U.S. patent application number 14/772477 was filed with the patent office on 2016-01-07 for a process to prepare a polyester polymer composition comprising a polyester polymer having furanic units and a polyester polymer composition obtainable thereby and the use thereof.
This patent application is currently assigned to Sulzer Chemtech AG. The applicant listed for this patent is SULZER CHEMTECH AG. Invention is credited to Liborio Ivano Costa, Massimo Morbidelli, Philip Nising, David Pfister, Giuseppeu Storti, Francesca Tancini.
Application Number | 20160002397 14/772477 |
Document ID | / |
Family ID | 47900841 |
Filed Date | 2016-01-07 |
United States Patent
Application |
20160002397 |
Kind Code |
A1 |
Costa; Liborio Ivano ; et
al. |
January 7, 2016 |
A Process to Prepare a Polyester Polymer Composition Comprising a
Polyester Polymer Having Furanic Units and a Polyester Polymer
Composition Obtainable Thereby and the use Thereof
Abstract
A process to prepare a polyester polymer composition comprising
a polyester polymer having furanic units is disclosed. The process
comprises the step of reacting a cyclic polyester oligomer in the
presence of a catalyst in a ring-opening polymerization step under
conditions of a reaction temperature and reaction time sufficient
to yield a polyester polymer having furanic units. The invention
further relates to a polyester polymer composition obtainable by
said process, wherein the polyester polymer composition comprises a
polyester polymer having furanic units and a cyclic polyester
oligomer comprising either structure Y.sup.1 or Y.sup.2, preferably
in a concentration of less than 5 wt %, more preferably less than
1, more preferably less than 0.5 in the composition. The present
invention further relates also to the use of said polyester polymer
composition in extrusion, injection molding, or blow molding.
Inventors: |
Costa; Liborio Ivano;
(Winterthur, CH) ; Nising; Philip; (Oetwil am See,
CH) ; Tancini; Francesca; (Wettingen, CH) ;
Pfister; David; (Zurich, CH) ; Storti; Giuseppeu;
(Zurich, CH) ; Morbidelli; Massimo; (Zurich,
CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SULZER CHEMTECH AG |
Winterthur |
|
CH |
|
|
Assignee: |
Sulzer Chemtech AG
Winterthur
CH
|
Family ID: |
47900841 |
Appl. No.: |
14/772477 |
Filed: |
November 27, 2013 |
PCT Filed: |
November 27, 2013 |
PCT NO: |
PCT/EP2013/074882 |
371 Date: |
September 3, 2015 |
Current U.S.
Class: |
264/572 ;
264/176.1; 264/328.1; 526/64; 528/306 |
Current CPC
Class: |
C08G 63/916 20130101;
C08G 63/85 20130101; C08G 63/181 20130101; C08G 63/78 20130101;
C08L 67/02 20130101; B29C 45/0001 20130101; B29C 48/022 20190201;
B29K 2067/00 20130101; C08G 63/83 20130101; B29C 49/0005 20130101;
C08G 63/84 20130101 |
International
Class: |
C08G 63/78 20060101
C08G063/78; B29C 49/00 20060101 B29C049/00; B29C 47/00 20060101
B29C047/00; B29C 45/00 20060101 B29C045/00; C08G 63/85 20060101
C08G063/85; C08G 63/91 20060101 C08G063/91 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 15, 2013 |
EP |
13159394.9 |
Claims
1-15. (canceled)
16. A process to prepare a polyester polymer composition comprising
a polyester polymer having furanic units, wherein the process
comprises the step of: reacting a cyclic polyester oligomer in the
presence of a catalyst in a ring-opening polymerization step under
conditions of a reaction temperature and a reaction time sufficient
to yield a polyester polymer having furanic units, wherein either:
(I) the cyclic polyester oligomer comprises the structure:
##STR00012## wherein each of the groups A is an
optionally-substituted linear, branched or cyclic alkyl, phenyl,
aryl, or alkylaryl group, and m is an integer from 1 to 20, and the
polyester polymer having furanic units comprises the structure:
##STR00013## wherein A is as previously defined and n is an integer
from 10 to 1,000,000, or (II) the cyclic polyester oligomer
comprises the structure: ##STR00014## wherein each of the groups B
is an optionally-substituted linear, branched or cyclic alkyl,
phenyl, aryl, or alkylaryl group, and n' is an integer from 1 to
20, and m is as previously defined, and the polyester polymer
having furanic units comprises the structure: ##STR00015## wherein
B, n' and n are as previously defined.
17. The process of claim 16, wherein the reaction temperature is
from 25 to 350.degree. C., and wherein the reaction time is from 10
to 300 minutes.
18. The process of claim 16, wherein the catalyst is selected from
a base, or a Lewis acid catalyst.
19. The process of claim 18, wherein the ring-opening
polymerization step takes place in the presence of an initiator
having at least one or more hydroxyl groups.
20. The process of claim 18, wherein the catalyst is a Lewis acid
catalyst, and wherein the initiator is present and it is selected
from the group consisting of water, 1-octanol, 2-ethylhexanol,
1-decanol, isodecyl alcohol, 1-undecanol, 1-dodecanol,
2-methyl-2-propanol, 4-phenyl-2-butanol, 1,3-propandiol, and
pentaerytrol.
21. The process of claim 20, wherein the Lewis acid catalyst is tin
octoate and the initiator is either 1-octanol or
2-ethylhexanol.
22. The process of claim 18, wherein the initiator is present in an
amount of from 1 to 100 mmol per kg cyclic polyester oligomer.
23. The process of claim 16, wherein the catalyst is present in an
amount relative to the mass of the cyclic polyester oligomer of
from 1 ppm to 1 mass %.
24. The process of claim 16, wherein the ring-opening
polymerization step takes place in a loop reactor and a plug flow
reactor.
25. The process of claim 24, wherein at least one of the loop
reactor and the plug flow reactor is equipped with static mixing
elements and heat transfer equipment.
26. The process of claim 16, wherein the process additionally
comprises a subsequent devolatization step in which unreacted
cyclic oligomer or other volatile components are removed from the
polyester polymer having furanic units obtained from the
ring-opening polymerization step.
27. The process of claim 26, wherein the devolatization step takes
place in the molten state using a vacuum and/or a purge of inert
atmosphere.
28. The process of claim 27, wherein the devolatilization step
takes place in one or more extruders, twin screw extruders, wiped
film evaporators, falling film evaporators, rotary devolatilisers,
rotary disk devolatilisers, centrifugal devolatilisers, flat plate
devolatilisers, static expansion chambers having special
distributors, or their combinations.
29. The process of claim 16, wherein either: (A) the cyclic
polyester oligomer comprising the structure Y.sup.1 comprises the
specific structure: ##STR00016## wherein m is as previously
defined, and the polyester polymer having furanic units and
comprising the structure Z.sup.1 comprises the specific structure:
##STR00017## wherein n is as previously defined, or (B) the cyclic
polyester oligomer comprising the structure Y.sup.1 comprises the
specific structure: ##STR00018## wherein m is as previously
defined, and the polyester polymer having furanic units and
comprising the structure Z.sup.1 comprises the specific structure:
##STR00019## wherein n is as previously defined.
30. A polyester polymer composition obtainable by a process
according to claim 1, wherein the polyester polymer composition
comprises: a polyester polymer having furanic units and comprising
either structure Z.sup.1 or Z.sup.2, and a cyclic polyester
oligomer comprising either structure Y.sup.1 or Y.sup.2.
31. The polyester polymer composition of claim 30, wherein the
cyclic polyester oligomer is present in a concentration of less
than 5 wt % in the composition.
32. The polyester polymer composition of claim 30, wherein the
polyester polymer having furanic units and comprising either
structure Z.sup.1 or Z.sup.2 also has a polydispersity of less than
3.
33. The polyester polymer composition of claim 30, wherein either:
(A) the polyester polymer having furanic units comprises more
specifically the structure Z'' and the cyclic polyester oligomer
comprises more specifically the structure Y.sup.1', or (B) the
polyester polymer having furanic units comprises more specifically
the structure Z.sup.1'' and the cyclic polyester oligomer comprises
more specifically the structure Y.sup.1''.
34. The use of the polyester polymer composition of claim 30 in
extrusion, injection molding, or blow molding.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a process to prepare a
polyester polymer composition comprising a polyester polymer having
furanic units, as well as said polyester polymer composition
obtainable by said process and the use of said polyester polymer
composition in extrusion, injection molding, or blow molding.
[0002] Polyesters are an important class of commercial polymers
with useful physical and mechanical properties and numerous
applications. Polyesters find wide utility, for example, as fibres,
coatings, films, or in composites. Most industrial polyesters such
as polyethylene terephtalate (PET), polybutylene terephthalate
(PBT), and polyacrylates are produced from monomers derived from
petrochemical feedstocks. Due to limited oil reserves, fluctuations
of oil price, political instability in some production areas, and
increased environmental awareness, there is growing interest for
biobased polyesters produced from renewable feedstocks.
[0003] Currently, there are only few biobased polyesters in
commercial or pilot production. Representative examples of natural
occurring polyesters are polyhydroxyalkanoates (PHA), which are
linear polyesters produced by microbial fermentation from sugars or
lipids. However PHA has not been widely industrialized due to
limitations in production yields and downstream processing.
[0004] Another example of a commercially-produced biobased
semisynthetic polyester is polylactic acid (PLA), which may be
prepared from polycondensation of lactic acid or ring-opening
polymerization of the cyclic diester lactide. Although PLA has a
wide range of applications, it is an aliphatic polyester and
therefore not suitable for replacing petrochemical-based aromatic
polyesters in applications such as higher temperature extrusion or
molding or the production of bottles. Since most biobased building
blocks are derived from non-aromatic compounds such as sugars or
starch, most biobased polymers suffer this disadvantage. Examples
of other such aliphatic biobased polymers include polybutylene
succinate (PBS) or polymers based on sebacic or adipic acids.
[0005] For these reasons, biobased polymers having aromatic
building blocks are highly sought today. An interesting class of
biobased aromatic monomers are the furanics such as
furan-2,5-dicarboxylic acid (FDA),
5-(hydroxymethyl)furan-2-carboxylic acid (HMFA), and
2,5-bis(hydroxyl methyl)furan (BHMF), which may be prepared from
the intermediates furfural (2-furan carboxaldehyde) and
5-hydroxymethyl 2-furan carboxaldehyde (HMF) which may be produced
by the acid-catalyzed thermal dehydration of pentoses (C5) and
hexoses (C6). The chemical similarity of the furan ring to the
phenyl ring makes it possible to replace phenyl-based polymers such
as polyethylene terephthalate (PET) by furan-based polymers.
[0006] The production of polyesters from furanic building blocks by
polycondensation reactions involving heating a mixture of
dialcohols and diacids or diesters at high temperatures in the
presence of organometallic or acid catalyst is known, for example,
from U.S. Pat. No. 2,551,731 and U.S. Pat. No. 8,143,355 B2. To
allow the progress in this equilibrium reaction towards the
formation of the polymer, the formed water or side products such as
alcohol must be removed, typically by reduced pressure or gas
streams at elevated temperatures in the process. Therefore complex
and costly reaction and devolatilization equipments effective at
driving the reaction to completion, devolatilizing significant
amounts of volatile compounds from highly viscous polymer melts,
and having the capacity to remove and condense these volatile
compounds are required. If the polycondensation and
devolatilization is insufficient, then an high molecular weight
polyester having useful mechanical and other properties will not be
produced.
[0007] Furthermore the high temperatures and long residence times
used for driving the polymerization and devolatilization lead often
to undesired side reactions such as degradation of the monomer,
oligomer or polymer, formation of intermolecular bonds leading to
branching, and oxidation of the final product with the consequent
color development. In addition, significant amounts of volatile
organic compounds such as alcohol side products cannot simply be
emitted to the atmosphere, and they must be instead recovered for
recycling to make new monomer or for thermal recycling. This
recovery and recycling to make new monomer entails costly storage
and transport aspects unless the polymerization plant is integrated
with an on-site monomer production plant.
[0008] In conclusion, it would be desirable to have a process to
prepare polyesters from furanic building blocks that does not
produce large quantities of water or alcoholic side products and
that therefore does not require complex reaction and high-capacity
devolatilization equipment or harsh high temperature reaction and
devolatization steps to drive the polymerization to completion and
allow high molecular weight polymers having furanic units to be
produced from furanic building blocks.
SUMMARY OF THE INVENTION
[0009] Starting from this state of the art, it is an object of the
invention to provide a simplified process to prepare a polyester
polymer composition comprising a polyester polymer having furanic
units and that does not suffer from the previous mentioned
deficiencies, particularly a high polymerization reaction time, a
tendency to form large quantities of volatile side products such as
water or alcohol, which requires complex and costly high-capacity
devolatilization systems, especially when producing high molecular
weight polyester polymers. A related object is avoid thermal
degradation and polymer discoloration due to harsh polymerization
and devolatization conditions of high temperatures and long times.
Further objects of the invention include providing a polyester
polymer composition obtainable by said process and a use of said
polyester polymer in extrusion, injection molding, or blow
molding.
[0010] According to the invention, these objects are achieved by a
process to prepare a polyester polymer composition comprising a
polyester polymer having furanic units, wherein the process
comprises the step of: reacting a cyclic polyester oligomer in the
presence of a catalyst in a ring-opening polymerization step under
conditions of a reaction temperature and a reaction time sufficient
to yield a polyester polymer having furanic units, wherein either
(I) the cyclic polyester oligomer comprises the structure:
##STR00001##
[0011] wherein each of the groups A is an optionally-substituted
linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl group,
and m is an integer from 1 to 20, preferably 2 to 15, most
preferably 3 to 10,
[0012] and the polyester polymer having furanic units comprises the
structure:
##STR00002##
[0013] wherein A is as previously defined and n is an integer from
10 to 1,000,000,
[0014] OR
[0015] (II) the cyclic polyester oligomer comprises the
structure:
##STR00003##
[0016] wherein each of the groups B is an optionally-substituted
linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl group,
and n' is an integer from 1 to 20, preferably 2 to 10, and m=1 to
20, preferably 2 to 15, most preferably 3 to 10, and m is as
previously defined,
[0017] and the polyester polymer having furanic units comprises the
structure:
##STR00004##
[0018] wherein B, n' and n are as previously defined.
[0019] According to the invention, these further objects are
achieved firstly by a polyester polymer composition obtainable by
said process, wherein the polyester polymer composition comprises:
a polyester polymer having furanic units and comprising either
structure Z.sup.1 or Z.sup.2, and a cyclic polyester oligomer
comprising either structure Y.sup.1 or Y.sup.2, preferably in a
concentration of less than 5, more preferably less than 1, more
preferably less than 0.5 wt % in the composition.
[0020] Said polyester polymer composition is used in accordance
with the invention in extrusion, injection molding, or blow
molding.
[0021] The present invention achieves these objects and provides a
solution to this problem by means of the cyclic polyester oligomer
comprising either structure Y.sup.1 or Y.sup.2. These cyclic
oligomers are preferably prepared by condensation reactions carried
out to high conversion and with linear impurities removed, and thus
they do not contain carboxylic acid or free OH groups, as would
monomers such as 2,5-furandicarboxlic acid or ethylene glycol,
propanediol or butanediol. Therefore the further reaction of the
cyclic oligomers of the invention to form a high molecular weight
polymer will not release large amounts of water as do those
monomers. These cyclic oligomers also do not contain esters of
volatile monofunctional alcohols, as does 2,5-furandicarboxlic acid
dimethyl or diethyl ester. Therefore the further reaction of these
cyclic oligomers of the invention to form a high molecular weight
polymer will not release large amounts of volatile alcohol
byproducts as do those monomers.
[0022] The lack of production of large quantities of volatile water
or alcohol components during the polymerization and any subsequent
devolatilization allows simpler devolatilization systems and milder
devolatilization conditions to be used as only relatively small
amounts of volatile compounds will be present in the polymer
composition after polymerization of the cyclic oligomer. In
particular, due to its molecular weight, the cyclic oligomer is not
very volatile. Furthermore since the cyclic oligomer lacks free
acid and/or hydroxyl groups, residual unreacted cyclic oligomer
species will not negatively impact the chemical, color, and thermal
stability of the polymer composition. Thus due to its design and
nature, the cyclic polyester oligomer conveniently allows a high
molecular weight polymer to be prepared at relatively mild
conditions of time and temperature for both the polymerization
reaction and the devolatilization such that significant thermal
degradation of the polymer composition may be avoided.
[0023] These results are then surprisingly achieved without the
need for any special elaborate reaction and devolatilization
apparatuses involving the application of vacuum and/or inert gas
streams at elevated temperatures over long periods of time. In the
present invention the reactions and operations involving the
formation of significant volatile species such as water and
alcohols have all been conveniently moved upstream to the cyclic
polyester oligomer production stage, and thus only relatively small
amounts of such volatile species will be generated in the
polymerization process. In this manner the removal and recovery
and/or recycle of such species is integrated within the oligomer
production facility. This then eliminates the need for the
transport of such materials between monomer and polymer production
plants, which may be geographically quite distant from one
another.
[0024] In a preferred embodiment of the process, the reaction
temperature is from 25 to 350, preferably 80 to 300, most
preferably 110 to 280.degree. C., and wherein the reaction time in
the ring opening polymerization step is from 10 to 300, preferably,
20 to 240, most preferably 30 to 180 minutes. It has been found
that such reaction times and temperatures are sufficient to allow a
high molecular weight polymer to be produced but avoid the
occurrence of significant thermal degradation leading to
undesirable discoloration, chain scission, or branching.
[0025] In a specific preferred embodiment of the process, the
catalyst is selected from a base, preferably a metal alkoxide, or a
Lewis acid catalyst, and the ring-opening polymerization step
preferably takes place in the presence of an initiator having at
least one or more hydroxyl groups. The use of such catalysts and
initiators allows high molecular weight polyester polymer
compositions to be prepared under relatively mild conditions of
temperature and time. This then improves productivity and minimizes
degradation and discoloration in the product.
[0026] In more specific preferred embodiment of the process, the
catalyst is a Lewis acid catalyst and it is preferably a tin, zinc
or aluminium or titanium alkoxide or carboxylate, and the
initiator, if present, is selected from the group consisting of
water, 1-octanol, 2-ethylhexanol, 1-decanol, isodecyl alcohol,
1-undecanol, 1-dodecanol, 2-methyl-2-propanol, 4-phenyl-2-butanol,
1,3-propandiol, and pentaerytrol. In an even more specific
preferred embodiment of the process, the Lewis acid catalyst is tin
octoate and the initiator is either 1-octanol or 2-ethylhexanol.
Such catalysts and initiators have been found to be particularly
effective in the process of the invention.
[0027] In a preferred embodiment of the process, the catalyst is
present in an amount relative to the mass of the cyclic polyester
oligomer of from 1 ppm to 1 mass %, preferably from 10 to 1,000
ppm, more preferably from 50 to 500 ppm. The use of such catalyst
loading has been found to allow the ring-opening polymerization to
take place under relatively mild conditions of temperature and time
while avoiding the catalysis of undesired side reactions during the
process. Furthermore contamination is avoided of the polyester
polymer composition product by large quantities of unquenched
residual catalysts, which may lead to degradation and/or
discoloration in subsequent thermal processing such as extrusion or
molding. Also an effective balance between catalyst cost and
productivity is obtained.
[0028] Similarly, in another preferred embodiment of the process,
the initiator, if present, it is in an amount of from 1 to 100,
preferably from 10 to 50 mmol per kg cyclic polyester oligomer.
Such levels lead to a high productivity of the process while
minimizing side reactions, contamination of the resulting polyester
polymer composition product, and raw material consumption and
costs.
[0029] In yet another preferred embodiment of the process, the
ring-opening polymerization step takes place in a loop reactor and
a plug flow reactor, wherein one or both of the reactors are
preferably equipped with static mixing elements. In the loop
reactor, the added cyclic oligomer and catalyst are intimately
mixed with partially polymerised product that is already present in
the reactor and pre-polymerized. Alternatively, the cyclic oligomer
and the catalyst are premixed in a continuous flow apparatus and
the resulting mixture is then fed to the loop reactor. One
beneficial result of this is that the rheological behaviour of the
reaction mixture only changes gradually within the loop reactor,
and this helps controlling the fluid flow within the reactor. Major
jumps in viscosity over short distances are avoided and the heat
released by the reaction is distributed uniformly in the reactor.
Due to the increased flow rate and the mixing elements that are
preferably present, the rate of heat removal from the reactor is
significantly enhanced, further helping in the control of reaction
conditions. More in particular, the combination of high flow rate
and mixing elements results in enhanced temperature homogeneity,
and thus a more even temperature distribution in the loop reactor.
It also results in a narrow residence time distribution. Hot spots
are avoided so there is less discoloration of the polymer.
[0030] Pre-polymerised reaction mixture is continuously withdrawn
from the loop reactor and continuously provided to a plug flow
reactor, where it is polymerised further to a degree of conversion
of at least 90%. In the plug flow reactor, which is preferably
equipped with static mixing elements and/or heat exchange
equipment, the polymerisation can be completed up to high
conversions. The use of static mixing elements and/or heat exchange
equipment in the plug flow reactor provide for further intense
mixing and homogeneous temperature distribution. Due to this, the
molecular weight distribution, degree of conversion, and residence
time distribution can all be tightly controlled. Furthermore, the
temperature profile of the reaction along the plug flow reactor can
be controlled to a high degree, enabling optimisation of the
polymerisation process.
[0031] In another preferred embodiment of the process, the process
additionally comprises a subsequent devolatization step in which
unreacted cyclic oligomer or other volatile components are removed
from the polyester polymer composition. Preferably the
devolatization step takes place in the molten state using a vacuum
and/or a purge of inert atmosphere. Low molecular weight residual
species including any unconverted monomeric or oligomeric species
present in polyester polymer compositions may lead to discoloration
and/or molecular weight degradation during subsequent thermal
processing such as extrusion or molding. Low molecular weight
residual species may also cause plate-out during molding or even
lead to degradation of the mechanical properties of the polyester
polymer composition at high concentrations. Although the process of
the invention generally has the benefit of high conversion and not
producing large quantities of volatile components during the
process, nonetheless small amounts may be present as impurities in
the cyclic polyester oligomer and/or may form during the
ring-opening polymerization step. Therefore these other volatile
species, as well as potentially any residual unreacted oligomer of
sufficiently low molecular weight, may beneficially be removed by a
devolatilization step subsequent to the ring-opening polymerization
step. It is noted that one of the advantages of the present
invention is that it typically uses fairly high molecular weight
cyclic polyester oligomers as reactants, and such high molecular
weight species will not tend to give significant problems due to
degradation, discoloration, or plate out when remaining unconverted
in the final product polymer composition.
[0032] In a related preferred embodiment of the process, the
devolatilization step takes place in one or more extruders,
preferably twin screw extruders, wiped film evaporators, falling
film evaporators, rotary devolatilisers, rotary disk
devolatilisers, centrifugal devolatilisers, flat plate
devolatilisers, static expansion chambers having special
distributors, or their combinations. Such devolatilization
equipment is effective in removing residual cyclic oligomer and
other volatile components from highly viscous polymer melts.
[0033] In yet another preferred embodiment of the process, the
cyclic polyester oligomer comprising the structure Y.sup.1
comprises the specific structure:
##STR00005##
[0034] wherein m is as previously defined, and the polyester
polymer having furanic units and comprising the structure Z.sup.1
comprises the specific structure:
##STR00006##
[0035] wherein n is as previously defined. This process has the
advantage of producing poly(2,5-ethylene furandicarboxylate) (PEF),
which is the heterocycle homologue of the most important commercial
polyester, poly(ethylene terephthalate) (PET). PEF is currently in
pilot-scale development and shows potential as a biobased
alternative to PET for packaging and bottle applications.
[0036] In an alternative other preferred embodiment of the process,
the cyclic polyester oligomer comprising the structure Y.sup.1
comprises the specific structure:
##STR00007##
[0037] wherein m is as previously defined, and the polyester
polymer having furanic units and comprising the structure Z.sup.1
comprises the specific structure:
##STR00008##
[0038] wherein n is as previously defined. This process has the
advantage of producing poly(2,5-butylene furandicarboxylate) (PBF),
which is the heterocycle homologue of another important commercial
polyester, poly(butylene terephthalate) (PBT). PBT has excellent
mechanical and electrical properties with robust chemical
resistance, and PBF is of interest as a biobased alternative.
[0039] Related to these two alternative preferred embodiments of
the process and sharing their advantages is a preferred embodiment
of the polyester polymer composition wherein either: (A) the
polyester polymer having furanic units comprises more specifically
the structure Z1' and the cyclic polyester oligomer comprises more
specifically the structure Y1', or (B) the polyester polymer having
furanic units comprises more specifically the structure Z1'' and
the cyclic polyester oligomer comprises more specifically the
structure Y1''.
[0040] Another preferred embodiment of the polyester polymer
composition of the invention is one where the polyester polymer has
a polydispersity of less than 3, preferably 2.5, most preferably
2.1.
[0041] Further aspects of the present invention include the use of
the polyester polymer composition of the invention in extrusion,
injection molding, or blow molding. Such use benefits then from the
previously discussed advantages of the composition and the process
of the invention.
[0042] One skilled in the art will understand that the combination
of the subject matters of the various claims and embodiments of the
invention is possible without limitation in the invention to the
extent that such combinations are technically feasible. In this
combination, the subject matter of any one claim may be combined
with the subject matter of one or more of the other claims. In this
combination of subject matters, the subject matter of any one
process claim may be combined with the subject matter of one or
more other process claims or the subject matter of one or more
composition claims or the subject matter of a mixture of one or
more process claims and composition claims. By analogy, the subject
matter of any one composition claim may be combined with the
subject matter of one or more other composition claims or the
subject matter of one or more process claims or the subject matter
of a mixture of one or more process claims and system claims.
[0043] One skilled in the art will understand that the combination
of the subject matters of the various embodiments of the invention
is also possible without limitation in the invention to the extent
that such combinations are technically feasible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] The invention will be explained in more detail hereinafter
with reference to various embodiments of the invention as well as
to the drawings. The schematic drawings show:
[0045] FIG. 1 shows a reaction scheme for the synthesis of a
polyester polymer having furanic units and comprising the structure
Z.sup.1 from a cyclic polyester oligomer Y.sup.1.
[0046] FIG. 2 shows a reaction scheme for the synthesis of a
polyester polymer having furanic units and comprising the structure
Z.sup.2 from a cyclic polyester oligomer Y.sup.2.
[0047] FIG. 3 shows a reaction scheme for the synthesis of a
specific polyester polymer having furanic units and comprising the
structure Z.sup.1' from a cyclic polyester oligomer Y.sup.1'.
[0048] FIG. 4 shows a reaction scheme for the synthesis of a
specific polyester polymer having furanic units and comprising the
structure Z.sup.1'' from a cyclic polyester oligomer Y.sup.1''.
[0049] FIG. 5 shows a schematic drawing (not to scale) of an
apparatus suitable for performing the process according to the
present invention for preparing a polyester polymer composition
comprising a polyester polymer having furanic units from the
corresponding cyclic polyester oligomer.
[0050] FIG. 6 Example 1: .sup.1H NMR spectrum (400 MHz, d-TFA,
25.degree. C.) for Polyester Polymer Composition (Embodiment of
Z.sup.1').
[0051] FIG. 7 Example 1: a) DSC trace for Cyclic Polyester Oligomer
Composition (Embodiment of Y.sup.1') in the temperature range
between 50 and 250.degree. C. (2nd heating scan); b) DSC trace for
Polyester Polymer Composition (Embodiment of Z.sup.1') in the
temperature range between 30 and 250.degree. C. (2nd heating
scan).
[0052] FIG. 8 Example 2: .sup.1H NMR spectrum (400 MHz, d-TFA,
25.degree. C.) for Polyester Polymer Composition (Embodiment of
Z.sup.1'').
[0053] FIG. 9 Example 2: a) DSC trace for Cyclic Polyester Oligomer
Composition (Embodiment of Y.sup.1'') in the temperature range
between 25 and 200.degree. C. (2nd heating scan); b) DSC trace for
Polyester Polymer Composition (Embodiment of Z.sup.1'') in the
temperature range between 0 and 200.degree. C. (2nd heating
scan).
DETAILED DESCRIPTION OF THE INVENTION
[0054] The claimed invention relates to a process to prepare a
polyester polymer composition comprising a polyester polymer having
furanic units, wherein the polyester polymer having furanic units
comprises the structure Z.sup.1 or Z.sup.2:
##STR00009##
[0055] wherein n' is an integer from 1 to 20, preferably 2 to 10,
and n is an integer from 10 to 1,000,000.
[0056] The polyester polymer composition of the current invention
is not specifically limited and it may comprise other components in
addition to the polyester polymer having furanic units and
comprising the structure Z.sup.1 or Z.sup.2. For example, the
polyester polymer composition may additionally comprise small
amounts of one or more unreacted and/or unremoved reaction
components such as a cyclic oligomer, a catalyst, a initiator, a
catalyst quencher, an endcapping agent, or a solvent. In addition,
the polyester polymer composition may additionally comprise low
levels of impurities introduced as a contaminant in one of the
reaction components or formed due to a side reaction during a
ring-opening polymerization step or an optional additional step
such as a subsequent devolatization step. Finally the polyester
polymer composition may additionally comprise additional components
such as typical polymer additives added to polymers during
compounding like plasticizers, flow modifiers, release agents, or
stabilizers against oxidation, thermal degradation, light or UV
radiation. One skilled in the art will understand that blends with
other polymers in order to combine the favorable properties of
different polymers are also contemplated as being within the scope
of the present invention.
[0057] One advantage of the polyester polymer composition of the
current invention is that in contrast with prior art methods of
preparing polyesters, such as the direct reaction of diacid and
diol or acidol monomers, the composition of the invention will
contain little or no residue of such diacid, diol, or acidol
monomers. In one embodiment, the content of diacid, diol, or acidol
monomers is less than 1 wt %, preferably less than 0.5 wt %, more
preferably less than 0.1 wt %, and most preferably not detectable
by FTIR or NMR spectroscopic methods or extraction of soluble
species followed by GC-MS or HPLC analysis. In the present
application, the content of diacid, diol, or acidol monomers refers
to their content as measured by the extraction of soluble species
followed by GC-MS analysis.
[0058] The process of the invention comprises the step of reacting
a cyclic polyester oligomer in the presence of a catalyst in a
ring-opening polymerization step under conditions of a reaction
temperature and reaction time sufficient to yield the polyester
polymer having furanic units and comprising the structure Z.sup.1
or Z.sup.2.
[0059] In one embodiment, the cyclic polyester oligomer comprises
the structure Y.sup.1
##STR00010##
[0060] wherein each of the groups A is an optionally-substituted
linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl group,
and m is an integer from 1 to 20, preferably 2 to 15, most
preferably 3 to 10, and the polyester polymer comprises the
structure Z.sup.1, wherein A is as previously defined and n is an
integer from 10 to 1,000,000, as shown in the reaction scheme in
FIG. 1.
[0061] In an alternative embodiment, the cyclic polyester oligomer
comprises the structure Y.sup.2
##STR00011##
[0062] wherein each of the groups B is an optionally-substituted
linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl group,
and m is an integer from 1 to 20, preferably 2 to 15, most
preferably 3 to 10, and the polyester polymer comprises the
structure Z.sup.2, wherein B, n' and n are as previously defined,
as shown in the reaction scheme in FIG. 2.
[0063] FIG. 3 shows a reaction scheme for the synthesis of a
specific polyester polymer having furanic units and comprising the
structure Z.sup.1' from a cyclic polyester oligomer Y.sup.1', and
FIG. 4 shows a reaction scheme for the synthesis of a specific
polyester polymer having furanic units and comprising the structure
Z.sup.1'' from a cyclic polyester oligomer Y.sup.1'', wherein m and
n are as previously defined for the case of both figures.
[0064] The cyclic polyester oligomer of the current invention is
not specifically limited and it may comprise other components in
addition to the structures Y.sup.1, Y.sup.2, Y.sup.1', or
Y.sup.1''. For example, the cyclic polyester oligomer may contain
low levels of impurities such as linear oligomers, residual
catalysts, water, solvent or unreacted diacid, diol, or acidol
reagents used in the preparation of the cyclic polyester oligomer.
The amount of these impurities in the cyclic polyester oligomer
will preferably be less than 10, more preferably less than 5, and
most preferably less than 1 mass % based on the total mass of the
cyclic polyester oligomer.
[0065] Ring opening polymerization processes are well known in the
art, for example, as disclosed in Handbook of Ring-Opening
Polymerization, by P. Dubois, O. Coulembier, and J.-M. Roquez,
Published in 2009 by Wiley-VCH, Weinheim (ISBN 978-3-527-31953-4)
or Ring-Opening Polymerization: Kinetics, Mechanisms, and
Synthesis, ACS Symposium Series 286, by J. E. McGrath, published in
1985 by ACS (ISBN-13: 978-0894645464).
[0066] Unless indicated otherwise, conventional ring-opening
polymerization processes and their various reagents, operating
parameters and conditions may be used in the processes according to
the invention and making use of the cyclic polyester oligomers
comprising the structures Y.sup.1, Y.sup.2, Y.sup.1', or
Y.sup.1''.
[0067] The conditions of a reaction temperature and reaction time
sufficient to yield a polyester polymer having furanic units in the
ring-opening polymerization step are not specifically limited.
Sufficient here means that the reaction temperature and time are
sufficient to cause a ring-opening reaction to occur such that a
polymer having the claimed values of n is produced from the cyclic
oligomers. One skilled in the art will understand that appropriate
specific reaction temperatures and reaction times may vary somewhat
due to the interaction between the reaction temperature and
time.
[0068] For example, increasing the reaction temperature may allow
the reaction to take place in a shorter time, or increasing the
reaction time may allow lower reaction temperatures to be used.
Lower reaction temperatures and/or shorter reaction times may be
appropriate if a lower molecular weight polyester polymer is to be
produced and/or a lower conversion of cyclic polyester oligomer to
polymer may be tolerated. Alternatively, higher reaction
temperatures and/or longer reaction times may be appropriate if a
higher molecular weight polyester polymer is to be produced and/or
a higher conversion of cyclic polyester oligomer is desired.
[0069] Furthermore the use of more effective catalysts or a higher
concentration of catalyst or the use of an optional initiator may
allow milder reaction conditions (e.g. lower reaction temperatures
and shorter reaction times) to be used. Conversely the presence of
impurities, particularly catalyst-quenching or chain-stopping
impurities may require more intensive reaction conditions.
[0070] In one embodiment the reaction temperature is from 25 to
350, preferably 80 to 300, most preferably 110 to 280.degree. C.,
and the reaction time is from 10 to 300, preferably, 20 to 240,
most preferably 30 to 180 minutes. In certain specific embodiments,
the various specific temperature and time range combinations
obtained by combining any of these disclosed ranges may be
used.
[0071] In the execution of the present invention, any catalyst
which is able to catalyze the polymerization of a cyclic polyester
oligomer into its corresponding polymeric form may be used.
Suitable catalysts for use in the present invention are those known
in the art for polymerization of cyclic esters, such as a base,
preferably a metal alkoxide, or a Lewis acid catalyst. The Lewis
acid catalyst may be a metal coordination compound comprising a
metal ion having more than one stable oxidation state. Of this
class of catalysts, the tin-or zinc- or aluminium- or titanium
containing compounds are preferred, of which their alkoxides and
carboxylates are more preferred, and tin octoate is the most
preferred catalyst. The cyclic polyester oligomer may be in the
solid phase when it is mixed with the catalyst. However, bringing
the cyclic polyester oligomer into the molten phase and then adding
the catalyst afterwards is preferred.
[0072] The ring-opening polymerization step preferably takes place
in the presence of an optional initiator having at least one or
more hydroxyl groups. The initiator is not specifically limited,
and, in one embodiment, it is selected from the group consisting of
water, 1-octanol, 2-ethylhexanol, 1-decanol, isodecyl alcohol,
1-undecanol, 1-dodecanol, 2-methyl-2-propanol, 4-phenyl-2-butanol,
1,3-propandiol, and pentaerytrol.
[0073] Specific combinations of catalysts and initiators have been
proven to be particularly effective, and their use is preferred. In
one preferred embodiment, the catalyst is a Lewis acid catalyst,
preferably a tin or zinc or aluminium or titanium alkoxide or
carboxylate, and the initiator is present and it is selected from
the group consisting of water, 1-octanol, 2-ethylhexanol,
1-decanol, isodecyl alcohol, 1-undecanol, 1-dodecanol,
2-methyl-2-propanol, 4-phenyl-2-butanol, 1,3-propandiol, and
pentaerytrol. In a more specific preferred embodiment, the Lewis
acid catalyst is tin octoate and the initiator is either 1-octanol
or 2-ethylhexanol.
[0074] The amount of catalyst in the process of the invention is
not specifically limited. In general, the amount of catalyst is
sufficient to cause a ring-opening reaction to occur for the
selected reaction temperature and time such that a polymer having
the claimed values of n is produced from the cyclic oligomers. In
one embodiment, the catalyst is present in an amount relative to
the mass of the cyclic polyester oligomer of from 1 ppm to 1 mass
%, preferably from 10 to 1,000 ppm, more preferably from 50 to 500
ppm. Similarly the amount of optional initiator is not specifically
limited, and in one embodiment the initiator is present in an
amount of from 1 to 100, preferably from 10 to 50 mmol per kg
cyclic polyester oligomer. The concentration of the catalyst and
the initiator may be readily determined by the masses or mass flow
rates used of these reagents relative to that of the cyclic
polyester oligomer.
[0075] The process to prepare the polyester polymer composition of
the invention is not specifically limited, and it may be conducted
in a batch, semi-continuous, or continuous manner. Polymerisation
processes suitable for preparing the polyester polymer composition
of the invention can be divided into two groups, viz.
polymerisation in the presence of a solvent, e.g., suspension or
precipitation or emulsion polymerisation, and polymerisation in the
substantial absence of solvent, e.g., melt polymerisation, carried
out at a temperature above the melting temperature of the cyclic
oligomer and polymer, or mass polymerisation, carried out at a
temperature below the melting temperature of the polymer. The
latter may be in some embodiments subjected after
melt-polymerisation to solid-state post-polymerisation (SSP) in
order to increase the average molecular weight to values that are
not achievable in the molten state.
[0076] The apparatus suitable for carrying out the process of the
invention is not specifically limited. For example, batch reactors,
continuous stirred tank reactors, plug flow reactors and any
combination of them (e.g. cascades of stirred tank reactors) can be
used.
[0077] In one embodiment, the ring-opening polymerization step
takes place in a loop reactor 100 and a plug flow reactor 200,
wherein one or both of the reactors 100 and 200 are preferably
equipped with static mixing elements and heat transfer equipment.
Suitable static mixing elements are described in U.S. Pat. No.
4,314,606 and US2008/0219086. The use of static mixing elements
ensures a good homogeneity of the reaction mixture comprising
polymerised products in combination with optimal removal of
reaction heat provided by the heat transfer equipment.
[0078] In such a loop reactor, the added cyclic polyester oligomer
and catalyst are intimately mixed with partially-polymerised
product that is already present in the reactor. One beneficial
result of this is that the rheological behaviour of the reaction
mixture only changes gradually within the loop reactor, thus
helping control the fluid flow within the reactor.
[0079] In the loop reactor, the reaction mixture is
pre-polymerised. The degree of conversion in the continuous mixing
reactor is generally at least 5 wt. %, more in particular at least
10 wt. %. The degree of conversion may be as high as 40 wt. %, or
even 50 wt. %. The degree of conversion is generally below 90 wt.
%, more in particular at most 85 wt. %. The degree of conversion is
defined as the wt of the linear form polymer relative to that of
the wt of the total reaction mixture (e.g. linear form
polymer+cyclic form oligomer) expressed in wt %. The optimal degree
of conversion aimed for in the continuous mixing reactor will
depend, among the other factors, on the viscosity of the reaction
mixture.
[0080] Pre-polymerised reaction mixture is continuously withdrawn
from the loop reactor and continuously provided to a plug flow
reactor, where it is preferably polymerised further to a degree of
conversion of at least 90%. In the plug flow reactor, which is
preferably equipped with static mixing elements and heat transfer
equipment, the polymerisation may preferentially be completed up to
high conversions. Furthermore intense mixing and homogeneous and
controllable temperature distribution enable an optimisation of the
polymerisation process.
[0081] As the presence of substantial amounts of unreacted cyclic
polyester oligomer or other volatile species in the polyester
polymer composition may detrimentally affect the mechanical
properties and processing behaviour of the polymer composition, the
polymer composition is preferably also subjected to a
devolatilization step. As noted earlier, due to its relatively high
molecular weight, most of the unreacted cyclic polyester oligomer
will not be very volatile. Due to its lack of free acid or hydroxyl
groups, the presence of unreacted cyclic polyester oligomer will
not generally be detrimental to the polymer composition properties.
Thus in a preferred embodiment, the process additionally comprises
a subsequent devolatilization step in which unreacted cyclic
oligomer or preferably other volatile components are removed from
the the polyester polymer having furanic units obtained from the
ring-opening polymerization step, and preferably where the
devolatization step takes place in the molten state using a vacuum
and/or a purge of inert atmosphere. In alternative embodiments,
unreacted cyclic polyester oligomer or other volatile species may
be removed by extraction with suitable solvents or precipitation
from solution or treatment by a suitable column or bed.
[0082] The devolatilization step is carried out to remove
volatiles, in particular liberated monomer species, unreacted
reactants, impurities, or degradation products from molten or solid
polymer compositions. The volatiles are preferably removed at
increased temperature under reduced pressure, e.g. under vacuum,
preferably below 10 mbar. Additionally, it is possible to purge by
passing an inert gas through the polymer composition in the molten
liquid phase.
[0083] In the polyester polymer composition product that is
obtained after the devolatilisation step, cyclic polyester oligomer
is generally present in an amount of less than 2 wt. %, more in
particular in an amount of less than 1 wt. %, still more in
particular in an amount of less than 0.5 wt. %.
[0084] Examples of devolatilisers include extruders, especially
twin screw extruders, wiped film evaporators, falling film
evaporators, rotary devolatilisers, rotary disk devolatilisers,
centrifugal devolatilisers, flat plate devolatilisers, and static
expansion chambers involving special distributors, e.g., Sulzer
devolatilization technology as described in EP1800724. The use of a
static expansion chamber is considered preferred. Devolatilization
in various stages and/or a combination of various types of
apparatus is also possible. Stripping gas such as nitrogen can be
applied to one or several stages in order to facilitate
devolatilization. Devolatilization may also be conducted in
solid-state post-polymerisation equipment or by drying of solid
pelletised polyester polymer composition product under vacuum or
inert gas flow, e.g., in a tumble dryer. Optionally, a
crystallisation step may be performed before the drying step.
[0085] FIG. 5 shows a schematic view of a preferred apparatus
suitable for the continuous process of preparing high molecular
weight polyester polymer compositions in high quality from cyclic
polyester oligomers in an economically attractive manner on an
industrial scale. In FIG. 5 an embodiment of a continuous
polymerization apparatus 1 is depicted, which comprises an inlet 2,
a loop reactor 3, a plug flow reactor 4 and a two-stage vacuum
devolatilisation unit, containing devolatilisation tanks 5 and 6,
and an outlet 7. A continuous polymerization apparatus of this type
has been described in more detail in the international patent
application with publication number WO2010/012770-A1.
[0086] The cyclic polyester oligomer from which a polyester polymer
composition should be prepared and a polymerization catalyst are
mixed in molten form and added via inlet 2 to the polymerization
apparatus. The temperature of the mixture is chosen such that the
mixture remains in liquid form. If an initiator having at least one
or more hydroxyl groups should be added, they can be introduced in
the system at the same position, for example as alcohols. The
mixture is transported in a continuous way to and circulated in the
loop reactor 3. Part of the partially polymerized mixture is
separated from the loop reactor 3 and transported in a continuous
manner through the plug flow reactor 4. In some embodiments, the
recirculation ratio in the loop will be between 1 and 50,
preferably between 2 and 20, more preferable between 2 and 4. In
the present application, the term "recirculation ratio" is defined
as the ratio between the flowrate in the lower part of the loop
reactor and the flowrate of the fresh monomer stream fed to the
loop reactor. Reaction conditions (temperature, flow speed,
catalyst concentration, etc) are chosen such that the conversion of
the cyclic polyester oligomer in the reaction mixture is (almost)
complete and close to equilibrium with the corresponding polymer at
the end of plug flow reactor 4. Both the loop and the plug flow
reactor may be sub-divided into different zones having different
temperatures. The polyester polymer composition is then
devolatilized in tanks 5 and 6 and removed from the polymerization
apparatus 1 via outlet 7.
[0087] After removal, the polyester polymer composition may be
subjected to secondary operations such as compounding, blending,
pelletizing, extrusion, molding, or various combinations of these
operations.
[0088] The invention relates to a polyester polymer composition
comprising a polyester polymer having furanic units, wherein the
polyester polymer having furanic units comprises the structure
Z.sup.1 or Z.sup.2, and wherein the polyester polymer composition
is obtainable with the above-described method. Said polyester
polymer composition is characterized in that the polyester polymer
having furanic units has a number average molar mass (Mn) relative
to Polystyrene Standards ranging between 10,000 and 10,000,000
g/mol as determined by Gel Permeation Chromatography (GPC, also
referred to as Size Exclusion Chromatography). Such polymer can
answer most requirements posed by the current applications. The Mn
of the polyester polymer composition is preferably at least 30,000,
still more preferably at least 50,000 g/mol. The upper limit of the
molar mass is not critical to the process according to the
invention. Generally it is below 500,000 g/mol, more specifically
below 300,000 g/mol.
[0089] The polyester polymer composition of the invention
additionally comprises a cyclic polyester oligomer comprising
either structure Y.sup.1 or Y.sup.2, preferably in a concentration
of less than 5 wt %, more preferably less than 1, more preferably
less than 0.5 in the composition. The concentration of the cyclic
polyester oligomer in the composition may be determined by
analytical methods known in the art, as described earlier.
[0090] In a preferred embodiment of the polyester polymer
composition, the polyester polymer having furanic units and
comprising either structure Z.sup.1 or Z.sup.2 also has a
polydispersity of less than 3, preferably 2.5, most preferably
2.1.
[0091] In another preferred embodiment of the composition, either:
(A) the polyester polymer having furanic units comprises more
specifically the structure Z1' and the cyclic polyester oligomer
comprises more specifically the structure Y1', or (B) the polyester
polymer having furanic units comprises more specifically the
structure Z1'' and the cyclic polyester oligomer comprises more
specifically the structure Y1''.
[0092] Yet another aspect of the present invention is the use of
the polyester polymer composition of the invention in extrusion,
injection molding, or blow molding.
EXAMPLES
[0093] The following examples are set forth to provide those of
ordinary skill in the art with a detailed description of how the
processes, polyester polymer compositions, and uses claimed herein
are evaluated, and they are not intended to limit the scope of what
the inventors regard as their invention.
[0094] In these examples, the following characterization methods
and parameters were used for the characterization of the polyester
polymer composition prepared in the examples.
[0095] .sup.1H NMR
[0096] Measurements were performed on a Bruker AV 400 spectrometer
operating at a frequency of 400 MHz and using d-TFA as solvent.
[0097] MALDI-TOF
[0098] The matrix was
T-2-[3-(4-t-Butyl-phenyl)-2-methyl-2-propenylidene]malononitrile
(DCTB)+Na Mix 10:1, and the instrument type was a Bruker Daltonics
Ultraflex II, and the acquisition mode was reflector.
[0099] DSC
[0100] Analysis were performed on a "Mettler Toledo Polymer DSC" or
on a "PerkinElmer DSC8000" differential scanning calorimeters,
calibrated with indium standard. Standard aluminum pans were used
for the analysis.
Example 1
A Polyester Polymer Composition (Embodiment of Z.sup.1')
[0101] In this example, the preparation is described of the
polyester polymers shown in FIG. 3. The reaction was performed in a
Mettler Toledo Polymer DSC. Tetrakis(2-ethylhexyl)titanate was
added in 0.1 mol % ratio to a solution of PEF cyclics dissolved in
dry tetrahydrofuran (THF). THF was removed by vacuum evaporation,
and the resulting solid mixture was transferred into a glove box
under nitrogen. 15 mg of the obtained solid were weighted into a 40
uL aluminum DSC pan, which was sealed under inert atmosphere. The
pan was heated to 270.degree. C. for 15 minutes in the DSC machine.
After 15 minutes the pan was cooled to room temperature, opened,
and the solid residue was dissolved in trifluoroacetic acid (TFA).
The polyester polymers were precipitated from the solution by
addition of THF. The mixture was centrifuged and the supernatant
was removed by decantation. The separation procedure was repeated
for two more times. The remaining solid residue, which consists of
a purified mixture of PEF polyester polymers (Z.sup.1'), was
finally dried under vacuum and analyzed. FIGS. 6 and 7b feature
respectively representative .sup.1H NMR spectrum and DSC trace for
embodiment of Z.sup.1' (PEF polyester polymers).
[0102] .sup.1H NMR (400 MHz, d-TFA, 25.degree. C.): .delta.=4.06
(H''.sub.a), 4.90 (H.sub.a+H'.sub.a), 7.48
(H.sub.b+H'.sub.b+H''.sub.b) see FIG. 6 for atom labeling;
MALDI-TOF-MS: m/z (for HO-[M].sub.n-CO)C.sub.4H.sub.2OC(O)OH, with
[M]=[C(O)C.sub.4H.sub.2OC(O)OCH.sub.2CH.sub.2O]): 1271.45
([M.sub.6+Na].sup.+, calcd for C.sub.64H.sub.40O.sub.35Na.sup.+:
1271.13), 1453.53 ([M.sub.7+Na].sup.+, calcd for
C.sub.62H.sub.46O.sub.40Na.sup.+: 1453.15), 1635.56
([M.sub.8+Na].sup.+, calcd for C.sub.70H.sub.52O.sub.45Na.sup.+:
1635.17), 1817.56 ([M.sub.9+Na].sup.+, calcd for
C.sub.78H.sub.58O.sub.50Na.sup.+: 1817.19); 1999.54
([M.sub.10+Na].sup.+, calcd for C.sub.86H.sub.64O.sub.55Na.sup.+:
1999.21), 2181.48 ([M.sub.11+Na].sup.+, calcd for
C.sub.94H.sub.70O.sub.60Na.sup.+: 2181.23), 2363.39
([M.sub.12+Na].sup.+, calcd for C.sub.102H.sub.76O.sub.65Na.sup.+:
2363.25), 2545.29 ([M.sub.13+Na].sup.+, calcd for
C.sub.110H.sub.82O.sub.70Na.sup.+: 2545.28), 2728.12
([M.sub.14+Na].sup.+, calcd for C.sub.118H.sub.88O.sub.75Na.sup.+:
2727.30), 2909.97 ([M.sub.15+Na].sup.+, calcd for
C.sub.126H.sub.94O.sub.80Na.sup.+: 2909.32), 3091.80
([M.sub.16+Na].sup.+, calcd for C.sub.134H.sub.100O.sub.85Na.sup.+:
3093.17), 3273.58 ([M.sub.17+Na].sup.+, calcd for
C.sub.142H.sub.106O.sub.90Na.sup.+: 3273.36), 3455.34
([M.sub.18+Na].sup.+, calcd for C.sub.150H.sub.112O.sub.95Na.sup.+:
3455.38), 3637.14 ([M.sub.19+Na].sup.+, calcd for
C.sub.158H.sub.118O.sub.100Na.sup.+: 3637.40), 3818.90
([M.sub.20+Na].sup.+, calcd for
C.sub.166H.sub.124O.sub.105Na.sup.+: 3819.43), 4000.58
([M.sub.21+Na].sup.+, calcd for
C.sub.174H.sub.130O.sub.110Na.sup.+: 4001.45), 4182.29
([M.sub.22+Na].sup.+, calcd for
C.sub.182H.sub.136O.sub.115Na.sup.+: 4183.47); DSC (temperature
program: heat from 30 to 250.degree. C. at 10.degree. C./min; cool
to -196.degree. C. by direct quenching in liquid nitrogen;
equilibrate at 30.degree. C.; heat from 30 to 250.degree. C. at
10.degree. C./min; data taken from 2.sup.nd heating scan): Tg=73,
T.sub.cold crystallization (peak)=156, Tm (peak)=203.degree. C.
Example 2
A Polyester Polymer Composition (Embodiment of Z.sup.1'')
[0103] In this example, the preparation is described of the
polyester polymers shown in FIG. 4. The reaction was performed in a
Mettler Toledo Polymer DSC. Tetrakis(2-ethylhexyl)titanate was
added in 0.1 mol % ratio to a solution of PBF cyclics dissolved in
dry THF. THF was removed by vacuum evaporation, and the resulting
solid mixture was transferred into a glove box under nitrogen. 15
mg of the obtained solid were weighted into a 40 uL aluminum DSC
pan, which was sealed under inert atmosphere. The pan was heated to
270.degree. C. for 15 minutes in the DSC machine. After 15 minutes
the pan was cooled to room temperature, opened, and the solid
residue was dissolved in trifluoroacetic acid (TFA). The polyester
polymers were precipitated from the solution by addition of THF.
The mixture was centrifuged and the supernatant was removed by
decantation. The separation procedure was repeated for two more
times. The remaining solid residue, which consists of a purified
mixture of PBF polyester polymers (Z.sup.1''), was finally dried
under vacuum and analyzed. FIGS. 8 and 9b show respectively a
typical .sup.1H NMR-spectrum and a representative DSC trace for
embodiment of Z.sup.1'' (PBF polyester polymers).
[0104] .sup.1H NMR (400 MHz, d-TFA, 25.degree. C.): .delta.=1.46
(H''.sub.b), 2.19 (H.sub.b+H'.sub.b), 4.09 (H''.sub.a), 4.72
(H.sub.a+H'.sub.a), 7.54 (H.sub.c+H'.sub.c), 7.62 (H''.sub.c) see
FIG. 8 for atom labeling; DSC (temperature program: hold for 1 min
at 0.degree. C.; heat from 0 to 200.degree. C. at 10.00.degree.
C./min; hold for 3 min at 200.degree. C.; cool from 200 to
0.degree. C. at -150.00.degree. C./min; hold for 2 min at 0.degree.
C.; heat from 0 to 200.degree. C. at 10.00.degree. C./min; data
taken from 2.sup.nd heating scan): Tg=36, T.sub.cold
crystallization (peak)=94, Tm (peak)=170.degree. C.
[0105] In these additional examples, a series of small-scale
oligomerization and polymerization reactions may be carried out in
a glass tube reactor. The batch reactor tube may be charged at
ambient temperature and pressure with the cyclic polyester oligomer
and the catalyst and the optional initiator having one or more
hydroxyl groups. After charging, the reactor is sealed shut, and
the reactor may be deoxygenated by purging with nitrogen.
[0106] The reactor tube may be heated using a sand or oil bath. The
ring-opening polymerization may be initiated and carried out by
increasing the temperature of the reactor tube stepwise. Preferably
the reactor tube will be mixed during the polymerization reaction.
After the reaction conditions provide sufficient reaction
temperature and reaction time to yield a polyester polymer having
furanic units, the polyester polymer product may be removed from
the reactor tube and analyzed. Preferably GPC analysis will be used
to determine the molecular weight properties of the polyester
polymer product, and MALDI analysis may be used to confirm that the
cyclic polyester oligomer has been converted to a linear polyester
polymer. Compositional information on the polyester polymer, such
as concerning the content of any diacid, diol, or acidol monomers
or degradation products, may be obtained by NMR, FTIR and/or Raman
spectroscopies. The content of such monomers and cyclic polyester
oligomers may be determined by extraction of these soluble species
followed by GC-MS analysis.
[0107] In one set of examples, the polyester polymer having furanic
units and comprising the specific structure Z1' may be prepared
from the cyclic polyester oligomer comprising the specific
structure Y1'. In this example, the polyester oligomer is charged
to the reactor together with tin octoate as catalyst (500 ppm
concentration of catalyst relative to the mass of the cyclic
oligomer) and 2-ethylhexanol as initiator (100 mmol per kg cyclic
polyester oligomer). The reactor is heated slowly to a temperature
of 280.degree. C., and the reactor is maintained at this
temperature over a period of several hours. Samples are regularly
withdrawn from the reactor at 20 minute intervals and analyzed as
described previously. The sample analyses will indicate that the
extent of conversion of the cyclic polyester oligomer and the
molecular weight of the polyester polymer obtained will
progressively increase until at least about 80% conversion is
achieved. These analytical data and polymer properties at higher
conversions will compare favorably with those of PEF prepared by
methods known in art, for example, the data and properties as
disclosed in the publication of J. Ma, Y. Pang, M. Wang, J. Xu, H.
Ma and X. Nie, in J. Mater. Chem. 2012, 22, 3457-3461. Carrying out
such examples as a function of reaction time and temperature will
allow one to determine the required reaction temperature and
reaction time conditions sufficient to obtain the desired molecular
weight and conversion properties for a particular charge of cyclic
polyester oligomer and type and concentration of catalyst and
initiator.
[0108] In another set of examples, the polyester polymer having
furanic units and comprising the specific structure Z1'' may be
prepared from the cyclic polyester oligomer comprising the specific
structure Y1'' and the required reaction temperature and reaction
time conditions sufficient to obtain the desired molecular weight
and conversion properties may be determine for a particular charge
of cyclic polyester oligomer and type and concentration of catalyst
and initiator. These analytical data and polymer properties at
higher conversions will compare favorably with those of PBF
prepared by methods known in art, for example, the data and
properties as disclosed in the publication of J. Ma, Y. Pang, M.
Wang, J. Xu, H. Ma and X. Nie, in J. Mater. Chem. 2012, 22,
3457-3461.
[0109] While various embodiments have been set forth for the
purpose of illustration, the foregoing descriptions should not be
deemed to be a limitation on the scope herein. Accordingly, various
modifications, adaptations, and alternatives can occur to one
skilled in the art without departing from the spirit and scope
herein.
* * * * *