U.S. patent application number 13/398262 was filed with the patent office on 2013-08-22 for clear semi-crystalline articles with improved heat resistance.
This patent application is currently assigned to EASTMAN CHEMICAL COMPANY. The applicant listed for this patent is Emmett Dudley Crawford, Michael Eugene Donelson. Invention is credited to Emmett Dudley Crawford, Michael Eugene Donelson.
Application Number | 20130217830 13/398262 |
Document ID | / |
Family ID | 47755037 |
Filed Date | 2013-08-22 |
United States Patent
Application |
20130217830 |
Kind Code |
A1 |
Crawford; Emmett Dudley ; et
al. |
August 22, 2013 |
Clear Semi-Crystalline Articles with Improved Heat Resistance
Abstract
The present invention relates to a clear, semicrystalline
article comprising a polyester comprising terephthalic acid
residues as the dicarboxylic acid component, and 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 99 mole
% of 1,4-cyclohexanedimethanol residues as the glycol component.
The article may be in the form of a film or sheet, a bottle, or a
fiber. The article, when produced by a process involving
strain-induced crystallization, is characterized with high
crystallinity.
Inventors: |
Crawford; Emmett Dudley;
(Kingsport, TN) ; Donelson; Michael Eugene;
(Kingsport, TN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Crawford; Emmett Dudley
Donelson; Michael Eugene |
Kingsport
Kingsport |
TN
TN |
US
US |
|
|
Assignee: |
EASTMAN CHEMICAL COMPANY
Kingsport
TN
|
Family ID: |
47755037 |
Appl. No.: |
13/398262 |
Filed: |
February 16, 2012 |
Current U.S.
Class: |
525/173 ;
206/524.6; 525/439; 525/448; 528/302 |
Current CPC
Class: |
C08L 2205/02 20130101;
C08L 2201/10 20130101; C08L 67/02 20130101; C08L 2203/10 20130101;
C08G 63/199 20130101 |
Class at
Publication: |
525/173 ;
528/302; 525/448; 525/439; 206/524.6 |
International
Class: |
C08G 63/199 20060101
C08G063/199; C08L 69/00 20060101 C08L069/00; B65D 23/00 20060101
B65D023/00; C08L 67/02 20060101 C08L067/02 |
Claims
1. A clear, semicrystalline article comprising at least one
polyester which comprises: (a) a dicarboxylic acid component
comprising: i) 70 to 100 mole % of terephthalic acid residues; ii)
0 to 30 mole % of aromatic dicarboxylic acid residues having up to
20 carbon atoms; and iii) 0 to 30 mole % of aliphatic dicarboxylic
acid residues having up to 16 carbon atoms; and (b) a glycol
component comprising: i) 1 to 14 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 86 to 99
mole % of 1,4-cyclohexanedimethanol residues, wherein the total
mole % of the dicarboxylic acid component is 100 mole %, and the
total mole % of the glycol component is 100 mole %; wherein the
inherent viscosity of the polyester is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; wherein said
polyester has a Tg of 85 to 115.degree. C.; and wherein said
article has a strain induced crystallinity of greater than zero
when stretched at a temperature above the Tg of the polyester.
2. The article of claim 1, wherein the inherent viscosity of the
polyester is from 0.35 to less than 1.0 dL/g.
3. The article of claim 1, wherein the inherent viscosity of the
polyester is from 0.35 to 0.80 dL/g.
4. The article of claim 1, wherein the inherent viscosity of the
polyester is from 0.50 to 0.75 dL/g.
5. The article of claim 1, wherein the inherent viscosity of the
polyester is from 0.60 to 0.75 dL/g.
6. The article of claim 1, wherein said polyester has a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds at 170.degree. C.
7. The article of claim 1, wherein said polyester has a Tg of 90 to
110.degree. C.
8. The article of claim 1, wherein the dicarboxylic acid component
of the polyester comprises 80 to 100 mole % of terephthalic acid
residues.
9. The article of claim 1, wherein the dicarboxylic acid component
of the polyester comprises 90 to 100 mole % of terephthalic acid
residues.
10. The article of claim 1, wherein the dicarboxylic acid component
of the polyester comprises 95 to 100 mole % of terephthalic acid
residues.
11. The article of claim 1, wherein the dicarboxylic acid component
of the polyester comprises 99 to 100 mole % of terephthalic acid
residues.
12. The article of claim 1, wherein said polyester is blended with
at least one polymer chosen from at least one of the following:
poly(etherimides), polyesters other than those of claim 1,
polyphenylene oxides, poly(phenylene oxide)/polystyrene blends,
polystyrene resins, polyphenylene sulfides, polyphenylene
sulfide/sulfones, poly(ester-carbonates), polycarbonates,
polysulfones; polysulfone ethers, and poly(ether-ketones).
13. The article of claim 1, wherein said polyester comprises
residues of at least one branching agent.
14. The article of claim 13, wherein said polyester comprises
residues of at least one branching agent an amount of 0.01 to 10
weight % based on the total mole percentage of the diacid or diol
residues.
15. The article of claim 1, wherein the yellowness index of said
polyester according to ASTM D-1925 is less than 50.
16. The article of claim 1, wherein the polyester has a b* value of
from -10 to less than 10 and a L* value from 50 to 90 according to
the L*, a* and b* color system of the CIE (International Commission
on Illumination.
17. A clear strain induced crystallized article according to claim
1.
18. The article of claim 1 wherein said article has a strain
induced crystallinity of from 0.8% to 35% when stretched at a
temperature above the Tg of the polyester.
19. The article of claim 1 wherein said article has a strain
induced crystallinity of from 8% to 35% when stretched at a
temperature 10.degree. C. above the Tg of the polyester.
20. The article of claim 1 wherein said article has a strain
induced crystallinity of from 8% to 35% when stretched at a
temperature 20.degree. C. above the Tg of the polyester.
21. The article of claim 1 wherein said article has a strain
induced crystallinity of from 10% to 35% when stretched at a
temperature 10.degree. C. above the Tg of the polyester.
22. The article of claim 1 wherein said article has a strain
induced crystallinity of from 10% to 35% when stretched at a
temperature 20.degree. C. above the Tg of the polyester.
23. The article of claim 1 wherein said article has a strain
induced crystallinity of from 10% to 30% when stretched at a
temperature 10.degree. C. above the Tg of the polyester.
24. The article of claim 1 wherein said article has a strain
induced crystallinity of from 10% to 30% when stretched at a
temperature 20.degree. C. above the Tg of the polyester.
25. A film or sheet according to claim 1.
26. A bottle according to claim 1.
27. A fiber according to claim 1.
28. A clear, semicrystalline, strain induced crystallized article
comprising at least one polyester which comprises: (a) a
dicarboxylic acid component comprising: i) 70 to 100 mole % of
terephthalic acid residues; ii) 0 to 30 mole % of aromatic
dicarboxylic acid residues having up to 20 carbon atoms; and iii) 0
to 30 mole % of aliphatic dicarboxylic acid residues having up to
16 carbon atoms; and (b) a glycol component comprising: i) 1 to 14
mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii)
86 to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; wherein the
inherent viscosity of the polyester is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein said
polyester has a Tg of 85 to 115.degree. C., and a crystallization
half-time of less than 10 minutes but greater than about 30 seconds
at 170.degree. C.
29. The article of claim 28, wherein the inherent viscosity of the
polyester is from 0.35 to less than 1.0 dL/g.
30. The article of claim 28, wherein the inherent viscosity of the
polyester is from 0.35 to 0.80 dL/g.
31. The article of claim 28, wherein the inherent viscosity of the
polyester is from 0.50 to 0.75 dL/g.
32. The article of claim 28, wherein the inherent viscosity of the
polyester is from 0.60 to 0.75 dL/g.
33. The article of claim 28, wherein said polyester has a Tg of 90
to 115.degree. C.
34. The article of claim 28, wherein said polyester has a Tg of 90
to 110.degree. C.
35. The article of claim 28, wherein the dicarboxylic acid
component of the polyester comprises 80 to 100 mole % of
terephthalic acid residues.
36. The article of claim 28, wherein the dicarboxylic acid
component of the polyester comprises 90 to 100 mole % of
terephthalic acid residues.
37. The article of claim 28, wherein the dicarboxylic acid
component of the polyester comprises 95 to 100 mole % of
terephthalic acid residues.
38. The article of claim 28, wherein the polyester comprises 5 to
14 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and
86 to 95 mole % of 1,4-cyclohexanedimethanol residues.
39. The article of claim 28, wherein said polyester comprises
ethylene glycol residues.
40. The article of claim 28, wherein said polyester is blended with
at least one polymer chosen from at least one of the following:
poly(etherimides), polyesters other than those of claim 28,
polyphenylene oxides, poly(phenylene oxide)/polystyrene blends,
polystyrene resins, polyphenylene sulfides, polyphenylene
sulfide/sulfones, poly(ester-carbonates), polycarbonates,
polysulfones; polysulfone ethers, and poly(ether-ketones).
41. The article of claim 28, wherein said polyester comprises
residues of at least one branching agent.
42. The article of claim 28, wherein said polyester comprises
residues of at least one branching agent an amount of 0.01 to 10
weight % based on the total mole percentage of the diacid or diol
residues.
43. The article of claim 28 wherein the yellowness index of said
polyester according to ASM D-1925 is less than 50.
44. The article of claim 28 wherein the polyester has a b* value of
from -10 to less than 10 and a L* value from 50 to 90 according to
the L*, a* and b* color system of the CIE (International Commission
on Illumination.
45. The article of claim 28 wherein said article has a strain
induced crystallinity of from 5% to 35% when stretched at a
temperature 10.degree. C. above the Tg of the polyester.
46. The article of claim 28 wherein said article has a strain
induced crystallinity of from 8% to 35% when stretched at a
temperature 20.degree. C. above the Tg of the polyester.
47. The article of claim 28 wherein said article has a strain
induced crystallinity of from 10% to 35% when stretched at a
temperature 10.degree. C. above the Tg of the polyester.
48. The article of claim 28 wherein said article has a strain
induced crystallinity of from 10% to 35% when stretched at a
temperature 20.degree. C. above the Tg of the polyester.
49. The article of claim 28 wherein said article has a strain
induced crystallinity of from 10% to 30% when stretched at a
temperature 10.degree. C. above the Tg of the polyester.
50. The article of claim 28 wherein said article has a strain
induced crystallinity of from 10% to 30% when stretched at a
temperature 20.degree. C. above the Tg of the polyester.
51. A film or sheet according to claim 28.
52. A bottle according to claim 28.
53. A fiber according to claim 28.
Description
FIELD OF THE INVENTION
[0001] The present invention generally relates to clear
semi-crystalline articles made from polyesters comprising
terephthalic acid, or an ester thereof, or mixtures thereof; 1 to
15 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85
to 99 mole % 1,4-cyclohexanedimethanol residues. These polyesters
have a surprising combination of a certain crystallization rate
along with a certain melting temperatures (Tm) and certain glass
transition temperatures (Tg). These polyesters are useful in
preparing clear semi-crystalline articles with improved heat
resistance by strain induced crystallization processes known in the
art.
BACKGROUND OF THE INVENTION
[0002] To date, copolyester compositions comprising terephthalic
acid or an ester thereof or mixtures thereof,
2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and
1,4-cyclohexanedimethanol (CHDM) residues have been focused
primarily for use in the injection molding and extrusion of
amorphous articles even in relatively thick parts due to slow
crystallization rates. These slow crystallization rates are
achieved by modifying the polyester (PCT), which is based on
terephthalic acid (TPA) or ester thereof such as dimethyl
terephthalate (DMT), or mixture thereof, and CHDM (70/30 trans/cis)
with TMCD at levels greater than 20 mole percent of the diol
fraction.
[0003] On the other hand, unmodified PCT is known to crystallize
extremely fast making it extremely difficult to mold or extrude
even thin parts without thermal crystallization. Thermal
crystallization of PCT and other polyesters typically leads to
opacity in parts.
[0004] In order to slow down the crystallization rate of PCT,
additional dicarboxylic acids or glycols can be used to modify PCT
in order to slow down the crystallization rate. In particular,
ethylene glycol or isophthalic acid-modified PCTs are known in the
art and are commercially available. Polyethylene terephthalate
(PET) or slightly modified PET's have been proven useful in clear
semi-crystalline articles such as soft drink bottles, oriented
films, and oriented fibers. These articles from PET are prepared by
processes that take advantage of PET's ability to strain induce
crystallize above Tg from an amorphous state. These PETs have
slower thermal crystallization rates than unmodified PCT allowing
them to be used in such processes.
[0005] In order to achieve similar crystallization rates to PET,
PCT has to be modified with certain levels, approximately 15 to 30
mole % of the diol fraction coming from ethylene glycol or 15 to 30
mole % of the acid fraction coming from isophthalic acid. This
results in modified PCT materials with melting temperatures (Tm)
and glass transition temperatures (Tg) similar to PET
(Tm=.about.240.degree. C., Tg=.about.80.degree. C.). Given the
similar Tm and Tg to PET, these modified PCT materials provide
little benefit in terms of heat resistance compared to PET and are
typically more costly to produce.
[0006] Thus, there is a need in the art for a modification of PCT
that slows down the thermal crystallization rate enough, similar to
PET, to permit the molding of amorphous articles and extrusion of
amorphous films that can be subsequently strain induced
crystallized by orientation processes known in the art such as
fiber drawing, film stretching, stretch blow molding, injection
stretch blow molding and the like, to produce clear
semi-crystalline articles with superior heat resistance (higher Tg
and higher Tm) to clear semi-crystalline articles from PCT modified
by ethylene glycol or isophthalic acid or PET.
SUMMARY OF THE INVENTION
[0007] We have surprisingly found a range of TMCD modification of
PCT that slows down the crystallization rate enough to permit the
molding of articles and extrusion of films without thermal
crystallization occurring yet still allows for strain induced
crystallinity to occur above Tg in various orientation based
processes allowing for production of clear semi-crystalline
articles with improved heat resistance compared to PCT modified by
ethylene glycol or isophthalic acid and PET.
[0008] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0009] (a) a dicarboxylic acid component comprising:
[0010] i) 70 to 100 mole % of terephthalic acid residues; [0011]
(b) a glycol component comprising: [0012] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0013] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.
[0014] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0015] (a) a dicarboxylic acid component
comprising: [0016] i) 70 to 100 mole % of terephthalic acid
residues; [0017] (b) a glycol component comprising: [0018] i) 1 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0019] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C.
[0020] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0021] (a) a dicarboxylic acid component comprising:
[0022] i) 70 to 100 mole % of terephthalic acid residues; [0023]
(b) a glycol component comprising: [0024] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0025] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.
[0026] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0027] (a) a dicarboxylic acid component comprising:
[0028] i) 70 to 100 mole % of terephthalic acid residues; [0029]
(b) a glycol component comprising: [0030] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0031] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0032] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0033] (a) a dicarboxylic acid component
comprising: [0034] i) 70 to 100 mole % of terephthalic acid
residues; [0035] (b) a glycol component comprising: [0036] i) 1 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0037] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes.
[0038] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0039] (a) a dicarboxylic acid component comprising:
[0040] i) 70 to 100 mole % of terephthalic acid residues; [0041]
(b) a glycol component comprising: [0042] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0043] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0044] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0045] (a) a dicarboxylic acid component comprising:
[0046] i) 70 to 100 mole % of terephthalic acid residues; [0047]
(b) a glycol component comprising: [0048] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0049] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds.
[0050] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0051] (a) a dicarboxylic acid component
comprising: [0052] i) 70 to 100 mole % of terephthalic acid
residues; [0053] (b) a glycol component comprising: [0054] i) 1 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0055] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds.
[0056] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0057] (a) a dicarboxylic acid component comprising:
[0058] i) 70 to 100 mole % of terephthalic acid residues; [0059]
(b) a glycol component comprising: [0060] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0061] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds. In one aspect, the
invention relates to a clear, semi-crystalline article comprising
at least one polyester which comprises: [0062] (a) a dicarboxylic
acid component comprising: [0063] i) 70 to 100 mole % of
terephthalic acid residues; [0064] (b) a glycol component
comprising: [0065] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0066] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0067] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0068] (a) a dicarboxylic acid component
comprising: [0069] i) 70 to 100 mole % of terephthalic acid
residues; [0070] (b) a glycol component comprising: [0071] i) 5 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0072] ii) 85 to 95 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes.
[0073] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0074] (a) a dicarboxylic acid component comprising:
[0075] i) 70 to 100 mole % of terephthalic acid residues; [0076]
(b) a glycol component comprising: [0077] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0078] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0079] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0080] (a) a dicarboxylic acid component comprising:
[0081] i) 70 to 100 mole % of terephthalic acid residues; [0082]
(b) a glycol component comprising: [0083] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0084] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds.
[0085] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0086] (a) a dicarboxylic acid component
comprising: [0087] i) 70 to 100 mole % of terephthalic acid
residues; [0088] (b) a glycol component comprising: [0089] i) 5 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0090] ii) 85 to 95 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds.
[0091] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0092] (a) a dicarboxylic acid component comprising:
[0093] i) 70 to 100 mole % of terephthalic acid residues; [0094]
(b) a glycol component comprising: [0095] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0096] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds.
[0097] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0098] (a) a dicarboxylic acid
component comprising: [0099] i) 70 to 100 mole % of terephthalic
acid residues; [0100] (b) a glycol component comprising: [0101] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0102] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C.
[0103] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized, oriented article
comprising at least one polyester which comprises: [0104] (a) a
dicarboxylic acid component comprising: [0105] i) 70 to 100 mole %
of terephthalic acid residues; [0106] (b) a glycol component
comprising: [0107] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0108] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.
[0109] In one aspect, the invention relates to a clear
semi-crystalline, strain induced crystallized, oriented article
produced by strain induced crystallization processes comprising at
least one polyester which comprises: [0110] (a) a dicarboxylic acid
component comprising: [0111] i) 70 to 100 mole % of terephthalic
acid residues; [0112] (b) a glycol component comprising: [0113] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0114] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.0 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C.
[0115] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0116] (a) a dicarboxylic acid
component comprising: [0117] i) 70 to 100 mole % of terephthalic
acid residues; [0118] (b) a glycol component comprising: [0119] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0120] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes.
[0121] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized, oriented article
comprising at least one polyester which comprises: [0122] (a) a
dicarboxylic acid component comprising: [0123] i) 70 to 100 mole %
of terephthalic acid residues; [0124] (b) a glycol component
comprising: [0125] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0126] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0127] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0128] (a) a dicarboxylic acid component comprising:
[0129] i) 70 to 100 mole % of terephthalic acid residues; [0130]
(b) a glycol component comprising: [0131] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0132] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0133] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0134] (a) a dicarboxylic acid
component comprising: [0135] i) 70 to 100 mole % of terephthalic
acid residues; [0136] (b) a glycol component comprising: [0137] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0138] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds.
[0139] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized, oriented article
comprising at least one polyester which comprises: [0140] (a) a
dicarboxylic acid component comprising: [0141] i) 70 to 100 mole %
of terephthalic acid residues; [0142] (b) a glycol component
comprising: [0143] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0144] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds.
[0145] In one aspect, the invention relates to a clear
semi-crystalline, strain induced crystallized, oriented article
produced by strain induced crystallization processes comprising at
least one polyester which comprises: [0146] (a) a dicarboxylic acid
component comprising: [0147] i) 70 to 100 mole % of terephthalic
acid residues; [0148] (b) a glycol component comprising: [0149] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0150] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.0 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds.
[0151] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0152] (a) a dicarboxylic acid component comprising:
[0153] i) 70 to 100 mole % of terephthalic acid residues; [0154]
(b) a glycol component comprising: [0155] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0156] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0157] In one aspect, the invention relates to a clear,
semi-crystalline, oriented, strain induced crystallized article
comprising at least one polyester which comprises: [0158] (a) a
dicarboxylic acid component comprising: [0159] i) 70 to 100 mole %
of terephthalic acid residues; [0160] (b) a glycol component
comprising: [0161] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0162] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0163] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0164] (a) a dicarboxylic acid component comprising:
[0165] i) 70 to 100 mole % of terephthalic acid residues; [0166]
(b) a glycol component comprising: [0167] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0168] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes.
[0169] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0170] (a) a dicarboxylic acid
component comprising: [0171] i) 70 to 100 mole % of terephthalic
acid residues; [0172] (b) a glycol component comprising: [0173] i)
5 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0174] ii) 85 to 95 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds.
[0175] In one aspect, the invention relates to a clear,
semi-crystalline, oriented, strain induced crystallized article
comprising at least one polyester which comprises: [0176] (a) a
dicarboxylic acid component comprising: [0177] i) 70 to 100 mole %
of terephthalic acid residues; [0178] (b) a glycol component
comprising: [0179] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0180] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds.
[0181] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0182] (a) a dicarboxylic acid component comprising:
[0183] i) 70 to 100 mole % of terephthalic acid residues; [0184]
(b) a glycol component comprising: [0185] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0186] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds.
[0187] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0188] (a) a dicarboxylic acid component comprising:
[0189] i) 70 to 100 mole % of terephthalic acid residues; [0190]
(b) a glycol component comprising: [0191] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0192] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and
[0193] wherein said article has a strain induced crystallinity of
greater than zero when stretched at a temperature above the Tg of
the polyester.
[0194] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0195] (a) a dicarboxylic acid component comprising:
[0196] i) 70 to 100 mole % of terephthalic acid residues; [0197]
(b) a glycol component comprising: [0198] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0199] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and
[0200] wherein said article has a strain induced crystallinity of
greater than zero to 50 when stretched at a temperature above the
Tg of the polyester.
[0201] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0202] (a) a dicarboxylic acid component comprising:
[0203] i) 70 to 100 mole % of terephthalic acid residues; [0204]
(b) a glycol component comprising: [0205] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0206] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and
[0207] wherein said article has a strain induced crystallinity of
from 5% to 50% when stretched at a temperature above the Tg of the
polyester.
[0208] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0209] (a) a dicarboxylic acid component comprising:
[0210] i) 70 to 100 mole % of terephthalic acid residues; [0211]
(b) a glycol component comprising: [0212] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0213] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and
[0214] wherein said article has a strain induced crystallinity of
from 5% to 45% when stretched at a temperature above the Tg of the
polyester.
[0215] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0216] (a) a dicarboxylic acid component comprising:
[0217] i) 70 to 100 mole % of terephthalic acid residues; [0218]
(b) a glycol component comprising: [0219] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0220] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and
[0221] wherein said article has a strain induced crystallinity of
from 5% to 40% when stretched at a temperature above the Tg of the
polyester.
[0222] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0223] (a) a dicarboxylic acid component comprising:
[0224] i) 70 to 100 mole % of terephthalic acid residues; [0225]
(b) a glycol component comprising: [0226] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0227] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and
[0228] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0229] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0230] (a) a dicarboxylic acid component
comprising: [0231] i) 70 to 100 mole % of terephthalic acid
residues; [0232] (b) a glycol component comprising: [0233] i) 1 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0234] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C.;
[0235] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0236] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0237] (a) a dicarboxylic acid component comprising:
[0238] i) 70 to 100 mole % of terephthalic acid residues; [0239]
(b) a glycol component comprising: [0240] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0241] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.;
[0242] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0243] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0244] (a) a dicarboxylic acid component comprising:
[0245] i) 70 to 100 mole % of terephthalic acid residues; [0246]
(b) a glycol component comprising: [0247] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0248] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes;
[0249] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0250] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0251] (a) a dicarboxylic acid component
comprising: [0252] i) 70 to 100 mole % of terephthalic acid
residues; [0253] (b) a glycol component comprising: [0254] i) 1 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0255] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes; and
[0256] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0257] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0258] (a) a dicarboxylic acid component comprising:
[0259] i) 70 to 100 mole % of terephthalic acid residues; [0260]
(b) a glycol component comprising: [0261] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0262] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0263] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0264] (a) a dicarboxylic acid component comprising:
[0265] i) 70 to 100 mole % of terephthalic acid residues; [0266]
(b) a glycol component comprising: [0267] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0268] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0269] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0270] (a) a dicarboxylic acid component
comprising: [0271] i) 70 to 100 mole % of terephthalic acid
residues; [0272] (b) a glycol component comprising: [0273] i) 1 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0274] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0275] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0276] (a) a dicarboxylic acid component comprising:
[0277] i) 70 to 100 mole % of terephthalic acid residues; [0278]
(b) a glycol component comprising: [0279] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0280] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0281] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0282] (a) a dicarboxylic acid component comprising:
[0283] i) 70 to 100 mole % of terephthalic acid residues; [0284]
(b) a glycol component comprising: [0285] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0286] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0287] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0288] (a) a dicarboxylic acid component
comprising: [0289] i) 70 to 100 mole % of terephthalic acid
residues; [0290] (b) a glycol component comprising: [0291] i) 5 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0292] ii) 85 to 95 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes; and
[0293] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0294] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0295] (a) a dicarboxylic acid component comprising:
[0296] i) 70 to 100 mole % of terephthalic acid residues; [0297]
(b) a glycol component comprising: [0298] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0299] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
10.degree. C. above the Tg of the polyester.
[0300] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0301] (a) a dicarboxylic acid component comprising:
[0302] i) 70 to 100 mole % of terephthalic acid residues; [0303]
(b) a glycol component comprising: [0304] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0305] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0306] In one aspect, the invention relates to a clear,
semi-crystalline, oriented article comprising at least one
polyester which comprises: [0307] (a) a dicarboxylic acid component
comprising: [0308] i) 70 to 100 mole % of terephthalic acid
residues; [0309] (b) a glycol component comprising: [0310] i) 5 to
15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
[0311] ii) 85 to 95 mole % of 1,4-cyclohexanedimethanol residues,
wherein the total mole % of the dicarboxylic acid component is 100
mole %, and the total mole % of the glycol component is 100 mole %;
and wherein the inherent viscosity is 0.35 to 1.2 dL/g as
determined in 60/40 (wt/wt) phenol/tetrachloroethane at a
concentration of 0.5 g/100 ml at 25.degree. C.; and wherein the
polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0312] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0313] (a) a dicarboxylic acid component comprising:
[0314] i) 70 to 100 mole % of terephthalic acid residues; [0315]
(b) a glycol component comprising: [0316] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0317] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; wherein the
inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and
[0318] wherein said article has a strain induced crystallinity of
from 8% to 35% when stretched at a temperature above the Tg of the
polyester.
[0319] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0320] (a) a dicarboxylic acid
component comprising: [0321] i) 70 to 100 mole % of terephthalic
acid residues; [0322] (b) a glycol component comprising: [0323] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0324] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C.; and
wherein said article has a strain induced crystallinity of from 8%
to 35% when stretched at a temperature above the Tg of the
polyester.
[0325] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized, oriented article
comprising at least one polyester which comprises: [0326] (a) a
dicarboxylic acid component comprising: [0327] i) 70 to 100 mole %
of terephthalic acid residues; [0328] (b) a glycol component
comprising: [0329] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0330] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C.; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0331] In one aspect, the invention relates to a clear
semi-crystalline, strain induced crystallized, oriented article
produced by strain induced crystallization processes comprising at
least one polyester which comprises: [0332] (a) a dicarboxylic acid
component comprising: [0333] i) 70 to 100 mole % of terephthalic
acid residues; [0334] (b) a glycol component comprising: [0335] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0336] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.0 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C.; and
wherein said article has a strain induced crystallinity of from 8%
to 35% when stretched at a temperature above the Tg of the
polyester.
[0337] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0338] (a) a dicarboxylic acid
component comprising: [0339] i) 70 to 100 mole % of terephthalic
acid residues; [0340] (b) a glycol component comprising: [0341] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0342] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0343] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized, oriented article
comprising at least one polyester which comprises: [0344] (a) a
dicarboxylic acid component comprising: [0345] i) 70 to 100 mole %
of terephthalic acid residues; [0346] (b) a glycol component
comprising: [0347] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0348] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0349] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0350] (a) a dicarboxylic acid component comprising:
[0351] i) 70 to 100 mole % of terephthalic acid residues; [0352]
(b) a glycol component comprising: [0353] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0354] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0355] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0356] (a) a dicarboxylic acid
component comprising: [0357] i) 70 to 100 mole % of terephthalic
acid residues; [0358] (b) a glycol component comprising: [0359] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0360] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0361] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized, oriented article
comprising at least one polyester which comprises: [0362] (a) a
dicarboxylic acid component comprising: [0363] i) 70 to 100 mole %
of terephthalic acid residues; [0364] (b) a glycol component
comprising: [0365] i) 1 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0366] ii) 85
to 99 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0367] In one aspect, the invention relates to a clear
semi-crystalline, strain induced crystallized, oriented article
produced by strain induced crystallization processes comprising at
least one polyester which comprises: [0368] (a) a dicarboxylic acid
component comprising: [0369] i) 70 to 100 mole % of terephthalic
acid residues; [0370] (b) a glycol component comprising: [0371] i)
1 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0372] ii) 85 to 99 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.0 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0373] In one aspect, the invention relates to a clear,
semi-crystalline article comprising at least one polyester which
comprises: [0374] (a) a dicarboxylic acid component comprising:
[0375] i) 70 to 100 mole % of terephthalic acid residues; [0376]
(b) a glycol component comprising: [0377] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0378] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0379] In one aspect, the invention relates to a clear,
semi-crystalline, oriented, strain induced crystallized article
comprising at least one polyester which comprises: [0380] (a) a
dicarboxylic acid component comprising: [0381] i) 70 to 100 mole %
of terephthalic acid residues; [0382] (b) a glycol component
comprising: [0383] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0384] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0385] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0386] (a) a dicarboxylic acid component comprising:
[0387] i) 70 to 100 mole % of terephthalic acid residues; [0388]
(b) a glycol component comprising: [0389] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0390] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0391] In one aspect, the invention relates to a clear,
semi-crystalline, strain induced crystallized article comprising at
least one polyester which comprises: [0392] (a) a dicarboxylic acid
component comprising: [0393] i) 70 to 100 mole % of terephthalic
acid residues; [0394] (b) a glycol component comprising: [0395] i)
5 to 15 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;
and [0396] ii) 85 to 95 mole % of 1,4-cyclohexanedimethanol
residues, wherein the total mole % of the dicarboxylic acid
component is 100 mole %, and the total mole % of the glycol
component is 100 mole %; and wherein the inherent viscosity is 0.35
to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane
at a concentration of 0.5 g/100 ml at 25.degree. C.; and wherein
the polyester has a Tg of 90.degree. C. to 115.degree. C. and a
crystallization half-time of less than 10 minutes but greater than
about 30 seconds; and wherein said article has a strain induced
crystallinity of from 8% to 35% when stretched at a temperature
above the Tg of the polyester.
[0397] In one aspect, the invention relates to a clear,
semi-crystalline, oriented, strain induced crystallized article
comprising at least one polyester which comprises: [0398] (a) a
dicarboxylic acid component comprising: [0399] i) 70 to 100 mole %
of terephthalic acid residues; [0400] (b) a glycol component
comprising: [0401] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0402] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.2 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0403] In one aspect, the invention relates to a clear
semi-crystalline, oriented article produced by strain induced
crystallization processes comprising at least one polyester which
comprises: [0404] (a) a dicarboxylic acid component comprising:
[0405] i) 70 to 100 mole % of terephthalic acid residues; [0406]
(b) a glycol component comprising: [0407] i) 5 to 15 mole % of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and [0408] ii) 85
to 95 mole % of 1,4-cyclohexanedimethanol residues, wherein the
total mole % of the dicarboxylic acid component is 100 mole %, and
the total mole % of the glycol component is 100 mole %; and wherein
the inherent viscosity is 0.35 to 1.0 dL/g as determined in 60/40
(wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml
at 25.degree. C.; and wherein the polyester has a Tg of 90.degree.
C. to 115.degree. C. and a crystallization half-time of less than
10 minutes but greater than about 30 seconds; and wherein said
article has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0409] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of greater than zero
when stretched at a temperature above the Tg of the polyester.
[0410] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 50%
when stretched at a temperature above the Tg of the polyester.
[0411] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 45%
when stretched at a temperature above the Tg of the polyester.
[0412] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 40%
when stretched at a temperature above the Tg of the polyester.
[0413] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 35%
when stretched at a temperature above the Tg of the polyester.
[0414] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of greater than zero
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0415] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 50%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0416] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 45%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0417] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 40%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0418] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 35%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0419] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of greater than zero
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0420] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 50%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0421] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 45%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0422] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 40%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0423] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 5% to 35%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0424] In one aspect of the invention, the articles of the
invention have a strain induced crystallinity of from 8% to 35%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0425] In one aspect of the invention, the article of the invention
has a strain induced crystallinity of from 8% to 35% when stretched
at a temperature 20.degree. C. above the Tg of the polyester.
[0426] In one aspect of the invention, the article of the invention
has a strain induced crystallinity of from 10% to 35% when
stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0427] In one aspect of the invention, the article of the invention
has a strain induced crystallinity of from 10% to 35% when
stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0428] In one aspect of the invention, the article of the invention
has a strain induced crystallinity of from 10% to 30% when
stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0429] In one aspect of the invention, the article of the invention
has a strain induced crystallinity of from 10% to 30% when
stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0430] In one aspect, the clear semi-crystalline article can
comprise the polyester of the invention having a crystallization
half-time of less than 10 minutes but greater than about 30
seconds.
[0431] In another aspect, the clear semi-crystalline article of the
invention can comprise the polyester of the invention having a
melting temperature (Tm) from 260.degree. C. to 300.degree. C.
[0432] In another aspect, the clear semi-crystalline article of the
invention can comprise the polyester of the invention having a
glass transition temperature (Tg) from 90.degree. C. to 115.degree.
C.
[0433] In another aspect, the clear semi-crystalline article of the
invention can comprise the polyester of the invention having a
fastest crystallization half-time of less than 10 minutes but
greater than about seconds.
[0434] In another aspect, the clear semi-crystalline article of the
invention can comprise the polyester of the invention having a
fastest crystallization half-time of less than 10 minutes but
greater than about seconds and a melting temperature from
260.degree. C. to 300.degree. C.
[0435] In another aspect, the clear semi-crystalline article of the
invention can comprise the polyester of the invention having a
fastest crystallization half-time of less than 10 minutes but
greater than about seconds and a glass transition temperature from
90.degree. C. to 115.degree. C.
[0436] In another aspect, the clear semi-crystalline article of the
invention can comprise the polyester of the invention having a
fastest crystallization half-time of less than 10 minutes but
greater than about seconds, a glass transition temperature from
90.degree. C. to 115.degree. C., and a melting temperature from
260.degree. C. to 300.degree. C.
[0437] In one aspect, the polyesters useful in the invention
contain no branching agent or, alternatively, at least one
branching agent is added either prior to or during polymerization
of the polyester.
[0438] In one aspect, the polyesters useful in the invention
contain at least one branching agent without regard to the method
or sequence in which it is added.
[0439] In one aspect, the polyester compositions are useful in
clear semi-crystalline articles of manufacture, prepared by
orientation processes known in the industry, including but not
limited to, blown bottles, oriented films and oriented fibers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0440] FIG. 1 depicts the effect of comonomer on the fastest
crystallization half-times of copolyesters containing terephthalic
acid, cyclohexanedimethanol and another monomer (modified PCT
copolyesters)
DETAILED DESCRIPTION OF THE INVENTION
[0441] The present invention may be understood more readily by
reference to the following detailed description of certain
embodiments of the invention and the working examples. In
accordance with the purpose(s) of this invention, certain
embodiments of the invention are described in the Summary of the
Invention and are further described herein below. Also, other
embodiments of the invention are described herein.
[0442] The term "polyester", as used herein, is intended to include
"copolyesters" and is understood to mean a synthetic polymer
prepared by the reaction of one or more difunctional carboxylic
acids and/or multifunctional carboxylic acids with one or more
difunctional hydroxyl compounds and/or multifunctional hydroxyl
compounds. Typically the difunctional carboxylic acid can be a
dicarboxylic acid and the difunctional hydroxyl compound can be a
dihydric alcohol such as, for example, glycols and diols. The term
"glycol" as used in this application includes, but is not limited
to, diols, glycols, and/or multifunctional hydroxyl compounds, for
example, branching agents. Alternatively, the difunctional
carboxylic acid may be a hydroxy carboxylic acid such as, for
example, p-hydroxybenzoic acid, and the difunctional hydroxyl
compound may be an aromatic nucleus bearing 2 hydroxyl substituents
such as, for example, hydroquinone. The term "residue", as used
herein, means any organic structure incorporated into a polymer
through a polycondensation and/or an esterification reaction from
the corresponding monomer. The term "repeating unit", as used
herein, means an organic structure having a dicarboxylic acid
residue and a diol residue bonded through a carbonyloxy group.
Thus, for example, the dicarboxylic acid residues may be derived
from a dicarboxylic acid monomer or its associated acid halides,
esters, salts, anhydrides, or mixtures thereof. As used herein,
therefore, the term dicarboxylic acid is intended to include
dicarboxylic acids and any derivative of a dicarboxylic acid,
including its associated acid halides, esters, half-esters, salts,
half-salts, anhydrides, mixed anhydrides, or mixtures thereof,
useful in a reaction process with a diol to make polyester.
Furthermore, as used in this application, the term "diacid"
includes multifunctional acids, for example, branching agents. As
used herein, the term "terephthalic acid" is intended to include
terephthalic acid itself and residues thereof as well as any
derivative of terephthalic acid, including its associated acid
halides, esters, half-esters, salts, half-salts, anhydrides, mixed
anhydrides, or mixtures thereof or residues thereof useful in a
reaction process with a diol to make polyester.
[0443] In one embodiment, terephthalic acid may be used as the
starting material. In another embodiment, dimethyl terephthalate
may be used as the starting material. In yet another embodiment,
mixtures of terephthalic acid and dimethyl terephthalate may be
used as the starting material and/or as an intermediate
material.
[0444] The polyesters used in the present invention typically can
be prepared from dicarboxylic acids and diols which react in
substantially equal proportions and are incorporated into the
polyester polymer as their corresponding residues. The polyesters
of the present invention, therefore, can contain substantially
equal molar proportions of acid residues (100 mole %) and diol
(and/or multifunctional hydroxyl compounds) residues (100 mole %)
such that the total moles of repeating units is equal to 100 mole
%. The mole percentages provided in the present disclosure,
therefore, may be based on the total moles of acid residues, the
total moles of diol residues, or the total moles of repeating
units. For example, a polyester containing 30 mole % isophthalic
acid, based on the total acid residues, means the polyester
contains 30 mole % isophthalic acid residues out of a total of 100
mole % acid residues. Thus, there are 30 moles of isophthalic acid
residues among every 100 moles of acid residues. In another
example, a polyester containing 15 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on the total diol
residues, means the polyester contains 15 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of
100 mole % diol residues. Thus, there are 15 moles of
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues among every 100
moles of diol residues.
[0445] In other aspects of the invention, the Tg of the polyesters
useful in the invention can be at least one of the following
ranges: 90 to 115.degree. C.; 90 to 110.degree. C.; 90 to
105.degree. C.; 90 to 100.degree. C.; 90 to 95.degree. C.; 95 to
115.degree. C.; 95 to 110.degree. C.; 95 to 105.degree. C.; 95 to
100.degree. C.; 100 to 115.degree. C.; 100 to 110.degree. C.; 100
to 105.degree. C.; 105 to 115.degree. C.; 105 to 110.degree. C.;
and 110 to 115.degree. C.
[0446] In other aspects of the invention, the glycol component for
the polyesters useful in the invention include but are not limited
to at least one of the following combinations of ranges: 1 to 15
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 14 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 86 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 13 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 87 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 12 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 88 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 11 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 89 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 10 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 9 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 91 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 8 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 92 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 7 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 93 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 6 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 94 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 5 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 4 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 96 to 99 mole %
1,4-cyclohexanedimethanol; 1 to 3 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 97 to 99 mole %
1,4-cyclohexanedimethanol; and 1 to 2 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 98 to 99 mole %
1,4-cyclohexanedimethanol.
[0447] In other aspects of the invention, the glycol component for
the polyesters useful in the film or sheet of the invention include
but are not limited to at least one of the following combinations
of ranges: 5 to 15 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol
and 85 to 95 mole % 1,4-cyclohexanedimethanol; and 5 to 10 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90 to 95 mole %
1,4-cyclohexanedimethanol.
[0448] For certain embodiments of the invention, the polyesters
useful in the invention may exhibit at least one of the following
inherent viscosities as determined in 60/40 (wt/wt)
phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at
25.degree. C.: 0.10 to 1.2 dL/g; 0.10 to 1.1 dL/g; 0.10 to 1 dL/g;
0.10 to less than 1 dL/g; 0.10 to 0.98 dL/g; 0.10 to 0.95 dL/g;
0.10 to 0.90 dL/g; 0.10 to 0.85 dL/g; 0.10 to 0.80 dL/g; 0.10 to
0.75 dL/g; 0.10 to less than 0.75 dL/g; 0.10 to 0.72 dL/g; 0.10 to
0.70 dL/g; 0.10 to less than 0.70 dL/g; 0.10 to 0.68 dL/g; 0.10 to
less than 0.68 dL/g; 0.10 to 0.65 dL/g; 0.20 to 1.2 dL/g; 0.20 to
1.1 dL/g; 0.20 to 1 dL/g; 0.20 to less than 1 dL/g; 0.20 to 0.98
dL/g; 0.20 to 0.95 dL/g; 0.20 to 0.90 dL/g; 0.20 to 0.85 dL/g; 0.20
to 0.80 dL/g; 0.20 to 0.75 dL/g; 0.20 to less than 0.75 dL/g; 0.20
to 0.72 dL/g; 0.20 to 0.70 dL/g; 0.20 to less than 0.70 dL/g; 0.20
to 0.68 dL/g; 0.20 to less than 0.68 dL/g; 0.20 to 0.65 dL/g; 0.35
to 1.2 dL/g; 0.35 to 1.1 dL/g; 0.35 to 1 dL/g; 0.35 to less than 1
dL/g; 0.35 to 0.98 dL/g; 0.35 to 0.95 dL/g; 0.35 to 0.90 dL/g; 0.35
to 0.85 dL/g; 0.35 to 0.80 dL/g; 0.35 to 0.75 dL/g; 0.35 to less
than 0.75 dL/g; 0.35 to 0.72 dL/g; 0.35 to 0.70 dL/g; 0.35 to less
than 0.70 dL/g; 0.35 to 0.68 dL/g; 0.35 to less than 0.68 dL/g;
0.35 to 0.65 dL/g; 0.40 to 1.2 dL/g; 0.40 to 1.1 dL/g; 0.40 to 1
dL/g; 0.40 to less than 1 dL/g; 0.40 to 0.98 dL/g; 0.40 to 0.95
dL/g; 0.40 to 0.90 dL/g; 0.40 to 0.85 dL/g; 0.40 to 0.80 dL/g; 0.40
to 0.75 dL/g; 0.40 to less than 0.75 dL/g; 0.40 to 0.72 dL/g; 0.40
to 0.70 dL/g; 0.40 to less than 0.70 dL/g; 0.40 to 0.68 dL/g; 0.40
to less than 0.68 dL/g; 0.40 to 0.65 dL/g; greater than 0.42 to 1.2
dL/g; greater than 0.42 to 1.1 dL/g; greater than 0.42 to 1 dL/g;
greater than 0.42 to less than 1 dL/g; greater than 0.42 to 0.98
dL/g; greater than 0.42 to 0.95 dL/g; greater than 0.42 to 0.90
dL/g; greater than 0.42 to 0.85 dL/g; greater than 0.42 to 0.80
dL/g; greater than 0.42 to 0.75 dL/g; greater than 0.42 to less
than 0.75 dL/g; greater than 0.42 to 0.72 dL/g; greater than 0.42
to less than 0.70 dL/g; greater than 0.42 to 0.68 dL/g; greater
than 0.42 to less than 0.68 dL/g; and greater than 0.42 to 0.65
dL/g.
[0449] For certain embodiments of the invention, the polyesters
useful in the invention may exhibit at least one of the following
inherent viscosities as determined in 60/40 (wt/wt)
phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at
25.degree. C.: 0.45 to 1.2 dL/g; 0.45 to 1.1 dL/g; 0.45 to 1 dL/g;
0.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90 dL/g; 0.45 to
0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 to less than
0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to less than
0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to
0.65 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1.1 dL/g; 0.50 to 1 dL/g; 0.50
to less than 1 dL/g; 0.50 to 0.98 dL/g; 0.50 to 0.95 dL/g; 0.50 to
0.90 dL/g; 0.50 to 0.85 dL/g; 0.50 to 0.80 dL/g; 0.50 to 0.75 dL/g;
0.50 to less than 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g;
0.50 to less than 0.70 dL/g; 0.50 to 0.68 dL/g; 0.50 to less than
0.68 dL/g; 0.50 to 0.65 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1.1 dL/g;
0.55 to 1 dL/g; 0.55 to less than 1 dL/g; 0.55 to 0.98 dL/g; 0.55
to 0.95 dL/g; 0.55 to 0.90 dL/g; 0.55 to 0.85 dL/g; 0.55 to 0.80
dL/g; 0.55 to 0.75 dL/g; 0.55 to less than 0.75 dL/g; 0.55 to 0.72
dL/g; 0.55 to 0.70 dL/g; 0.55 to less than 0.70 dL/g; 0.55 to 0.68
dL/g; 0.55 to less than 0.68 dL/g; 0.55 to 0.65 dL/g; 0.58 to 1.2
dL/g; 0.58 to 1.1 dL/g; 0.58 to 1 dL/g; 0.58 to less than 1 dL/g;
0.58 to 0.98 dL/g; 0.58 to 0.95 dL/g; 0.58 to 0.90 dL/g; 0.58 to
0.85 dL/g; 0.58 to 0.80 dL/g; 0.58 to 0.75 dL/g; 0.58 to less than
0.75 dL/g; 0.58 to 0.72 dL/g; 0.58 to 0.70 dL/g; 0.58 to less than
0.70 dL/g; 0.58 to 0.68 dL/g; 0.58 to less than 0.68 dL/g; 0.58 to
0.65 dL/g; 0.60 to 1.2 dL/g; 0.60 to 1.1 dL/g; 0.60 to 1 dL/g; 0.60
to less than 1 dL/g; 0.60 to 0.98 dL/g; 0.60 to 0.95 dL/g; 0.60 to
0.90 dL/g; 0.60 to 0.85 dL/g; 0.60 to 0.80 dL/g; 0.60 to 0.75 dL/g;
0.60 to less than 0.75 dL/g; 0.60 to 0.72 dL/g; 0.60 to 0.70 dL/g;
0.60 to less than 0.70 dL/g; 0.60 to 0.68 dL/g; 0.60 to less than
0.68 dL/g; 0.60 to 0.65 dL/g; 0.65 to 1.2 dL/g; 0.65 to 1.1 dL/g;
0.65 to 1 dL/g; 0.65 to less than 1 dL/g; 0.65 to 0.98 dL/g; 0.65
to 0.95 du/g; 0.65 to 0.90 dL/g; 0.65 to 0.85 du/g; 0.65 to 0.80
dL/g; 0.65 to 0.75 dL/g; 0.65 to less than 0.75 dL/g; 0.65 to 0.72
dL/g; 0.65 to 0.70 dL/g; or 0.65 to less than 0.70 dL/g; It is
contemplated that the polyester compositions of the invention can
possess at least one of the inherent viscosity ranges described
herein and at least one of the monomer ranges for the compositions
described herein unless otherwise stated. It is also contemplated
that the polyester compositions of the invention can posses at
least one of the Tg ranges described herein and at least one of the
monomer ranges for the compositions described herein unless
otherwise stated. It is also contemplated that the polyester
compositions of the invention can posses at least one of the Tg
ranges described herein, at least one of the inherent viscosity
ranges described herein, and at least one of the monomer ranges for
the compositions described herein unless otherwise stated.
[0450] For the desired polyester, the molar ratio of cis/trans
2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary from the pure form
of each or mixtures thereof. In certain embodiments, the molar
percentages for cis and/or trans
2,2,4,4-tetramethyl-1,3-cyclobutanediol are greater than 50 mole %
cis and less than 50 mole % trans; or greater than 55 mole % cis
and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30%
trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to
70 mole % trans and 50 to 30 mole % cis; or 50 to 70 mole % cis and
50 to 30% trans or 60 to 70 mole % cis and 30 to 40 mole % trans;
or greater than 70 mole % cis and less than 30 mole % trans;
wherein the total sum of the mole percentages for cis- and
trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mole
%. The molar ratio of cis/trans 1,4-cyclohexandimethanol can vary
within the range of 50/50 to 0/100, for example, between 40/60 to
20/80.
[0451] In certain embodiments, terephthalic acid, or an ester
thereof, such as, for example, dimethyl terephthalate, or a mixture
of terephthalic acid and an ester thereof, makes up most or all of
the dicarboxylic acid component used to form the polyesters useful
in the invention. In certain embodiments, terephthalic acid
residues can make up a portion or all of the dicarboxylic acid
component used to form the present polyester at a concentration of
at least 70 mole %, such as at least 80 mole %, at least 90 mole %,
at least 95 mole %, at least 99 mole %, or the preferred embodiment
of 100 mole %. In certain embodiments, polyesters with higher
amounts of terephthalic acid can be used in order to produce higher
impact strength properties. For purposes of this disclosure, the
terms "terephthalic acid" and "dimethyl terephthalate are used
interchangeably herein. In one embodiment, dimethyl terephthalate
is part or all of the dicarboxylic acid component used to make the
polyesters useful in the present invention. In all embodiments,
ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100
mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and/or
dimethyl terephthalate and/or mixtures thereof may be used.
[0452] In addition to terephthalic acid residues, the dicarboxylic
acid component of the polyesters useful in the invention can
comprise up to 30 mole %, up to 20 mole %, up to 10 mole %, up to 5
mole %, or up to 1 mole % of one or more modifying aromatic
dicarboxylic acids. The preferred embodiment contains 0 mole %
modifying aromatic dicarboxylic acids. Thus, if present, it is
contemplated that the amount of one or more modifying aromatic
dicarboxylic acids can range from any of these preceding endpoint
values including, for example, from 0.01 to 30 mole %, from 0.01 to
20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole %, or from
0.01 to 1 mole % of one or more modifying aromatic dicarboxylic
acids. In one embodiment, modifying aromatic dicarboxylic acids
that may be used in the present invention include but are not
limited to those having up to 20 carbon atoms, and that can be
linear, para-oriented, or symmetrical. Examples of modifying
aromatic dicarboxylic acids which may be used in this invention
include, but are not limited to, isophthalic acid,
4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-,
2,7-naphthalenedicarboxylic acid, and
trans-4,4'-stilbenedicarboxylic acid, and esters thereof. In one
embodiment, isophthalic acid is the modifying aromatic dicarboxylic
acid. The preferred embodiment of the invention is for 100% of the
dicarboxylic acid component based on terephthalic acid
residues.
[0453] The carboxylic acid component of the polyesters useful in
the invention can be further modified with up to 10 mole %, such as
up to 5 mole % or up to 1 mole % of one or more aliphatic
dicarboxylic acids containing 2-16 carbon atoms, such as, for
example, malonic, succinic, glutaric, adipic, pimelic, suberic,
azelaic and dodecanedioic dicarboxylic acids. Certain embodiments
can also comprise 0.01 or more mole %, such as 0.1 or more mole %,
1 or more mole %, 5 or more mole %, or 10 or more mole % of one or
more modifying aliphatic dicarboxylic acids. The preferred
embodiment contains 0 mole % modifying aliphatic dicarboxylic
acids. Thus, if present, it is contemplated that the amount of one
or more modifying aliphatic dicarboxylic acids can range from any
of these preceding endpoint values including, for example, from
0.01 to 10 mole % and from 0.1 to 10 mole %. The total mole % of
the dicarboxylic acid component is 100 mole %.
[0454] Esters of terephthalic acid and the other modifying
dicarboxylic acids or their corresponding esters and/or salts may
be used instead of the dicarboxylic acids. Suitable examples of
dicarboxylic acid esters include, but are not limited to, the
dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl
esters. In one embodiment, the esters are chosen from at least one
of the following: methyl, ethyl, propyl, isopropyl, and phenyl
esters.
[0455] The 1,4-cyclohexanedimethanol may be cis, trans, or a
mixture thereof, for example, a cis/trans ratio of 60:40 to 40:60.
In another embodiment, the trans-1,4-cyclohexanedimethanol can be
present in the amount of 60 to 80 mole %.
[0456] The glycol component of the polyester portion of the
polyester compositions useful in the invention can contain 14 mole
% or less of one or more modifying glycols which are not
2,2,4,4-tetramethyl-1,3-cyclobutanediol or
1,4-cyclohexanedimethanol; in another embodiment, the polyesters
useful in the invention can contain 10 mole % or less of one or
more modifying glycols. In another embodiment, the polyesters
useful in the invention can contain 5 mole % or less of one or more
modifying glycols. In another embodiment, the polyesters useful in
the invention can contain 3 mole % or less of one or more modifying
glycols. In the preferred embodiment, the polyesters useful in the
invention may contain 0 mole % modifying glycols. Certain
embodiments can also contain 0.01 or more mole %, such as 0.1 or
more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole
% of one or more modifying glycols. Thus, if present, it is
contemplated that the amount of one or more modifying glycols can
range from any of these preceding endpoint values including, for
example, from 0.1 to 10 mole %.
[0457] Modifying glycols useful in the polyesters useful in the
invention refer to diols other than
2,2,4,4-tetramethyl-1,3-cyclobutanediol and
1,4-cyclohexanedimethanol and may contain 2 to 16 carbon atoms.
Examples of suitable modifying glycols include, but are not limited
to, ethylene glycol, diethylene glycol, 1,2-propanediol,
1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, p-xylene glycol or mixtures thereof. In one
embodiment, the modifying glycol is ethylene glycol. In another
embodiment, the modifying glycols include but are not limited to
1,3-propanediol and/or 1,4-butanediol. In another embodiment,
ethylene glycol is excluded as a modifying diol. In another
embodiment, 1,3-propanediol and 1,4-butanediol are excluded as
modifying diols. In another embodiment,
2,2-dimethyl-1,3-propanediol is excluded as a modifying diol. The
polyesters useful the invention can comprise from 0 to 10 mole
percent, for example, from 0.01 to 5 mole percent, from 0.01 to 1
mole percent, from 0.05 to 5 mole percent, from 0.05 to 1 mole
percent, or from 0.1 to 0.7 mole percent, or 0.1 to 0.5 mole
percent, based the total mole percentages of either the diol or
diacid residues; respectively, of one or more residues of a
branching monomer, also referred to herein as a branching agent,
having 3 or more carboxyl substituents, hydroxyl substituents, or a
combination thereof. In certain embodiments, the branching monomer
or agent may be added prior to and/or during and/or after the
polymerization of the polyester. The polyester(s) useful in the
invention can thus be linear or branched. In certain embodiments,
the branching monomer or agent may be added prior to and/or during
and/or after the polymerization.
[0458] Examples of branching monomers include, but are not limited
to, multifunctional acids or multifunctional alcohols such as
trimellitic acid, trimellitic anhydride, pyromellitic dianhydride,
trimethylolpropane, glycerol, pentaerythritol, citric acid,
tartaric acid, 3-hydroxyglutaric acid and the like. In one
embodiment, the branching monomer residues can comprise 0.1 to 0.7
mole percent of one or more residues chosen from at least one of
the following: trimellitic anhydride, pyromellitic dianhydride,
glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol,
trimethylolethane, and/or trimesic acid. The branching monomer may
be added to the polyester reaction mixture or blended with the
polyester in the form of a concentrate as described, for example,
in U.S. Pat. Nos. 5,654,347 and 5,696,176, whose disclosure
regarding branching monomers is incorporated herein by
reference.
[0459] The polyesters useful in the invention can be made by
processes known from the literature such as, for example, by
processes in homogenous solution, by transesterification processes
in the melt, and by two phase interfacial processes. Suitable
methods include, but are not limited to, the steps of reacting one
or more dicarboxylic acids with one or more glycols at a
temperature of 100.degree. C. to 315.degree. C. at a pressure of
0.1 to 760 mm Hg for a time sufficient to form a polyester. See
U.S. Pat. No. 3,772,405 for methods of producing polyesters, the
disclosure regarding such methods is hereby incorporated herein by
reference.
[0460] In another aspect, the invention relates to a process for
producing a polyester. The process comprises: [0461] (I) heating a
mixture comprising the monomers useful in any of the polyesters
useful in the invention in the presence of a catalyst at a
temperature of 150 to 240.degree. C. for a time sufficient to
produce an initial polyester; [0462] (II) heating the initial
polyester of step (I) at a temperature of 240 to 320.degree. C. for
1 to 4 hours; and
[0463] (III) removing any unreacted glycols.
[0464] Suitable catalysts for use in this process include, but are
not limited to, organo-zinc or tin compounds. The use of this type
of catalyst is well known in the art. Examples of catalysts useful
in the present invention include, but are not limited to, zinc
acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate,
and/or dibutyltin oxide. Other catalysts may include, but are not
limited to, those based on titanium, zinc, manganese, lithium,
germanium, and cobalt. Catalyst amounts can range from 10 ppm to
20,000 ppm or 10 to 10,000 ppm, or to 5000 ppm or 10 to 1000 ppm or
10 to 500 ppm, or 10 to 300 ppm or 10 to 250 based on the catalyst
metal and based on the weight of the final polymer. The process can
be carried out in either a batch or continuous process.
[0465] Typically, step (I) can be carried out until 50% by weight
or more of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol has been
reacted. Step (I) may be carried out under pressure, ranging from
atmospheric pressure to 100 psig. The term "reaction product" as
used in connection with any of the catalysts useful in the
invention refers to any product of a polycondensation or
esterification reaction with the catalyst and any of the monomers
used in making the polyester as well as the product of a
polycondensation or esterification reaction between the catalyst
and any other type of additive.
[0466] Typically, Step (II) and Step (III) can be conducted at the
same time. These steps can be carried out by methods known in the
art such as by placing the reaction mixture under a pressure
ranging from 0.002 psig to below atmospheric pressure, or by
blowing hot nitrogen gas over the mixture.
[0467] The polyesters useful in this invention can also be prepared
by reactive melt blending and extrusion of two polyesters. For
example: a polyester containing 100% terephthalic acid residues; 10
mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 90
mole % 1,4-cyclohexanedimethanol can be prepared by reactive melt
blending and extrusion of equal amounts of a polyester containing
100 mole % terephthalic residues and 100% 1,4-cyclohexanedimethanol
with another polyester containing 100 mole % terephthalic residues;
80 mole % 1,4-cyclohexanedimethanol residues, and 20 mole %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
[0468] The polyesters of this invention, prepared in a reactor or
by melt blending/extrusion, can subsequently be crystallized if
needed and solid stated by techniques known in the art to further
increase the IV.
[0469] Strain induced crystallization refers to a phenomenon in
which an initially amorphous solid material undergoes a phase
transformation in which some amorphous domains are converted to
crystalline domains due to the application of strain. This
phenomenon has important effects in strength and fatigue
properties.
[0470] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature above the Tg of the polyester.
[0471] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0472] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 8% to 35% when
stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0473] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 10% to 35%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0474] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 10% to 35%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0475] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 10% to 30%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0476] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 10% to 30%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0477] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 10% to 25%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0478] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 10% to 25%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0479] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 15% to 30%
when stretched at a temperature 10.degree. C. above the Tg of the
polyester.
[0480] In one embodiment of the invention, the article of the
invention has a strain induced crystallinity of from 15% to 30%
when stretched at a temperature 20.degree. C. above the Tg of the
polyester.
[0481] In addition, the polyester useful in this invention may also
contain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01
to 15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight
of the total weight of the polyester composition of common
additives such as colorants, dyes, mold release agents, reheat
additives, flame retardants, plasticizers, stabilizers, including
but not limited to, UV stabilizers, thermal stabilizers and/or
reaction products thereof, fillers, and impact modifiers. Examples
of typical commercially available impact modifiers well known in
the art and useful in this invention include, but are not limited
to, ethylene/propylene terpolymers; functionalized polyolefins,
such as those containing methyl acrylate and/or glycidyl
methacrylate; styrene-based block copolymeric impact modifiers; and
various acrylic core/shell type impact modifiers. For example, UV
additives can be incorporated into articles of manufacture through
addition to the bulk, through application of a hard coat, or
through coextrusion of a cap layer. Residues of such additives are
also contemplated as part of the polyester composition.
[0482] The polyesters useful in the invention can comprise at least
one chain extender. Suitable chain extenders include, but are not
limited to, multifunctional (including, but not limited to,
bifunctional) isocyanates, multifunctional epoxides, including for
example, epoxylated novolacs, and phenoxy resins. In certain
embodiments, chain extenders may be added at the end of the
polymerization process or after the polymerization process. If
added after the polymerization process, chain extenders can be
incorporated by compounding or by addition during conversion
processes such as injection molding or extrusion. The amount of
chain extender used can vary depending on the specific monomer
composition used and the physical properties desired but is
generally about 0.1 percent by weight to about 10 percent by
weight, preferably about 0.1 to about 5 percent by weight, based on
the total weight of the polyester.
[0483] Thermal stabilizers are compounds that stabilize polyesters
during polyester manufacture and/or post polymerization including,
but not limited to, phosphorous compounds including but not limited
to phosphoric acid, phosphorous acid, phosphonic acid, phosphinic
acid, phosphonous acid, and various esters and salts thereof. These
can be present in the polyester compositions useful in the
invention. The esters can be alkyl, branched alkyl, substituted
alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted
aryl. In one embodiment, the number of ester groups present in the
particular phosphorous compound can vary from zero up to the
maximum allowable based on the number of hydroxyl groups present on
the thermal stabilizer used. The term "thermal stabilizer" is
intended to include the reaction products thereof. The term
"reaction product" as used in connection with the thermal
stabilizers of the invention refers to any product of a
polycondensation or esterification reaction between the thermal
stabilizer and any of the monomers used in making the polyester as
well as the product of a polycondensation or esterification
reaction between the catalyst and any other type of additive.
[0484] Reinforcing materials may be useful in the compositions of
this invention. The reinforcing materials may include, but are not
limited to, carbon filaments, silicates, mica, clay, talc, titanium
dioxide, Wollastonite, glass flakes, glass beads and fibers, and
polymeric fibers and combinations thereof. In one embodiment, the
reinforcing materials are glass, such as, fibrous glass filaments,
mixtures of glass and talc, glass and mica, and glass and polymeric
fibers.
[0485] The invention further relates to articles of manufacture.
These articles include, but are not limited to, injection blow
molded articles, injection stretch blow molded articles, extrusion
blow molded articles, extrusion stretch blow molded articles,
calendered articles, compression molded articles, and solution
casted articles. Methods of making the articles of manufacture,
include, but are not limited to, extrusion blow molding, extrusion
stretch blow molding, injection blow molding, injection stretch
blow molding, calendering, compression molding, and solution
casting.
[0486] The invention further relates to the film(s) and/or sheet(s)
comprising the polyester compositions of the invention. The methods
of forming the polyesters into film(s) and/or sheet(s) are well
known in the art. Examples of film(s) and/or sheet(s) of the
invention including but not limited to extruded film(s) and/or
sheet(s), calendered film(s) and/or sheet(s), compression molded
film(s) and/or sheet(s), solution casted film(s) and/or sheet(s).
Methods of making film and/or sheet include but are not limited to
extrusion, calendering, compression molding, and solution
casting.
[0487] Examples of potential articles made from film and/or sheet
include, but are not limited, to uniaxially stretched film,
biaxially stretched film, shrink film (whether or not uniaxially or
biaxially stretched), liquid crystal display film (including, but
not limited to, diffuser sheets, compensation films and protective
films), thermoformed sheet, graphic arts film, outdoor signs,
skylights, coating(s), coated articles, painted articles,
laminates, laminated articles, and/or multiwall films or
sheets.
[0488] As used herein, the abbreviation "wt" means "weight".
[0489] The following examples further illustrate how the
compositions of matter of the invention can be made and evaluated,
and are intended to be purely exemplary of the invention and are
not intended to limit the scope thereof. Unless indicated
otherwise, parts are parts by weight, temperature is in degrees C.
or is at room temperature, and pressure is at or near
atmospheric.
EXAMPLES
[0490] The inherent viscosity of the polyesters was determined in
60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5
g/100 ml at 25.degree. C.
[0491] The glycol content and the cis/trans ratio of the
compositions were determined by proton nuclear magnetic resonance
(NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse
Plus 600 MHz nuclear magnetic resonance spectrometer using either
chloroform-trifluoroacetic acid (70-30 volume/volume) for polymers
or, for oligomeric samples, 60/40 (wt/wt) phenol/tetrachloroethane
with deuterated chloroform added for lock. Peak assignments for
2,2,4,4-tetramethyl-1,3-cyclobutanediol resonances were made by
comparison to model mono- and dibenzoate esters of
2,2,4,4-tetramethyl-1,3-cyclobutanediol. These model compounds
closely approximate the resonance positions found in the polymers
and oligomers.
[0492] The crystallization half-time, t.sub.1/2, was determined by
measuring the light transmission of a sample via a laser and photo
detector as a function of time on a temperature controlled hot
stage. This measurement was done by exposing the polymers to a
temperature, T.sub.max, and then cooling it to the desired
temperature. The sample was then held at the desired temperature by
a hot stage while transmission measurements were made as a function
of time. Initially, the sample was visually clear with high light
transmission and became opaque as the sample crystallized. The
crystallization half-time was recorded as the time at which the
light transmission was halfway between the initial transmission and
the final transmission. T.sub.max is defined as the temperature
required to melt the crystalline domains of the sample (if
crystalline domains are present). The T.sub.max reported in the
examples below represents the temperature at which each sample was
heated to condition the sample prior to crystallization half time
measurement. The T.sub.max temperature is dependant on composition
and is typically different for each polyester. For example, PCT may
need to be heated to some temperature greater than 290.degree. C.
to melt the crystalline domains.
[0493] Differential scanning calorimetry (DSC) was performed using
TA Instruments Model 2920 with a liquid nitrogen cooling accessory.
The sample weight, in the range of 8 to 12 mg, was measured and
recorded. Samples were first heated (1.sup.st heating scan) from 0
to 320.degree. C. at 20.degree. C./min, followed by cooling to
0.degree. C. at 20.degree. C./min (cooling scan), and then heated
again from 0 to 320.degree. C. at 20.degree. C. min. Various
thermal parameters were measured and recorded. .DELTA.H.sub.cc
(cal/g) is the heat of crystallization measured from the cooling
scan. T.sub.cc is the crystallization peak temperature on the
cooling scan. T.sub.g is the glass transition temperature measured
from 2.sup.nd heating scan. T.sub.m is the melting point measured
during the 2.sup.nd heating scan. .DELTA.H.sub.ch1 (cal/g) is the
heat of crystallization measured during the 1.sup.st heating scan.
.DELTA.H.sub.m1 (cal/g) is the heat of melting measured during the
1.sup.st heating scan.
[0494] Unless otherwise specified, the cis/trans ratio of the 1,4
cyclohexanedimethanol used in the following examples was
approximately 30/70, and could range from 35/65 to 25/75. Unless
otherwise specified, the cis/trans ratio of the
2,2,4,4-tetramethyl-1,3-cyclobutanediol used in the following
examples was approximately 50/50.
[0495] The following abbreviations apply throughout the working
examples and figures:
TABLE-US-00001 TPA Terephthalic acid DMT Dimethyl therephthalate
TMCD 2,2,4,4-tetramethy-1,3-cyclobutanediol CHDM
1,4-cyclohexanedimethanol EG ethylene glycol IPA Isophthalic
acid
Example 1
[0496] This example illustrates that TMCD is more effective at
reducing the crystallization rate of PCT than EG or IPA.
[0497] A variety of copolyesters were prepared as described below.
These copolyesters were all made with 200 ppm dibutyl tin oxide as
the catalyst in order to minimize the effect of catalyst type and
concentration on nucleation during crystallization studies. The
cis/trans ratio of the 1,4-cyclohexanedimethanol was 31/69 while
the cis/trans ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol
is reported in Table 1.
[0498] For purposes of this example, the samples had sufficiently
similar inherent viscosities thereby effectively eliminating this
as a variable in the crystallization rate measurements.
[0499] Crystallization half-time measurements from the melt were
made at temperatures from 140 to 200.degree. C. at 10.degree. C.
increments and are reported in Table 1. The fastest crystallization
half-time for each sample was taken as the minimum value of
crystallization half-time as a function of temperature, typically
occurring around 170 to 180.degree. C. The fastest crystallization
half-times for the samples are plotted in FIG. 1 as a function of
mole % comonomer modification to PCT.
[0500] The data shows that 2,2,4,4-tetramethyl-1,3-cyclobutanediol
is more effective than ethylene glycol and isophthalic acid at
decreasing the crystallization rate (i.e., increasing the
crystallization half-time). In addition,
2,2,4,4-tetramethyl-1,3-cyclobutanediol increases T.sub.g and
lowers density.
TABLE-US-00002 TABLE 1 Crystallization Half-times (min) at at at at
at at at Comonomer IV Density T.sub.g T.sub.max 140.degree. C.
150.degree. C. 160.degree. C. 170.degree. C. 180.degree. C.
190.degree. C. 200.degree. C. Example (mol %).sup.1 (dl/g) (g/ml)
(.degree. C.) (.degree. C.) (min) (min) (min) (min) (min) (min)
(min) 1A 20.2% A.sup.2 0.630 1.198 87.5 290 2.7 2.1 1.3 1.2 0.9 1.1
1.5 1B 19.8% B 0.713 1.219 87.7 290 2.3 2.5 1.7 1.4 1.3 1.4 1.7 1C
20.0% C 0.731 1.188 100.5 290 >180 >60 35.0 23.3 21.7 23.3
25.2 1D 40.2% A.sup.2 0.674 1.198 81.2 260 18.7 20.0 21.3 25.0 34.0
59.9 96.1 1E 34.5% B 0.644 1.234 82.1 260 8.5 8.2 7.3 7.3 8.3 10.0
11.4 1F 40.1% C 0.653 1.172 122.0 260 >10 days >5 days >5
days 19204 >5 days >5 days >5 days 1G 14.3% D 0.646.sup.3
1.188 103.0 290 55.0 28.8 11.6 6.8 4.8 5.0 5.5 1H 15.0% E
0.728.sup.4 1.189 99.0 290 25.4 17.1 8.1 5.9 4.3 2.7 5.1 .sup.1The
balance of the diol component of the polyesters in Table 1 is
1,4-cyclohexanedimethanol; and the balance of the dicarboxylic acid
component of the polyesters in Table 1 is dimethyl terephthalate;
if the dicarboxylic acid is not described, it is 100 mole %
dimethyl terephthalate. .sup.2100 mole % 1,4-cyclohexanedimethanol.
.sup.3A film was pressed from the ground polyester of Example 1G at
240.degree. C. The resulting film had an inherent viscosity value
of 0.575 dL/g. .sup.4A film was pressed from the ground polyester
of Example 1H at 240.degree. C. The resulting film had an inherent
viscosity value of 0.0.652 dL/g.
where: [0501] A is Isophthalic Acid [0502] B is Ethylene Glycol
[0503] C is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (approx. 50/50
cis/trans) [0504] D is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol
(98/2 cis/trans) [0505] E is
2,2,4,4-Tetramethyl-1,3-cyclobutanediol (5/95 cis/trans)
[0506] As shown in Table 1 and FIG. 1,
2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than
other comonomers, such ethylene glycol and isophthalic acid, at
increasing the crystallization half-time, i.e., the time required
for a polymer to reach half of its maximum crystallinity. By
decreasing the crystallization rate of PCT (increasing the
crystallization half-time), amorphous articles based on
2,2,4,4-tetramethyl-1,3-cyclobutanediol-modified PCT as described
herein may be fabricated by methods known in the art. As shown in
Table 1, these materials can exhibit higher glass transition
temperatures and lower densities than other modified PCT
copolyesters.
[0507] Preparation of the polyesters shown on Table 1 is described
below.
Example 1A
[0508] This example illustrates the preparation of a copolyester
with a target composition of 80 mol % dimethyl terephthalate
residues, 20 mol % dimethyl isophthalate residues, and 100 mol %
1,4-cyclohexanedimethanol residues (28/72 cis/trans).
[0509] A mixture of 56.63 g of dimethyl terephthalate, 55.2 g of
1,4-cyclohexanedimethanol, 14.16 g of dimethyl isophthalate, and
0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask
equipped with an inlet for nitrogen, a metal stirrer, and a short
distillation column. The flask was placed in a Wood's metal bath
already heated to 210.degree. C. The stirring speed was set to 200
RPM throughout the experiment. The contents of the flask were
heated at 210.degree. C. for 5 minutes and then the temperature was
gradually increased to 290.degree. C. over 30 minutes. The reaction
mixture was held at 290.degree. C. for 60 minutes and then vacuum
was gradually applied over the next 5 minutes until the pressure
inside the flask reached 100 mm of Hg. The pressure inside the
flask was further reduced to 0.3 mm of Hg over the next 5 minutes.
A pressure of 0.3 mm of Hg was maintained for a total time of 90
minutes to remove excess unreacted diols. A high melt viscosity,
visually clear and colorless polymer was obtained with a glass
transition temperature of 87.5.degree. C. and an inherent viscosity
of 0.63 dl/g. NMR analysis showed that the polymer was composed of
100 mol % 1,4-cyclohexanedimethanol residues and 20.2 mol %
dimethyl isophthalate residues.
Example 1B
[0510] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 20 mol % ethylene glycol residues, and 80 mol %
1,4-cyclohexanedimethanol residues (32/68 cis/trans).
[0511] A mixture of 77.68 g of dimethyl terephthalate, 50.77 g of
1,4-cyclohexanedimethanol, 27.81 g of ethylene glycol, and 0.0433 g
of dibutyl tin oxide was placed in a 500-milliliter flask equipped
with an inlet for nitrogen, a metal stirrer, and a short
distillation column. The flask was placed in a Wood's metal bath
already heated to 200.degree. C. The stirring speed was set to 200
RPM throughout the experiment. The contents of the flask were
heated at 200.degree. C. for 60 minutes and then the temperature
was gradually increased to 210.degree. C. over 5 minutes. The
reaction mixture was held at 210.degree. C. for 120 minutes and
then heated up to 280.degree. C. in 30 minutes. Once at 280.degree.
C., vacuum was gradually applied over the next 5 minutes until the
pressure inside the flask reached 100 mm of Hg. The pressure inside
the flask was further reduced to 0.3 mm of Hg over the next 10
minutes. A pressure of 0.3 mm of Hg was maintained for a total time
of 90 minutes to remove excess unreacted diols. A high melt
viscosity, visually clear and colorless polymer was obtained with a
glass transition temperature of 87.7.degree. C. and an inherent
viscosity of 0.71 dl/g. NMR analysis showed that the polymer was
composed of 19.8 mol % ethylene glycol residues.
Example 1C
[0512] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 20 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol
residues, and 80 mol % 1,4-cyclohexanedimethanol residues (31/69
cis/trans).
[0513] A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of
1,4-cyclohexanedimethanol, 17.86 g of
2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin
oxide was placed in a 500-milliliter flask equipped with an inlet
for nitrogen, a metal stirrer, and a short distillation column.
This polyester was prepared in a manner similar to that described
in Example 1A. A high melt viscosity, visually clear and colorless
polymer was obtained with a glass transition temperature of
100.5.degree. C. and an inherent viscosity of 0.73 dl/g. NMR
analysis showed that the polymer was composed of 80.5 mol %
1,4-cyclohexanedimethanol residues and 19.5 mol %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
Example 1D
[0514] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 40 mol % dimethyl isophthalate residues, and 100 mol %
1,4-cyclohexanedimethanol residues (28/72 cis/trans).
[0515] A mixture of 42.83 g of dimethyl terephthalate, 55.26 g of
1,4-cyclohexanedimethanol, 28.45 g of dimethyl isophthalate, and
0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask
equipped with an inlet for nitrogen, a metal stirrer, and a short
distillation column. The flask was placed in a Wood's metal bath
already heated to 210.degree. C. The stirring speed was set to 200
RPM throughout the experiment. The contents of the flask were
heated at 210.degree. C. for 5 minutes and then the temperature was
gradually increased to 290.degree. C. over 30 minutes. The reaction
mixture was held at 29.degree. C. for 60 minutes and then vacuum
was gradually applied over the next 5 minutes until the pressure
inside the flask reached 100 mm of Hg. The pressure inside the
flask was further reduced to 0.3 mm of Hg over the next 5 minutes.
A pressure of 0.3 mm of Hg was maintained for a total time of 90
minutes to remove excess unreacted diols. A high melt viscosity,
visually clear and colorless polymer was obtained with a glass
transition temperature of 81.2.degree. C. and an inherent viscosity
of 0.67 dl/g. NMR analysis showed that the polymer was composed of
100 mol % 1,4-cyclohexanedimethanol residues and 40.2 mol %
dimethyl isophthalate residues.
Example 1E
[0516] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 40 mol % ethylene glycol residues, and 60 mol %
1,4-cyclohexanedimethanol residues (31/69 cis/trans).
[0517] A mixture of 81.3 g of dimethyl terephthalate, 42.85 g of
1,4-cyclohexanedimethanol, 34.44 g of ethylene glycol, and 0.0419 g
of dibutyl tin oxide was placed in a 500-milliliter flask equipped
with an inlet for nitrogen, a metal stirrer, and a short
distillation column. The flask was placed in a Wood's metal bath
already heated to 200.degree. C. The stirring speed was set to 200
RPM throughout the experiment. The contents of the flask were
heated at 200.degree. C. for 60 minutes and then the temperature
was gradually increased to 210.degree. C. over 5 minutes. The
reaction mixture was held at 210.degree. C. for 120 minutes and
then heated up to 280.degree. C. in 30 minutes. Once at 280.degree.
C., vacuum was gradually applied over the next 5 minutes until the
pressure inside the flask reached 100 mm of Hg. The pressure inside
the flask was further reduced to 0.3 mm of Hg over the next 10
minutes. A pressure of 0.3 mm of Hg was maintained for a total time
of 90 minutes to remove excess unreacted diols. A high melt
viscosity, visually clear and colorless polymer was obtained with a
glass transition temperature of 82.1.degree. C. and an inherent
viscosity of 0.64 dl/g. NMR analysis showed that the polymer was
composed of 34.5 mol % ethylene glycol residues.
Example 1F
[0518] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 40 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol
residues, and 60 mol % 1,4-cyclohexanedimethanol residues (31/69
cis/trans).
[0519] A mixture of 77.4 g of dimethyl terephthalate, 36.9 g of
1,4-cyclohexanedimethanol, 32.5 g of
2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin
oxide was placed in a 500-milliliter flask equipped with an inlet
for nitrogen, a metal stirrer, and a short distillation column. The
flask was placed in a Wood's metal bath already heated to
210.degree. C. The stirring speed was set to 200 RPM throughout the
experiment. The contents of the flask were heated at 210.degree. C.
for 3 minutes and then the temperature was gradually increased to
260.degree. C. over 30 minutes. The reaction mixture was held at
260.degree. C. for 120 minutes and then heated up to 290.degree. C.
in 30 minutes. Once at 290.degree. C., vacuum was gradually applied
over the next 5 minutes until the pressure inside the flask reached
100 mm of Hg. The pressure inside the flask was further reduced to
0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg
was maintained for a total time of 90 minutes to remove excess
unreacted diols. A high melt viscosity, visually clear and
colorless polymer was obtained with a glass transition temperature
of 122.degree. C. and an inherent viscosity of 0.65 dl/g. NMR
analysis showed that the polymer was composed of 59.9 mol %
1,4-cyclohexanedimethanol residues and 40.1 mol %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
Example 1G
[0520] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 20 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues
(98/2 cis/trans), and 80 mol % 1,4-cyclohexanedimethanol residues
(31/69 cis/trans).
[0521] A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of
1,4-cyclohexanedimethanol, 20.77 g of
2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin
oxide was placed in a 500-milliliter flask equipped with an inlet
for nitrogen, a metal stirrer, and a short distillation column. The
flask was placed in a Wood's metal bath already heated to
210.degree. C. The stirring speed was set to 200 RPM throughout the
experiment. The contents of the flask were heated at 210.degree. C.
for 3 minutes and then the temperature was gradually increased to
260.degree. C. over 30 minutes. The reaction mixture was held at
260.degree. C. for 120 minutes and then heated up to 290.degree. C.
in 30 minutes. Once at 290.degree. C., vacuum was gradually applied
over the next 5 minutes until the pressure inside the flask reached
100 mm of Hg and the stirring speed was also reduced to 100 RPM.
The pressure inside the flask was further reduced to 0.3 mm of Hg
over the next 5 minutes and the stirring speed was reduced to 50
RPM. A pressure of 0.3 mm of Hg was maintained for a total time of
60 minutes to remove excess unreacted diols. A high melt viscosity,
visually clear and colorless polymer was obtained with a glass
transition temperature of 103.degree. C. and an inherent viscosity
of 0.65 dl/g. NMR analysis showed that the polymer was composed of
85.7 mol % 1,4-cyclohexanedimethanol residues and 14.3 mol %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
Example 1H
[0522] This example illustrates the preparation of a copolyester
with a target composition of 100 mol % dimethyl terephthalate
residues, 20 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues
(5/95 cis/trans), and 80 mol % 1,4-cyclohexanedimethanol residues
(31/69 cis/trans).
[0523] A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of
1,4-cyclohexanedimethanol, 20.77 g of
2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin
oxide was placed in a 500-milliliter flask equipped with an inlet
for nitrogen, a metal stirrer, and a short distillation column. The
flask was placed in a Wood's metal bath already heated to
210.degree. C. The stirring speed was set to 200 RPM at the
beginning of the experiment. The contents of the flask were heated
at 210.degree. C. for 3 minutes and then the temperature was
gradually increased to 260.degree. C. over 30 minutes. The reaction
mixture was held at 260.degree. C. for 120 minutes and then heated
up to 290.degree. C. in 30 minutes. Once at 290.degree. C., vacuum
was gradually applied over the next 5 minutes with a set point of
100 mm of Hg and the stirring speed was also reduced to 100 RPM.
The pressure inside the flask was further reduced to a set point of
0.3 mm of Hg over the next 5 minutes and the stirring speed was
reduced to 50 RPM. This pressure was maintained for a total time of
60 minutes to remove excess unreacted diols. It was noted that the
vacuum system failed to reach the set point mentioned above, but
produced enough vacuum to produce a high melt viscosity, visually
clear and colorless polymer with a glass transition temperature of
99.degree. C. and an inherent viscosity of 0.73 dl/g. NMR analysis
showed that the polymer was composed of 85 mol %
1,4-cyclohexanedimethanol residues and 15 mol %
2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
Example 2
[0524] This example illustrates that TMCD is more effective at
reducing the crystallization rate of PCT than EG or IPA. This
example also illustrates the improvements in heat resistance, as
measured by T.sub.m and T.sub.g, provided by TMCD modification over
EG or IPA modification of PCT at similar crystallization rates.
[0525] Materials were prepared via melt compounding Tritan.TM.
TX1000 (IV=0.72 dl/g) with PCT 13787 (IV=0.76 dl/g) at 300.degree.
C. on a Sterling 1.5 inch pelletizing single screw extruder at
different weight ratios. Tritan.TM. TX1000 and PCT 13787 are
produced commercially by Eastman Chemical Company. The resulting
compositions and IVs are shown as materials A, B, and C in Table 2.
A portion of materials A, B, and C were solid stated to higher IVs,
materials D, E, and F respectively, in a reactor at 225.degree. C.
using nitrogen. Materials G, H, and I are produced commercially by
Eastman Chemical Company. Materials J and K were produced in a
pilot plant at Eastman Chemical Company.
[0526] Material G is unmodified PCT. During the cooling scan of the
DSC, crystallization releases 10 cal/g of heat (.DELTA.H.sub.cc).
This corresponds to about 34% crystallinity being formed during
cooling from the melt at 320.degree. C. to 0.degree. C. at
20.degree. C. per minute assuming a specific heat of fusion of 29
cal/g. The percent crystallinity formed during cooling is
calculated by equation (1).
X c = ( .DELTA. H cc ) 29 .times. 100 ( 1 ) ##EQU00001##
The peak temperature in the crystallization exotherm (T.sub.cc)
occurs at 227.degree. C. for unmodified PCT.
[0527] Comonomer modification of PCT will slow down the
crystallization rate of PCT. As a result modified PCT materials
will release less heat during the cooling from the melt at
320.degree. C. to 0.degree. C. than unmodified PCT. The data in
Table 2 shows that TMCD is more effective than IPA or EG
modification of PCT at slowing down the crystallization rate as
evidenced by a lower .DELTA.H.sub.cc on a mole percent modification
of PCT. For example, unmodified PCT (Material G) releases 10 cal/g
during the cooling scan. Modification of PCT with 17 mole % IPA
(Material I), results in a slower crystallization rate as evidenced
by .DELTA.H.sub.cc=8.0 cal/g being released during the cooling scan
due to crystallization. Modification of PCT with EG, results in a
slower crystallization rate as evidenced by .DELTA.H.sub.cc=9.0
cal/g for PCT modified by 16.6 mole % EG (Material J) and
.DELTA.H.sub.cc=5.8 cal/g for PCT modified by 22.6 mole % EG
(Material K). In comparison, PCT only needs to be modified by
approximately 5 mole % TMCD (Materials A, D, and E) to slow down
the crystallization rate to achieve a similiar heat release
(.DELTA.H.sub.cc.about.8.0 cal/g) during the cooling scan compared
with .about.17 mole % modification by EG or IPA. At similar
crystallization rates or .DELTA.H.sub.cc, PCT modified by TMCD have
higher melting points (T.sub.m) and glass transition temperatures
(T.sub.g) than PCT modified by IPA or EG. For example, at
.DELTA.H.sub.cc.about.8.0 cal/g, PCT requires approximately 17 mole
% EG or IPA modification resulting in a Tm.about.261.degree. C. and
Tg.about.89.degree. C. (Materials I, J, and K). At
.DELTA.H.sub.cc.about.8.0 cal/g, PCT requires only about 5 mole %
TMCD (Materials A, D, and E) modification resulting in a
Tm.about.279.degree. C. and Tg.about.94.degree. C. As a result, the
PCT materials modified by TMCD will have better heat resistance.
T.sub.cc is also reduced more effectively for PCT modified by TMCD
than PCT modified by EG or IPA on a mole % basis. This is another
indicator that TMCD is more effective at slowing down the
crystallization rate of PCT than either EG or IPA on a mole %
basis.
TABLE-US-00003 TABLE 2 Thermal Properties of Unmodified and
Modified PCT Composition by NMR (mole %, IV .DELTA.H.sub.cc
T.sub.cc T.sub.m Tg Material comonomer) (dl/g) (cal/g) (.degree.
C.) (.degree. C.) (.degree. C.) A 4.4, TMCD 0.73 7.6 203 280 92 B
7.7, TMCD 0.72 5.5 184 275 95 C 9.1, TMCD 0.72 3.2 176 270 98 D
4.2, TMCD 0.81 8.3 202 279 93 E 6.7, TMCD 0.84 7.9 194 275 98 F
9.7, TMCD 0.85 3.0 175 268 100 G 0 0.76 10.0 227 288 93 H 5.0, IPA
0.84 9.3 207 280 92 I 17.0, IPA 0.77 8.0 182 262 91 J 16.6, EG 0.69
9.0 189 265 87 K 22.6, EG 0.74 5.8 165 257 86
Example 3
[0528] This example illustrates that PCT materials modified by TMCD
can be extruded as amorphous films and subsequently stretched above
Tg to create clear semi-crystalline films as a result of strain
induced crystallinity.
[0529] Three modified PCT materials targeting approximately 5, 10,
and 15 mole percent TMCD were prepared by melt compounding PCT
13787 and Tritan.TM. TX1000 at different weight ratios at
300.degree. C. on a Sterling 1.5 inch pelletizing single screw
extruder. Tritan.TM. TX1000 and PCT 13787 are produced commercially
by Eastman Chemical Company. The resulting samples are described in
Table 3.
TABLE-US-00004 TABLE 3 Materials prepared by melt blending Tritan
.TM. TX1000 and PCT 13787. PCT/TX 1000 Mole % TMCD IV Material
Weight Ratio Composition by NMR (dl/g) A ~3/1 4.9 0.72 B ~1/1 10.2
0.72 C ~1/3 15.5 0.71
A sample of Material A, B, and C was solid stated, as shown in
Table 4, at 225.degree. C. under vacuum (0.5 torr). Materials A, B,
and C were also solid stated using nitrogen flow at 225.degree. C.
These results are shown in Table 5.
TABLE-US-00005 TABLE 4 Solid stating of PCT modified by TMCD at
225.degree. C. at 0.5 torr. IV IV IV t = 0 hr t = 6 hr t = 24 hr
Material (dl/g) (dl/g) (dl/g) A 0.72 0.78 0.88 B 0.72 0.80 0.90 C
0.71 0.73 0.86
TABLE-US-00006 TABLE 5 Solid stating of PCT modified by TMCD at
225.degree. C. with nitrogen. Mole % Temp Time IV Material TMCD
(.degree. C.) (hr) (dl/g) A 4.9 0 0.72 A1 4.9 225 5 0.77 A2 4.9 225
11 0.82 A3 4.9 225 17 0.87 B 10.2 0 0.72 B1 10.2 225 5 0.74 B2 10.2
225 11 0.76 B3 10.2 225 17 0.84 C 15.5 0 0.71 C1 15.5 225 5 0.75 C2
15.5 225 11 0.83 C3 15.5 215 25 0.87
[0530] Materials A, A1, A2, A3, B, B1, B2, B3, C, C1, C2, and C3
were extruded into 20 mil clear amorphous film using a Killian 1
inch single screw extruder operating at 300.degree. C. The 20 mil
(0.51 mm) films were then cut into 4.5'' squares for stretching in
a Bruckner KARO IV Laboratory stretching machine. The grip
distances were 110 mm. Films of all the materials were unaxially
stretched to different draw ratios (.lamda.) at temperatures
relative to T.sub.g (T.sub.g+10 and T.sub.g+20.degree. C.) and a
nominal strain rate of 100% sec.sup.1. All the stretched films were
visually clear. The percentage of strain induced crystallinity
(X.sub.c) in the stretched films was determined by equation (2)
from the first heating scan of films evaluated in a DSC.
X c = ( .DELTA. H m 1 - .DELTA. H CH 1 ) 29 .times. 100 ( 2 )
##EQU00002##
[0531] Table 6 shows the various stretched films had developed
crystallinity as result of strain induced crystallization for
materials with different levels of TMCD with similar IVs (Materials
A2, B2, and C2). The amount of crystallinity developed in the
stretch films was higher for a given material stretched at
Tg+20.degree. C. compared to Tg+10.degree. C. For a given
stretching temperature relative to Tg, materials with higher
amounts of TMCD developed less strain induced crystallinity. There
was little effect of draw ratio from 3 to 4.5 on the amount of
crystallinity developed for the various materials and stretching
temperature. Higher stretching temperatures relative to Tg allowed
the films to be stretched to higher draw ratios. In summary, PCT
films modified by TMCD could be extruded into clear amorphous films
that could be subsequently stretched above Tg to produce clear
semi-crystalline films as a result of strain induced
crystallization.
TABLE-US-00007 TABLE 6 Amount of strain induced crystallinity
(X.sub.c) of clear stretched films of PCT modified by TMCD. Film
X.sub.c (%) X.sub.c (%) Mole % Tg IV Stretched at Stretched at
Material TMCD (.degree. C.) (dl/g) .lamda. Tg + 10.degree. C. Tg +
20.degree. C. A2 5 98 0.76 3 23.5 A2 5 98 0.76 3.5 24.4 26.8 A2 5
98 0.76 4.0 22.2 30.2 A2 5 98 0.76 4.5 31.4 B2 10. 101 0.76 3 17.4
B2 10 101 0.76 3.5 18.7 23.2 B2 10 101 0.76 4.0 17.9 23.4 B2 10 101
0.76 4.5 24.7 C2 15 106 0.76 3 8.6 C2 15 106 0.76 3.5 10.5 15.3 C2
15 106 0.76 4.0 10.7 14.7 C2 15 106 0.76 4.5 14.3
Example 4
[0532] This example illustrates that PCT materials modified by TMCD
can be injection molded into an amorphous bottle preform and
subsequently reheated above Tg and blown into a bottle with clear
semi-crystalline side-walls. In addition, this example illustrates
that similar levels of side wall crystallinity are achieved in
comparison to PET and PCT modified by IPA with significantly higher
Tm's than PET and PCT modified by IPA.
[0533] Materials were prepared at 3 levels of TMCD (.about.5, 7.5,
and 10 mole %) modification to PCT and two IV levels (.about.0.72
and .about.0.84 dl/g) in a similar manner to Examples 2 and 3 by
melt blending Tritan.TM. TX1000 with PCT 13378 and subsequent solid
stating. During the melt blending, black iron oxide at 20 ppm was
compounded in to serve as a reheat aid for the blow molding of
bottles. In addition, Material G, a commercial grade material based
on PCT modified by 17 mole % IPA and Material H (Parastar 3000), a
commercial grade PET material produced by Eastman Chemical Company
Materials, were used for comparison. All the materials are
described in Table 7. Materials were dried and injection molded
into 16 oz. Boston round preforms using an Arburg injection molding
machine at melt temperatures approximately 20.degree. C. above the
Tm of each material. The preforms were all clear and amorphous
prior to blow molding. The amorphous preforms were then reheat
blown into 16 oz. Boston round bottles using a Sidel SBO1 blow
molding machine. Bottles were reheat blown at preform surface
temperatures approximately 20.degree. C. above Tg for each material
into the blow mold operating at 7.degree. C. All the blown bottles
were visually clear. Samples were cut out of the sidewall of each
bottle and analyzed in a DSC to determine the amount of
crystallinity that was developed in the blow molding process. The
percentage of strain induced crystallinity (X.sub.c) in the
sidewalls of the blown bottle was determined by equation (3) from
the first heating scan of films evaluated in a DSC.
X c = ( .DELTA. H m 1 - .DELTA. H CH 1 ) 29 .times. 100 ( 3 )
##EQU00003##
The Tm reported in Table 8 was also taken from the first heating
scan. Table 8 shows that the PCT materials modified by TMCD
(Materials A thru F) developed similar levels of crystallinity in
the sidewall in comparison to commercial materials G and H. At
these similar levels of crystallinity, the PCT modified materials
have significantly higher melting points, Tm, than materials
commercial materials G and H.
TABLE-US-00008 TABLE 7 Materials used in the reheat blow molding of
16 oz. Boston round bottles. Mole % IV Tg Tm Material TMCD (dl/g)
(.degree. C.) (.degree. C.) A 5.2 0.72 92 280 B 7.5 0.72 95 276 C
9.5 0.72 98 272 D 4.6 0.85 93 278 E 7.0 0.85 98 276 F 9.7 0.83 100
269 G n.a. 0.77 91 262 H n.a. 0.80 78 235
TABLE-US-00009 TABLE 8 Amount of strain induced crystallinity
(X.sub.c) and Tm of blown bottle sidewalls. X.sub.c Tm Material (%)
(.degree. C.) A 27 282 B 28 279 C 27 276 D 30 279 E 27 274 F 25 271
G 31 259 H 30 243
[0534] It can be clearly seen from a comparison of the data in the
above relevant working examples that the polyesters of the present
invention offer a definite advantage over the commercially
available polyesters with regard to glass transition temperature,
density, slow crystallization rate, melt viscosity, and
toughness.
[0535] The invention has been described in detail with reference to
the embodiments disclosed herein, but it will be understood that
variations and modifications can be effected within the spirit and
scope of the invention.
* * * * *