U.S. patent application number 10/961724 was filed with the patent office on 2006-02-23 for fluorescent poly(alkylene terephthalate) compositions.
Invention is credited to Gyorgyi Fenyvesi, Joseph V. Kurian.
Application Number | 20060041039 10/961724 |
Document ID | / |
Family ID | 35910490 |
Filed Date | 2006-02-23 |
United States Patent
Application |
20060041039 |
Kind Code |
A1 |
Fenyvesi; Gyorgyi ; et
al. |
February 23, 2006 |
Fluorescent poly(alkylene terephthalate) compositions
Abstract
Fluorescent poly(alkylene terephthalate) compositions are
provided. The fluorescent poly(alkylene terephthalate) compositions
contain fluorescent poly(alkylene terephthalate)s and are made from
fluorescent compounds and poly(alkylene terephthalate) oligomers,
or by polymerizing amine and acid monomers in the presence of
fluorescent compounds.
Inventors: |
Fenyvesi; Gyorgyi;
(Wilmington, DE) ; Kurian; Joseph V.; (Hockessin,
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: |
35910490 |
Appl. No.: |
10/961724 |
Filed: |
October 8, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60603064 |
Aug 20, 2004 |
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Current U.S.
Class: |
524/107 |
Current CPC
Class: |
C08K 5/0041
20130101 |
Class at
Publication: |
524/107 |
International
Class: |
C08K 5/15 20060101
C08K005/15 |
Claims
1. A fluorescent poly(trimethylene terephthalate) composition
comprising: at least one fluorescent compound, and a
poly(trimethylene terephthalate) oligomer or polymer.
2. The composition of claim 1, wherein said composition comprises a
blend comprising at least one of poly(trimethylene terephthalate)
and at least one other polymer.
3. The composition of claim 2 wherein said other polymer is a
polyester.
4. The composition of claim 2 wherein said other polymer is
selected from poly(ethylene terephthalate), nylon 6, nylon 6,6, and
poly(tetramethylene terephthalate).
5. The composition of claim 2 wherein said blend contains 70 mole %
or more of the poly(trimethylene terephthalate).
6. The composition of claim 1, wherein said oligomer comprises, as
a monomer unit thereof, said fluorescent compound.
7. The composition of claim 1, wherein said fluorescent compound is
a monomer and is copolymerized with one or more other monomers to
form a fluorescent oligomer.
8. The composition of claim 4, wherein said poly(trimethylene
terephthalate) comprises, as a polymerized unit, said fluorescent
monomer.
9. The composition of claim 1, comprising the poly(trimethylene
terephthalate) polymer, the poly(trimethylene terephthalate)
polymer having an inherent viscosity of about 0.85 to about 1.2
dL/g.
10. The composition of claim 1 wherein said fluorescent compound is
selected from coumarins, flavones, and derivatives thereof.
11. The composition of claim 1 wherein said fluorescent compound is
selected from: 1,2-disubstituted benzopyrones,
7-hydroxybenzopyrones, 10-carboxybenzopyrones, and
trihydroxybenzopyrones.
12. The composition of claim 11 wherein said fluorescent compound
is selected from: 6-hydroxy-flavone
[6-hydroxy-2-phenyl-4-benzopyrone]; 7-hydroxy-4-methylcoumarin
[2H-1-benzopyran-2-one, 7-hydroxy-4-methyl-]; 3-hydroxyflavone
[4H-1-benzopyran-4-one, 3-hydroxy-2-phenyl-];
3,5,7-trihydroxyflavone [3,5,7-trihydroxy-2-phenyl-4-benzopyrone,
4H-1-benzopyran-4-one, 3,5,7-trihydroxy-2-phenyl-];
4',5,7-trihydroxyflavone
[5,7-dihydroxy-2-(4-hydroxyphenyl)-4-benzopyrone,
4H-1-benzopyran-4-one, 5,7-dihydroxy-2-(4-hydroxyphenyl)];
5,7,4'-trihydroxy-4'-methoxyflavone
[5,7-dihydroxy-2-(4-hydroxy-3-methoxyphenyl)-4-benzopyrone];
coumarin 314
[1H,5H,11H-[1]-benzopyrano[6,7,8-ij]quinolizine-10-carboxylic acid,
2,3,6,7-tetrahydro-11-oxo-, ethyl ester]; coumarin 343
[1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizine-10-carboxylic acid,
2,3,6,7-tetrahydro-11-oxo-]; 4-methylesculetin
[2H-1-benzopyran-2-one, 6,7-dihydroxy-4-methyl-];
4-methyl-7-aminocoumarin [2H-1-benzopyran-2-one, 7-amino-4-methyl];
and 7-hydroxy-4-(trifluoromethyl)coumarin [2H-1-benzopyran-2-one,
7-hydroxy-4-(trifluoromethyl)-].
13. A fiber comprising the composition of claim 1.
14. An oriented fiber according to claim 13.
15. A bicomponent fiber according to claim 13.
16. A multicomponent fiber according to claim 13.
17. A fabric comprising a fiber according to claim 13.
18. A carpet fiber according to claim 13.
19. A textile fiber according to claim 13.
20. A monofilament fiber according to claim 13.
21. A nonwoven fiber article comprising a fiber according to claim
13.
22. A molded article comprising the composition of claim 1.
23. A film comprising the composition of claim 1.
24. An engineering plastic comprising the composition of claim
1.
25. A powder coating comprising the composition of claim 1.
26. A process for making a fluorescent composition comprising a
fluorescent oligomer comprising: providing 1,3-propanediol and
diacids, esters or diesters; and combining said one or more
1,3-propanediol and diacids, esters or diesters and a fluorescent
compound, under conditions to form an oligomer, to form said
fluorescent oligomer.
27. The process of claim 26 wherein said diacids, esters or
diesters is said diacids, and said diacids are selected from
isophthalic acid; 1,4-cylohexanedicarboxylic acid;
2,6-naphthalenedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid;
succinic acid; glutaric acid; adipic acid; sebacic acid;
1,12-dodecanedioic acid; and derivatives thereof.
28. (canceled)
29. The process of claim 26, further comprising melt blending said
fluorescent oligomer with a poly(alkylene terephthalate) to provide
a fluorescent poly(alkylene terephthalate).
30. The process of claim 29 wherein said poly(alkylene
terephthalate) comprises poly(trimethylene terephthalate).
31. The process of claim 30 wherein the amount of said fluorescent
compound is at least about 5 mg/kg of poly(alkylene
terephthalate).
32. The process of claim 30 wherein the amount of said fluorescent
compound is at least about 10 mg/kg of poly(alkylene
terephthalate).
33. The process of claim 30 wherein the amount of said fluorescent
compound is at least about 50 mg/kg of poly(alkylene
terephthalate).
34. The process of claim 30 wherein the amount of said fluorescent
compound is at least about 60 mg/kg of poly(alkylene
terephthalate).
35. The process of claim 30 wherein the amount of said fluorescent
compound is about 20,000 mg/kg of poly(alkylene terephthalate) or
less.
36. The process of claim 30 wherein the amount of said fluorescent
compound is about 10,000 mg/kg of poly(alkylene terephthalate) or
less.
37. The process of claim 30 wherein the amount of said fluorescent
compound is about 5,000 mg/kg of poly(alkylene terephthalate).
38. The process of claim 30 wherein the amount of fluorescent
compound is from about 0.6% to about 20% by weight, based on the
total combined weight of fluorescent oligomer and poly(alkylene
terephthalate).
39. The process of claim 30 wherein the amount of fluorescent
compound is from about 0.6% to about 15% by weight, based on the
total combined weight of fluorescent oligomer and polyester.
40. The process of claim 30 wherein the amount of fluorescent
compound is from about 0.6% to about 10% by weight, based on the
total combined weight of fluorescent oligomer and polyester.
41. The process of claim 30 wherein the fluorescent compound is
selected from coumarins, flavones and derivatives thereof.
42. The process of claim 26, wherein said process is carried out in
the presence of an inorganic acid.
43. The process of claim 26, wherein said process is carried out at
a temperature of about 200.degree. C. or less.
44. The process of claim 26 wherein the fluorescent compound is
selected from: 1,2-disubstituted benzopyrones,
7-hydroxybenzopyrones, 10-carboxybenzopyrones, and
trihydroxybenzopyrones.
45. The process of claim 26 wherein said fluorescent compound is
selected from: 1,2-disubstituted benzopyrones,
7-hydroxybenzopyrones, 10-carboxybenzopyrones, and
trihydroxybenzopyrones. Preferred fluorescent compounds are
6-hydroxy-flavone [6-hydroxy-2-phenyl-4-benzopyrone];
7-hydroxy-4-methylcoumarin [2H-1-benzopyran-2-one,
7-hydroxy-4-methyl-]; 3-hydroxyflavone [4H-1-benzopyran-4-one,
hydroxy-2-phenyl-1; 3,5,7-trihydroxyflavone
[3,5,7-trihydroxy-2-phenyl-4-benzopyrone, 4H-1-benzopyran-4-one,
3,5,7-trihydroxy-2-phenyl-]; 4',5,7-trihydroxyflavone
[5,7-dihydroxy-2-(4-hydroxyphenyl)-4-benzopyrone,
4H-1-benzopyran-4-one, 5,7-dihydroxy-2-(4-hydroxyphenyl];
5,7,4'-trihydroxy-3'-methoxyflavone
(5,7-dihydroxy-2-(4-hydroxy-3-methoxyphenyl)-4-benzopyrone];
coumarin 314
[1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizine-10-carboxylic acid,
2,3,6,7-tetrahydro-11-oxo-, ethyl ester]; coumarin 343
[1H,5H,11H-[1]benzopyrano[6,7,8-ij]-quinolizine-10-carboxylic acid,
2,3,6,7-tetrahydro-11-oxo-]; 4-methylesculetin
[2H-1-benzopyran-2-one, 6,7-dihydroxy-4-methyl-];
4-methyl-7-aminocoumarin [2H-1-benzopyran-2-one,
7-amino-4-methyl-]; and 7-hydroxy-4-(trifluoromethyl)coumarin
[2H-1-benzopyran-2-one, 7-hydroxy-4-(trifluoromethyl)-].
46. A process for making a fluorescent poly(trimethylene
terephthalate) composition comprising: providing a fluorescent
compound and a poly(trimethylene terephthalate) oligomer; and
contacting said fluorescent compound with said poly(trimethylene
terephthalate) oligomer in an inert environment at a temperature of
about 240.degree. C. to about 255.degree. C., to form a mixture,
and allowing said mixture to polymerize, forming said fluorescent
poly(trimethylene terephthalate).
47. The process of claim 46, further comprising applying vacuum to
said mixture.
48. The process of claim 46 wherein the amount of said fluorescent
compound is at least about 5 mg/kg of poly(trimethylene
terephthalate).
49. The process of claim 46 wherein the amount of said fluorescent
compound is at least about 10 mg/kg of poly(trimethylene
terephthalate).
50. The process of claim 46 wherein the amount of said fluorescent
compound Is at least about 50 mg/kg of poly(trimethylene
terephthalate).
51. The process of claim 46 wherein the amount of said fluorescent
compound is at least about 60 mg/kg of poly(trimethylene
terephthalate).
52. The process of claim 46 wherein the amount of said fluorescent
compound is about 20,000 mg/kg of poly(trimethylene terephthalate)
or less.
53. The process of claim 46 wherein the amount of said fluorescent
compound is about 10,000 mg/kg of poly(trimethylene terephthalate)
or less.
54. The process of claim 46 wherein the amount of said fluorescent
compound is about 5,000 mg/kg of poly(trimethylene terephthalate).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. .sctn.119
from U.S. Provisional Application Ser. No. 60/603,064 (filed Aug.
10, 2004), which is incorporated by reference herein for all
purposes as if fully set forth.
FIELD OF THE INVENTION
[0002] This invention relates to fluorescent compositions
comprising a poly(alkylene terephthalate), such as a
poly(trimethylene terephthalate), poly(ethylene terephthalate)
and/or poly(tetramethylene terephthalate), and one or more
fluorescent poly(alkylene terephthalate) or polyamide oligomers.
The fluorescent poly(alkylene terephthalate) or polyamide oligomers
can be prepared from one or more amines, diols, acids and
fluorescent compounds, or from one or more polyester oligomers and
one or more fluorescent compounds. The compositions are suitable
for use in manufacturing polyester fibers, fabrics, films and other
shaped articles and as markers for such fibers, fabrics, films and
other shaped articles.
BACKGROUND
[0003] Polyesters, especially poly(alkylene terephthalate)s, have
excellent physical and chemical properties and have been widely
used for resins, films and fibers. In particular, polyester fibers
have a high melting point, and can attain high orientation and
crystallinity. Accordingly, polyesters have properties that are
highly desirable in fibers, such as chemical, heat and light
stability, and high strength. The term poly(alkylene terephthalate)
is well known to those skilled in the art, and encompasses, for
example, poly(trimethylene terephthalate), poly(tetramethylene
terephthalate), and poly(ethylene terephthalate). Poly(trimethylene
terephthalate), also called poly(1,3-propyleneterephthalate) is
prepared from terephthalic acid, or an ester thereof, and
1,3-propylene glycol (1,3-propanediol). The abbreviation "3GT" is
also used to refer to poly(trimethylene terephthalate).
Poly(tetramethylene terephthalate), also called poly(butylene
terephthalate) or 4GT, is prepared from terephthalic acid or an
ester thereof and 1,4-butanediol.
[0004] Some fluorescent polymers and oligomers are known. For
Example, Weaver et al., in U.S. Pat. No. 5,091,501 discloses the
conversion of certain cinnamic acid derivatives, under
polyester-forming conditions and in the presence of suitable diol
and acidic monomers, to form coumarin-containing polyesters. The
diol and acidic monomers included 1,3-propanediol and terephthalic
acid.
[0005] Krutak et al., in WO92/07913, describe polyester powders
containing copolymerized therein at least 1% of a visible colorant.
The colorant is introduced in solution in an organic solvent.
[0006] DiPietro in U.S. Pat. No. 6,103,006 discloses a fluorescent
dye comprising: 3,4-benzoxanthrene dicarboxylic anhydride or the
diacid (BXDA), a monomer having at least one carboxyl group, and a
second monomer having at least one amine group or at least one
alcohol group.
[0007] New and/or improved fluorescent polyesters are desirable.
Fluorescent polyesters suitable for use in making fibers are also
desirable. The present invention is directed to these and other
important ends.
SUMMARY OF THE INVENTION
[0008] One aspect of the present invention is a fluorescent
poly(alkylene terephthalate) composition comprising a fluorescent
compound and a poly(alkylene terephthalate). In some embodiments,
the fluorescent compound can be in the form of a preformed
polyamide or a preformed polyester oligomer, which can be made by
blending or coextruding the fluorescent compound with a
poly(alkylene terephthalate). In some embodiments, the fluorescent
poly(alkylene terephthalate) composition can be made by preblending
a fluorescent compound with a carrier polymer that is subsequently
blended with a poly(alkylene terephthalate). The fluorescent
poly(alkylene terephthalate) composition can be prepared by batch
or continuous processes.
[0009] In some embodiments, the intrinsic viscosity (IV) of the
fluorescent polymeric composition can be increased by solid phase
polymerization, a process comprising heating the polymer to an
elevated temperature that is below the melting point of the
polymeric composition, optionally in a vacuum.
[0010] In some embodiments, the fluorescent poly(alkylene
terephthalate) composition is prepared by melt blending the
fluorescent poly(alkylene terephthalate) with one or more polymers
at a temperature within the range of 230-290.degree. C. In some
embodiments in which the poly(alkylene terephthalate) is
poly(ethylene terephthalate), the temperature is preferably within
the range of 255-290C.degree.. In some embodiments in which the
poly(alkylene terephthalate) is poly(trimethylene terephthalate),
the temperature is preferably within the range of 240-255.degree.
C. In some embodiments in which the poly(alkylene terephthalate) is
poly(tetramethylene terephthalate), the temperature is preferably
within the range of 230-250.degree. C.
[0011] Another aspect of the invention is a process for making a
fluorescent poly(alkylene terephthalate) composition, which
includes contacting one or more amine monomers, acids, diols,
diacids, esters or diesters and one or more fluorescent compounds,
optionally in the presence of an inorganic acid, optionally in the
presence of water, and preferably at a temperature of about
200.degree. C. or less, to form a fluorescent oligomer. For
example, about 3 to 15 parts by weight of water is preferred, when
an inorganic acid is present, based on the weight of the solid
inorganic acid. The oligomer can be blended with a poly(alkylene
terephthalate). In some embodiments, the fluorescent compound is
copolymerized in the process as a monomer unit within the
fluorescent oligomer.
[0012] In some embodiments, the oligomer can be blended with one or
more polymers to form a fluorescent poly(alkylene terephthalate)
composition. In some embodiments, the oligomer can be further
polymerized to form the fluorescent poly(alkylene terephthalate)
composition.
[0013] A further aspect of the invention is a process for making a
fluorescent poly(alkylene terephthalate) composition, which
includes: providing one or more fluorescent compounds and at least
one poly(alkylene terephthalate) oligomer; contacting the
fluorescent compound with the poly(alkylene terephthalate) oligomer
in an inert environment at a temperature of about 240.degree. C. to
about 255.degree. C. to form a mixture; and allowing the mixture to
polymerize, to form a polymeric fluorescent poly(alkylene
terephthalate) composition. In preferred embodiments, the
poly(alkylene terephthalate) oligomer is selected from:
poly(trimethylene terephthalate) oligomer, poly(ethylene
terephthalate) oligomer and poly(tetramethylene terephthalate)
oligomer. In some embodiments the process further includes applying
vacuum to the mixture.
[0014] A further aspect of the invention is a process for making a
fluorescent poly(alkylene terephthalate) composition, which
includes blending at least one oligomer selected from
poly(trimethylene terephthalate), poly(ethylene terephthalate) and
poly(tetramethylene terephthalate) oligomers, with one or more
fluorescent compounds in an inert environment at a temperature of
about 240.degree. C. to about 255.degree. C., to form a fluorescent
poly(alkylene terephthalate) oligomer. In some embodiments the
fluorescent poly(alkylene terephthalate) oligomer can be further
polymerized to form a fluorescent poly(alkylene terephthalate)
composition. In some embodiments, the fluorescent poly(alkylene
terephthalate) oligomer can be blended with a polymer to form a
fluorescent poly(alkylene terephthalate) composition.
[0015] The compositions can be made in batch or continuous
processes.
[0016] These and other aspects will be apparent to persons skilled
in the art in view of the present disclosure and the appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIGS. 1-3 show excitation and emission spectra prepared
using Test Method 2 (Fluorescent Spectra Analysis, below). Spun
fibers were used in each case. In each Figure, Curve 1 is the
excitation profile for the fluorescent poly(trimethylene
terephthalate) containing the fluorescent compound; Curve 2 is the
excitation profile for the control poly(trimethylene terephthalate)
without the fluorescent compound; Curve 3 is the emission spectrum
of the fluorescent poly(trimethylene terephthalate) containing the
fluorescent compound; and Curve 4 is the emission spectrum for the
control poly(trimethylene terephthalate) without the fluorescent
compound.
[0018] FIG. 1 shows the excitation profile and emission spectra of
a fluorescent polymer prepared using the fluorescent oligomer
poly(dimethyl adipate/methyl-bis-hexamethylene
triamine/3-hydroxyflavone) and poly(trimethylene terephthalate),
compared to poly(trimethylene terephthalate) without the
fluorescent oligomer.
[0019] FIG. 2 shows the excitation profile and emission spectra of
a fluorescent polymer prepared using the fluorescent oligomer
poly(dimethyl adipate/methyl-bis-hexamethylene
triamine/7-hydroxy-4-(trifluoromethyl)coumarin) and
poly(trimethylene terephthalate), compared to poly(trimethylene
terephthalate) without the fluorescent oligomer.
[0020] FIG. 3 shows the excitation profile and emission spectra of
a fluorescent polymer prepared using the fluorescent oligomer,
poly(dimethyl adipate/methyl-bis-hexamethylene
triamine/4,5,7-trihydroxyflavone) and poly(trimethylene
terephthalate), compared to poly(trimethylene terephthalate)
without the fluorescent oligomer.
DETAILED DESCRIPTION
[0021] The present invention provides fluorescent poly(alkylene
terephthalate) compositions comprising poly(alkylene
terephthalate)s; fibers, fabrics, films and other articles made
from the fluorescent poly(alkylene terephthalate) compositions
comprising poly(alkylene terephthalate)s; and processes for making
such compositions. The compositions can be made from a fluorescent
compound and one or more poly(alkylene terephthalate) oligomers or
polymers, or from a fluorescent compound and one or more amines,
acids, diols, diacids or esters.
[0022] In the absence of an indication to the contrary, the term
"poly(alkylene terephthalate)" as used herein is meant to encompass
homopolymers and copolymers containing at least about 70 mole %
alkylene terephthalate repeat units and compositions, e.g., blends,
containing at least about 70 mole % of poly(alkylene terephthalate)
homopolymers or copolyesters based on the total number of moles of
the diol and diacid components of the polymers. The poly(alkylene
terephthalate) can contain minor amounts of other comonomers, and
such comonomers are preferably selected so that they do not have
significant adverse affect on properties. Such other comonomers
include 5-sodium-sulfoisophthalate, for example, at a level in the
range of about 0.2 to about 5 mole %. Minor amounts of
trifunctional comonomers, such as, for example trimellitic acid in
an amount less than about 5 mole %, can be incorporated for
viscosity control.
[0023] While it is not intended that the present invention be bound
by any particular theory, it is believed that the fluorescent
compound can act as a chain terminator at a temperature of about
200.degree. C. or less by reacting with free carboxylic acid end
groups present in the oligomers, esters and acids used in the
preparation of the fluorescent compositions. While the fluorescent
oligomer may have an intrinsic viscosity (IV) that is undesirably
low for satisfactory spinning, in contrast to conventional
fluorescent compounds, it is stable enough to be compounded into
poly(alkylene terephthalate) and the poly(alkylene terephthalate)
so compounded can be spun at temperatures of about 265.degree.
C.
[0024] When an amount, concentration, or other value or parameter
is recited herein as either a range, preferred range or a list of
upper preferable values and lower preferable values, the recited
amount, concentration, or other value or parameter is intended to
include all ranges formed from any pair of any upper range limit or
preferred value and any lower range limit or preferred value,
regardless of whether such ranges are separately disclosed. Where a
range of numerical values is recited herein, unless otherwise
stated, the range is intended to include the endpoints thereof, and
all integers and fractions within the range. It is not intended
that the scope of the invention be limited to the specific values
recited when defining a range.
[0025] Compounding of a fluorescent oligomer with a polymer can be
carried out by melt blending. The preferred temperature for melt
blending, as well as for other processes such as spinning, depends
upon properties of the poly(alkylene terephthalate), particularly
its melting point and molecular weight. The processes disclosed
herein that include melt blending of a fluorescent compound or
oligomer with a polymer can be desirably carried out at
temperatures from about 200 to about 290.degree. C. More
specifically, preferred melt blending temperatures are
255-290.degree. C. for poly(ethylene terephthalate), and
240-255.degree. C. for poly(trimethylene terephthalate) and
poly(tetramethylene terephthalate). Preferred melt blending
temperatures are about 275-290.degree. C. for poly(ethylene
terephthalate), and about 255-265.degree. C. for poly(trimethylene
terephthalate) and poly(tetramethylene terephthalate).
[0026] The number average molecular weight, M.sub.n, of a
poly(alkylene terephthalate) polymer for use in the processes
disclosed herein is preferably at least about 15,000, more
preferably at least about 18,000, and is preferably about 40,000 or
less, more preferably about 35,000 or less. When the poly(alkylene
terephthalate) is poly(ethylene terephthalate), the M.sub.n is even
more preferably in a range of from about 15,000 to about 25,000,
with a M.sub.n of about 25,000 still more preferred. For
poly(trimethylene terephthalate), the M.sub.n is even more
preferably in a range of from about 25,000 to about 35,000, with a
M.sub.n range of from about 28,000 to about 29,000 still more
preferred. For poly(tetramethylene terephthalate), the M.sub.n is
more preferably in a range of from about 25,000 to about 35,000,
with a M.sub.n of about 27,000 still more preferred.
[0027] The term "fluorescent compound" as used herein means a
non-polymeric compound, including monomers, having a fluorescent
moiety.
[0028] The term "fluorescent oligomer" as used herein means a
polyamide oligomer, poly(trimethylene terephthalate) oligomer,
poly(ethylene terephthalate) oligomer, or poly(tetramethylene
terephthalate) oligomer prepared from monomers in the presence of
one or more fluorescent compounds. The term "poly(alkylene)
terephthalate" is also used herein to encompass poly(trimethylene
terephthalate), poly(ethylene terephthalate), and
poly(tetramethylene terephthalate), when used to refer to oligomers
or polymers.
[0029] Polyamide and some poly(alkylene terephthalate) oligomers
typically have an IV within the range of about 0.2 dL/g to about
0.8 dL/g, which is undesirable for some uses such as, for example,
spinning, where an IV of at least about 0.85-1.2 dL/g is preferred.
The term "poly(trimethylene terephthalate) oligomer" is used herein
to refer to a poly(trimethylene terephthalate) preferably having an
IV less than about 0.8 dL/g. In making the present fluorescent
poly(alkylene terephthalate) compositions, poly(alkylene
terephthalate) oligomers are contacted with fluorescent compounds,
and subsequently heated to raise the IV to at least about 0.6 dL/g
and preferably at least about 0.8 dL/g.
[0030] The term "poly(trimethylene terephthalate)", when used alone
herein without further characterization, refers to a
poly(trimethylene terephthalate) having an IV of at least 0.85
dL/g, generally up to about 1.2 dL/g. The term "fluorescent
poly(trimethylene terephthalate)", as used herein, refers to a
blend of fluorescent oligomer and poly(trimethylene terephthalate),
or a poly(trimethylene terephthalate) having incorporated therein a
fluorescent compound or fluorescent oligomer. More generally, the
term "fluorescent poly(alkylene terephthalate)" is also used herein
to refer to poly(alkylene terephthalate)s having incorporated
therein a fluorescent compound or fluorescent oligomer, with the
same guidelines for IV as recited hereinabove in connection with
fluorescent poly(trimethylene terephthalate). The term
"incorporated therein" is not intended to require that the
fluorescent compound or fluorescent oligomer be necessarily
chemically bound to the poly(alkylene terephthalate), although such
chemical bonding is not outside the scope of the present
invention.
[0031] The weight proportion of fluorescent compound incorporated
(as the fluorescent compound itself or in a fluorescent oligomer)
in the fluorescent poly(alkylene terephthalate) is preferably at
least about 5 mg/kg of poly(alkylene terephthalate), more
preferably at least about 10 mg/kg of poly(alkylene terephthalate),
even more preferably at least about 50 mg/kg of poly(alkylene
terephthalate), and still more preferably at least about 60 mg/kg
of poly(alkylene terephthalate). Also, the weight proportion of
fluorescent compound incorporated (as the fluorescent compound
itself or in a fluorescent oligomer) in the fluorescent
poly(alkylene terephthalate) is preferably about 20,000 mg/kg of
poly(alkylene terephthalate) or less, more preferably about 10,000
mg/kg of poly(alkylene terephthalate) or less, and even more
preferably about 5,000 mg/kg of poly(alkylene terephthalate) or
less. Quantities of fluorescent compound greater than about 10,000
mg/kg can cause progressively increasing deterioration of the fiber
grade polymer properties, which may be evidenced by a lowered IV
and discoloration. Quantities less than about 10 mg/kg may not
fluoresce to a useful degree for some applications.
[0032] Fluorescent compounds suitable for use in making the
fluorescent poly(alkylene terephthalate) compositions include
coumarins, flavones, and derivatives thereof. Examples of suitable
fluorescent compounds include 1,2-disubstituted benzopyrones,
7-hydroxybenzopyrones, 10-carboxybenzopyrones, and
trihydroxybenzopyrones. Preferred fluorescent compounds are
6-hydroxy-flavone [6-hydroxy-2-phenyl-4-benzopyrone];
7-hydroxy-4-methylcoumarin [2H-1-benzopyran-2-one,
7-hydroxy-4-methyl-]; 3-hydroxyflavone [4H-1-benzopyran-4-one,
3-hydroxy-2-phenyl-]; 3,5,7-trihydroxyflavone
[3,5,7-trihydroxy-2-phenyl-4-benzopyrone, 4H-1-benzopyran-4-one,
3,5,7-trihydroxy-2-phenyl-]; 4',5,7-trihydroxyflavone
[5,7-dihydroxy-2-(4-hydroxyphenyl)-4-benzopyrone,
4H-1-benzopyran-4-one, 5,7-dihydroxy-2-(4-hydroxyphenyl)-];
5,7,4'-trihydroxy-3'-methoxyflavone
[5,7-dihydroxy-2-(4-hydroxy-3-methoxyphenyl)-4-benzopyrone];
coumarin 314
[1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizine-10-carboxylic acid,
2,3,6,7-tetrahydro-11-oxo-, ethyl ester]; coumarin 343
[1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizine-10-carboxylic acid,
2,3,6,7-tetrahydro-11-oxo-]; 4-methylesculetin
[2H-1-benzopyran-2-one, 6,7-dihydroxy-4-methyl-];
4-methyl-7-aminocoumarin [2H-1-benzopyran-2-one,
7-amino-4-methyl-]; and 7-hydroxy-4-(trifluoromethyl)coumarin
[2H-1-benzopyran-2-one, 7-hydroxy-4-(trifluoromethyl)-].
[0033] In a first embodiment, which can be carried out as a
two-step process, a fluorescent polyamide oligomer is prepared by
contacting a fluorescent compound with one or more amine monomers
and one or more diacid and/or ester monomers, e.g., acids, diols,
diacids, aromatic and aliphatic esters and diesters, optionally in
the presence of an inorganic acid, at an elevated temperature,
preferably at least about 170.degree. C. Also preferably, the
temperature is less than about 200.degree. C. Volatiles can be
stripped by applying vacuum. The fluorescent oligomers thus
produced are polyamides and contain from about 0.6% to about 20%,
preferably up to about 15%, and more preferably up to about 10%, of
the fluorescent compound based on the weight of the polyamide.
[0034] Examples of diols useful in the processes disclosed herein
include ethylene glycol; diethylene glycol; triethylene glycol;
1,2-propanediol; 1,3-propanediol; 1,3-butanediol; 1,4-butanediol;
1,5-pentanediol; 1,6-hexanediol; 1,2-, 1,3- and 1,4
cyclohexanedimethanol; and the longer chain diols and polyols made
by the reaction of diols or polyols with alkylene oxides. Examples
of diacids useful in the processes disclosed herein include
isophthalic acid; 1,4-cyclohexanedicarboxylic acid;
2,6-naphthalenedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid;
succinic acid; glutaric acid; adipic acid; sebacic acid;
1,12-dodecanedioic acid; and derivatives thereof such as the
dimethyl, diethyl, or dipropyl esters of the dicarboxylic
acids.
[0035] Examples of suitable inorganic acids are mineral acids such
as phosphoric acid, pyrophosphoric acid, and phosphorous acid.
Phosphorous acid is preferred.
[0036] Examples of suitable amine monomers include diamines, such
as hexamethylene diamine and bis(hexamethylene triamine). Other
amine monomers known to those skilled in the art for use in making
polymers can be used.
[0037] Suitable diesters include aromatic and aliphatic esters such
as, for example, dimethyl adipate, dimethyl terephthalate, dimethyl
isophthalate, dimethyl naphthalate and mixtures thereof.
[0038] The fluorescent polyamide oligomer can then be melt blended
with a poly(alkylene terephthalate) (as defined hereinabove), to
provide a fluorescent poly(alkylene terephthalate) polymer. The
amount of fluorescent polyamide oligomer used is an amount
sufficient to form a fluorescent poly(alkylene terephthalate)
polyester comprising about 5-20,000 mg/kg of fluorescent compound
in the polyester, preferably from about 50-10,000 mg/kg, and most
preferably from about 60-5,000 mg/kg. The ratio of the amount of
the fluorescent oligomer to poly(alkylene terephthalate) thus
depends on the concentration of the fluorescent compound in the
fluorescent oligomer and the desired concentration of fluorescent
compound in the fluorescent poly(alkylene terephthalate). While the
desirable amount of fluorescent compounds can vary, it is generally
advantageous that the amount of fluorescent oligomer be from about
0.5% to about 10% fluorescent oligomer by weight, based on the
total combined weight of fluorescent oligomer and poly(alkylene
terephthalate). Poly(trimethylene terephthalate) is a preferred
poly(alkylene terephthalate).
[0039] In another embodiment, which can be carried out as a
two-step process, a fluorescent poly(alkylene terephthalate)
oligomer, preferably poly(trimethylene terephthalate), is prepared
by contacting a fluorescent compound with poly(alkylene
terephthalate) oligomer. This embodiment is generally preferred for
use with oligomers having melting points less than about
240.degree. C., and/or IV less than 0.8. If desired, the IV can be
raised by subjecting the oligomer to heat and vacuum in a process
known to those skilled in the art as "solid phase polymerization."
In a preferred embodiment of such a process, the oligomer is heated
at a temperature about 20.degree. C. below its melting point, e.g.,
about 200.degree. C. to about 220.degree. C., in a vacuum oven at a
vacuum of about 300 mm Hg (39 kPa) under a slow nitrogen stream.
Solid-phase polymerization can raise the intrinsic viscosity to
about 1.0 dL/g or higher for subsequent spinning of fibers. It is
preferred that the poly(alkylene terephthalate) have an IV of about
1.2 or less for ease of processing and spinning, while
poly(alkylene terephthalate)s having an IV of about 0.85 or lower
may not have desirable fiber properties.
[0040] In one embodiment of a solid phase polymerization process
for making a fluorescent poly(alkylene terephthalate) polymer, a
poly(alkylene terephthalate) oligomer is contacted with the
fluorescent compound in an inert environment at temperatures above
the melting point of the oligomer, preferably no higher than about
240.degree. C., to form a reaction mixture containing the
fluorescent compound and the poly(alkylene terephthalate) oligomer.
By "inert environment" is meant in an atmosphere containing or
consisting of an inert gas such as nitrogen. The reaction mixture
is then stripped of volatiles under vacuum to form a reaction
product, which is a fluorescent poly(alkylene terephthalate)
oligomer.
[0041] The fluorescent poly(alkylene terephthalate) oligomer can be
melt blended with a preformed poly(alkylene terephthalate) polymer
to form a fluorescent poly(alkylene terephthalate) composition that
comprises a fluorescent poly(alkylene terephthalate) oligomer
blended with a poly(alkylene terephthalate) polymer. For example,
if a fluorescent poly(trimethylene terephthalate) oligomer is
blended with poly(trimethylene terephthalate) polymer, the
composition comprises a fluorescent poly(trimethylene
terephthalate) oligomer blended with a poly(trimethylene
terephthalate) polymer. In some embodiments, two or more different
poly(alkylene terephthalate)s can be used, i.e., blended together
with a fluorescent oligomer. Concentrations of the fluorescent
compound in the fluorescent oligomer and fluorescent
poly(trimethylene terephthalate) are as disclosed hereinabove.
[0042] In another embodiment, a preformed poly(alkylene
terephthalate) polymer is directly blended with a fluorescent
compound to form a fluorescent poly(alkylene terephthalate). In
preferred embodiments, poly(trimethylene terephthalate) is blended
with a fluorescent compound to form a fluorescent poly(trimethylene
terephthalate). The concentration of the fluorescent compound is as
disclosed above.
[0043] In another embodiment, the fluorescent compound can be
blended with a carrier polymer. Carrier polymers include, for
example, aliphatic and aromatic polyesters, polyamides, polyolefins
such as polyethylene and polypropylene, polyacrylates and
polymethacrylates, and polystyrene and copolymers of polystyrene.
The blended fluorescent compound and carrier polymer are then melt
blended or coextruded with a poly(alkylene terephthalate), such as
poly(ethylene terephthalate), poly(trimethylene terephthalate), or
poly(tetramethylene terephthalate), to yield a fluorescent
poly(alkylene terephthalate). The carrier polymer and fluorescent
compound can be blended with a poly(trimethylene terephthalate) to
form a fluorescent poly(trimethylene terephthalate), containing a
concentration of the fluorescent compound as disclosed above.
Alternatively, a fluorescent poly(alkylene terephthalate)
prepolymer, having a number average molecular weight (M.sub.n), for
example, from about 1,000 to about 10,000, can be prepared and
added to a batch or continuous polymerization, or added to
preformed polymer pellets. Solid phase polymerization can be
carried out, as disclosed hereinabove.
[0044] The fluorescent poly(alkylene terephthalate)s formed
according to the processes disclosed herein can be melt-processed
using conventional temperatures and procedures to produce desired
fibers, fabrics, films, and other useful products. Products made
from the fluorescent poly(alkylene terephthalate)s, when viewed
under low wavelength ultraviolet light (e.g., about 365 nm or
longer), fluoresce, enhancing the whiteness of polyester articles
made with delusterants (such as titanium dioxide) and enhancing the
color of polyester articles containing colorants. The whiteness and
color enhancement also brightens articles in daylight, due to
fluorescence following absorption of the UV components of daylight.
The effect is most pronounced when the article is viewed in "black
light". "Black light", as used herein, means ultraviolet (UV) light
having a wavelength of about 340 to 400 nm.
[0045] For spinning into fibers, the moisture content of the
fluorescent poly(alkylene terephthalate) is preferably less than
about 40 mg/kg polymer. Pellets of fluorescent poly(trimethylene
terephthalate) can be dried in a vacuum oven, for example, at about
120.degree. C., preferably for a minimum of about 16 hours. The
drying temperature and vacuum can be adjusted as necessary to
obtain the desired moisture content.
[0046] The fluorescent poly(alkylene terephthalate)s can also
contain conventional additives such as antioxidants, delusterants,
white pigments such as titanium dioxide and zinc oxide, colorants,
dyes, stabilizers, flame retardants, fillers such as calcium
carbonate, antimicrobial agents, antistatic agents, heat
stabilizers, viscosity boosters, extenders, processing aids, and
other functional additives known to those skilled in the art. For
example, TiO.sub.2 or other pigments can be added, as disclosed in
U.S. Pat. Nos. 3,671,379, 5,798,433 and 5,340,909, and in EP 699
700 and 847 960, and WO 00/26301, the disclosures of which are
incorporated herein by reference in their entirety. The fluorescent
polymers can be processed conventionally, into, for example, chips,
pellets, or flakes, of various sizes and shapes.
[0047] The fluorescent poly(alkylene terephthalate)s can be used in
the forms of films; fibers such as, for example; monofilaments,
bulk continuous fiber as used for carpet; staple fiber;
multifilament fibers; oriented and partially oriented fibers;
semi-drawn, spun drawn, textured, or fully-drawn yarns; and
products made therefrom, including apparel, carpets, woven and
nonwoven fabrics, nonwoven fiber, and shaped and molded articles,
including engineering plastic components.
[0048] The fluorescent poly(alkylene terephthalate)s in fiber form
can be used in knits, woven fabrics, and non-woven fabrics, and in
blends with wool, cotton, poly(alpha-hydroxyacid), and/or other
natural and synthetic fibers. The fluorescent poly(alkylene
terephthalate)s can be fabricated into films and shaped articles
including as engineering plastics, in powder coatings, and in
molded products including molded surfaces (e.g., molded articles
having a surface made from the fluorescent poly(alkylene
terephthalate), surface coatings and coatings for paper and paper
products. Such textile fabrics, fibers, films, and shaped articles
are useful as fabrics, floor coverings, wall coverings, display,
signs, designer garments, safety and emergency signs, advertising,
and merchandising.
[0049] The fluorescent poly(alkylene terephthalate)s can be
acid-dyeable as disclosed in U.S. Pat. No. 6,723,799 B2, the
disclosures of which are incorporated herein by reference.
[0050] In some embodiments, the fluorescent polymers are
substantially colorless. Colorless polymers are desired for some
applications, for example, in colorless, transparent or white
products. While fluorescence may improve the brightness of white
and some colored products, colored fluorescent polymers can distort
the color of colored products containing them.
[0051] Examples of copolymers that can be used in making the
fluorescent poly(alkylene terephthalate)s include copolyesters made
using 3 or more reactants, each having two ester forming groups.
For example, a copoly(alkylene terephthalate) can be used in which
the comonomer used to make the copolyester is selected from linear,
cyclic, and branched aliphatic dicarboxylic acids having 4-12
carbon atoms, such as, for example: butanedioic acid, pentanedioic
acid, hexanedioic acid, dodecanedioic acid, and
1,4-cyclo-hexanedicarboxylic acid; aromatic dicarboxylic acids
other than terephthalic acid and having 8-12 carbon atoms, such as,
for example isophthalic acid and 2,6-naphthalenedicarboxylic acid;
linear, cyclic, and branched aliphatic diols having 2-8 carbon
atoms, other than 1,3-propanediol, such as, for example:
ethanediol, 1,2-propanedio, 1,4-butanediol,
3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol,
2-methyl-1,3-propanediol, and 1,4-cyclohexanediol; aliphatic and
aromatic ether glycols having 4-10 carbon atoms, such as, for
example: hydroquinone bis(2-hydroxyethyl) ether; and poly(ethylene
ether) glycols having a molecular weight below about 460, including
diethylene ether glycol. The comonomer typically is present in the
copolyester at from about 0.5 to about 15 mole %, and can be
present in amounts up to 30 mole %.
[0052] Blends of poly(alkylene terephthalate)s can be used in the
process to make fluorescent poly(alkylene terephthalate)s, or
fluorescent poly(alkylene terephthalate)s made according to the
processes disclosed herein can be blended with other
non-fluorescent poly(alkylene terephthalate)s. Blends containing
poly(trimethylene terephthalate) can be made, preferably containing
about 70 mole % or more of poly(trimethylene terephthalate). For
example, poly(trimethylene terephthalate) can be admixed with up to
30 mole % of one or more polyesters made from other diols or
diacids. Also useful are polymeric compositions and copolymers
comprising one or more functional additives or monomers.
[0053] In some preferred embodiments, blends are made that contain
at least about 70 mole % poly(alkylene terephthalate) and one or
more other polymers. For example, poly(trimethylene terephthalate)
can be blended with other polymers such as poly(ethylene
terephthalate), nylon 6, nylon 6,6, poly(tetramethylene
terephthalate). Preferably, blends contain 70 mole % or more
poly(trimethylene terephthalate), more preferably at least 80, 90,
95 or 99 mole % poly(trimethylene terephthalate). However, in some
embodiments, blends can be made that contain 70 mole % or more,
such as at least 80, 90, 95 or 99 mole % poly(ethylene
terephthalate). In some embodiments, blends contain 70 mole % or
more, such as at least 80, 90, 95 or 99 mole % poly(tetramethylene
terephthalate). In other embodiments, blends are made that contain
70 mole % or more, preferably at least 80, 90, 95 or 99 mole % of
two or more poly(alkylene terephthalate)s, which can include
poly(trimethylene terephthalate). Blends can be made of the
fluorescent poly(alkylene terephthalate)s and polystyrenes, for
example, as disclosed in U.S. Patent Application Serial No.
2004/0001950 A1.
[0054] The fluorescent poly(alkylene terephthalate) can be blended
with up to 30 mole percent of one or more other polymers. Examples
are polyesters prepared from other diols, such as those disclosed
above. Polymeric additives can be added to improve strength, to
facilitate post extrusion processing or provide other benefits. For
example, hexamethylene diamine can be added in minor amounts of
about 0.5 to about 5 mole % to add strength and processability to
the acid dyeable polyester compositions of the invention.
Polyamides such as Nylon 6 or Nylon 6,6 can be added in minor
amounts of about 0.5 to about 5 mole % to add strength and
processability to the acid-dyeable polyester compositions of the
invention. A nucleating agent, preferably 0.005 to 2 weight % of a
mono-sodium salt of a dicarboxylic acid selected from monosodium
terephthalate, mono sodium naphthalene dicarboxylate and mono
sodium isophthalate, can be added as disclosed in U.S. Pat. No.
6,245,844, which is incorporated herein by reference.
[0055] For some applications, particularly for spinning, the IV of
the fluorescent poly(ethylene terephthalate) is preferably at least
about 0.5 dL/g, more preferably at least about 0.8 dL/g, and even
more preferably at least about 0.85 dL/g. Also preferably, the IV
is about 1.2 dL/g or less, more preferably about 1.1 dL/g or less.
Poly(trimethylene terephthalate) homopolymers particularly useful
in making the fluorescent poly(trimethylene terephthalate)s have a
melting point of approximately 225-231.degree. C. Poly(alkylene
terephthalate)s having varied inherent viscosities are commercially
available, and can be selected and/or blended for particular
applications by one skilled in the art.
[0056] The fluorescent poly(alkylene terephthalate)s can be
manufactured by batch, semi-batch, continuous and other known
techniques. Poly(trimethylene terephthalate) and preferred
manufacturing techniques for making poly(trimethylene
terephthalate) are disclosed in U.S. Pat. Nos. 5,015,789,
5,276,201, 5,284,979, 5,334,778, 5,364,984, 5,364,987, 5,391,263,
5,434,239, 5,510454, 5,504,122, 5,532,333, 5,532,404, 5,540,868,
5,633,018, 5,633,362, 5,677,415, 5,686,276, 5,710,315, 5,714,262,
5,730,913, 5,763,104, 5,774,074, 5,786,443, 5,811,496, 5,821,092,
5,830,982, 5,840,957, 5,856,423, 5,962,745, 5,990,265, 6,235,948,
6,245,844, 6,255,442, 6,277,289, 6,281,325, 6,312,805, 6,325,945,
6,331,264, 6,335,421, 6,350,895, and 6,353,062, EP 998 440, WO
00/14041 and 98/57913, H. L. Traub, "Synthese und textilchemische
Eigenschaften des Poly-Trimethyleneterephthalats", Dissertation
Universitat Stuttgart (1994), S. Schauhoff, "New Developments in
the Production of Poly(trimethylene terephthalate) (PTT)", Man-Made
Fiber Year Book (September 1996), and U.S. patent application Ser.
No. 10/057,497, all of which are incorporated herein by reference.
Continuous processes such as disclosed in U.S. Pat. No. 6,353,062,
and U.S. Pat. No. 6,538,076, which are incorporated herein by
reference, are preferred. Similar techniques are used for
poly(ethylene terephthalate) and poly(tetramethylene
terephthalate).
[0057] In some embodiments, when the fluorescent polymers are made
into yarns, the yarns are partially oriented. Partially oriented
yarns of poly(trimethylene terephthalate) are disclosed in U.S.
Pat. Nos. 6,287,688 and 6,333,106, and U.S. Patent Publication No.
2001/30378, all of which are incorporated herein by reference. The
basic steps of manufacturing partially oriented yarns including
spinning, interlacing and winding poly(trimethylene terephthalate)
filaments are disclosed therein. Spinning can be practiced using
methods conventionally used for making partially oriented polyester
yarns.
[0058] Multicomponent fibers can be formed from the fluorescent
polymers, for example, bicomponent fibers comprising fluorescent
poly(ethylene terephthalate) and fluorescent poly(trimethylene
terephthalate), fluorescent poly(ethylene terephthalate) and
fluorescent poly(tetramethylene terephthalate) or two different
fluorescent poly(trimethylene terephthalate)s may contain color
pigment in one or both components. The components can be arranged
in a sheath-core, eccentric sheath-core, or side-by-side
arrangement. When it is desired that the bicomponent fiber is
crimpable on drawing, heat-treating, and relaxing to form a
stretchable fiber, an eccentric sheath-core or side-by-side
relationship can be used; side-by-side is preferred for higher
crimp levels. The preferred 2GT/poly(trimethylene terephthalate)
bicomponent fibers can be manufactured as disclosed in copending
U.S. patent application Ser. Nos. 09/708,314 and 09/758,309 which
are incorporated herein by reference.
EXAMPLES
Test Methods
[0059] The following test methods were used in the evaluation of
fluorescent polymers.
Test Method 1. Intrinsic Viscosity
[0060] The intrinsic viscosity (IV) was determined using viscosity
measured with a Viscotek Forced Flow Viscometer Y900 (Viscotek
Corporation, Houston, Tex.) for the poly(trimethylene
terephthalate) or poly(tetramethylene terephthalate) dissolved in
50/50 weight % trifluoroacetic acid/methylene chloride at a 0.4
grams/dL concentration at 19.degree. C. following an automated
method based on ASTM D 5225-92. These measured IV values were
correlated to IV values measured manually in 60/40 weight %
phenol/1,1,2,2-tetrachloroethane following ASTM D 4603-96.
Test Method 2. Fluorescent Spectra Analysis
[0061] Luminescence excitation and emission spectra were obtained
for the fluorescent fibers and on the fluorescent polymers prepared
as written in the Examples. A Fluorolog 322 instrument (Jobin Yvon
Inc/Edison/NJ) was used, the illumination parameters were 450 W
Xenon lamp, two 300 nm blazed gratings with 1200 lines/nm. Sample
parameters: no polarizers, 45.degree. quartz triangular cell solid
sample holder, and excitation 90.degree. to emission. Detection
parameters: two 500 nm blazed gratings 1200 lines/nm, Hamamatsu
R928 photomultiplier tube, 950V.
Example 1
[0062] A mixture of dimethyl adipate (61.8 g, 0.35 moles),
methyl-bis-hexamethylene triamine (82.0 g, 0.35 moles),
7-hydroxy-4-methyl-coumarin (1.270 g, 7.2.times.10.sup.-3 moles),
phosporous acid (0.54 g, 6.5.times.10.sup.-3 moles) and water (1.90
g, 0.11 moles) was heated slowly up to 200.degree. C. By-product
methanol was distilled from the system. Reduced pressure
(.about.0.4-0.5 mmHg, 53-67 Pa) was applied for approximately 10-15
minutes to complete the polymerization. The fluorescent polymer was
cooled under nitrogen.
[0063] A control polymer was prepared in the same way without the
fluorescent compound (7-hydroxy-4-methyl-coumarin). The polymers
were compared by fluorescence spectroscopy.
Example 2
[0064] A mixture of dimethyl adipate (43.4 g, 0.25 moles),
hexamethylene diamine (29.0 g, 0.25 moles),
7-hydroxy-4-methyl-coumarin (0.891 g, 5.06.times.10.sup.-3 moles),
phosporous acid (0.378 g, 4.61.times.10.sup.-3 moles) and water
(1.295 g, 0.07 moles) was heated slowly to 200.degree. C.
By-product methanol was distilled from the system. Reduced pressure
(.about.0.4-0.5 mmHg, 53-67 Pa) was applied for approximately 10-15
minutes to complete the reaction. The fluorescent polymer cooled
under nitrogen.
[0065] A control polymer was prepared in the same way without the
fluorescent compound (7-hydroxy-4-methyl-coumarin). The polymers
were compared by fluorescence spectroscopy.
Example 3
[0066] A mixture of dimethyl adipate (18.45 g, 0.11 moles),
methyl-bis-hexamethylene triamine (24.35 g, 0.11 moles),
6-hydroxyflavone (0.108 g, 4.5.times.10.sup.-4 moles was heated
slowly up to 190.degree. C. By-product methanol was distilled from
the system. Reduced pressure (.about.0.4-0.5 mmHg, 53-67 Pa) was
applied for approximately 10-15 minutes to complete the reaction
and to remove unreacted chemicals. The fluorescent polymer was
cooled under nitrogen.
[0067] A control polymer was prepared in the same way without the
fluorescent compound (6-hydroxyflavone). The polymers were compared
by fluorescence spectroscopy.
Example 4
[0068] A mixture of dimethyl adipate (36.9 g, 0.21 moles),
methyl-bis-hexamethylene triamine (48.7 g, 0.21 moles),
3-hydroxyflavone (0.295 g, 1.24.times.10.sup.-3 moles), phosporous
acid (0.424 g, 5.2.times.10.sup.-3 moles) and water (5.660 g, 0.31
moles) was heated slowly up to 200.degree. C. By-product methanol
was distilled from the system. Reduced pressure (.about.0.4-0.5
mmHg, 53-67 Pa) was applied for approximately 10-15 minutes to
complete the reaction and to remove unreacted chemicals. The
fluorescent polymer was cooled under nitrogen.
Example 5
[0069] A mixture of dimethyl adipate (54.75 g, 0.31 moles),
methyl-bis-hexamethylene triamine (72.62 g, 0.31 moles),
7-hydroxy-4-(trifluoromethyl)coumarin (0.735 g,
3.19.times.10.sup.-3 moles), phosporous acid (0.480 g,
5.85.times.10.sup.-3 moles) and water (2.157 g, 0.12 moles) was
heated slowly to 200.degree. C. By-product methanol was distilled
from the system. Reduced pressure (.about.0.4-0.5 mmHg, 53-67 Pa)
was applied for approximately 10-15 minutes to complete the
reaction. The fluorescent polymer was cooled under nitrogen.
Example 6
[0070] A mixture of dimethyl adipate (12.0 g, 0.068 moles),
methyl-bis-hexamethylene triamine (16.0 g, 0.069 moles),
7-hydroxy-4-methyl-coumarin (0.135 g, 7.66.times.10.sup.-4 moles),
phosporous acid (0.1 g, 1.22.times.10.sup.-3 moles) and water (0.4
g, 0.02 moles) was heated slowly to 200.degree. C. By-product
methanol was distilled from the system. Reduced pressure
(.about.0.4-0.5 mmHg, 53-67 Pa) was applied for approximately 10-15
minutes to complete the reaction. The fluorescent polymer was
cooled under nitrogen.
Example 7
[0071] A mixture of dimethyl adipate (12.0 g, 0.068 moles),
methyl-bis-hexamethylene triamine (16.0 g, 0.069 moles),
7-hydroxy-4-methyl-coumarin (0.0675 g, 3.83.times.10.sup.-4 moles),
phosporous acid (0.1 g, 1.22.times.10.sup.-3 moles) and water (0.4
g, 0.02 moles) was heated slowly to 200.degree. C. By-product
methanol was distilled from the system. Reduced pressure
(.about.0.4-0.5 mmHg, 53-67 Pa) was applied for approximately 10-15
minutes to complete the reaction. The fluorescent polymer was
cooled under nitrogen.
Example 8
[0072] A mixture of dimethyl adipate (12.0 g, 0.068 moles),
methyl-bis-hexamethylene triamine (16.0 g, 0.069 moles),
7-hydroxy-4-methyl-coumarin (0.540 g, 3.07.times.10.sup.-3 moles)
was heated slowly to 200.degree. C. By-product methanol was
distilled from the system. Reduced pressure (.about.0.4-0.5 mmHg,
53-67 Pa) was applied for approximately 10-15 minutes to complete
the reaction. The fluorescent polymer was cooled under
nitrogen.
Example 9
[0073] A mixture of dimethyl adipate (12.0 g, 0.068 moles),
methyl-bis-hexamethylene triamine (16.0 g, 0.069 moles),
4-methylesculetin (0.192 g, 1.00.times.10.sup.-3 moles) was heated
slowly to 200.degree. C. By-product methanol was distilled from the
system. Reduced pressure (.about.0.4-0.5 mmHg, 53-67 Pa) was
applied for approximately 10-15 minutes to complete the reaction.
The fluorescent polymer was cooled under nitrogen.
[0074] A control polymer was prepared in the same way without the
fluorescence compound (4-methylesculetin). The polymers were
compared by fluorescence spectroscopy.
Example 10
[0075] A mixture of dimethyl adipate (86.8 g), hexamethylene
diamine (58.1 g, 0.5 moles), 4,5,7-trihydroxyflavone (0.272 g,
1.0.times.10.sup.-3 moles), phosporous acid (0.19 g,
2.3.times.10.sup.-3 moles) and water (0.67 g, 0.037 moles) was
heated slowly to 200.degree. C. By-product methanol was distilled
from the system. Reduced pressure (.about.0.4-0.5 mmHg, 53-67 Pa)
was applied for approximately 10-15 minutes to complete the
reaction. The fluorescent polymer was cooled under nitrogen.
Example 11
[0076] Poly(trimethylene terephthalate) oligomer (38.0 g) was
slowly melted and 7-amino-4-methyl-coumarin (0.050 g,
2.85.times.10.sup.-4 moles) was mixed with the oligomer. The
mixture was stirred under nitrogen, at atmospheric pressure and the
temperature was kept under 240.degree. C. By-product water was
collected for 120 minutes and then vacuum was applied (.about.1
mmHg, 133 Pa) for an additional 20 minutes. The fluorescent polymer
was cooled under nitrogen.
Example 12
[0077] Poly(trimethylene terephthalate) oligomer (38.0 g) was
slowly melted and coumarin 343 (0.050 g, 1.76.times.10.sup.-4
moles) was mixed with the oligomer. The mixture was stirred under
nitrogen, at atmospheric pressure and the temperature was kept
under 240.degree. C. By-product water was collected for 120 minutes
and then vacuum was applied (.about.1 mmHg, 133 Pa) for and
additional 20 minutes. The fluorescent polymer was cooled under
nitrogen.
Example 13
[0078] Fluorescent polymer (105 g), prepared as in Example 1, was
blended and reacted with poly(trimethylene terephthalate) polymer,
(3031 g) in a twin-screw extruder and formed into copolymer pellets
to give an effective concentration of fluorescent compound in the
polymer of about 30-100 mg/kg. Before spinning the pellets were
dried at 120.degree. C. for 16 hours. After drying, the pellets had
an IV of 0.99 dL/g and were spun at 265.degree. C. through a
34-hole, 12.times.22 spinneret at 2500 m/min. A control sample of
poly(trimethylene terephthalate) was spun under the same
conditions.
Example 14
[0079] Fluorescent polymer (66.5 g), prepared as in Example 4, was
blended and reacted with poly(trimethylene terephthalate) polymer,
(3031 g) in a twin-screw extruder and formed into copolymer
pellets. Before spinning the pellets were dried at 120.degree. C.
for 16 hours. The pellets were spun at 265.degree. C. through a
34-hole, 12.times.22 spinneret at 2500 m/min. A control sample of
poly(trimethylene terephthalate) was spun under the same
conditions. The control and fluorescent fiber samples were checked
by fluorescence spectroscopy (FIG. 1).
Example 15
[0080] Fluorescent polymer (102.5 g), prepared as in Example 5, was
blended and reacted with poly(trimethylene terephthalate) polymer,
(3030 g) in a twin-screw extruder and formed into copolymer pellets
to give an effective concentration of fluorescent compound in the
polymer of about 30-100 mg/kg. Before spinning the pellets were
dried at 120.degree. C. for 16 hours. The pellets were spun at
265.degree. C. through a 34-hole, 12.times.22 spinneret at 2500
m/min. A control sample of poly(trimethylene terephthalate) was
spun under the same conditions. The control and fluorescent fiber
samples were checked by fluorescence spectroscopy (FIG. 2).
Example 16
[0081] Fluorescent polymer (106.5 g), prepared as in Example 10,
was blended and reacted with poly(trimethylene terephthalate)
polymer, (3031 g) in a twin-screw extruder and formed into
copolymer pellets to give an effective concentration of fluorescent
compound in the polymer of about 30-100 mg/kg. Before spinning the
pellets were dried at 120.degree. C. for 16 hours. The pellets were
spun at 265.degree. C. through a 34-hole, 12.times.22 spinneret at
2500 m/min. A control sample of poly(trimethylene terephthalate)
was spun under the same conditions. The control and fluorescent
fiber samples were checked by fluorescence spectroscopy (FIG.
3).
* * * * *