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US 8,283,427 B2Granted
Heterogeneous perfluoroaryl substituted Lewis acid catalysts for cationic polymerizations
OwnerStewart P. Lewisinventor
Life of this patent
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Abstract
A process for cationically polymerizing olefin monomers in a reaction mixture includes the step of contacting olefin monomers and a catalytically effective amount of an initiating composition containing (A) a heterogeneous perfluoroaryl substituted Lewis acid coinitiator selected from the group consisting of open chain and cyclic aluminoxane compounds or Group 13 perfluoroaryl Lewis acid compounds of formula (III) and (B) an initiator selected from the group consisting of (i) organic compounds, (ii) halogens, (iii) interhalogens; (iv) Brönsted acids, (v) boron halides; (vi) silicon compounds; and (vii) germanium compounds. A novel initiator system is further disclosed.
Claims14
A process for cationically polymerizing olefin monomers in a reaction mixture, the process comprising the steps of:
- contacting olefin monomers and a catalytically effective amount of an initiating composition containing (A) a heterogeneous Lewis acid coinitiator compound selected from the group consisting of (1) open chain and cyclic, perfluoroaryl substituted aluminoxane compounds of the formulas (I) and (II):
- wherein (a) at least one of Rv, Rw, and Rx, if a formula (I) compound is used, and Ry, if a formula (II) compound is used, is a perfluoroaryl substituent, (b) at least one other of Rv, Rw, and Rx, if the formula (I) compound is used, and Rz, if a formula (II) compound is used, is selected from the group consisting of C1-C10 alkyls and a halide, (c) wherein, optionally, boron can be substituted for Al when bound to a perfluoroaryl substituent in both formula (I) and (II), (d) n is an integer from about 1 to about 40, (e) n′ is an integer from about 1 to about 40;
- and (2) Group 13 perfluoroaryl Lewis acid compounds of the general formula (III):
- wherein M is a Group 13 element;
- and wherein the heterogeneous Lewis acid coinitiator compound is essentially insoluble in the reaction mixture and is supported on an inert substrate containing reactive functionalities that can chemically bind to the Lewis acid coinitiator compound;
- and (B) an initiator compound selected from the group consisting of (i) organic compounds having the formula (IV):
- wherein X is selected from the group consisting of halogens, N3, CN, and CF3SO3 and R1, R2, and R3 are selected from the group consisting of a hydrogen atom, halogens, N3, NO2, CN, CF3SO3, SIR34, OSiR34, OR4, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof, and derivatives thereof containing substituents thereof, including R1 and R2 or R1, R2, and R3 being combined together so that they represent a single substituent wherein C is a member, and wherein each R4 can be the same or different and is selected from the group consisting of a hydrogen atom, halogens, N3, CN, CF3SO3, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof, and derivatives thereof containing substituents thereof;
- and C is a carbon atom;
- (ii) halogens;
- (iii) interhalogens;
- (iv) Brönsted acids, (v) boron halides;
- (vi) silicon compounds having the formula (V):
- wherein X is selected from the group consisting of halogens, N3, CN, CF3SO3, SiR34, and OSiR34;
- R1, R2, R3 and each R4 can be the same or different and is selected from the group consisting of a hydrogen atom, X, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof and derivatives thereof containing substituents thereof, including R1 and R2 or R1, R2, and R3 being combined together so that they represent a single substituent wherein Si is a member;
- and (vii) germanium compounds having the formula (VI):
- wherein X is selected from the group consisting of halogens, N3, CN, and CF3SO3;
- R1, R2, and R3 is selected from the group consisting of a hydrogen atom, X, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof and derivatives thereof containing substituents thereof, including R1 and R2 or R1, R2, and R3 being combined together so that they represent a single substituent wherein Ge is a member;
- with the provisos that, 1) where the Lewis acid coinitiator is a Group 13 perfluoroaryl Lewis acid compound of formula (III), then the initiator is selected from (i) the organic compounds of formula (IV), under cationic polymerization reaction conditions;
- and 2) where M is Al or Ga as the Group 13 element, then the Lewis acid coinitiator compound may catalyze polymerization of the monomer via erotic initiation under cationic polymerization conditions without purposeful addition of the initiator compound (B).
16 more elements
An initiator system for use with a reaction mixture in the cationic polymerization of olefins, the initiator system comprising:
- (A) a heterogeneous Lewis acid coinitiator compound selected from the group consisting of
- (1) open chain and cyclic aluminoxane compounds of the formula (I) and (II):
- wherein (a) at least one of Rv, Rw, and Rx, if a formula (I) compound is used, and Ry, if a formula (II) compound is used, is a perfluoroaryl substituent, (b) at least one other of Rv, Rw, and Rx, if the formula (I) compound is used, and Rz, if a formula (II) compound is used, is selected from the group consisting of C1-C10 alkyls and a halide, (c) wherein, optionally, boron can be substituted for Al when bound to a perfluoroaryl substituent in both formula (I) and (II), (d) n is an integer from about 1 to about 40, (e) n′ is an integer from about 1 to about 40;
- and
- (2) Group 13 perfluoroaryl Lewis acid compounds of the general formula (III):
- wherein M is a Group 13 element, and wherein the heterogeneous Lewis acid coinitiator is essentially insoluble in the reaction mixture and is supported on a inert substrate containing reactive functionalities that can chemically bind to the Lewis acid coinitiator compound;
- and
- (B) an initiator selected from the group consisting of
- (i) organic compounds having the formula (IV):
- wherein X is selected from the group consisting of halogens, N3, CN, and CF3SO3 and R1, R2, and R3 are selected from the group consisting of a hydrogen atom, halogens, N3, NO2, CN, CF3SO3, SiR34, OSiR34, OR4, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof, and derivatives thereof containing substituents thereof, including R1 and R2 or R1, R2, and R3 being combined together so that they represent a single substituent wherein C is a member, and wherein each R4 can be the same or different and is selected from the group consisting of a hydrogen atom, halogens, N3, CN, CF3SO3, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof, and derivatives thereof containing substituents thereof;
- and C is a carbon atom;
- (ii) halogens;
- (iii) interhalogens;
- (iv) Brönsted acids;
- (v) boron halides;
- (vi) silicon compounds having the formula (V):
- wherein X is selected from the group consisting of halogens, N3, CN, CF3SO3, SiR34, and OSiR34;
- R1, R2, R3 and each R4 can be the same or different and is selected from the group consisting of a hydrogen atom, X, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof and derivatives thereof containing substituents thereof, including R1 and R2 or R1, R2, and R3 being combined together so that they represent a single substituent wherein Si is a member;
- and
- (vii) germanium compounds having the formula (VI):
- wherein X is selected from the group consisting of halogens, N3, CN, and CF3SO3;
- R1, R2, and R3 is selected from the group consisting of a hydrogen atom, X, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C18 aryl, combinations thereof and derivatives thereof containing substituents thereof, including R1 and R2 or R1, R2, and R3 being combined together so that they represent a single substituent wherein Ge is a member;
- and
- with the provisos that, 1) where the Lewis acid coinitiator is a Group 13 perfluoroaryl Lewis acid compound of formula (III), then the initiator is selected from (i) the organic compounds of formula (IV), under cationic polymerization reaction conditions;
- and 2) where M is Al or Ga as the Group 13 element, then the initiator may alternatively be a proton donor obtained from adventitious moisture or from the inert substrate.
22 more elements
Dependencies are inferred from the claim text.