Process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby and a process to polymerize it
11149111 · 2021-10-19
Assignee
Inventors
- Liborio Ivano Costa (Winterthur, CH)
- Peter Joachim Fleckenstein (Zürich, CH)
- Jan-Georg Rosenboom (Zürich, CH)
- Giuseppe Storti (Zürich, CH)
- Massimo Morbidelli (Zürich, CH)
Cpc classification
Y02P20/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C08G63/91
CHEMISTRY; METALLURGY
Abstract
A process to prepare a (iv) cyclic polyester oligomer composition includes a cyclic polyester oligomer having furanic units and two to five repeat units. The process includes (a) reacting a monomer composition including: (i) a bifunctional furan-derivative and (ii) a diol in an linear oligomerization step to produce a (iii) linear oligomer composition including a linear oligomer species, (b) reacting the (iii) linear oligomer composition in a distillation-assisted cyclization (DA-C) step to form a (iv) cyclic polyester oligomer composition and a (v) diol byproduct. The (v) diol byproduct is removed by evaporation in the distillation-assisted cyclization (DA-C) step.
Claims
1. A process to produce a (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units, the process comprising: (a) reacting a monomer composition comprising: (i) a bifunctional furan-derivative having two functional groups selected from the group consisting of carboxylic acid, ester, acid halide and their combinations and (ii) a diol in a linear oligomerization step to produce a (iii) linear polyester oligomer composition comprising a linear oligomer species containing one or more furanic units and two to four repeat units; and (b) reacting the (iii) linear polyester oligomer composition in a distillation-assisted cyclization (DA-C) step to form a (iv) cyclic polyester oligomer composition comprising cyclic oligomers having two to five repeat units and containing furan units and a (v) diol byproduct, the (v) diol byproduct being removed by evaporation in the distillation-assisted cyclization (DA-C) step, and the distillation-assisted cyclization (DA-C) step comprising a cyclization reaction in a reaction vessel that is accompanied by simultaneous removal of condensation reaction byproducts and a solvent through evaporation, followed by collection of the condensation reaction byproducts and the solvent via condensation in a separate vessel.
2. The process of claim 1, wherein the (b) distillation-assisted cyclization (DA-C) step takes place in the presence of the solvent.
3. The process of claim 1, wherein the viscosity during the (a) linear oligomerization step remains less than 50 centipoise.
4. The process of claim 1, wherein the pressure during the (a) linear oligomerization step remains at least about 0.8 atm.
5. The process of claim 1, wherein the (ii) diol or (v) diol byproduct are ethylene glycol or butylene glycol.
6. The process of claim 1, wherein the (i) bifunctional furan-derivative having two functional groups is 2,5-furandicarboxylic acid (FDCA) or a derivative of FDCA.
7. The process of claim 6, wherein the derivative of FDCA is a diester derivative.
8. The process of claim 1, wherein one or more catalysts are present during the (a) linear oligomerization step or the (b) distillation-assisted cyclization (DA-C) step.
9. The process of claim 1, wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units is directly polymerized without intermediate purification to yield a polyester polymer having an Mn of at least about 5,000 Dalton.
10. The process of claim 1, wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furan units is subsequently purified by selective precipitation to form a (iv.a) purified cyclic polyester oligomer composition by separating one or more linear oligomers or monomeric species.
11. The process of claim 10, wherein the separated one or more linear oligomers or monomeric species are recycled to produce a (iv.b.) further cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units.
12. The process of claim 10, wherein the (iv.a) purified cyclic polyester oligomer composition or the (iv.b) further cyclic polyester oligomer composition are polymerized to yield a polyester polymer having an Mn of at least about 5,000 Dalton.
13. The process of claim 2, wherein the viscosity during the (a) linear oligomerization step remains less than 50 centipoise.
14. The process of claim 3, wherein the pressure during the (a) linear oligomerization step remains at least about 0.8 atm.
15. The process of claim 4, wherein the (ii) diol or (v) diol byproduct are ethylene glycol or butylene glycol.
16. The process of claim 5, wherein the (i) bifunctional furan-derivative having two functional groups is 2,5-furandicarboxylic acid (FDCA) or a derivative of FDCA.
17. The process of claim 7, wherein one or more catalysts are present during the (a) linear oligomerization step or the (b) distillation-assisted cyclization (DA-C) step.
18. The process of claim 8, wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units is directly polymerized without intermediate purification to yield a polyester polymer having an Mn of at least about 5,000 Dalton.
19. The process of claim 8, wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furan units is subsequently purified by selective precipitation to form a (iv.a) purified cyclic polyester oligomer composition by means of separating one or more linear oligomers or monomeric species.
20. The process of claim 11, wherein the (iv.a) purified cyclic polyester oligomer composition or the (iv.b) further cyclic polyester oligomer composition are polymerized to yield a polyester polymer having an Mn of at least about 5,000 Dalton.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The invention will be explained in more detail hereinafter with reference to the drawings.
(2)
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(10)
DETAILED DESCRIPTION OF THE EMBODIMENTS
(11) The claimed invention relates to a process to prepare a cyclic polyester oligomer composition comprising a cyclic polyester oligomer having furanic units, such as that known from WO2014/139603 (A1) or EP 16191553.3, both of which are hereby incorporated by reference.
(12) 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.
(13) 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 devolatilization 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.
(14) 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.
(15) As shown in
(16) ##STR00011##
and wherein each of the groups A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein I is an integer from 1 to 100, preferably 2 to 50, most preferably 3 to 25, and wherein
R.sub.1=OH, OR, halogen, or O-A-OH,
R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
(17) ##STR00012##
wherein the monomer component D.sup.1 comprises the structures
(18) ##STR00013##
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.
(19) As shown in
(20) ##STR00014##
and wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, wherein 1 is an integer as defined above, and wherein n′ is an integer from 1 to 20, preferably 2 to 10, 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,
(21) ##STR00015##
the monomer component D.sup.2 comprises the structure
(22) ##STR00016##
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.
(23) 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.
(24)
(25) Unless specifically indicated otherwise, conventional ring-closing oligomerization processes and their various reagents, operating parameters and conditions, such as that known from WO2014/139603 (A1), 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″.
(26) 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.
(27) 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.
(28) 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.
(29) In preferred embodiments of the DA-C process, the pressure in the linear oligomerization step is typically between 0.05-1.2 bar, preferably between 0.5-1.1 bar, and most preferably between 0.8 and 1.05 bar. The temperature in the linear oligomerization step is typically between about 140 and about 300° C., preferably between about 160° C. and about 280° C., and most preferably between about 170° C. and 220° C. The reaction time will generally be between 0.5 and 2 h, preferably between 0.75 and 1.5 h, and most preferably between 0.9 and 1.1 h. The molar catalyst concentration with respect to the monomer, such as the dimethyl ester, meFDCA, is typically between 0.01 and 5%, preferably between 0.02 and 3%, most preferably between 0.05 and 1%.
(30) In one embodiment the cyclization 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.
(31) In another embodiment the cyclization 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.
(32) 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.
(33) 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.
(34) 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.
(35) 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.
(36) 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 1 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.
(37) In preferred embodiments of the DA-C process, the pressure in the distillation-assisted cyclization (DA-C) step is typically between 0.5 and 5 bar, preferably between 0.8 and 3 bar, and most preferably between 1 and 2 bar. The temperature is typically between 140-300° C., preferably between 180° C.-240° C., and most preferably between 190° C. and 210° C. The reaction time is typically between 1 and 10 h, preferably between 2 and 8 h, and most preferably between 3 and 7 h. The concentration of the oligomer composition in this distillation-assisted cyclization (DA-C) step is typically between about 1 and about 500 g/L, preferably between about 5 and about 100 g/L, most preferably about 10 to about 20 g/L.
(38) 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.
(39) As the presence of substantial amounts of unreacted monomer component, linear oligomers, or other low molecular weight species, particularly those having acidic or other free OH groups, 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, such as low molecular weight (e.g. less than 100 g/mol) species having acidic and/or hydroxyl groups, are removed.
(40) 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).
(41) 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.
(42) 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.
(43) 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.
(44) 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 (or solvent) 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 (and solvent) components refers to the concentration as determined by HPLC.
(45) 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. The cyclic polyester oligomer composition is characterized in that the composition contains: (i) a residual solvent in a concentration of less than 5, preferably 2, more preferably 1 wt %, and selected from the group consisting of an ionic liquid, an optionally-substituted napthalene, optionally-substituted aromatic compound, and their mixtures, (ii) linear oligomeric polyester species having furanic units and present in a concentration of less than 5%, preferably 3, most preferably 1 wt %, and (iii) optionally a zeolite, in a concentration of less than of less than 5, preferably 2, more preferably 1 wt %, wherein the weight percentages are relative to the total weight of the cyclic polyester oligomer composition. Such oligomer compositions can answer most requirements posed by the current polymerization applications.
(46) 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.
(47) 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.
(48) 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. Suitable ring opening polymerization catalysts, process conditions, apparatuses and methods are those disclosed in the earlier discussed WO2014/139602, which is hereby incorporated by reference. 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.
(49) Particularly preferred is a polyester polymer composition obtainable, preferably obtained, by the ring opening polymerization process of the invention, wherein the composition contains: (i) a plasticizer selected from the group consisting of an optionally-substituted phenyl ether, an ionic liquid, an optionally-substituted xylene, a polyether, and their mixtures, (ii) a cyclic polyester oligomer having furanic units, preferably one characterized by the presence of an endotherm at about 370° C., more preferably a double endotherm at about 285° C. and about 370° C., and (iii) EITHER: (a) a PEF polymer OR (b) a PBF polymer. The residual plasticizer is preferably present in an amount of less than 10, more preferably 5, even more preferably 2, and most preferably 1 wt %. The content of plasticizer in the polymer may be measured by conventional methods such as that disclosed in Quantifying Polymer Plasticizer Content Through Direct Analysis of Tracer Compounds, IP.com Disclosure Number: IPCOM000246667D, Publication Date: 2016 Jun. 24. The residual unreacted cyclic polyester oligomer having furanic units is preferably present in an amount of less than 5, more preferably 2, even more preferably 1 wt %. In some embodiments, the content of residual plasticizer and unreacted cyclic oligomer is measured by their separation from the polymer via solvent extraction, high temperature distillation or column chromatography and then followed by their identification by UV, NMR, or IR spectroscopies and/or mass spectrometry. The PEF and PBF polymers will often preferably have molecular weights of at least 10,000, preferably 15,000, more preferably 20,000 Daltons relative to polystyrene standards as measured by SEC.
(50)
(51) In one embodiment (A) the cyclic polyester oligomerization under reactive distillation is carried out to give a cyclic polyester oligomer product having a purity of from about 95 to less than about 99% as measured by HPLC analysis. In another embodiment (B) the cyclic polyester oligomerization under reactive distillation is carried out to give a cyclic polyester oligomer product having a purity of at least about 99% as measured by HPLC analysis. The difference in purity as measured by HPLC in these two embodiments will be primarily due to linear oligomers. It is important to remove linear oligomers in order to prepare high molecular weight polyester polymers, for example, those suitable for bottle grade applications as the hydroxyl, ether, or carboxylic acid or ester end groups of the linear oligomers results in a production of more chains and thus a lower molecular weight polyester polymer produced by ring-opening polymerization. However, removal of linear oligomers may often also incidentally remove the catalyst for the cyclization reaction. Removal of linear oligomers may be carried out, for example, by adsorption on a zeolite or selective precipitation of cyclic polyester oligomers by cooling and/or addition of an antisolvent. This catalyst may subsequently be used advantageously in the polymerization. Incidentally-removed catalyst however may be replaced by the addition of fresh catalyst in the subsequent polymerization process.
(52) In the case of embodiment (B) yielding a cyclic polyester oligomer product having a purity of at least about 99% as measured by HPLC analysis, the inventors have surprisingly found that this product may be readily directly polymerized to produce a “BG polyester polymer” having a weight average molecular weight, Mw, of at least about 50,000, preferably 55,000, more preferably 60,000 Dalton as measured by Size Exclusion Chromatography (SEC) analysis. This embodiment is quite advantageous as it has been found that it is not generally necessary to add catalyst. Furthermore, it has surprisingly been found that it is also not necessary to add plasticizer (PL) in order to carry out the polymerization. Without wishing to be bound to any particular mechanism, the inventors believe that plasticizer addition is not necessary as the formed polymeric species are themselves effective in plasticizing the high-melting C2 cyclic dimer polyester oligomer species.
(53) Cyclic polyester oligomer products having a purity of from about 95 to less than about 99% as measured by HPLC analysis may be directly polymerized by ring-opening polymerization to yield a fibre grade (FG) polyester polymer. A “FG polyester polymer” has a weight average molecular weight, Mw, of from about 15,000 to 50,000, preferably 20,000 to 40,000, more preferably 25,000 to 35,000 Dalton as measured by Size Exclusion Chromatography (SEC) analysis.
(54) Alternatively, cyclic polyester oligomer products having a purity of from about 95 to less than about 99% as measured by HPLC analysis may be next purified (PUR) to yield a purified dimer (C2)- or trimer (C3)-rich cyclic polyester product. Suitable purification methods (PUR) may include selective precipitation, fractionation chromatography such as over silica gel, extraction, or crystallization. Selective precipitation may often be preferred as the C2 and C3 species readily precipitate apart from each other. Crystallization may often be preferred for larger-scale or commercial processes as the melting points are quite different for the C2 and C3 species. One skilled in the art will understand that the C2- and C3-rich purified products may contain lesser amounts of other cyclic species; however, the purified C3-rich products will generally preferably have little or no high-melting C2 species.
(55) Due to the high melting properties of the C2-rich purified cyclic polyester oligomer products due to the high-melting C2 component, it is generally necessary to add a plasticizer (PL) to them in order to polymerize them to produce bottle grade (BG) polyester polymer. Generally, it is also necessary to add catalyst again, and the addition of the plasticizer (PL) helps to efficiently distribute this added catalyst.
(56) Since most or preferably essentially all of the high-melting C2 species has been removed from the purified C3-rich cyclic polyester oligomer, it is generally not necessary to add plasticizer (PL) for carrying out the polymerization to produce bottle grade (BG) polyester polymer. Generally, it is also necessary to add catalyst again, but the addition of the plasticizer (PL) is not required in order to efficiently distribute this added catalyst.
EXAMPLES
(57) 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.
(58) In these examples, the following characterization methods are parameters were used for the characterization of the cyclic polyester oligomer compositions prepared in the examples.
(59) SEC-MALS
(60) Conversion and Molecular weight distributions of the polyesters were analyzed using size exclusion chromatography coupled with multi-angle light scattering (SEC-MALS) on an Agilent 1100 GPC using two PFG linear M columns (PSS) connected in series with an Agilent 1100 VWD/UV detector operated at 290 nm, a DAWN HELEOS II multi-angle laser light scattering (MALS) detector (Wyatt Technology Europe) followed by an Agilent 1100 RI detector. Samples were eluted in HFIP with 0.02 M K-TFAc at 1 mL/min at room temperature.
(61) .sup.1H NMR
(62) Measurements were made on a Bruker AV 300 spectrometer operating at a frequency of 300 MHz and using CDCl.sub.3 as solvent.
(63) HPLC-MS
(64) An Agilent 1200 Series HPLC with a quaternary pump, autosampler and UV detector was equipped with an Agilent Eclipse XDB-C18, 5 m, 4.6×150 mm column. The eluent mixture was composed of (A) Water stabilized with formic acid (1 mL/L) and (B) Acetonitrile stabilized with formic acid (1 mL/L). A gradient was run at 1 mL/min for 60 min. Solvent ratio of B was changed linearly from 20% to 45.2% during 11 min, then from 45.2% to 80% during 29 min, followed by 10 minutes at 97% and 10 minutes at 20%. Samples were dissolved at 1 mg/mL in HFIP/CHCL3 (15%). Injection volume was 10 □L and UV detection was carried out at 280 nm. Peaks were characterized by online-mass spectroscopy with an Agilent 1640 single-quadrupol MS.
(65) MALDI-TOF
(66) 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 Y.SUP.1′.) for Production of PEF
(67) In this example, the preparation is described of the cyclic polyester oligomer shown in
(68) The pre-polymer C.sup.1′ was dissolved in 2-methylnaphthalene as solvent at a concentration of 10 g/l, and the resulting solution was reacted under inert atmosphere at 200° C. (in the absence of added additional catalyst) for 3 hours in order to transform the pre-polymer C.sup.1′ into the cyclic oligomer Y.sup.1′. Next Zeolite Y was added at a concentration of 10 g/l. HPLC analysis confirmed that the concentrations of the cyclic oligomers (m=2 to 5) remained essentially unchanged, but that the linear species (I=1 to 8) were essentially removed from the solution. This result confirms that unreacted linear residual species can be easily removed from the reaction system by adsorption on zeolites.
(69) Comparative Example 1 and 2: Lack of Polymerization of Cyclic Polyester Oligomer Composition (Y.sup.1′) In the Presence of Low Amount of Plasticizer Without Catalyst or Without Catalyst or Plasticizer
(70) In this example, the cyclic oligomer Y1′ (m=2) of Example 1 was reacted for 30 min each at different temperatures between 260° C. and 320° C. with tetra-glyme as plasticizer at a concentration of 60 uL tetra-glyme per 180 mg of cyclic oligomer Y1′ and in the absence of added catalyst under inert atmosphere. No reaction occurred and the material remained unchanged.
(71) In a second comparative example, a mixed cyclic oligomer Y1′ (m=2 to 7) of Example 1 was reacted at a temperature of 280° C. for 60 min without added plasticizer or catalyst. GPC analysis confirmed that no reaction of the m=2 cyclic oligomer occurred. Therefore, these comparative examples show that the typically most-abundant species, the low Mw cyclic oligomers (m=2), will not polymerize in the absence of catalyst or plasticizer.
Example 2: Production of PEF from Cyclic Polyester Oligomer Composition (Y.SUP.1′.): in the Presence of Low Amount of Plasticizer with Catalyst
(72) In this example, the cyclic oligomer Y1′ (m=2) of Example 1 was reacted as in the Comparative Example 1, but in the presence of cyclic stannoxane as catalyst in a concentration of 0.1 mol % per mol cyclic oligomer repeat units. In this case, a conversion of greater than 95% was achieved within 20 min.
(73)
(74) In other runs of the polymerization, other metal oxide catalysts such as Sb.sub.2O.sub.3 or Bi.sub.2O.sub.3 were compared to tin-based catalysts. It was observed that the polymers prepared using the Sb.sub.2O.sub.3 or Bi.sub.2O.sub.3 were more water-white in appearance than the somewhat yellowish-brown colour obtained with the tin-based catalysts.
Example 3: Production of PEF from Cyclic Polyester Oligomer Composition (Y.SUP.1′.): In the Presence of Higher Amount of Plasticizer without Catalyst
(75) In this example, the cyclic oligomer Y1′ (m=2) of Example 1 was reacted as in the Comparative Example 1, with tetra-glyme as plasticizer at a higher concentration of 240 μL tetra-glyme per 180 mg of cyclic oligomer Y1′. In this case, a conversion of greater than 95% was achieved within 60 min at all temperatures.
Example 4: Production of PEF from Cyclic Polyester Oligomer Composition: In the Presence of Catalyst
(76) In this example, the cyclic oligomer was prepared by reactive distillation of this species:
(77) ##STR00017##
in dichlorobenzene (DCB) with a purity of about 95% as determined by HPLC. It was then purified over silica gel using DCB to greater than 99% purity as determined by HPLC. Ring-opening polymerization was then conducted using 0.1% cySTOX as catalyst to yield a bottle-grade PEF polymer having a molecular weight of 60,000 Dalton as determined by SEC analysis.
Example 5: Production of PEF from Cyclic Polyester Oligomer Composition
(78) In this example, the cyclic oligomer was prepared by prepolymerization of dimethyl FDCA and ethylene glycol (EG) over two hours to yield EG-FDCA-EG with an Mn of less than 1,000 Dalton. Subsequent reactive distillation over 2 hours in dichlorobenzene (DCB) yielded the cyclic oligomer with a purity of about 95% as determined by HPLC. It was then purified over silica gel using DCB to greater than 99% purity as determined by HPLC. Ring-opening polymerization was then conducted to yield a bottle-grade PEF polymer having a molecular weight of 60,000 Dalton as determined by SEC analysis.
Example 6: Production of PEF from Cyclic Polyester Oligomer Composition
(79) In this example, the cyclic oligomer was prepared by reactive distillation of this species:
(80) ##STR00018##
in dichlorobenzene (DCB), which yielded the cyclic oligomer with a purity of about 95% as determined by HPLC. It was then directly polymerized by ring-opening polymerization to yield a fiber-grade PEF polymer having a molecular weight of 35,000 Dalton as determined by SEC analysis.
Example 7
(81) In an example of the invented DA-C process, 1 g of the dimethyl ester, meFDCA, was charged together with 1.3 g of ethylene glycol (EG) under inert atmosphere in a 100 mL flask equipped with a distillation bridge and a collection flask. The mixture was heated to 140° C. at which 16 mg of cyclic stannoxane were added to the melt and the temperature was increased to 200° C. The mixture was kept at 200° C. for 1 h during which 0.2 mL of MeOH and EG were collected in the collection flask. Subsequently 125 mL of o-dichlorobenzene (o-DCB) were added to the melt. Over a course of 7 h, 25 mL of EG and o-DCB were collected by evaporation. The resulting mixture contained 10 g/L cyclic polyester oligomers at a cyclic purity of 96%, where the remaining impurities were linear oligomers.
Example 8
(82) In another example of the invented DA-C process, 2 g of meFDCA was charged together with 2.6 g of EG under inert atmosphere in a 100 mL flask equipped with a distillation bridge and a collection flask. The mixture was heated to 140° C. at which 32 mg of cyclic stannoxane were added to the melt and the temperature was increased to 200° C. The mixture was kept at 200° C. for 1 h during which 0.2 mL of MeOH and EG were collected in the collection flask. Subsequently 125 mL of o-DCB were added to the melt. Over a course of 7 h, 25 mL of EG and o-DCB were collected by evaporation. The resulting mixture contained 20 g/L cyclic polyester oligomers at a cyclic purity of 93%, where the remaining impurities were linear oligomers.
Example 9
(83) In yet another example of the invented DA-C process, 3 g of meFDCA was charged together with 3.9 g of EG under inert atmosphere in a 100 mL flask equipped with a distillation bridge and a collection flask. The mixture was heated to 140° C. at which 48 mg of cyclic stannoxane were added to the melt and the temperature was increased to 200° C. The mixture was kept at 200° C. for 1 h during which 0.2 mL of MeOH and EG were collected in the collection flask. Subsequently 125 mL of o-DCB were added to the melt. Over a course of 7 h, 25 mL of EG and o-DCB were collected by evaporation. The resulting mixture contained 30 g/L cyclic polyester oligomers at a cyclic purity of 91%, where the remaining impurities were linear oligomers.
Example 10
(84) In still yet another example of the invented DA-C process, 1 g of meFDCA was charged together with 1.3 g of EG under inert atmosphere in a 100 mL flask equipped with a distillation bridge and a collection flask. The mixture was heated to 140° C. at which 16 mg of cyclic stannoxane were added to the melt and the temperature was increased to 200° C. The mixture was kept at 200° C. for 40 min during which 0.15 mL of MeOH and EG were collected in the collection flask. Subsequently 10 mL of o-DCB were added to the melt. Over a course of 20 min, 10 mL of EG and o-DCB were collected by evaporation. Finally, 125 mL of o-DCB were added to the melt. Over a course of 3 h 25 mL of EG and o-DCB were removed. The resulting mixture contained 10 g/L cyclic polyester oligomers at a cyclic purity of 97%, where the remaining impurities were linear oligomers.
Example 11
(85) In yet a further example of the invented DA-C process, 1 g of meFDCA was charged together with 1.3 g of EG under inert atmosphere in a 100 mL flask equipped with a distillation bridge with a collection flask and a dripping funnel. The mixture was heated to 140° C. at which 16 mg of cyclic stannoxane were added to the melt and the temperature was increased to 200° C. The mixture was kept at 200° C. for 1 h during which 0.2 mL of MeOH and EG were collected in the collection flask. Subsequently 100 mL of o-DCB were added to the melt. Over a course of 7 h, 60 mL of EG and o-DCB were removed by distillation and in parallel the same amount was fed back to the system. The resulting mixture contained 10 g/L cyclic polyester oligomers at a cyclic purity of 98.5%, where the remaining impurities were linear oligomers.
Example 12
(86) In still yet a further example of the invented DA-C process, the reaction solution from example 1 was cooled down stepwise from 180° C. to 50° C. At 150° C., 120° C., 100° C., 80° C. and 50° C., the product was left at constant temperature for 1 h after which a sample was taken, filtered and the composition of the solid and the liquid phase was determined. From this data yield and purity of the precipitated cyclics were determined, as shown in
Example 13
(87) In even yet a further example of the invented DA-C process, cyclic polyester oligomers with varying purities, obtained from similar reactions as described in the examples above were charged in flasks under inert atmosphere and heated rapidly to 260° C. Depending on the purity of the cyclic polyester oligomers, different Mw products were obtained as illustrated in
(88) 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.
EMBODIMENTS
(89) i. 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
(90) ##STR00019##
and wherein each of the groups A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein I is an integer from 1 to 100, preferably 2 to 50, most preferably 3 to 25,
and wherein
R.sub.1=OH, OR, halogen, or O-A-OH,
R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
(91) ##STR00020##
wherein the monomer component D.sup.1 comprises the structure
(92) ##STR00021##
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
(93) ##STR00022##
wherein m is an integer from 1 to 20, preferably 2 to 15, most preferably 3 to 10,
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
(94) ##STR00023##
and wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, wherein 1 is an integer as defined above, and wherein n′ is an integer from 1 to 20, preferably 2 to 10, 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,
(95) ##STR00024##
the monomer component D.sup.2 comprises the structures
(96) ##STR00025##
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
(97) ##STR00026##
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, preferably 2 to 15, most preferably 3 to 10,
AND an optional subsequent step (III) in which linear oligomeric polyester species having furanic units are separated and removed from the cyclic oligomeric composition comprises one or more of the following sub-steps: (a) passing a mobile phase of the cyclic oligomeric composition through a stationary phase, preferably silica gel, (b) selective precipitation, (c) distillation, (d) extraction, (e) crystallization, (f) adding a zeolite and absorbing impurities onto the zeolite, (g) cooling the cyclic oligomeric composition in order to precipitate out cyclic polyester oligomers having furanic units, (h) adding an antisolvent in order to precipitate out cyclic polyester oligomers having furanic units, (i) separating zeolites having absorbed impurities from the cyclic oligomeric composition,
characterized in that the reacting of the monomer component C1 or D1 or 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 is carried out by reactive distillation in the presence of a solvent, wherein the solvent is selected from the group consisting of an ionic liquid, an optionally-substituted napthalene, optionally-substituted aromatic compound, and their mixtures, and wherein an excess of a monomer component C1 or D1 or C2 or D2, preferably ethylene glycol, and a condensation byproduct, preferably water, alcohol, or a halogen acid, and optionally some solvent are removed in the reactive distillation, and wherein a cyclic polyester oligomer composition is formed with a purity as measured by HPLC of EITHER (a) from about 95 to about 99% OR (b) about 99% or more during the reactive distillation.
(98) ii. The process of embodiment i, wherein the cyclic polyester oligomer composition is formed with a purity as measured by HPLC of from about 95 to about 99%, and a ring-opening polymerization is subsequently carried out on the cyclic polyester oligomer composition, preferably in the absence of an optional added catalyst and preferably in the absence of an optional plasticizer, to yield a polyester polymer having furanic units and a weight average molecular weight, Mw, of from about 15,000 to 50,000, preferably 20,000 to 40,000, more preferably 25,000 to 35,000 Dalton as measured by Size Exclusion Chromatography (SEC) analysis.
(99) iii. The process of embodiment i, wherein the cyclic polyester oligomer composition is formed with a purity as measured by HPLC of from about 95 to about 99%, and wherein the cyclic polyester oligomer composition is next further purified, preferably by selective precipitation, fractionation chromatography preferably over silica gel, extraction or crystallization, to yield a cyclic polyester oligomer composition having a substantially increased content of cyclic dimer polyester oligomer, preferably the cyclic dimer polyester oligomer having a double endotherm and preferably a melting point at about 370° C. as measured by DSC, and a ring-opening polymerization is carried out on the further purified cyclic polyester oligomer composition, optionally in the presence of an optional added catalyst, and in the presence of an added plasticizer to yield a polyester polymer having furanic units and a weight average molecular weight, Mw, of at least about 50,000, preferably 55,000, and more preferably 60,000 Dalton as measured by Size Exclusion Chromatography (SEC) analysis.
(100) iv. The process of embodiment i, wherein the cyclic polyester oligomer composition is formed with a purity as measured by HPLC of from about 95 to about 99%, and wherein the cyclic polyester oligomer composition is next further purified, preferably by selective precipitation, fractionation chromatography preferably over silica gel, extraction or crystallization, to yield a cyclic polyester oligomer composition having:
(101) (i) a substantially reduced, preferably substantially eliminated content of cyclic dimer polyester oligomer, wherein the cyclic dimer polyester oligomer preferably has a double endotherm and preferably a melting point at about 370° C. as measured by DSC,
(102) (ii) a substantially increased content of cyclic trimer polyester oligomer, wherein the cyclic polyester trimer preferably has a melting point of about 272° C. as measured by DSC, and a ring-opening polymerization is carried out on the further purified cyclic polyester oligomer composition, optionally in the presence of an optional added catalyst and preferably in the absence of an optional added plasticizer, to yield a polyester polymer having furanic units and a weight average molecular weight, Mw, of at least about 50,000, preferably 55,000, and more preferably 60,000 Dalton as measured by Size Exclusion Chromatography (SEC) analysis.
(103) v. The process of embodiment i, wherein the cyclic polyester oligomer composition is formed with a purity as measured by HPLC of from at least about 99%, and a ring-opening polymerization is carried out on the cyclic polyester oligomer composition, optionally in the presence of an optional added catalyst and preferably in the absence of an optional added plasticizer, to yield a polyester polymer having furanic units and a weight average molecular weight, Mw, of at least about 50,000, preferably 55,000, and more preferably 60,000 Dalton as measured by Size Exclusion Chromatography (SEC) analysis.
(104) vi. The process of any one of embodiments i to v, wherein the optional subsequent step (III) in which linear oligomeric polyester species having furanic units are separated and removed from the cyclic oligomeric composition is carried out.
(105) vii. The process of any one of embodiments i to vi, wherein either:
(106) (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, and m is an integer from 3 to 10,
(107) OR
(108) 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, 1 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.
(109) viii. The process of any one of embodiments I to vii, 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 1 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, 1 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.
(110) ix. The process of any one of embodiments i to viii, wherein the monomer component is C.sup.1 or C.sup.2 and the reaction temperature is from 100 to 350, preferably 150 to 300, most preferably 180 to 280° C., and wherein the reaction time is from 30 to 600, preferably 40 to 400, most preferably 50 to 300 minutes,
(111) OR
(112) wherein the monomer component is D.sup.1 or D.sup.2 and the reaction temperature is from −10 to 150, preferably −5 to 100, most preferably 0 to 80° C., and wherein the reaction time is from 5 to 240, preferably 10 to 180, most preferably 15 to 120 minutes.
(113) x. The process of any one of claims i to ix, wherein either the monomer component C.sup.1 comprises the specific structure
(114) ##STR00027##
or the monomer component D.sup.1 comprises the specific structure
(115) ##STR00028##
and the structure Y.sup.1 of the cyclic polyester oligomer having furanic units is the specific structure
(116) ##STR00029##
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,
(117) ##STR00030##
and X, l, and m are defined as indicated in the previous claim(s) on which this claim depends.
(118) xi. The process of any one of embodiments i to ix, wherein either the monomer component C.sup.1 comprises the specific structure C.sup.1″
(119) ##STR00031##
or the monomer component D.sup.1 comprises the specific structure D.sup.1″
(120) ##STR00032##
and the structure Y.sup.1 of the cyclic polyester oligomer having furanic units is the specific structure Y.sup.1″
(121) ##STR00033##
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,
(122) ##STR00034##
and X, l, and m are defined as indicated in the previous claim(s) on which this claim depends.
(123) xii. The process of any one of embodiments i to xi, wherein the optional organic base E is present and it is a monoamine compound or a compound having the structure
(124) ##STR00035##
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, preferably wherein the organic base E is either:
(i) DABCO, having the structure:
(125) ##STR00036##
OR
(ii) DBU, having the structure:
(126) ##STR00037##
and wherein DABCO or DBU are optionally used together with an alkyl amine, more preferably trimethylamine, and wherein the optional organic base E is preferably 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.
xiii. The process of any one of embodiments i to xii, wherein the optional catalyst is either absent or it is present and it is a metal alkoxide or metal carboxylate, preferably one of tin, zinc, magnesium, calcium, titanium, iron, or aluminium, or it is selected from a cyclic dibutyltin compound, Sb.sub.2O.sub.3, and SnOct.sub.2, more preferably wherein the cyclic dibutyltin compound is 1,1,6,6-Tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxyacyclodecane.
(127) xiv. The process of any one of embodiments ii to v, wherein the plasticizer is present and is one or more selected from the group consisting of a supercritical fluid and a polyether, preferably wherein the supercritical fluid is carbon dioxide or the polyether is a glyme, preferably tetraethylene glycol dimethyl ether.
(128) xv. A polyester polymer composition obtainable, preferably obtained, by the process of any one of embodiments ii to xiv, wherein the composition contains: (i) optionally a plasticizer selected from the group consisting of an optionally-substituted phenyl ether, an ionic liquid, an optionally-substituted xylene, a polyether, and their mixtures,
(129) (ii) a cyclic polyester oligomer having furanic units, preferably one characterized by the presence of an endotherm at about 370° C., more preferably a double endotherm at about 285° C. and about 370° C., and (iii) EITHER:
(130) (a) a PEF polymer comprising the structure
(131) ##STR00038##
OR
(b) a PBF polymer comprising the structure
(132) ##STR00039##
wherein n is an integer from 10 to 100,000, preferably 100 to 10,000.