초록 ▼

The present invention relates to a synthetic method comprising contacting at least one diaryl carbonate with one or more dihydroxy aromatic compounds in the presence of a transesterification catalyst under melt polymerization conditions to afford a product polycarbonate. The transesterifcation catal

The present invention relates to a synthetic method comprising contacting at least one diaryl carbonate with one or more dihydroxy aromatic compounds in the presence of a transesterification catalyst under melt polymerization conditions to afford a product polycarbonate. The transesterifcation catalysts used according to the method of the present invention are polyhydropolyborates in combination with tetraalkylammonium or tetraalkylphosphonium compounds which serve as co-catalysts. The transesterification catalysts employed according to the method of the present invention provide polycarbonates having reduced levels of Fries rearrangement product relative to conventionally employed catalysts such as sodium hydroxide in combination with tetramethylammonium hydroxide co-catalyst.

대표청구항 ▼

The present invention relates to a synthetic method comprising contacting at least one diaryl carbonate with one or more dihydroxy aromatic compounds in the presence of a transesterification catalyst under melt polymerization conditions to afford a product polycarbonate. The transesterifcation catal

The present invention relates to a synthetic method comprising contacting at least one diaryl carbonate with one or more dihydroxy aromatic compounds in the presence of a transesterification catalyst under melt polymerization conditions to afford a product polycarbonate. The transesterifcation catalysts used according to the method of the present invention are polyhydropolyborates in combination with tetraalkylammonium or tetraalkylphosphonium compounds which serve as co-catalysts. The transesterification catalysts employed according to the method of the present invention provide polycarbonates having reduced levels of Fries rearrangement product relative to conventionally employed catalysts such as sodium hydroxide in combination with tetramethylammonium hydroxide co-catalyst. ch occurrence hydrogen, C1-10alkyl or C3-10cycloalkyl, Y, or two or more of R9can combine to form a ring structure, or one or more of R9can form a ring structure with Y provided the ring structure is conjugated with respect to the double bond of the imine nitrogen; R9is independently in each occurrence hydrogen, C1-10alkyl, or C3-10cycloalkyl; R10is separately in each occurrence C1-10alkyl, C3-10cycloalkyl or --(C(R1)2)d--W; W is separately in each occurrence hydrogen, C1-10alkyl or X; X is OR10,SR10or a halogen; Y is independently in each occurrence hydrogen, SR4,OR4,C(O)OR4,a halogen or an alkylene group which forms a cyclic ring with R7or R9; Z is separately in each occurrence oxygen or --NR4; a is separately in each occurrence an integer of from about 1 to about 10; b is separately in each occurrence 0 or 1, with the proviso that the sum of a and b should be from about 2 to about 10; c is separately in each occurrence an integer of from about 1 to about 10; d is separately in each occurrence an integer of about 1 to about 4; x is separately in each occurrence an integer of about 1 to about 10, with the proviso that the total of all occurrences of x is from about 2 to about 10: and y is separately in each occurrence 0 or 1. 3. a method according to claim 2 wherein: R1is separately in each occurrence hydrogen or methyl; R2is separately in each occurrence a C2-4alkyl group; R3is separately in each occurrence hydrogen, methyl, or forms a double bond with an R3or R4on an adjacent atom; R4is separately in each occurrence hydrogen, C1-4alkyl or; R7is separately in each occurrence hydrogen or methyl, X is separately in each occurrence a SR10or --OR10; Y is separately in each occurrence SR4,or OR4,an alkylene group which can also form a cyclic ring with R7or R9; R9is separately in each occurrence hydrogen, a C1-10alkyl, Y, or two or more of R9can form a cyclic ring one or more of R9or one or more of R9; and R9is separately in each occurrence C1-10alkyl, hydrogen or Y. 4. A method according to claim 2 comprising an aliphatic heterocyclic amine wherein the amine is five or six membered heterocylic compound. 5. A method according to claim 2 wherein the amine is a conjugated imine. 6. A method according to claim 2 wherein the amine is an alicyclic compound having bound to the ring a substituent having an amine moiety wherein the alicyclic compound may have a second substitutent which can contain one or more nitrogen, oxygen or sulfur atoms and/or one or two double bonds. 7. A method according to claim 6 wherein the alicyclic ring is a 5 or 6 membered ring. 8. A method according to claim 4 wherein the decomplexing agent is an acid. 9. A method according to claim 2 which comprises a) from about 0.2 to about 8 precent by weight of complex; b) from about 20 to about 95 percent by weight or less of monomers, oligomers or polymers; c) from about 1 to about 8 percent by weight of decomplexing agent; which further comprises d) from about 10 to about 60 percent by weight of a thickener and e) from about 5 to about 35 percent by weight of an elastomeric material. 10. A method of coating a substrate composition which comprises I. contacting the components of the composition comprising a) an organoborane/amine complex wherein the organoborane is a trialkyl borane or an alkyl cycloalkyl borane and the amine is selected from the group of amines having an amidine structural component; aliphatic heterocycles having at least one nit rogen in the heterocyclic ring wherein the heterocyclic compound may also contain one or more nitrogen atoms, oxygen atoms, sulfur atoms, or double bonds in the heterocycle; an alicyclic compound having bound to the ring a substituent having an amine moiety wherein the alicyclic compound may have a second substituent which can contain one or more nitrogen, oxygen or sulfur atoms and/or one or two double bonds; primary amines which in addition to a primary amine have one or more hydrogen bond accepting groups or an ether, polyether, thioether or halogen wherein there is an alkylene chain of at least two carbon atoms between the primary amine and the hydrogen bond accepting group and conjugated imines; d) one or more of monomers, oligomers or polymers having an olefinic unsaturation which is capable of polymerization by free radical polymerization; and, e) an effective amount of a compound which causes the complex to disassociate freeing the borane to initiate polymerization of the one or more monomers, oligomers or polymers having olefinic unsaturation; wherein the compound which causes disassociation of the complex is kept separate from the complex until initiation of polymerization is desired together under conditions such that polymerization is initiated; II. coating a substrate with the composition; and III. heating the coated substrate to cure the composition coated thereon. 11. The method of claim 10 wherein the composition is heated to a temperature of about 30° C. to about 120° C. 12. The method of claim 11 wherein the composition is heated to a temperature of about 50° C. to about 100° C. 13. A method according to claim 11 wherein the complex of the organoborane and the primary amine corresponds to the formula the organoborane heterocyclic amine complex corresponds to the formula the organoborane amidine complex corresponds to the formula the organoborane conjugated imine complex corresponds to the formula and an amine substituted alicyclic compound which corresponds to wherein B is boron; R1is separately in each occurrence hydrogen, a C1-10alkyl or C3-10cycloalkyl; R2is separately in each occurrence a C1-10alkyl, C3-10cycloalkyl or two or more R2may combine to form a cycloaliphatic ring structure; R3is separately in each occurrence hydrogen, a C1-10alkyl C3-10cycloalkyl or forms a double bond with a R3or R4on an adjacent atom; R4is separately in each occurrence hydrogen, C1-10alkyl, C3-10cycloalkyl, C6-10aryl or C6-10alkaryl; R5and R6are separately in each occurrence hydrogen, C1-10alkyl, C3-10cycloalkyl N(R4)2R7is separately in each occurrence hydrogen, C1-10alkyl, C3-10cycloalkyl or two or more of R5,R6and R7in any combination can combine to form a ring structure which can be a single ring or a multiple ring structure and the ring structure can include one or more of nitrogen, oxygen or unsaturation in the ring structure; R9is independently in each occurrence hydrogen, C1-10alkyl or C3-10cycloalkyl, Y, or two or more of R9can combine to form a ring structure, or one or more of R9can form a ring structure with Y provided the ring structure is conjugated with respect to the double bond of the imine nitrogen; R9is independently in each occurrence hydrogen, C1-10alkyl, C3-10cycloalkyl or Y; R10is separately in each occurrence C1-10alkyl, C3-10cycloalkyl or --(C(R1)2)d--W; W is separately in each occurrence hydrogen, C1-10alkyl or X; X is OR10,SR10or a halogen; Y is independently in ea