Polymerizable compositions comprising alpha-olefin hydrocarbon monomers and methods of use therefor

Abstract

A polymerizable composition comprises an alpha-olefin hydrocarbon monomer, an effective amount of an organometallic catalyst of a Group VIII metal, preferably Ni or Pd, and at least one of water and air. Novel catalysts for polymerizing alpha-olefin hydrocarbon monomers provide improved processes and products. Methods of the invention include polymerizing the composition in open air and in the presence of water to provide novel polymers.

We claim:  
     
         1 . A polymerizable composition comprising: 
 a) an alpha-olefin hydrocarbon monomer,    b) one or both of water and air, and    c) an effective amount of an organometallic catalyst comprising a Group VIII metal and a polydentate ligand having steric bulk sufficient to permit formation of high polymer.    
     
     
         2 . The polymerizable composition according to    claim 1    wherein said composition further comprises a copolymerizable monomer.  
     
     
         3 . The polymerizable composition according to    claim 1    wherein said alpha-olefin comprises one or more of 1-octene, 1-pentene, 1-hexene, and 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and cyclopentene.  
     
     
         4 . The polymerizable composition according to    claim 1    further comprising one or both of a stabilizer and a surfactant.  
     
     
         5 . The polymerizable composition according to    claim 4    wherein said stabilizer is a hindered phenol-type stabilizer.  
     
     
         6 . The polymerizable composition according to    claim 1    wherein air is present.  
     
     
         7 . The polymerizable composition according to    claim 1    wherein water is present in the range of 0.001 to 99 weight percent.  
     
     
         8 . The polymerizable composition according to    claim 1    wherein said catalyst is a one-part catalyst comprising an organometallic salt or a two-part catalyst comprising a neutral organometallic compound and a cocatalyst.  
     
     
         9 . The polymerizable composition according to    claim 8    wherein said one-part catalyst comprises a cationic portion having the formula LM-R + wherein M is a Group VIII metal, L is a two-electron donor ligand or ligands, as defined above, stabilizing the Group VIII metal, and R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical wherein the substituting groups can be alkyl having 1 to 10 carbon atoms, aryl having 5 to 20 carbon atoms, or halogen substituted alkyl.  
     
     
         10 . The polymerizable composition according to    claim 8    wherein said one-part catalyst comprises an anionic counterion selected from the group consisting of (R f SO 2 ) 2 CH − , (R f SO 2 ) 3 C − , (R f SO 2 ) 2 N − , R f SO 3   − , B(C 6 F 5 ) 4   − , PF 6   − , SbF 6   − , AsF 6   − , BF 4   − , and B(3,5-C 6 H 3 (CF 3 ) 2 ) 4   − , wherein each R f  is independently selected from the group consisting of highly fluorinated or perfluorinated alkyl groups having 1 to 20 carbon atoms, or fluorinated aryl groups having 6 to 22 ring carbon atoms.  
     
     
         11 . The polymerizable composition according to    claim 8    wherein said one-part catalyst has the formula  
       {(ArN═C(R 1 )C(R 1 )═NAr)Pd(Me)(ether)} + Q −   
       wherein 
 Ar is 2,6-C 6 H 3 (R 3 ) 2  wherein R 3  is isopropyl or methyl, and each R 1  independently is H or methyl, or the two R 1  groups taken together are 1,8-naphthalene-diyl,  
 ether is tetrahydrofuran or methyl t-butyl ether, Me is methyl, and  
 Q is selected from B(C 6 F 5 ) 4 , PF 6 , SbF 6 , AsF 6 , BF 4 , B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 , (R f  SO 2 ) 2 CH, (R f  SO 2 ) 3 C, (R f  SO 2 ) 2 N, and R f SO 3 , wherein R f  is as previously defined.  
 
     
     
         12 . The polymerizable composition according to    claim 8    wherein said one-part catalyst comprises {(ArN═C(R 1 )C(R 1 )═NAr)M(CH 3 )(OEt 2 )} + B(C 6 F 5 ) 4   − wherein M═Ni or Pd, Et═ethyl, Ar is 2,6-C 6 H 3 (R 3 ) 2  where each R 3  independently is isopropyl or methyl, and each R 1  independently is H or methyl, or the two R 1  groups taken together are 1,8-naphthalene-diyl.  
     
     
         13 . The polymerizable composition according to    claim 8    wherein the neutral organometallic compound of said two-part catalyst has the formula  
       {ArN═C(R 1 )C(R 1 )═NAr}M(R)X 
       wherein Ar, R 1 , M, and R are as previously defined, and X is a halogen atom.  
     
     
         14 . The polymerizable composition according to    claim 8    wherein said cocatalyst of said two-part catalyst has the formula  
       A + Q −   
       wherein A is a metal selected from the group consisting of silver, and Group IA metals, and Q is selected from the group consisting of B(C 6 H 3 (CF 3 ) 2 ) 4 , B(C 6 F 5 ) 4 , PF 6 , SbF 6 , AsF 6 , BF 4 , (R f SO 2 ) 2 CH, (R f  SO 2 ) 3 C, (R f SO 2 ) 2 N, and R f SO 3 , wherein R f  is as previously defined.  
     
     
         15 . The polymerizable composition according to    claim 13    wherein R is methyl.  
     
     
         16 . The polymerizable composition according to    claim 1    wherein said Group VIII metal of said catalyst is one or both of Pd and Ni.  
     
     
         17 . A compound having a formula selected from the group consisting of Ag{B(C 6 F 5 ) 4 }(arene) p  and Ag{B(C 6 H 3 (CF 3 ) 2 ) 4 }(arene) p  wherein arene is an aromatic hydrocarbon group having 6 to 18 carbon atoms that can be substituted by up to 6 alkyl or aryl groups each having up to 12 carbon atoms.  
     
     
         18 . The compound according to    claim 17    wherein arene is selected from the group consisting of benzene, toluene, ortho-, meta-, or para-xylene, and mesitylene, and p=1, 2, or 3.  
     
     
         19 . The compound according to    claim 17    having the formula Ag + {B(C 6 F 5 ) 4 } − (toluene) 3 , Ag + {B(C 6 F 5 ) 4 } − (xylene) 3 , and Ag + {B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 } − (toluene).  
     
     
         20 . The polymerized composition according to    claim 1   .  
     
     
         21 . The polymerized composition according to    claim 20    which comprises a plurality of C 3  or higher alpha-olefin units wherein the polymer M w  is greater than 90,000 and the polymer has an average number of branch points less than one per alpha-olefin unit.  
     
     
         22 . The polymerized composition according to    claim 20    which comprises one or more of 1) a plurality of C 3  or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per monomer unit, and 2) a plurality of C 2  alpha-olefin units wherein the polymer has an average number of branch points greater than 0.01, and water in an amount sufficient to form a second phase.  
     
     
         23 . The polymerized composition according to    claim 20    which comprises a crosslinked alpha-olefin polymer.  
     
     
         24 . The polymerized composition according to    claim 23    which has been crosslinked by one or more of electron beam irradiation, ultraviolet irradiation, and optionally UV-activated crosslinking agents.  
     
     
         25 . The polymerized composition according to    claim 22    wherein said polymer M w  is greater than 90,000.  
     
     
         26 . A composition of matter comprising a compound having the formula  
       {(ArN═C(R 1 )C(R 1 )═NAr)Pd(Me)(ether)} + Q −   XIII 
       wherein 
 Ar is 2,6-C 6 H 3 (R 3 ) 2  wherein each R 3  independently is isopropyl or methyl, and each R 1  independently is H or methyl, or the two R 1  groups taken together are 1,8-napthalene-diyl,  
 ether is diethyl ether, tetrahydrofuran, diethyl ether, or methyl t-butyl ether, and  
 Q is selected from the group consisting of B(C 6 F 5 ) 4 , PF 6 , SbF 6 , AsF 6 , BF 4 , (R f SO 2 ) 2 CH, (R f SO 2 ) 3 C, (R f  SO 2 ) 2 N, and R f SO 3 , wherein R f  is as previously defined,  
 and X is a halogen atom.  
 
     
     
         27 . The composition according to    claim 26    wherein compounds of formula XIII are selected from the group consisting of 
 {((2,6-C 6 H 3 (i-Pr) 2 )N═C(CH 3 )C(CH 3 )═N(2,6-C 6 H 3 (i-Pr) 2 ))Pd(CH 3 )(Me t-butyl ether)} + {B(C 6 F 5 ) 4 } − ,  
 {((2,6-C 6 H 3 (i-Pr) 2 )N═C(CH 3 )C(CH 3 )═N(2,6-C 6 H 3 (i-Pr) 2 ))-Pd(CH 3 )(Et 2 O)} + {B(C 6 F 5 ) 4 } − ,  
 {((2,6-C 6 H 3 (i-Pr) 2 )N═C(CH 3 )C(CH 3 )═N(2,6-C 6 H 3 (i-Pr) 2 ))Pd(CH 3 )(Me t-butyl ether)} + {N(SO 2 CF 3 ) 2 } − ,  
 {((2,6-C 6 H 3 (i-Pr) 2 )N═C(CH 3 )C(CH 3 )═N(2,6-C 6 H 3 (i-Pr) 2 ))Pd(CH 3 )-(Et 2 O)} + {N(SO 2 CF 3 ) 2 } − ,  
 {((2,6-C 6 H 3 (i-Pr) 2 )N═C(CH 3 )C(CH 3 )═N(2,6-C 6 H 3 (i-Pr) 2 ))Pd(CH 3 )(Me t-butyl ether)} + {N(SO 2 C 2 F 5 ) 2 } − , and  
 {((2,6-C 6 H 3 (i-Pr) 2 )N═C(CH 3 )C(CH 3 )═N(2,6-C 6 H 3 (i-Pr) 2 ))Pd(CH 3 )-(Et 2 O} + {N(SO 2 C 2 F 5 ) 2 } − .  
 
     
     
         28 . A process comprising the step of 
 admixing an alpha-olefin hydrocarbon monomer, optionally a copolymerizable monomer, with an organometallic catalyst comprising a Group VIII metal and a polydentate ligand having steric bulk sufficient to permit formation of high polymer, in the presence of one or both of air and water to provide a polymerized alpha-olefin.    
     
     
         29 . The process according to    claim 28    further comprising the step of crosslinking the resulting polymer.  
     
     
         30 . The process according to    claim 29    wherein said crosslinking step is effected by one or more of electron beam irradiation, ultraviolet irradiation, and optionally UV-activated crosslinking agents.  
     
     
         31 . The process according to    claim 28    wherein said catalyst is a one-part catalyst comprising an organometallic salt or a two-part catalyst comprising a neutral organometallic compound and a cocatalyst.  
     
     
         32 . The process according to    claim 28    wherein said alpha-olefin monomer is 1-octene, 1-pentene, 1-hexene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and cyclopentene.  
     
     
         33 . The process according to    claim 28    wherein said admixture further comprises one or both of a stabilizer and a surfactant.  
     
     
         34 . The process according to    claim 28    wherein said water is present in sufficient quantity to provide a second phase.  
     
     
         35 . A process for preparing a one-part or two-part organometallic catalyst comprising the step of admixing a neutral organometallic compound of the formula  
       {(Ar)N═C(R 1 )C(R 1 )═N(Ar)}Pd(CH 3 )(halogen) 
       wherein Ar and R 1  are as previously defined, and a salt of a non-coordinating counterion of the formula A + Q − wherein A and Q are as previously defined.  
     
     
         36 . The process according to    claim 35    wherein said admixture further comprises one or more of AgNO 3 , an alpha-olefin hydrocarbon monomer, diethyl ether, tetrahydrofuran, methyl t-butyl ether, water, and air.  
     
     
         37 . A process according to    claim 35    wherein A is silver.  
     
     
         38 . A process according to    claim 35    wherein A is a Group IA metal, and AgNO 3 , water and one or more of diethyl ether, tetrahydrofuran and methyl t-butyl ether are present.  
     
     
         39 . A process according to    claim 36    wherein A is a Group IA metal and one of diethyl ether, tetrahydrofuran and methyl t-butyl ether are present.  
     
     
         40 . A process according to    claim 35    wherein A is a Group IA metal and water is present in an amount sufficient to form a second phase.