US2003078347A1PendingUtilityA1
Triazine compounds, polymers comprising triazine structural units, and method
Est. expiryAug 28, 2021(expired)· nominal 20-yr term from priority
C07D 251/34C07D 405/14C07D 405/12C07D 251/26C08G 65/485
48
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Claims
Abstract
In various embodiments the present invention comprises 2,4,6-trisubstituted-1,3,5-triazine capping agents comprising one, two, or three leaving groups as substituents with any remaining substituents being essentially inert to reaction with a nucleophilic group on a polymer or monomer, or reactive with a nucleophilic group on a polymer or monomer at a slower rate than any leaving group. The invention also comprises polymers or monomers with nucleophilic groups capped with a triazine moiety. Still other embodiments of the invention comprise processes for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1 . Triazine-comprising capping agents of the formula (I):
wherein L 1 is an aryloxy group comprising at least one electron withdrawing group ortho, meta, or para to the linkage between the aryloxy group and the triazine ring, and Z 1 and Z 2 are each independently groups which are essentially inert to reaction with a nucleophilic group on a polymer or monomer, or which react with a nucleophilic group on a polymer or monomer at a slower rate than the group, L 1 .
2 . The capping agents of claim 1 wherein Z 1 and Z 2 are each independently alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino or aryloxy.
3 . The capping agents of claim 1 wherein L 1 is an aryloxy group comprising at least one electron withdrawing group ortho or para to the linkage between the aryloxy group and the triazine ring, selected from the group consisting of carboalkoxy, carboaryloxy, carboaryl, halo, cyano, and nitro, and mixtures thereof.
4 . The capping agents of claim 1 wherein L 1 is selected from the group consisting of o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy, o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy, o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, and o-nitrophenoxy.
5 . The capping agents of claim 2 wherein Z 1 and Z 2 are each independently selected from the group consisting of methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.
6 . The capping agents of claim 1 wherein Z 1 and Z 2 are the same.
7 . The capping agents of claim 1 wherein L 1 is o-carbomethoxyphenoxy, and Z 1 and Z 2 are the same and are each selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.
8 . The capping agents of claim 1 wherein either Z 1 , or Z 2 , or both Z 1 and Z 2 are selected from the group consisting of vinyl, allyl, propargyloxy, olefinic groups of formula (VII; Fu 1 ), epoxy groups of formula (VIII; Fu 2 ), and cyclic orthoester groups of formula (IX; Fu 3 ):
wherein R 1 is alkyl or aryl; R 2 is hydrogen, alkyl, or aryl; Y 1 is nitrogen or oxygen; R 3 is a C 1-6 alkylene radical, and R 4 is a C 1-4 primary or secondary alkyl radical or is an alkylene radical forming a second 5- or 6-membered ring with C*, R 5 is a C 1-4 primary or secondary alkyl or C 6-10 aromatic radical, or R 4 and R 5 together with the atoms connecting them form a 5-, 6-, or 7-membered ring; R 6 is hydrogen or a C 1-4 primary or secondary alkyl; m is zero or one, and n is from 1 to 2 m; and x is zero when R 4 and C* form a ring and is otherwise one.
9 . The capping agents of claim 8 wherein L 1 is an aryloxy group comprising at least one electron withdrawing group ortho or para to the linkage between the aryloxy group and the triazine ring, selected from the group consisting of carboalkoxy, carboaryloxy, carboaryl, halo, cyano, and nitro, and mixtures thereof.
10 . The capping agents of claim 8 wherein L 1 is selected from the group consisting of o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy, o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy, o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, and o-nitrophenoxy.
11 . The capping agents of claim 8 wherein Z 1 and Z 2 are the same.
12 . The capping agents of claim 8 wherein Z 1 is alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino or aryloxy.
13 . The capping agents of claim 12 wherein Z 1 is selected from the group consisting of methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.
14 . The capping agents of claim 8 wherein L 1 is o-carbomethoxyphenoxy; Z 1 is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy; and Z 2 is selected from the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
15 . The capping agents of claim 14 wherein Z 2 is selected from the group consisting of glycidoxy and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
16 . The capping agents of claim 8 wherein L 1 is o-carbomethoxyphenoxy; and Z 1 and Z 2 are the same and are selected from the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
17 . The capping agents of claim 16 wherein Z 1 and Z 2 are the same and are selected from the group consisting of glycidoxy and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
18 . Triazine-comprising capping agents of the formula (I):
wherein L 1 is chloro; Z 1 is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy; and Z 2 is selected from the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, and propargyloxy.
19 . Triazine-comprising capping agents of the formula (I):
wherein L 1 is chloro; and Z 1 and Z 2 are the same and are selected from the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, and propargyloxy.
20 . Triazine-comprising capping agents of the formula (II):
wherein L 1 and L 2 are each independently an aryloxy group comprising at least one electron withdrawing group ortho, meta, or para to the linkage between the aryloxy group and the triazine ring, and Z 1 is a group which is essentially inert to reaction with a nucleophilic group on a polymer or monomer, or which reacts with a nucleophilic group on a polymer or monomer at a slower rate than either of the groups, L 1 and L 2 .
21 . The capping agents of claim 20 wherein Z 1 is alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino or aryloxy.
22 . The capping agents of claim 20 wherein L 1 and L 2 are each independently an aryloxy group comprising at least one electron withdrawing group ortho or para to the linkage between the aryloxy group and the triazine ring, selected from the group consisting of carboalkoxy, carboaryloxy, carboaryl, halo, cyano, and nitro, and mixtures thereof.
23 . The capping agents of claim 20 wherein L 1 and L 2 are each independently selected from the group consisting of o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy, o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy, o-carbophenylphenoxy, o-carbophenoxyphenoxy, carbobenzoxyphenoxy, and o-nitrophenoxy.
24 . The capping agents of claim 23 wherein L 1 and L 2 are the same.
25 . The capping agents of claim 21 wherein Z 1 is selected from the group consisting of methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.
26 . The capping agents of claim 20 wherein L 1 and L 2 are each o-carbomethoxyphenoxy, and Z 1 is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.
27 . The capping agents of claim 20 wherein Z 1 is selected from the group consisting of vinyl, allyl, propargyloxy, olefinic groups of formula (VII; Fu 1 ), epoxy groups of formula (VIII; Fu 2 ), and cyclic orthoester groups of formula (IX; Fu 3 ):
wherein R 1 is alkyl or aryl; R 2 is hydrogen, alkyl, or aryl; Y 1 is nitrogen or oxygen; R 3 is a C 1-6 alkylene radical, and R 4 is a C 1-4 primary or secondary alkyl radical or is an alkylene radical forming a second 5- or 6-membered ring with C*, R 5 is a C 1-4 primary or secondary alkyl or C 6-10 aromatic radical, or R 4 and R 5 together with the atoms connecting them form a 5-, 6-, or 7-membered ring; R 6 is hydrogen or a C 1-4 primary or secondary alkyl; m is zero or one, and n is from 1 to 2 m; and x is zero when R 4 and C* form a ring and is otherwise one.
28 . The capping agents of claim 27 wherein L 1 and L 2 are each independently an aryloxy group comprising at least one electron withdrawing group ortho or para to the linkage between the aryloxy group and the triazine ring, selected from the group consisting of carboalkoxy, carboaryloxy, carboaryl, halo, cyano, and nitro, and mixtures thereof.
29 . The capping agents of claim 27 wherein L 1 and L 2 are each independently selected from the group consisting of o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy, o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy, o-carbophenylphenoxy, o-carbophenoxyphenoxy, carbobenzoxyphenoxy, and o-nitrophenoxy.
30 . The capping agents of claim 29 wherein L 1 and L 2 are the same.
31 . The capping agents of claim 27 wherein L 1 and L 2 are each o-carbomethoxyphenoxy; and Z 1 is selected from the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
32 . The capping agents of claim 31 wherein Z 1 is selected from the group consisting of glycidoxy and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
33 . Triazine-comprising capping agents of the formula (II):
wherein L 1 and L 2 are each chloro; and Z 1 is selected from the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, and propargyloxy.
34 . Triazine-comprising capping agents of the formula (III):
wherein L 1 , L 2 , and L 3 are each independently an aryloxy group comprising at least one electron withdrawing group ortho, meta, or para to the linkage between the aryloxy group and the triazine ring.
35 . The capping agents of claim 34 wherein L 1 , L 2 , and L 3 are each independently an aryloxy group comprising at least one electron withdrawing group ortho or para to the linkage between the aryloxy group and the triazine ring, selected from the group consisting of carboalkoxy, carboaryloxy, carboaryl, halo, cyano, and nitro, and mixtures thereof.
36 . The capping agents of claim 34 wherein L 1 , L 2 , and L 3 are each independently selected from the group consisting of o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy, o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy, o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, and o-nitrophenoxy.
37 . The capping agents of claim 36 wherein L 1 , L 2 , and L 3 are the same.
38 . The capping agent of claim 36 wherein L 1 , L 2 , and L 3 are each o-carbomethoxyphenoxy.
39 . A polymer with nucleophilic groups capped with a triazine moiety comprising at least one vinyl, allyl, or propargyloxy group, or olefinic group of formula (VII; Fu 1 ):
wherein R 1 is alkyl or aryl; and R 2 is hydrogen, alkyl, or aryl.
40 . The polymer of claim 39 wherein the triazine moiety comprises at least one vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, or propargyloxy group.
41 . The polymer of claim 39 in which the nucleophilic groups capped are hydroxy or amino groups.
42 . The polymer of claim 41 which is a nucleophile-containing polyether, poly(arylene ether), poly(phenylene ether), polyethersulfone, polyetherester, polyetherimide, polyamideimide, polyimide, polyetherketone, polyetheretherketone, polyetherketoneketone, poly(arylene sulfide), poly(phenylene sulfide), polycarbonate, polyester, poly(alkylene terephthalate), polyarylate, liquid crystalline polyester, polyestercarbonate, polysulfone, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, siloxane, copolymer containing hydroxyalkylacrylate, oxidized polyolefins, or phenoxy resin.
43 . The polymer of claim 42 which is a hydroxy-terminated poly(phenylene ether) or a hydroxy-terminated polycarbonate.
44 . The polymer of claim 43 which is a poly(phenylene ether) comprising 2,6-dimethylphenylene structural units.
45 . The polymer of claim 43 which is a polycarbonate comprising bisphenol A structural units.
46 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 1 .
47 . The process of claim 46 which comprises a catalyst.
48 . The process of claim 47 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
49 . The process of claim 46 wherein L 1 is removed from a reaction mixture by devolatilization as leaving group compound and recovered.
50 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 7 .
51 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 8 .
52 . The process of claim 51 which comprises a catalyst.
53 . The process of claim 52 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
54 . The process of claim 51 wherein L 1 is removed from a reaction mixture by devolatilization as leaving group compound and recovered.
55 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 14 .
56 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 16 .
57 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 18 .
58 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 19 .
59 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 20 .
60 . The process of claim 59 which comprises a catalyst.
61 . The process of claim 60 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
62 . The process of claim 59 wherein L 1 is removed from a reaction mixture by devolatilization as leaving group compound and recovered.
63 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 26 .
64 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 27 .
65 . The process of claim 64 which comprises a catalyst.
66 . The process of claim 65 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
67 . The process of claim 64 wherein L 1 is removed from a reaction mixture by devolatilization as leaving group compound and recovered.
68 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 31 .
69 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 33 .
70 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 34 .
71 . The process of claim 70 which comprises a catalyst.
72 . The process of claim 71 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
73 . The process of claim 70 wherein L 1 is removed from a reaction mixture by devolatilization as leaving group compound and recovered.
74 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 35 .
75 . A process for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent of claim 38 .
76 . A process for capping terminal hydroxy groups in a polycarbonate which comprises combining and reacting the polymer with a triazine-comprising capping agent of the formula (I):
wherein L 1 is o-carbomethoxyphenoxy, and Z 1 and Z 2 are each independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, 2,4,6-trichlorophenoxy, vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
77 . The process of claim 76 wherein the polycarbonate is derived from a melt reaction process with reactants comprising bisphenol A and diphenylcarbonate.
78 . The process of claim 76 which comprises a catalyst.
79 . The process of claim 78 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
80 . The process of claim 76 wherein L 1 is removed from a reaction mixture by devolatilization as methyl salicylate and recovered.
81 . A process for capping terminal hydroxy groups in a polycarbonate which comprises combining and reacting the polymer with a triazine-comprising capping agent of the formula (II):
wherein L 1 and L 2 are each o-carbomethoxyphenoxy; and Z 1 is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, 2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman, 2-(4′-oxyphenyl)-2,4,4-trimethylchroman, 1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene, 4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy, 2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy, 3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy, 2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy, halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy, dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy, 2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy, 2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy, trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy, 2,4,6-tribromophenoxy, 2,4,6-trichlorophenoxy, vinyl, allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
82 . The process of claim 81 wherein at least a portion of polycarbonate chains are chain extended.
83 . The process of claim 81 wherein the polycarbonate number average molecular weight increases by at least 1,000 Daltons.
84 . The process of claim 81 wherein the polycarbonate is derived from a melt reaction process with reactants comprising bisphenol A and diphenylcarbonate.
85 . The process of claim 81 which comprises a catalyst.
86 . The process of claim 85 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
87 . The process of claim 81 wherein L is removed from a reaction mixture by devolatilization as methyl salicylate and recovered.
88 . A process for capping terminal hydroxy groups in a polycarbonate which comprises combining and reacting the polymer with a triazine-comprising capping agent of the formula (III):
wherein L 1 , L 2 , and L 3 are each o-carbomethoxyphenoxy.
89 . The process of claim 88 wherein at least a portion of polycarbonate chains are branched.
90 . The process of claim 88 wherein the value for polycarbonate melt volume rate decreases by at least 10% compared to its initial value.
91 . The process of claim 88 wherein the polycarbonate is derived from a melt reaction process with reactants comprising bisphenol A and diphenylcarbonate.
92 . The process of claim 88 which comprises a catalyst.
93 . The process of claim 92 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
94 . The process of claim 88 wherein L is removed from a reaction mixture by devolatilization as methyl salicylate and recovered.
95 . A process for preparing polycarbonate which comprises melt transesterification in the presence of at least one triazine-comprising capping agent comprising at least one o-carbomethoxyphenoxy substituent.
96 . The process of claim 95 wherein the polycarbonate comprises structural units derived from the reaction of bisphenol A and diphenylcarbonate.
97 . The process of claim 95 which comprises a catalyst.
98 . The process of claim 97 wherein the catalyst is at least one member selected from the group consisting of a nitrogen-containing basic compound, a phosphorus-containing basic compound, an alkali metal compound, sodium hydroxide, an alkaline earth metal compound, a boric acid, and a boric ester.
99 . The process of claim 95 wherein methyl salicylate is removed from a reaction mixture by devolatilization and recovered.Join the waitlist — get patent alerts
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