U.S. patent application number 10/455887 was filed with the patent office on 2003-11-13 for polymers made from bis(2-hydroxyethyl)isosorbide and enduses thereof.
Invention is credited to Brandenburg, Charles, Hayes, Richard.
Application Number | 20030212244 10/455887 |
Document ID | / |
Family ID | 27733518 |
Filed Date | 2003-11-13 |
United States Patent
Application |
20030212244 |
Kind Code |
A1 |
Hayes, Richard ; et
al. |
November 13, 2003 |
Polymers made from bis(2-hydroxyethyl)isosorbide and enduses
thereof
Abstract
This invention provides a new, biomass-derived glycol,
bis(2-hydroxyethyl)isosorbide, which is found to be a valuable
monomer for a wide variety of polymeric materials
Inventors: |
Hayes, Richard; (Brentwood,
TN) ; Brandenburg, Charles; (Newark, 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: |
27733518 |
Appl. No.: |
10/455887 |
Filed: |
June 6, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10455887 |
Jun 6, 2003 |
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10108023 |
Mar 26, 2002 |
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6608167 |
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60365590 |
Mar 19, 2002 |
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Current U.S.
Class: |
528/296 ;
528/298 |
Current CPC
Class: |
C08G 18/3218 20130101;
C08G 63/672 20130101; C07D 493/04 20130101; C08G 64/0208 20130101;
C08G 65/405 20130101 |
Class at
Publication: |
528/296 ;
528/298 |
International
Class: |
C08G 063/02; C08G
063/12; C08G 063/18 |
Claims
What is claimed is:
1. Bis(2-hydroxyethyl)isosorbide.
2. A polymer composition comprising a polymer and
bis(2-hydroxyethyl)isoso- rbide comonomer.
3. The polymer composition of claim 2 wherein the polymer is
selected from the group consisting of polyester, polyamide ester,
polyurethane, polycarbonate, polycarbonate ester, polyether
sulfone, polyether ketone, and polyether ether ketone.
4. The polymer composition of claim 2 further comprising a
dicarboxylic acid.
5. The polymer composition of claim 4 further comprising at least a
second glycol.
6. The polymer composition of claim 2 or claim 4 further comprising
at least one polyfunctional branching agent.
7. A polyester comprising: (a) 45.0 to 50.0 mole percent of a
dicarboxylic acid, (b) 0.1 to 50.0 mole percent of
bis(2-hydroxyethyl)isosorbide, (c) 0 to 49.9 mole percent of at
least one additional glycol, and (d) 0 to 5.0 mole percent of at
least one polyfunctional branching agent.
8. The polymer composition of claim 4, wherein said dicarboxylic
acid is selected from the group consisting of unsubstituted and
substituted aromatic, aliphatic, unsaturated, and acyclic
dicarboxylic acids; and the lower alkyl esters of aromatic,
aliphatic, unsaturated, and acyclic dicarboxylic acids having from
8 carbons to 36 carbons.
9. The polymer composition of claim 4 wherein said dicarboxylic
acid is selected from the group consisting of terephthalic acid,
dimethyl terephthalate, isophthalic acid, dimethyl isophthalate,
2,6-naphthalene dicarboxylic acid, dimethyl-2,6-naphthalate, metal
salts of 5-sulfo-dimethylisophthalate, oxalic acid, dimethyl
oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl
succinate, methylsuccinic acid, glutaric acid, dimethyl glutarate,
2-methylglutaric acid, 3-methylglutaric acid, adipic acid, dimethyl
adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid,
pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic
acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid,
undecanedioic acid, 1,12-dodecanedicarboxylic acid, hexadecanedioic
acid, docosanedioic acid, tetracosanedioic acid, dimer acid,
1,4-cyclohexanedicarboxylic acid,
dimethyl-1,4-cyclohexanedicarboxylate, 1,3-cyclohexanedicarboxylic
acid, dimethyl-1,3-cyclohexanedicarboxylate,
1,1-cyclohexanediacetic acid, fumaric acid, maleic anhydride,
maleic acid, hexahydrophthalic acid, phthalic acid, and
combinations thereof.
10. The polymer composition of claim 5 wherein said glycol is
selected from the group consisting of unsubstituted, substituted,
straight chain, branched, cyclic aliphatic, aliphatic-aromatic and
aromatic diols having from 2 carbon atoms to 36 carbon atoms; and
poly(alkylene ether) glycols with molecular weights between about
250 to 4,000.
11. The polymer composition of claim 5 wherein said glycol is
selected from the group consisting ethylene glycol,
1,3-propanediol, 1,2-propanediol,1,2-butanediol, 1,3-butanediol,
1,3-2-methylpropanediol, neopentyl glycol, 1,4-butanediol,
1,3-hexanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol,
1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,
1,14-tetradecanediol, 1,16-hexadecanediol, dimer diol,
4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane,
1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene
glycol), poly(ethylene ether) glycols, poly(butylene ether) glycols
and combinations thereof.
12. A process for producing bis(2-hydroxyethyl)isosorbide
comprising the steps of: (a) contacting isosorbide with a
stoichiometric excess of ethylene carbonate in the presence of a
catalyst, (b) heating the product of step (a) gradually, with
mixing, at a temperature sufficient to substantially evolve carbon
dioxide from said product, and (c) cooling the product of step (b)
to ambient temperature.
13. The process of claim 12 wherein the temperature is from
50.degree. C. to 300.degree. C.
14. The process of claim 12 wherein the temperature is from
75.degree. C. to 200.degree. C.
15. The polymer composition of claim 3 wherein said polyester is
biodegradable.
16. A polyurethane comprising: (a) 45.0 to 50.0 mole percent of
polyisocyanate, (b) 0.1 to 50.0 mole percent of
bis(2-hydroxyethyl)isosor- bide, (c) 0 to 49.9 mole percent of at
least one additional glycol, and (d) 0 to 5.0 mole percent at least
one polyester polyol.
17. The polymer composition of claim 16, wherein the polyisocyanate
is selected from unblocked polyisocyanates and blocked
isocyanates.
18. The polymer composition of claim 17 wherein the blocked
isocyanate is chemically blocked with a compound selected from the
group consisting of methanol, oximes, lactams, imidazole, and
phenols.
19. The polymer composition of claim 17 wherein the polyisocyanate
is selected from the group consisting of diphenylmethane
diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene
diisocyanate, naphthalene diisocyanate,
4,4'-methylene-bis-(cyclohexyl isocyanate), isophorone
diisocyanate, 1,6-hexamethylene diisocyanate, a biuret from
1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate,
mixtures thereof.
20. The polymer composition of claim 2 in the form of a shaped
article.
21. The shaped article of claim 20 in the form of a film, sheet,
fiber, container or foamed article.
Description
FIELD OF THE INVENTION
[0001] This invention provides a new, biomass-derived glycol,
bis(2-hydroxyethyl)isosorbide, which is found to be a valuable
monomer for a wide variety of polymeric materials.
TECHNICAL BACKGROUND OF THE INVENTION
[0002] There is a desire to utilize polymeric components ultimately
derived from biomass. The diol 1,4:3,6-dianhydro-D-sorbitol,
hereinafter referred to as isosorbide, is readily made from
renewable resources, such as sugars and starches. For example,
isosorbide can be made from D-glucose by hydrogenation followed by
acid-catalyzed dehydration. The preparation of isosorbide is known
within the literature in, for example, G. Fleche, et. al.,
Starch/Starke, 38(1), pp. 26-30 (1986). Isosorbide has the
additional advantage of increasing the heat resistance of a
polyester into which it is incorporated by raising-its glass
transition temperature (Tg).
[0003] Charbonneau, et. al., in U.S. Pat. No. 6,063,464, describe a
process to produce polyesters which incorporate isosorbide, that
have an inherent viscosity of at least 0.35 dL/g when measured as a
1% (weight/volume) solution of the polyester in o-chlorophenol at a
temperature of 25.degree. C. They generally teach the use of
aromatic and alicyclic diacids. A shortcoming found in this
disclosure was the low incorporation rate of the isosorbide
monomer. Of the 16 preparative examples included within this
disclosure where the percentage of incorporated isosorbide into the
polymer could be assessed, the incorporation level of added
isosorbide monomer into the as produced polymer ranged from 12 to
70 percent. The average incorporation rate of added isosorbide
monomer into the polymer was disclosed to be 48 percent. As one
skilled in the art would appreciate, this inefficiency of
isosorbide monomer incorporation into the polymer leads to complex
glycol recovery and separation processes.
[0004] The present invention overcomes this shortcoming and
provides chemically modified isosorbide derivatives which allow for
essentially complete incorporation into high molecular weight
polymers derived therefrom. The essentially complete incorporation
of isosorbide allows avoidance of complex glycol recovery and
separation processes.
[0005] The present invention provides valuable polymeric materials,
such as polyesters, polyamide esters, polyurethanes and
polycarbonates which incorporate said chemically modified
isosorbide derivatives.
[0006] One aspect of the present invention includes
1,4:3,6-dianhydro-2,5-bis-O-(2-hydroxyethyl)-D-sorbitol,
hereinafter referred to as bis(2-hydroxyethyl)isosorbide.
Heretofore, bis(2-hydroxyethyl)isosorbide has not been reported
within the art. Similar derivatives of D-mannitol have been
reported. 1,4:3,6-dianhydro-2,5-bis-O-(2-hydroxyethyl)-D-mannitol,
hereinafter referred to as bis(2-hydroxyethyl)mannitol, has been
prepared as an intermediate in the preparation of crown ethers. For
example, Ashton, et. al., in Eur. J. Org. Chem., (5), pp. 995-1004
(1999), reported the preparation of bis(hydroxyethyl)mannitol for
use in the preparation of crown ethers. El'perina, et. al., in Izv.
Akad. Nauk SSSR, Ser. Khim., (3), pp. 627-632 (1988) and in Izv.
Akad. Nauk SSSR, Ser. Khim., (3), pp. 632-637 (1988), prepared
bis(2-hydroxyethyl)mannitol through base-catalyzed alkylation of
mannitol with 2-(2-bromoethoxy)tetrahydropyr- an, followed by
deprotection of the alcohol function. This material was further
utilized in the production of crown ethers. As one skilled in the
art would appreciate, the stereo- and regiochemistry of said
bis(2-hydroxyethyl)mannitol, which makes it useful as a precursor
for crown ethers, would lead to significant cyclic oligomer
formation in the production of the valuable polymeric materials
described herein. Significant cyclic oligomer levels in polymeric
materials are not desirable for most end uses described herein.
SUMMARY OF THE INVENTION
[0007] One aspect of the present invention includes a new
composition of matter termed bis(2-hydroxyethyl)isosorbide.
Bis(2-hydroxyethyl)isosorbid- e may be prepared through chemical
modification of isosorbide. Polymeric materials derived from
bis(2-hydroxyethyl)isosorbide, such as polyesters, polyamide
esters, polyurethanes, polycarbonates, and the like, are useful in
a wide variety of shaped articles, such as films, sheets,
containers, fibers, molded parts, coatings, foamed articles, and
the like.
[0008] A further aspect of the present invention includes
polyesters which incorporate bis(2-hydroxyethyl)isosorbide. Said
polyesters which incorporate bis(2-hydroxyethyl)isosorbide are
comprised essentially of 45.0 to 50.0 mole percent dicarboxylic
acid component, 50.0-0.1 mole percent
bis(2-hydroxyethyl)isosorbide, 0 to 49.9 mole percent of a glycol
component, and 0 to 5.0 mole percent of a polyfunctional branching
agent. Said polyesters which incorporate
bis(2-hydroxyethyl)isosorbide of the present invention are found to
have a greater monomer incorporation rate than the isosorbide
polyesters of the art.
[0009] A further aspect of the present invention includes
polyurethanes which incorporate bis(2-hydroxyethyl)isosorbide. Said
polyurethanes which incorporate bis(2-hydroxyethyl)isosorbide are
comprised essentially of 45.0 to 50.0 mole percent of a
polyisocyanate component, 50.0 to 0.1 mole percent of
bis(2-hydroxyethyl)isosorbide and/or a polyester polyol which
contains bis(2-hydroxyethyl)isosorbide, and 0 to 49.9 mole percent
of a glycol component.
[0010] A further aspect of the present invention includes shaped
articles produced from polymeric materials which incorporate
bis(2-hydroxyethyl)isosorbide. Said polymeric materials which
incorporate bis(2-hydroxyethyl)isosorbide may be selected from the
group consisting of polyesters, polyamide esters, polyurethanes,
polyether sulfones, polyether ketones, polycarbonates, and
polycarbonate esters. Said shaped articles produced from the
polymeric materials which incorporate bis(2-hydroxyethyl)isosorbide
of the present invention may include film, sheets, fiber, melt
blown containers, molded parts, such as cutlery, foamed parts,
polymeric melt extrusion coatings onto substrates, polymeric
solution coatings onto substrates and the like.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Preparation of bis(2-hydroxyethyl)Isosorbide:
[0012] The bis(2-hydroxyethyl)isosorbide of the present invention
may be readily prepared from isosorbide, which is derived from
renewable resources, such as sugars and starches, as described
above. For example, isosorbide may be modified with ethylene oxide,
ethylene carbonate and the like, to produce
bis(2-hydroxyethyl)isosorbide.
[0013] The conversion of alcohols to 2-hydroxyethyl ethers is known
within the art. Any known method in the art may be used to convert
isosorbide to bis(2-hydroxyethyl)isosorbide.
[0014] Ethylene Oxide:
[0015] For example, ethylene oxide has been used in the production
of 2-hydroxyethyl ethers from alcohols. Typically such a process is
performed by heating the ethylene oxide, the alcohol and a catalyst
system together, followed by recovery and purification of the
resultant 2-hydroxyethyl ether product. The reaction may be
performed with an inert solvent. Catalyst systems which have found
use in such processes include; acids, bases, ammonia, urea, alkali
metal hydroxides, alkali metal phenates, potassium hydroxide,
alkali metal bases, organoaluminum zinc compounds, nitrogen
containing catalysts, calcium acetates, strontium acetates, barium
acetates, aluminum trifluoride, trialkyl aluminum, mixtures of
boron trifluoride and trialkyl phosphoric compounds, zinc dialkyl
materials, mixtures of boron trifluoride with metal alkyls or metal
alkoxides, mixtures of silicon tetrafluoride with metal alkyls or
metal alkoxides, mixtures of an alkali metal borohydride and an
alkali metal hydroxide. Representative art which describes the
preparation of 2-hydroxyethyl ethers from alcohols would include;
U.S. Pat. Nos. 2,716,137, 2,852,566, 2,879,220, 3,350,462,
3,354,227, 3,364,267, 3,395,185, 3,525,773, 3,597,502, 3,642,911,
3,644,534, 3,682,849, 3,719,636, 3,910,878, 3,969,417, 4,098,818,
4,210,764, 4,223,164, 4,239,917, 4,254,287, 4,282,387, 4,302,613,
4,306,093, 4,453,022, 4,453,023, 4,483,941, 4,533,759, 4,754,075,
4,775,653, 4,820,673, 4,886,917, 4,892,977, 4,902,658, 5,608,116
British Patent No. 1,399,966, British Patent No. 1,462,133, British
Patent No. 1,462,134, European Patent Application No. A0095562,
European Patent Application No. 339426, French Patent No.
1,365,945, German Patent No. 2406293, Japanese Patent No. 50017976,
Japanese Patent No. 50000654, Japanese Patent No. 49033183,
Japanese Patent No. 62289537, Japanese Patent No. 52003923,
Japanese Patent No. 52051307, Japanese Patent No. 51059809 and
references cited therein. These preparative references and the
references cited therein are herein incorporated by reference into
the present invention.
[0016] Catalysts that may be used with the ethylene oxide include
acids, bases, ammonia, urea, alkali metal hydroxides, alkali metal
phenates, potassium hydroxide, alkali metal bases, organoaluminum
zinc compounds, nitrogen containing catalysts, calcium acetates,
strontium acetates, barium acetates, aluminum trifluoride, trialkyl
aluminum, mixtures of boron trifluoride and trialkyl phosphoric
compounds, zinc dialkyl materials, mixtures of boron trifluoride
with metal alkyls or metal alkoxides, mixtures of silicon
tetrafluoride with metal alkyls or metal alkoxides, mixtures of an
alkali metal borohydride and an alkali metal hydroxide, and the
like and mixtures thereof. These are generally known in the art and
a skilled practitioner may readily select the specific catalyst or
combination or sequence of catalysts used. The preferred catalyst
and preferred conditions differ depending on, for example, the type
and scale of reactor to be used.
[0017] Ethylene carbonate:
[0018] Ethylene carbonate has been used in the conversion of
alcohols to 2-hydroxyethyl ethers. Typically this operation is
performed by heating the alcohol, ethylene carbonate and certain
catalyst systems together, followed by recovery of the resultant
2-hydroxyethyl ether product. The process may be carried out with
an inert solvent. Generally, the catalyst systems may be composed
of acids, bases, alkali salts of phenols, phosphonium materials,
potassium carbonate, alkali metal hydrides, alkali metal
hydroxides, inorganic halide salts, triorganophosphine compounds,
potassium iodide, imidazole, sodium stannate, potassium fluoride,
mixed metal oxide. Representative art would include U.S. Pat. Nos.
2,448,767, 2,967,892, 2,987,555, 3,283,030, 3,967,892, 4,261,922,
4,310,706, 4,310,707, 4,310,708, 4,341,905, 5,059,723, 5,104,987,
5,157,159, 5,679,871, 5,998,568, Japanese Patent No. 03052838,
Japanese Patent No. 50004012 and references cited therein. Dow
Chemical U.S.A., Experimental Ethylene carbonate XAS-1666.00L
Product Bulletin (1982), pp. 4-9, discloses hydroxyethylation
reactions in which ethylene carbonate reacts with compounds
containing active hydrogen, such as alcohols, to give hydroxyethyl
derivatives. The reactions are carried out at temperatures between
100.degree. C. to 200.degree. C. in the presence of metal salts
such as potassium carbonate. Carbon dioxide is the principle
byproduct. It is stated that ethylene carbonate yields, in most
cases, the mono-ethylene oxide insertion product. Texaco Chemical
Company, TEXACAR.RTM. Ethylene and Propylene Carbonates Product
Bulletin (1987), pp. 23-24, describes hydroxyalkylation reactions
in which ethylene carbonate react with compounds which contain an
active hydrogen, such as alcohols, to give the corresponding
hydroxyethyl derivatives. The reactions are run between 100 and
200.degree. C. employing a basic catalyst, such as potassium
carbonate at a 0.5 weight percent level. These preparative
references and the references cited therein are hereby incorporated
by reference into the present invention.
[0019] Catalysts that may be used with the ethylene carbonate
include, for example, acids, bases, alkali salts of phenols,
phosphonium materials, potassium carbonate, alkali metal hydrides,
alkali metal hydroxides, inorganic halide salts, triorganophosphine
compounds, potassium iodide, imidazole, sodium stannate, potassium
fluoride, mixed metal oxide, and the like and mixtures thereof.
These are generally known in the art and a skilled practitioner may
readily select the specific catalyst or combination or sequence of
catalysts used. The preferred catalyst and preferred conditions
differ depending on, for example, the type and scale of reactor to
be used.
[0020] Chemical Modification:
[0021] In the chemical modification process, the isosorbide and the
ethylene oxide or the ethylene carbonate are combined and are
heated gradually with mixing with a catalyst or a catalyst mixture
to a temperature in the range of 50 to about 300.degree. C.,
preferably between 75 and 200.degree. C. Typically a stoichiometric
excess of ethylene carbonate will be employed. Optionally, a
solvent inert under the reaction conditions, such as a hydrocarbon,
may be employed. The exact conditions and catalysts used will
depend on the exact nature of the reactor to be employed. The
catalyst may be included initially with the reactants and/or may be
added one or more times to the mixture as it is heated. The
catalyst used may be modified as the reaction proceeds. The heating
and stirring are continued for a sufficient time and a sufficient
temperature to yield a significant conversion of isosorbide to
bis(hydroxyethyl)isosorbide.
[0022] Purification of bis(2-hydroxyethyl)Isosorbide:
[0023] The resulting bis(2-hydroxyethyl)isosorbide product may be
purified by any method known within the art, for example, by
distillation. As is known within the art, hydroxyethylation
processes with ethylene oxide or ethylene carbonate generally lead
to a mixture of products. Said mixture typically is the result of
the initially formed bis(2-hydroxyethyl)isosor- bide product
further reacting with additional ethylene carbonate to form higher
hydroxy terminated polyethers. Formation of such higher polyethers
may be controlled by the amount of added ethylene carbonate, the
exact nature of the catalyst system, and the reaction conditions.
While it is most preferred that the bis(2-hydroxyethyl)isosorbide
to be used in the preparation of the polymeric materials described
below be essentially pure, it is contemplated that
bis(2-hydroxyethyl)isosorbide may include said higher hydroxy
terminated polyethers derived from additional hydroxyethylation
reactions between ethylene carbonate and the as formed products. It
is preferred that such impurities be below 10 weight percent of the
bis(2-hydroxyethyl)isosorbide product.
[0024] A wide variety of other preparative methods for the
preparation of 2-hydroxyethyl ethers have been reported within the
art. For example, Shibatani, et. al., in Japanese Patent 53098917,
describe the conversion of alcohols to 2-hydroxyethyl ethers by
reacting the alcohols with formaldehyde, hydrogen, and carbon
monoxide in the presence of oxo catalysts. Any known preparative
method to produce 2-hydroxyethyl ethers may find use in the present
invention. Uses of bis(2-hydroxyethyl)isosorb- ide:
[0025] Uses of bis(2-hydroxyethyl)Isosorbide:
[0026] Bis(2-hydroxyethyl)isosorbide will find many valuable uses
in the art. Bis(2-hydroxyethyl)isosorbide may be chemically
modified to form, for example bisacrylate esters or bis vinyl
ethers, which will find use in photochemical or thermal cured vinyl
resin compositions. Alternatively, bis(2-hydroxyethyl)isosorbide
may be reacted with epichlorohydrin and base to form bis(glycidyl
ether) adducts which may serve in epoxy resins. For example,
bis(2-hydroxyethyl)isosorbide will find use as a monomer in
polymeric compositions, such as polyesters, polyamide esters,
polycarbonates, polycarbonate esters, polyurethanes, polyether
sulfones, polyether ketones, polyether ether ketones, and the
like.
[0027] Polyesters:
[0028] One further aspect of the present invention includes
polyesters which incorporate bis(2-hydroxyethyl)isosorbide. Said
polyesters with bis(2-hydroxyethyl)isosorbide comonomer are
comprised essentially of:
[0029] (a) 45.0 to 50.0 mole percent of a dicarboxylic acid
component,
[0030] (b) 50.0 to 0.1 mole percent of
bis(2-hydroxyethyl)isosorbide,
[0031] (c) 0 to 49.9 mole percent of at least one additional glycol
component, and
[0032] (d) 0 to 5.0 mole percent of at least one polyfunctional
branching agent.
[0033] Said dicarboxylic acid component is meant to include
unsubstituted and substituted aromatic, aliphatic, unsaturated, and
acyclic dicarboxylic acids and the lower alkyl esters of aromatic,
aliphatic, unsaturated, and acyclic dicarboxylic acids having from
8 carbons to 36 carbons. Specific examples of the desirable
dicarboxylic acid component include terephthalic acid, dimethyl
terephthalate, isophthalic acid, dimethyl isophthalate,
2,6-napthalene dicarboxylic acid, dimethyl-2,6-naphthalate,
2,7-naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate,
3,4'-diphenyl ether dicarboxylic acid, dimethyl-3,4'diphenyl ether
dicarboxylate, 4,4'-diphenyl ether dicarboxylic acid,
dimethyl-4,4'-diphenyl ether dicarboxylate, 3,4'-diphenyl sulfide
dicarboxylic acid, dimethyl-3,4'-diphenyl sulfide dicarboxylate,
4,4'-diphenyl sulfide dicarboxylic acid, dimethyl-4,4'-diphenyl
sulfide dicarboxylate, 3,4'-diphenyl sulfone dicarboxylic acid,
dimethyl-3,4'-diphenyl sulfone dicarboxylate, 4,4'-diphenyl sulfone
dicarboxylic acid, dimethyl-4,4'-diphenyl sulfone dicarboxylate,
3,4'-benzophenonedicarboxylic acid,
dimethyl-3,4'-benzophenonedicarboxylate,
4,4'-benzophenonedicarboxylic acid,
dimethyl-4,4'-benzophenonedicarboxylate, 1,4-naphthalene
dicarboxylic acid, dimethyl-1,4-naphthalate, 4,4'-methylene
bis(benzoic acid), dimethyl-4,4'-methylenebis(benzoate), and the
like and mixtures derived therefrom. Preferably, the aromatic
dicarboxylic acid component is derived from terephthalic acid,
dimethyl terephthalate, isophthalic acid, dimethyl isophthalate,
2,6-naphthalene dicarboxylic acid, dimethyl-2,6-naphthalate, metal
salts of 5-sulfo-dimethylisophthalate, oxalic acid, dimethyl
oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl
succinate, methylsuccinic acid, glutaric acid, dimethyl glutarate,
2-methylglutaric acid, 3-methylglutaric acid, adipic acid, dimethyl
adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid,
pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic
acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid,
undecanedioic acid, 1,12-dodecanedicarboxylic acid, hexadecanedioic
acid, docosanedioic acid, tetracosanedioic acid, dimer acid,
1,4-cyclohexanedicarboxylic acid, dimethyl-1,4-cyclohexaned
icarboxylate, 1,3-cyclohexanedicarboxylic acid,
dimethyl-1,3-cyclohexanedicarboxylate, 1,1-cyclohexanediacetic
acid, fumaric acid, maleic anhydride, maleic acid,
hexahydrophthalic acid, phthalic acid, and the like and mixtures
derived therefrom. These examples should not be considered
limiting. Essentially any dicarboxylic acid known within the art
may find utility within the present invention.
[0034] Said other glycol component is meant to include
unsubstituted, substituted, straight chain, branched, cyclic
aliphatic, aliphatic-aromatic or aromatic diols having from 2
carbon atoms to 36 carbon atoms and poly(alkylene ether) glycols
with molecular weights between about 250 to 4,000. Specific
examples of the desirable other glycol component include ethylene
glycol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol,
1,3-butanediol, 1,3-2-methylpropanediol, neopentyl glycol,
1,4-butanediol, 1,3-hexanediol, 1,6-hexanediol,
2-ethyl-2-methyl-1,3-propanediol, 1,8-octanediol, 1,10-decanediol,
1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, dimer
diol, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane,
1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene
glycol), poly(ethylene ether) glycols, poly(butylene ether) glycols
and the like and mixtures derived therefrom. These examples should
not be interpreted as limiting. Essentially any other glycol known
within the art may find use within the present invention.
[0035] Said optional polyfunctional branching agent is meant to
include any material with three or more carboxylic acid functions,
hydroxy functions or a mixture thereof. Specific examples of the
desirable polyfunctional branching agent component include
1,2,4-benzenetricarboxyl- ic acid, (trimellitic acid),
trimethyl-1,2,4-benzenetricarboxylate, 1,2,4-benzenetricarboxylic
an hydride, (trimellitic anhydride), 1,3,5-benzenetricarboxylic
acid, 1,2,4,5-benzenetetracarboxylic acid, (pyromellitic acid),
1,2,4,5-benzenetetracarboxylic dianhydride, (pyromellitic
anhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride, citric acid,
tetrahydrofuran-2,3,4,5-tetracarboxylic acid,
1,3,5-cyclohexanetricarboxy- lic acid, pentaerythritol,
2-(hydroxymethyl)-1,3-propanediol, 2,2-bis(hydroxymethyl)propionic
acid, trimer acid, and the like and mixtures therefrom. This should
not be considered limiting. Essentially any polyfunctional material
which includes three or more carboxylic acid or hydroxyl functions
may find use within the present invention. Said polyfunctional
branching agent may be included when higher resin melt viscosity is
desired for specific end uses. Examples of said end uses may
include melt extrusion coatings, melt blown films or containers,
foam and the like.
[0036] To give the desired physical properties for many end uses,
the polyesters which incorporate bis(2-hydroxyethyl)isosorbide of
the present invention need to have an inherent viscosity, which is
an indicator of molecular weight, of at least equal to or greater
than 0.15. More desirably, the inherent viscosity, (IV), of
polyesters which include bis(2-hydroxyethyl)isosorbide will be at
least equal to 0.35 dL/g, as measured on a 0.5 percent
(weight/volume) solution of the copolyester in a 50:50 (weight)
solution of trifluoroacetic acid:dichloromethane solvent system at
room temperature. These inherent viscosities will be sufficient for
some applications. Higher inherent viscosities are desirable for
many other applications, such as films, bottles, sheet, molding
resin and the like. The polymerization conditions may be adjusted
to obtain the desired inherent viscosities up to at least about 0.5
and desirably higher than 0.65 dL/g. Further processing of the
polyester may achieve inherent viscosities of 0.7, 0.8, 0.9, 1.0,
1.5, 2.0 dL/g and even higher.
[0037] The molecular weight is normally not measured directly.
Instead, the inherent viscosity of the polymer in solution or the
melt viscosity is used as an indicator of molecular weight. The
inherent viscosities are an indicator of molecular weight for
comparisons of samples within a polymer family, such as
poly(ethylene terephthalate), poly(butylene terephthalate), etc.,
and are used as the indicator of molecular weight herein.
[0038] Alternatively, certain polyester end uses prefer relatively
low molecular weight materials. For example, polyester polyols are
used in the preparation of, for example, polyurethanes and
polycarbonate esters. The polyester polyols of the present
invention which incorporate bis(2-hydroxyethyl)isosorbide may have
molecular weights in the range between 500 and 10,000.
[0039] The polyesters of the present invention may be prepared by
conventional polycondensation techniques. A review reference on
polyesters and their manufacture is Anthony J. East, Michael
Golden, and Subhash Makhija, in Encyclopedia of Chemical
Technology, vol. 19, fourth edition, Executive Editor, Jacqueline
I. Kroschwitz, Editor, Mary Howe-Grant, pp. 609-653 (1996), which
is hereby incorporated by reference in the present invention. The
product compositions may vary somewhat based on the method of
preparation used, particularly in the amount of diol that is
present within the polymer. These methods include the reaction of
the diol monomers with the acid chlorides. For example, acid
chlorides of the dicarboxylic acid component may be combined with
the bis(2-hydroxyethyl)isosorbide and the other glycol component in
a solvent, such as toluene, in the presence of a base, such as
pyridine, which neutralizes the hydrochloric acid as it is
produced. Such procedures are known. See, for example, R. Storbeck,
et. al., in J. Appl. Polymer Science, Vol. 59, pp. 1199-1202
(1996). Other well known variations using acids chlorides may also
be used, such as the interfacial polymerization method, or the
monomers may simply be stirred together while heating.
[0040] When an isosorbide-containing polyester is made using acid
chlorides, the ratio of the monomer units in the product polymer is
about the same as the ratio of reacting monomers. Therefore, the
ratio of monomers charged to the reactor is about the same as the
desired ratio in the product. A stoichiometric equivalent of the
diol components and the diacid components generally will be used to
obtain a high molecular weight polymer.
[0041] Polyester Preparation:
[0042] Preferably, the polyesters which incorporate
bis(2-hydroxyethyl)isosorbide of the present invention will be
produced through a melt polymerization method. In the melt
polymerization method, the dicarboxylic acid component, (either as
acids, esters, or mixtures thereof), the
bis(2-hydroxyethyl)isosorbide, the other glycol component and
optionally the polyfunctional branching agent, are combined in the
presence of a catalyst to a high enough temperature that the
monomers combine to form esters and diesters, then oligomers, and
finally polymers. The polymeric product at the end of the
polymerization process is a molten product. Generally, the other
diol component is volatile and distills from the reactor as the
polymerization proceeds. Such procedures are known. See, for
example, U.S. Pat. Nos. 3,563,942, 3,948,859, 4,094,721, 4,104,262,
4,166,895, 4,252,940, 4,390,687, 4,419,507, 4,585,687, 5,053,482,
5,292,783, 5,446,079, 5,480,962, and 6,063,464 and the references
cited therein, which are herein incorporated by reference.
[0043] The melt process conditions of the present invention,
particularly the amounts of monomers used, depend on the polymer
composition that is desired. The amount of
bis(2-hydroxyethyl)isosorbide, other glycol component, dicarboxylic
acid component, and branching agent are desirably chosen so that
the final polymeric product contains the desired amounts of the
various monomer units, desirably with equimolar amounts of monomer
units derived from the respective diol and diacid components.
Because of the volatility of some of the monomers, especially some
of the other glycol components, and depending on such variables as
whether the reactor is sealed, (i.e., is under pressure), the
polymerization temperature ramp rate, and the efficiency of the
distillation columns used in synthesizing the polymer, some of the
monomers may need to be included in excess at the beginning of the
polymerization reaction and removed by distillation as the reaction
proceeds. This is particularly true of the other glycol
component.
[0044] The exact amount of monomers to be charged to a particular
reactor is readily determined by a skilled practitioner, but often
will be in the ranges below. Excesses of the diacid, diol, and
bis(2-hydroxyethyl)isosor- bide are often desirably charged, and
the excess diacid, diol and bis(2-hydroxyethyl)isosorbide is
desirably removed by distillation or other means of evaporation as
the polymerization reaction proceeds. The other glycol component is
desirably charged at a level 0 to 100 percent greater than the
desired incorporation level in the final product. For examples of
the other glycol component which are volatile under the
polymerization conditions, such as ethylene glycol,
1,3-propanediol, or 1,4-butanediol, 30 to 100 percent excesses are
desirably charged. For less volatile examples of the other glycol
component, such as dimer diol, no excesses need be desirably
charged.
[0045] The amount of monomers varies widely because of the wide
variation in the monomer loss during polymerization, depending on
the efficiency of distillation columns and other kinds of recovery
and recycle systems and the like, and are only an approximation.
Exact amounts of monomers that are charged to a specific reactor to
achieve a specific composition are readily determined by a skilled
practitioner.
[0046] In the polymerization process, the monomers are combined,
and are heated gradually with mixing with a catalyst or catalyst
mixture to a temperature in the range of 200.degree. C. to about
300.degree. C., desirably 250.degree. C. to 295.degree. C. The
exact conditions and the catalysts depend on whether the diacids
are polymerized as true acids or as dimethyl esters. The catalyst
may be included initially with the reactants, and/or may be added
one or more times to the mixture as it is heated. The catalyst used
may be modified as the reaction proceeds. The heating and stirring
are continued for a sufficient time and to a sufficient
temperature, generally with removal by distillation of excess
reactants, to yield a molten polymer having a high enough molecular
weight to be suitable for making fabricated products.
[0047] Catalysts that may be used include salts of Li, Ca, Mg, Mn,
Zn, Pb, Sb, Sn, Ge, and Ti, such as acetate salts and oxides,
including glycol adducts, and Ti alkoxides. These catalysts are
generally known in the art, and a skilled practitioner may readily
select the specific catalyst or combination or sequence of
catalysts used. The preferred catalyst and preferred conditions
differ depending on, for example, whether the diacid monomer is
polymerized as the free diacid or as a dimethyl ester and the exact
chemical identity of the other glycol component.
[0048] The monomer composition of the polymer is chosen for
specific uses and for specific sets of properties. For uses where a
partially crystalline polymer is desired, as for example food and
beverage containers, specifically, such as hot fill or cold fill
bottles, fibers, and films, the polymer will generally have a
monomer composition which allows for some crystallinity in the
final polymer product.
[0049] For applications where it is desirable to have an amorphous
polymer, for example, transparent optical articles or solvent
soluble copolyesters, the amount of bis(2-hydroxyethyl)isosorbide
moiety is generally greater than 2.0 mole percent. As one skilled
in the art will appreciate, the exact thermal properties observed
will be a complex function of the exact chemical identity and level
of each component utilized in the copolyester composition.
[0050] Polymers can be made by the melt condensation process above
having adequate inherent viscosity for many applications. Solid
state polymerization may be used to achieve even higher inherent
viscosities (molecular weights).
[0051] Crystallinity:
[0052] The product made by melt polymerization, after extruding,
cooling and pelletizing, may be essentially noncrystalline.
Noncrystalline material can be made semicrystalline by heating it
to a temperature above the glass transition temperature for an
extended period of time. This induces crystallization so that the
product can then be heated to a higher temperature to raise the
molecular weight.
[0053] The polymer may also be crystallized prior to solid state
polymerization by treatment with a relatively poor solvent for
polyesters which induces crystallization. Such solvents reduce the
glass transition temperature (Tg) allowing for crystallization.
Solvent induced crystallization is known for polyesters and is
described in U.S. Pat. Nos. 5,164,478 and 3,684,766, which are
incorporated herein by reference.
[0054] The semicrystalline polymer is subjected to solid state
polymerization by placing the pelletized or pulverized polymer into
a stream of an inert gas, usually nitrogen, or under a vacuum of 1
Torr, at an elevated temperature, but below the melting temperature
of the polymer for an extended period of time.
[0055] Some of the above described polyesters which incorporate
bis(2-hydroxyethyl)isosorbide are found to be t soluble in common,
non-halogenated, polar solvents. Examples of said non-halogenated,
polar solvents include tetrahydrofuran, dimethyl acetamide,
dimethyl formamide, N-methylpyrollidone, dimethylsulfoxide, and the
like. Tetrahydrofuran is preferred. Certain examples of the
polyesters which incorporate bis(2-hydroxyethyl)isosorbide of the
current invention are found to be readily soluble in said solvents
and the resulting polymer solutions are found to provide clear
films.
[0056] Additives:
[0057] It is understood that the polyesters which incorporate
bis(2-hydroxyethyl)isosorbide of the present invention may be used
with additives known within the art. Such additives may include
thermal stabilizers, for example, phenolic antioxidants, secondary
thermal stabilizers, for example, thioethers and phosphites, UV
absorbers, for example benzophenone- and benzotriazole-derivatives,
UV stabilizers, for example, hindered amine light stabilizers,
(HALS), and the like. Said additives may further include
plasticizers, processing aides, flow enhancing additives,
lubricants, pigments, flame retardants, impact modifiers,
nucleating agents to increase crystallinity, antiblocking agents
such as silica and the like. In addition, the compositions of the
present invention may be filled with, for example, wood flour,
gypsum, wollastonite, chalk, kaolin, clay, silicon oxide, calcium
terephthalate, aluminum oxide, titanium oxide, calcium phosphate,
lithium fluoride, cellulose, starch, chemically modified starch,
thermoplastic starch, calcium carbonate, reinforcing agents, such
as glass, and the like. The compositions of the present invention
may also find use as a component of a polymer blend with other
polymers, such as cellulose ethers, thermoplastic starch,
poly(vinyl alcohol), other polyesters, polycarbonates, nylons,
polyamides, polyolefins, polyolefin elastomers, and the like. This
should not be considered limiting. Essentially any additive and
filler of the art may find use in the polyesters which incorporate
bis(2-hydroxyethyl)isosorbide of the present invention.
[0058] Biodegradability:
[0059] Some of the polyester compositions of the present invention
which incorporate bis(2-hydroxyethyl)isosorbide will be found to be
biodegradable, as determined through the below mentioned ISO 14855
composting method. Preferably, said biodegradable copolyester of
the present invention which incorporate
bis(2-hydroxyethyl)isosorbide will contain, at least as a portion
of the dicarboxylic acid component, aliphatic dicarboxylic
acids.
[0060] The inadequate treatment of municipal solid waste which is
being put in landfills and the increasing addition of nondegradable
materials, including plastics, to municipal solid waste streams are
combining to drastically reduce the number of landfills available
and to increase the costs of municipal solid waste disposal. While
recycling of reusable components of the waste stream is desirable
in many instances, the costs of recycling and the infrastructure
required to recycle materials is sometimes prohibitive. In
addition, there are some products which do not easily fit into the
framework of recycling. The composting of non-recyclable solid
waste is a recognized and growing method to reduce solid waste
volume for landfilling and/or making a useful product from the
waste to improve the fertility of fields and gardens. One of the
limitations to marketing such compost is the visible contamination
by undegraded plastic, such as film or fiber fragments.
[0061] It is desired to provide components which are useful in
disposable products and which are degraded into less contaminating
forms under the conditions typically existing in waste composting
processes. These conditions may involve temperatures no higher than
70 degrees C., and averaging in the 55-60 degrees C. range, humid
conditions as high as 100 percent relative humidity, and exposure
times which range from weeks to months. It is further desirable to
provide disposable components which will not only degrade
aerobically/anaerobically in composting, but will continue to
degrade in the soil or landfill. As long as water is present, they
will continue to break down into low molecular weight fragments
which can be ultimately biodegraded by microorganisms completely
into biogas, biomass, and liquid leachate, as for natural organics
like wood.
[0062] Polyesters have been considered for biodegradable articles
and end uses in the past. Said biodegradable polyesters can be
described as belonging to three general classes; aliphatic
polyesters, aliphatic-aromatic polyesters and sulfonated
aliphatic-aromatic polyesters.
[0063] Aliphatic polyesters are meant to include polyesters derived
solely from aliphatic dicarboxylic acids, such as poly(ethylene
succinate), poly(1,4-butylene adipate), and the like, as well as
poly(hydroxyalkanates), such as polyhydroxybutyrate, polylactide,
polycaprolactone, polyglycolide and the like. Representative art in
the area of aliphatic polyesters includes, for example;
Clendinning, et. al., in U.S. Pat. No. 3,932,319, Casey, et. al.,
in U.S. Pat. No. 4,076,798, Tokiwa, et. al., in U.S. Pat. No.
5,256,711, Buchanan, et. al., in U.S. Pat. Nos. 5,292,783,
5,559,171, 5,580,911, and 5,599,858, Tajima, et. al., in U.S. Pat.
No. 5,300,572, Taka, et. al., in U.S. Pat. No. 5,324,794,
Takahashi, in U.S. Pat. No. 5,349,028, Imaizumi, in U.S. Pat. No.
5,530,058, Itoh, et. al., in U.S. Pat. No. 5,391,700 and U.S. Pat.
No. 5,616,681, Noda, et. al., in U.S. Pat. Nos. 5,653,930 and
5,780,368, Imaizumi, et. al., in U.S. Pat. No. 5,714,569, Kuroda,
et. al., in U.S. Pat. No. 5,786,408, and Sugimoto, in U.S. Pat. No.
6,083,621.
[0064] Aliphatic-aromatic polyesters are meant to include
polyesters derived from a mixture of aliphatic dicarboxylic acids
and aromatic dicarboxylic acids. Representative teachings in the
area of aliphatic-aromatic copolyesters include, for example;
Sublett, et. al., in U.S. Pat. No. 3,948,859, Buxbaum, et. al., in
U.S. Pat. No. 4,166,895, Horlbeck, et. al., in U.S. Pat. No.
4,328,059, Sublett, in U.S. Pat. No. 4,419,507, Buchanan, et. al.,
in U.S. Pat. No. 5,446,079, Gordon, et. al., in U.S. Pat. No.
5,594,076, Khemani, in U.S. Pat. Nos. 5,661,193 and 6,020,393, and
Lorcks, et. al., in U.S. Pat. No. 6,096,809.
[0065] Sulfonated aliphatic-aromatic polyesters are meant to
include polyesters derived from a mixture of aliphatic dicarboxylic
acids and aromatic dicarboxylic acids and, in addition, incorporate
a sulfonated monomer, such as the metal salts of 5-sulfoisophthalic
acid. Representative art teachings in the area of sulfonated
aliphatic-aromatic copolyesters includes, for example; King, et.
al., in U.S. Pat. No. 3,936,389, Griffing, et. al., in U.S. Pat.
No. 3,018,272, Kotera, et. al., in U.S. Pat. No. 4,340,519, Tung,
in U.S. Pat. No. 4,390,687, Miller, in U.S. Pat. No. 4,394,442,
Posey, et. al., in U.S. Pat. Nos. 4,476,189, 4,525,419, and
4,585,687, Tietz, in U.S. Pat. No. 5,053,482, Tietz, in U.S. Pat.
No. 5,097,005, Gallagher, et. al., in U.S. Pat. No. 5,097,004,
Gallagher, et. al., in U.S. Pat. No. 5,171,308, Romesser, et. al.,
in U.S. Pat. No. 5,295,985, Gallagher, et. al., in U.S. Pat. No.
5,171,309, Gallagher, et. al., in U.S. Pat. No. 5,219,646, Fish,
et. al., in U.S. Pat. No. 5,354,616, Warzelhan, et. al., in U.S.
Pat. Nos. 5,817,721, 5,880,220, 5,889,135, and 6,018,004, and
Yamamoto, et. al., in U.S. Pat. No. 6,103,858.
[0066] Other Polyester Embodiments:
[0067] Unsaturated polyesters are also known within the art.
Reference is made to Jeffrey Selley in Encyclopedia of Chemical
Technology, vol. 19. Fourth ed., Executive Editor, Jacqueline I.
Kroschwitz, Editor, Mary Howe-Grant, pp. 654-678 (1996).
Unsaturated polyesters which incorporate
bis(2-hydroxyethyl)isosorbide of the present invention may be
prepared as described therein.
[0068] Polyester polyols are known within the art. They are used,
for example, in the preparation of coatings, paints and
polyurethanes. Polyester polyols which incorporate
bis(2-hydroyethyl)isosorbide of the present invention may be
produced by any known method in the art. Generally this includes
adding a dicarboxylic acid component, a bis(2-hydroxyethyl)
isosorbide component, an other glycol component and optionally a
catalyst and a branching agent together, typically utilizing a
molar excess of the glycol component, (the combination of the
bis(2-hydroxyethyl)isosorbide component and the other glycol
component), and heating to the desired molecular weight, typically
as measured by the hydroxyl or acid number. The acid number is
defined by DIN 53 402 and the hydroxyl number is defined by DIN 53
240. Typically, polyester polyols will preferably have molecular
weights between 500 and 10,000, more preferably between 500 and
5,000. However, higher molecular weight polyester polyols are
producible. Representative references include U.S. Pat. Nos.
3,994,851, 4,104,240, 4,243,705, 4,540,771, 4,888,441, 4,922,002,
5,976,706, 6,087,466, and 6,087,466, and the references cited
therein. These references are hereby incorporated by reference in
the present invention.
[0069] Polyester amides are known within the art. Polyester amides
of the present invention which incorporate
bis(2-hydroxyethyl)isosorbide are producible by any known methods
in the art. Representative references include, for example, U.S.
Pat. Nos. 4,709,004, 4,835,248, 5,349,011, 5,457,144, and the
references cited therein.
[0070] Polyurethanes:
[0071] A further aspect of the present invention includes
polyurethanes which incorporate bis(2-hydroxyethyl)isosorbide. Said
polyurethanes which incorporate bis(2-hydroxyethyl)isosorbide are
comprised essentially of:
[0072] (a) 45.0 to 50.0 mole percent of a polyisocyanate
component,
[0073] (b) 50.0 to 0.1 mole percent of
bis(2-hydroxyethyl)isosorbide,
[0074] (c) 0 to 5.0 mole percent at least one polyester polyol,
and
[0075] (d) 0 to 49.9 mole percent of at least one additional glycol
component.
[0076] Said polyisocyanate component is meant to include both
polyisocyanates and chemically blocked isocyanates, such as with
methanol, oximes such as methylethyl ketone oxime, lactams such as
caprolactam, imidazole or phenols. Specific examples of useful
polyisocyanate components includes diphenylmethane diisocyanate,
toluene diisocyanate, xylene diisocyanate, phenylene diisocyanate,
naphthalene diisocyanate, 4,4'-methylene-bis-(cyclohexyl
isocyanate), isophorone diisocyanate, 1,6-hexamethylene
diisocyanate, the biuret from 1,6-hexamethylene diisocyanate
commercially available from Mobay Chemical Company as DESMODUR N,
1,12-dodecane diisocyanate and the like and mixtures thereof.
[0077] Said other glycol component is meant to include
unsubstituted, substituted, straight chain, branched, cyclic
aliphatic, aliphatic-aromatic or aromatic diols having from 2
carbon atoms to 36 carbon atoms and poly(alkylene ether) glycols
with molecular weights between about 250 to 4,000. Specific
examples of the desirable other glycol component include ethylene
glycol, 1,3-propanediol, 1,2-propanediol,1,2-butanediol,
1,3-butanediol, 1,3-2-methylpropanediol, neopentyl glycol,
1,4-butanediol, 1,3-hexanediol, 1,6-hexanediol,
2-ethyl-2-methyl-1,3-propanediol, 1,8-octanediol, 1,10-decanediol,
1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, dimer
diol, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0/2.6]decane,
1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene
glycol), poly(ethylene ether) glycols, poly(butylene ether) glycols
and the like and mixtures derived therefrom. This should not be
taken as limiting. Essentially any other glycol known within the
art may find use within the present invention.
[0078] Catalysts, for example, such as organotin compounds, may be
employed in the polymerization reaction to form polyurethanes.
[0079] Methods to prepare polyurethanes are known within the art.
Reference is made to a recent review by Henri Ulrich in
Encyclopedia of Chemical Technology, vol. 24, fourth ed., Executive
Editor, Jacqueline I. Kroschwitz, Editor, Mary Howe-Grant, pp.
695-726 (1996). Polyurethanes which incorporate
bis(2-hydroxyethyl)isosorbide or polyester polyols which
incorporate bis(2-hydroxyethyl)isosorbide of the present invention
may be produced by any known method in the art. Representative art
includes, for example U.S. Pat. Nos. 3,943,077, 4,139,501,
4,251,635, 4,258,141, 4,284,730, 4,317,889, 4,433,071, 6,087,466,
6,103,822, 6,111,048, 6,114,403, and the references cited
therein.
[0080] Polyethers:
[0081] Polyethers, including polyether sulfones and polyether
ketones, are known within the art. The polyethers of the present
invention, which includes polyether sulfones and polyether ketones
which incorporate bis(2-hydroxyethyl)isosorbide, are producible by
any known method in the art. Reference is made to Dwain M. White in
Encyclopedia for Chemical Technology, vol. 19, fourth editions,
Executive Editor, Jacqueline I. Kroschwitz, Editor, Mary
Howe-Grant, pp. 678-701 (1996) and the references cited
therein.
[0082] Polycarbonates:
[0083] Polycarbonates and polycarbonate esters are known within the
art. The polycarbonates and polycarbonate esters which incorporate
bis(2-hydroxyethyl)isosorbide and polyester polyols which
incorporate bis(2-hydroxyethyl)isosorbide of the present invention
are producible by any known method of the art. Reference is made to
Daniel J. Brunelle in Encyclopedia of Chemical Technology, volume
19, fourth edition, Executive Editor, Jacqueline I. Kroschwitz,
Editor, Mary Howe-Grant, pp. 584-608 (1996) and the references
cited therein. Further art references include, for example, U.S.
Pat. Nos. 4,041,018, 4,104,217, 4,267,120, and the references cited
therein.
[0084] Shaped Articles:
[0085] As a further aspect of the present invention, the polymeric
materials which incorporate bis(2-hydroxyethyl)isosorbide of the
present invention have been found to be useful within a wide
variety of shaped articles. Said polymeric materials of the present
invention which incorporate bis(2-hydroxyethyl)isosorbide and/or
polyester polyols which incorporate bis(2-hydroxyethyl)isosorbide
may include, for example, polyesters, polyamide esters,
polyurethanes, polycarbonates, polycarbonate esters, polyether
sulfones, polyether ketones and the like. Examples of shaped
articles include film, sheets, fiber, melt blown containers, molded
parts, such as cutlery, foamed parts, polymeric melt extrusion
coatings onto substrates, polymeric solution coatings onto
substrates and the like. The polymeric materials which incorporate
bis(2-hydroxyethyl)isosorbide of the present invention may be
solution or melt processed to form coatings, films and the like.
Coatings may be produced by coating a substrate with polymer
solutions of the polymeric materials of the present invention
followed by drying, by coextruding the polymeric materials of the
present invention with other materials, or by melt coating a
preformed substrate with the polymeric materials of the present
invention. This should not be considered limiting. The polymeric
materials of the present invention will find utility in essentially
any process known within the art. Said coatings derived from the
polymeric materials of the present invention will find utility as
barriers to moisture, oxygen, carbon dioxide and the like. Said
coatings derived from the polymeric materials of the present
invention will also be useful as adhesives. Films of the polymeric
materials of the present invention may be produced by any known art
method, including, for example, solution or melt casting.
[0086] Films and Sheets:
[0087] A further specific aspect of the present invention includes
shaped articles in the form of films produced from polymeric
materials which incorporate bis(2-hydroxyethyl)isosorbide. Said
films and sheets of the present invention which incorporate
bis(2-hydroxyethyl)isosorbide and/or polyester polyols which
incorporate bis(2-hydroxyethyl)isosorbide may include, for example,
polyesters, polyamide esters, polyurethanes, polycarbonates,
polycarbonate esters, polyether sulfones, polyether ketones and the
like.
[0088] Film Applications:
[0089] Polymeric films have a variety of uses, such as in
packaging, especially of foodstuffs, adhesives tapes, insulators,
capacitors, photographic development, x-ray development and as
laminates, for example. For many of these uses, the heat resistance
of the film is an important factor. Therefore, a higher melting
point and glass transition temperature are desirable to provide
better heat resistance and more stable electrical characteristics.
Further, it is desired that these films have good tensile strength
and a high elongation at break.
[0090] The polymeric materials which incorporate
bis(2-hydroxyethyl)isosor- bide of the present invention may be
formed into a film for use in any one of the many different
applications, such as food packaging, labels, dielectric
insulation, a water vapor barrier or the like. The monomer
composition of the polymeric material is preferably chosen to
result in a partially crystalline polymer desirable for the
formation of film, wherein the crystallinity provides strength and
elasticity. As first produced, the polymeric material is generally
semi-crystalline in structure. The crystallinity increases on
reheating and/or stretching of the polymer, as occurs in the
production of film.
[0091] In the process of the invention, film is made from the
polymer by any process known in the art. The difference between a
film and a sheet is the thickness, but there is no set industry
standard as to when a film becomes a sheet. For purposes of this
invention, a film is less than or equal to 0.25 mm (10 mils) thick,
preferably between about 0.025 mm and 0.15 mm (1 mil and 6 mils).
However, thicker films can be formed up to a thickness of about
0.50 mm (20 mils).
[0092] Film Extrusion:
[0093] The film of the present invention is preferably formed by
either solution casting or extrusion. Extrusion is particularly
preferred for formation of "endless" products, such as films and
sheets, which emerge as a continuous length. In extrusion, the
polymeric material, whether provided as a molten polymer or as
plastic pellets or granules, is fluidized and homogenized. This
mixture is then forced through a suitably shaped die to produce the
desired cross-sectional film shape. The extruding force may be
exerted by a piston or ram (ram extrusion), or by a rotating screw
(screw extrusion), which operates within a cylinder in which the
material is heated and plasticized and from which it is then
extruded through the die in a continuous flow. Single screw, twin
screw, and multi-screw extruders may be used as known in the art.
Different kinds of die are used to produce different products, such
as blown film (formed by a blow head for blown extrusions), sheets
and strips (slot dies) and hollow and solid sections (circular
dies). In this manner, films of different widths and thickness may
be produced, and, in some cases, such as when film is used as a
coating, it may be extruded directly onto the object to be coated.
For example, wires and cables can be sheathed directly with
polymeric films extruded from oblique heads. As a further example,
laminated paper coatings can be produced by melt extruding the
polymer directly onto paperboard. After extrusion, the polymeric
film is taken up on rollers, cooled and taken off by means of
suitable devices which are designed to prevent any subsequent
deformation of the film.
[0094] Using extruders as known in the art, film can be produced by
extruding a thin layer of polymer over chilled rolls and then
further drawing down the film to size by tension rolls. Preferably,
the finished film is less than or equal to 0.25 mm thick. Blown
film, which is generally stronger, tougher, and made more rapidly
than cast film, is made by extruding a tube. In producing blown
film, the melt flow is turned upward from the extruder and fed
through an annular die. As this tube leaves the die, internal
pressure is introduced through the die mandrel with air, which
expands the tube from about 1.5 to about 2.5 times the die diameter
and simultaneously draws the film, causing a reduction in
thickness. The resulting sleeve is subsequently slit along one
side, making a larger film width than could be conveniently made
via the cast film method. In extrusion coating, the substrate
(paper, foil, fabric, polymeric film, and the like) is compressed
together with the extruded polymeric melt by means of pressure
rolls so that the polymer impregnates the substrate for maximum
adhesion.
[0095] For manufacturing large quantities of film, a sheeting
calender is employed. The rough film is fed into the gap of the
calender, a machine comprising a number of heatable parallel
cylindrical rollers which rotate in opposite directions and spread
out the polymer and stretch it to the required thickness. The last
roller smooths the film thus produced. If the film is required to
have a textured surface, the final roller is provided with an
appropriate embossing pattern. Alternatively, the film may be
reheated and then passed through an embossing calender. The
calender is followed by one or more cooling drums. Finally, the
finished film is reeled up.
[0096] Alternatively, as mentioned previously, a supporting
material may be coated directly with a film. For example, textile
fabrics, paper, cardboard, metals, various building materials and
the like, may be coated directly with the polymeric material for
the purpose of electrical insulation, protection against corrosion,
protection against the action of moisture or chemicals,
impermeability to gases and liquids, or increasing the mechanical
strength. One process to achieve this is referred to as melt
extrusion of the polymeric melt onto a substrate. Coatings are
applied to textiles, foil, and other sheet materials by
continuously operating spread-coating machines. A coating knife,
such as a "doctor knife", ensures uniform spreading of the coating
materials (in the form of solution, emulsions, or dispersions in
water or an organic medium) on the supporting material, which is
moved along by rollers. The coating is then dried. Alternatively,
when the coating is applied to the supporting material in the form
of a polymeric film, the process is called laminating.
[0097] Metal articles can also be coated with the polymeric film by
means of the whirl sintering process. The articles, heated to above
the melting point of the polymer, are introduced into a fluidized
bed of powdered polymer wherein the polymer particles are held in
suspension by a rising stream of air, thus depositing a coating on
the metal by sintering.
[0098] Extruded films may also be used as the starting material for
other products. For example, the film may be cut into small
segments for use as feed material for other processing methods,
such as injection molding.
[0099] A film may also be made by solution casting, which produces
more consistently uniform gauge film than that made by melt
extrusion. Solution casting comprises dissolving polymeric
granules, powder or the like in a suitable solvent with any desired
formulant, such as a plasticizer or colorant. The solution is
filtered to remove dirt or large particles and cast from a slot die
onto a moving belt, preferably of stainless steel, dried, whereon
the film cools. The extrudate thickness is five to ten times that
of the finished film. The film may then be finished in a like
manner to the extruded film.
[0100] One of ordinary skill in the art will be able to identify
appropriate process parameters based on the polymeric composition
and process used for film formation.
[0101] Sheet Applications:
[0102] For purposes of this invention, a sheet is greater than
about 0.25 mm (10 mils) thick, preferably between about 0.25 mm and
25 mm, more preferably from about 2 mm to about 15 mm, and even
more preferably from about 3 mm to about 10 mm. In a preferred
embodiment, the sheets of the present invention have a thickness
sufficient to cause the sheet to be rigid, which generally occurs
at about 0.50 mm and greater. However, sheets greater than 25 mm,
and thinner than 0.25 mm may be formed.
[0103] Polymeric sheets have a variety of uses, such as in signage,
glazing, (such as in bus stop shelters, sky lights or recreational
vehicles), thermoforming articles, automobile lights, displays and
display substrates, for example. For many of these uses, the heat
resistance of the sheet is an important factor. Therefore, a higher
melting point and glass transition temperature are desirable to
provide better heat resistance and greater stability. Further, it
is desired that these sheets have ultraviolet (UV) and scratch
resistance, good tensile strength, high optical clarity, and good
impact strength, particularly at low temperatures.
[0104] Various polymeric compositions have been used in an attempt
to meet all of the above criteria. In particular, poly(ethylene
terephthalate) (PET) has been used to form low-cost sheets for many
years. However, these PET sheets have poor low temperature impact
strength, a low glass transition temperature (Tg) and a high rate
of crystallization. Thus, PET sheets cannot be used at low
temperatures because of the danger of breakage and they cannot be
used at high temperatures because the polymer crystallizes, thereby
diminishing optical clarity.
[0105] Polycarbonate sheets can be used in applications where low
temperature impact strength is needed, or a high service
temperature is required. In this regard, polycarbonate sheets have
high impact strengths at low temperatures as well as a high Tg
which allows them to be used in high temperature applications.
However, polycarbonate has poor solvent resistance, thereby
limiting its use in certain applications, and is prone to stress
induced cracking. Polycarbonate sheets also provide greater impact
strength than is needed for certain applications, making them
costly and inefficient for use.
[0106] Sheet Preparation:
[0107] The polymeric sheets of the present invention may be formed
by any process known in the art, such as extrusion, solution
casting or injection molding. The parameters for each of these
processes can be easily determined by one of ordinary skill in the
art depending upon viscosity characteristics of the copolyester and
the desired thickness of the sheet. The sheet of the present
invention is preferably formed by either solution casting or
extrusion as described above for film extrusion and film casting.
Further, sheets and sheet-like articles, such as discs, may be
formed by injection molding by any method known in the art.
[0108] The sheets of the present invention as described above may
be thermoformed by any known method into any desirable shape, such
as covers, skylights, shaped greenhouse glazing, displays, food
trays, and the like. The thermoforming is accomplished by heating
the sheet to a sufficient temperature and for sufficient time to
soften the polymeric material of the present invention so that the
sheet can be easily molded into the desired shape. In this regard,
one of ordinary skill in the art can easily determine the optimal
thermoforming parameters depending upon the viscosity and
crystallization characteristics of the polymeric sheet.
[0109] Laminate and Multilayer Applications:
[0110] The polymeric films and sheet of the invention may be
combined with other polymeric materials during extrusion and/or
finishing to form laminates or multilayer films and sheets with
improved characteristics, such as water vapor resistance. In
particular, the polymeric sheet of the invention may be combined
with one or more of the following: poly(ethylene terephthalate)
(PET), aramid, polyethylene sulfide (PES), polyphenylene sulfide
(PPS), polyimide (PI), polyethylene imine (PEI), poly(ethylene
naphthalate) (PEN), polysulfone (PS), polyether ether ketone
(PEEK), olefins, polyethylene, poly(cyclic olefins), cellulose,
polyamides, nylons, elastomers, poly(phenylene oxide) (PPO), and
cyclohexylene dimethylene terephthalate and the like, for example.
Other polymers may also find utility within the present invention.
A multilayer or laminate sheet may be made by any method known in
the art, and may have as many as five or more separate layers
joined together by heat, adhesive and/or tie layer, as known in the
art.
[0111] Post-Forming Operations:
[0112] The film and sheet extrusion processes of the invention can
be combined with a variety of post-extruding operations for
expanded versatility. Such post-forming operations include altering
round to oval shapes, blowing the film or sheet to different
dimensions, machining and punching, biaxial stretching and the
like, as known to those skilled in the art.
[0113] Regardless of how the film or sheet is formed, it is
desirably subjected to biaxial orientation by stretching in both
the machine and transverse direction after formation. The machine
direction stretch is initiated in forming the film or sheet simply
by rolling out and taking up the film or sheet. This inherently
stretches the film or sheet in the direction of take-up, orienting
some of the fibers. Although this strengthens the film or sheet in
the machine direction, it allows the film or sheet to tear easily
in the direction at right angles because all of the fibers are
oriented in one direction.
[0114] Therefore, biaxially stretched films and sheets are
preferred for certain uses where uniformity is desired. Biaxial
stretching orients the fibers parallel to the plane of the film or
sheet, but leaves the fibers randomly oriented within the plane of
the film or sheet. This provides superior tensile strength,
flexibility, toughness and shrinkability, for example, in
comparison to non-oriented films or sheets. It is desirable to
stretch the film or sheet along two axes at right angles to each
other. This increases tensile strength and elastic modulus in the
directions of stretch. It is most desirable for the amount of
stretch in each direction to be roughly equivalent, thereby
providing similar properties or behavior within the film or sheet
when tested from any direction.
[0115] The biaxial orientation may be obtained by any process known
in the art. However, tentering is preferred, wherein the material
is stretched while heating in the transverse direction
simultaneously with, or subsequent to, stretching in the machine
direction.
[0116] Shrinkage can be controlled by holding the sheet in a
stretched position and heating for a few seconds before quenching.
This heat stabilizes the oriented film or sheet, which then may be
forced to shrink only at temperatures above the heat stabilization
temperature.
[0117] Film and Sheet Properties:
[0118] The properties exhibited by a film or sheet will depend on
several factors indicated above, including the polymeric
composition, the method of forming the polymer, the method of
forming the film or sheet, and whether the film or sheet was
treated for stretch or biaxially oriented. These factors affect
many properties of the film or sheet, such as shrinkage, tensile
strength, elongation at break, impact strength, dielectric strength
and constant, tensile modulus, chemical resistance, melting point,
heat deflection temperature, and the like.
[0119] The film or sheet properties may be further adjusted by
adding certain additives and fillers to the polymeric composition,
such as colorants, dyes, UV and thermal stabilizers, antioxidants,
plasticizers, lubricants antiblock agents, slip agents, and the
like, as recited above. Alternatively, the polymeric materials
which incorporate bis(2-hydroxyethyl)isosorbide of the present
invention may be blended with one or more other polymers, such as
starch, elastomers, polyolefins, polyesters, polyamides, nylons,
and the like to improve certain characteristics. Other polymers may
be added to change such characteristics as air permeability,
optical clarity, strength and/or elasticity, for example.
[0120] Containers:
[0121] A further specific aspect of the present invention includes
shaped articles in the form of containers produced from polymeric
materials which incorporate bis(2-hydroxyethyl)isosorbide. Said
polymeric materials of the present invention which incorporate
bis(2-hydroxyethyl)isosorbide and/or polyester polyols which
incorporate bis(2-hydroxyethyl)isosorbide may include, for example,
polyesters, polyamide esters, polyurethanes, polycarbonates,
polycarbonate esters, polyether sulfones, polyether ketones and the
like.
[0122] Plastic containers are widely used for foods and beverages,
and also for non-food materials. Poly(ethylene terephthalate) (PET)
is used to make many of these containers because of its appearance
(optical clarity), ease of blow molding, chemical and thermal
stability, and its price. PET is generally fabricated into bottles
by blow molding processes, and generally by stretch blow
molding.
[0123] In stretch blow molding, PET is first shaped by injection
molding into a thick-walled preformed parison (a "preform"), which
typically is in the shape of a tube with a threaded opening at the
top. The parison may be cooled and then used later in a subsequent
step, or the process may be carried out in one machine with cooling
just to the stretch blow molding temperature. In the stretch blow
molding step, the parison is heated to a high enough temperature in
a mold to allow shaping, but not so hot that it crystallizes or
melts (i.e., just above the glass transition temperature Tg). The
parison is expanded to fill the mold by rapidly stretching it
mechanically in the axial direction (e.g.; by using a mandrel)
while simultaneously forcing air under pressure into the heated
parison to expand it radially. PET is typically modified for blow
molding with a small amount of comonomer, usually
1,4-cyclohexanedimethan- ol or isophthalic acid, which increases
the width of the temperature window for successful blow molding to
about 9 C. The comonomer is necessary because of the need to have a
wider temperature window, and also to decrease the rate of stress
induced crystallization. At the same time, the comonomer may have
the undesirable effect of lowering the glass transition temperature
and reducing the crystallinity of PET. Stretch blow molding of PET,
and blow molding processes in general, are well known in the art.
Reviews are widely available, as for example, "Blow Molding" by C.
Irwin in Encyclopedia of Polymer Science And Engineering, Second
Edition, Vol. 2, John Wiley and Sons, New York, 1985, pp.
447-478.
[0124] The technology is widely used, but there are still
improvements that need to be made. Containers which are derived
from a renewable resource would be an improvement.
[0125] The containers described herein may be made by any method
known in the art, such as extrusion, injection molding, injection
blow molding, rotational molding, thermoforming of a sheet, and
stretch-blow molding.
[0126] In the present invention, the preferred method for molding a
container is stretch-blow molding, which generally used in the
production of poly(ethylene terephthalate) (PET) containers, such
as bottles. In this case, use may be made of any of the cold
parison methods, in which a preformed parison (generally made by
injection molding) is taken out of the mold and then subjected to
stretch blow molding in a separate step. The hot parison method as
known in the art may also be used, wherein the hot parison is
immediately subjected to stretch blow molding in the same equipment
without complete cooling after injection molding to make the
parison. The parison temperature will vary based on the exact
composition of the polymer to be used. Generally, parison
temperatures in the range from about 90.degree. C. to about
160.degree. C. are found useful. The stretch blow molding
temperature will also vary dependant on the exact material
composition used, but a mold temperature of about 80.degree. C. to
about 150.degree. C. is generally found to be useful.
[0127] Containers of the invention may have any shape desirable,
and particularly include narrow-mouth bottles and wide-mouth
bottles having threaded tops and a volume of about 400 mL to about
3 liters, although smaller and larger containers may be formed.
[0128] The containers can be used in standard cold fill
applications. For some of the compositions of the present
invention, hot fill applications may also be used.
[0129] The containers of the invention are suitable for foods and
beverages, and other solids and liquids. The containers are
normally clear and transparent, but can be modified to have color
or to be opaque, rather than transparent, if desired, by adding
colorants or dyes, or by causing crystallization of the polymer,
which results in opaqueness.
[0130] Fibers:
[0131] A further specific aspect of the present invention includes
shaped articles in the form of fiber produced from polymeric
materials which incorporate bis(2-hydroxyethyl)isosorbide. Said
polymeric materials of the present invention which incorporate
bis(2-hydroxyethyl)isosorbide and/or polyester polyols which
incorporate bis(2-hydroxyethyl)isosorbide may include, for example,
polyesters, polyamide esters, polyurethanes, polycarbonates,
polycarbonate esters, polyether sulfones, polyether ketones and the
like.
[0132] Polyester fibers are produced in large quantities for use in
a variety of applications. In particular, these fibers are
desirable for use in textiles, particularly in combination with
natural fibers such as cotton and wool. Clothing, rugs, and other
items may be fashioned from these fibers. Further, polyester fibers
are desirable for use in industrial applications due to their
elasticity and strength. In particular, they are used to make
articles such as tire cords and ropes.
[0133] The term "fibers" as used herein is meant to include
continuous monofilaments, non-twisted or entangled multifilament
yarns, staple yarns, spun yarns, and non-woven materials. Such
fibers may be used to form uneven fabrics, knitted fabrics, fabric
webs, or any other fiber-containing structures, such as tire
cords.
[0134] Synthetic fibers, such as nylon, acrylic, polyesters,
polyurethanes, and others, are made by spinning and drawing the
polymer into a filament, which is then formed into a yarn by
winding many filaments together. These fibers are often treated
mechanically and/or chemically to impart desirable characteristics
such as strength, elasticity, heat resistance, hand (feel of
fabric), and the like as known in the art based on the desired end
product to be fashioned from fibers.
[0135] The monomer composition of the polymeric materials which
incorporates bis(2-hydroxyethyl)isosorbide of the present invention
is desirably chosen to result in a partially crystalline polymer.
The crystallinity is desirable for the formation of fibers,
providing strength and elasticity. As first produced, the polymeric
material is mostly amorphous in structure. In preferred
embodiments, the polymer readily crystallizes on reheating and/or
extension of the polymer.
[0136] In the process of the invention, fibers are made from the
polymer by any process known in the art. Generally, however, melt
spinning is preferred for polymer fibers.
[0137] Melt spinning, which is most commonly used for polyesters,
such as poly(ethylene terephthalate), polyurethanes, and nylons
comprises heating the polymer to form a molten liquid, or melting
the polymer against a heated surface. The molten polymer is forced
through a spinneret with a plurality of fine holes. Upon contact
with air or a non-reactive gas stream after passing through the
spinneret, the polymer solution from each spinneret solidifies into
filaments. The filaments are gathered together downstream from the
spinneret by a convergence guide, and may be taken up by a roller
or a plurality of rollers. This process allows filaments of various
sizes and cross sections to be formed, including filaments having a
round, elliptical, square, rectangular, lobed or dog-boned cross
section, for example.
[0138] Following the extrusion and uptake of the fiber, the fiber
is usually drawn, thereby increasing the crystallization and
maximizing desirable properties such as orientation along the
longitudinal axis, which increases elasticity, and strength. The
drawing may be done in combination with take-up by using a series
of rollers, some of which are generally heated, as known in the
art, or may be done as a separate stage in the process of fiber
formation.
[0139] The polymer may be spun at speeds of from about 600 to 6000
meters per minute or higher, depending on the desired fiber size.
For textile applications, a fiber with a denier per filament of
from about 0.1 to about 100 is desired. Preferably, the denier is
about 0.5 to 20, more preferably 0.7 to 10. However, for industrial
applications the fiber should be from about 0.5 to 100 denier per
filament, preferably about 1.0 to 10.0, most preferably 3.0 to 5.0
denier per filament. The required size and strength of a fiber can
be readily be determined by one of ordinary skill in the art for
any given application.
[0140] The resulting filamentary material is amenable to further
processing through the use of additional processing equipment, or
it may be used directly in applications requiring a continuous
filament textile yarn. If desired, the filamentary material
subsequently may be converted from a flat yarn to a textured yarn
through known false twist texturing conditions or other processes
known in the art. In particular, it is desirable to increase the
surface area of the fiber to provide a softer feel and to enhance
the ability of the fibers to breathe, thereby providing better
insulation and water retention in the case of textiles, for
example. The fibers may therefore be crimped or twisted by the
false twist method, air jet, edge crimp, gear crimp, or stuffer
box, for example. Alternatively, the fibers may be cut into shorter
lengths, called staple, which may be processed into yarn. A skilled
artisan can determine the best method of crimping or twisting based
on the desired application and the composition of the fiber.
[0141] After formation, the fibers are finished by any method
appropriate to the desired final use. In the case of textiles, this
may include dyeing, sizing, or addition of chemical agents such as
antistatic agents, flame retardants, UV light stabilizers,
antioxidants, pigments, dyes, stain resistants, antimicrobial
agents and the like, which are appropriate to adjust the look and
hand of the fibers. For industrial applications, the fibers may be
treated to impart additional desired characteristics such as
strength, elasticity or shrinkage, for example.
[0142] The continuous filament fiber of the invention may be used
either as produced or texturized for use in a variety of
applications such as textile fabrics for apparel and home
furnishings, for example. High tenacity fiber can be used in
industrial applications such as high strength fabrics, tarpaulins,
sail cloth, sewing threads and rubber reinforcement for tires and
V-belts, for example.
[0143] The staple fiber of the invention may be used to form a
blend with natural fibers, especially cotton and wool. In
particular, the polymeric materials form a chemically resistant
fiber which is generally resistant to mold, mildew, and other
problems inherent to natural fibers. The polymer fiber further
provides strength and abrasion resistance and lowers the cost of
material. Therefore, it is ideal for use in textiles and other
commercial applications, such as for use in fabrics for apparel,
home furnishings and carpets.
[0144] Further, the polymer of the invention may be used with
another synthetic or natural polymer to form heterogeneous fiber,
thereby providing a fiber with improved properties. The
heterogeneous fiber may be formed in any suitable manner, such as
side-by-side, sheath-core, and matrix designs, as is known within
the art.
[0145] Processes to produce polyurethane fibers are known within
the art. See, for example, U.S. Pat. No. 6,096,252 and the
references cited therein.
[0146] Shaped Foamed Articles:
[0147] A further specific aspect of the present invention includes
shaped foamed articles produced from the polymeric materials which
incorporate bis(2-hydroxyethyl)isosorbide. Said polymeric materials
of the present invention which incorporate
bis(2-hydroxyethyl)isosorbide and/or polyester polyols which
incorporate bis(2-hydroxyethyl)isosorbide may include, for example,
polyesters, polyamide esters, polyurethanes, polycarbonates,
polycarbonate esters, polyether sulfones, polyether ketones and the
like.
[0148] Thermoplastic polymeric materials are foamed to provide low
density articles, such as films, cups, food trays, decorative
ribbons, furniture parts and the like. For example, polystyrene
beads containing low boiling hydrocarbons, such as pentane, are
formed into light weight foamed cups for hot drinks such as coffee,
tea, hot chocolate and the like. Polypropylene can be extruded in
the presence of blowing agents such as nitrogen or carbon dioxide
gas to provide decorative films and ribbons for package wrappings.
Also, polypropylene can be injection molded in the presence of
blowing agents to form lightweight furniture parts such as table
legs and to form lightweight chairs.
[0149] Polyesters, such as poly(ethylene terephthalate), typically
have a much higher density, (e.g.; 1.3 g/cc), than other polymers.
It would, therefore, be desirable to be able to foam polyester
materials to decrease the weight of molded parts, films, sheets,
food trays, thermoformed parts and the like. Such foamed articles
also provide improved insulating properties than unfoamed
articles.
[0150] It has been generally been found in the art that the
polyester to be foamed should desirably have a high melt viscosity.
This is desired in order to have sufficient melt viscosity to hold
the as formed foamed shape sufficiently long for the polyester to
solidify to form the final foamed article. This can be achieved by
raising the as produced polyester inherent viscosity through
post-polymerization processes, such as the solid state
polymerization method, as described above. Alternatively, the
polyester may incorporate a branching agent, such as described in
U.S. Pat. Nos. 4,132,707, 4,145,466, 4,999,388, 5,000,991,
5,110,844, 5,128,383, and 5,134,028. Such branched polyesters may
additionally be subjected to the solid state polymerization, as
described above, to further enhance the melt viscosity. It has also
been found that the incorporation of sulfonate substituents onto
the polyester backbone raise the apparent melt viscosity of the
polyester, providing an adequately foamable polyester. More
recently, it has been suggested that such sulfonated polyesters may
be reacted with divalent cations to enhance the melt viscosity even
greater, allowing for more desirable foamable polyesters, (see, for
example, U.S. Pat. No. 5,922,782).
[0151] The polyesters of the present invention may be readily
foamed by a wide variety of methods. These include the injection of
an inert gas such as nitrogen or carbon dioxide into the melt
during extrusion or molding operations. Alternatively, inert
hydrocarbon gases such as methane, ethane, propane, butane, and
pentane, or chlorofluorocarbons, hydrochlorofluorocarbons,
hydrofluorocarbons, and the like may be used. Another method
involves the dry blending of chemical blowing agents with the
polyester and then extruding or molding the compositions to provide
foamed articles. During the extrusion or molding operation, an
inert gas such as nitrogen is released from the blowing agents and
provides the foaming action. Typical blowing agents include
azodicarbonamide, hydrazocarbonamide,
dinitrosopentamethylenetetramine, p-toluenesul fonyl
hydrazodicarboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxa-diazin-2-one,
sodium borohydride, sodium bicarbonate, 5-phenyltetrazole,
p,p'-oxybis(benzenesulfonylhydrazide) and the like. Still another
method involves the blending of sodium carbonate or sodium
bicarbonate with one portion of the polyester pellets, blending of
an organic acid, such as citric acid, with another portion of the
polyester pellets and then blending of the two types of pellets
through extrusion or molding at elevated temperatures. Carbon
dioxide gas is released from the interaction of the sodium
carbonate and citric acid to provide the desired foaming action in
the polymeric melt.
[0152] It is desirable that the foamable polyester compositions
incorporate nucleation agents to create sites for bubble
initiation, influence the cell size of the foamed sheet or object
and to hasten the solidification of the as foamed article. Examples
of said nucleation agents may include sodium acetate, talc,
titanium dioxide, polyolefin materials such as polyethylene,
polypropylene, and the like.
[0153] Polymeric foaming equipment and processes are generally
known within the art. See, for example, U.S. Pat. Nos. 5,116,881,
5,134,028, 4,626,183, 5,128,383, 4,746,478, 5,110,844, 5,000,844,
and 4,761,256. Additional reviews on foaming technology may be
found in Kirk-Othmer Encyclopedia of Chemical Technology, Third
Edition, Volume 11, pp. 82-145 (1980), John Wiley and Sons, Inc.,
New York, N.Y. and the Encyclopedia of Polymer Science and
Engineering, Second Edition, Volume 2, pp. 434-446 (1985), John
Wiley and Sons, Inc., New York, N.Y. These references are herein
incorporated into the present invention.
[0154] As described above, the foamable polyester compositions may
include a wide variety of additives, fillers, or be blended with
other materials. For biodegradable foams, the addition of starch,
starch derivatives, cellulose and cellulose derivatives is
especially preferred.
[0155] Polyurethane foams are known within the art. Representative
references include, for example, U.S. Pat. Nos. 4,139,501,
4,284,730, 4,317,889, 4,365,025, 4,374,207, 4,384,051, 4,451,588,
4,529,742, 4,535,096, 4,668,708, 5,023,280, 5,059,633, 5,063,253,
5,100,925, 5,270,348, 5,369,138, 5,397,811, 5,418,261, 5,506,278,
5,536,757, 6,107,355, 6,114,402 6,114,403, 6,117,917, and the
references cited therein. Polyurethane foams of the present
invention which incorporate bis(2-hydroxyethyl)isosorbide and/or
polyester polyols which incorporate bis(2-hydroxyethyl)isosorbide
may be produced by any known method in the art.
EXAMPLES
[0156] Test Methods:
[0157] Differential Scanning Calorimetry, (DSC), is performed on a
TA Instruments Model Number 2920 machine. Samples are heated under
a nitrogen atmosphere at a rate of 20 degrees C./minute to 300
degrees C., programmed cooled back to room temperature at a rate of
20 degrees C./minute and then reheated to 300 degrees C. at a rate
of 20 degrees C./minute. The observed sample glass transition
temperature, (Tg), and crystalline melting temperature, (Tm), noted
below were from the second heat.
[0158] Inherent Viscosity, (IV), is defined in "Preparative Methods
of Polymer Chemistry", W. R. Sorenson and T. W. Campbell, 1961, p.
35. It is determined at a concentration of 0.5 g/100 mL of a 50:50
weight percent trifluoroacetic acid:dichloromethane acid solvent
system at room temperature by a Goodyear R-103B method.
[0159] Biodegradation is performed according to the ISO 14855
method: "Determination of the ultimate aerobic biodegradability and
disintegration of plastic materials under controlled composting
conditions--Method by analysis of evolved carbon". This test
involved injecting an inoculum consisting of a stabilized and
mature compost derived from the organic fraction of municipal solid
waste with ground powder of the polymer to be tested, composting
under standard conditions at an incubation temperature controlled
at 58.degree. C.+/-2.degree. C. The test is conducted with one
polymer sample. The carbon dioxide evolved is used to determine the
extent of biodegradation.
Example 1
[0160] To a reactor is charged isosorbide, (146.14 grams), ethylene
carbonate, (184.93 grams), and potassium carbonate, (1.66 grams).
The reactor is purge with nitrogen and then is slowly heated with
stirring to 150.degree. C. with a slight nitrogen purge. The
resulting, reaction mixture is stirred at 150.degree. C. with a
slight nitrogen purge until the carbon dioxide evolution ceases.
The resulting reaction mixture is then stirred an additional hour
at 150.degree. C. with a slight nitrogen purge. The resulting
reaction product is allowed to cool to room temperature.
[0161] The as produced reaction product is purified through vacuum
distillation to provide the bis(2-hydroxyethyl)isosorbide
product.
Example 2
[0162] To a 200 gallon autoclave is charged dimethyl terephthalate,
(126.16 pounds), bis(2-hydroxyethyl)isosorbide, (152.11 pounds),
manganese(II) acetate tetrahydrate, (37.65 grams), and
antimony(III) trioxide, (13.6 grams). The autoclave is purged three
times with nitrogen and heated to 245.degree. C. over 4.5 hours
with stirring. Over this heating cycle, distillate is recovered.
With continued heating and stirring, vacuum is staged onto the
autoclave over 1.5 hours. The resulting reaction mixture is stirred
at 275.degree. C. under full vacuum, (pressure equal to or less
than 2 mm Hg) for 4 hours. The vacuum is then released and the
resulting reaction mixture is extruded out of the autoclave as a
ribbon, the polymer ribbon is cooled and chopped.
[0163] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
Comparative Example CE1
[0164] To a 200 gallon autoclave is charged dimethyl terephthalate,
(126.16 pounds), isosorbide, (9.5 pounds), ethylene glycol, (73.4
pounds), manganese(II) acetate tetrahydrate, (37.65 grams), and
antimony(III) trioxide, (13.6 grams). The autoclave is purged three
times with nitrogen and heated to 245.degree. C. over 4.5 hours
with stirring. Over this heating cycle, distillate is recovered.
With continued heating and stirring, vacuum is staged onto the
autoclave over 1.5 hours. The resulting reaction mixture is stirred
at 275.degree. C. under full vacuum (pressure equal to or less than
2 mm Hg) for 4 hours. The vacuum is then released and the resulting
reaction mixture is extruded out of the autoclave as a ribbon, the
polymer ribbon is cooled and chopped.
[0165] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0166] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 2.5 mole percent isosorbide. This
would suggest that 50 percent of the added isosorbide is
incorporated within the polymer.
Example 3
[0167] To a 200 gallon autoclave is charged dimethyl terephthalate,
(126.16 pounds), bis(2-hydroxyethyl)isosorbide, (15.22 pounds),
ethylene glycol, (73.4 pounds), manganese(II) acetate tetrahydrate,
(37.65 grams), and antimony(III) trioxide, (13.6 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 275.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0168] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0169] The polymer is analyzed for composition with proton NMR and
found to essentially incorporated mole percent
bis(2-hydroxyethyl)isosorbide. This would suggest that essentially
100 percent of the added bis(2-hydroxyethyl)isosorbide is
incorporated within the polymer.
[0170] The above prepared polymer of the present invention is found
to have essentially quantitative incorporation of the
bis(2-hydroxyethyl)isosorbide monomer. This is twice the
incorporation rate of the isosorbide monomer into comparable
polymers such as Comparative Example CE1.
Example 4
[0171] To a 200 gallon autoclave is charged dimethyl terephthalate,
(98.4 pounds), dimethyl 5-sulfoisophthalate, sodium salt, (3.8
pounds), dimethyl glutarate, (20.8 pounds),
bis(2-hydroxyethyl)isosorbide, (15.22 pounds), ethylene glycol,
(73.4 pounds), manganese(II) acetate tetrahydrate, (37.65 grams),
and antimony(III) trioxide, (13.6 grams). The autoclave is purged
three times with nitrogen and heated to 245.degree. C. over 4.5
hours with stirring. Over this heating cycle, distillate is
recovered. With continued heating and stirring, vacuum is staged
onto the autoclave over 1.5 hours. The resulting reaction mixture
is stirred at 275.degree. C. under full vacuum (pressure equal to
or less than 2 mm Hg) for 4 hours. The vacuum is then released and
the resulting reaction mixture is extruded out of the autoclave as
a ribbon, the polymer ribbon is cooled and chopped.
[0172] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0173] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 5 mole percent
bis(2-hydroxyethyl)isosorbide. This would suggest that essentially
100 percent of the added bis(2-hydroxyethyl)isosorbide is
incorporated within the polymer.
[0174] The above prepared polymer is ground to powder and subjected
to a biodegradation test as detailed above. This copolyester of the
present invention is found to biodegrade.
Example 5
[0175] To a 200 gallon autoclave is charged dimethyl isophthalate,
(126.11 pounds), bis(2-hydroxyethyl)isosorbide, (152.11 pounds),
manganese(II) acetate tetrahydrate, (37.65 grams), and
antimony(III) trioxide, (13.6 grams). The autoclave is purged three
times with nitrogen and heated to 245.degree. C. over 4.5 hours
with stirring. Over this heating cycle, distillate is recovered.
With continued heating and stirring, vacuum is staged onto the
autoclave over 1.5 hours. The resulting reaction mixture is stirred
at 275.degree. C. under full vacuum (pressure equal to or less than
2 mm Hg) for 4 hours. The vacuum is then released and the resulting
reaction mixture is extruded out of the autoclave as a ribbon, the
polymer ribbon is cooled and chopped.
[0176] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
Example 6
[0177] To a 200 gallon autoclave is charged dimethyl adipate,
(113.2 pounds), bis(2-hydroxyethyl)isosorbide, (15.22 pounds),
ethylene glycol, (73.4 pounds), manganese(II) acetate tetrahydrate,
(37.65 grams), and antimony(III) trioxide, (13.6 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 275.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0178] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0179] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 5 mole percent
bis(2-hydroxyethyl)isosorbide. This would suggest that essentially
100 percent of the added bis(2-hydroxyethyl)isosorbide is
incorporated within the polymer.
Example 7
[0180] To a 200 gallon autoclave is charged dimethyl
2,6-naphthalenedicarboxylate, (158.68 pounds),
bis(2-hydroxyethyl)isosorb- ide, (152.11 pounds), manganese(II)
acetate tetrahydrate, (37.65 grams), and antimony(III) trioxide,
(13.6 grams). The autoclave is purged three times with nitrogen and
heated to 245.degree. C. over 4.5 hours with stirring. Over this
heating cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 275.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0181] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
Example 8
[0182] To a 200 gallon autoclave is charged dimethyl terephthalate,
(98.1 pounds), dimethyl 5-sulfoisophthalate, sodium salt, (3.8
pounds), dimethyl succinate, (19.0 pounds), trimethyl
1,2,4-benzenetricarboxylate, (0.4 pounds),
bis(2-hydroxyethyl)isosorbide, (15.2 pounds), ethylene glycol,
(73.4 pounds), manganese(II) acetate tetrahydrate, (37.65 grams),
and antimony(III) trioxide, (13.6 grams). The autoclave is purged
three times with nitrogen and heated to 245.degree. C. over 4.5
hours with stirring. Over this heating cycle, distillate is
recovered. With continued heating and stirring, vacuum is staged
onto the autoclave over 1.5 hours. The resulting reaction mixture
is stirred at 275.degree. C. under full vacuum, (pressure equal to
or less than 2 mm Hg), for 4 hours. The vacuum is then released and
the resulting reaction mixture is extruded out of the autoclave as
a ribbon, the polymer ribbon is cooled and chopped.
[0183] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0184] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 5 mole percent
bis(2-hydroxyethyl)isosorbide. This would suggest that essentially
100 percent of the added bis(2-hydroxyethyl)isosorbide is
incorporated within the polymer.
Example 9
[0185] To a 200 gallon autoclave is charged dimethyl terephthalate,
(60.6 pounds), dimethyl adipate, (56.6 pounds),
bis(2-hydroxyethyl)isosorbide, (29.83 pounds), ethylene glycol,
(61.3 pounds), manganese(II) acetate tetrahydrate, (37.65 grams),
and antimony(III) trioxide, (13.6 grams). The autoclave is purged
three times with nitrogen and heated to 245.degree. C. over 4.5
hours with stirring. Over this heating cycle, distillate is
recovered. With continued heating and stirring, vacuum is staged
onto the autoclave over 1.5 hours. The resulting reaction mixture
is stirred at 275.degree. C. under full vacuum (pressure equal to
or less than 2 mm Hg) for 4 hours. The vacuum is then released and
the resulting reaction mixture is extruded out of the autoclave as
a ribbon, the polymer ribbon is cooled and chopped.
[0186] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0187] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 10 mole percent
bis(2-hydroxyethyl)isosorbide. This would suggest that essentially
100 percent of the added bis(2-hydroxyethyl)isosorbide is
incorporated within the polymer.
[0188] The above prepared polymer is ground to powder and subjected
to a biodegradation test as detailed above. This copolyester of the
present invention is found biodegrade.
Example 10
[0189] To a 200 gallon autoclave is charged dimethyl terephthalate,
(73.8 pounds), dimethyl adipate, (22.6 pounds), isophthalic acid,
(21.0 pounds), bis(2-hydroxyethyl)isosorbide, (29.78 pounds),
ethylene glycol, (61.3 pounds), manganese(II) acetate tetrahydrate,
(37.65 grams), and antimony(III) trioxide, (13.6 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 275.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0190] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0191] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 10 mole percent isosorbide. This
would suggest that essentially 100 percent of the added
bis(2-hydroxyethyl)isosorbide is incorporated within the
polymer.
[0192] The above prepared polymer is ground to powder and subjected
to a biodegradation test as detailed above. This copolyester of the
present invention was found to biodegrade
[0193] 1.1 grams of this polymer of the present invention is
dissolved in 10.0 grams of tetrahydrofuran at room temperature.
After mixing for 4 hours at room temperature, a clear solution is
obtained. The solution is poured into a 2-inch diameter aluminum
pan and allowed to dry at room temperature overnight. The resulting
film is clear and pliable.
Example 11
[0194] To a 5 gallon autoclave is charged terephthalic acid, (14.9
pounds), adipic acid, (3.4 pounds), bis(2-hydroxyethyl)isosorbide,
(2.7 pounds), ethylene glycol, (13.5 pounds), cobalt(II) acetate
tetrahydrate, (1.83 grams), and antimony(III) trioxide, (3.10
grams). The polymerization autoclave is equipped with a fractional
distillation column and a stirrer. The autoclave is purged three
times with nitrogen, closed under 50 psig of nitrogen pressure and
heated to 265.degree. C. over 5 hours with stirring. The pressure
rises to 70 psig during this time, as esterification takes place.
At the end of this time period, the pressure is vented back to
psig. Water and ethylene glycol distill from the autoclave. The
temperature is maintained at 265.degree. C. Within an hour, the
contents of the autoclave are a clear, viscous melt. The excess
pressure in the autoclave is then vented. A solution of ethylene
glycol and polyphosphoric acid (3.45 weight percent phosphorous) is
pumped into the autoclave. With continued heating and stirring,
vacuum is staged onto the autoclave. The autoclave is then heated
to 275.degree. C. The resulting reaction mixture is stirred at
275.degree. C. under full vacuum (pressure equal to or less than 2
mm Hg), for 4 hours. The vacuum is then released and the resulting
reaction mixture is extruded out of the autoclave as a ribbon, the
polymer ribbon is cooled and chopped.
[0195] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g. This
polymer is tested for glass transition temperature by the above
mentioned DSC test.
Example 12
[0196] To a 200 gallon autoclave is charged dimethyl
2,6-naphthalenedicarboxylate, (92.1 pounds), dimethyl adipate,
(45.3 pounds), bis(2-hydroxyethyl)isosorbide, (30.4 pounds),
ethylene glycol, (61.3 pounds), manganese(II) acetate tetrahydrate,
(37.65 grams), and antimony(III) trioxide, (13.6 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 275.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0197] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
Example 13
[0198] To a 200 gallon autoclave is charged dimethyl terephthalate,
(60.6 pounds), dimethyl adipate, (56.6 pounds),
bis(2-hydroxyethyl)isosorbide, (30.4 pounds), 1,4-butanediol, (75.0
pounds), and titanium(IV) isopropoxide, (19.57 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 255.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0199] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
[0200] The above prepared polymer is ground to powder and subjected
to a biodegradation test as detailed above. This copolyester of the
present invention was found to biodegrade.
Example 14
[0201] To a 200 gallon autoclave is charged dimethyl terephthalate,
(60.6 pounds), dimethyl adipate, (56.6 pounds),
bis(2-hydroxyethyl)isosorbide, (30.4 pounds), 1,3-propanediol,
(63.3 pounds), and titanium(IV) isopropoxide, (19.57 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 255.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0202] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g.
Example 15
[0203] To a 200 gallon autoclave is charged dimethyl terephthalate,
(126.16 pounds), bis(2-hydroxyethyl)isosorbide, (7.61 pounds),
ethylene glycol, (73.4 pounds), manganese(II) acetate tetrahydrate,
(37.65 grams), and antimony(III) trioxide, (13.6 grams). The
autoclave is purged three times with nitrogen and heated to
245.degree. C. over 4.5 hours with stirring. Over this heating
cycle, distillate is recovered. With continued heating and
stirring, vacuum is staged onto the autoclave over 1.5 hours. The
resulting reaction mixture is stirred at 275.degree. C. under full
vacuum (pressure equal to or less than 2 mm Hg) for 4 hours. The
vacuum is then released and the resulting reaction mixture is
extruded out of the autoclave as a ribbon, the polymer ribbon is
cooled and chopped.
[0204] The polymer is tested for inherent viscosity, as described
above and is found to have an IV greater than 0.35 dL/g. Its Tg is
found by DSC to be above the Tg of a comparative polyester without
the isosorbide derivative.
[0205] The polymer is analyzed for composition with proton NMR and
found to essentially incorporate 2.5 mole percent
bis(2-hydroxyethyl)isosorbide- . This would suggest that
essentially 100 percent of the added bis(2-hydroxyethyl)isosorbide
is incorporated within the polymer.
Example 16
[0206] To a 2 liter three necked glass flask was added adipic acid,
(438.42 grams), bis(2-hydroxyethyl)isosorbide, (234.14 grams),
di(ethylene glycol), (106.12 grams), and 1,4-butanediol, (225.30
grams). With stirring, the reaction mixture was slowly heated to a
final temperature of 200.degree. C. under a slight nitrogen purge.
Vacuum (pressure=10-15 mmHg) was applied while the reaction was
stirring and heating were allowed to continue. Distillates were
collected until a molecular weight of 2000 was achieved, as is
measurable by the acid value (KOH mg/g). The resulting polyester
polyol was allowed to cool to room temperature.
Example 17
[0207] A reactor is charged with bis(2-hydroxyethyl)isosorbide,
(234.14 grams). The reaction mixture is heated to 70.degree. C.
with stirring under a slight nitrogen purge. Tolylene
2,6-diisocyanate, (174.16 grams), is dropwise added over 1 hour to
the stirred reaction mixture at 70.degree. C. The resulting
reaction mixture is allowed to stir for an additional hour at
70.degree. C. and then the resulting polyurethane product is
allowed to cool to room temperature and recovered.
Example 18
[0208] A reactor is charged with the polyester polyol prepared in
Example 16, (200.00 grams). The reaction mixture is heated to
70.degree. C. with stirring under a slight nitrogen purge.
4,4'-Methylenebis(phenyl isocyanate), (25.03 grams), is dropwise
added over 1 hour to the stirred reaction mixture at 70.degree. C.
The resulting reaction mixture is allowed to stir for an additional
hour at 70.degree. C. and then the resulting polyurethane product
is allowed to cool to room temperature and recovered.
Example 19
[0209] The polymer of the present invention produced in Example 15,
above, is extruded as a film using a Killion PL 100 Film extrusion
line. The processing conditions are as follows:
1 Extruder Barrel Temperature zone 1 190.degree. C. zone 2
270.degree. C. zone 3 280.degree. C. zone 4 280.degree. C. Clamp
ring temperature 280.degree. C. Adaptor temperature (inlet)
290.degree. C. Melt pump temperature 290.degree. C. Melt pump rpm
10 Throughput 3 lb./hr. Adapter temperature (outlet) 280.degree. C.
Extruder melt pressure .about.1500 psi Die adapter temperature
290.degree. C. Die temperature 290.degree. C. Die Lip temperature
290.degree. C. Die gap 0.25 mm (10 mil) Die size 4-inch Casting
temperature 50.degree. C. Casting speed 5 & 3 in/min. Filter
size 25 microns
[0210] The film exiting the die is 4 inches wide and 0.10 mm (4
mils) thick.
[0211] The extruded film is stretched uniaxially and biaxially
using a modified Bruckner Stretching Frame (Bruckner, Siegsdorf,
Germany). The sample is inserted with the machine direction (MD) on
the Y axis of the machine. Draw speed is 1.50 in/sec. Typical
machine settings include; Plaque preheat temp=110.degree. C.,
Shutter Close Temperature=115.degree. C., and Emitter
temperature=600.degree. C. When a Draw ratio X (X 100%)=1 and a
Draw ratio Y (X 100%)=2 is performed on the as extruded film, the
film modulus and elongation at break are both significantly
improved over that found for the unstretched film.
Example 20
[0212] The material produced in Example 15, above, is injection
molded into discs (thickness 1/8 inch, diameter 4 inches) and
tensile bars. A Boy 30M (Boy Gmbh, Fernthalr, Germany) is used to
injection mold the parts. The conditions used are as follows:
2 Barrel temperature 280.degree. C. Mold temperature 50.degree. C.
Screw speed 210 rpm Injection speed 100% Injection pressure 13 bar
Hold pressure 12 bar Back pressure 3 bar Injection time 2 seconds
Cooling time 25 seconds
Example 21
[0213] The polymer produced in Example 3, above, is used to produce
a 14 mil thick sheet by extrusion using a film/sheet pilot line
made by Egan Machinery (Somerville, N.J.). The conditions for
extrusion are as follows: Extruder barrel temperatures
3 Zone 1 255.degree. C. Zone 2 255.degree. C. Zone 3 255.degree. C.
Zone 4 255.degree. C. Zone 5 275.degree. C. Zone 6 275.degree. C.
Melt line temp. 50.degree. C. Die temp. 280.degree. C. Roller 1
25.degree. C. Roller 2 25.degree. C. Roller 3 20.degree. C.
[0214] The sheet is trimmed to 6 to 7 inches wide and approximately
11 inches long. After heating in a rectangular retaining bracket at
165.degree. C. in a convection oven until softening takes place,
the sheet is vacuum thermoformed into 11/2 inch and 2 inch deep
room temperature molds to demonstrate ability to thermoform. The
obtained containers are optically clear and mechanically
robust.
Example 22
[0215] The polymers of the present invention produced in Examples 3
and 15, above, are made into 460 mL jars on a commercial Nissei
ASB100DH Injection Single Blow stretch-blow molding unit using a
one-stage stretch-blow molding process, and using a 132.5 mm rod
for the stretch. The polymer is injection molded at a melt
temperature of 275.degree. C. to make a preform, which is then
subjected to the stretch-blow molding process at 100.degree. C. in
the same equipment without complete cooling.
Example 23
[0216] The polymer of the present invention produced in Example 15,
above, is ground and dried at 130.degree. C. overnight in a vacuum.
Rods are made from the polymer by first placing it in a mold which
is then heated under gentle pressure from a plunger. The pressure
is provided by a hydraulic press. When the polymer began to soften,
more pressure (500-1000 lbs/in.sup.2) is applied to compress the
polymer into a hard rod. The ingress of moisture is reduced by
encasing the equipment in a Lucite .RTM. box which is continuously
purged by a flow of dry nitrogen.
[0217] Spinning is immediately carried out on a single filament
spinning machine. The polymer is rod form is melted by pressing it
against a heated "grid" which is conical in shape with a hole at
the apex. The machine temperatures are slowly raised until the
melted polymer starts to flow through this hole. In the present
example, this occurs at approximately 270.degree. C. The polymer is
then filtered through a bed of 80/120 shattered metal, and finally
emerges from the single hole spinneret capillary, 0.020 inch in
diameter and 0.030 inch long. The throughput is 0.30 grams per
minute (gpm), and the fiber, which is to be drawn, is taken up at
50 meters per minute (mpm). These condition are found to give low
orientation single filaments of about 70 denier per filament (dpf).
A temperature scan is made to produce the optimum spun fiber for
subsequent drawing. A fiber sample is also made at the maximum take
up speed possible in order to obtain a feel for the draw down and
to measure the spun fiber properties.
[0218] Single filament drawing is performed on modular draw units
with hot shoes between each roll. The fiber is drawn in two stages
using the second stage to develop the maximum fiber tenacity and
crystallinity. In this way, a single filament is collected and
small samples cut from the last roll. A sample is tested for its
thermal properties by the above-mentioned DSC method and for
tensile properties using ASTM test method D3822. Its Tg is found by
DSC to be above the Tg of a comparative polyester fiber without the
isosorbide derivative.
* * * * *