HIGH HEAT POLYETHERSULFONE COMPOSITIONS
High heat polyethersulfone compositions are provided which possess unexpectedly high glass transition temperatures. The polyethersulfone compositions comprise structural units derived from fluorenone bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene, and structural units derived from at least one biphenyl-bissulfone such as 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl. The novel polyethersulfone compositions may further comprise structural units derived from one or more biphenols such as 4,4′-biphenol, bisphenols such as BPA, or other electrophilic sulfone monomers, such as bis(4-chlorophenyl)sulfone. In one embodiment, the polyethersulfone composition of the present invention comprises structural groups derived exclusively from 9,9-bis(4-hydroxyphenyl)fluorene and 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl and exhibits a single glass transition of greater than 300° C.
1 . A polyethersulfone composition comprising structural units I
wherein R 1 , R 2 , R 3 , and R 4 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “a”, “b”, “c”, “d”, “e”, “f”, “g” and “h” are independently integers from 0 to 4 and
structural units III
wherein R 3 , R 4 , and R 5 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “e”, “f”, “g”, “h”, “i”, and “j” are independently integers from 0 to 4;
wherein, the molar ratio of structural unit I to structural unit III is from 1:3 to 1:1 and the Tg of the polyethersulfone exceeds the value predicted by the Fox Equation by 5° C. or more.
2 . The polyethersulfone composition according to claim 1 , said composition having a glass transition temperature of at least 270° C.
3 . The polyethersulfone composition according to claim 1 , said composition having a glass transition temperature of at least 250° C.
4 . The polyethersulfone composition according to claim 1 , further comprising structural units II
wherein R 5 and R 6 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “i”, “j”, “k”, and “l” are independently integers from 0 to 4.
5 . (canceled)
6 . The polyethersulfone composition according to claim 1 , further comprising structural units IV
wherein R 1 , R 2 , and R 6 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “a”, “b”, “c”, “d”, “k”, and “l” are independently integers from 0 to 4.
7 . The polyethersulfone composition according to claim 1 , wherein “a”, “b”, “c”, “d”, “e”, “f”, “g” and “h” are each zero.
8 . The polyethersulfone composition according to claim 4 , wherein “i”, “j”, “k”, and “l” are each zero.
9 . The polyethersulfone composition according to claim 5 , wherein “e”, “f”, “g”, “h”, “i”, and “j” are each zero.
10 . The polyethersulfone composition according to claim 6 , wherein “a”, “b” “c” “d” “k”, and “l” are each zero.
11 . The polyethersulfone composition according to claim 1 , further comprising structural units derived from at least one bisphenol V
wherein R 7 is independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; W an oxygen atom, a sulfur atom, a selenium atom, a divalent C 1 -C 20 aliphatic radical, a divalent C 3 -C 20 cycloaliphatic radical, or a divalent C 2 -C 20 aromatic radical; and “m”, and “n” are independently integers from 0 to 4.
12 . The polyethersulfone composition according to claim 1 , further comprising structural units derived from bisphenol A.
13 . A polyethersulfone composition comprising structural units derived from at least one fluorenone bisphenol VI
wherein R 1 and R 2 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “a”, “b”, “c”, and “d” are independently integers from 0 to 4;
structural units derived from at least one biphenyl-bissulfone VII
wherein X 1 and X 2 are independently halogen, or nitro; R 3 and R 4 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “e”, “f”, “g”, and “h” are independently integers from 0 to 4; and
structural units derived from at least one biphenol VIII
wherein R 5 is independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “i” and “j” are independently integers from 0 to 4;
wherein:
the structural units derived from at least one fluorenone bisphenol VI represent 10 to 90 mole percent of all structural units derived from a dihydroxy aromatic compound;
the structural units derived from at least one biphenol VIII represent up to 90 mole percent of all structural units derived from a dihydroxy aromatic compound;
and the Tg of the polyethersulfone exceeds the value predicted by the Fox Equation by 5° C. or more.
14 . The polyether sulfone composition according to claim 13 , wherein the structural units derived from fluorenone bisphenol VI represent from about 25 mole percent to about 50 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition.
15 . The polyether sulfone composition according to claim 13 , wherein the structural units derived from biphenol VIII represent from about 50 mole present to about 75 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition.
16 . The polyethersulfone composition according to claim 13 , further comprising structural units derived from at least one sulfone IX
wherein X 3 and X 4 are independently halogen, or nitro; R 6 is independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “k” and “l” are independently integers from 0 to 4.
17 . The polyethersulfone composition according to claim 16 , wherein the structural units derived from biphenyl-bissulfone VII represent from about 10 mole percent to about 70 mole percent of all structural groups derived from an electrophilic sulfone monomer.
18 . The polyethersulfone composition according to claim 16 , wherein the structural units derived from sulfone IX represent from about 5 mole percent to about 50 mole percent of all structural groups derived from an electrophilic sulfone monomer.
19 . A polyethersulfone composition comprising structural groups derived from 10 to 90 mole percent 9,9-bis(4-hydroxyphenyl)fluorene; and up to 90 mole percent 4,4′-biphenol, based on structural groups derived from dihydroxy aromatic compounds, and 10 to 100 mole percent 4,4′-bis((4 chlorophenyl)sulfonyl)-1,1′-biphenyl based on structural groups derived from an electrophilic sulfone monomer, wherein the Tg of the polyethersulfone exceeds the value predicted by the Fox Equation by 5° C. or more.
20 . The polyethersulfone composition according to claim 19 , further comprising of structural groups derived from bis(4-chlorophenyl)sulfone.
21 . (canceled)
22 . An article comprising the polyethersulfone composition of claim 1 .
23 . A method of making a polyethersulfone composition; said method comprising:
(a) heating a reaction mixture comprising at least one solvent, at least one organic phase transfer catalyst, at least one dialkali metal salt of a fluorenone bisphenol VI
wherein R 1 and R 2 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “a”, “b”, “c”, and “d” are independently integers from 0 to 4 and a dialkali metal salt of 4,4′-biphenol;
and at least one biphenyl-bissulfone VII
wherein X 1 and X 2 are independently halogen, or nitro; R 3 and R 4 are independently at each occurrence halogen, nitro, a C 1 -C 20 aliphatic radical, a C 3 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and “e”, “f”, “g”, and “h” are independently integers from 0 to 4 to provide a reaction product; and
(b) recovering a product polyethersulfone.
24 . A polyethersulfone composition consisting essentially of structural groups derived from 9,9-bis(4-hydroxyphenyl)fluorene; 4.4′-biphenol, and 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyls, wherein the Tg of the polyethersulfone exceeds the value predicted by the Fox Equation by 5° C. or more.