USOO6204347B1 (12) United States Patent (10) Patent No.: US 6,204,347 B1 Hafner et al. (45) Date of Patent: Mar. 20, 2001 (54) TWO-COMPONENT CATALYST FOR ROMP FOREIGN PATENT DOCUMENTS 0348852 1/1990 (EP). (75) Inventors: Andreas Hafner, Laupen; Paul 0376198 7/1990 (EP). Adriaan Van Der Schaaf, Fribourg; 96.16100 5/1996 (WO). Andreas Miihlebach, Belfaux, all of 9620235 7/1996 (WO). (CH) 97/20865 6/1997 (WO). (73) Assignee: Ciba Specialty Chemicals * cited by examiner Corporation, Tarrytown, NY (US) Primary Examiner-David W. Wu (*) Notice: Subject to any disclaimer, the term of this ASSistant Examiner-Caixia Lu patent is extended or adjusted under 35 (74) Attorney, Agent, or Firm-David R. Crichton; Luther U.S.C. 154(b) by 0 days. A. R. Hall (57) ABSTRACT (21) Appl. No.: 09/376,453 A catalyst System for the ring-opening metathesis (22) Filed: Aug. 18, 1999 polymerization, which consists of at least two components Related U.S. Application Data (a) and (b), wherein (a) is a ruthenium compound of formula I or II (62) Division of application No. 09/075,637, filed on May 11, 1998, now Pat. No. 5,998,326. RuX2(L1), (L.2),(L3)(L) (I), (30) Foreign Application Priority Data ARuX2(L1), (L.2), (II), May 23, 1997 (CH) ................................................... 1204/97 wherein L,L,L and L are each independently of the (51) Int. Cl." ........................................................ C08F 4/26 other C-C alkylcyanide, C-C-aralkylcyanide, (52) U.S. Cl. .......................... 526/172; 526/171; 526/280; tertiary amine, tertiary phosphine which does not 526/283; 526/307,8; 502/155; 502/162 contain any Secondary alkyl or cycloalkyl radicals bound to the phosphorus atom, or phosphite, X is (58) Field of Search ..................................... 526/280, 283, halogen, A is arene, m, n, O and p are integers from 526/307,8, 171, 172; 502/155, 162 0 to 4, where 2s m+n+O+ps 4, r and S are integers (56) References Cited from 0 to 2, where 1sr--Ss2, and (b) is a tertiary phosphine containing at least one Second U.S. PATENT DOCUMENTS ary alkyl radical or cycloalkyl radical bound to the 3,933,919 1/1976 Wilkinson ..... ... 260/604 phosphorus atom, 4,426,502 1/1984 Minchak ........... ... 526/172 is particularly Suitable for the polymerization of 4,519,954 5/1985 Burrington et al. .. 260/465.8 strained cycloolefins by the RIM process. 5,710,298 1/1998 Grubbs et al. ......................... 556/22 5,861,443 * 1/1999 Hafner et al. .......................... 522/64 6,001,909 12/1999 Setiabudi ............................. 524/265 4 Claims, No Drawings US 6,204,347 B1 1 2 TWO-COMPONENT CATALYST FOR ROMP Tertiary amines Suitable as ligands L to L are, for example, trimethylamine, triethylamine, tri-n-propylamine, This is a divisional of application Ser. No. 09/075,637, triisopropylamine, tri-n-butylamine, triisobutylamine, tri filed on May 11, 1998 now U.S. Pat. No. 5,998,326. tert-butylamine, benzyldimethylamine, triphenylamine, The present invention relates to a two-component cata tricyclohe Xyla mine, phenyl dimethylamine, lyst System for the ring-opening metathesis polymerization phenyldiethylamine, cyclohexyl dimethylamine, (ROMP), to a curable system comprising Such a catalyst cyclohexyldiethylamine, urotropine, triethylenediamine, System, to a process for the preparation of moulded articles N-methylpiperidine and N-ethylpiperidine. as well as to the use of the curable System as encapsulating L to L. defined as tertiary phosphine may be, for material for electrical or electronic components. example, trimethylphosphine, triethylphosphine, tri-n- U.S. Pat. No. 4,426,502 and EP-A-348852 describe the ring-opening metathesis polymerization (ROMP) of Strained propylphosphine, tri-n-butylphosphine, triphenylphosphine, cycloolefins by the RIM process (reaction injection methyldiphenylphosphine, dimethylphenylphosphine, tri-n- moulding). In this case a two-component System consisting octylphosphine, tritolylphosphine or a compound of formula of a catalyst and a co-catalyst is used for the ring-opening III metathesis polymerisation. According to the process 15 described in the above publications, the polymerizable (III) cycloolefin is divided into two portions, one half comprising the catalyst and the other half the corresponding co-catalyst. When the two portions are mixed and injected into the preheated mould, the mixture cures quickly. However, the use of organo aluminium compounds as co-catalysts requires the exclusion of moisture. WO 96/16100 and WO 96/20235 describe ruthenium R-O / catalysts which are not Susceptible to moisture but which are 25 unsuitable for the RIM process because of their high reac \O tivity. It is the object of this invention to provide a two component catalyst System for the ring-opening metathesis polymerisation which is stable against air and moisture and which is sufficiently reactive for the RIM process. It has now been found that certain ruthenium complexes and tertiary phosphines containing Secondary alkyl or wherein R is C-C salkyl, C-C aryl or C-C aralkyl. cycloalkyl groups form a Suitable storage-stable two The alkyl groups in formula III may be Straight-chain or component System which affords cured products having branched and preferably contain 1 to 12, particularly pref excellent properties, in particular high heat Stability, high 35 erably 1 to 8 and, most preferably, 1 to 4, carbon atoms. toughness and mechanical Strength. Alkyl encompasses, for example, methyl, ethyl, Accordingly, this application relates to a catalyst System isopropyl, n-propyl, n-butyl, isobutyl, Sec-butyl, tert-butyl as for the ring-opening metathesis polymerization, which con well as the different isomeric pentyl, hexyl, heptyl, octyl, Sists of at least two components (a) and (b), wherein nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, 40 pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl (a) is a ruthenium compound of formula I or II and eicosyl groups. R defined as aryl preferably contains 6 to 10 carbon atoms (I), and is typically phenyl, tolyl, pentalinyl, indenyl, naphtyl, (II), aZulinyl and anthryl. wherein L,L,L, and L are each independently of the 45 R defined as aralkyl preferably contains 7 to 12 carbon other C-C alkylcyanide, C2C-aralkylcyanide, atoms, particularly preferably 7 to 10 carbon atoms, and is tertiary amine, tertiary phosphine which does not typically benzyl, phenylethyl, 3-phenylpropyl, contain any Secondary alkyl or cycloalkyl radicals C.-methylbenzyl, 4-phenylbutyl and C.C.-dimethylbenzyl. bound to the phosphorus atom, or phosphite, X is Phosphites Suitable as ligands L to L are, for example, halogen, A is arene, m, n, o and p are integers from 50 trimethylphosphite, triethylphosphite, tri-n- 0 to 4, where 2s m+n+o-ps 4, r and S are integers propylphosphite, triisopropylphosphite, tri-n- from 0 to 2, where 1sr--Ss2, and butyl phosphite, trip he nylphosphite, (b) is a tertiary phosphine containing at least one second methyldiphenylphosphite, dimethylphenylphosphite, tri-n- ary alkyl radical or cycloalkyl radical bound to the octylphosphite, tritolylphosphite or tris(p-nonylphenyl) phosphorus atom. 55 phosphite, or compounds of the above formula III. The ruthenium compounds of formula I or II can be X in formula I or II is fluoro, chloro, bromo or iodo. prepared by known processes by reacting ruthenium diha Chloro is preferred. lides with the corresponding arenes, nitriles, amines, phos The term "arene’ generally Stands for aromatic com phines or phosphites. pounds. A in formulae II and III is preferably a monocyclic, C-C Alkylcyanides which are Suitable as ligands L to 60 polycyclic or condensed arene which is unsubstituted or L are, for example, acetonitrile, propio nitrile, Substituted by OH, C-C alkyl, C-C alkoxy, Co-Caryl or n-butyronitrile, isobutyronitrile, pivalonitrile, neo halogen and which contains 6 to 24, preferably 6 to 18, pentylcyanide, Valeronitrile, capronitrile, n-heptylcyanide, particularly preferably 6 to 12, carbon atoms. n-octylcyanide, n-nonylcyanide and n-decylcyanide. Typical Some examples of arenes and heteroarenes are benzene, examples of Suitable Co-Caralkylcyanides are 65 toluene, O-Xylene, p-Xylene, mesitylene, ethylbenzene, phenylace to nitrile, 3-phenylprop io nitrile, cumene, 1,3,5-triisopropylbenzene, p-cymene, durene, 4-phenylbutyronitrile and naphthylacetonitrile. he Xa methylben Zene, naphthale ne, biphenyl, US 6,204,347 B1 3 4 diphenylmethane, anthracene, acenaphthene, fluorene, Components (a) and (b) are both not reactive against phenanthrene, pyrene, chrysene, fluoranthrene, furan, Strained cycloolefins, i.e. mixtures comprising a cycloolefin thiophene, pyrrole, pyridine, Y-pyran, Y-thiopyran, and component (a) or a cycloolefin and component (b), are pyrimidine, pyrazine, indole, coumarone, thionaphthene, Storage-Stable at room temperature for Several months. Only carbazole, diben Zo furan, ben Zo thiophene, when the two components are mixed is a product obtained dibenzothiophene, pyrazole, imidazole, benzimidazole, which acts as catalyst for the ring-opening metathesis poly oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, merisation. The novel two-component System is thus par phenothiazine, triazine, thianthrene and purine. Preferred ticularly suitable for the RIM process because the polymer arenes and heteroarenes are unsubstituted or Substituted isable cycloolefin can be divided into two portions before benzene, naphthalene, thiophene and benzothiophene. processing, to which the corresponding