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US4567247A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for forming thermally stable thermotropic liquid crystalline polyesters of predetermined chain length utilizing aromatic hydroxyl monomer and/or aromatic amine monomer

Assignee: CNA Holdings LLC
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Filing: 1984-05-17
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Granted: 1986-01-28
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Expires: 2004-05-17
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Abstract

Abstract An improved polymerization process is provided for the formation of a polyester which is capable of forming an anisotropic melt phase and which optionally may include amide linkages. An approximately 0.25 to 4 percent molar excess of aromatic hydroxyl monomer and/or aromatic amine monomer and/or an esterified and/or amidated derivative thereof is provided in the polymerization zone during the polymerization reaction. Such monomer imparts dioxyaryl, diaminoaryl, or oxyaminoaryl units to the interior of the resulting polymer chains and causes the polymer chains to terminate in hydroxyl end groups and/or an esterified derivative thereof and/or amino end groups and/or an amidated derivative thereof wherein the polymer chains achieve a predetermined average chain length through the depletion of other monomers present in the polymerization zone. The resulting polyester unlike the usual product of the prior art is substantially incapable of additional chain growth upon subsequent heating and accordingly may be relied upon to maintain a substantially constant viscosity during melt processing regardless of the duration of heating.

Inventors

  • 👤 Hyun-Nam Yoon

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-03 22:40
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/02; C08G63/60; C08G63/605; C08G69/00; C08G69/44; C09; C09K; C09K19/00; C09K19/04; C09K19/38; C09K19/3804; C09K19/3809

Claims Analysis

Total Claims: 26
Claim 1
Independent Claim 299 words
In a process for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase and which optionally may include amide linkages through a polymerization reaction of ester-forming and optionally also amide-forming monomers to form a polymer having recurring moieties selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (a) ##STR11## and (b) a mixture of ##STR12## where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group; the improvement of providing in the polymerization zone during the polymerization reaction an approximately 0.25 to 4 percent molar excess of an aromatic monomer selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (c) HO--Ar--OH, and/or an esterified derivative thereof, (d) H 2 N--Ar--NH 2 , and/or an amidated derivative thereof, (e) HO--Ar--NH 2 , and/or an esterified and/or an amidated derivative thereof, and (f) mixtures of the foregoing, which during the polymerization reaction imparts units to the interior of the polymer chains selected from the group consisting of: (g) dioxyaryl units, (h) diaminoaryl units, (i) oxyaminoaryl units, and (j) mixtures of the foregoing, and causes the polymer chains to end in groups selected from group consisting of: (k) hydroxyl end groups and/or an esterified derivative thereof, (l) amino end groups and/or an amidated derivative thereof, and (m) mixtures of the foregoing, wherein the polymer chains achieve a predetermined average chain length through the depletion of other monomers present in the polymerization zone to yield a polyester product which is substantially incapable of additional chain growth upon subsequent heating.
Claim 2
Dependent Claim 299 words
In a process for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase and which optionally may include amide linkages through a polymerization reaction of ester-forming and optionally also amide-forming monomers to form a polymer having recurring moieties selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (a) ##STR11## and (b) a mixture of ##STR12## where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group; the improvement of providing in the polymerization zone during the polymerization reaction an approximately 0.25 to 4 percent molar excess of an aromatic monomer selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (c) HO--Ar--OH, and/or an esterified derivative thereof, (d) H 2 N--Ar--NH 2 , and/or an amidated derivative thereof, (e) HO--Ar--NH 2 , and/or an esterified and/or an amidated derivative thereof, and (f) mixtures of the foregoing, which during the polymerization reaction imparts units to the interior of the polymer chains selected from the group consisting of: (g) dioxyaryl units, (h) diaminoaryl units, (i) oxyaminoaryl units, and (j) mixtures of the foregoing, and causes the polymer chains to end in groups selected from group consisting of: (k) hydroxyl end groups and/or an esterified derivative thereof, (l) amino end groups and/or an amidated derivative thereof, and (m) mixtures of the foregoing, wherein the polymer chains achieve a predetermined average chain length through the depletion of other monomers present in the polymerization zone to yield a polyester product which is substantially incapable of additional chain growth upon subsequent heating.
Claim 3
Dependent Claim 17 words
A process in accordance with claim 1 wherein said polymerization reaction is carried out in the melt.
Claim 4
Dependent Claim 22 words
A process in accordance with claim 1 wherein said polymerization reaction is carried out while the monomers are suspended as a slurry.
Claim 5
Dependent Claim 43 words
A process in accordance with claim 1 wherein any monomer present in the polymerization zone which would otherwise include a hydroxyl group and/or an amine group is provided as a lower acyl ester and/or amide of about 2 to about 4 carbon atoms.
Claim 6
Dependent Claim 35 words
A process in accordance with claim 1 wherein any monomer present in the reaction zone which would otherwise include a hydroxyl group and/or an amine group is provided as an acetate ester and/or an acetamide.
Claim 7
Dependent Claim 25 words
A process in accordance with claim 1 wherein said aromatic monomer which is provided in said molar excess is HO--Ar--OH, or an esterified derivative thereof.
Claim 8
Dependent Claim 29 words
A process in accordance with claim 1 wherein said aromatic monomer which is provided in said molar excess is H 2 N--Ar--NH 2 , or an amidated derivative thereof.
Claim 9
Dependent Claim 29 words
A process in accordance with claim 1 wherein said aromatic monomer which is provided in said molar excess is HO--Ar--NH 2 , and/or an esterified and/or amidated derivative thereof.
Claim 10
Dependent Claim 34 words
A process in accordance with claim 1 wherein said aromatic monomer which is provided in said molar excess is provided in the polymerization zone in a molar excess of approximately 0.5 to 4 percent.
Claim 11
Dependent Claim 36 words
A process in accordance with claim 1 wherein said polyester product exhibits an inherent viscosity of approximately 0.8 to 10.0 dl./g. when dissolved in a concentration of 0.1 percent by weight in pentafluorophenol at 60° C.
Claim 12
Dependent Claim 130 words
A process in accordance with claim 1 wherein said polyester product consists essentially of moieties I and II which optionally may include substitution of at least some of the hydrogen atoms present upon an aromatic ring wherein: I is ##STR13## and II is ##STR14## with said optional substitution if present being selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen, phenyl, and mixtures of the foregoing, and wherein said polyester comprises approximately 10 to 90 mole percent of moiety I, and approximately 10 to 90 mole percent of moiety II, and which additionally incorporates an approximately 0.25 to 4 percent of said units derived from said aromatic monomer which is provided in molar excess.
Claim 13
Dependent Claim 215 words
A process in accordance with claim 1 wherein said product consists essentially of moieties I, II, and optionally III, which optionally may include substitution of at least some of the hydrogen atoms present upon an aromatic ring wherein: I is ##STR15## II is ##STR16## where Ar comprises at least one aromatic ring and where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group, and III is ##STR17## wherein at least some of the hydrogen atoms present upon the rings optionally may be replaced by substitution selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen, phenyl, and mixtures thereof, and wherein moiety I is present in a concentration of approximately 10 to 90 mole percent, moiety II is present in a concentration of approximately 5 to 45 mole percent, and moiety III is present in a concentration of approximately 0 to 45 mole percent, with the total concentrations of moieties I and III being within the range of approximately 55 to 95 mole percent, and which additionally incorporates an approximately 0.25 to 4 percent of said units derived from said aromatic monomer which is provided in molar excess.
Claim 14
Dependent Claim 30 words
A polyester formed in accordance with the process of claim 1 which is capable of forming an anisotropic melt phase, and is substantially incapable of further chain growth upon heating.
Claim 15
Dependent Claim 173 words
In a process for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase through a polymerization reaction of ester-forming monomers to form a polymer which consists essentially of moieties I and II wherein: I is ##STR18## and II is ##STR19## wherein said polyester comprises approximately 25 to 45 mole percent of moiety I, and approximately 55 to 75 mole percent of moiety II; the improvement of providing in the polymerization zone during said polymerization reaction an approximately 0.25 to 4 percent molar excess of an aromatic monomer of the formula: HO--Ar--OH, and/or an esterified derivative thereof, which during the polymerization reaction imparts dioxyaryl units to the interior of the polymer chains and causes the polymer chains to end in hydroxy end groups and/or an esterified derivative thereof, wherein the polymer chains achieve a predetermined average chain length through the depletion of other monomers present in the polymerization zone to yield a polyester product which is substantially incapable of additional chain growth upon subsequent heating.
Claim 16
Dependent Claim 173 words
In a process for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase through a polymerization reaction of ester-forming monomers to form a polymer which consists essentially of moieties I and II wherein: I is ##STR18## and II is ##STR19## wherein said polyester comprises approximately 25 to 45 mole percent of moiety I, and approximately 55 to 75 mole percent of moiety II; the improvement of providing in the polymerization zone during said polymerization reaction an approximately 0.25 to 4 percent molar excess of an aromatic monomer of the formula: HO--Ar--OH, and/or an esterified derivative thereof, which during the polymerization reaction imparts dioxyaryl units to the interior of the polymer chains and causes the polymer chains to end in hydroxy end groups and/or an esterified derivative thereof, wherein the polymer chains achieve a predetermined average chain length through the depletion of other monomers present in the polymerization zone to yield a polyester product which is substantially incapable of additional chain growth upon subsequent heating.
Claim 17
Dependent Claim 17 words
A process in accordance with claim 14 wherein said polymerization reaction is carried out in the melt.
Claim 18
Dependent Claim 39 words
A process in accordance with claim 14 wherein the oxy portions of the ester-forming monomers which form moieties I and II are provided in said polymerization zone as lower acyl esters of about 2 to about 4 carbon atoms.
Claim 19
Dependent Claim 30 words
A process in accordance with claim 14 wherein the oxy portions of the ester-forming monomers which form moieties I and II are provided in said polymerization zone as acetate esters.
Claim 20
Dependent Claim 25 words
A process in accordance with claim 14 wherein the aromatic monomer which is provided in a molar excess is 2,6-dihydroxynaphthalene and/or an esterified derivative thereof.
Claim 21
Dependent Claim 25 words
A process in accordance with claim 14 wherein the aromatic monomer which is provided in a molar excess is p,p'-biphenol and/or an esterified derivative thereof.
Claim 22
Dependent Claim 37 words
A process in accordance with claim 14 wherein the aromatic monomer which is provided in said molar excess is provided in said polymerization zone as a lower acryl ester of about 2 to about 4 carbon atoms.
Claim 23
Dependent Claim 28 words
A process in accordance with claim 14 wherein the aromatic monomer which is provided in said molar excess is provided in said polymerization zone as an acetate ester.
Claim 24
Dependent Claim 34 words
A process in accordance with claim 14 wherein the aromatic monomer which is provided in said molar excess is provided in the polymerization zone in a molar excess of approximately 0.5 to 4 percent.
Claim 25
Dependent Claim 36 words
A process in accordance with claim 14 wherein said polyester product exhibits an inherent viscosity of approximately 0.8 to 10.0 dl./g. when dissolved in a concentration of 0.1 percent by weight in pentafluorophenol at 60° C.
Claim 26
Dependent Claim 30 words
A polyester formed in accordance with the process of claim 14 which is capable of forming an anisotropic melt phase, and is substantially incapable of further chain growth upon heating.

References Cited (Backward Citations)

US4219461A Cited
US4256624A Cited
US4337190A Cited
US4318842A Cited
US4318841A Cited
US4359569A Cited
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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1989-01-27 1989-07-29 1990-01-28 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1993-01-27 1993-07-29 1994-01-28 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1997-01-27 1997-07-29 1998-01-28 $7700.00 Window Closed / Lapsed

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