U.S. patent application number 10/768080 was filed with the patent office on 2004-08-05 for methods for the preparation of polyesters, poly(ester amide)s and poly(ester imide)s and uses of the materials obtained therefrom.
Invention is credited to Bikson, Benjamin, Ding, Yong.
Application Number | 20040152863 10/768080 |
Document ID | / |
Family ID | 29419577 |
Filed Date | 2004-08-05 |
United States Patent
Application |
20040152863 |
Kind Code |
A1 |
Ding, Yong ; et al. |
August 5, 2004 |
Methods for the preparation of polyesters, poly(ester amide)s and
poly(ester imide)s and uses of the materials obtained therefrom
Abstract
The present invention relates to methods for the preparation of
polyesters, poly(ester amide)s and poly(ester imide)s. The
materials obtained by the methods of present invention are useful
as fluid separation membranes and as high performance
materials.
Inventors: |
Ding, Yong; (Norwood,
MA) ; Bikson, Benjamin; (Brookline, MA) |
Correspondence
Address: |
PRAXAIR, INC.
LAW DEPARTMENT - M1 557
39 OLD RIDGEBURY ROAD
DANBURY
CT
06810-5113
US
|
Family ID: |
29419577 |
Appl. No.: |
10/768080 |
Filed: |
February 2, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10768080 |
Feb 2, 2004 |
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10153703 |
May 24, 2002 |
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6740728 |
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Current U.S.
Class: |
528/188 ;
528/179; 528/353 |
Current CPC
Class: |
C08G 63/19 20130101;
B01D 71/56 20130101; C08G 73/16 20130101; C08G 63/40 20130101; C08G
63/87 20130101; C08G 69/44 20130101; B01D 53/228 20130101; B01D
71/48 20130101; B01D 71/64 20130101 |
Class at
Publication: |
528/188 ;
528/353; 528/179 |
International
Class: |
C08G 063/00; C08G
069/26 |
Claims
What is claimed is:
1. A process for separating one or more gases from a mixture of
gases comprising the steps of bringing said gaseous mixture into
contact with a first side of a gas separation membrane such that a
portion of said gas mixture permeates to a second side of said
membrane and a portion of said gas mixture is collected as a
nonpermeate, the resulting gas mixture on said second side of said
membrane being enriched in one or more components over that of the
mixture on the first side of said membrane, wherein said gas
separation membrane is formed from a polymer containing a
main-chain ester linkage, wherein said polymer is formed by a
polycondensation reaction between an acetyl chloride and a phenol
in presence of a catalyst.
2. The process of claim 1 wherein said polycondensation reaction is
catalyzed independently by toluenesulfonyl chloride,
benzenesulfonylchloride, trimethylsilane chloride, and triphenyl
phosphite or a mixture thereof.
3. The process of claim 1 wherein said polymer is a polyester, a
poly(ester amide), or a poly(etser imide).
4. The process of claim 3 wherein said polymer is a poly(ester
imide) of the following general formula: 26Where x is an integer
larger than 10 and Ar is independently 27mixture thereof;
--Ar.sub.1-- is independently 28mixture thereof; --R'-- is 29Z and
Z' are: --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,iso-propyl, iso-butyl, tert-butyl, --Br,
--Cl, --F, --NO.sub.2, --CN 30n 32 0-4; --Ar.sub.2-- is
independently 31or a mixture thereof; Where Ar.sub.3 is
independently 32or a mixture thereof; 33
5. The process of claim 4 wherein said Ar is 34
6. The process of claim 4 wherein said --Ar.sub.1-- is: 35
7. The process of claim 4 wherein said --Ar.sub.2-- is: 36
8. The process of claim 4 wherein said poly(ester imide) is formed
by reacting tetrabromobisphenol A with one of the following
dianilines: 4,4'-oxy-dianiline, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylidene dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
9. The process of claim 4 wherein said poly(ester imide) is formed
by reacting 4,4'-hexafluoroisopropylidene bisphenol with one of the
following dianilines: 4,4'-oxy-dianiline, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylide- ne dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
10. The process of claim 3 wherein said polymer is a poly(ester
amide) of the following general formula: 37Where y is between 0.01
and 0.99 and --Ar.sub.1-- is independently 38or a mixture thereof;
--R'-- is 39Z and Z' are: --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,i- so-propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN 40n=0-4; --Ar.sub.2-- is
independently 41or a mixture thereof; Where Ar.sub.3 is
independently 42or a mixture thereof; --Ar.sub.4--is 43
11. The process of claim 10 wherein said --Ar.sub.1-- is: 44
12. The process of claim 10 wherein said --Ar.sub.2-- is: 45
13. The process of claim 10 wherein said poly(ester amide) is
formed by reacting tetrabromobisphenol A with one of the following
dianilines: 4,4'-oxy-dianiline, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylidene dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
14. The process of claim 10 wherein said poly(ester amide) is
formed by reacting 4,4'-hexafluoroisopropylidene bisphenol with one
of the following dianilines: 4,4'-oxy-dianiline,
1,3-phenylenediamine, 1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylide- ne dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
15. The process of claim 3 wherein said polymer is a polyester of
the following general formula: 46Where x is an integer larger than
10 and --Ar.sub.1-- is independently 47or a mixture thereof; --R'--
is 48Z and Z' are: --H, --C H.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,- iso-propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, ----NO.sub.2, --CN 49n=0-4.
16. The process of claim 15 wherein said --Ar.sub.1-- is: 50
17. A polymer containing a main-chain ester linkage which is formed
by the solution polycondensation reaction between an acetyl
chloride and a phenol in presence of a catalyst.
18. The polymer of claim 17 wherein the solution polycondensation
reaction is catalyzed independently by toluenesulfonyl chloride,
benzenesulfonylchloride, trimethylsilane chloride, and triphenyl
phosphite or a mixture thereof.
19. The process of claim 17 wherein said polymer is a polyester, a
poly(ester amide), or a poly(etser imide).
20. The polymer of claim 19 wherein said polymer is a poly(ester
imide) of the following general formula: 51Where x is an integer
larger than 10 and Ar is independently 52or a mixture thereof;
--Ar.sub.1-- is independently 53or a mixture thereof; --R'-- is
54--R"-- is 55Z and Z' are: --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,iso-- propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN 56n=0-4; --Ar.sub.2-- is
independently 57or a mixture thereof; Where Ar.sub.3 is
independently 58or a mixture thereof; --Ar.sub.4-- is 59
21. The polymer of claim 20 wherein said Ar is 60
22. The polymer of claim 20 wherein said --Ar.sub.1-- is: 61
23. The polymer of claim 20 wherein said --Ar.sub.2-- is: 62
24. The polymer of claim 20 wherein said poly(ester imide) is
formed by reacting tetrabromobisphenol A with one of the following
dianilines: 4,4'-oxy-dianiline, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylidene dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
25. The polymer of claim 20 wherein said poly(ester imide) is
formed by reacting 4,4'-hexafluoroisopropylidene bisphenol with one
of the following dianilines: 4,4'-oxy-dianiline,
1,3-phenylenediamine, 1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylide- ne dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
26. The polymer of claim 19 wherein said polymer is a poly(ester
amide) of the following general formula: 63Where y is between 0.01
and 0.99 and --Ar.sub.1-- is independently 64or a mixture thereof;
--R'-- is 65Z and Z' are: --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,i- so-propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN 66n=0-4; --Ar.sub.2-- is
independently 67or a mixture thereof; Where Ar.sub.3 is
independently 68or a mixture thereof; --Ar.sub.4-- is 69
27. The polymer of claim 26 wherein said --Ar.sub.1 -- is: 70
28. The polymer of claim 26 wherein said --Ar.sub.2-- is: 71
29. The polymer of claim 26 wherein said poly(ester amide) is
formed by reacting tetrabromobisphenol A with one of the following
dianilines: 4,4'-oxy-dianiline, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylidene dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
30. The polymer of claim 26 wherein said poly(ester amide) is
formed by reacting 4,4'-hexafluoroisopropylidene bisphenol with one
of the following dianilines: 4,4'-oxy-dianiline,
1,3-phenylenediamine, 1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylide- ne dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
31. The polymer of claim 19 wherein said polymer is a polyester of
the following general formula: 72Where x is an integer larger than
10 and --Ar.sub.1-- is independently 73or a mixture thereof; --R'--
is 74Z and Z' are: --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,i- so-propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN 75n=0-4.
32. The polymer of claim 31 wherein said --Ar.sub.1-- is: 76
33. A poly(ester imide) comprised of chemically combined aromatic
units of the following general formula: 77where --Ar.sub.1-- is a
divalent aromatic organic radical having the following structure
78or a mixture thereof, and --Ar.sub.2-- is independently a
divalent aromatic radical having the following structure: 79or a
mixture thereof; Where Ar.sub.3 is independently 80or a mixture
thereof.; --Ar.sub.4-- is 81or a mixture thereof.
34. The poly(ester imide) of claim 33 where said --Ar.sub.2-- is
82
35. The polymer of claim 34 wherein said poly(ester imide) is
formed by reacting tetrabromobisphenol A with one of the following
dianilines: 4,4'-oxy-dianiline, 1,3-phenylenediamine,
1,4-phenylenediamine, 1,5-naphthalenediamine,
4,4'-hexafluoroisopropylidene dianiline,
2,4,6-trimethyl-1,3-phenylene diamine, or a mixture thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to methods for the preparation
of polyesters, poly(ester amide)s and poly(ester imide)s. The
materials obtained by the methods of present invention are useful
as fluid separation membranes and as high performance
materials.
BACKGROUND OF THE INVENTION
[0002] Polymers containing the ester linkage, such as polyesters,
poly(ester amide)s, and poly(ester imide)s have been extensively
studied and used in variety of applications. General information
about the polymers containing the ester linkages can be found in
the following and other monographs and reviews:
[0003] P. E. Cassidy, "Thermally Stable Polymers", Marcel Dekker,
1980.
[0004] R. A. Gaudiana, et al., "Progress in Polymer Science",
Volume 14, page 47-89, 1989.
[0005] H. R. Kricheldorf, "Handbook of Polymer Synthesis", Marcel
Dekker, 1992.
[0006] F. Millich, C. E. Carraher, Jr., "Interfacial Synthesis",
Marcel Dekker, 1977.
[0007] Interfacial polymerization and high temperature melt
polymerization methods are two commonly used methods for the
preparation of polyesters. Although both methods provide sufficient
high molecular weight polyesters, the interfacial polymerization
method uses large amount of chlorinated solvents and melt
polymerization method uses very high polymerization temperature
(under the conditions of pyrolysis). The direct polymerization
between aromatic dicarboxylic acids and diols was reported by
Higashi et al in "Journal of Polymer Science, Polymer Chemistry
Edition", Volume 23, page 1361, 1985. The method used pyridine as
the polymerization media and the polymerization temperature needed
to be higher than 100.degree. C.
[0008] The low temperature solution polymerization method between
an aromatic dicarboxylic chloride and a diol is well known in the
art but it affords only low molecular weight oligomers, see for
example, H. Jeong et al. in "Journal of Polymer Science, Polymer
Chemistry Edition", Volume 32, page 1057, 1994; Y.-T. Chern, in
"Macromolecules", Volume 28, page 5561, 1995; and M. Bruma, et al.
in "Journal of Macromolecular Science, Review of Macromolecular
Chemistry and Physics", Volume C36, page 119, 1996.
[0009] U.S. Pat. No. 4,387,210 disclosed the synthesis of selected
poly(etser amide)s from aminophenols by interfacial polymerization
reaction. Due to the significant solubility differences between
aromatic diamines and the salts of aromatic diols, the preparation
of poly(ester amide)s by interfacial polymerization starting from
an aromatic diamine and an aromatic diol is very difficult to
practice. U.S. Pat. Nos. 3,859,251, 4,075,179 and 5,243,017
disclosed certain poly(ester amide)s prepared by melt
polymerization method at high temperature under vacuum.
[0010] The synthesis of poly(ester imide)s is known in the art. For
example, U.S. Pat. Nos. 4,631,333; 4,383,105 and 3,542,731 describe
processes in which the monomeric trimellitic acid imide is first
prepared from trimellitic acid anhydride and aminophenol and then
is polymerized under conditions of pyrolysis. U.S. Pat. Nos.
5,349,039 and 5,708,122 describe a processes in which the monomeric
imide diacid is first prepared from trimellitic acid anhydride and
a dianiline or aminobenzoic acid and then poly(ester imide)s are
obtained by polymerization with a bisphenol. Wang and Yang describe
the process in which a monomeric ester dianiline is first prepared
and then is polymerized with a dianhydride, see, Polymer Preprint,
American Chemical Society, Volume 39(2), 1998, page 800. Loncrini
describes a process in which a monomeric ester dianhydride is first
synthesized and isolated and then is polymerized with a dianiline,
see, Journal of Polymer Science, Part A-1, Volume 4, page 1531,
1966. All processes disclosed so far either involve the isolation
and purification of the intermediate monomers or use very high
polymerization temperature (under the conditions of pyrolysis).
OBJECTS OF THE INVENTION
[0011] Accordingly, one object of the present invention is to
provide a novel low temperature solution polymerization method for
the preparation of polyesters.
[0012] Another object of the present invention is to provide a
novel low temperature solution polymerization method for the
preparation of poly(ester amide)s.
SUMMARY OF THE INVENTION
[0013] The invention comprises a novel low temperature solution
polymerization method for the preparation of polyesters and
poly(ester amide)s.
[0014] One embodiment is a novel one-pot process for the
preparation of poly(ester imide)s with the general formula I by
reacting an anhydride chloride with a diol and a diamine. 1
[0015] Where x is an integer larger than 10.
[0016] Another embodiment of the present invention provides
improved catalysts to catalyze the formation of ester linkage in a
polymerization reaction.
[0017] Another embodiment provides catalysts to catalyze the
formation of ester anhydride and the formation of high molecular
weight poly(ester imide)s therefrom in one-pot reaction.
[0018] Still another embodiment of the present invention provides a
process to form novel soluble polyamic acids and derivatives
therefrom, in particular polyester amic acid salts.
[0019] A further embodiment of the present invention provides novel
soluble poly(ester amide)s and poly(ester imide)s derived from the
following diols. 2
[0020] where n=0-2 and R is:
[0021] --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,iso- -propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN, 3
[0022] Z and Z' are: 4
[0023] Still a further embodiment of the present invention provides
novel poly(ester amide) and poly(ester imide) polymeric fluid
separation membrane materials with improved separation
characteristics.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Other objects, features and advantages will occur to those
skilled in the art from the following description of (a) preferred
embodiment(s) and the accompanying drawing(s), in which:
[0025] FIG. 1 is a schematic illustration of the novel one-pot
process for the preparation of poly(etser imide)s.
[0026] FIG. 2 is a .sup.1H-NMR spectrum of poly(ester imide)
TBBA-ODA (CDCl.sub.3) (Symbols are defined in Table 1).
[0027] FIG. 3 is a .sup.1H-NMR spectrum of poly(ester imide)
TBBA-TMPDA (CDCl.sub.3) (Symbols are defined in Table 1).
DETAILED DESCRIPTION OF THE INVENTION
[0028] 1. Polyesters
[0029] We have unexpectedly discovered a low temperature solution
polymerization method for the preparation of polyesters. High
molecular weight polyesters are prepared from aromatic dicarboxylic
chlorides and aromatic diols at room temperature. The key for the
success is the use of certain catalysts. The preferred catalyst are
toluenesulfonyl chloride, trimethylsilane chloride, triphenyl
phosphite and mixtures thereof and the like compounds. High
molecular weight polyesters could not be obtained without the
presence of the catalyst. High molecular weight is defined as
sufficient for a polymer to form an integral film. Generally, the
inherent viscosity of the polymer should be higher than 0.2 dL/g
for the polymer to be a film former. The amounts of the catalyst
used can be in the range of 0.1 to 2 per mole of aromatic diol,
preferably in the range of 0.1 to 0.5.
[0030] The synthesis of polyesters can be carried out in an aprotic
solvent. Aprotic solvents include, but are not limited to
N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc),
N-methylpyrrolidinone (NMP), and the like. An aromatic diol, an
aromatic dicarboxylic chloride and a catalyst are first disssolved
in the aprotic solvent. All the reactants can be added into the
reaction vessel at the same time or the reactants can be added into
the reaction vessel sequentially. The molar ratio between the diol
and the aromatic dicarboxylic chloride is maintained in the range
of 0.95:1 or 1:1.1. If the molar ratio is out of the specified
range, high molecular weight polymers will not be formed. When
different aromatic diols or different aromatic dicarboxylic
chloride are used, random copolyesters are obtained. Cooling may be
applied to bring the temperature of the reaction mixture down to
below room temperature, for example, 0.degree. C., if necessary. On
the other hand, for the low reactivity diols, elevated temperatures
may be further applied to facilitate the formation of the ester
bond. An organic base, such as pyridine or triethylamine, is then
added to the reaction mixture over a period of time, preferably
from 10 minutes to 10 hours. The reaction mixture may be further
stirred for 1-24 hours to complete the polymerization.
[0031] The general structure of an aromatic diol of the instant
invention is depicted as
HO--Ar.sub.1--OH
[0032] Where --Ar.sub.1-- is independently 5
[0033] or a mixture thereof;
[0034] --R'-- is 6
[0035] Z and Z' are:
[0036] --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,iso- -propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN 7
[0037] n=0-4.
[0038] An organic base, typically a tertiary amine, is used to
neutralize the byproduct acid formed from reaction of the acid
chloride and the diol. Suitable tertiary amines include
heterocyclic, alicyclic or aromatic amines or amines of the
following general formula: R.sub.1R.sub.2R.sub.3N, wherein R.sub.1,
R.sub.2 and R.sub.3, may be the same or different but are as
defined above. Illustrative examples of suitable amines are
trimethylamine, triethylamine, tri-n-propylamine,
tri-isopropylamine, N,N-dimethylhexylamine,
N,N-dimethyldodecylamine, N,N-ethylethanol-amine,
N-methyldiethanolamine, tri-n-butyl-amine, tri-n-hexyl-amine,
tri-iso-octylamine, N,N,N',N'-tetramethyl-ethylenediam- ine,
DABCO.RTM. (1,4-di-aza-bi-cyclo-[2,2,2]octane), pyridine,
imidazole, 1,2,4-triazole, benzimidazole, naphthimidazole, purine,
quinoline, isoquinoline, pyridazine, phthalazine, quinazoline,
cinnoline, naphthylidine, acridine, phenanthridine, benzoquinoline,
benzisoquinoline, benzocinnoline, benzophthalazine,
benzoquinazoline, phenanthroline, phenazine, carboline, perimidine,
2,2'-dipyridyl, 2,4'-dipyridyl, 4,4'-dipyridyl, 2,2'-diquinolyl,
picolinamide, nicotinamide, isonicotinamide,
N,N-dimethylnicotinamide, N,N-diethylnicotinamide,
N,N-dimethylisonicotinamide, N,N-diethylisonicotinamide, picolinic
ester, nicotinic ester, isonicotinic ester, 2-pyridine sulfonamide,
3-pyridine sulfonamide, 4-pyridine sulfonamide, picolinaldehyde,
nicotinaldehyde, isonicotinaldehyde, 3-nitropyridine,
3-acetoxypyridine, and the like.
[0039] 2. Poly(ester amide)s
[0040] We have also discovered the low temperature solution
polymerization method for the preparation of random poly(ester
amide)s. Specifically, an aromatic diol and an aromatic diamine are
copolymerized with an aromatic dicarboxylic dichloride in the
presence of a catalyst. Toluenesulfonyl chloride, trimethylsilane
chloride, triphenyl phosphite and the like compounds are the
preferred catalyst. High molecular weight poly(ester amide)s could
not be obtained without the presence of the catalyst,. The amounts
of the catalyst used can be in the range of 0.1 to 2 per mole of
the aromatic dicarboxylic chloride, preferably in the range of 0.1
to 0.5.
[0041] The synthesis of poly(ester amide)s can be carried out in an
aprotic solvent. Aprotic solvents include, but are not limited to
N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc),
N-methylpyrrolidinone (NMP), and the like. The following procedures
represent the best mode to carry out the synthesis of high
molecular weight poly(ester amide)s. First, the aromatic diamine
should be dissolved in the reaction vessel with stirring. An
inorganic salt, for example, anhydrous lithium chloride, calcium
chloride, and so on, can be optionally added to aid the solubility
of the resulting polymers. The desired amounts of aromatic
dicarboxylic chloride is then added over a period of time. The
period of time can be in the range from 10 minutes or less and up
to 10 hours or more. If necessary, cooling may be applied to bring
the temperature of the reaction mixture down to below room
temperature, for example, 0.degree. C. After the addition of the
aromatic dicarboxylic chloride, an organic base, such as pyridine
or triethylamine, can be optionally added to the reaction mixture
over a period of time, preferably from 10 minutes to 10 hours. The
reaction mixture may be further stirred for 0.5-24 hours,
preferably for 1-8 hours to substantially complete the formation of
the amide. In the next step, predetermined amounts of an aromatic
diol along with a catalyst are added to the reaction mixture in one
portion or in several portions. If an organic base has not been
added before this point, it should be added into the reaction
mixture. The reaction mixture is further stirred under an inert
atmosphere at room temperature for 2 to 24 hours, preferable 3 to
16 hours to obtain high molecular weight poly(ester amide)s.
[0042] The general structure of an aromatic diol of the instant
invention is depicted as
HO--Ar.sub.1--OH
[0043] where Ar.sub.1 is the same as defined in the previous
section.
[0044] The general structure of an aromatic diamine of the instant
invention is depicted as:
H.sub.2N--Ar.sub.2--NH.sub.2
[0045] Where --Ar.sub.2-- is independently 8
[0046] or a mixture thereof;
[0047] Where Ar.sub.3 is independently 9
[0048] or a mixture thereof;
[0049] --Ar.sub.4-- is 10
[0050] An organic base, typically a tertiary amine, is used to
neutralize the byproduct acid formed from the reaction of the acid
chloride and a diol. Suitable tertiary amines include heterocyclic,
alicyclic or aromatic amines or amines of the following general
formula: R.sub.1R.sub.2R.sub.3N, wherein R.sub.1, R.sub.2 and
R.sub.3, may be the same or different but are as defined above.
[0051] 3. Poly(ester imide)s
[0052] We have discovered a novel one-pot process for the
preparation of poly(ester imide)s. This is carried out under mild
polymerization conditions Specifically, a diol is reacted with an
anhydride chloride, for example, trimellitic anhydride chloride, to
form an intermediate ester anhydride in the presence of a catalyst
and an organic base, such as pyridine. High molecular weight
poly(ester imide)s are formed in one-pot process by sequentially
adding a diamine to the reaction mixture without isolation of the
moisture sensitive intermediate, ester dianhydride, as shown in
FIG. 1. It was found that the presence of a catalyst is essential
to the formation of high molecular weight polymers in the instant
process.
[0053] The synthesis of poly(ester imide)s can be carried out in an
aprotic solvent. Aprotic solvents include, but are not limited to
N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc),
N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO), and the
like. A diol, the trimellitic anhydride chloride and a catalyst are
first disssolved in the aprotic solvent. The molar ratio between
the diol and the trimellitic anhydride chloride is maintained in
the range of 0.95: 2 or 1: 2.2. If the molar ratio is out of the
specified range, high molecular weight polymers will not be formed.
If necessary, cooling may be applied to bring the temperature of
the reaction mixture down to below room temperature, for example,
0.degree. C. On the other hand, for the low reactivity diols,
elevated temperatures may be further applied to facilitate the
formation of the ester bond. An organic base, such as pyridine or
triethylamine, is then added to the reaction mixture over a period
of time, preferably from 10 minutes to 10 hours. The reaction
mixture may be further stirred for 1-24 hours to complete formation
of ester dianhydride. A diamine monomer is then added in one
portion, or in several small portions, to the reaction mixture and
a high molecular weight polyamic acid is formed. The thus formed
polyamic acid can be mixed polyamic acids with some of its
carboxylic acid neutralized with the tertiary amine added at the
stage of formation of ester linkage. The amount of neutralized
carboxylic acid depends on the amount of tertiary amine added
thereof. The polymeric precursor can be isolated prior to use or
converted directly to poly(ester imide)s. A dehydration agent, for
example, acetic anhydride, or heat can be applied to effect the
imidization, as known to those skilled in the art. The polymeric
precursor can be further neutralized with a base, such as a
tertiary amine to form a soluble polyamic acid salt, as disclosed
in our separate patent filing, herein incorporated by reference.
Poly(ester imide)s or polyamic acid salts may be isolated and
purified by pouring into a non-solvent or used without isolation,
depending on the desired application.
[0054] The general structure of poly(ester imide)s of the instant
invention is depicted as general formula I. Where --Ar.sub.1-- and
--Ar.sub.2-- are the same as the ones defined in the previous
sections and Ar is independently 11
[0055] or a mixture thereof.
[0056] An organic base, typically a tertiary amine, is used to
neutralize the byproduct acid formed from the acid chloride and a
diol. Suitable tertiary amines include heterocyclic, alicyclic or
aromatic amines or amines of the following general formula:
R.sub.1R.sub.2R.sub.3N, wherein R.sub.1, R.sub.2 and R.sub.3, may
be the same or different but are as defined above.
[0057] It was further found that incorporation of a catalyst is an
essential part of the novel one-pot process. Toluenesulfonyl
chloride, trimethylsilane chloride, triphenyl phosphite and
mixtures thereof and the like compounds are the preferred catalyst.
Without the presence of the catalyst, high molecular weight
poly(ester imide)s could not be obtained. High molecular weight is
defined as sufficient to form an integral film. Generally, the
inherent viscosity must be higher than 0.2 dL/g for the polymer to
be a film former. The amounts of catalyst used can be in the range
of 0.1 to 2 per mole of the aromatic diol, preferably in the range
of 0.1 to 0.5.
[0058] The instant invention provides a convenient process for the
preparation of novel poly(ester amide)s and poly(ester imide)s,
which are very difficult to form by other methods. These novel
poly(ester amide)s and poly(ester imide)s are derived from the
following diols. 12
[0059] where n=1-2 and R is:
[0060] --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3,iso- -propyl, iso-butyl, tert-butyl,
--Br, --Cl, --F, --NO.sub.2, --CN 13
[0061] Z and Z' are:
[0062] --CH.sub.3,
[0063] --CF.sub.3, 14
[0064] The polyesters, poly(ester amide)s and poly(ester imide)s
prepared by the teachings of present invention are useful materials
for high temperature applications, such as fireproofing articles
and as membranes for fluid separations.
[0065] We have found that polyesters, poly(ester amide)s and
poly(ester imide)s of this invention exhibit excellent combination
of gas separation/permeation characteristics and are extremely
useful for gas separation applications. The polymers of this
invention can be fabricated into different membrane shapes such as
flat sheets or hollow fibers. Furthermore, the membranes can be
porous or dense and composite or asymmetric in structure, including
the multicomponent structure. The resulting polymeric materials may
then, if desired, be blended using conventional solution blending
technology to yield a blend having specifically tailored
properties. Gas separation membranes prepared from these materials
containing ester linkages of the present invention possess an
excellent balance of gas permeation rates and selectivities for one
gas over the other gases in a multicomponent gas mixture. For
example, the poly(ester imide) material described in Example 3 of
this invention was found to have a high permeation rate for oxygen
of 8.9 Barrers while maintaining a good oxygen/nitrogen selectivity
of 5.8.
[0066] The following examples will serve to illustrate the utility
of this invention but should not be construed as limiting. The gas
permeability of the flat sheet polymeric membranes was determined
by the following procedure. In the test, the membrane to be tested
was sandwiched between two aluminum foils exposing a 2.54 cm
diameter area, placed in a permeation cell and sealed with epoxy
resin. The downstream side of the cell was evacuated up to
2.times.10.sup.-2 mmHg and the permeate feed gas was introduced
from the upstream side. The pressure of the permeate gas on the
downstream side was measured using a MKS-Barathon pressure
transducer. The permeability coefficient P was calculated from the
steady-state gas permeation rate according to the equation:
P=C.times.V.times.L'dp/dt.times.1/h
[0067] C=constant
[0068] V=volume of collection receiver
[0069] L=thickness of film
[0070] h=upstream pressure
[0071] dp/dt=slope of steady-state line
[0072] The permeability coefficient P is reported in Barrer units
(1 Barrer=10.sup.-10 cm.sup.3 cm/cm.sup.2 cmHg sec).
EXAMPLE 1
[0073] A 500 mL four neck round flask equipped with a nitrogen
inlet, a thermometer, a dropping funnel and a mechanical stirrer
was charged with 10.53 g (0.05 mol) of trimellitic anhydride
chloride (Aldrich), 1.5 g (0.008 mol) of toluenesulfonyl chloride
(Aldrich), 13.60 g (0.025 mol) of tetrabromobisphenol A (TBBA) and
80 mL of NMP. The mixture was stirred until a homogeneous solution
was obtained. Subsequently, the mixture was cooled down to
5.degree. C. with an ice-water bath. 8.0 mL of pyridine was then
added through the dropping funnel over a period of 20 min. The
solution was stirred at 5.degree. C. for 2 hours and then gradually
warmed up to room temperature overnight. At this point, 5.01 g
(0.025 mol) of 4,4'-oxydianiline (ODA) was added in one portion and
the mixture was stirred for additional 3 hours. A very viscous
solution was thus obtained. 10 mL of acetic anhydride were then
added to the mixture and the reaction mixture was further stirred
overnight. The polyester imide (TBBA-ODA) was isolated by pouring
the solution into excess amount of methanol and further purified by
redissolving in methylene chloride and reprecipitating into
methanol. The inherent viscosity of the polymer was 0.54 dL/g
measured in the methylene chloride at the concentration of 0.4
g/dL. The H-NMR spectrum of the polymer is shown in FIG. 2. A dense
film of TBBA-ODA polyester imide was cast from methylene chloride
solution on a clean glass plate in a glove bag. The film was
further dried at 100.degree. C. under vacuum for 48 hours. The gas
permeation characteristics of the polymer were measured as
described above and are summarized in Table 1.
EXAMPLES 2-5
[0074] Poly(ester imide)s in Examples 2-5 were prepared as
described in Example 1. The H-NMR spectrum of the poly(ester imide)
TBBA-TMPDA is shown in FIG. 3. The gas permeation characteristics
of the novel poly(ester imide)s are summarized in Table 1.
1TABLE 1 P(O.sub.2)/ P(CO.sub.2)/ P(CO.sub.2)/ Example
Polyesterimide P(He) P(O.sub.2) P(N.sub.2) P(CH.sub.4) P(CO.sub.2)
P(N.sub.2) P(N.sub.2) P(CH.sub.4) 1 TBBA-ODA 14.3 1.2 0.17 6.8 2
TBBA-1,3-PDA 18.6 1.3 0.17 7.5 3 TBBA-TMPDA 58.3 8.9 1.5 1.3 42 5.8
27 34 4 TBBA-HAB 7.2 0.4 0.06 6.8 5 TMBA-ODA 19.1 1.6 0.26 0.2 6.6
6.1 26 34
[0075] The permeability is in Barrer unit;
[0076] TBBA: tetrabromobisphenol A;
[0077] TMBA: tetramethylbisphenol A;
[0078] ODA: 4,4'-oxydianiline;
[0079] PDA: phenylenediamine;
[0080] TMPDA: 2,4,6-trimethyl-m-phenylenediamine;
[0081] HAB: 3,3'-dihydroxybenzidine.
EXAMPLE 6
[0082] The polyester with the following structure was prepared by
the following procedure: 15
[0083] A 500 mL four neck round flask equipped with a nitrogen
inlet, a thermometer, a dropping funnel and a mechanical stirrer
was charged with 10.15 g (0.05 mol) of terephthaloyl chloride
(Aldrich), 1.7 g (0.009 mol) of toluenesulfonyl chloride (Aldrich),
16.30 g (0.025 mol) of
hexafluoroisopropylidene-bis(2,6-dibromophenol) (6FTBBA), 5.71 g
(0.025 mol) of bisphenol A and 80 mL of NMP. The mixture was
stirred until a homogeneous solution was obtained. Subsequently,
the mixture was cooled down to 5.degree. C. with an ice-water bath.
8.0 mL of pyridine was then added through the dropping funnel over
a period of 20 min. The solution was stirred at 5.degree. C. for 2
hours and then gradually warmed up to room temperature overnight. A
very viscous solution was thus obtained. The polymer was isolated
by pouring the solution into excess amount of methanol and further
purified by redissolving in methylene chloride and reprecipitating
into methanol. The inherent viscosity of the polymer was 0.38 dL/g
measured in the methylene chloride at the concentration of 0.4 g/dL
at 25.degree. C.
EXAMPLE 7
[0084] The poly(ester amide) with the following structure was
prepared by the following procedure: 16
[0085] A 500 mL four neck round flask equipped with a nitrogen
inlet, a thermometer, a dropping funnel and a mechanical stirrer
was charged with 5.01 g (0.025 mol) of 4,4'-oxydianiline and 80 mL
of NMP. The mixture was stirred until a homogeneous solution was
obtained. 10.15 g (0.05 mol) of terephthaloyl chloride was added
into the reaction mixture in several portions. The mixture was
stirred at room temperature for 2 hours and 8.0 mL of pyridine was
then added through the dropping funnel over a period of 20 min. The
solution was further stirred for 1 hour. 1.7 g (0.009 mol) of
toluenesulfonyl chloride (Aldrich), 16.30 g (0.025 mol) of
hexafluoroisopropylidene-bis(2,6-dibromophenol) (6FTBBA) were then
added in one portion. After stirring at room temperature for 4
hours, very viscous solution was thus obtained. The poly(ester
amide) was isolated by pouring the solution into excess amount of
methanol. The inherent viscosity of the polymer was 0.57 dL/g
measured in the NMP containing 0.1% LiCl at the concentration of
0.4 g/dL at 25.degree. C.
EXAMPLE 8
[0086] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 17
[0087] The inherent viscosity of the polymer was 0.62 dL/g measured
in the NMP containing 0.1% LiCl at the concentration of 0.4 g/dL at
25.degree. C.
EXAMPLE 9
[0088] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 18
[0089] The inherent viscosity of the polymer was 0.31 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
EXAMPLE 10
[0090] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 19
[0091] The inherent viscosity of the polymer was 0.51 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
EXAMPLE 11
[0092] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 20
[0093] The inherent viscosity of the polymer was 0.37 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
EXAMPLE 12
[0094] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 21
[0095] The inherent viscosity of the polymer was 0.92 dL/g measured
in the NMP containing 0.1% of LiCl at the concentration of 0.4 g/dL
at 25.degree. C.
EXAMPLE 13
[0096] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 22
[0097] The inherent viscosity of the polymer was 0.59 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
EXAMPEL 14
[0098] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 23
[0099] The inherent viscosity of the polymer was 0.89 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
EXAMPLE 15
[0100] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 24
[0101] The inherent viscosity of the polymer was 0.67 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
EXAMPLE 16
[0102] The poly(ester amide) with the following structure was
synthesized using the same procedure as the one described in
Example 7. 25
[0103] The inherent viscosity of the polymer was 0.40 dL/g measured
in the NMP at the concentration of 0.4 g/dL at 25.degree. C.
[0104] The term "comprising" is used herein as meaning "including
but not limited to", that is, as specifying the presence of stated
features, integers, steps or components as referred to in the
claims, but not precluding the presence or addition of one or more
other features, integers, steps, components, or groups thereof.
[0105] Specific features of the invention are shown in one or more
of the drawings for convenience only, as each feature may be
combined with other features in accordance with the invention.
Alternative embodiments will be recognized by those skilled in the
art and are intended to be included within the scope of the
claims.
* * * * *