture is thereafter filtered and evaporated under 1,3-dicyclohexyl-O-(N-cyclododecanylidene reduced pressure. The residue is crystallized from acetonitrile amino)-isourea (Cmpd. 9) and again from acetonitrile-dichloromethane-hexane to afford 2.93 g of the title compound as a colorless solid, mp. A mixture of cyclododecanone oxime (19.73 g, 100 104-107° C. mmol), dicyclohexylcarbodiimide (20.63 g, 100 mmol) and ESI-MS for CHNO (403.6) found M+1'=403.8 potassium-t-butylate (0.12 g) in hexane (75 ml) is stirred 23h 'H-NMR (CDC1,300 MHz): 7.6-7.3 (m, 10H, ArH), 5.4- at 50° C. under argon. The mixture is then allowed to crys 5.2 (bs, 1H, NH), 3.7-3.5 (m, 1H), 3.1-2.9 (m. 1H), 2.2-0.9 10 tallize overnight at -18°C. The solid is filtered off and recrys (m. 20H, residual aliphatic H). tallized from dichloromethane-hexane to afford 17.4 g of the title compound as white solid, mp. 108-111° C. Example 6 H-NMR (CDC1,300 MHz): 3.6-3.4 (bs, 2H), 2.6-2.5 (m, 2H) 2.5-2.4 (m, 2H), 2.1-1.1 (m, 38H). 15 C-NMR (CDC1, 75.5 MHz): 163.22 (>C=N), 148.57 1,3-Dicyclohexyl-O-(N-cyclohexylideneamino)- (O C (NH )—N ). isourea (Cmpd. 6) Example 10 To a solution of cyclohexanone oxime (5.65 g, 0.05 mol) in dry THF (30 ml) is added finely powdered NaOH (0.2g) and 1-Pivaloyl-1,3-dicyclohexyl-O-(N-2-butylidene dicyclohexylcarbodiimide (11.34g, 0.055 mol). The mixture amino)-isourea (Cmpd. 10) is then stirred 5hat room temperature under argon. The turbid mixture is thereafter diluted with dichloromethane (25 ml), To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene filtered and evaporated under reduced pressure. The residue is amino)-isourea (Cmpd. 2) (5.87 g. 20 mmol) and 4-dimethy stirred 10 minutes with acetonitrile (30 ml), the acetonitrile 25 laminopyridine (60 mg) in dichloromethane (25 ml) and tri phase is then discarded, the oily residue is dissolved indichlo ethylamine (3.1 ml, 22 mmol) is added pivaloyl chloride (2.46 romethane (30 ml), filtered and evaporated to afford 14.27g g, 21 mmol). The mixture is stirred 43 hat room temperature, of the title compound as a slightly yellow liquid. diluted with hexane (200 ml), washed with water (4x20 ml), ESI-MS for CHNO (319.49) found M+1=320 dried over MgSO and evaporated. The residue is chromato 30 graphed on silica gel (hexanes-ethyl acetate 4:1) to afford 'H-NMR (CDC1, 300 MHz): 5.4-5.1 (bs, 1H, NH), 3.6- 5.49 g of the title compound as a colorless oil. 3.4 (m, 2H), 2.6-2.5 (m, 2H), 2.3-2.2 (m, 2H), 2.1-1.1 (m, H-NMR (CDC1,300 MHz): 4.2-4.0 (m, 1H), 3.6-3.5 (m, 26H, residual aliphatic H). 1H), 2.5-1.0 (m. 2H), 2.1-1.1 (m. 28H), 1.20 (s, t-Bu). C-NMR (CDC1, 75.5 MHz): 177.70 (t-Bu-CO), 163.12, Example 7 35 162.38 (>C=N, E, Z isomers), 146.53 (O C (NH-) —N ). 1.3-(2,6-Diisopropylphenyl)-O-(N-diphenylmeth ylideneamino)-isourea (Cmpd. 7) Example 11 40 1-Benzoyl-1,3-dicyclohexyl-O-(N-2-butylidene A mixture of benzophenone oxime (1.97 g. 10 mmol), bis(2,6-diisopropylphenyl)carbodiimide (3.63 g, 10 mmol) amino)-isourea (Cmpd. 11) and powdered NaOH (0.04 g) in dry THF (30 ml) is stirred 20 hat room temperature under argon. The mixture is thereafter To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene evaporated and the residue is chromatographed on silica gel amino)-isourea (Cmpd. 2) (7.34g, 25 mmol) and 4-dimethy 45 laminopyridine (100 mg) in dichloromethane (25 ml) and (hexanes-ethyl acetate 15:1) to afford 1.1 g of the title com triethylamine (3.9 ml, 27.5 mmol) is added benzoyl chloride pound as a colorless glassy Solid. (3.58 g. 25.5 mmol). The mixture is stirred 6 h at room ESI-MS for CHNO (559.80) found M+1'=559.89 temperature, diluted with hexane (200 ml), washed with 'H-NMR (CDC1, 300 MHz): 7.5-6.7 (m, 16 ArH), 3.6-3.4 water (4x20 ml), dried over MgSO and evaporated. The (m. 2H), 3.1-2.9 (m, 2H), 1.5-0.8 (m, 24H). 50 residue is chromatographed on silica gel (hexanes-ethyl acetate 4:1) and the pure fractions are recrystallized from Example 8 hexane to afford 7.2 g of the title compound as white crystals, mp 74-78° C. 1-Acetyl-1,3-dicyclohexyl-O-(N-2-butylidene 'H-NMR (CDC1,300 MHz): 7.7-7.2 (m, 5 ArH), 4.5-4.3 55 (m. 1H), 3.6-3.4 (m. 1H), 2.6-1.0 (m. 28H). amino)-isourea (Cmpd. 8) 'C-NMR (CDC1, 75.5 MHz): 169.90 (Ph-CO), 163.56 To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene (>C=N), 146.94 (O C (NH )—N ). amino)-isourea (Cmpd. 2) (10.5 g., 35.7 mmol) and 4-dim Example 12 ethylaminopyridine (100 mg) in pyridine (25 ml) is dropwise 60 added acetanhydride (5 ml, 52.9 mmol). The mixture is Terephthalic acid-bis-N-(1,3-dicyclohexyl-O-(N-2- stirred 2 hand evaporated. The residue is dissolved in toluene butylideneamino)-isoure-1-yl)-amide (Cmpd. 12) (100 ml), washed with water (5x20 ml), dried over MgSO and evaporated to afford 9.58g of the title compound as a light To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene yellow oil. 65 amino)-isourea (Cmpd. 2) (5.87 g. 20 mmol) and 4-dimethy 'H-NMR (CDC1, 300 MHz): mixture of isomers, 4.3-3.3 laminopyridine (80 mg) in dichloromethane (25 ml) and tri (m. 2H), 2.5-1.1 (m, 31H). ethylamine (2.8 ml, 20 mmol) is added terephthaloyl chloride US 9,127,098 B2 23 24 (1.63 g, 8 mmol). The mixture is stirred 19 hat room tem Example 16 perature, diluted with dichloromethane (30 ml), washed with water (3x10 ml), dried over MgSO and evaporated. The 1-Acetyl-1,3-dicyclohexyl-O-(N-isopropylidene residue is chromatographed on silica gel (hexanes-ethyl amino)-isourea (Cmpd. 16) acetate 3:1+5% CH,Cl)) and the pure fractions are recrys To a solution of 1,3-dicyclohexyl-O-(N-isopropylidene tallized from hexane to afford 3.97g of the title compound as amino)-isourea (Cmpd. 3) (16.7 g. 60 mmol) and 4-dimethy white crystals, mp 146-150° C. laminopyridine (180 mg) in pyridine (40 ml) is added acetic 'H-NMR (CDC1,300 MHz): 7.6-7.5 (m, 4 ArH), 4.5-4.3 anhydride (8.9 ml, 90 mmol). The mixture is stirred 2 hand (m. 2H), 3.6-3.4 (m. 2H), 2.2-1.0 (m, 56H). then evaporated under reduced pressure. The residue is C-NMR (CDC1, 75.5 MHz): 169.17 (OC-Ph-CO), 10 diluted with hexane (150 ml), washed with water (5x20 ml), 163.62 (>C=N), 146.69 (O C (NH )—N ). dried over MgSO and evaporated. The solid residue is recrystallized from hexane to afford 13.3 g of the title com Example 13 pound as white crystals, mp 74-78°C. 'H-NMR (CDC1,300 MHz): 4.2-4.0 (m, 1H), 3.7-3.3 (m, Trimesic acid-tris-N-(1,3-dicyclohexyl-O-(N-2- 15 1H), 2.1-1.0 (m. 29H). butylideneamino)-isoure-1-yl)-amide (Cmpd. 13) 'C-NMR (CDC1, 75.5 MHz): 169.56, 169.35 (CH, CO), 161.83, 159.49 (>C=N), 146.52 (O C (NH ) To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene —N ). amino)-isourea (Cmpd. 2) (7.04g, 24 mmol) and 4-dimethy Polymerization Examples Using Selected Compounds From laminopyridine (100 mg) in dichloromethane (25 ml) and Table 1 triethylamine (3.35 ml, 24 mmol) is added trimesic acid chlo Materials and Methods: ride (1.6 g. 6 mmol). The mixture is stirred 20 hat room All solvents and monomers are distilled under argon or temperature, diluted with dichloromethane (80 ml), washed under reduced pressure via a Vigreux column shortly with water (4x20ml), dried over MgSO and evaporated. The before use. residue is chromatographed on silica gel (hexanes-ethyl 25 All reaction mixtures are freed of oxygen by purging with acetate 3:1) to afford 4.95g of the title compound as a color argon using the freeze? thaw technique and Subsequently less resin. maintained under argon gas prior to the polymerization. 'H-NMR (CDC1, 300 MHz): 8.0-7.7 (m, 3 ArH), 4.3-4.1 The reactants are in the form of a clear homogeneous (m,3H), 3.5-3.3 (m, 3H), 2.4-1.0 (m, 84H). Solution before commencement of the polymerization 'C-NMR (CDC1, 75.5 MHz): 168.69 (CH(CO)4), 30 reaction. 163.83 (>C=N), 145.62 (O C (NH )—N ). The monomer conversion is determined via H-NMR by integrating the signals of the polymer and unreacted Example 14 OOC. The polymers are characterized by GPC (gel permeation 1-Phenylaminocarbonyl-1,3-dicyclohexyl-O-(N-2- 35 chromatography). butylideneamino)-isourea (Cmpd. 14) GPC: a two-piston production model pump RHEOS 4000 from FLUX INSTRUMENTS (represented by Ercatech To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene AG, Bern, Switzerland) is used. The pump output is 1 amino)-isourea (Cmpd. 2) (2.93 g, 10 mmol) in dichlo ml/min. The chromatography is carried out on two Plgel romethane (15 ml) is phenylisocyanate (1.19 g, 10 mmol). 40 5 um mixed-C columns from POLYMER INSTRU The mixture is stirred 1 hat room temperature and evaporated MENTS, Shropshire UK connected in series at 40° C. in to afford 4.12 g of the title compound as a light yellow oil. THF. These columns are calibrated using polystyrene H-NMR (CDC1, 300 MHz): 7.6-7.1 (m, 5 ArH), 4.1-3.9 having M values in the range from 200 to 2 000 000. (m. 1H), 3.6-3.5 (m, 1H), 2.5-1.0 (m. 28H). The fractions are measured using an RI detector ERC C-NMR (CDC1, 75.5 MHz): 164.22, 163.54 (>C=N, 45 7515A from ERCATECH AG at 30° C. Isomers), 153.37 (PhNHCO), 149.75 (O C (NH ) —N ). Example 100 Example 15 Polymerization of n-butyl acrylate using the 50 Compound 4 at 120° C. 1-t-Butyloxycarbonyl-1,3-dicyclohexyl-O-(N-2- butylideneamino)-isourea (Cmpd. 15) 238 mg (0.5 mmol) of the compound 4 and 6.43 g (50 mmol) of n-butyl acrylate are placed in a 50 ml three-necked To a solution of 1,3-dicyclohexyl-O-(N-2-butylidene round-bottom flask provided with thermometer, condenser amino)-isourea (Cmpd. 2) (5.87 g. 20 mmol) and 4-dimethy 55 and magnetic stirrer and the mixture is degassed. The clear laminopyridine (125 mg) in dichloromethane (25 ml) is solution is heated 5h to 120° C. under argon and then cooled added di-t-butyl-dicarbonate (5.96 g. 27.3 mmol). The mix to room temperature to afford a slightly yellow viscous poly ture is stirred 48 hat room temperature, diluted with methanol mer. Conversion of the monomer–77%, GPC: M-7796, (2 ml), stirred for an additional hour and evaporated. The M=583.08. residue is chromatographed on silica gel (hexanes-ethyl 60 acetate 3:1) to afford 5.3 g of the title compound as a colorless Example 101 oil. 'H-NMR (CDC1,300 MHz): 3.9-3.3 (m, 2H), 2.4-1.0 (m, Polymerization of n-butyl acrylate using the 28H), 1.4 (s, t-Bu) Compound 5 at 100° C. 'C-NMR (CDC1, 75.5 MHz): 161.78 (>C=N), 153.28, 65 152.96 (t-BuOCO, isomers), 145.28, 146.02 (O–C– 202 mg (0.5 mmol) of the compound 5 and 6.43 g (50 (NH )—N , isomers). mmol) of n-butyl acrylate are placed in a 50 ml three-necked US 9,127,098 B2 25 26 round-bottom flask provided with thermometer, condenser Example 104 and magnetic stirrer and the mixture is degassed. The clear solution is heated 5h to 100°C. under argon and then cooled Determination of the Conversion of Double Bonds to room temperature to afford a slightly yellow viscous poly Via ATR-IR mer. Conversion of the monomer–72%, GPC: M-72491, M=143925. A) Polymerization Between 2 PET Films The acrylate formulation (0.2 g) was laminated between Example 102 two PET films and then cured in an oven at 120° C. during 25 min. The conversion of double bonds was elucidated by ATR Polymerization of n-butyl acrylate using the 10 IR (peak area at 810 cm). The results are summarized in compound 6 at 80° C. Table 3.

319 mg (1 mmol) of the compound 6 and 12.85 g (100 TABLE 3 mmol) of n-butyl acrylate are placed in a 50 ml three-necked round-bottom flask provided with thermometer, condenser 15 Conversion of double bonds and magnetic stirrer and the mixture is degassed. The clear Compound from Concentration Remaining solution is heated 5h to 120°C. under argon and then cooled example (%) acrylate (%) to room temperature to afford a colorless viscous polymer. Acrylate 1 1OO Conversion=86%, GPC: M-9262, M=70597. Coatings system Benzopinakol 1 23.4 Example 103 1 1 10.3 8 1 15.3 Polymerization of a Coating Composition 9 1 19.6

The following unsaturated polymerizable composition is 25 B) Polymerization on a White Coil Sheet used (w/w %) The acrylate formulation (0.2 g) was coated as a 200 um thick film on a white coil sheet, then covered with a PET film and cured in an oven at 130° C. during 25 minutes. The Urethane-acrylate (Ebecryl 4858, UCB Chemicals/Cytec) SO% 1,6-Hexandiol diacrylate (UCB Chemicals. Cytec) 30% conversion of double bonds was elucidated by ATR-IR (peak Tripropylene glycol diacrylate (UCB Chemicals/Cytec) 20% 30 area at 810 cm). The results are summarized in Table 4.

1% of a compound (see Table 1) is dissolved in this com TABLE 4 position and the resulting mixture is submitted to Differential Conversion of double bonds scanning calorimetry (DSC) measurement. The activity of the tested compound is manifested by the exothermic curing 35 Compound from Concentration Remaining reaction which is characterized by the Onset, Peak and Endset example (%) acrylate (%) temperatures as well as the amount of heat liberated (exo Acrylate 1 1OO thermy). Coatings system Benzopinakol 1 17.6 The following DSC parameters are used: 40 8 1 10.6 Apparatus: DSC 30 (Mettler) 10 1 11.4 Temperature Gradient: 5°C/Min 11 1 14.4 Temperature Range: 30-300° C. 12 1 7.8 13 1 6.3 Measurement under Nitrogen, flow rate 5 ml/Min 15 1 13.0 Sample amount: approx. 10 mg compound in an aluminum 45 16 1 12.4 Cup The results summarized in the Table 2 show that no curing occurs with the blank formulation but that distinct exothemic The invention claimed is: curing is observed with the examples of the inventive com 1. An O-limino-isourea compound of formula I' pounds. 50 (I) TABLE 2 R101 R103 v DSC evaluation R100 N

Compound 55 from Exothermy N-O-(N-I-R104 example Onset C. Peak C. Endset C. Jg M R102 O O O O (blank) 1 50.72 68 82.08 239.74 2 60.00 75.60 110 315.60 60 wherein: 3 64.27 76.44 85.33 245.88 n is 1, 2, 3 or 4: 4 73.43 80.99 84.90 244.25 Roo and Rio are each independently Cisalkyl, 5 7S.04 86.OS 93.91 237.99 C-C cycloalkyl, Co-Caryl, C-Cheteroaryl, 6 53.07 60.61 66.28 220.37 8 91.82 106.83 121.38 368.60 C7-Caralkyl, C-Cheteroaralkyl, Cyano, or Roo and 9 71.98 79.93 86.51 314.78 65 Roi form together with a carbon to which they are attached a mono or polycyclic C-Cs carbocyclic or C-Cls heterocyclic ring; US 9,127,098 B2 27 28 Ro and Rios are each independently C1-Cisalkyl, -continued C-Cacycloalkyl, C-Caryl, C-Caryl Substituted NHMe Me with a C-C salkyl, C7-Caralkyl, (CH)-Si-; or Me N-O-CEN-C-Me Ro and Rios are C-C salkyl, Ca-C12cycloalkyl, Co-Caryl, C7-Cisaralkyl, or Ro, and Ros are Me-CH-C-CH-Me Me C-C salkyl, C-C cycloalkyl which are interrupted or substituted by O or by N containing groups selected Me from the group consisting of C-C salkylamino, bis Me2C=N-O Me (C-C salky)amino and tris(C-C alkyl)ammonium; NEC-NH-CH-Me and picrate salt 10 Roa if n is 1 is H. C-C salkyl, C-Cacycloalkyl, Me-CH-Me C7-Caralkyl, C-Caryl or acyl selected from the Me group consisting of —C(=O)—H. —C(=O)—C-C salkyl, —C(=O)— Me-CH-NH Me C-C salkenyl, —C(=O)—C-Caryl, N-O-CEN-CH-Me —C(=O)—C-C salkenyl-C-Caryl, —C(=O)— 15 O-C-Cisalkyl, —C(=O)—O—C-Caryl, Me-C-CH2-Me —C(=O) NH C-C alkyl, —C(=O)—NH Me Co-Caryland —C(=O)—N(C-C salkyl); or Me-CH-NH Me Ro and Roa if n is 1 form together with a nitrogen atom to which they are attached a 5 to 12 membered ring N-O-CEN-CH-Me which optionally comprises an additional heteroatom, Me-C-CH-Et Roa if n is more than 1 is di-, tri-, tetra-C-Cisalkylidene, diacyl, triacyl or tetraacyl and salts thereof, 25 with the proviso that the following compounds are excluded y isopropyl isopropyl 30 M--- y N 1. CH3 s isopropyl, and Me =n-1-y and HBF4 salt O Me O O 35 I -' (- s -(- C CH3 CH3 y methyl Me-C-NH 40 Me Me N isopropyl -o-c---M. and HBF4 salt C-Me Me

45 HN N-isopropyl isopropyl NHBl-t -o-c-s-s and the following O-Imino-isoureas derived from ketoximes: 50 M

NHMe i-M y N-o--N--Me and HBF4salt 55 i? . Me-C-Me

Me M--M.Me NHMe Me y N-O-CEN-C-Me 60 NH-C - Me Me Me-C-CH-Me Me Me NHMe Me =c-o-n=c-ch-e and HBF4 salt N-O-CEN-C-Me 65 M--M. Me-C-CH-Et Me Me US 9,127,098 B2 29 30 -continued Me2C=N-O Me N=C-NH-C-Me and HBF salt. Me-C-Me Me

Me

2. The compound of claim 1, wherein n is 1. 3. A composition, comprising: 10 an ethylenically unsaturated, polymerizable monomer or oligomer, a compound of the formula I" as defined in claim 1; and optionally a photoinitiator. 4. A process for preparing an oligomer, a cooligomer, a 15 polymer or a copolymer, comprising reacting the composi tion of claim 3 under conditions of free radical polymeriza tion. 5. A coating process comprising: applying a coating formulation comprising the compound of claim 1 to a substrate; and polymerizing. 6. A crosslinking process, comprising heating a mixture comprising an unsaturated polymer resin and the compound of claim 1. 25