United States Patent (19) : 11 Patent Number: 5,959,066 (45) Date of Patent: Sep. 28, 1999
United States Patent (19) : 11 Patent Number: 5,959,066 (45) Date of Patent: Sep. 28, 1999
United States Patent (19) : 11 Patent Number: 5,959,066 (45) Date of Patent: Sep. 28, 1999
55
The pelletized polymer is loaded into a tumble dryer and It is to be understood that the above described embodi
under a stream of nitrogen is heated to 115 C. over a period ments are illustrative only and that modification throughout
of 4 hours and then held at that temperature for another 6 may occur to one skilled in the art. Accordingly, this
hours. This allows the polymer to partially crystallize. After invention is not to be regarded as limited to the embodiments
this treatment, a vacuum is applied to the tumble dryer 60 disclosed herein.
ulitmately achieving a vacuum less than 1 mm of Hg. The What is claimed is:
heating is continued and reaches a maximum of 213 C. It 1. A method for making a polyester polymer comprising:
is then held at this elevated temperature for a total of (1) combining in a reactor a monomer comprising a
approximately 15 hours. This effects a Solid-State polymer terephthaloyl moiety, optionally, one or more other
ization and allows the molecular weight to be significantly 65 monomers containing an aromatic diacid moiety; a
increased, as judged by the inherent Viscosity (I.V.) of the monomer comprising an ethylene glycol moiety, a
polymer Solution in ortho-chlorophenol. The solution I.V. of monomer comprising an isosorbide moiety, optionally,
5,959,066
17 18
one or more other monomers comprising a diol moiety; thaloyl moieties are present in an amount of about 45 mole
and optionally, a monomer comprising a diethylene % to about 50 mole % of said polyester, one or more optional
glycol moiety, with a condensation catalyst Suitable for other aromatic diacid moieties are present in an amount up
condensing aromatic diacids and glycols, and to about 5 mole % of Said polyester, Said ethylene glycol
(2) heating said monomers and Said catalyst to a tempera moieties are present in an amount of about 10 mole % to
ture Sufficient to polymerize Said monomers into a about 49.5 mole % of said polyester, diethylene glycol
polyester polymer having at least terephthaloyl moieties are present in an amount of about 0.25 mole % to
moieties, ethylene glycol moieties nd isosorbide moi about 5 mole % of said polyester, said isosorbide moieties
eties; are present in an amount of about 0.25 mole % to about 30
wherein Said heating is continued for a Sufficient time to mole % of Said polyester, and other diol moieties are present
yield an isotropic polyester having an inherent Viscosity in an amount up to about 10 mole % of Said polyester.
of at least about 0.35 dL/g when measured as a 1% 13. The method according to claim 1, further comprising
(weight/volume) Solution of Said polyester in increasing the molecular weight of Said polyester by Solid
o-chlorophenol at a temperature of 25 C. State polymerization.
2. The method according to claim 1, wherein Said proceSS 15 14. The method according to claim 13, wherein said solid
further includes Stirring of Said monomers during Said State polymerization comprises:
heating and the concurrent removal of by-products by dis a) crystallizing said polyester by heating said polyester to
tillation and/or evaporation. a temperature in the range of about 115 C. to about
3. The method according to claim 1, wherein Said mono 140 C. or treating said polyester with a solvent which
mer comprising a terephthaloyl moiety is terephthalic acid.
4. The method according to claim 3, wherein water and reduces the glass transition temperature of the polyester
unreacted monomer are removed while Said monomers allowing for crystallization; and
polymerize. b) heating said polyester under vacuum or in a stream of
5. The method according to claim 1, wherein Said mono inert gas at an elevated temperature above about 140
mer comprising a terephthaloyl moiety is dimethyl tereph C. but below the melting temperature of Said copoly
thalate. 25 ester to yield a copolyester having an increased inher
6. The method according to claim 5, wherein methanol ent Viscosity.
and unreacted monomer are removed while Said monomers 15. The method according to claim 14, wherein said
polymerize. heating step (b) is carried out at a temperature of about 195
7. The method according to claim 1, wherein Said proceSS to about 198 C. for about 10 hours.
further comprises adding an additive to Said process to help 16. The method according to claim 13, wherein said
retain volatile components. inherent Viscosity is increased to at least about 0.8 dL/g.
8. The method according to claim 7, wherein said additive 17. The method according to claim 13, wherein said
is tetrahydronapthalene. polyester comprises from about 0.25 mole % to about 10
9. The method according to claim 1, wherein said one or mole % isosorbide moieties.
more optional other diols are Selected from the group 35 18. An isotropic polyester comprising terephthaloyl moi
consisting of aliphatic alkylene glycols and branched ali eties, optionally, other aromatic diacid moieties, ethylene
phatic glycols having from 3-12 carbon atoms and having glycol moieties; diethylene glycol moieties, isosorbide moi
the empirical formula HO-CH-OH, where n is an eties, and, optionally, one or more other diol moieties,
integer from 3-12, cis and trans-1,4-cyclohexanedimethanol wherein Said polyester has an inherent Viscosity of at least
and mixtures thereof; triethylene glycol; 2.2-bis(4-(2- 40 about 0.35 dL/g when measured as a 1% (weight/volume)
hydroxyethoxy) phenylprop a ne; 1,1-bis(4-(2- Solution of Said polyester in o-chlorophenol at a temperature
hydroxyethoxy)phenyl)cyclohexane; 9,9-bis(4-(2- of 25° C.
hydroxyethoxy) phenylfluore ne; 1, 4:3, 6 19. The isotropic polyester according to claim 18, wherein
dianhydromannitol, 1,4:3,6-dianhydroiditol, and 1,4- said polyester comprises about 40% to about 50% of said
anhydroerythritol. 45 terephthaloyl moieties and a total of up to about 10 mole %
10. The method according to claim 1, wherein said one or of Said one or more optional other aromatic diacid moieties.
more optional other aromatic diacids are Selected from the 20. The isotropic polyester according to claim 19, wherein
group consisting of isophthalic acid, 2.5-furandicarboxylic Said terephthaloyl moieties are derived from terephthalic
acid, 2,5-thiophe ne dicarboxylic acid, 2, 6 acid or dimethyl terephthalate.
naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic 50 21. The isotropic polyester according to claim 19, wherein
acid, and 4,4'-bibenzoic acid. Said ethylene glycol moieties are present in an amount of
11. The method according to claim 1, wherein Said about 10 mole % to about 49.5 mole % of the polyester, said
monomers are included in amounts Such that Said tereph diethylene glycol moieties are present in an amount of about
thaloyl moieties are present in an amount of about 40 mole 0.25 mole % to about 10 mole % of the polyester, said
% to about 50 mole % of said polyester, one or more optional 55 isosorbide moieties are present in an amount of about 0.25
other aromatic diacid moieties are present in an amount up mole % to about 40 mole % of the polyester, and said one
to about 10 mole % of said polyester, said ethylene glycol or more other diol moieties are present in an amount up to
moieties are present in an amount of about 10 mole % to about 15 mole % of the polyester.
about 49.5 mole % of said polyester, diethylene glycol 22. The isotropic polyester according to claim 18, wherein
moieties are present in an amount of about 0.25 mole % to 60 Said one or more other diol moieties are derived from
about 10 mole % of said polyester, said isosorbide moieties aliphatic alkylene glycols or branched aliphatic glycols
are present in an amount of about 0.25 mole % to about 40 having from 3-12 carbon atoms and having the empirical
mole % of Said polyester, and Said one or more other diol formula HO-CH-OH, where n is an integer from
moieties are present in an amount up to about 15 mole % of 3-12, cis or trans-1,4-cyclohexanedimethanol or mixtures
Said polyester. 65 thereof; triethylene glycol; 2.2-bis(4-(2-hydroxyethoxy)
12. The method according to claim 11, wherein said phenylpropane; 1,1-bis(4-(2-hydroxyethoxy)phenyl
monomers are included in amounts Such that Said tereph cyclohexane; 9.9-bis(4-(2-hydroxyethoxy)phenylfluorene;
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19 20
14:3,6-dianhydromannitol; 1,4:3,6-dianhydroiditol; or 1,4- pigment, flame retardant, reinforcing agent, thermal
anhydroerythritol. stabilizer, ultraviolet light stabilizer, impact modifier or flow
23. The isotropic polyester according to claim 18, wherein enhancer.
Said one or more optional other aromatic diacid moieties are 31. The isotropic polyester according to claim 30, wherein
derived from isophthalic acid, 2.5-furandicarboxylic acid, Said additive is glass fibers.
2,5-thiophenedicarboxylic acid, 2, 6 32. An isotropic polyester comprising terephthaloyl moi
naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic eties, optionally, other aromatic diacid moieties, ethylene
acid, or 4,4'-bibenzoic acid. glycol moieties, optionally, diethylene glycol moieties, isoS
24. The isotropic polyester according to claim 18, wherein orbide moieties, and optionally, one or more other diol
terephthaloyl moieties are present in an amount of about 45 moieties wherein Said polyester has an inherent Viscosity of
mole % to about 50 mole % of said polyester, said optional at least about 0.5 dL/g when measured as a 1% (weight/
other aromatic diacid moieties are present in an amount up Volume) Solution of Said polyester in o-chlorophenol at a
to about 5 mole % of Said polyester, Said ethylene glycol temperature of 25 C.
moieties are present in an amount of about 10 mole % to 33. The isotropic polyester according to claim 32, wherein
about 49.5 mole % of said polyester, said diethylene glycol 15
said polyester comprises about 40% to about 50% tereph
moieties are present in an amount of about 0.25 mole % to thaloyl moieties and a total of up to about 10 mole % of one
about 5 mole % of said polyester, said isosorbide moieties or more optional other aromatic diacid moieties.
are present in an amount of about 0.25 mole % to about 30 34. The isotropic polyester according to claim 33, wherein
mole % of Said polyester, and Said other diol moieties are Said terephthaloyl moieties are derived from terephthalic
present in an amount up to about 10 mole % of Said acid or dimethyl terephthalate.
polyester. 35. The isotropic polyester according to claim 33, wherein
25. The isotropic polyester according to claim 24, wherein Said ethylene glycol moieties are present in an amount of
Said other diol moieties are derived from cis-1,4- about 10 mole % to about 49.5 mole % of the polyester, said
cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, diethylene glycol moieties are present in an amount of about
or mixtures thereof. 0.25 mole % to about 10 mole % of the polyester, said
26. The isotropic polyester according to claim 25, wherein 25 isosorbide moieties are present in an amount of about 0.25
Said optional other aromatic diacid moieties are derived mole % to about 40 mole % of the polyester, and said one
from isophthalic acid, 2,6-naphthalenedicarboxylic acid, or more other diol moieties are present in an amount up to
4,4'-bibenzoic acid, or mixtures thereof. about 15 mole % of the polyester.
27. The isotropic polyester according to claim 18, wherein 36. The isotropic polyester according to claim 32, wherein
Said polyester has an inherent Viscosity of at least about 0.40 Said one or more other diol moieties are derived from
dL/g. aliphatic alkylene glycols or branched aliphatic glycols
28. The isotropic polyester according to claim 18, wherein having from 3-12 carbon atoms and having the empirical
Said terephthaloyl moieties are present in an amount of about formula HO-CH-OH, where n is an integer from
45 mole % to about 50 mole % of said polyester; said one 3-12, cis or trans-1,4-cyclohexanedimethanol or mixtures
or more optional other aromatic diacid moieties are present 35 thereof; triethylene glycol; 2.2-bis(4-(2-hydroxyethoxy)
in an amount up to about 5 mole % of Said polyester and are phenylpropane; 1,1-bis(4-(2-hydroxyethoxy)phenyl
derived from isophthalic acid, 2,6-naphthalenedicarboxylic cyclohexane; 9.9-bis(4-(2-hydroxyethoxy)phenylfluorene;
acid, 4,4'-bibenzoic acid, or mixtures thereof; Said ethylene 14:3,6-dianhydromannitol; 14:3,6-dianhydroiditol; or 1,4-
glycol moieties are present in an amount of about 38 mole anhydroerythritol.
% to about 49.5 mole % of said polyester; said diethylene 40 37. The isotropic polyester according to claim 32, wherein
glycol moieties are present in an amount of about 0.25 mole Said one or more optional other aromatic diacid moieties are
% to about 5 mole % of said polyester; said isosorbide derived from isophthalic acid, 2.5-furandicarboxylic acid,
moieties are present in an amount of about 0.25 mole % to 2,5-thiophenedicarboxylic acid, 2, 6
about 5 mole % of said polyester; and said optional other naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic
diol moieties are present in an amount up to about 2 mole % 45 acid, or 4,4'-bibenzoic acid.
of Said polyester and are cis-1,4-cyclohexanedimethanol 38. The isotropic polyester according to claim 32, wherein
moieties, trans-1,4-cyclohexanedimethanol moieties, or Said terephthaloyl moieties are present in an amount of about
mixtures thereof; wherein Said polyester has an inherent 45 mole % to about 50 mole % of said polyester, said
viscosity of at least about 0.45 dL/g. optional other aromatic diacid moieties are present in an
29. The isotropic polyester according to claim 18, wherein 50 amount up to about 5 mole % of Said polyester, Said ethylene
Said terephthaloyl moieties are present in an amount of about glycol moieties are present in an amount of about 10 mole
45 mole % to about 50 mole % of said polyester; said one % to about 49.5 mole % of said polyester, said isosorbide
or more optional other aromatic diacid moieties are present moieties are present in an amount of about 0.25 mole % to
in an amount up to about 5 mole % of Said polyester and are about 30 mole % of said polyester, and said optional other
derived from isophthalic acid, 2,6-naphthalenedicarboxylic 55 diol moieties are present in an amount up to about 10 mole
acid, 4,4'-bibenzoic acid or mixtures thereof; Said ethylene % of said polyester.
glycol moieties are present in an amount of about 10 mole 39. The isotropic polyester according to claim 38, wherein
% to about 49.5 mole % of said polyester; said diethylene Said other diol moieties are derived from cis-1,4-
glycol moieties are present in an amount of about 0.25 mole cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol,
% to about 5 mole % of said polyester; said isosorbide 60 or mixtures thereof.
moieties are present in an amount of about 6 mole % to about 40. The isotropic polyester according to claim 39, wherein
30 mole % of said polyester; and said other diol moieties are Said optional other aromatic diacid monomer units are
present in an amount up to about 10 mole % of Said polyester derived from isophthalic acid, 2,6-naphthalenedicarboxylic
and are cis-1,4-cyclohexanedi-methanol moieties, trans-1,4- acid, 4,4'-bibenzoic acid, or mixtures thereof.
cyclohexanedimethanol moieties or mixtures thereof. 65 41. The isotropic polyester according to claim 32, wherein
30. The isotropic polyester according to claim 18, further said polyester has an inherent viscosity of at least about 0.65
comprising an additive wherein Said additive is a plasticizer,
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21 22
42. The isotropic polyester according to claim 32, wherein derived from isophthalic acid, 2,6-naphthalenedicarboxylic
Said terephthaloyl moieties are present in an amount of about acid, 4,4'-bibenzoic acid, or mixtures thereof; Said ethylene
45 mole % to about 50 mole % of said polyester; said one glycol moieties are present in an amount of about 10 mole
or more optional other aromatic diacid moieties are present % to about 44 mole % of said polyester; said diethylene
in an amount up to about 5 mole % of Said polyester and are glycol moieties are present in an amount of about 0.25 mole
derived from isophthalic acid, 2,6-naphthalenedicarboxylic % to about 5 mole % of said polyester; said isosorbide
acid, 4,4'-bibenzoic acid, or mixtures thereof; Said ethylene moieties are present in an amount of about 6 mole % to about
glycol moieties are present in an amount of about 38 mole 30 mole % of said polyester; and said other diol moieties are
% to about 49.5 mole % of said polyester; said diethylene present in an amount up to about 10 mole % of Said polyester
glycol moieties are present in an amount of about 0.25 mole and are derived from cis-1,4-cyclohexanedimethanol, trans
% to about 5 mole % of said polyester; said isosorbide 1,4-cyclohexanedimethanol or mixtures thereof, wherein
moieties are present in an amount of about 0.25 mole % to said polyester has an inherent viscosity of at least about 0.65
about 5 mole % of said polyester; and said optional other dL/g.
diol moieties are present in an amount up to about 2 mole % 44. The isotropic polyester according to claim 32, further
of Said polyester and are derived from cis-1,4- 15
cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, comprising an additive wherein Said additive is a plasticizer,
or mixtures thereof; wherein Said polyester has an inherent pigment, flame retardant, reinforcing agent, thermal
viscosity of at least about 0.45 dL/g. stabilizer, ultraviolet light stabilizer, impact modifier or flow
43. The isotropic polyester according to claim 32, wherein enhancer.
Said terephthaloyl moieties are present in an amount of about 45. The isotropic polyester according to claim 44, wherein
45 mole % to about 50 mole % of said polyester; said one Said additive is glass fibers.
or more optional other aromatic diacid moieties are present
in an amount up to about 5 mole % of Said polyester and are