U.S. patent application number 14/600072 was filed with the patent office on 2015-05-14 for amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof.
The applicant listed for this patent is SABIC Global Technologies B.V.. Invention is credited to Navinchandra S. ASTHANA, Ganesh KANNAN, Kenneth F. MILLER.
Application Number | 20150133599 14/600072 |
Document ID | / |
Family ID | 47553384 |
Filed Date | 2015-05-14 |
United States Patent
Application |
20150133599 |
Kind Code |
A1 |
ASTHANA; Navinchandra S. ;
et al. |
May 14, 2015 |
AMORPHOUS, HIGH GLASS TRANSITION TEMPERATURE COPOLYESTER
COMPOSITIONS, METHODS OF MANUFACTURE, AND ARTICLES THEREOF
Abstract
An amorphous copolyester comprising the reaction product of: (a)
a monomer of formula I ##STR00001## wherein R.sup.1, R.sup.2,
R.sup.3, and R.sup.5 are each independently hydrogen or a C.sub.1-3
alkyl group, a is 0-1, b is 0-4, c is 0-4 and d is 0-3, and each
R.sup.4 is independently hydrogen or a C.sub.1-3 alkyl group; (b) a
virgin monomer selected from terephthalic acid, a di(C.sub.1-3
alkyl) terephthalate, and combinations thereof, and (c)
1,4-cyclohexane dimethanol; wherein the residue of monomer (a) is
present in an amount from 7 to less than 12 mole % of the
copolyester based on moles of repeat units in the polyester; and
the copolyester has a glass transition temperature of at least
107.degree. C., an intrinsic viscosity of at least 0.7 dl/g, and a
molded sample has a Notched Izod value of at least 290 J/m
determined in accordance with ASTM D256.
Inventors: |
ASTHANA; Navinchandra S.;
(Evansville, IN) ; MILLER; Kenneth F.; (Posey,
IN) ; KANNAN; Ganesh; (Evansville, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC Global Technologies B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
47553384 |
Appl. No.: |
14/600072 |
Filed: |
January 20, 2015 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
13397200 |
Feb 15, 2012 |
8969506 |
|
|
14600072 |
|
|
|
|
Current U.S.
Class: |
524/539 ;
524/605; 525/168; 525/169; 525/170; 528/298 |
Current CPC
Class: |
C08L 51/04 20130101;
C08L 67/02 20130101; C08G 63/185 20130101; C08L 67/02 20130101;
C08G 63/553 20130101; C08L 55/02 20130101; C08L 67/02 20130101;
C08L 67/02 20130101; C08L 2205/025 20130101; C08L 67/02 20130101;
C08L 2205/02 20130101; C08L 25/06 20130101; C08L 55/02 20130101;
C08L 67/02 20130101; C08L 51/04 20130101 |
Class at
Publication: |
524/539 ;
528/298; 524/605; 525/168; 525/169; 525/170 |
International
Class: |
C08G 63/553 20060101
C08G063/553; C08L 67/02 20060101 C08L067/02 |
Claims
1. An amorphous copolyester comprising, based on the total moles of
repeat units of the polymer, the polymerization reaction product
of: (a) from 7 to less than 12 mole % of a monomer of formula I
##STR00007## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.5 are
each independently a C.sub.1-3 alkyl group, a is 0-1, b is 0-4, c
is 0-4, and d is 0-3, and each R.sup.4 is independently hydrogen or
a C.sub.1-3 alkyl group; (b) from 38 to 43 mole % of a virgin
monomer selected from terephthalic acid, a di(C.sub.1-3 alkyl)
terephthalate, and combinations thereof, and (c) a third monomer
consisting essentially of 1,4-cyclohexane dimethanol; wherein the
copolyester has a glass transition temperature of at least
107.degree. C., an intrinsic viscosity of at least 0.7 dl/g, and a
molded sample has a Notched Izod value of at least 290 J/m
determined in accordance with ASTM D256.
2. The amorphous polymer of claim 1, wherein the monomer (a) is of
formula II ##STR00008## wherein R.sup.1, R.sup.2, and R.sup.4 are
each independently hydrogen or a C.sub.1-3 alkyl group.
3. The amorphous copolyester of claim 1 wherein the monomer (a) of
formula I is of formula III ##STR00009## wherein R.sup.4 is each
the same and is hydrogen or a C.sub.1-3 alkyl group.
4. The amorphous copolyester of claim 1, wherein the virgin monomer
is selected from dimethyl terephthalate, diethyl terephthalate, and
combinations thereof.
5. The amorphous copolyester of claim 1, wherein the
1,4-cyclohexane dimethanol has an isomer distribution of 60 to 80%
trans and 20 to 40% cis isomers.
6. (canceled)
7. The amorphous copolyester of claim 1, comprising reacted
1,4-cyclohexane dimethanol in an amount of 50%, based on the total
repeat units of the polymer.
8. (canceled)
9. A composition comprising the amorphous copolyester of claim 1
and an additive.
10. The composition of claim 9, wherein the additive is selected
from reinforcing fillers, non-reinforcing fillers, antioxidants,
thermal stabilizers, radiation stabilizers, ultraviolet light
absorbing additives, mold release agents, plasticizers, quenchers,
lubricants, antistatic agents, dyes, pigments, laser marking
additives, processing aids, and combinations thereof.
11. The composition of claim 9, further comprising a polymer
selected from polycarbonate, poly(ethylene terephthalate),
poly(butylene terephthalate), poly(butylene naphthalate),
poly(1,2-propylene terephthalate),
poly(cyclohexylene-1,4-dimethylene terephthalate), poly(ethylene
terephthalate), poly(1,3-propylene terephthalate),
poly(cyclohexylene-1,4-dimethylene
cyclohexylene-1,4-dicarboxylate),
poly(cyclohexylene-1,4-dimethylene-co-ethylene terephthalate),
poly(cyclohexylene-1,4-dimethylene-co-1,3-cyclobutylene
terephthalate), and combinations thereof.
12. An article comprising the amorphous copolyester composition of
claim 9.
13. The article of claim 10, wherein the article is in the form of
a bottle.
14. The article of claim 12, wherein the bottle has a volume
capacity from 250 milliliters to 5 liters.
15. (canceled)
16. A composition comprising the amorphous copolyester of claim 1
and an impact modifier.
17. The composition of claim 16, wherein the impact modifier is
selected from acrylonitrile-butadiene-styrene,
methacrylate-butadiene-styrene, high impact polystyrene, and
combinations thereof.
18. An article comprising the composition of claim 16.
19. (canceled)
20. The article of claim 18, wherein the article is in the form of
a bottle.
21. The article of claim 20, wherein the bottle has a volume
capacity from 250 milliliters to 5 liters.
22. (canceled)
23. An amorphous copolyester, consisting essentially of three
monomers, which copolyester is the polymerization reaction product
of: (b) from 7 to less than 12 mole % of a monomer of formula I
##STR00010## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.5 are
each independently a C.sub.1-3 alkyl group, a is 0-1, b is 0-4, c
is 0-4, and d is 0-3, and each R.sup.4 is independently hydrogen or
a C.sub.1-3 alkyl group; (b) from 38 to 43 mole % of a virgin
monomer selected from terephthalic acid, a di(C.sub.1-3 alkyl)
terephthalate, and combinations thereof, and (c) a third monomer
that is 1,4-cyclohexane dimethanol; wherein the copolyester has a
glass transition temperature of at least 107.degree. C., an
intrinsic viscosity of at least 0.7 dl/g, and a molded sample has a
Notched Izod value of at least 290 J/m determined in accordance
with ASTM D256.
Description
BACKGROUND
[0001] This disclosure relates to amorphous, high glass transition
temperature copolyester compositions, methods of manufacture, and
articles thereof.
[0002] Thermoplastic polyesters are readily molded into useful
articles, and articles comprising such polyesters have valuable
characteristics, including strength, toughness, high gloss, and
solvent resistance. Polyesters therefore have utility in a wide
range of applications, including automotive parts, electric
appliances, and electronic devices.
[0003] Although polyesters can have a range of desirable
performance properties, most of the commercially available
amorphous polyesters, such as polyethylene terephthalate (PET),
glycol-modified polyethylene terephthalate (PETG), and
glycol-modified polycyclohexylenedimethylene terephthalate (PCTG),
have useful impact properties, but low glass transition
temperatures. This can significantly limit the range of
applications for the polyesters. There accordingly remains a need
in the marketplace for a new class of amorphous polyesters with
better heat performance than those currently available.
BRIEF SUMMARY OF THE INVENTION
[0004] An amorphous copolyester is disclosed, comprising the
reaction product of: [0005] (a) a monomer of formula I
##STR00002##
[0005] wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.5 are each
independently a C.sub.1-3 alkyl group, a is 0-1, b is 0-4, c is 0-4
and d is 0-3, and each R.sup.4 is independently a hydrogen or a
C.sub.1-3 alkyl group; [0006] (b) a virgin monomer selected from
terephthalic acid, a di(C.sub.1-3 alkyl) terephthalate, and
combinations thereof, and [0007] (c) 1,4-cyclohexane dimethanol;
wherein
[0008] the residue of monomer (a) is present in an amount from 7 to
less than 12 mole % of the copolyester based on the total moles of
repeat units in the polyester; and
[0009] the copolyester has a glass transition temperature of at
least 107.degree. C., an intrinsic viscosity of at least 0.7 dl/g,
and a molded sample has a Notched Izod value of at least 290 J/m
determined in accordance with ASTM D256 at 25.degree. C.
[0010] In another embodiment, the method for the manufacture of the
copolyester composition is disclosed, which comprises polymerizing
the components in the presence of an esterification catalyst.
[0011] Compositions comprising the amorphous polyester are also
disclosed.
[0012] Further disclosed are articles comprising the copolyester
composition. Methods of manufacturing an article comprise
extruding, shaping, calendaring, molding, or injection molding the
copolyester composition.
[0013] The described and other features are exemplified by the
following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Our invention is based on the discovery that it is now
possible to make an amorphous copolyester composition having a
combination of high glass transition temperature, high strength,
and good flow. These properties are achieved using a specific
combination of monomer units, including a combination of
1-phenylindane dicarboxylic acid and a terephthalyl component,
together with 1,4-cyclohexanedimethanol. In a particularly
advantageous feature, the terephthalyl component is a virgin
monomer selected from terephthalic acid, a di(C.sub.1-3 alkyl)
terephthalate, and combinations thereof.
[0015] The prefix "bio-", "bio-based" or "bio-derived" as used
herein means that the compound or composition is ultimately
derived, in whole or in part, from a biological source, e.g.,
"bio-based terephthalic acid" is derived from a biological (e.g.,
plant or microbial source) rather than a petroleum source.
Similarly, the prefix "petroleum-" or "petroleum-derived" means
that the compound or composition is ultimately derived from a
petroleum source, e.g., a "petroleum-derived poly(ethylene
terephthalate) is derived from reactants that are themselves
derived from petroleum. For example, U.S. patent application Ser.
No. 12/347,423, filed Dec. 31, 2008 and published as US
2010/0168371 A1 on Jul. 1, 2010, describes bio-based polyesters
produced from a biomass containing a terpene or terpenoid, such as
limonene, as well as the process of making these products. The
bio-based polyesters include poly(alkylene terephthalate)s such as
bio-based poly(ethylene terephthalate) (bio-PET), bio-based
poly(trimethylene terephthalate) (bio-PTT), bio-based poly(butylene
terephthalate), bio-based poly(cyclohexylene terephthalate)
(bio-PCT), bio-based poly(cyclohexylene terephthalate glycol)
(bio-PCTG), bio-based (polyethylene terephthalate glycol)
(bio-PETG).
[0016] As used herein the singular forms "a," "an," and "the"
include plural referents. "Or" means "and/or." The term
"combination" is inclusive of blends, mixtures, alloys, reaction
products, and the like. Unless defined otherwise, technical and
scientific terms used herein have the same meaning as is commonly
understood by one of skill. Compounds are described using standard
nomenclature. The term "and a combination thereof" is inclusive of
the named component and/or other components not specifically named
that have essentially the same function.
[0017] Other than in the operating examples or where otherwise
indicated, all numbers or expressions referring to quantities of
ingredients, reaction conditions, and the like, used in the
specification and claims are to be understood as modified in all
instances by the term "about." Various numerical ranges are
disclosed in this patent application. Because these ranges are
continuous, they include every value between the minimum and
maximum values. The endpoints of all ranges reciting the same
characteristic or component are independently combinable and
inclusive of the recited endpoint. Unless expressly indicated
otherwise, the various numerical ranges specified in this
application are approximations. The term "from more than 0 to" an
amount means that the named component is present in some amount
that is greater than 0, and up to and including the higher named
amount.
[0018] Polyesters are generally manufactured by polymerization of a
dicarboxylic acid or reactive derivative thereof and a diol or
reactive derivative thereof. The copolyesters herein are
manufactured by polymerization of two dicarboxylic acids (a) a
phenyl indane dicarboxylic acid or a reactive derivative thereof;
and (b) a virgin terephthalic acid or reactive derivative thereof.
The diol is 1,4-cyclohexanedimethanol or a reactive derivative
thereof.
[0019] The 1-phenylindane dicarboxylic acid monomer is a monomer of
formula I:
##STR00003##
wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.5 are each
independently a C.sub.1-3 alkyl group, a is 0-1, b is 0-4, c is 0-4
and d is 0-3, and each R.sup.4 is independently a hydrogen or a
C.sub.1-3 alkyl group. The acid or its C.sub.1-3 alkyl ester can be
used.
[0020] One skilled in the art will recognize this general class of
monomers as the dicarboxylic acid derivatives of phenyl indane.
Among these dicarboxylic acids are
3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid;
3-(4-carboxyphenyl)-1,3-diethyl-1-methyl-5-indan carboxylic acid;
3-(4-carboxyphenyl)-1,3-dipropyl-1-methyl-5-indan carboxylic acid;
and the like
[0021] In a specific embodiment the monomers are of the formula
II
##STR00004##
wherein R.sup.1, R.sup.2, and R.sup.4 are each independently
hydrogen or a C.sub.1-3 alkyl group.
[0022] Monomers of formula III can be specifically mentioned
##STR00005##
wherein R.sup.4 is each independently hydrogen or a C.sub.1-3 alkyl
group. In an embodiment, each R.sup.4 is the same and is a methyl
or ethyl group, specifically a methyl group. This monomer is known
in the literature, and when R.sup.4 is hydrogen, is also known as
1,3,3-trimethyl-1-phenylindan-4',5-dicarboxylic acid;
1,1,3-trimethyl-5-carboxy-3-(p-carboxy-phenyl)indan;
1,1,3-trimethyl-5-carboxy-3-(4-carboxyphenyl)indan; and
3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid. As
described in U.S. Pat. No. 3,859,364, the diacid of monomer III is
a commercially available material, generally referred to as
phenylindan dicarboxylic acid, or, abbreviated, PIDA. The
Preparation of PIDA have been disclosed by Petropoulous in, for
example, U.S. Pat. Nos. 2,780,609; 2,830,966; and 2,873,262 and
3,102,135. Copolyesters of PIDA with terephthalic acid and ethylene
glycol have been described in Belgian 731,258 and Netherlands
6905547. Alternatively, the monomer I, II, or III is a bio-based
material, i.e., derived wholly or in part from a biological
material, which excludes organic material that has been transformed
by geological processes into petroleum, petrochemicals, and
combinations thereof.
[0023] The terephthalate group is provided by copolymerization with
terephthalic acid, a dialkyl terephthalate monomer, or a
combination thereof, particularly a virgin di(C.sub.1-3) alkyl
ester of terephthalic acid, preferably the diethyl ester (DET) or
dimethyl ester (DMT). The terephthalyl-containing polyester can
contain virgin monomers, recycle monomers, including
petroleum-based monomers and bio-based monomers. Thus, the
terephthalyl component can be bio-based, i.e., derived in whole or
in part from a biological material, which excludes organic material
that has been transformed by geological processes into petroleum,
petrochemicals, and combinations thereof.
[0024] In addition to the monomers I, II, or III and the
terephthalyl component, the copolyester is manufactured from
1,4-cyclohexane dimethanol. In an embodiment, the 1,4-cyclohexane
dimethanol has an isomer distribution of 60 to 80% trans and 20 to
40% cis isomers. In a specific embodiment, the amorphous
copolyester comprises reacted 1,4-cyclohexane dimethanol in an
amount of 50 mole %, based on the total moles of repeat units in
the copolyester. The CHDM can be virgin monomer, derived from a
polyester, or bio-based. For example, one skilled in the art will
recognize that DMT or DET derived from a terephthalic-containing
polyester homopolymer, terephthalic-containing copolymer, or a
combination thereof can be further hydrogenated to 1,4-CHDM. In
this instance, the resulting 1,4-CHDM will also contain 1,3-CHDM
by-product generated by DMI hydrogenation. Accordingly, where
1,4-CHDM derived from recycle DMT or DET is used, the copolyester
can further comprise units derived from 1,3-CHDM. For example, the
copolyester can comprise from 0.01 to 5 mole %, from 0.01 to 1 mole
%, or from 0.01 to 0.5 mole % of 1,3-cyclohexane dimethanol units,
based on the total moles of repeat units in the copolyester.
[0025] Methods for the manufacture of the copolyesters from virgin
terephthalic acid or di(C.sub.1-3)alkyl terephthalic esters,
1-phenylindane monomers I, II, or III, in particular PIDA and
1,4-cyclohexane dimethanol are known and can be used. For example,
the copolyesters can be obtained by melt-process condensation, or
solution phase condensation in the presence of an acid catalyst.
The catalyst facilitates the transesterification reaction, and can
be selected from antimony compounds, tin compounds, titanium
compounds, combinations thereof as well as many other metal
catalysts and combinations of metal catalysts that have been
disclosed in the literature. The amount of catalyst required to
obtain an acceptable polymerization rate at the desired
polymerization temperature will vary, and can be determined by
experimentation. The catalyst amount can be 1 to 5000 ppm, or more.
It is possible to prepare a branched polyester in which a branching
agent, for example, a glycol having three or more hydroxyl groups
or a trifunctional or multifunctional carboxylic acid has been
incorporated. Furthermore, it is sometimes desirable to have
various concentrations of acid and hydroxyl end groups on the
polyester, depending on the ultimate end use of the
composition.
[0026] In an advantageous feature, the copolyesters have an
advantageous combination of properties, including an improved Tg,
good intrinsic viscosity, and good impact strength.
[0027] The copolyesters manufactured from 1,4-cyclohexane
dimethanol, 1-phenylindane I, II, or III, in particular PIDA and
the virgin terephthalic acid/dialkyl terephthalate have a Tg of at
least 107.degree. C., specifically 107 to 117.degree. C.
[0028] In general, the copolyester manufactured from
1,4-cyclohexane dimethanol, 1-phenylindane I, II, or III, in
particular PIDA and the virgin terephthalic acid/dialkyl
terephthalate will have an intrinsic viscosity of at least 0.7
deciliters per gram (dL/g), as measured in a 60:40 by weight
phenol/1,1,2,2-tetrachloroethane mixture at 23.degree. C.
[0029] The copolyester further has good impact strength, in
particular, a molded sample has a Notched Izod value of at least
290 J/m, at least 400 J/m, or at least 600 J/m, determined in
accordance with ASTM D256 at 25.degree. C.
[0030] The copolyester can have a weight average molecular weight
of 10,000 to 200,000 atomic mass units (amu), specifically 50,000
to 150,000 atomic mass units (amu) as measured by gel permeation
chromatography (GPC) using polystyrene standards. The copolyester
can also comprise a mixture of different batches of copolyester
prepared under different process conditions in order to achieve
different intrinsic viscosities and/or weight average molecular
weights.
[0031] The copolyester can be clear or translucent. In an
embodiment, the copolyesters are clear. For example, molded sample
of the copolyester can have a haze less of less than 20%, less than
15%, less than 10%, less than 5%, or less than 3%, and a
transmission greater than 70%, greater than 80%, greater than 85%,
or greater than 90%, each measured according to ASTM D 1003-07
using illuminant C at a 0.062 inch (1.5 mm) thickness.
[0032] The copolyester can be used as a component in thermoplastic
compositions for a variety of purposes. The copolyester can be
present in the thermoplastic composition in an amount from 20 to
99.99 wt. %, or from 20 to 95 wt. %, or from 30 to 80 wt. % based
on the total weight of the composition. Within this range, at least
50 wt. %, specifically at least 70 wt. %, of the copolyester can be
present. In an embodiment, the polyester is present in an amount
from 50 to 99 wt. %, based on the total weight of the thermoplastic
composition, specifically from 60 to 98 wt. %, more specifically
from 70 to 95 wt. %, each amount based on the total weight of the
thermoplastic composition. The remaining components of the
thermoplastic compositions can be other additives, including other
polymers as further described below.
[0033] Such thermoplastic composition can optionally comprise other
polyesters and/or other polymers, for example other polyesters or
polycarbonates. As used herein, "polyesters" is inclusive of
homopolymers and copolymers comprising ester units, and
"polycarbonate" is inclusive of homopolymers and copolymers
comprising carbonate units. Exemplary polyesters include
poly(ethylene terephthalate) ("PET"), poly(1,4-butylene
terephthalate), ("PBT"), poly(ethylene naphthalate) ("PEN"),
poly(butylene naphthalate), ("PBN"), poly(1,3-propylene
terephthalate) ("PPT"), poly(cyclohexane-1,4-dimethylene
terephthalate) ("PCT"), poly(cyclohexane-1,4-dimethylene
cyclohexane-1,4-dicarboxylate) also known as
poly(1,4-cyclohexane-dimethanol 1,4-dicarboxylate) ("PCCD"), and
poly(cyclohexylene-1,4-dimethylene-co-ethylene terephthalate), also
known as cyclohexanedimethanol-terephthalic acid-ethylene glycol
("PCTG" or "PETG") copolymers. When the molar proportion of
cyclohexanedimethanol is higher than that of ethylene glycol the
polyester is termed PCTG. When the molar proportion of ethylene
glycol is higher than that of cyclohexane dimethanol the polyester
is termed PETG. As is known in the art, the foregoing polyesters
can further comprise units derived from isophthalic acid.
Combinations of the foregoing polymers can be used. The other
polymer can be present in an amount of from more than 0.01 to 80
wt. %, or from 5 to 80 wt. %, or from 30 to 70 wt. %, each based on
the total weight of the copolyester and the other polymers in the
thermoplastic polyester composition. For example, a thermoplastic
polyester composition comprising copolyester manufactured from
combination of the monomer I, II, or III, virgin terephthalic acid
or dialkyl terephthalate and the CHDM, can comprise from 1 to 30
wt. % percent, based on the total weight of the polyesters and
other polymers in the thermoplastic polyester composition, of a
second polyester, for example poly(ethylene terephthalate),
poly(ethylene naphthalate), poly(1,4-butylene naphthalate),
poly(trimethylene terephthalate), poly(1,4-cyclohexanedimethylene
1,4-cyclohexanedicarboxylate), poly(1,4-cyclohexanedimethylene
terephthalate), poly(1,4-butylene-co-1,4-but-2-ene diol
terephthalate), poly(1,4-cyclohexanedimethylene-co-ethylene
terephthalate), or a combination comprising at least one of the
foregoing polyesters. Alternatively, the thermoplastic polyester
composition can comprise 1 to 50 wt. %, or 1 to 30 wt. %, or 1 to
10 wt. %, based on the total weight of the polyester and other
polymers in the composition, of a polycarbonate and/or an aromatic
copolyester carbonate. In a specific embodiment, the polymer
component of the thermoplastic composition consists only of the
copolyester. In another embodiment, the polymer component comprises
at least 70 wt. % of the copolyester.
[0034] In a specific embodiment, the other polymer includes one or
more impact modifiers. The thermoplastic copolyester composition
can thus optionally comprise the amorphous copolyester and an
impact modifier.
[0035] For example, the thermoplastic composition can optionally
further comprise an impact modifier in an amount from 0.25 to 40
wt. %, or from 0.5 to 25 wt. %, or from 1 to 10 wt. %, based on the
total weight of the composition. In other embodiments, the impact
modifier is present in an amount from 0.5 to 8 wt. %, specifically
from 1.0 to 6 wt. %, still more specifically 0 to 1.0 wt. %, based
on the total weight of the composition. In another embodiment, the
thermoplastic composition does not include an impact modifier or
does not contain appreciable amounts of an impact modifier. In such
embodiments, the impact modifier is present in an amount, based on
wt. %, ranging from 0 to less than an integer selected from the
group consisting of 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29,
28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12,
11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 wt. %, and combinations
thereof.
[0036] Useful impact modifiers include olefin-containing copolymers
such as olefin acrylates and olefin diene terpolymers. An example
of an olefin acrylate copolymer impact modifier is ethylene ethyl
acrylate copolymer available from Union Carbide as DPD-6169. Other
higher olefin monomers can be employed as copolymers with alkyl
acrylates, for example, propylene and n-butyl acrylate. Olefin
diene terpolymers known in the art and generally fall into the EPDM
(ethylene propylene diene monomer) family of terpolymers. They are
commercially available such as, for example, EPSYN.RTM. 704 from
Copolymer Rubber Company. Examples of such rubber polymers and
copolymers that can be used as impact modifiers are polybutadiene,
polyisoprene, and various other polymers or copolymers having a
rubbery dienic monomer, for example random copolymers of styrene
and butadiene (SBR).
[0037] Other thermoplastic impact modifiers are unit copolymers,
for example, A-B diblock copolymers and A-B-A triblock copolymers
having of one or two alkenyl aromatic units A, which are typically
styrene units, and a rubber unit, B, which is typically an isoprene
or butadiene unit. The butadiene unit can be partially
hydrogenated. Mixtures of these diblock and triblock copolymers are
especially useful. Examples of A-B and A-B-A copolymers include
polystyrene-polybutadiene, polystyrene-poly(ethylene-propylene),
polystyrene-polyisoprene,
poly(.alpha.-methylstyrene)-polybutadiene,
polystyrene-polybutadiene-polystyrene (SBS),
polystyrene-poly(ethylene-propylene)-polystyrene,
polystyrene-polyisoprene-polystyrene and
poly(alpha-methylstyrene)-polybutadiene-poly(alpha-methylstyrene),
as well as the selectively hydrogenated versions thereof, and the
like. Mixtures of the aforementioned unit copolymers are also
useful. Styrene-containing polymers can also be used as impact
modifiers.
[0038] Other copolymers containing vinyl aromatic compounds, for
example styrene, para-methyl styrene, or alpha methyl styrene and
vinyl cyanides, for example acrylonitrile or methacrylonitrile, can
also be useful as impact modifiers. One example is
styrene-acrylonitrile (SAN), comprising 15 to 30 percent by weight
acrylonitrile (AN) with the remainder styrene. The SAN can be
further modified by grafting to a rubbery substrate such as a
1,4-polybutadiene to produce a rubber graft polymer, e.g.,
acrylonitrile-butadiene-styrene (ABS), and
methacrylonitrile-butadiene-styrene (MBS). High rubber content
(greater than about 50 wt %) resins of this type (e.g., HRG-ABS)
can be especially useful.
[0039] These types of polymers are often available as core-shell
polymers. The core usually consists substantially of an acrylate
rubber or a butadiene rubber, wherein one or more shells have been
grafted on the core. Usually these shells are built up from a vinyl
aromatic compound, a vinyl cyanide, an alkyl acrylate or
methacrylate, acrylic acid, methacrylic acid, or a combination of
the foregoing. The core and/or the shell(s) often comprise
multi-functional compounds that can act as a cross-linking agent
and/or as a grafting agent. These polymers are usually prepared in
several stages. Still other impact modifiers include various
elastomeric materials such as organic silicone rubbers, elastomeric
fluorohydrocarbons, elastomeric polyesters, random unit
polysiloxane-polycarbonate copolymers, and the like.
[0040] Specific examples of useful impact modifiers include
acrylonitrile-butadiene-styrene, methacrylate-butadiene-styrene,
high impact polystyrene, and combinations thereof. With the proviso
that desired properties, such as high heat properties, mold
shrinkage, tensile elongation, heat deflection temperature, and the
like are not adversely affected, the thermoplastic compositions
comprising the copolyester can optionally further comprise other
known additives used in thermoplastic polyester compositions such
as reinforcing fillers, non-reinforcing fillers, stabilizers such
as antioxidants, thermal stabilizers, radiation stabilizers, and
ultraviolet light absorbing additives, as well as mold release
agents, plasticizers, quenchers, lubricants, antistatic agents,
dyes, pigments, laser marking additives, and processing aids. A
combination comprising one or more of the foregoing or other
additives can be used. A specific example of an additive
combination is a hindered phenol stabilizer and a waxy mold release
agent such as pentaerythritol tetrastearate. When used, the
additives are generally present in an amount of 0.01 to 5 wt. %,
specifically 0.05 to 2 wt. % each. Alternatively, such additives
may be absent from the composition. In one embodiment, such
additives are present in an amount ranging from 0 to a number
selected from the group consisting of 5, 4, 3, 2, 1, wt. %,
[0041] The thermoplastic copolyester compositions can be prepared
by blending the components of the composition so that they are
homogeneously dispersed in a continuous matrix of the polyester. A
number of blending processes can be used. In an exemplary process,
the copolyester, other optional polymers, and/or other additives
are mixed in an extrusion compounder and extruded to produce
molding pellets. In another process, the components, including any
reinforcing fibers and/or other additives, are mixed with the
copolyester by dry blending, fluxed on a mill and either comminuted
or extruded and chopped. The components can also be mixed and
directly molded, e.g. by injection or transfer molding. All of the
components are dried as much as possible prior to blending. In
addition, compounding is carried out with as short a residence time
in the machine as possible and at the lowest possible temperature
to minimize loss of components by decomposition or volatilization.
The temperature is carefully controlled, and friction heat is
utilized.
[0042] Methods of manufacture of articles include molding,
extruding, shaping, injection molding, or calendaring the amorphous
copolyester, in particular thermoplastic compositions comprising
the amorphous copolyester. In one embodiment, the components are
pre-compounded, pelletized, and then molded. Pre-compounding can be
carried out in known equipment. For example, after pre-drying the
polyester composition (e.g., for four hours at 120.degree. C.), a
single screw extruder can be fed with a dry blend of the
ingredients, the screw employed having a long transition section to
ensure proper melting. Alternatively, a twin-screw extruder with
intermeshing co-rotating screws can be fed with polyester and other
components at the feed port and reinforcing fibers (and other
additives) can optionally be fed downstream. In either case, a
generally suitable melt temperature will be 230.degree. C. to
300.degree. C. The pre-compounded components can be extruded and
cut up into molding compounds such as granules, pellets, and the
like by standard techniques. The granules or pellets can then be
molded in any known equipment used for molding thermoplastic
compositions, such as a Newbury or van Dorn type injection-molding
machine with cylinder temperatures at 230.degree. C. to 280.degree.
C., and mold temperatures at 55.degree. C. to 95.degree. C. The
granules and pellets can also be extruded into films or sheets. The
articles formed by molding or extrusion of the thermoplastic
polyester compositions possess an excellent balance of
properties.
[0043] In particular, the thermoplastic copolyester composition can
be molded into useful articles such as heat resistant containers by
a variety of means for example, injection molding, blow molding,
extruding, and the like. The thermoplastic copolyester composition
can also be used to form at least parts in articles such as a wire,
an optical fiber, a cable, an automotive part, an outdoor product,
a biomedical intermediate or product, a composite material, a
melt-spun mono- or multi-filament fiber, an oriented or un-oriented
fiber, a hollow, porous or dense component; a woven or non-woven
fabric (e.g., a cloth or a felt), a filter, a membrane, a sheet, a
film (thin and thick, dense and porous), a multi-layer- and/or
multicomponent film, a barrier film, a container, a bag, a bottle,
a rod, a liner, a vessel, a pipe, a pump, a valve, an O-ring, an
expansion joint, a gasket, a heat exchanger, an injection-molded
article, a see-through article, a sealable packaging, a profile,
heat-shrinkable film, a thermoplastically welded part, a generally
simple and complex part, such as rods, tubes, profiles, linings and
internal components for vessels, tanks, columns, pipes, fittings,
pumps and valves; an O-ring, a seal, a gasket, a heat exchanger, a
hose, an expansion joint, a shrinkable tube; a coating, such as
protective coatings, electrostatic coatings, cable and wire
coatings, optical fiber coatings; and the like. Articles that can
be made from our compositions include and not limited food
containers and medical devices, which may be FDA approved. Other
articles include houseware articles such as utensils, water
bottles, beer bottles, juice containers, soft drink containers, and
combinations thereof. Medical articles can include
hemodiafilteration housings, medical devices housings for Gamma
radiation, e-beam, and ethylene oxide sterilization devices. Infant
care articles include baby bottles, pacifier housings, baby food
makers, and combinations thereof. Consumer durable articles include
and are not limited to chair mats. Small appliance articles can
include blending jars, juice maker jars, frozen beverage
dispensers, food maker jars, coffee cups, hot drink cups and
containers, and sports drink bottles.
[0044] In a specific embodiment, a thermoplastic composition
comprising the copolyester, or comprising the copolyester and an
impact modifier, are formed into a container such as a bottle,
having a wall thickness from 1.0 mm 10.0 mm, and an internal volume
from 1 to 10,000 mL, from 10 to 5,000 mL, or from 250 to 5,000
mL.
[0045] In another specific embodiment, a thermoplastic composition
comprises an amorphous copolyester comprising the polymerization
reaction product of: (a) a monomer of formula III
##STR00006##
wherein R.sup.4 is each the same and is methyl or ethyl; (b) a
virgin monomer selected from dimethyl or diethyl terephthalate, and
combinations thereof, and (c) 1,4-cyclohexane dimethanol having an
isomer distribution of 60 to 80% trans and 20 to 40% cis isomers;
wherein the residue of monomer (a) is present in an amount from 7
to less than 12 mole % of and the residue of monomer (b) is present
in an amount from more than 38 to 43 mol %, each based on moles of
repeat units in the polyester; and the copolyester has a glass
transition temperature of at least 107.degree. C., an intrinsic
viscosity of at least 0.7 dl/g, and a molded sample has a Notched
Izod value of at least 290 J/m determined in accordance with ASTM
D256. This thermoplastic composition can further comprise an
additive is selected from reinforcing fillers, non-reinforcing
fillers, antioxidants, thermal stabilizers, radiation stabilizers,
ultraviolet light absorbing additives, mold release agents,
plasticizers, quenchers, lubricants, antistatic agents, dyes,
pigments, laser marking additives, processing aids, and
combinations thereof, and optionally a polymer selected from
polycarbonate, poly(ethylene terephthalate), poly(butylene
terephthalate), poly(butylene naphthalate), poly(1,2-propylene
terephthalate), poly(cyclohexylene-1,4-dimethylene terephthalate),
poly(ethylene terephthalate), poly(1,3-propylene terephthalate),
poly(cyclohexylene-1,4-dimethylene
cyclohexylene-1,4-dicarboxylate),
poly(cyclohexylene-1,4-dimethylene-co-ethylene terephthalate),
poly(cyclohexylene-1,4-dimethylene-co-1,3-cyclobutylene
terephthalate), and combinations thereof. In another specific
embodiment, this thermoplastic composition, optionally comprising
an impact modifier, are formed into a container such as a bottle,
having a wall thickness from 1.0 mm 10.0 mm, and an internal volume
from 1 to 10,000 mL, from 10 to 5,000 mL, or from 250 to 5,000
mL.
EXAMPLES
Materials
[0046] The materials in Table 1 were used in the Examples.
TABLE-US-00001 TABLE 1 Material Description Source DMT Dimethyl
terephthalate Fisher Scientific PIDA*
1,3,3-trimethyl-1-phenylindan- Amoco 4',5-dicarboxylic acid CHDM**
1,4-cyclohexane dimethanol Eastman Chemical Co. TPT Titanium
tetraisopropoxide DuPont Chemical (Tyzor .TM. Catalyst) *Used as
received without further purification **30 wt. % cis and 70 wt. %
trans configuration
Techniques and Procedures
Molding Procedures
[0047] The polymers were injection molded on a BOY molding machine.
The pellets were dried for 3 hours at 82.degree. C. in a forced
air-circulating oven prior to injection molding. The zone
temperature was set to 260.degree. C. The nozzle temperature was
also set at 260.degree. C. The mold temperature was 54.degree. C.
The screw speed was 100 rpm. The injection, holding, cooling and
cycle time were 1.5, 6, 18, and 32 seconds, respectively. All
standard parts were 0.125 inches (3.12 mm) thick.
Testing Procedures
[0048] Glass transition temperature (Tg) was determined according
to ASTM D3418 by Differential Scanning calorimetry (DSC) using
Perkin Elmer DSC 7 equipped with Pyris DSC 7 software. In a typical
procedure, polymer sample (10-20 mg) was heated from 40.degree. C.
to 290.degree. C. (20.degree. C./min), held at 290.degree. C. for 1
min, cooled back to 40.degree. C. (20.degree. C./min), then held at
40.degree. C. for 1 min, and the above heating/cooling cycle was
repeated. The second heating cycle is usually used to obtain the Tg
data.
[0049] Intrinsic viscosity (IV) was determined by automatic
Viscotek Microlab.RTM. 500 series Relative Viscometer Y501. In a
typical procedure, 0.5000 g of polymer sample was fully dissolved
in 60/40 mixture (by vol) of % phenol/1,1,2,2-tetrachloroethane
solution (Harrell Industries). Two measurements were taken for each
sample, and the result reported was the average of the two
measurements.
[0050] Weight average molecular weight (Mw) and number average
molecular weight (Mn) were determined by GPC. A Waters 2695
separation module equipped with a single PL HFIP gel (250.times.4 6
mm) and a Waters 2487 Dual .lamda. Absorbance Detector (signals
observed at 273 nm) was used for GPC analysis. The mobile phase was
a mixture of 5/95% HFIP/Chloroform solution. Typically, samples
were prepared by dissolving 50 mg of the polymer pellets in 50 mL
of 5/95% HFIP/Chloroform solution. The results were processed using
Millennium 32 Chromatography Manager V 4.0. Reported molecular
weights are relative to polystyrene standards
[0051] Injection molded parts as described were tested in
accordance with the ASTM and ISO procedures in Table 2.
[0052] Notched Izod testing is done on 3.times.1/2.times.1/8 inch
(76.2.times.12.7.times.3 2 mm) bars using ASTM method D256. Bars
were notched prior to oven aging; samples were tested at room
temperature, 25.degree. C.
Examples 1-11
[0053] Laboratory synthesis of copolyesters from DMT as shown in
Table 3 and further described was conducted in the presence of 250
ppm of titanium (TPT) as the catalyst.
TABLE-US-00002 TABLE 3 (DMT + EI Poly Poly Notched Ex. DMT PIDA
PIDA): Temp EI Time Temp Time T.sub.g Izod No. (Mol %) (Mol %) CHDM
(.degree. C.) (Min) (.degree. C.) (Min) (.degree. C.) I.V. (J/m) 1
43 7 1 220 90 270 112 110 0.78 1098 2 43 7 1 220 90 270 78 111 0.7
750 C3 43 7 1 220 90 270 63 107 0.66 110 C4 40 10 1 220 90 275 40
112 0.567 66 C5 40 10 1 220 90 275 44 114 0.62 99.1 6 40 10 1 220
90 275 62 116 0.79 291 C7 40 10 1 220 90 275 50 114 0.69 109 8 40
10 1 220 90 275 97 117 0.87 517 C9 35 15 1 220 90 275 76 121 0.58
69 C10 35 15 1 220 90 275 95 126 0.77 94.1 C11 35 15 1 220 90 275
105 124 0.69 84.3
Example 1
[0054] A mixture of 83.42 g (0.43 mol) of DMT, 22.68 g (0.07 mol)
of PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a
500 mL, three neck round bottom flask equipped with a nitrogen
inlet, glass stirrer with a metal blade, and a short distillation
column. The flask was placed in an oil bath already heated to
180.degree. C. with the stirring speed set at 260 RPM. After 5
minutes, 250 ppm of titanium catalyst was added to the reaction
mixture, and the temperature was gradually increased to 220.degree.
C. at a rate of 2.degree. C./minute while stirring under nitrogen.
The reaction mixture was heated at 220.degree. C. for 23 minutes
and then the temperature of reaction was increased to 270.degree.
C. After the reaction temperature reached 270.degree. C., pressure
inside the reactor was gradually reduced to 0.2 mm Hg (less than 1
torr) over the next 47 minutes. A pressure of less than 1 torr was
maintained for a total time of 112 minutes. During this period, the
stirring speed was reduced to 60 RPM, then maintained for 20
minutes, and subsequently reduced to 30 RPM for the remainder of
polymerization stage. The reaction was stopped and product was
collected for analysis. The results for this example are listed in
Table 4.
TABLE-US-00003 TABLE 4 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) 1 110 25444 71245 2.8 0.778
1098
Discussion
[0055] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) 1,4-cyclohexane dimethanol and wherein the
1-phenylindane dicarboxylic acid or ester, in particular PIDA is
present in an amount from 7 to less than 12 mol %, based on the
repeat unit of polymer, the polymer exhibited a combination of the
following useful properties: (i) the polymer had a Tg of at least
107.degree. C.; and (ii) the polymer had a Notched Izod of at least
290 Joules/m, and (iii) the polymer had an intrinsic viscosity IV
of at least 0.7 dl/g.
Example 2
[0056] A mixture of 83.42 g (0.43 mol) of DMT, 22.68 g (0.07 mol)
of PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a
500 mL, three neck round bottom flask equipped with a nitrogen
inlet, glass stirrer with a metal blade, and a short distillation
column. The flask was placed in an oil bath already heated to
180.degree. C. with the stirring speed set at 260 RPM. After 5
minutes, 250 ppm of titanium catalyst was added to the reaction
mixture, and the temperature was gradually increased to 220.degree.
C. at a rate of 2.degree. C./minute while stirring under nitrogen.
The reaction mixture was heated at 220.degree. C. for 23 minutes
and then the temperature of reaction was increased to 270.degree.
C. After the reaction temperature reached 270.degree. C., pressure
inside the reactor was gradually reduced to 0.2 mm Hg (less than 1
torr) over the next 47 minutes. A pressure of less than 1 torr was
maintained for a total time of 78 minutes. During this period, the
stirring speed was reduced to 60 RPM, was maintained for 20
minutes, and subsequently reduced to 30 RPM for the remainder of
polymerization stage. The reaction was stopped and product was
collected for analysis. The results for this example are listed in
Table 5.
TABLE-US-00004 TABLE 5 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) 2 111 23035 67095 2.9 0.71
750
Discussion
[0057] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) 1,4-cyclohexane dimethanol and wherein the
1-phenylindane dicarboxylic acid or ester, in particular PIDA is
present in an amount from 7 to less 12 mol %, based on the repeat
unit of polymer, the polymer exhibited a combination of the
following useful properties: (i) the polymer had a Tg of at least
107.degree. C.; and (ii) the polymer had a Notched Izod of at least
290 Joules/m, and (iii) the polymer had an intrinsic viscosity IV
of at least 0.7 dl/g.
Comparative Example 3
[0058] A mixture of 83.42 g (0.43 mol) of DMT, 22.68 g (0.07 mol)
of PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a
500 mL, three neck round bottom flask equipped with a nitrogen
inlet, glass stirrer with a metal blade, and a short distillation
column. The flask was placed in an oil bath already heated to
180.degree. C. with the stirring speed set at 260 RPM. After 5
minutes, 250 ppm of titanium catalyst was added to the reaction
mixture, and the temperature was gradually increased to 220.degree.
C. at a rate of 2.degree. C./minute while stirring under nitrogen.
The reaction mixture was heated at 220.degree. C. for 23 minutes
and then the temperature of reaction was increased to 270.degree.
C. After the reaction temperature reached 270.degree. C., pressure
inside the reactor was gradually reduced to 0.2 mm Hg (less than 1
torr) over the next 47 minutes. A pressure of less than 1 torr was
maintained for a total time of 63 minutes. During this period, the
stirring speed was reduced to 60 RPM, was maintained for 20
minutes, and subsequently reduced to 30 RPM for the remainder of
polymerization stage. The reaction was stopped and product was
collected for analysis. The results for this example are listed in
Table 6.
TABLE-US-00005 TABLE 6 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C3 107 20740 57923 2.8 0.659
110
Discussion
[0059] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) a dialkyl
terephthalate and (c) 1,4-cyclohexane dimethanol and wherein the
1-phenylindane dicarboxylic acid or ester, in particular PIDA is
present in an amount from 7 to less 12 mol %, based on the repeat
unit of polymer, the polymer did not exhibit a combination of the
following useful properties: (i) the polymer had Tg of at least
107.degree. C.; and (ii) the polymer did not have a Notched Izod of
at least 290 Joules/m, and (iii) the polymer did not have an
intrinsic viscosity IV of at least 0.7 dl/g.
Comparative Example 4
[0060] A mixture of 77.6 g (0.4 mol) of DMT, 32.4 g (0.1 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After 5 minutes, 250 ppm
of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 40 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 7.
TABLE-US-00006 TABLE 7 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C4 112 18035 48217 2.7 0.566
66
Discussion
[0061] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the 1-phenylindane
dicarboxylic acid or ester, in particular PIDA is present in an
amount from 7 to less 12 mol %, based on the repeat unit of
polymer, the polymer did not exhibit a combination of the following
useful properties: (i) the polymer had Tg of at least 107.degree.
C.; and (ii) the polymer did not have a Notched Izod of at least
290 Joules/m, and (iii) the polymer did not have an intrinsic
viscosity IV of at least 0.7 dl/g.
Comparative Example 5
[0062] A mixture of 77.6 g (0.4 mol) of DMT, 32.4 g (0.1 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After 5 minutes, 250 ppm
of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 44 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 8.
TABLE-US-00007 TABLE 8 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C5 114 25308 78656 0.623 0.623
99.1
Discussion
[0063] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the 1-phenylindane
dicarboxylic acid or ester, in particular PIDA is present in an
amount from 7 to less 12 mol %, based on the repeat unit of
polymer, the polymer did not exhibit a combination of the following
useful properties: (i) the polymer had a Tg of at least 107.degree.
C.; and (ii) the polymer did not have a Notched Izod of at least
290 Joules/m, and (iii) the polymer did not have an intrinsic
viscosity IV of at least 0.7 dl/g.
Example 6
[0064] A mixture of 77.6 g (0.4 mol) of DMT, 32.4 g (0.1 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After 5 minutes, 250 ppm
of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 62 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 9.
TABLE-US-00008 TABLE 9 Notched Example T.sub.g Izod No (.degree.
C.) M.sub.n M.sub.w PDI I.V. (J/m) 6 116 25308 78656 3.1 0.789
291
Discussion
[0065] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the 1-phenylindane
dicarboxylic acid or ester, in particular PIDA is present in an
amount from 7 to less 12 mol %, based on the repeat unit of
polymer, the polymer exhibited a combination of the following
useful properties: (i) the polymer had Tg of at least 107.degree.
C.; and (ii) the polymer had a Notched Izod of at least 290
Joules/m, and (iii) the polymer had an intrinsic viscosity IV of at
least 0.7 dl/g.
Comparative Example 7
[0066] A mixture of 77.6 g (0.4 mol) of DMT, 32.4 g (0.1 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After 5 minutes, 250 ppm
of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 50 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 10.
TABLE-US-00009 TABLE 10 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C7 114 21813 61522 2.8 0.691
109
Discussion
[0067] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the 1-phenylindane
dicarboxylic acid or ester, in particular PIDA is present in an
amount from 7 to less 12 mol %, based on the repeat unit of
polymer, the polymer did not exhibit a combination of the following
useful properties: (i) the polymer had a Tg of at least 107.degree.
C.; and (ii) the polymer did not have a Notched Izod of at least
290 Joules/m, and (iii) the polymer did not have an intrinsic
viscosity IV of at least 0.7 dl/g.
Example 8
[0068] A mixture of 77.6 g (0.4 mol) of DMT, 32.4 g (0.1 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After five minutes, 250
ppm of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 97 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 11.
TABLE-US-00010 TABLE 11 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) 8 117.3 26975 80967 3.0 0.868
517
Discussion
[0069] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the a
1-phenylindane dicarboxylic acid or ester, in particular PIDA is
present in an amount from 7 to less 12 mol %, based on the repeat
unit of polymer, the polymer exhibited a combination of the
following useful properties: (i) the polymer had Tg of at least
107.degree. C.; and (ii) the polymer had a Notched Izod of at least
290 Joules/m, and (iii) the polymer had an intrinsic viscosity IV
of at least 0.7 dl/g.
Comparative Example 9
[0070] A mixture of 67.9 g (0.35 mol) of DMT, 48.6 g (0.15 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After 5 minutes, 250 ppm
of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 76 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 min was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 12.
TABLE-US-00011 TABLE 12 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C9 120.6 22499 58108 2.6 0.580
69
Discussion
[0071] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the 1-phenylindane
dicarboxylic acid or ester, in particular PIDA is present in an
amount more than 12 mol %, based on the repeat unit of polymer, the
polymer did not exhibit a combination of the following useful
properties: (i) the polymer had Tg of at least 107.degree. C.; and
(ii) the polymer did not have a Notched Izod of at least 290
Joules/m, and (iii) the polymer did not have an intrinsic viscosity
IV of at least 0.7 dl/g.
Comparative Example 10
[0072] A mixture of 67.9 g (0.35 mol) of DMT, 48.6 g (0.15 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After 5 minutes, 250 ppm
of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 95 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 13.
TABLE-US-00012 TABLE 13 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C10 126 30151 89923 3.0 0.776
94.1
Discussion
[0073] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the a
1-phenylindane dicarboxylic acid or ester, in particular PIDA is
present in an amount more than 12 mol %, based on the repeat unit
of polymer, the polymer did not exhibit a combination of the
following useful properties: (i) the polymer had a Tg of at least
107.degree. C.; and (ii) the polymer did not have a Notched Izod of
at least 290 Joules/m, and (iii) the polymer did not have an
intrinsic viscosity IV of at least 0.7 dl/g.
Comparative Example 11
[0074] A mixture of 67.9 g (0.35 mol) of DMT, 48.6 g (0.15 mol) of
PIDA and 72 g (0.5 mol) of as obtained CHDM were placed into a 500
mL, three neck round bottom flask equipped with a nitrogen inlet,
glass stirrer with a metal blade, and a short distillation column.
The flask was placed in an oil bath already heated to 180.degree.
C. with the stirring speed set at 260 RPM. After five minutes, 250
ppm of titanium catalyst was added to the reaction mixture, and the
temperature was gradually increased to 220.degree. C. at a rate of
2.degree. C./minute while stirring under nitrogen. The reaction
mixture was heated at 220.degree. C. for 23 minutes and then the
temperature of reaction was increased to 275.degree. C. After the
reaction temperature reached 275.degree. C., pressure inside the
reactor was gradually reduced to 0.2 mm Hg (less than 1 torr) over
the next 15 minutes. A pressure of less than 1 torr was maintained
for a total time of 105 minutes. During this period, the stirring
speed was reduced to 60 RPM, was maintained for 20 minutes was
subsequently reduced to 30 RPM for the remainder of polymerization
stage. The reaction was stopped and product was collected for
analysis. The results for this example are shown in Table 14.
TABLE-US-00013 TABLE 14 Example T.sub.g Notched No (.degree. C.)
M.sub.n M.sub.w PDI I.V. Izod (J/m) C11 124 26248 73791 2.8 0.691
84.3
Discussion
[0075] The results indicate that when the copolyester having a
repeat unit comprising the reaction product of (a) a 1-phenylindane
dicarboxylic acid or ester, in particular PIDA, (b) dialkyl
terephthalate and (c) cyclohexane dimethanol and the 1-phenylindane
dicarboxylic acid or ester, in particular PIDA is present in an
amount more than 12 mol % based on the repeat unit of polymer, the
polymer did not exhibit a combination of the following useful
properties: (i) the polymer had a Tg of at least 107.degree. C.;
and (ii) the polymer did not have a Notched Izod of at least 290
Joules/m, and (iii) the polymer did not have an intrinsic viscosity
IV of at least 0.7 dl/g.
[0076] Table 15 shows the results of a compositional analysis of
terephthalate, PIDA, and CHDM units in the Examples as determined
by proton nuclear magnetic spectroscopy.
TABLE-US-00014 TABLE 15 Compositional Analysis by .sup.1H NMR
Example No. Terephthalate PIDA CHDM 1 41.68 7.30 51.02 2 42.14 7.26
50.33 C3 41.90 7.60 50.51 C4 39.53 10.37 50.10 C5 38.78 10.46 50.77
6 38.98 10.46 50.56 C7 38.91 10.30 50.79 8 38.98 10.25 50.77 C9
34.05 15.48 50.45 C10 33.97 15.08 50.95 C11 33.91 15.19 50.89
[0077] All cited patents, patent applications, and other references
are incorporated herein by reference in their entirety.
[0078] Although the present invention has been described in detail
with reference to certain preferred versions thereof, other
variations are possible. Therefore, the spirit and scope of the
appended claims should not be limited to the description of the
versions contained therein.
* * * * *