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    PROCESS FOR PREPARING A POLL POLYMER (ETILEN0-2,5- FURANDICARBOXILATE), BOTTLE OR FILM OR OBJECT CONTAINING FIBER The invention relates to a process for preparing a polymer with a 2,5-furandicarboxylate portion in the polymer structure, and with numerical average molecular weight equal to at least 25,000, comprising a transesterification step, a polycondensation step, a drying and / or crystallization step and a step in which the polymer is subjected to post-condensation conditions, and a bottle, film or woven or non-woven object containing polyester fiber made by fusion processing of poly (ethylene-2,5-furanedicarboxylate), wherein poly (ethylene-2,5-furanedicarboxylate) is obtainable by the process of the invention
    公开号:BR112014009029B1
    申请号:R112014009029-7
    申请日:2012-10-24
    公开日:2020-12-29
    发明作者:Gerardus Johannes Maria Gruter；Jeffrey John Kolstad；Laszlo Sipos；Matheus Adrianus Dam
    申请人:Furanix Technologies B.V；
    IPC主号:
    专利说明:

    Technical Field
    [001] This invention relates to a process for the preparation of polymers with portions of 2,5-furandicarboxylic acid (abbreviated as 2,5-FDCA) and to a process for the preparation of such polymers. In particular, this invention relates to polyesters and a process for preparing them with high molecular weight, without undergoing discoloration, which can be used in bottle, film or fiber applications. Prior Art
    [002] FDCA (also known as de-hydromucic or pyromucic acid), is a natural diacid that is produced in the healthy human body in quantities of 3 to 5 mg per day. The routes for its preparation using air oxidation of 2,5-disubstituted furans, such as 5-hydroxymethylfurfural, with catalysts comprising Co, Mn and / or Ce were recently reported in W02010 / 132740, W02011 / 043660 and W02011 / 043661.
    [003] In GB 621971, polyesters and polyester amides are prepared by reacting glycols with dicarboxylic acids, of which at least one contains a heterocyclic ring, such as 2,5-FDCA. Under melt polymerization conditions, using sodium and magnesium methoxide as catalyst, FDCA dimethyl ester and 1.6 equivalent of ethylene glycol reacted in a transesterification step under ambient pressure between 160 and 220 ° C, after which the polycondensation was carried out between 190 and 220 ° C under a pressure of 3 mm Hg. The product had a reported melting point of 205 to 210 ° C and promptly produced filaments from the molten material. No additional properties have been reported for PEF or other FDCA-based polyesters in this 1946 document.
    [004] In HACHIHAMA, Yoshikazu, syntheses of polyesters containing a Furan ring are described. In this work, polyesters are produced by the condensation of 2,5-FDCA with various a, u) -glycols. According to this work, the ester exchange proved to be the most convenient method for 2,5-furandicarboxylic acid polyesters, since the acid is difficult to be purified. The ester exchange reaction is promoted by the presence of a catalyst, such as lititarium, a natural form of the lead (II) oxide mineral. However, the polymers formed were brown to grayish white.
    [005] The publication describes polyethylene-furandicarboxylate (PEF) with a melting point between 220 and 225 ° C obtained using a lead catalyst. Polyester analogues tri, tetra, penta and hexamethylenediol have also been reported with reported melting intervals of 115 to 120 ° C, 163 to 165 ° C, 70 ° C and 143 to 145 ° C, respectively. For ethylene glycol and 1,4-butanediol polyesters, fiber forming properties have been reported. The manufactured polymers were reported to have brown to gray-white color.
    [006] In MOORE, J. A. polyesters derived from the furan and tetrahydrofuran nuclei are described. Polymers were prepared using 2,5-furandicarbonyl chloride as a monomer. As a result, polymers in the form of a white precipitate with very low intrinsic viscosity (and, therefore, low molecular weight) were obtained. In addition, a polymer was prepared from 1,6-hexanediol and dimethyl-2,5-furandicarboxylate, using calcium acetate and antimony oxide as a catalyst. The numerical average molecular weight was low (less than 10,000), while the molecular weight distribution was relatively high (2.54 instead of about 2). In addition, the product was greenish. Again, from this reference, it would seem almost impossible to produce polymers having a 2,5-furandicarboxylate portion within the polymer structure, with high molecular weight and without colored impurities, without having to use a precipitation and / or purification step.
    [007] WO 2007/052847, polymers with a 2,5-furandicarboxylate moiety within the polymeric structure and with a degree of polymerization equal to 185 or more and 600 or less are provided. These polymers are made in a three-step process that involves esterification of 2,5-FDCA with a first diol using a tin catalyst and a titanium catalyst, and a second stage involving polycondensation through an ester exchange reaction . The first step is carried out catalytically at a temperature within the preferred range of 150 to 180 ° C, while the polycondensation step is carried out under vacuum at a temperature within the preferred range of 180 to 230 ° C. The product is then purified by dissolving it in hexafluorisopropanol, and re-precipitating and drying it, followed by the third step, solid state polymerization at a temperature in the range of 140 to 180 ° C. Not disclosed, but verified by the present inventors, the intermediate product produced by the process of this reference has a dark color. This is, therefore, the reason for the purification step. This essential purification step and, particularly, using hexafluorisopropanol, is a serious disadvantage of this process, severely limiting its commercialization. The problem vis-à-vis this recent development is to produce polymers having a 2,5-furandicarboxylate portion within the polymer structure, with high molecular weight and without colored impurities, without having to use a purification step. 1,3-propanediol and 1,4-butanediol polyesters have also been reported.
    [008] The reported conditions and properties of the 3 steps for the 3 polyesters are summarized in Table 1 below. Table 1. Experimental results from JP2008 / 291244

    [009] In JP2008 / 291244, a method for producing polyester resin, including the furan structure, is provided. The method for producing a polyester resin, including a furan structure, comprises carrying out the ester exchange reaction of a furandicarboxylic dialkyl ester component with a diol component and then carrying out the polycondensation reaction in the presence of a mixed catalyst system of titanium tetrabutoxide / magnesium acetate. The molecular weight of the polyester resin leaves much to be desired, as well as the polymerization time (7.5 hours) to reach a reasonably high molecular weight.
    [0010] In W02010 / 077133, a tin catalyst was used for the transesterification stage and for the polycondensation stage. Although the color and Mn were better than any results reported at that time, the color of the resulting resin is not good enough for use in bottles, fibers and films.
    [0011] From the references above, it is clear that PEF has been known for over 70 years and that many different recipes have been used, in which temperatures, pressures, diacid / diol stoichiometries, catalysts and precursors (diacid or diester) have miscellaneous. Description of the Invention
    [0012] The invention thus relates to a process for the production of polymers and copolymers with a 2,5-furandicarboxylate moiety in the polymeric structure, as described in claim 1. The (co) polymers prepared in this way have a numerical average molecular weight of at least 25,000 (as determined by GPC based on polystyrene standards) and an absorbance in a 5 mg / mL solution in an 8: 2 dichloromethane: hexafluorisopropanol mixture at 400 nm below 0.05. It is believed that the use of these high molecular weight (co) polymers, as well as their use in the preparation of bottles, fibers or films, is new. Thus, the invention also concerns these bottles, fibers and films. Ways to Carry Out the Invention
    [0013] In more detail, the process of the present invention is similar to the process for the preparation of poly (ethylene terephthalate) (PET), but it has some distinctions that characterize it. Thus, although PET is typically made with catalysts such as manganese, cobalt and germanium, as mentioned above, we find that these catalysts result in a colored product.
    [0014] Likewise, while bright white PET can be made directly from a diol monomer and a diacid monomer, the present inventors have found that the use of 2,5-FDCA inevitably results in a colored product. In addition, while PET is normally made by esterification at polymerization temperatures of 250 to 280 ° C and higher, the inventors again found that the 2,5-FDCA-based polymers made at such polymerization temperatures were colored products. The color in this context can be quantitatively determined by measuring the absorbance at 400 nm of a 5 mg / mL solution of the (co) polymer in the 8: 2 mixture of dichloromethane: hexafluorisopropanol. If the absorbance is 0.05 or greater, then the product is considered to be of a lower grade.
    [0015] Furthermore, the present inventors have found that the analogous process results in the formation of a lower molecular weight by-product which, therefore, results in a wider molecular weight distribution. This negatively affects the properties of the polymers thus produced.
    [0016] These problems were addressed, as discussed below.
    [0017] Thus, the process of the present invention is a three-step process, in which first a prepolymer is made with a 2,5-furandicarboxylate portion within the polymeric structure. This intermediate product is preferably an ester composed of two diol monomers and a diacid monomer, in which at least part of the diacid monomers comprises 2,5-FDCA, followed by polymerization of the melt of the prepolymers under suitable polymerization conditions. Such conditions usually involve reduced pressure to remove the equimolar excess from the diol monomers.
    [0018] A person skilled in the art will realize that the amounts of diester and diol may vary. Suitably, the diol and diester are used in a molar diester ratio of 1.5 to 3.0, more preferably 2.0 to 2.5.
    [0019] For example, in the context of the present invention, in step 1, dimethyl-2,5-furandicarboxylate reacts in a catalyzed transesterification process in the presence of a metal catalyst with about 2 equivalents of a diol to generate the prepolymer concomitantly with the removal of 2 equivalents of methanol. Dimethyl-2,5-furandicarboxylate is preferred, as this transesterification step generates methanol, a volatile alcohol that is easy to remove. However, as starting materials, 2,5-FDCA diesters with other volatile alcohols, diols or phenols (for example, with a boiling point under atmospheric pressure less than 150 ° C) can be used in the same way. Preferred examples, therefore, include ethanol, methanol or a mixture of ethanol and methanol. Alternatively, instead of starting with dimethyl-2,5-furandicarboxylate, ethylene glycol diester, di (hydroxyethyl) -2,5-furandicarboxylate can be used in the same way. In this case, transesterification with ethylene glycol can be ignored.
    [0020] The inventors have found that it is preferable that, in case the FDCA dimethyl ester is used, the first step comprises transesterification, catalyzed by a specific transesterification catalyst, preferably for a period of 1 to 3 hours in a range of a preferred temperature of about 150 to about 220 ° C, preferably in the range of about 180 to 200 ° C and that is carried out until the initial ester content is reduced, preferably until reaching the range of less than 1% in mol to about 0.1 mol%. Transesterification should preferably be carried out for at least one, but more preferably at least 2 hours at a temperature above 180 ° C. Longer reaction times at a lower temperature can also be used, but this is less economically desirable. The transesterification catalyst can be removed or neutralized by adding a Lewis base to avoid interaction in the second stage of polycondensation, but it can be included in the second stage.
    [0021] Examples of alternative or additional transesterification catalysts that can be used in step 1 include one or more of titanium (IV) alkoxides or titanium (IV) chelates, mixtures of calcium, magnesium, strontium or zinc salts, or a mixture of any of these salts. In the case of polyesters containing ethylene glycol, one or more of the calcium, magnesium, strontium or zinc salts are particularly suitable. Although these alternative or additional catalysts may be suitable for transesterification, they can effectively interfere during the polycondensation step, which will require the addition of a Lewis base before starting the polycondensation step. Therefore, a preferred transesterification catalyst for the reaction of dimethyl-2,5-furandicarboxylate with ethylene glycol is a soluble calcium or zinc salt, such as calcium acetate or zinc. Regarding the catalyst, it should be understood that the active catalyst, as present during the reaction, can be different from the catalyst as added to the reaction mixture. Binders or counterions will be exchanged in the reactor.
    [0022] The catalysts are used in an amount of about 0.005 mol% with respect to the initial diester up to about 0.2 mol% with respect to the initial diester, more preferably in an amount of about 0.01% in mol of initial diester to about 0.05% in mol of initial diester.
    [0023] Step 2 of the process of the present invention is a catalyzed polycondensation step, in which the prepolymer is polycondensed under reduced pressure, at an elevated temperature and in the presence of a suitable catalyst.
    [0024] The intermediate product of step 1 (ie, the prepolymer) can, but with importance, does not need to be isolated and / or purified. Preferably, the product is used as such in the subsequent polycondensation step. In this catalyzed polycondensation step, the prepolymer is polycondensed under reduced pressure, at an elevated temperature and in the presence of a suitable catalyst. The temperature is in the range of approximately the melting point of the polymer to about 30 ° C from this melting point, but not less than 180 ° C. The pressure should be gradually reduced to the lowest possible level, preferably below 1 mbar.
    [0025] Again, the inventors have found that it is preferable that this second step is catalyzed by a specific polycondensation catalyst and that the reaction is carried out under light melting conditions.
    [0026] Examples of suitable polycondensation catalysts include titanium alkoxides or antimony salts, such as antimony oxide or solubilized antimony acetate.
    [0027] Polycondensation catalysts are used in an amount of about 0.005 mol% with respect to the initial diester up to about 0.2 mol% with respect to the initial diester, more preferably in an amount of about 0.02 mol% of initial diester to about 0.16 mol% of initial diester, and even more preferably in an amount of about 0.04 mol% of initial diester to about 0.16 mol% of initial diester .
    [0028] A preferred polycondensation catalyst is solubilized antimony oxide, for example, antimony glycolate, which can be obtained after refluxing antimony oxide overnight in ethylene glycol. Another option that is a combination of the transesterification catalyst and the polycondensation catalyst, which is of particular interest, is based on a type (IV) tin catalyst during transesterification, which is reduced to a type (II) tin catalyst during polycondensation. Reducing compounds to be used include phosphites, such as alkyl and arylphosphites, with triphenylphosphite and tris (nonylphenyl) phosphite, as preferred examples.
    [0029] It is of particular interest that the combination of the type (IV) tin catalyst and the type (II) tin catalyst preserves the activity, allowing the same catalyst to be used in a later solid state polycondensation, as the third step in the polymerization process.
    [0030] Step 3 is a solid state polycondensation (SSP), which is a common process used in the preparation of PET. In SSP processes, pellets, granules, chips or polymer flakes are subjected for a certain period of time to high temperatures (below the melting point) in a funnel, a tumbling dryer driered a vertical tube reactor, or similar.
    [0031] The inventors found that when preferred catalysts were used for steps 1 and 2, and when preferred process conditions were used for steps 1 and 2, the desired end groups can be obtained after the polycondensation step, allowing reaching a numerical average molecular weight greater than 25,000 during the solid determination step. These molecular weights are advantageous, as they make it possible to produce bottles through stretch injection-blow molding, fiber melt spinning and the extrusion of films with very good mechanical properties. These products obtained from high molecular weight FDCA polymers are considered new.
    [0032] In JP2008 / 291244, Mitsubishi dissolved and precipitated the resin based on the 2,5-furandicarboxylate portion and then solidified at a temperature of 140 to 180 ° C. Applicants have found that this is not a reasonable procedure for the production of polyesters useful in common goods applications. Applicants have found that solidification of the resin is critical and that temperatures of 190 ° C or higher, and preferably 200 ° C higher, are desirable. The upper limit is restricted by the tendency to adhere to itself as the temperature approaches the melting point of the resin. Therefore, the temperature must be raised very slowly in order to be above the desired temperature of 200 ° C.
    [0033] Applicants have found that the solidification process is slow, even at these relatively high temperatures, and it is preferable to use small pellets. A suitable pellet size, for example, can be about 100 or more pellets per gram, or preferably 200 or more pellets per gram. Even smaller pellets can be used to advantage and, for example, can be produced using "micropelletization" technology, such as that of Gala Industries. An alternative technology, using sintered particle technology, can also be advantageous. In this technology, very small particles are physically stuck in larger porous pellets, in order to have a shorter path length for the diffusion of vapors, but still retain a macro pellet size for transport and fusion reasons in the extrusion devices. An example of such technology used for PET recycling is applied at Phoenix Technologies International LLC of Ohio, USA.
    [0034] Polyesters and various copolymers (random or block) can be made according to the process of the present invention, depending on the selection of monomers used. For example, linear polyesters can be made with 2,5-FDCA (in the form of its methyl ester) and an aromatic, aliphatic or cycloaliphatic diol. The 2,5-FDCA ester can be used in combination with one or more other esters of dicarboxylic acid or lactones. Likewise, the diol can be a combination of two or more diols. Polyesters that have never been produced before and which are claimed in the present application are those having both a 2,5-furandicarboxylate portion within the polymeric structure, as well as 1,4-bis (hydroxymethyl) cyclohexane (either stereoisomers or a mixture thereof) or 1,1,3,3-tetramethylcyclobutanediol (any of the stereoisomers or a mixture thereof) or 2,2-dimethyl-1,3-propanediol or poly (ethylene glycol) or poly (tetraidofuran), glycerol or pentaerythritol, or lactic acid (for example, derived from L or D-lactide, or a mixture thereof) or 6-hydroxyhexanoic acid (for example, derived from caprolactone) in the polymeric structure.
    [0035] The polymers and copolymers according to the present invention need not be linear. If a polyfunctional aromatic, aliphatic or cycloaliphatic alcohol is used, or part of the diol is replaced by such a polyol, then a branched or even crosslinked polymer can be obtained. A cross-linked or branched polymer can also be obtained when part of the 2,5-FDCA ester is replaced by an ester of a polyacid.
    [0036] Examples of suitable diol and polyol monomers therefore include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 4-cyclohexanedimethanol, 1,1,3,3-tetramethylcyclobutanediol, 1,4-benzenedimethanol, 2,2-dimethyl-1,3-propanediol, poly (ethylene glycol), poly (tetrahydrofuran), 2,5-di ( hydroxymethyl) tetrahydrofuran, isosorbide, glycerol, pentaerythritol, sorbitol, mannitol, erythritol and treitol.
    [0037] Preferred examples of diols and polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, poly (ethylene glycol), poly (tetrahydrofuran), glycerol and pentaerythritol.
    [0038] Dicarboxylic acid esters or polycarboxylic acid esters suitable for use in combination with the 2,5-furandicarboxylate ester, therefore, include dimethyl terephthalate, dimethyl isophthalate, dimethyl adipate, dimethyl azelate, dimethyl sebacate , dimethyl dodecanedioate, dimethyl-1,4-cyclohexane dicarboxylate, dimethyl maleate, dimethyl succinate and trimethyl 1,3,5-benzene tricarboxylate.
    [0039] Preferred examples of dicarboxylic acid esters or polycarboxylic acid esters to be used in combination with the 2,5-furandicarboxylate ester are dimethyl terephthalate, dimethyl adipate, dimethyl maleate, dimethyl succinate, and trimethyl- 1,5,5-benzenotricarboxylate. More preferably, they can be present in a molar ratio of about 10: 1 to about 2.5-furandicarboxylate ester. This mixture of reagents is referred to as the acid ester reagent.
    [0040] Preferred examples of lactones to be used in combination with the 2,5-furandicarboxylate ester are pivalolactone, caprolactone and lactides (L, L; D, D; D, L).
    [0041] The polymers of the present invention are valuable in all forms of application, where currently PET and similar polyesters are used. For example, they can be used in fibers, films and packaging materials.
    [0042] The polymers of the present invention can be used as such or in mixtures and compounds. They can contain other components such as plasticizers, softeners, dyes, pigments, antioxidants, stabilizers, fillers and the like.
    [0043] As can be seen above, although resins based on the 2,5-furandicarboxylate portion have been produced in the last 70 years and are described in the literature, very little is known about the physical properties or performance of the material when it is subjected industrially relevant processing conditions to produce bottles, fibers and films. The inventors have discovered and describe in the present invention that the processing of these resins into useful products is possible, although the processing conditions and properties of the resin and, thus, its synthesis, need to be optimized for the desired processing to be successful.
    [0044] Examples are provided that detail the work that was carried out using a PEF resin, with direct comparison with a PET resin. As shown in the example, the PEF resin has a higher softening point, at about 10 to 12 ° C. This attribute can be used to obtain benefit when it is desired, for example, to pasteurize in a bottle or container, after it has been filled, or when it is desired to fill the package with a hot liquid.
    [0045] Example 4 shows a work comparing the tension-stretching ratio for pulling a PEF resin compared to a PET resin, at temperatures above the resin's glass transition temperature. PEF resin is more rigid (larger modulus) than PET resin and also has a more pronounced yield and a delayed stress-onset. This has significant implications for the production of useful materials and PEF resin packaging.
    [0046] Example 5 describes the production of injection-blow molded bottles using PEF. The distribution of material in these first bottles was not as uniform as desired, and the inventors believe that this is due, at least in part, due to the late start of the tension hardening. Still, the materials were tested and found to have better barrier properties for oxygen, CO2 and water, compared to PET bottles made using the same mold.
    [0047] Prior to the present invention, the superior barrier properties of PEF in an oriented structure, such as a bottle, were unknown. The use of PEF for a packaging material based on these barrier properties is new. The barrier properties are such that a container of carbonated drinks could be smaller than the current containers and still have a useful shelf life, because the rate of passage of CO2 gas through the container would be reduced. Current products are limited by an absolute loss of carbon dioxide pressure or by a change in carbon dioxide pressure and the resulting changes in properties.
    [0048] The use of PEF to pack oxygen-sensitive materials is also new. The barrier properties of the PEF bottle are such that the rate of oxygen penetration into the container is reduced by five times compared to a conventional PET container. This level of oxygen barrier can be sufficient to use the resin for packaging oxygen-sensitive materials, such as fruit juices, vitamin waters, beer and wine, without relying on expensive oxygen removers or multi-layer film technology. If oxygen removers are still used to further extend shelf life, for example, then the amount of oxygen removers can be reduced from the amount needed in a conventional PET bottle.
    [0049] When PEF or other resins based on the bioderivated 2,5-furandicarboxylate portion are used for packaging, such as bottles, then it may also be desirable to incorporate other packaging improvements, such as the use of a bio-based closure. Exemplary materials for closings include the use of poly (hydroxylbutyrate-co-valerate) (PHBV), other poly (hydroxyalkanoates), lactic polyfacid) or new bio-based materials such as poly (polybutylene succinate). The label can be made of a transparent or colored material and can be fixed with adhesives or used as a retractable sleeve. The adhesive or retractable sleeve could be made, for example, from bio-based materials including, but not limited to, poly (lactic acid) -based materials. It may also be desirable to include a dye in the resin formulation in order to give a special appearance to the package or to protect the materials within it from light. For example, a dark amber or green bottle could be more suitable for storing beer. For "transparent" bottles an appropriate amount of a blue coloring agent can be used to help mask the small amount of yellow color that is seen in many polymeric resins, including those based on the 2,5-furandicarboxylate portion. If it is desirable to print directly on the resin based on the 2,5-furandicarboxylate portion, then various surface treatments, such as crown treatment, may be useful to modify the nature of the impression adsorption. If used as a packaging material, then the resin can also be sterilized using any of the techniques known in the art, including, but not limited to, ozone treatment, UV treatment, electron beam treatment and the like .
    [0050] Based on the tension-stretch checks detailed in the example, the inventors believe that the optimal properties for a bottle, for example, will be based on presenting higher stretch ratios than a conventional PET bottle design. The inventors believe that the optimal axial stretch ratio can be in the range of 2.0 to 4.0, and more preferably in the range of 2.6 to 3.7. Optimal radial ratios can be in the range of 5 to 7.0 and, more preferably, in the range of 5.3 to 6.8. The total regional ratio will preferably be in the range of 16 to 25 and more preferably, in the range of 18 to 23.
    [0051] Preferred bottle sizes for the stretch ratios described above will be in the range of 300 mL to 2 liters.
    [0052] The inventors believe that the thickness of the side wall of the bottle can be properly in the range of 0.005 inch to 0.015 inch (0.13 to 0.38 mm), and more preferably in the range of 0.007 to 0.010 inch (0.18 0.25 mm). The combination of high modulus of elasticity and high barrier properties allows functional products to be made even when using a reduced amount of resin on a volume basis, compared to conventional PET resins. The high modulus can also translate into more rigid bottles with less pronounced deformation, further improving the stability of the package. It was found that the elasticity modulus of the PET bars is about 340,000 psi (23.4 Kbar) at room temperature, while the modulus of elasticity of the PEF bars is 590,000 psi (40.7 Kbar).
    [0053] The molecular weight of the ideal resin for the production of suitable bottles through injection-blow-by-stretch processes is not yet completely understood, but the inventors believe that the numerical average molecular weight of the resin should preferably be in the range of 25,000 to 50,000, and more preferably, in the range of 31,000 to 47,000, and more preferably, in the range of 35,000 to 44,000. The numerical average molecular weight is determined by gel permeation chromatography (GPC) using polystyrene standards. Applicants believe that the use of a higher molecular weight resin will help to overcome the late onset of stress hardening.
    [0054] As with other polyesters, it is desirable to crystallize the polymer pellet to prevent adhesion and to allow drying at high temperatures, to eliminate degradation due to hydrolysis of the processing equipment. Drying can be carried out at any convenient temperature below the melting point of the polymer. It is essential that the polymer used for critical applications, such as bottle manufacture, be completely dry before processing in order to maintain a consistent molecular weight. Preferably, the moisture content will be less than 200 ppm by weight and, more preferably, less than 50 ppm by weight.
    [0055] As an alternative to a high numerical average molecular weight, it is also possible to modify the resin by incorporating a high molecular weight component. The high molecular weight component can be based on the 2,5-furandicarboxylate portion or based on a completely different resin. If it is based on the 2,5-furandicarboxylate moiety, then a high molecular weight material can be produced by using coupling agents or branching agents, as are known in the art and which are available for reactions of the terminal hydroxyl groups or terminal acid groups. For the production methods described here, the predominant terminal group is believed to be hydroxyl. Suitable coupling agents include, but are not limited to, materials such as triphenylphosphite or other multisite phosphites, pyromelitic anhydride or other multifunctional anhydrides, isocyanates, multifunctional epoxides, multifunctional carbodiimides and so on.
    [0056] The applicants found that it was possible to heat the preforms to the desired temperature to blow without using any reheating additives. However, it can also be very desirable to include reheat additives to optimize cycle times and energy absorption in the preforms. Suitable materials are known in the art.
    [0057] A very relevant finding is that the resins based on the 2,5-furandicarboxylate portion thermally crystallize very slowly. In practice, this means that it is not necessary to reduce the rate of thermal crystallization in the resins used for bottle production. Most bottle-grade poly (ethylene terephthalate) resins include a small amount, on the order of 1 to 5 mol%, of a diacid, such as isophthalic acid, to retard crystallization. Applicants have found that no such crystallinity disruptor is required for resins based on the 2,5-furandicarboxylate moiety. The preferred bottle resin is believed to be a 2,5-furandicarboxylate portion-based resin that contains less than 2 mol% of any other diacid, more preferably less than 1 mol% of any other diacid, and more preferably less than 0.3 mol% of any other diacid. This is in contrast to the PET polymer resins used for bottles.
    [0058] The polymer production process invariably leads to the production of a small amount of diethylene glycol. Applicants have found that, similar to PET production, it is desirable to minimize the amount of this material that is formed. The preferred PEF resin has less than 2 mol% of diethylene glycol and, more preferably, less than 1 mol% of diethylene glycol, and more preferably, less than 0.7 mol% of diethylene glycol.
    [0059] Resins suitable for use in bottles will preferably not contain significant levels of acetaldehyde, which can impart unpleasant flavors to the drink. It is an important function to solidify the resin to allow any acetaldehyde that is present to diffuse out of the pellets. It is also important that, in subsequent melt processing steps, those conditions are selected in order to minimize the formation of any new amounts of acetaldehyde. Applicants have found that it is possible to melt a PEF resin at temperatures below 250 ° C and produce a useful material. For example, in the production of preforms for stretch-blow-molded bottles, it is common to process PET at temperatures of 260 ° C or higher and, often, 265 ° C or higher. For PEF, we found that it is possible, and preferable, to process at a temperature below 250 ° C and, more preferably, below 240 ° C. A temperature range of 230 ° C to 240 ° C is preferred, as it will provide the most desirable results for the drum temperature during injection molding of PEF preforms.
    [0060] The PEF resin has a higher modulus and a higher glass transition temperature than the PET resin and, thus, will require slightly higher temperatures to inflate the bottle. Applicants believe that the ideal temperature for injection-blow molding by stretching the bottles will be in the range of 98 ° C to 112 ° C and, more preferably, in the range of 102 ° C to 108 ° C. The parameters of the bottle machine, such as the timing of the various events, injection rod speed, swelling pressure, mold temperature, and so on, are all parameters that can be adjusted to influence the process of inflating the bottle. It is anticipated that the use of a heat adjustment step can also be useful to further increase the temperature stability of the bottle.
    [0061] Details of the preform design can also be used to modify the characteristics of the bottle and help to smooth the material distribution.
    [0062] The following examples illustrate the present invention. EXAMPLES Materials
    [0063] 2,5-Furandicarboxylic acid (FDCA) and dimethyl-2,5-furandicarboxylate (DMF) were prepared according to W02011043660. Diols, solvents and catalysts were supplied by Aldrich and used as received. Analytical techniques
    [0064] GPC measurements were performed on a Merck-Hitachi LaChrom HPLC system equipped with two MIXED-C 10 μm PLgel columns (300 x 7.5 mm). The 6: 4 chloroform: 2-chlorophenol solvent mixture was used as the eluent. The molecular weight calculation was based on polystyrene standards and was performed by Cirrus ™ PL DataStream software.
    [0065] UV-visible spectra and absorbances were recorded on a Heliosa spectrophotometer (ThermoSpectronic). Example 1
    [0066] Polymerization with Ca-Sb catalyst system. The polymerizations were carried out in a 15 liter agitated batch reactor. Dimethyl-2,5-furandicarboxylate (5.0 Kg; T1.Y1 mol), bioethylene glycol (4.02 Kg; 64.83 mol) and Ca acetate monohydrate (8.48 g (48.1 mmol)) mixed under nitrogen in the pre-dried reactor, while heating to a temperature of 130 ° C, when methanol started to be removed by distillation.The temperature is maintained at about 130 ° C until most of the methanol is removed by distillation Thereafter, the temperature is raised to 190 ° C (blanket temperature) under nitrogen flow for 2 hours, then Sb glycolate (3.48 g of Sb2O3 dissolved in 200 ml of bioethylene glycol) was added under stirring at 40 ° C. The temperature increased to 210 ° C, while the vacuum was applied slowly. At 300 mbar, most of the ethylene glycol had been removed by distillation. Finally, the vacuum was reduced as much as possible, but definitely below 1 mbar. blanket temperature increased to 240 ° C and the increase in molecular weight was monitored by measuring the torque d the shaker.
    [0067] The polymer obtained from the reactor was shown to have an Mn of 16,000 g / mol and a Pm / Mn of 2.5. Solid state polymerization experiments were carried out in a dryer. During the first 12 hours, crystallization of the polymer was carried out at 145 ° C. Thereafter, over a 72 hour period, the temperature was slowly raised to above 200 ° C. Care has been taken that the polymer particles do not stick together. After 72 hours, the polymer had an Mn of 30000 and a Pm / Mn equal to 2.1. Example 2 Polymerization with Zn-Sb catalyst system Transesterification
    [0068] In a bottle with three 100 mL necks equipped with nitrogen inlet, mechanical stirrer and condenser in a horizontal position, 13.8 g of DMF, 11.1 g of ethylene glycol and 150 pL of zinc acetate stock solution ( II) (c = 25.5 mg / ml) in ethylene glycol were added. A slow flow of nitrogen was applied and then the flask was immersed in an oil bath at 220 ° C. Methanol began to distill at 137 ° C. After reducing the distillation of methanol (~ 20 minutes), the condenser was placed in an upright position for reflux of ethylene glycol. Nitrogen gas flowed continuously through it. Transesterification ended after 4 hours, when 200 μL of triethyl phosphonoacetate stock solution (c = 46.7 mg / mL) was added (1.5: 1.0 molar ratio of phosphonoacetate: Zn). After 5 minutes of stirring, 236 μL of stock antimony solution (c = 13.9 mg / mL of SbzO3) was measured and added to the mixture which was stirred for another 5 minutes. The iH NMR spectrum of a sample collected after 4 hours indicated less than 0.04 mol% of the methyl ester end group (relative to the furan ring). Polycondensation
    [0069] After the completion of the addition of catalyst, vacuum was applied slowly and the temperature was raised to 240 ° C (oil bath temperature). The agitator speed was set at 100 rpm. After 3 hours of polycondensation, the vacuum was released and PEF was removed with a spoon. Mn = 17900; Pm = 42800; PDI = 2.39; A (30 mg / mL) = 0.007 (measured in dichloromethane: hexafluorisopropanol 8: 2 at 400 nm) Solid State Polymerization (SSP)
    [0070] SSP experiments were carried out in small glass tubes (17 cm high, 8 mm inside diameter) closed with glass frits (Pl) at one end and placed in an aluminum block heater equipped with nitrogen inlet . The polymer was ground and sieved into 0.6 to 1.4 mm particles, then crystallized at 110 ° C overnight. After crystallization, 100 mg of polymer was measured in each tube. SSP was carried out at 210 ° C under a nitrogen flow of 4.0 mL / min. After two days of SSP (Table 2), Mn as high as 52000 was obtained. Table 2. SSP results of PEF prepared with the Zn-Sb catalyst system
    Example 3
    [0071] A sample of PEF resin, with a molecular weight equal to about 30,000 Mn, was transformed into a straight bar sample using an injection molding machine. A sample of PET resin, Eastar EN052 PET, was also molded using the same equipment. The bars were subjected to a thermal distortion measure in accordance with ASTM E2092. It was found that the thermal distortion temperature of the PET sample was 64.5 ° C and the thermal distortion temperature of the PEF sample was 76.6 ° C, or 12 ° C higher than the thermal distortion temperature of the reference bar of PET. Figure 1 shows the test results. Example 4 Stress-stretch curves for PEF and PET above Tg.
    [0072] Sample films were prepared from a PET resin and a PEF resin, and were subjected to tensile tests using an ARES instrument from TA instruments. The resulting stress-stretch curves are shown in figures 2 and 3. PEF films show a very marked yield, with stress hardening over high extensions. The onset of tension hardening at 90 ° C was an extension of about 3x, and at 95 ° C it was 4x. PET films have a less pronounced yield and premature onset of tension hardening. For PET, the onset at 90 ° C was an extension of about 2.5, and at 95 ° C it was only 4x. For PET, the resulting stress was about 2 to 3 x 106 Pa, while for PEF, it was 6 to 18 * 10 Pa at the same temperatures. Typically, PEF will need to be processed (for the blow molding stage) at a temperature slightly higher than that of PET, in order to reduce the modulus for inflation to occur. In that case, for example, at 100 ° C, the onset of tension hardening was about 5x for PEF, with a resulting elasticity equal to 3 * 106 Pa. This is equivalent to PET at 90 ° C, where the resulting elasticity was similar, but the beginning of the tension hardening was at 2.5 x. Example 5 Insufflation of the bottle using PEF resin.
    [0073] The PEF resin with an average molecular weight of about 29,900 was crystallized and dried. Several kilograms were used in an Arburg 320 M injection molding machine to injection mold a preform of 26.4 grams in weight. The same preform, when used with PET resin, produces a preform weighing 24.5 grams. PEF preforms were produced using an injection molding drum temperature of 235 ° C, while PET was produced using a temperature equal to 268 ° C. The total cycle time for PEF injection molding was faster than PET injection molding at 21 seconds and 25 seconds, respectively.
    [0074] The preforms were later fused into bottles using a Sidel SB01 / 2 blow molding machine, using a straight-wall model weighing 24 ounces, suitable for carbonated soft drink bottles. A wide variety of conditions were tested and, eventually, a preform temperature of 102 ° C was found to be the best for PEF resin. The material distribution was even less uniform than desired, but bottles could be made and tested. PET was blown into bottles with a preform temperature of 98 ° C.
    [0075] The side panel test revealed that PEF had an oxygen barrier more than five times better than the PET bottle panel, and CO2 was about twice as good. Testing the entire package revealed that the water barrier was about twice as good, in the same way.
    [0076] The molecular weight of the resin in the final bottle was determined to be about 27,000 Mn. REFERENCES [1] Hachihama, Y .; Shono, T .; Hyono, K. Synthesis of Polyesters containing Furan Ring, Technol. Repts. Osaka University 1958, 8, 475-480. [2] Moore, J.A .; Kelly, J.E. Polyesters Derived from Furan and Tetrahydrofuran Nuclei. Macromolecules, 1978.11, 568-573.
    权利要求:
    Claims (13)
    [0001]
    1. PROCESS TO PREPARE A POLY POLYMER (ETHYLENE-2,5-FURANDICARBOXYLATE), with a numerical average molecular weight of at least 25000 (as determined by GPC, based on polystyrene standards), characterized by the fact that the process comprises : (a) a first step which is (i) a transesterification step, in which the dimethyl-2,5-furandicarboxylate ester (diester) is transesterified with ethylene glycol (diol) in the presence of a transesterification catalyst; or (ii) providing a reaction mixture of molten material comprising bis (2-hydroxyethyl) -2,5-furandicarboxylate; (b) a polycondensation step under reduced pressure, below 1 mbar and at an elevated temperature below 240 ° C, where under melting conditions, the product prepared in step (a) reacts in the presence of a polycondensation and removal catalyst the reactor condensate; (c) drying and / or crystallizing the condensate obtained at a temperature of 90 to 160 ° C; (d) subjecting the polymer of step (c) to post-condensation conditions that comprise a high temperature treatment, ending at a temperature of at least 190 ° C to obtain a poly (ethylene-2,5-furandicarboxylate) polymer ) having a numerical average molecular weight of at least 25,000.
    [0002]
    2. PROCESS, according to claim 1, characterized by the fact that diol and diester are used in a diol: diester molar ratio of 1.5 to 3.0.
    [0003]
    PROCESS, according to one of claims 1 to 2, characterized by the fact that transesterification is carried out at a temperature of 150 to 230 ° C.
    [0004]
    4. PROCESS according to one of claims 1 to 3, characterized by the fact that methanol is removed from step (a) (i) up to a temperature of 210 to 230 ° C.
    [0005]
    5. PROCESS according to one of claims 1 to 4, characterized in that the transesterification catalyst is a calcium or zinc catalyst, and the polycondensation catalyst is an antimony catalyst.
    [0006]
    6. PROCESS according to one of claims 1 to 5, characterized in that the numerical average molecular weight of the condensate of step (b) is between 13,000 and 20,000.
    [0007]
    7. PROCESS, according to one of claims 1 to 6, characterized by the fact that, after removing the reactor, the condensate is cooled and molded into pellets for the subsequent solidification stage.
    [0008]
    8. PROCESS according to one of claims 1 to 7, characterized by the fact that the conditions in step (d) further comprise providing an inert gas or vacuum.
    [0009]
    9. PROCESS according to one of claims 1 to 8, characterized in that the drying and / or crystallization is carried out at a temperature of 90 ° C to 145 ° C.
    [0010]
    10. PROCESS according to one of claims 1 to 9, characterized in that the high temperature treatment of step (d) comprises a start treatment temperature of 180 ° C to a temperature of at least 205 ° C.
    [0011]
    11. PROCESS according to one of claims 1 to 10, characterized by the fact that the numerical average molecular weight is determined by GPC based on polystyrene standards.
    [0012]
    12. PROCESS according to one of claims 1 to 11, characterized by the fact that the polymer obtained after step (d) has an absorbance with a 5 mg / mL solution in a dichloromethane: hexafluorisopropanol ratio of 8: 2 to 400 nm less than 0.05, without purification step and / or intermediate or subsequent washing.
    [0013]
    13. PROCESS according to one of claims 1 to 12, characterized in that the polymer is subjected to stress hardening.
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    法律状态:
    2019-04-30| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161550707P| true| 2011-10-24|2011-10-24|
    US61/550,707|2011-10-24|
    NL2007650|2011-10-25|
    NL2007650|2011-10-25|
    PCT/NL2012/050738|WO2013062408A1|2011-10-24|2012-10-24|A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications|BR122020002668-5A| BR122020002668B1|2011-10-24|2012-10-24|BOTTLE OR FILM OR OBJECT CONTAINING FIBERSCONTAINING POLYESTER MANUFACTURED FROM FUSION PROCESSING POLY|
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