U.S. patent application number 10/171924 was filed with the patent office on 2003-12-18 for process for making poly(ethylene-co-isosorbide) terephthalate polymer.
Invention is credited to Adelman, Douglas J., Charbonneau, Larry F., Ung, Sophie.
Application Number | 20030232959 10/171924 |
Document ID | / |
Family ID | 29549481 |
Filed Date | 2003-12-18 |
United States Patent
Application |
20030232959 |
Kind Code |
A1 |
Adelman, Douglas J. ; et
al. |
December 18, 2003 |
PROCESS FOR MAKING POLY(ETHYLENE-CO-ISOSORBIDE) TEREPHTHALATE
POLYMER
Abstract
The present invention is a process for making a low color
copolymer of ethylene glycol, isosorbide and terephthalic acid or
dimethyl terephthalate. This copolymer,
poly(ethylene-co-isosorbide) terephthalate, is useful for making
bottles, hot-fill containers, films, sheet, fiber, strand and
optical article applications. It can also be used to make polymer
blends and alloys.
Inventors: |
Adelman, Douglas J.;
(Wilmington, DE) ; Charbonneau, Larry F.; (West
Chester, PA) ; Ung, Sophie; (New Castle, DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY
LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
29549481 |
Appl. No.: |
10/171924 |
Filed: |
June 14, 2002 |
Current U.S.
Class: |
528/272 |
Current CPC
Class: |
Y10T 428/249921
20150401; C08G 63/82 20130101; Y10T 428/29 20150115; Y10T 428/31786
20150401; C08G 63/672 20130101; C08G 63/80 20130101; C08G 63/78
20130101; C08L 67/02 20130101 |
Class at
Publication: |
528/272 |
International
Class: |
C08G 063/02 |
Claims
What is claimed is:
1. A melt polymerization process for the preparation of
poly(ethylene-co-isosorbide) terephthalate (PEIT), comprising: a)
providing a mixture comprising terephthalic acid or its alkyl
ester, ethylene glycol and isosorbide, wherein the molar ratio of
diols to terephthalic acid or its alkyl ester is from about 1.05:1
to about 1.3:1 and the molar ratio of ethylene glycol to isosorbide
is from about 1.2:1 to about 24:1; b) reacting the mixture in an
inert atmosphere at a temperature in the range 180-255.degree. C.
and a pressure in the range of 0-60 psig, with concurrent removal
of a distillate comprising water or volatile alkanol products
derived from the reaction of terephthalic acid or its ester with
ethylene glycol and isosorbide, wherein the distillate contains
less than about 5 wt % ethylene glycol and less than about 1 wt %
isosorbide; and c) continuing the reaction in the presence of a
polycondensation catalyst at a pressure of about 0.25 to about 2 mm
and a temperature of 260 to 275.degree. C. to form a PEIT having a
Hunter b* color value between about -2.0 and about +2.0.
2. The process of claim 1, wherein the mixture comprises
terephthalic acid, ethylene glycol and isosorbide and the
distillate comprises water.
3. The process of claim 2, wherein the mixture further comprises a
polycondensation catalyst.
4. The process of claim 2, wherein the mixture further comprises a
base selected from the group consisting of sodium acetate, sodium
hydroxide and tetramethylammonium hydroxide.
5. The process of claim 4, wherein the molar ratio of base to
terephthalic acid is about 1:1800 to 1:13400, preferably about
1:2700 to 1:6800.
6. The process of claim 5, wherein the base is tetramethylammonium
hydroxide.
7. The process of claim 1, wherein the mixture comprises dimethyl
terephthalate, ethylene glycol and isosorbide, and wherein the
volatile alkanol product is methanol.
8. The process of claim 7, wherein the mixture further comprises a
polycondensation catalyst.
9. The process of claims 1, 3 or 8, wherein said polycondensation
catalyst is chosen from the group consisting of Sb(III) salts;
Ti(IV) salts; acetate salts of Co(II); acetate salts of Sb(II);
alkanoate salts of Co(II); alkanoate salts of Sb(III); oxides of
Sb(III); oxides of Sb(III); oxides of Ge(IV); glycol-solubilized
oxides of Sb(II), Sb(III) and Ge(IV); and Ti(OR).sub.4, where R is
an alkyl group having 2 to 12 carbon atoms.
10. The process of claim 9, wherein the molar ratio of catalyst to
.backslash. terephthalic acid or its alkyl ester is about 1:1000 to
1:7300, preferably about 1:2200 to 1:4400.
11. The process of claim 10, wherein the polycondensation catalyst
is GeO.sub.2.
12. The process of claim 2, wherein the temperature and pressure of
the reaction are controlled in such a way that water is removed as
a distillate only when the temperature of the overhead vapor is
less than or equal to the boiling point of water at the pressure of
the reaction.
13. The process of claim 7, wherein the temperature and pressure of
the reaction are controlled in such a way that methanol is removed
as a distillate only when the temperature of the overhead vapor is
less than or equal to the boiling point of methanol at the pressure
of the reaction.
14. The process of claim 1, wherein the mixture further comprises
additives selected from the group consisting of infrared absorbing
agents, dyes, pigments, and UV stabilizers.
15. The process of claim 2, wherein additives selected from the
group consisting of infrared absorbing agents, dyes, pigments, and
UV stabilizers are added to the mixture after removal of at least
80% of the water derived from the condensation of terephthalic acid
with ethylene glycol and isosorbide.
16. The process of claim 7, wherein additives selected from the
group consisting of infrared absorbing agents, dyes, pigments, and
UV stabilizers are added to the mixture after removal of at least
80% of the methanol derived from the condensation of dimethyl
terephthalate with ethylene glycol and isosorbide
17. The process of claims 15 or 16, wherein said infrared absorbing
agent is chosen from the group consisting of graphite and carbon
black.
18. The process of claims 15 or 16, wherein said dyes and pigments
are chosen from the group consisting of red, orange, yellow, blue,
green, indigo and violet.
19. The process of claims 18, wherein said dyes and pigments are
chosen from the group consisting of cobalt acetate, HS-325
Sandoplast.RTM. Red BB, HS-510 Sandoplast.RTM. Blue 2B,
Polysynthren.RTM. Blue R, and Clariant.RTM. RSB violet.
20. The process of claim 1, wherein the isosorbide has a UV
absorbance at 220 nm of less than 0.2, preferably less than
0.1.
21. The process of claim 1, further comprising the steps of: a)
isolating the PEIT polymer in the form of pellets, flakes or
strands; b) crystallizing the isolated PEIT polymer by heating the
isolated PEIT polymer to a temperature in the range of about
125.degree. C. to about 145.degree. C. or treating the isolated
PEIT polymer with a crystallization-inducing solvent; and c)
heating the crystallized PEIT polymer under vacuum or in a stream
of inert gas at an elevated temperature above about 190.degree. C.
but below the melting temperature of the crystallized PEIT polymer
to yield a solid state polymerized PEIT polymer.
22. The process according to claim 20, further comprising the steps
of melting mixing the solid state polymerized PEIT polymer with
additives selected from the group consisting of infrared absorbing
agents, dyes, pigments, and uv stabilizers.
23. The process according to claim 1, wherein the molar ratio of
ethylene glycol to isosorbide is from about 6:1 to about 18:1.
24. A PEIT polymer made according to claims 1, 2, 7, 19 or 20
wherein the Hunter b* color of the PEIT polymer is between about
-2.0 and about +2.0.
25. A PEIT polymer of claim 23, wherein the Hunter b* color is
between about -1.0 and about +1.0.
26. A PEIT polymer made according to claims 14, 15, 16, or 21
wherein the Hunter b* color is between about -2.0 and about
+2.0.
27. A shaped article made according to claim 26.
28. A rigid container made from the PEIT polymer of claims 23, or
25.
29. A film or sheet made from the PEIT polymer of claims 23, or
25.
30. A fiber or monofilament strand made from the PEIT polymer of
claims 23 or 25.
31. An optical article made from the PEIT polymer of claims 23 or
25.
32. A polymer blend or alloy made from the PEIT polymer of claims
23 or 25.
Description
FIELD OF THE INVENTION
[0001] The present invention is a process for making
poly(ethylene-co-isosorbide) terephthalate polymer that has low
color and low diethylene glycol (DEG) content.
TECHNICAL BACKGROUND OF THE INVENTION
[0002] The diol 1,4:3,6-dianhydro-D-sorbitol, referred to herein as
isosorbide, is readily made from renewable resources, such as
sugars and starches. For example, isosorbide can be made from
D-glucose by hydrogenation followed by acid-catalyzed
dehydration.
[0003] Poly(ethylene-co-isosorbide) terephthalate polymer (PEIT) is
a polymer with a higher glass transition temperature (Tg) than
polyethylene terephthalate (PET). This positions it for use in
products such as bottles, hot-fill containers, film, thick sheet,
fibers, strand and optical articles. In many of these markets,
aesthetics are important, and having a very low color resin is
highly desirable. To maximize the Tg-enhancing effects of
isosorbide, it may also be desirable to minimize the presence of
Tg-reducing impurities, such as diethylene glycol (DEG).
[0004] U.S. Pat. No. 5,912,307 discloses the use of
tetramethylammonium hydroxide (TMAH) to suppress DEG formation in
the melt polymerization of ethylene glycol with mixtures of the
aromatic diacids, terephthalic acid, isophthalic acid and
2,6-naphthalenedicarboxylic acid.
[0005] U.S. Pat. No. 5,959,066 discloses polyesters that include
isosorbide as a co-monomer and methods for making them (Charbonneau
et al.). This patent discloses process steps to obtain
isosorbide-containing polymers from esterification to solid-state
polymerization. No mention is made concerning the need to obtain
polymer with low color. Example 2 describes the preparation of
isosorbide-containing polyesters with 1% DEG content without the
use of TMAH.
[0006] U.S. Pat. No. 6,063,465 discloses the range of isosorbide
content in PEIT resins suitable for making polyester containers,
processes for making such resin, and a method for making containers
from that resin. Melt polymerization processes are described using
either dimethyl terephthalate or terephthalic acid as the acid
component. This patent is hereby incorporated by reference
(Charbonneau, Johnson).
[0007] U. S. Pat. No. 6,063,464 describes isosorbide-containing
polyesters and methods for making same (Charbonneau et al.). The
patent claims the composition of isosorbide containing polyesters
and a process for their solid-state polymerization. The possible
applications include beverage bottle, film or sheet, fibers,
optical materials, and compact disc or digital versatile disc. The
patent does not make mention of any process conditions aimed at the
minimization of color or DEG content.
[0008] U.S. Pat. No. 5,958,581 describes polyester film and methods
for making the same (Khanarian et al.). Film comprised of
isosorbide-containing polyester is claimed. Several compositions
are claimed. No mention is made concerning color or DEG
content.
[0009] U.S. Pat. No. 6,063,495 describes PEIT fiber and methods for
making the same. It is noted that DEG may be produced as a
by-product of the polymerization process. It is noted that polymer
without DEG is obtainable in a solution polymerization process.
However, there is no disclosure concerning minimizing DEG formation
in a melt polymerization process. There is also no mention of color
formation.
SUMMARY OF THE INVENTION
[0010] This invention provides a melt polymerization process for
the preparation of poly(ethylene-co-sosorbide) terephthalate
(PEIT), comprising:
[0011] a) providing a mixture comprising terephthalic acid or its
alkyl ester, ethylene glycol and isosorbide, wherein the molar
ratio of diols to terephthalic acid or its alkyl ester is from
about 1.05:1 to about 1.3:1 and the molar ratio of ethylene glycol
to isosorbide is from about 1.2:1 to about 24:1;
[0012] b) reacting the mixture in an inert atmosphere at a
temperature in the range 180-255.degree. C. and a pressure in the
range of 0-60 psig, with concurrent removal of a distillate
comprising water or volatile alkanol products derived from the
reaction of terephthalic acid or its ester with ethylene glycol and
isosorbide, wherein the distillate contains less than about 5 wt %
ethylene glycol and less than about 1 wt % isosorbide; and
[0013] c) continuing the reaction in the presence of a
polycondensation catalyst at a pressure of about 0.25 to about 2 mm
and a temperature of 260 to 275.degree. C. to form a PEIT having a
Hunter b* color value between about -2.0 and about +2.0.
[0014] The present invention also relates to the low color PEIT
polymers made by this process.
[0015] The present invention also relates to bottles, hot-fill
containers, films, thick sheet, optical articles, fibers, strand
and polymer blends and alloys made from the PEIT polymer of the
process described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The present invention is a process to make PEIT polymer that
has low color for use in hot-fill container, bottle, thick sheet,
film, fiber, strand, optical articles and other applications. Color
is commonly expressed in terms of Hunter numbers which correspond
to the lightness or darkness ("L") of a sample, the color value
("a*") on a red-green scale, and the color value ("b*") on a
yellow-blue scale. It is usually desired to produce polymers with
"L" between 80 and 100, preferably 90 to 100. Similarly, for low
color polymers, "a*" and "b*" are preferably between about -2.0 and
about +2.0, more preferably between about -1.0 and about +1.0, as
measured by the process described herein. It has been found that
these objectives can be met for PEIT without the use of
color-correcting additives by controlling critical process
parameters at each stage of the process, especially temperature and
pressure.
[0017] For low color PEIT, it is also important to eliminate, or at
least minimize, the color-forming impurities present in the monomer
diols. Preferably, the UV absorbance of ethylene glycol and
isosorbide are less than 0.20 at 220 nm, more preferably less than
0.10.
[0018] The choice of polycondensation catalyst also influences the
color of the final polymer. Suitable catalysts include Sb(III) or
Ti(IV) salts; acetate and other alkanoate salts of Co(II), and
Sb(III); oxides of Sb(III); oxides of Sb(III) and Ge(IV); and
Ti(OR).sub.4, where R is an alkyl group having 2 to 12 carbon
atoms. Glycol solubilized oxides of these metal salts may also be
used. Oxides of Ge such as GeO.sub.2 are preferred. The preferred
amount of polycondensation catalyst is generally from about 10 to
about 300 ppm by weight. More specifically, the molar ratio of
catalyst to terephthalic acid or its ester is about 1:1000 to about
1:7300, preferably about 1:2200 to about 1:4400.
[0019] Inclusion of the isosorbide monomer raises the Tg of the
final PEIT polymer (relative to PET), while DEG incorporation into
the polymer tends to lower the Tg. DEG can be formed, and
subsequently incorporated into the polymer, when terephthalic acid
is used in the polymerization process. For applications in which
low DEG is desired and the polymerization process uses terephthalic
acid, one can add a suitable base and also minimize the ratio of
ethylene glycol to diacid in the initial esterification reaction.
It has been found that adding suitable bases with the monomers
charged to the reactor suppresses DEG formation in PEIT polymers.
Suitable bases include sodium acetate, sodium hydroxide, and
tetramethylammonium hydroxide (TMAH). An effective amount of base
is about 10 to about 300 ppm, based on terephthalic acid. In
examples herein, the combination of germanium oxide (GeO.sub.2) and
TMAH give especially low color and low DEG content polymer when
terephthalic acid is used in the process. For applications needing
high Tg values, the DEG content is preferably less than about 1.5
mol %, more preferably less than about 1.0 mol %.
[0020] The polymerization process of this invention is a
condensation polymerization of ethylene glycol, isosorbide, and
terephthalic acid or its alkyl ester. Suitable terephthalic acid
esters for the process of this invention include mono- and di-alkyl
esters of terephthalic acid, wherein the alkyl group is chosen from
the group of C.sub.1 to C.sub.6 alkyls. Dimethyl terephthalate is a
preferred terephthalic acid ester. The molar ratio of diols
(ethylene glycol and isosorbide) to terephthalic acid (or its
ester) is from about 1.05:1 to about 1.3:1, and the molar ratio of
ethylene glycol to isosorbide is from about 1.2:1 to about 24:1,
preferably from about 6:1 to 18:1.
[0021] The polymerization process can be carried out in either
batch, semi-continuous or continuous mode. The process is best
carried out in a reactor equipped with a distillation column and a
stirrer or other means for agitation. The distillation column
separates the volatile product of reaction (water and/or alkanol)
from volatile reactants (e.g., ethylene glycol and isosorbide). Use
of a distillation column allows for operation at a lower molar
ratio of ethylene glycol to terephthalic acid, which serves to
suppress the formation of DEG. When terephthalic acid is used in
the polymerization process, the volatile reaction product will be
water; when an ester such as dimethyl terephthalate is used, the
volatile reaction product will be the corresponding alkanol (such
as methanol), together with smaller amounts of water.
[0022] The reactants (terephthalic acid or its ester, ethylene
glycol and isosorbide) and other optional catalysts and additives
are loaded into the reactor, and if necessary, the reactor is
purged to remove traces of oxygen. Inert gases such as nitrogen can
be used for this purpose. Polymerization starts by heating the
reactants in an inert atmosphere at a pressure between about 0 and
about 60 psig and removing the water and/or alkanol and other
volatile by-products via distillation. The temperature is initially
increased to about 220.degree. C. when terephthalic acid is used or
to about 180.degree. C. when a terephthalic acid ester is used, and
then more slowly to a final temperature of between 230 to
255.degree. C. The bulk of the water and/or alkanol are removed
over about a 1 to 8 hour period.
[0023] The pressure chosen depends on the efficiency of the
distillation column and on the ratio of ethylene glycol to
isosorbide. At a ratio of 9 or less, one may generally operate at
about 0 psig. At higher ratios, the pressure is increased to make
it easier to separate ethylene glycol from the water and/or alkanol
formed during the reaction of ethylene glycol, isosorbide and
terephthalic acid or its ester. However, increasing the pressure
also makes it more difficult to remove volatile color-forming
impurities by distillation, so it is generally preferred to operate
at the minimum pressure necessary to maintain acceptably low
ethylene glycol losses in the distillate.
[0024] It should also be noted that the boiling point of the
reaction mixture is a function of the composition of the mixture,
and more specifically of the ratio of isosorbide to ethylene
glycol. At high ratios, the boiling point increases, and the higher
temperature of the reaction mixture results in an increased rate of
reaction and associated water and/or alkanol production.
Conversely, when the ratio of isosorbide to ethylene glycol is low,
the boiling point of the reaction mixture is lower, leading to a
lower temperature of the reaction mixture. The overall effect of a
low isosorbide to ethylene glycol ratio is that the esterification
reaction proceeds more slowly and the percentage of ethylene glycol
in the distillate increases.
[0025] At least 80%, preferably at least 90%, of the water and/or
alkanol of reaction is removed as the temperature of the reaction
mixture is increased, for example from 220.degree. C. (for
terephthalic acid) or 180.degree. C. (for terephthalic acid
esters), to a temperature between 230 and 255.degree. C. Limiting
the maximum reaction mixture temperature to 255.degree. C.
minimizes the formation of color-forming by-products. It is
preferred that this step also be conducted under temperature and
pressure conditions that selectively remove water and/or alkanol
and return ethylene glycol to the reactor. Preferably, the
distillate contains less than about 5 wt % ethylene glycol and less
than about 1 wt % isosorbide. This can be achieved by adjusting the
temperature of the reaction mixture so that the temperature of the
vapor at the top of the distillation column (overhead vapor) does
not exceed the boiling point of water (if terephthalic acid is used
in the process) or alkanol (if a terephthalic acid ester is used in
the process) at the reactor pressure. If the temperature of the
overhead vapor exceeds the boiling point of water (or alkanol),
then the temperature of the reaction mixture is lowered and no
distillate is taken off until the overhead vapor temperature goes
below the boiling point of water (or alkanol) at the reactor
pressure.
[0026] When the temperature of the reaction mixture reaches a
temperature between 230 and 255.degree. C. and the overhead vapor
temperature drops to about 2 to 20.degree. C., preferably about
5.degree. C., below the boiling point of water or alkanol at the
reactor pressure, the reactor pressure is reduced to about
atmospheric pressure at a rate of about 0.5 to 5 psi/min,
preferably about 1-2 psi/min. As the reactor pressure drops,
additional water or alkanol will distill from the reactor. The
optimal rate of pressure reduction is determined by the temperature
of the overhead vapor. If the overhead vapor temperature exceeds
that of the boiling point of water or alkanol at the reactor
pressure, the rate of pressure reduction is decreased. Conversely,
if the temperature of the overhead vapor is below the temperature
of the boiling point of water or alkanol at the reactor pressure,
the rate of pressure reduction is increased. If the total amount of
water or alkanol removed when the reactor is at atmospheric
pressure is less than the desired amount, the pressure can be
lowered to about 80 mm Hg (for terephthalic acid) or to about 125
mm Hg (for dimethyl terephthalate) to further drive the
esterification reaction. For other terephthalic acid esters, the
pressure can be lowered to that at which the alkanol boils at
ambient temperature. Generally, it is preferable to remove a total
of at least 90% of the volatile reaction products (water and/or
alkanol) before going on to the next stage of the polymerization
process.
[0027] The next stage of the polymerization process is
polycondensation, in which the esters and oligomers are reacted to
form polymer, with removal of residual ethylene glycol, isosorbide
and water and/or alkanol. If a polycondensation catalyst was not
added with the monomers, it is added at this stage, optionally with
other desired additives such as infrared absorbing agents, dyes,
pigments, UV stabilizers and other thermally stable additives.
[0028] Color-correcting additives can be added selected from the
group consisting of red, orange, yellow, blue, green, indigo and
violet. Examples of such dyes or piments include cobalt acetate,
HS-325 Sandoplast.RTM. Red BB, HS-510 Sandoplast.RTM. Blue 2B,
Polysynthren.RTM. Blue R, and Clariant.RTM. RSB violet are
especially useful to lower the b* value of the PEIT polymer. The
reactor pressure is then reduced to about 0.25 to 2 mm Hg,
preferably to about 0.25-1 mm Hg. The temperature of the reaction
mixture is raised to 260 to 275.degree. C. while the pressure is
lowered. The reaction mixture is held at this temperature and
pressure for about 1 to 4 hours to form the desired PEIT polymer.
Minimizing time at high temperatures helps to minimize color
generation in the PEIT polymer.
[0029] The polymer can be removed from the reactor and isolated in
any of several conventional processes as strands, pellets or flake.
An inherent viscosity (IV) of 0.5 dL/g or higher can be achieved by
this melt polymerization process. The IV can be further increased
by solid state polymerization of the isolated polymer.
[0030] The defined process conditions give a PEIT polymer product
that has low color and low DEG content resin for use in hot-fill
container, bottle, fiber, optical articles, film and thick sheet
applications. The PEIT of this invention can also be used in making
polymer blends and alloys
EXAMPLES
[0031] Molecular weights were determined by size exclusion
chromatography (SEC). The SEC system consists of a Waters (Milford,
Mass.) Alliance 2690 with the solvent vacuum degasser and
auotoinjection system. A Viscotek (Houston, Tex.) T60A combination
viscometer/light scattering detector is followed by a Waters 410
refractive index detector. Two Shodex (Tokyo, Japan) GPC HFIP-806M
linear columns are proceeded by a corresponding precolumn. The
chromatograph oven holds the columns at 35.degree. C. The T60A
detectors are at ambient temperature and the refractive index
detector is held at 35.degree. C. A 10 mg sample is weighed into a
20 ml glass vial. To the vial is added 5 ml of
hexafluoroisopropanol. The sample is placed on a shaker for 1-2
hours for dissolution. If the sample requires heat to dissolve, it
is place on a dry bath (VWR, South Plainfield, N.J.) containing
plastic beads. The surface temperature of the dry bath is held at
80.degree. C. The sample never reaches the boiling point of HFIP
(59.degree. C.). The sample is filtered through a 0.5 micron PTFE
filter (Millipore) prior to injection of 100 .mu.l into the SEC
unit. The data are collected and analyzed using the Viscotek TriSec
3.0 software.
[0032] DSC was used to determine Tg values. The polymer sample (10
mg) is analyzed with a TA Instruments 2920 DSC from room
temperature to 280.degree. C. using a heating rate of 10.degree.
C./min. The sample is then held at 280.degree. C. for two minutes,
quenched in liquid nitrogen, and then reheated from room
temperature to 280.degree. C. The associated software calculates a
Tg, Tc, and Tm.
[0033] Isosorbide and diethylene glycol content were determined by
NMR. The PEIT is prepared for analysis by hot pressing at about
260.degree. C. and cold quenching (ice bath). About 20 mg of the
resulting film is dissolved in about 1 mL trichloroethane-d2. The
sample is analyzed at 100.degree. C. using a Varian (Palo Alto,
Calif.) 500 MHz spectrometer.
[0034] The color and brightness of the PEIT samples were determined
using a Varian Cary 5 UV/Vis/NIR spectrophotometer with a diffuse
reflectance accessory. The reflectance data were obtained at an
observer dangle of 2 degrees with Illuminant D65 and were processed
using the color analysis application within Grams/32 software to
calculate Hunter L*a*b* values. The L* coordinate indicates
brightness, where 0 is black and 100 is white. The a* value can be
positive or negative, where positive values are indicative of red
color and negative indicate green. Similar is the b* value, where
positive values indicate yellow and negative values indicate
blue.
[0035] Intrinsic viscosities were measured using a Viscotek Forced
Flow Viscometer model Y-900. Polymers were dissolved in 50/50 w/w
trifluoroacetic acid/methylene chloride at a 0.4% (wt/vol)
concentration and were tested at 19.degree. C. The intrinsic
viscosities determined by this method are equivalent to Goodyear
intrinsic viscosities.
[0036] COOH end groups were determined using Fourier Transform
Infrared spectroscopy on polyester samples that had been dried and
pressed into film. Peak absorptions were found at 3434 cm-1 with
respect to a baseline drawn from 3473 to 3386 and at 3266 with
respect to a baseline drawn from 3717 to 620. The ratio of the 3434
to 3266 peak absorptions was compared to a calibration chart of
such ratios versus titration data to obtain the concentration of
COOH end groups. OH end groups were then calculated from the COOH
end groups and the DP that had been determined from the IV, using
the formula 1 OHends , meq / kg = ( 2 * 106 ( 192 * DP + 33 ) ) - [
COOH ]
[0037] Germanium oxide solution was supplied by Teck Cominco LTD,
North Vancouver, BC, Canada. Isosorbide was supplied by Roquette
Freres in Lestrem, France. Ethylene glycol was supplied by PD
Glycol in Beaumont, Tex. Terephthalic acid was supplied by Amoco,
in Naperville, Ill. Dimethyl terephthalate was supplied by Kosa, in
Wilmington, N.C. Cobalt acetate is available from Aldrich
(Milwaukee, Wis.). HS-325 Sandoplast.RTM. Red BB, HS-510
Sandoplast.RTM. Blue 2B, Polysynthren.RTM. Blue R, and
Clariant.RTM. RSB violet are available from Clariant Corporation
(Coventry, R.I.). Graphite was supplied by Timcal America, Inc. of
Westlake, Ohio.
[0038] The following examples are for illustrative purposes and are
not limiting.
Example 1
[0039] A 100 gal agitated vessel, equipped with a column and
in-line condenser, was charged with 87.88 lb. of terephthalic acid
(Amoco TA-33-LP), 36.81 lb ethylene glycol, 6.16 lb of isosorbide,
99.8 ml of GeO.sub.2 solution (0.15 g Ge/ml), 31.9 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution),
and 0.3819 graphite (Timrex KS-4). After 3 nitrogen pressure/purge
cycles, the unit was pressured to 40 psig and the circulated oil
heat setpoint was set to 285.degree. C. The condensate valve
setpoint was 145.degree. C. If the vapor temperature at the top of
the column (overhead vapor) was less than 145.degree. C., the
condensate valve remained open and water was removed. When the
temperature of the reaction mixture reached 250.degree. C. and the
overhead vapor temperature dropped to less than 140.degree. C., the
pressure was dropped at a rate such that the overhead vapor
temperature did not exceed the boiling point of water at the batch
pressure. After 6.5 liters of water were removed, the reaction
mixture was clear. The reaction mixture was then transferred to a
30 gal autoclave and heated to 265.degree. C. as the pressure was
dropped to 0.5 mm Hg over 30 minutes. After 2 hours and 15 minutes,
the batch had reached the target agitator torque value of 1900
watts. The melt was extruded under nitrogen pressure through a die
plate to make strands. The strands were pulled through water
troughs and into a cutter to make {fraction (1/8)}" pellets. The
yield was 88.9 lb of wet pellets. The condensate contained 95.9 wt
% water and 4.1 wt % ethylene glycol. The product IV was 0.58 dL/g.
The Hunter b* and L values were 0.88 and 86.6. The isosorbide
incorporation was 2.73 M % and the DEG was 1.04 M %. The Tg was
86.3.degree. C. and the Tm was 238.5.degree. C. The meq/kg acid
ends were 18.8. The Mw/Mn value was 1.83 with 8.4% having a
MW<10,000.
Example 2
[0040] A 100 gal agitated vessel, equipped with a column and
in-line condenser, was charged with 87.88 lb. of terephthalic acid
(Amoco TA-33-LP), 37.56 lb ethylene glycol, 4.40 lb of isosorbide,
99.8 ml of GeO2 solution (0.15 g Ge/ml), 31.9 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution),
and 0.3782 graphite (Timrex KS-4). After 3 nitrogen pressure/purge
cycles, the unit was pressure to 30 psig and the circulated oil
heat setpoint was set to 275.degree. C. The condensate valve
setpoint was 140.degree. C. If the vapor temperature at the top of
the column was less than 140.degree. C., the condensate valve
remained open and water was removed. When the temperature of the
reaction mixture reached 250.degree. C. and the overhead vapor
temperature dropped to less than 140.degree. C., the pressure was
dropped at a rate such that the overhead vapor temperature did not
exceed the boiling point of water at the batch pressure. After 6.4
liters of water were removed, the batch was clear. The batch was
then transferred to a 30 gal autoclave and heated to 265.degree. C.
as the pressure was dropped to 0.5 mm Hg over 30 minutes. After 1
hour and 41 minutes, the batch had reached the target agitator
torque value of 1900 watts. The melt was extruded under nitrogen
pressure through a die plate to make strands. The strands were
pulled through water troughs and into a cutter to make {fraction
(1/8)}"pellets. The yield was 88 lb of wet pellets. The condensate
contained 95.5 wt % water and 4.5 wt % ethylene glycol. The product
IV was 0.61 dL/g. The Hunter b* and L values were 1.2 and 80.0. The
isosorbide incorporation was 2.11 M % and the DEG was 0.97 M %. The
Tg was 85.4.degree. C. and the Tm was 242.0.degree. C. The meq/kg
acid ends were 27.2. The Mw/Mn value was 1.90 with 8.4% having a
MW<10,000.
Example 3
[0041] A 100 gal agitated vessel, equipped with a column and
in-line condenser, was charged with 117.18 lb. of terephthalic acid
(Amoco TA-33-LP), 45.20 lb ethylene glycol, 7.04 lb of isosorbide,
128 ml of GeO.sub.2 solution (0.15 g Ge/ml), 38.2 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution),
0.630 g graphite (Timrex KS-4) and 0.252 g of Clariant RSB violet
toner. After 3 nitrogen pressure/purge cycles, the unit was
pressured to 40 psig and the circulated oil heat setpoint was set
to 285.degree. C. The condensate valve setpoint was 145.degree. C.
If the vapor temperature at the top of the column was less than
145.degree. C., the condensate valve remained open and water was
removed. When the temperature of the reaction mixture reached
250.degree. C. and the overhead vapor temperature dropped to less
than 140.degree. C., the pressure was dropped at a rate such that
the overhead vapor temperature did not exceed the boiling point of
water at the batch pressure. After 8.8 liters of water were
removed, the reaction mixture was clear. The batch was then
transferred to a 30 gal autoclave and heated to 275.degree. C. as
the pressure was dropped to 0.5 mm Hg over 30 minutes. After 1 hour
and 45 minutes, the batch had reached the target agitator torque
value of 1500 watts. The melt was extruded under nitrogen pressure
through a die plate to make strands. The strands were pulled
through water troughs and into a cutter to make {fraction
(1/8)}"pellets. The yield was 88 lb of wet pellets. The condensate
was 100 wt % water. The product IV was 0.62 dL/g. The Hunter b* and
L values were 1.5 and 80.0. The isosorbide incorporation was 2.71 M
% and the DEG was 1.09M %. The Tg was 86.9.degree. C.
Example 4
[0042] A 10 liter agitated vessel, equipped with a column and
in-line condenser, was charged with 9.15 lb. of terephthalic acid
(Amoco TA-33-LP), 3.37 lb ethylene glycol, 0.53 lb of isosorbide,
8.0 ml of GeO.sub.2 solution (0.10 g Ge/ml), 1.95 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution),
4.4 ml Clariant RSB violet dye (0.00485 g/ml), and 0.05 g graphite
(Timrex KS-4). After 3 nitrogen pressure/purge cycles, the unit was
pressured to 30 psig and the Dow heater setpoint was adjusted to
give an initial batch temperature of 210.degree. C. The condensate
valve setpoint was 135.degree. C. If the vapor temperature at the
top of the column was less than 135.degree. C., the condensate
valve remained open and water was removed. After 774 ml of water
were removed, the batch was heated to 275.degree. C. while the
pressure was dropped to 0.5 mm Hg over 30 minutes. After 2 hour and
10 minutes, the batch had reached the target agitator torque value.
The melt was extruded under nitrogen pressure through a die plate
to make strands. The strands were pulled through water troughs and
into a cutter to make {fraction (1/8)}"pellets. The condensate
contained 98.9 wt % water and 1.1 wt % ethylene glycol. The product
IV was 0.59 dL/g. The Hunter b* and L values were -1.12 and 73.7.
The isosorbide incorporation was 2.58 M % and the DEG was 0.84 M %.
The Tg was 86.30.degree. C.
Example 5
[0043] A 10 liter agitated vessel, equipped with a column and
in-line condenser, was charged with 4.58 lb. of terephthalic acid
(Amoco TA-33-LP), 2.09 lb. ethylene glycol, 0.33 lb. of isosorbide,
9.4 ml of GeO.sub.2 solution (0.15 g Ge/ml), and 0.2 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution).
The isosorbide used had a UV absorbance of 0.124 at 220 nm for a 20
wt % water solution. After 3 nitrogen pressure/purge cycles, the
unit was pressured to 10 psig and the Dow heater setpoint was
adjusted to give an initial batch temperature of 210.degree. C. The
condensate valve setpoint was 115.degree. C. If the vapor
temperature at the top of the column was less than 115.degree. C.,
the condensate valve remained open and water was removed. The batch
was slowly heated to 250.degree. C. while condensate was removed.
After 417 ml of water were removed, the batch was heated to
270.degree. C. while the pressure was dropped to 0.5 mm Hg over 10
minutes. After 1.5 hour, melt was extruded under nitrogen pressure
through a die plate to make strands. The strands were pulled
through water troughs and into a cutter to make {fraction
(1/8)}"pellets. The condensate contained 96.6 wt % water and 3.4 wt
% ethylene glycol. The product IV was 0.33 dL/g. The Hunter b*
value was 1.63. The isosorbide incorporation was 2.54 M % and the
DEG was 1.30 M %. The Tg was 89.8.degree. C.
Example 6
[0044] A 100 gal agitated vessel, equipped with a column and
in-line condenser, was charged with 87.88 lb. of terephthalic acid
(Amoco TA-33-LP), 36.81 lb. ethylene glycol, 6.16 lb. of
isosorbide, 99.8 ml of GeO.sub.2 solution (0.15 g Ge/ml), 31.9 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution),
and 0.381 g graphite (Timrex KS-4). After 3 nitrogen pressure/purge
cycles, the unit was pressured to 40 psig and the circulated oil
heat setpoint was set to 280.degree. C. The condensate valve
setpoint was 145.degree. C. If the vapor temperature at the top of
the column was less than 145.degree. C., the condensate valve
remained open and water was removed. When the temperature of the
reaction mixture reached 250.degree. C. and the overhead vapor
temperature dropped to less than 140.degree. C., the pressure was
dropped at a rate such that the overhead vapor temperature did not
exceed the boiling point of water at the batch pressure. After 6.3
liters of water were removed, the reaction mixture was clear. The
reaction mixture was then transferred to a 30 gal autoclave and
heated to 265.degree. C. as the pressure was dropped to 0.5 mm Hg
over 30 minutes. After 2.1 hours, the batch had reached the target
agitator torque value of 1900 watts. The melt was extruded under
nitrogen pressure through a die plate to make strands. The strands
were pulled through water troughs and into a cutter to make
{fraction (1/8)}"pellets. The yield was 67 lb. of wet pellets. The
condensate contained 95.7 wt % water and 4.3 wt % ethylene glycol.
The product IV was 0.59 dL/g. The Hunter b* and L values were 1.74
and 77.5. The isosorbide incorporation was 2.84 M % and the DEG was
1.05 M %. The Tg was 86.3.degree. C. and the Tm was 237.2.degree.
C. The meq/kg acid ends were 19.2. The Mw/Mn value was 2.0 with
10.4% having a MW<10,000.
Example 7
[0045] A 2 liter agitated glass vessel, equipped with a column and
in-line condenser, was charged with 388.4 g of dimethyl
terephthalate, 152.2 g ethylene glycol, 21.8 g of isosorbide
(Roquette 3085), 0.80 ml of GeO.sub.2 solution (0.15 g Ge/ml), and
0.5 ml tetramethylammonium hydroxide (Aldrich 25 wt % aqueous
solution). After 3 vacuum/nitrogen refill cycles, the pressure was
about 0 psig and the oil bath heater setpoint was adjusted to
180.degree. C. The condensate valve setpoint was 67.degree. C. If
the vapor temperature at the top of the column was less than
67.degree. C., the condensate valve remained open and MeOH was
removed. After 154 ml of MeOH were removed without exceeding a
batch temperature of 250.degree. C., the batch was heated to
270.degree. C. while the pressure was dropped to 1.1 mm Hg. After 1
hour and 35 minutes, the batch had reached the target agitator
torque value. The melt was poured into cold water to make strands.
The condensate contained approximately 98.0 wt % MeOH,
approximately 1.5 wt % water, and no ethylene glycol. The product
IV was 0.36 dL/g. The Hunter b* and L values were 2.24 and 90.3.
The isosorbide incorporation was 2.33 M % and the DEG was 1.75 M
%.
Example 8
[0046] A 2 liter agitated glass vessel, equipped with a column and
in-line condenser, was charged with 388.4 g of dimethyl
terephthalate, 133.6 g ethylene glycol, 21.8 g of isosorbide
(Roquette 3085), 0.80 ml of GeO.sub.2 solution (0.15 g Ge/ml), and
0.45 ml tetramethylammonium hydroxide (Aldrich 25 wt % aqueous
solution). After 3 vacuum/nitrogen refill cycles, the pressure was
about 0 psig and the oil bath heater setpoint was adjusted to
150.degree. C. The condensate valve setpoint was 67.degree. C. If
the vapor temperature at the top of the column was less than
67.degree. C., the condensate valve remained open and MeOH was
removed. After 144 ml of MeOH were removed without exceeding a
batch temperature of 255.degree. C., the batch was heated to
270.degree. C. while the pressure was dropped to 1 mm Hg. After 1
hour and 30 minutes, the batch had reached the target agitator
torque value. The melt was poured into cold water to make strands.
The condensate contained approximately 98.6 wt % MeOH,
approximately 1.4 wt % water, and no ethylene glycol. The product
IV was 0.29 dL/g. The Hunter b* and L values were 1.93 and 91.4.
The isosorbide incorporation was 2.72 M % and the DEG was 1.36 M
%.
[0047] Examples 7 and 8 were run at relatively small scale (2
liter) and one skilled in the art will recognize that equipment
limitations at this scale could have contributed to the relatively
large b* values (2.24 and 1.93, respectively) of the PEIT polymer
produced in these examples. It is expected that these process
conditions, if duplicated at 10 liter or 100 gal or larger scale,
would give b* values less than about 2.0 for the PEIT polymers so
produced.
Comparative Example 1
Demonstrating the Effect of High Esterification and
Polycondensation Temperatures
[0048] A 10 liter agitated vessel, equipped with a column and
in-line condenser, was charged with 4.58 lb of terephthalic acid
(Amoco TA-33-LP), 2.09 lb ethylene glycol, 0.33 lb of isosorbide,
9.4 ml of GeO.sub.2 solution (0.15 g Ge/ml), and 0.2 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution).
The isosorbide used had a UV absorbance of 0.124 at 220 nm for a 20
wt % water solution. After 3 nitrogen pressure/purge cycles, the
unit was pressured to 10 psig and the Dow heater setpoint was
adjusted to give an initial batch temperature of 210.degree. C. The
condensate valve setpoint was 115.degree. C. If the vapor
temperature at the top of the column was less than 115.degree. C.,
the condensate valve remained open and water was removed. The batch
was slowly heated to 270.degree. C. while condensate was removed.
After 406 ml of water were removed, the batch was heated to
285.degree. C. while the pressure was dropped to 0.5 mm Hg over 10
minutes. After 1.5 hour, melt was extruded under nitrogen pressure
through a die plate to make strands. The strands were pulled
through water troughs and into a cutter to make {fraction
(1/8)}"pellets. The condensate contained 96.6 wt % water and 3.4 wt
% ethylene glycol. The product IV was 0.61 dL/g. The Hunter b*
value was 2.21. The isosorbide incorporation was 2.37 M % and the
DEG was 1.54 M %. The Tg was 87.8.degree. C.
Comparative Example 2
Demonstrating the Effect of Isosorbide Containing UV-Absorbing
Impurities
[0049] A 100 gal agitated vessel, equipped with a column and
in-line condenser, was charged with 117.2 lb of terephthalic acid
(Amoco TA-33-LP), 51.3 lb ethylene glycol, 8.25 lb of isosorbide,
133.1 ml of GeO.sub.2 solution (0.15 g Ge/ml), and 49.9 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution).
The isosorbide had a UV absorbance of 3.83 at 220 nm for a 20 wt %
aqueous solution. After 3 nitrogen pressure/purge cycles, the unit
was pressured to 40 psig and the circulated oil heat setpoint was
set to 280.degree. C. The condensate valve setpoint was 145.degree.
C. If the vapor temperature at the top of the column was less than
145.degree. C., the condensate valve remained open and water was
removed. When the temperature of the reaction mixture reached
250.degree. C. and the overhead vapor temperature dropped to less
than 140.degree. C., the pressure was dropped at a rate such that
the overhead vapor temperature did not exceed the boiling point of
water at the batch pressure. After 6.3 liters of water were
removed, the reaction mixture was clear. The batch was then
transferred to a 30 gal autoclave and heated to 270.degree. C. as
the pressure was dropped to 0.5 mm Hg over 30 minutes. After 2 hour
and 55 minutes, the batch had reached the target agitator torque
value of 1600 watts. The melt was extruded under nitrogen pressure
through a die plate to make strands. The strands were pulled
through water troughs and into a cutter to make {fraction
(1/8)}"pellets. The yield was 110 lb of wet pellets. The condensate
contained 98.5 wt % water and 1.5 wt % ethylene glycol. The product
IV was 0.59 dL/g. The Hunter b* and L values were 5.1 and 67.0. The
isosorbide incorporation was 2.24 M % and the DEG was 1.40 M %. The
Tg was 84.9.degree. C. and the Tm was 238.2.degree. C.
Comparative Example 3
Demonstrating the Effect of High Polycondensation Temperature
[0050] To a 10 liter agitated vessel, equipped with a column and
in-line condenser, was charged 4.58 lb. of terephthalic acid (Amoco
TA-33-LP), 1.68 lb. ethylene glycol, 0.82 lb. of isosorbide, 9.4 ml
of GeO.sub.2 solution (0.15 g Ge/ml), and 0.2 ml
tetramethylammonium hydroxide (Aldrich 25 wt % aqueous solution).
After 3 nitrogen pressure/purge cycles, the unit was pressured to
10 psig and the Dow heater setpoint was adjusted to give an initial
batch temperature of 210.degree. C. The condensate valve setpoint
was 115.degree. C. If the vapor temperature at the top of the
column was less than 115.degree. C., the condensate valve remained
open and water was removed. The batch was slowly heated to
250.degree. C. while condensate was removed. After 403 ml of water
were removed, the batch was heated to 285.degree. C. while the
pressure was dropped to 0.5 mm Hg over 10 minutes. After 1.5 hour,
melt was extruded under nitrogen pressure through a die plate to
make strands. The strands were pulled through water troughs and
into a cutter to make {fraction (1/8)}"pellets. The isosorbide used
had a UV absorbance of 0.124 at 220 nm for a 20 wt % water
solution. The condensate contained 99.0 wt % water and 1.0 wt %
ethylene glycol. The product IV was 0.62 dL/g. The Hunter b value
was 3.2. The isosorbide incorporation was 2.66 M % and the DEG was
1.1 M %. The Tg was 83.4.degree. C.
* * * * *