Process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby
09725558 · 2017-08-08
Assignee
Inventors
- Liborio Ivano Costa (Winterthur, CH)
- Philip Nising (Oetwil am See, CH)
- Francesca Tancini (Wettingen, CH)
- David Pfister (Zürich, CH)
- Giuseppe Storti (Zürich, CH)
- Massimo Morbidelli (Zürich, CH)
Cpc classification
International classification
C08G63/91
CHEMISTRY; METALLURGY
Abstract
A process to prepare a cyclic polyester oligomer composition having a cyclic polyester oligomer having furanic units, includes the step of reacting a monomer component, for example, 2,5-furan dicarboxylic acid and, for example, ethylene glycol, in a ring closing oligomerization at a reaction temperature and reaction time, for example, at 100° C. to 350° C. for 30 to 600 minutes to obtain a cyclic polyester oligomer having furanic units. The process yields a cyclic polyester oligomer composition which can be used in further ring-opening polymerization reactions to produce a polyester polymer. The cyclic polyester oligomer composition has a cyclic polyester oligomer having furanic units and less than 5% linear oligomeric polyester species in the composition.
Claims
1. A process to prepare a cyclic polyester oligomer composition comprising a cyclic polyester oligomer having furanic units, wherein the process comprises: a step of either: (I) reacting a monomer component C.sup.1 or D.sup.1 in the presence of an optional catalyst and/or optional organic base in a ring closing oligomerization step under conditions of a reaction temperature and reaction time sufficient to yield a cyclic polyester oligomer having furanic units and of structure Y.sup.1, wherein the monomer component C.sup.1 comprises the structure ##STR00030## and wherein each of the groups A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein l is an integer from 1 to 100, and wherein R.sub.1=OH, OR, halogen, or O-A-OH, R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl, R.sub.2=H or ##STR00031## wherein the monomer component D.sup.1 comprises the structure ##STR00032## and wherein A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein each of the groups X is an OH, a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, and wherein the groups X are not OH when A is n-butyl, and wherein the structure Y.sup.1 of the cyclic polyester oligomer having furanic units is ##STR00033## wherein m is an integer from 1 to 20, OR (II) reacting a monomer component C.sup.2 or D.sup.2 in the presence of an optional catalyst and/or optional organic base in a ring closing oligomerization step under conditions of a reaction temperature and reaction time sufficient to yield a cyclic polyester oligomer having furanic units and of structure Y.sup.2, wherein the monomer component C.sup.2 comprises the structure ##STR00034## and wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, wherein l is an integer as defined above, and wherein n′ is an integer from 1 to 20, and wherein R.sub.3=OH, OR, halogen, or O—(B—O).sub.n—H, R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl, R.sub.4=H or ##STR00035## the monomer component D.sup.2 comprises the structures ##STR00036## and wherein each of the groups X is an OH, a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and n′ is an integer as defined above, and wherein the structure Y.sup.2 of the cyclic polyester oligomer having furanic units is ##STR00037## wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, n′ is an integer as defined above, and m is an integer from 1 to 20, AND a subsequent step (III) in which linear oligomeric polyester species having furanic units are separated and removed from the cyclic oligomeric composition.
2. The process of claim 1, wherein either: (I)—the monomer component is C.sup.1 and A is an optionally-substituted linear, branched or cyclic alkyl, l is an integer from 3 to 25, OR the monomer component is D.sup.1 and A is an optionally-substituted linear, branched or cyclic alkyl, X is a halogen, or optionally-substituted alkyloxy or phenoxy, and m is as defined previously in this claim, and wherein the structure of the cyclic polyester oligomer having furanic units is one of Y.sup.1, OR (II)—the monomer component is C.sup.2 and wherein B is an optionally-substituted linear, branched or cyclic alkyl, l and m are integers as defined above, and n′ is an integer from 2 to 10, OR the monomer component is D.sup.2, and wherein X is an OH, a halogen, or optionally-substituted alkyloxy, phenoxy, or aryloxy, B is an optionally-substituted linear, branched or cyclic alkyl, or phenyl, and n′ and m are integers as defined previously in this claim, and wherein the structure of the cyclic polyester oligomer having furanic units is one of Y.sup.2.
3. The process of claim 1, wherein either the monomer component is C.sup.1 and A is an optionally-substituted linear, branched or cyclic C.sub.1 to C.sub.6 alkyl, and l is an integer from 3 to 25, and m is an integer from 3 to 10, the monomer component is D.sup.1 and A is an optionally-substituted linear, branched or cyclic C.sub.1 to C.sub.6 alkyl, X is a halogen, or optionally-substituted alkyloxy or phenoxy, and m is an integer as defined above, the monomer component is C.sup.2 and wherein B is an optionally-substituted linear, branched or cyclic C.sub.1 to C.sub.6 alkyl, l and m are integers as defined above and n′ is an integer from 2 to 10, OR the monomer component is D.sup.2, X is a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, B is an optionally-substituted linear, branched or cyclic C.sub.1 to C.sub.6 alkyl, or phenyl, and n′ and m are integers as defined in claim 2.
4. The process of claim 1, wherein the monomer component is C.sup.1 or C.sup.2 and the reaction temperature is from 100 to 350° C., and wherein the reaction time is from 30 to 600 minutes, OR wherein the monomer component is D.sup.1 or D.sup.2 and the reaction temperature is from −10 to 150° C., and wherein the reaction time is from 5 to 240 minutes.
5. The process of claim 1, wherein either the monomer component C.sup.1 comprises the specific structure ##STR00038## or the monomer component D.sup.1 comprises the specific structure ##STR00039## and the structure Y.sup.1 of the cyclic polyester oligomer having furanic units is the specific structure ##STR00040## wherein R.sub.5=OH, OR, halogen, or O—CH.sub.2CH.sub.2—OH, R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl, R.sub.6=H or ##STR00041## and X, l, and m are defined as indicated in the previous claim on which this claim depends.
6. The process of claim 1, wherein either the monomer component C.sup.1 comprises the specific structure C.sup.1″ ##STR00042## or the monomer component D.sup.1 comprises the specific structure D.sup.1″ ##STR00043## and the structure Y.sup.1 of the cyclic polyester oligomer having furanic units is the specific structure Y.sup.1″ ##STR00044## R.sub.7=OH, OR, halogen, or O—CH.sub.2CH.sub.2 CH.sub.2CH.sub.2—OH, R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl, R.sub.8=H or ##STR00045## and X, l, and m are defined as indicated in the previous claim on which this claim depends.
7. The process of claim 1, wherein the optional organic base E is present and it is a monoamine compound or a compound having the structure ##STR00046## wherein each of the groups R.sub.9 to R.sub.12 are hydrogen, optionally-substituted alkyl, phenyl, aryl, or alkaryl, and wherein each of the groups R.sub.9 to R.sub.12 may optionally be bonded together by a single or double bond group as part of a cyclic substituent in a cyclic optional organic base E.
8. The process of claim 1, wherein the optional organic base E is present and it is either: ##STR00047## (i) DABCO, having the structure: OR (ii) DBU, having the structure: ##STR00048## and wherein DABCO or DBU are optionally used together with an alkyl amine.
9. The process of claim 1, wherein the optional catalyst is either absent or it is present and it is a metal alkoxide or metal carboxylate.
10. The process of claim 1, wherein the optional organic base E is present in a stoichiometric ratio of from 0.5 to 6 mol relative to 1 mol of all monomer component species used as a reactant in the process.
11. The process of claim 1, wherein the step (III) in which linear oligomeric polyester species having furanic units are separated and removed from the cyclic oligomeric composition comprises one or more separation sub-steps of passing a mobile phase of the cyclic oligomeric composition through a stationary phase, selective precipitation, distillation, extraction, crystallization or their combinations.
12. A cyclic polyester oligomer composition made by the process according to claim 1, wherein the composition contains less than 5 weight % of linear oligomeric polyester species having furanic units relative to the total weight of the composition.
13. The cyclic polyester oligomer composition of claim 12, wherein the composition contains a halogenated impurity.
14. The cyclic polyester oligomer composition of claim 12, wherein the composition comprises the specific cyclic polyester oligomer having furanic units of structure Y.sup.1′ ##STR00049## wherein m is an integer from 1 to 20.
15. The cyclic polyester oligomer composition of claim 12, wherein the composition comprises the specific cyclic polyester oligomer having furanic units of structure Y.sup.1″ ##STR00050## wherein m is an integer from 1 to 20.
16. A process for preparing a polyester polymer, the process comprising the steps of: obtaining the cyclic polyester oligomer composition of claim 12 and using it in the production of a polyester polymer.
17. The process of claim 16, wherein the polyester polymer is: (i) a PEF polymer comprising the structure ##STR00051## OR (ii) a PBF polymer comprising the structure ##STR00052## wherein n is an integer from 10 to 100,000.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) 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:
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DETAILED DESCRIPTION OF THE INVENTION
(14) The claimed invention relates to a process to prepare a cyclic polyester oligomer composition comprising a cyclic polyester oligomer having furanic units, the cyclic polyester oligomer having either structure Y.sup.1 or Y.sup.2:
(15) ##STR00022##
(16) wherein A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and m is an integer from 1 to 20, preferably 2 to 15, most preferably 3 to 10,
(17) ##STR00023##
(18) wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, n′ is an integer from 1 to 20, preferably 2 to 10, and m is an integer as defined above for Y.sup.1.
(19) The cyclic polyester oligomer 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 Y.sup.1 or Y.sup.2. For example, the cyclic polyester oligomer composition may additionally comprise small amounts of one or more unreacted and/or unremoved reaction components such as a monomer component (unreacted diacid, diol, or acidol reagents), a catalyst, a templating agent, a base, a catalyst quencher, a solvent, 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, even more preferably less than 3, and most preferably less than 1 weight % based on the total weight of the cyclic polyester oligomer.
(20) In addition, the cyclic polyester oligomer 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 the ring-closing oligomerization step or an optional additional step such as a subsequent devolatization step. Examples of such impurities are linear oligomeric polyester species having furanic units. Finally the cyclic polyester oligomer composition may additionally comprise additional components such as typical monomer additives added during production or prior to use such as stabilizers against oxidation, thermal degradation, light or UV radiation. One skilled in the art will understand that blends with other monomers in order to combine the favorable properties of different monomers are also contemplated as being within the scope of the present invention.
(21) One advantage of the cyclic polyester oligomer composition of the current invention is that in contrast with prior art raw materials for 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. Thus the cyclic polyester oligomer composition of the current invention has a high reactivity and favorable equilibrium characterized by the formation of only very low quantities of low molecular weight volatile byproducts during its subsequent polymerization processing.
(22) In one embodiment, the content of diacid, diol, or acidol monomers in the cyclic polyester oligomer composition is less than 5 wt %, preferably less than 3 wt %, more preferably less than 1 wt %. 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.
(23) As shown in
(24) ##STR00024##
(25) and wherein each of the groups A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein l is an integer from 1 to 100, preferably 2 to 50, most preferably 3 to 25, and wherein
(26) R.sub.1=OH, OR, halogen, or O-A-OH,
(27) R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
(28) R.sub.2=H or
(29) ##STR00025##
(30) wherein the monomer component D.sup.1 comprises the structures
(31) ##STR00026##
(32) and wherein A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein each of the groups X is an OH, a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, and wherein the groups X are not OH when A is n-butyl.
(33) As shown in
(34) ##STR00027##
(35) and wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, wherein l is an integer as defined above, and wherein n′ is an integer from 1 to 20, preferably 2 to 10, and wherein
(36) R.sub.3=OH, OR, halogen, or O—(B—O).sub.n′—H,
(37) R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
(38) R.sub.4=H or
(39) ##STR00028##
(40) the monomer component D.sup.2 comprises the structure
(41) ##STR00029##
(42) and wherein each of the groups X is an OH, a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and n′ is an integer as defined previously for Y.sup.2.
(43) In a step (III) subsequent to either (I) or (II), linear oligomeric polyester species having furanic units are separated and removed from the cyclic oligomeric composition.
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(45) Ring-closing oligomerization processes and uses of cyclic oligomers are well known in the art, for example, as disclosed in Cyclic Polymers (Second Edition), edited by J. A. Semlyen, published in 2000 by Kluwer (Springer), Dordrecht (ISBN-13: 9780412830907), 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), or Macrocycles: Construction, Chemistry and Nanotechnology Applications, by F. Davis and S. Higson, published in 2011 by Wiley, Chichester (ISBN: 978-0-470-71462-1).
(46) Unless specifically indicated otherwise, conventional ring-closing oligomerization processes and their various reagents, operating parameters and conditions may be used in the processes according to the invention in preparing the cyclic polyester oligomers having the structures Y.sup.1, Y.sup.2, Y.sup.1′, or Y.sup.1″.
(47) The conditions of a reaction temperature and reaction time sufficient to yield a cyclic polyester oligomer having furanic units in the ring-closing oligomerization step are not specifically limited. Sufficient here means that the reaction temperature and time are sufficient to cause a ring-closing reaction to occur such that an oligomer having the claimed values of m is produced from the monomer components. 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.
(48) 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 cyclic polyester oligomer is to be produced and/or a lower conversion of monomer component to oligomer may be tolerated. Alternatively, higher reaction temperatures and/or longer reaction times may be appropriate if a higher molecular weight cyclic polyester oligomer is to be produced and/or a higher conversion of monomer component is desired.
(49) Furthermore the use of more effective catalysts or bases or a higher concentration of catalyst or organic base 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.
(50) In one embodiment the reaction temperature is from 100 to 350, preferably 150 to 300, most preferably 180 to 280° C., and the reaction time is from 30 to 600, preferably 40 to 400, most preferably 50 to 300 minutes. In certain specific embodiments, the various specific temperature and time range combinations obtained by combining any of these disclosed ranges may be used. In a more preferred embodiment, these temperature and/or time ranges are used in the ring closing oligomerization step with monomer components C.sup.1 or C.sup.2.
(51) In another embodiment the reaction temperature is from −10 to 150, preferably −5 to 100, most preferably 0 to 80° C., and the reaction time is from 5 to 240, preferably 10 to 180, most preferably 15 to 120 minutes. In certain specific embodiments, the various specific temperature and time range combinations obtained by combining any of these disclosed ranges may be used. In a more preferred embodiment, these temperature and/or time ranges are used in the ring closing oligomerization step with monomer components D.sup.1 or D.sup.2.
(52) In the execution of the present invention, any catalyst which is able to catalyze the ring-closing oligomerization to form cyclic polyester oligomers may be used. Suitable catalysts for use in the present invention are those known in the art for polymerization of cyclic esters, such as an inorganic base, preferably a metal alkoxide, a metal carboxylate, 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-containing compounds are preferred, of which their alkoxides and carboxylates are more preferred, and tin octoate is the most preferred catalyst.
(53) The ring-closing oligomerization step preferably takes place in the presence of an optional organic base. The organic base is not specifically limited, and, it may be an inorganic or organic base. In one embodiment, it has the general structure E, and in other embodiments it is an alkyl amine such as triethylamine or it is pyridine. In still other embodiments, it is a combination of E and an alkyl amine. In this application, a “catalyst” refers to an inorganic or metal-containing compound such as an organometallic species or a metal salt; whereas an “organic base” refers to a non-metallic and basic organic species.
(54) Specific combinations of catalysts and bases may be particularly effective, and their use may be preferred. In one preferred embodiment, the catalyst is a tin, zinc, titanium, or aluminum alkoxide or carboxylate, and the organic base is DABCO (CAS No. 280-57-9) or DBU (CAS No. 83329-50-4), preferably together with triethyl-amine. The monomer component may be in the solid phase when it is mixed with the catalyst and/or organic base. However, bringing the monomer component into the molten phase or a liquid phase using a solvent and then adding the catalyst and/or organic base afterwards is preferred.
(55) The amount of catalyst and/or organic base in the process of the invention is not specifically limited. In general, the amount of catalyst and/or organic base is sufficient to cause a ring-closing oligomerization step to occur for the selected reaction temperature and time such that an oligomer having the claimed values of l is produced from the monomer components. In one embodiment, the catalyst and/or organic base is present, and the catalyst is present in an amount relative to the total weight of the monomer components of from 1 ppm to 1 weight %, preferably from 10 to 1,000 ppm, more preferably from 50 to 500 ppm, and the organic base is present in a stoichiometric ratio of from 0.5 to 6, preferably 1 to 4, more preferably 2 to 3 mol relative to 1 mol of all monomer component species used as a reactant in the process. The concentration of the catalyst and the organic base may be readily determined by the masses or mass flow rates used of these reagents relative to that of the monomer components.
(56) The process to prepare the cyclic polyester oligomer composition of the invention is not specifically limited, and it may be conducted in a batch, semi-continuous, or continuous manner. Oligomerization processes suitable for preparing the cyclic polyester oligomer composition of the invention can be divided into two groups, solution oligomerization in the presence of a solvent, or oligomerization in the substantial absence of solvent, e.g., melt oligomerization, carried out at a temperature above the melting temperature of the monomer components and oligomeric species.
(57) The apparatus suitable for carrying out the oligomerization process of the invention is not specifically limited. For example, batch reactors, stirred tank reactors, plug flow reactors, static mixers, cascades of stirred tank reactors, and continuous flow stirred tank reactors may all be used.
(58) As the presence of substantial amounts of unreacted monomer component, linear oligomers, or other low molecular weight species in the cyclic polyester oligomer composition may detrimentally affect the storage stability and/or polymerization processing behaviour of the oligomer composition, the cyclic polyester oligomer composition is subjected to a step in which linear oligomeric polyester species, as well as optionally other impurities, are removed.
(59) The step in which linear oligomeric polyester species having furanic units, as well as optionally other impurities, are separated and removed from the cyclic polyester oligomer composition of the invention is not specifically limited. Examples of other impurities may be unreacted starting materials such as diacids or diols or residual reagents such as bases or their residues (e.g. amine residues). Separation and purification methods are well-known in the art, for example, as disclosed in Purification of Laboratory Chemicals, Sixth Ed., by W. E. Armarego and C. L. L. Chai, published in 2009 by Elsevier, Oxford (ISBN-13: 978-1856175678), and The Molecular World, Separation, Purification and Identification by L. E. Smart, published in 2002 by the Royal Society of Chemistry, Cambridge (ISBN: 978-1-84755-783-4).
(60) Unless specifically indicated otherwise, conventional separation and purification processes and their various apparatuses, operating parameters and conditions may be used in the processes according to the invention in preparing the cyclic polyester oligomers of structures Y.sup.1, Y.sup.2, Y.sup.1′, or Y.sup.1″ and their compositions.
(61) In one embodiment the separation step in which linear oligomeric species and optionally other impurities are removed comprises one or more separation sub-steps of passing a mobile phase of the cyclic oligomeric composition through a stationary phase, selective precipitation, distillation, extraction, crystallization or their combinations.
(62) In the cyclic polyester oligomer composition product that is obtained after the separation step, linear oligomeric polyester species having furanic units are generally present in an amount of less than 5 wt. %, more in particular in an amount of less than 3 wt. %, still more in particular in an amount of less than 1 wt. % relative to the total weight of the cyclic polyester oligomer composition. The content of linear oligomeric polyester species having furanic units in the cyclic polyester oligomer composition of the invention may be readily determined by conventional methods. For example, the content of linear oligomeric species may be determined by electrospray mass spectrometry, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, high-performance liquid chromatography (HPLC) method coupled to mass spectronomy, and gel filtration chromatography. In the present application and invention, the concentration of linear oligomeric polyester species having furanic units refers to the concentration as determined by HPLC.
(63) In a preferred embodiment of the composition, the content of residual monomer components, such as C.sup.1, D.sup.1, C.sup.2, or D.sup.2, in the cyclic polyester oligomer composition is less than 5, preferably 3, and most preferably 1 weight percent based on the total weight of the composition. The content of such residual monomer components may be determined by FTIR or NMR spectroscopic analysis of the composition. Alternatively the content may be determined by chromatographic methods such as HPLC or GC. In the present application and invention, the concentration of residual monomer components refers to the concentration as determined by HPLC.
(64) After removal, the cyclic polyester oligomer composition may be subjected to secondary operations such as compounding, blending, pelletizing, flaking or various combinations of these operations.
(65) The invention relates to a cyclic polyester oligomer composition comprising a cyclic polyester oligomer having furanic units, wherein the structure of the cyclic polyester oligomer having furanic units is Y.sup.1 or Y.sup.2, and wherein the polyester polymer composition is obtainable with the above-described method. Said cyclic polyester oligomer composition is characterized in that the composition contains less than 5%, preferably 3, most preferably 1 weight % of linear oligomeric polyester species having furanic units relative to the total weight of the composition. Such oligomer compositions can answer most requirements posed by the current polymerization applications.
(66) In another preferred embodiment, the composition comprises a halogenated impurity, preferably an acid chloride and/or its residue. Methods of detection of halogenated impurities in oligomers are well-known and include combustion ion chromatography (IC), optical atomic spectroscopy, and X-ray fluorescence analysis (XRF). However halogenated species may be corrosive and thus require special expensive construction materials for the subsequent polymerization plant. Therefore their content in the cyclic polyester oligomer composition of the invention will preferably be kept low, e.g. by removal during the subsequent separation and removal step.
(67) In a preferred embodiment of the cyclic polyester oligomer composition, the specific cyclic polyester oligomer having furanic units is one of structure Y.sup.1′ or Y.sup.1″, wherein m is an integer from 1 to 20, preferably 2 to 15, most preferably 3 to 10.
(68) Yet another aspect of the present invention is a process to produce a polyester polymer comprising (i) the process of the invention to prepare a cyclic oligomer composition comprising a cyclic polyester oligomer having furanic units together with (ii) a subsequent polymerization step to produce a polyester polymer. Related to this aspect is the aspect of the use of the cyclic polyester oligomer composition of the invention in the production of a polyester polymer. Preferred embodiments of this process or use are those in which the polyester polymer is a PEF polymer or a PBF polymer.
EXAMPLES
(69) 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.
(70) In these examples, the following characterization methods are parameters were used for the characterization of the cyclic polyester oligomer compositions prepared in the examples.
(71) GPC
(72) An Agilent 1100 Series GPC equipped with an Agilent Oligopore, 7.5×300 mm column using THF as solvent at a flow rate of 0.5 mL/min, with an injection size of 20 μL, and operating at a temperature of 30° C. was used. Detection was made using a UV detector at 280 nm.
(73) FT-IR
(74) A Nicolet Nexus 870 ESP was used and 100 scans were made with a 8 cm.sup.−1 step size.
(75) .sup.1H NMR
(76) Measurements were made on a Bruker AV 300 spectrometer operating at a frequency of 300 MHz and using CDCl.sub.3 as solvent.
(77) .sup.13C NMR
(78) Measurements were made on a Varian Mercury 300 spectrometer operating at a frequency of 75 MHz and using CDCl.sub.3 as solvent.
(79) HPLC
(80) An Agilent 1200 Series HPLC equipped with an Agilent Eclipse XDB-C18, 5 m, 4.6×150 mm column was used. The solvent mixture was composed of the buffers: (A) MQ water stabilized with 1 mL H3PO4 (85%) per liter, and (B) THF/Water (9:1 by volume) stabilized with 1 mL H3PO4 (85%) per liter, and the method was to change from 40% B to 80% over 25 minutes, followed by 10 minutes at 80% and 10 minutes at 40% to reequilibrate the column. The flow rate was 1 mL/min, the injection size was 10 μL, and the temperature was 30° C. and UV detection was carried out at 280 nm.
(81) MALDI-TOF
(82) 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.
Example 1: A Cyclic Polyester Oligomer Composition (Embodiment of Y1′) for Production of PEF
(83) In this example, the preparation is described of the cyclic polyester oligomer shown in
(84) .sup.1H NMR (300 MHz, CDCl.sub.3, 25° C.): δ=4.66 (4H; H.sub.a), 7.20 (2H, H.sub.b); .sup.13C NMR (75 MHz, CDCl.sub.3, 25° C.): 62.8 (C.sub.1), 119.1 (C.sub.4), 146.1 (C.sub.3), 157.3 (C.sub.2); MALDI-TOF-MS: m/z: 386.89 ([M.sub.2+Na].sup.+, calcd for C.sub.16H.sub.12O.sub.10Na.sup.+: 387.03), 568.92 ([M.sub.3+Na].sup.+, calcd for C.sub.24H.sub.16O.sub.16Na.sup.+: 569.05), 751.03 ([M.sub.4+Na].sup.+, calcd for C.sub.32H.sub.24O.sub.20Na.sup.+: 751.08), 933.08 ([M.sub.5+Na].sup.+, calcd for C.sub.40H.sub.30O.sub.25Na.sup.+: 933.10), 1115.13 ([M.sub.6+Na].sup.+, calcd for C.sub.48H.sub.36O.sub.30Na.sup.+: 1115.12), 1297.15 ([M.sub.7+Na].sup.+, calcd for C.sub.56H.sub.42O.sub.35Na.sup.+: 1297.14), 1479.17 ([M.sub.8+Na].sup.+, calcd for C.sub.64H.sub.48O.sub.40Na.sup.+: 1479.16), 1661.18 ([M.sub.9+Na].sup.+, calcd for C.sub.72H.sub.54O.sub.45Na.sup.+: 1661.18); FT-IR (neat): {tilde over (ν)}=2958-2918 (w), 1721 (s), 1288 (s), 760 cm.sup.−1 (m).
Example 2: A Cyclic Polyester Oligomer Composition (Embodiment of Y1″) for Production of PBF
(85) In this example, the preparation is described of the cyclic polyester oligomer shown in
(86) .sup.1H NMR (300 MHz, CDCl.sub.3, 25° C.): δ=1.95 (4H; H.sub.b), 4.41 (4H, H.sub.a), 7.22 (2H, H.sub.c); .sup.13C NMR (75 MHz, CDCl.sub.3, 25° C.): 25.5 (C.sub.2), 64.8 (C.sub.1), 118.6 (C.sub.5), 146.4 (C.sub.4), 157.7 (C.sub.3); MALDI-TOF-MS: m/z: 442.92 ([M.sub.2+Na].sup.+, calcd for C.sub.20H.sub.20O.sub.10Na.sup.+: 443.36), 653.05 ([M.sub.3+Na].sup.+, calcd for C.sub.30H.sub.30O.sub.15Na.sup.+: 653.15), 863.13 ([M.sub.4+Na].sup.+, calcd for C.sub.40H.sub.40O.sub.20Na.sup.+: 863.20), 1073.19 ([M.sub.5+Na].sup.+, calcd for C.sub.50H.sub.50O.sub.25Na.sup.+: 1073.25), 1283.25 ([M.sub.6+Na].sup.+, calcd for C.sub.60H.sub.60O.sub.30Na.sup.+: 1283.31), 1493.29 ([M.sub.7+Na].sup.+, calcd for C.sub.70H.sub.70O.sub.35Na.sup.+: 1493.36), 1703.33 ([M.sub.8+Na].sup.+, calcd for C.sub.80H.sub.80O.sub.40Na.sup.+: 1703.41); FT-IR (neat): {tilde over (ν)}=2960-2919 (w), 1716 (s), 1285 (s), 764 cm.sup.−1 (m).
Example 3: A Cyclic Polyester Oligomer Composition (Embodiment of Y1′) for Production of PEF
(87) In this example, the preparation is described of the cyclic polyester oligomer shown in
(88) Zinc acetate (6 mg) was added to a solution of hydroxy-terminated polyester oligomers (200 mg) in 1-methylnaphthalene (20 mL). The solution was heated to 230° C. for 24 h. The reaction was then cooled to 130° C. and the solvent was removed under vacuum. 100 mL of hexane was added to the mixture, inducing the precipitation of the crude products. The solvent mixture was removed by decantation. The precipitate was repeatedly washed with hexane (2×60 mL), and recovered by vacuum filtration. Flash chromatography (SiO.sub.2; CH.sub.2Cl.sub.2/MeOH 97:3) gave a purified mixture of PEF cyclics. The cyclic nature of the isolated products was confirmed by MALDI-TOF MS. MALDI-TOF-MS: m/z: 386.86 ([M.sub.2+Na].sup.+, calcd for C.sub.16H.sub.12O.sub.10Na.sup.+: 387.03), 568.94 ([M.sub.3+Na].sup.+, calcd for C.sub.24H.sub.15O.sub.15Na.sup.+: 569.05), 751.00 ([M.sub.4+Na].sup.+, calcd for C.sub.32H.sub.24O.sub.20Na.sup.+: 751.08), 933.04 ([M.sub.5+Na].sup.+, calcd for C.sub.40H.sub.30O.sub.25Na.sup.+: 933.10), 1115.06 ([M.sub.6+Na].sup.+, calcd for C.sub.48H.sub.36O.sub.30Na.sup.+: 1115.12), 1297.07 ([M.sub.7+Na].sup.+, calcd for C.sub.56H.sub.42O.sub.35Na.sup.+: 1297.14), 1479.06 ([M.sub.8+Na].sup.+, calcd for C.sub.64H.sub.48O.sub.40Na.sup.+: 1479.16), 1661.18 ([M.sub.9+Na].sup.+, calcd for C.sub.72H.sub.54O.sub.45Na.sup.+: 1661.18);
(89) Hydroxy-terminated polyester oligomers were conveniently prepared as follow: furandicarboxylic acid (FDCA) (800 mg, 5.12 5.0.Math.10.sup.−3 mol) was reacted with an excess of ethylenglycol (3 mL, 8.97 5.0.Math.10.sup.−2 mol) in a 5-mL glass reactor equipped with a magnetic stirrer, a nitrogen inlet and a distillation head connected to a condenser and a receiver flask. The reactor was heated to 190° C. and temperature was raised gradually to 220° C. under nitrogen, while excess diol distilled off. After 1.5 hour 2.5 mL of fresh diol was added and the reaction was continued again for 1.5 hours, distilling off the excess diol. The reaction was indeed cooled to 190° C., vacuum was applied and the reactor was sealed. The reaction was continued for 2 hours at this temperature. Finally, 1 mg of Ti(OBu).sub.4 was added and the reaction continued for 3 h at 220° C. in vacuum. Reaction was quenched by concentration to dryness. Polyester oligomers were washed with chloroform, to remove catalyst traces. Next they were suspended in hexane, recovered by vacuum filtration and used without additional purification in the following ring-closing reaction.
(90) 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.