• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Disclosed is a process for the production of refined anhydrosugar alcohols. The resulting purified anhydrosugar alcohol obtained by this process has a purity of at least 99.8% and is substantially colorless. Distillation, reflux of non-hydrogenated alcohol by recrystallization from methanol, ethanol or ethylene glycol, melt recrystallization, or a combination thereof. Preferably, distillation is followed by purification by recrystallization from methanol, ethanol or ethylene glycol. Discloses a test for measuring the purity of alcohol-free alcohol, in which the color of alcohol-free alcohol after annealing at a temperature of 260 ° C or more for 4 hours or more is tested. Alternatively, the purity can be determined by testing ultraviolet (UV) transmission at various wavelengths of the purified anhydrous alcohol. The purified anhydrosugar alcohol may be introduced into a polymer such as a polyester and the polymer may be used to prepare products such as containers, optical disks, fibers, sheets and films.
    公开号:KR20010108084A
    申请号:KR1020017008704
    申请日:1999-01-11
    公开日:2001-12-07
    发明作者:마이클 에이. 허바드；미카엘 볼러스；헬무트 베. 비텔러；에드워드 지. 제이；조오지 크바코프스즈키；토마스 에이치. 쇼클리；래리 에프. 샤르본느；노르베르트 콜；요헨 리이쓰
    申请人:메리 이. 보울러；이 아이 듀폰 디 네모아 앤드 캄파니；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a process for purifying anhydrous alcohol,
    [4] Dihydric alcohols, in particular derivatives of mannitol, iditol and sorbitol, are known for their therapeutic and food applications. Furthermore, at least isosorbide, i.e., 1,4: 3,6-dianhydroiso-sorbitol is being studied as a recoverable natural resource for the production of polymers, particularly polyesters, in which isosorbide is used as a raw material for corn starch and cassava starch (tapioca) Because it is a derivative of sorbitol that can be obtained from a variety of natural sources. 09 / 064,844, 09 / 064,950, 09 / 064,846 < / RTI > which are related applications to processes for the preparation of polymers having isosorbide, terephthaloyl and ethylene glycol mother- , 09 / 064,858, 09 / 064,826, 09 / 064,719, 09 / 064,862 and 09 / 064,720 (both filed on Apr. 20, 1998) Each of which is incorporated herein by reference in its entirety).
    [5] The purity requirement for the use of anhydrous alcohol varies depending on the intended use field. For example, one requirement in the field of food and medicinal uses is that there should be no impurities harmful to individuals or organisms that use substances containing alcohol without sugar. By this definition, anhydrous alcohol may contain a number of other substances or impurities that are not anhydrous alcohol, which may still be regarded as pure in the food or medicinal application field. In the field of polymer applications where optical transparency is required, such as polymers used in packaging, one monomer purity requirement is that the resulting polymer exhibits color unacceptably during synthesis and / or processing Any material or impurities that can be made should not be present in the monomer. Impurities which are acceptable in free sugar alcohols used in food and medicinal applications may not be acceptable for anhydrous alcohols which are actually used in polymer applications since these impurities may be tolerated during polymer synthesis or processing This is because color can be expressed at a level that can not be achieved.
    [6] Several methods of purifying alcohol-free alcohols are known in the art. For example, the alcohols may be separated by vacuum distillation, or by using ethyl acetate and / or a mixture of diastereoisomers, such as ethyl acetate and / or ethyl acetate, as described in Fleche and Huchette, Isosorbide Preparation, Properties and Chemistry, starch / starke 38 (1986) 26-30 at 29, or an organic solvent such as methyl ethyl ketone as disclosed in U.S. Patent No. 3,454,603. However, these methods do not sufficiently remove impurities that result in unacceptable levels of color development during polymer synthesis and / or processing.
    [7] Although the purity of the resultant product is only 97%, it is not surprising that the product of Dianhydrosorbitol-a new pharmaceutical ingredient, " Pharmaceutical Manufacturing International , p. 97-100 at 97-98 (1996)) are also known. Water-free is generally not preferred as a solvent since the moisture-free properties are highly hygroscopic.
    [8] Fleche and Huchette, p. 29 and U.S. Patent No. 3,160,641, there has also been proposed a method of purifying by distillation under reduced pressure in the presence of borohydride ions to reduce impurities consuming periodic acid in isosorbide using boric acid.
    [9] Methods for the purification of anhydrosugar alcohol derivatives and for the purification of anhydrosugar alcohol precursors are also known. Purification of certain anhydrous alcohol derivatives by recrystallization from methanol and ethanol is described, for example, in Hockett et al., J. Am. Chem. Soc. , Vol. 68, p. 930-935 (1946); Cope and Shen, J. Am. Chem. Soc. p.3177-3182, (1956); and Ojrzanowski et al., Acta Pol. Pharm. 43 (6) p.567-71 (1986).
    [10] In addition, purification of precursors such as D-mannitol and D-glucitol by extraction or recrystallization from a mixture of ethanol or ethanol and water, respectively, is described in Block et al., In Acta Chem. Scan. (43) p.264-268 (1989).
    [11] The use of methanol and ethanol in recrystallization of precursor and derivatives of anhydrosugar alcohols is also described in Defaye et al., Carb. Res. 205 p.191-202 (1990). Also, de faye et al. Disclose dianhydrosugar alcohols, specifically 1,4: 3,6-dianhydro-D-mannitol and 1,4: 3,6-dianhydro-D-glucitol And recrystallization is exemplified. However, these recrystallization methods do not use aliphatic alcohols such as methanol, ethanol or ethylene glycol as a solvent.
    [12] Methods for the purification of monoanhydrohexitol and dianhydrohexitol are also disclosed in U.S. Patent No. 4,564,692 to Feldmann et al. However, in this method, it is necessary to add anhydrous alcohol in a heavy liquid containing 1 to 20% by weight of water, and it is necessary to add the crystal nucleus of the desired alcohol per free alcohol to be recrystallized.
    [13] There is no known teaching for the purification of alcohol-free alcohols by recrystallization from aliphatic alcohols such as methanol, ethanol or ethylene glycol. As is known in the art, these methods are directed to the purification of alcohol-free sugars for use in food or pharmaceutical compositions. The present inventors do not know any method that can achieve the level of purity required for use in polymers as prior purification methods.
    [14] From the above point of view, there is a need for a simple and cost-effective method for purifying an alcohol without sugar, which can produce a very pure product. Furthermore, very pure free sugar alcohol is required, especially for use in the production of polymers.
    [1] The present invention relates to a method for purifying anhydrous alcohol by distillation and / or recrystallization in the presence of an aliphatic alcohol, preferably to a purified product which has a purity of 99.0% or more and which is substantially colorless even after heat treatment.
    [2] <Related application>
    [3] Filed by the same assignee as the present application and entitled " Continuous Process for the Production of Anhydrosugar Alcohols " Docket No. 032358-019] contains relevant content. The contents of which are incorporated herein by reference.
    [15] SUMMARY OF THE INVENTION [
    [16] The inventors of the present invention have found that recrystallization from lower aliphatic alcohols such as methanol and ethanol as well as melt recrystallization improves the purity and transparency of alcohol-free alcohols. Distillation may also improves the purity of the end product, optionally carried out on a sodium borohydride (NaBH 4), or other hydride ion containing compounds. The combination of distillation and solution or melt recrystallization significantly improves the purity of the final product. Similarly, multiple recrystallization from multiple distillation and / or lower aliphatic alcohols has been found to significantly increase the purity of alcohol free alcohol.
    [17] Further, it is disclosed herein that the purity of alcohol-free alcohols can best be measured in relation to the relative color of anhydrous alcohol and its ultraviolet (UV) permeability. Methods for performing such measurements are disclosed herein.
    [18] Also disclosed is a method of determining the quality of a polymer made from a purified anhydride alcohol wherein the anhydropoly alcohol is annealed at a temperature close to the temperature used to make the polymer, Color expression in alcohol is tested. The resulting color of the annealed anhydrous alcohol is indicative of a color that can be expressed during the synthesis and / or processing of the polymer produced.
    [19] Further, the use of the purified anhydrosugar alcohols obtained from the above process in the production of polymers and products made therefrom are disclosed.
    [20] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION [
    [21] The process of the present invention provides a process for the purification of alcohol-free alcohols which is directed to a product obtained from a commercially available product as a starting material or directly from a batch or continuous process for the production of anhydrous alcohol .
    [22] In the process of the present invention, the anhydrous alcohol is purified by distillation and / or recrystallization from a lower aliphatic alcohol. The term " lower alcohol " refers to a linear aliphatic alcohol, preferably from 1 to 4 carbon atoms. Most preferably, the alcohol is methanol, ethanol or ethylene glycol. The resulting purified anhydrosugar alcohol has a purity of at least 99.0%, or no contaminants, preferably colorless.
    [23] The free sugar alcohol of the present invention is a monoanhydro- or dianhydro sugar alcohol. Preferred dianhydro sugar alcohols include isosorbide, isomannide and isoidide. Preferably, the anhydrous alcohol of the present invention is isosorbide.
    [24] Distillation of anhydrosugar alcohols can be carried out in the presence or absence of hydride ion containing compounds such as borohydride ion containing compounds (e.g., NaBH 4 ) or lithium aluminum hydride. In a preferred embodiment, the distillation is carried out by placing anhydrous alcohol in a flask and vacuum distilling the flask at a temperature of at least 60 DEG C, preferably at least 70 DEG C. Keep free alcohol at this temperature until all volatile impurities have been distilled. The flask is then preferably purged with an inert gas such as nitrogen or argon. At this time, a hydride ion-containing compound, preferably a borohydride ion-containing compound, most preferably NaBH 4 , can be optionally added to the anhydrosugar alcohol in the flask. The flask is then heated to a temperature above 100 ° C, preferably above 120 ° C, most preferably above 140 ° C, followed by degassing under vacuum at about 1 mbar pressure and subsequent distillation. The alcohol-free alcohol is then distilled under vacuum. Preferably, the distillation is carried out in an apparatus equipped with a short distillation column. The distilled anhydrous alcohol is preferably further purified by one or more additional distillations and / or recrystallization.
    [25] In order to recrystallize from a solution according to the present invention, anhydrous alcohol may be added to the aliphatic alcohol, preferably methanol, ethanol or ethylene glycol solution. The temperature of the solution is lowered to less than 30 ° C, preferably less than 10 ° C, and most preferably less than -10 ° C, until recrystallization is complete, usually for about 4 hours. The resulting crystals are collected by filtration and washed with cold aliphatic alcohol, preferably at a temperature below the crystallization temperature, so that the crystals are not dissolved. Optionally, the crystals can be dried under vacuum at room temperature. Recrystallization from aliphatic alcohols and / or distillation may be additionally carried out.
    [26] Alternatively, melt-recrystallization of alcohol-free alcohol can be carried out. Melt recrystallization may be carried out before, after, or in place of distillation in any manner known in the art, or in place of distillation and recrystallization from solution. Typically, melt recrystallization involves heating the compound to a temperature slightly above its melting point in the absence of solvent, and then cooling the molten compound to form a purified crystal of the compound. The impurities generally form a liquid around the purified crystals and have a lower melting point than the crystals.
    [27] The purity of the anhydrous alcohol obtained by the above-mentioned method is not less than 99.0%, preferably not less than 99.5%, and most preferably not less than 99.8%. This level of purity can preferably be obtained by only three distillations, three recrystallizations from aliphatic alcohols, three melt recrystallizations, or a combination of only three of the purification methods described above.
    [28] The above methods of purifying anhydrous alcohol can be applied in a batch process. Also, as described in an application (herein incorporated by reference in its entirety) filed and pending in the same application as the present application and entitled " Continuous Process for the Production of Anhydrosugar Alcohols & The processes can be applied to a continuous process for the production of alcohol-free alcohols to which modifications known to the person skilled in the art are applied.
    [29] The formation of anhydrous alcohol from the continuous process can be effected by the reaction mechanism of the continuous process. Thus, the yield in the continuous purification process may be somewhat lower if the purification step is optimized for a separate reaction or rather than the batch process. In particular, distillation and / or recrystallization from a continuous process begins with the separation of anhydrous alcohol from the solvent of the continuous process. This can be achieved, for example, by directly recrystallizing anhydrous alcohol from the solvent used in the continuous process. Thus, the alcohol without sugar is obtained in solid form. Another means of separating anhydrous alcohol from a solvent in a continuous process is liquid-liquid extraction using water or aliphatic alcohols (e.g., methanol, ethanol or ethylene glycol). Thus, anhydrous alcohol is obtained in solution in water, methanol, ethanol or ethylene glycol. The separated free alcohol is then further purified by distillation and / or recrystallization as described above. Thereby, the reaction product has a better purity than other methods and provides a more economical method for producing refined anhydrosugar alcohols.
    [30] The purity of anhydrous alcohol obtained by distillation and / or recrystallization can be measured by conventional methods such as differential scanning calorimetry (DSC), where the measurement is in accordance with ASTM E 928-96. However, a simpler and very accurate measurement of the parenteral alcohol purity for use in polymer applications requiring optical transparency can be made by colorimetric determination of an alcohol-free alcohol (preferably in the form of a subcooled melt). Color measurement of alcohol-free alcohol can be performed by comparing an alcohol-free alcohol with any known color system.
    [31] For example, one of the color systems is known as an HSB system, where hues are determined by assigning numerical values associated with hue, saturation and brightness. Typically in this system the hue represented by the symbol H has a value from 0 to 360, with 0 and 360 being equal. For example, red has a value of about 0 (or 360), yellow has a value of about 60, and is the same for the remaining colors (green, blue, purple, etc.) on the color spectrum. The combination of colors such as orange (a combination of red and yellow) has a value between two numbers, for example, between 0 and 60 for orange. The saturation, typically represented by the symbol S, represents the concentration of the color and has a value from 0 to 100, where 0 represents white, no concentration. The brightness represented by the symbol B ranges from 0 (black) to 100 (white). In applying this color system to determine the degree of monomer or polymer hue, it is preferable that the saturation (S) value is close to 0 and the brightness (B) value is close to 100. When the saturation value is zero, the hue has no meaning.
    [32] For best results, it is desirable to compare the decolorization of the subcooled melt of anhydrous alcohol at room temperature. This excludes color differences that can be caused by the influence of solid particle size. For example, the use of crystals or pieces of anhydrous alcohol may indicate different colors based on the sample and particle size due to the amount of light refracted into or reflected from the sample. Further, it is desirable to evaluate the color of the alcohol without sugar after a similar temperature history as that used in polymer synthesis and / or processing to determine its usefulness for introduction into the polymer. Therefore, it is preferable to anneal the refined alcohol-free alcohol sample in a clear glass tube at 260 DEG C or higher, preferably 285 DEG C or higher for 4 hours, preferably 8 hours, and then cool to obtain a supercooled melt. The annealed alcohol-free alcohol melt is then compared to a known color chart. The closer to zero the alcohol is, the more pure it is.
    [33] Alternatively, the purified anhydrosugar alcohol can be tested by measuring the wavelength transmission using a UV / Vis spectrometer. The wavelength transmittance of anhydrous alcohol is an indicator of its color, which is at least partially dependent on the impurity in the alcohol free alcohol. The wavelength transmittance of anhydrous alcohol is measured with a UV / Vis spectrometer at a specific wavelength. The anhydrous alcohol is preferably maintained in the crystalline state after purification, so the spectrometer measurement is performed with a 20% solution of anhydrous alcohol in distilled water. Preferably, the UV transmittance of the purified anhydrous alcohol is greater than 50% at 224 nm, greater than 65% at 242 nm, greater than 75% at 276 nm, greater than 85% at 400 nm, Or more. The higher the transmittance percentage, the better.
    [34] Color measurements and UV / Vis spectrometry measurements can also be performed on polymers with purified, anhydrous alcohol. Whether measuring the purified anhydrosugar alcohol or measuring the polymer into which it is introduced, the color test of the sample utilizes all wavelengths of the visible light and thus gives the overall color of the sample as seen with the naked eye, / Vis is more advantageous than spectrometer measurement. The individual wavelength measurements do not indicate the overall color of the sample, so the judgment can be broken.
    [35] By the method described in the present specification, an alcohol free alcohol substantially colorless and having a purity of 99.0% or more can be obtained. Preferably, the purity is 99.5% or more, and most preferably 99.8% or more. The purity can be measured by color measurement or UV / Vis spectroscopy tests as well as other methods known in the art.
    [36] The purified anhydrosugar alcohol can be introduced into a polymer, especially a polymer for use in an optical grade polymer. No. 09 / 064,844, 09 / 064,826, and 09 / 064,720 (each of which is incorporated herein by reference in its entirety), filed April 23, 1998, (E.g., ethylene glycol) and a dicarboxylic acid (e.g., terephthaloylmonomer), or dimethyl esters thereof, as exemplified in U.S. Pat. 09 / 064,950, 09 / 064,846, 09 / 064,858, 09 / 064,719 and 09 / 064,862, all filed on April 23, 1998, The polyester can be used to produce commercial products such as fibers, sheets, films, containers and optical disks, as exemplified by reference herein. In particular, polymers in which anhydrosugar alcohol is prepared by the process described herein can be used in combination with polycarboxylic monomers, polycarboxylic acid halide compounds (e.g., acid chlorides), polycarbonate monomers (such as diphenyl carbonate) or phosgene, isocyanates (Such as toluene diisocyanate and methylene diphenyl isocyanate), and dicarboxylic acids (e.g., terephthaloyl macromolecule), or dimethyl esters thereof, and optionally aliphatic diols (such as ethylene glycols) Followed by condensation polymerization.
    [37] Embodiments of the invention described herein are described below. These embodiments are illustrative only and do not encompass the entire scope of the invention, which is known to those skilled in the art and includes equivalent means and materials as further defined in the specification and claims below.
    [38] The cited references are hereby incorporated by reference in their entirety.
    [39] Purification of isosorbide
    [40] A series of refinement experiments were performed using isosorbide as an alcohol-free alcohol. Not only the melting temperature but also the temperatures for the recrystallization itself varied. The isosorbide concentration in the mother liquor was also varied. The results are shown in Tables 1 to 3 below. The tables include a brief description of each experiment along with the purity data measured with differential scanning calorimetry (DSC) and the color of the sample after annealing at 285 DEG C for 4 hours.
    [41] In particular, the purification experiments were performed using the following general procedures.
    [42] Isosorbide is distilled from isosorbide
    [43] 1,300 g of isosorbide were placed in a Schlenk flask and held at 80 DEG C for 60 minutes under dynamic vacuum to remove residual solvent and other volatile impurities. The flask was purged with argon. 1.3 g of sodium borohydride (NaBH 4 ) was added to the flask. The flask was heated to 140 &lt; 0 &gt; C. The flask was degassed at about 1 mbar pressure and the isosorbide was distilled under vacuum.
    [44] If it shows that the NaBH 4 is not used and the procedure is except for the absence of the NaBH 4 it is the same in all embodiments.
    [45] Isosorbide recrystallization from methanol or ethanol
    [46] 1400 g of isosorbide was dissolved in 600 ml of methanol, and the solution was left to stand overnight in a refrigerator at -18 DEG C for recrystallization. The crystals were collected by filtration and washed with 600 ml of cold (-18 [deg.] C) methanol. The washed crystals were dried under vacuum at room temperature. The yield is 850 g (60%).
    [47] Recrystallization from ethanol was carried out in the same way, replacing methanol with ethanol.
    [48] In most recrystallization experiments, crystal nuclei were added to the mother liquor to initiate recrystallization of isosorbide.
    [49] Annealing test
    [50] The purified isosorbide was placed in a rear wall glass tube. The tube was degassed and sealed. The tube containing the isosorbide was heated at 285 [deg.] C for 4 hours and allowed to cool. Color numerical measurement was performed.
    [51] Color measurement
    [52] The measurement of the subcooled monomer melt color or polymer chip color was performed by comparing the material with two HSB color tables generated on a Hewlett-Packard HP-Deskjet (R) 890C color ink jet printer using the CorelDraw (TM) program . In one table, the brightness was fixed at 100, the hue was increased from 25 to 60 by 5, and the saturation was increased from 0 to 100 by 10. In the second table, the saturation was fixed at 100, the hue was increased from 25 to 60 by 5, and the brightness was increased from 0 to 100 by 10. These tables were compared with the samples and the most equal color was recorded. The lower the lightness value, the darker the material. The lower the saturation and hue values, the more colorless the material.
    [53] UV / vis spectroscopy
    [54] The UV / Vis spectra were measured using a Perkin Elmer Lambda 9 UV / Vis / NIR dual beam spectrometer (Perkin Elmer Lambda 9 UV / Vis / NIR dual beam spectrometer). A 20 wt% solution of isosorbide in distilled water (Aldrich, Optima grade) was prepared. Spectra were collected at 960 wavenumber per minute. Isosorbide solutions were measured in 5 cm quartz cells for distilled water standards.
    [55] Purity measurement by differential scanning calorimetry (DSC)
    [56] Absolute purity was measured with a differential scanning calorimeter according to ASTM E 928-96 (incorporated herein by reference). The measurement was carried out using a DSC7 differential scanning calorimeter obtained from PerkinElmer.
    [57] Abbreviations used in the table are as follows.
    [58] A-Isos = a pending application with the present application ["Continuous Process for the Production of Anhydrosugar Alcohols", U.S. Pat. Serial No. 09 / , (Atty. Docket No. 032358-019)], isosorbide,
    [59] BuOH = butanol,
    [60] C-Isos = isosorbide commercially available from Cerestar,
    [61] cold recryst. = Melting at up to 50 캜, recrystallization at -15 캜,
    [62] D = distillation,
    [63] dist. = Vacuum distillation to a short column at 1 mbar,
    [64] EtOH = ethanol,
    [65] EtOAc = ethyl acetate,
    [66] hot recryst. = Dissolution under reflux, recrystallization at 25 占 폚,
    [67] Isos = isosorbide,
    [68] Isos-Ref = isosorbide (a highly purified reference material),
    [69] MeOH = methanol,
    [70] (NaBH 4 ) = NaBH 4 is added to isosorbide before vacuum distillation,
    [71] R = recrystallization.
    [72] Table 1 illustrates the purity levels obtained by treating the commercially available isosorbide with various purification methods, including the methods disclosed herein. As can be seen from the results, the highest purity was obtained when a combination of recrystallization and distillation was used where the recrystallization was carried out from methanol or ethanol, or a number of distillations were carried out as in the sample labeled Isos-Ref. .
    [73] Purity of alcohol-free isosorbide without sugar ExperimentPurity (DSC) Isos-Ref * 99.95 C-Isos98.79C-Isos 1x recryst. MeOH cold (standard: 70% solution)99.20 C-Isos 2x recryst. MeOH cold99.35 C-Isos 1x recryst. MeOH hot (hot saturated solution)98.95 C-Isos 1x recryst. EtOH cold (standard: 50% solution)99.25 C-Isos 1x recryst. EtOH hot (hot saturated solution)98.77 C-Isos 1x recryst. EtOH hot (hot saturated solution), crystal wash99.54 C-Isos 1x recryst. Isopropanol hot (hot saturated solution)99.65 C-Isos 1x recryst. Acetone cold (standard: 40% solution)99.92 C-Isos 1x recryst. Acetone hot (hot saturated solution)99.81 C-Isos 1x recryst. THF cold (standard: 50% solution)99.72 C-Isos 1x recryst. THF hot (hot saturated solution)99.63 C-Isos 1x recryst. BuOH hot (hot saturated solution)96.40 C-Isos 1x recryst. BuOH / MeOH (80/20) (hot saturated solution)98.45C-Isos 1x dist.98.66 C-Isos 1x dist. (NaBH 4) 99.07 C-Isos 1x recryst. MeOH cold, 1x dist.99.94 C-Isos 1x recryst. MeOH cold, 1x dist. (NaBH 4) 99.85 C-Isos 1x dist. (NaBH 4 ), 1 x recryst. MeOH cold99.10
    [74] The above standard sample is a very pure sample of isosorbide produced by the inventors of the present invention in such a manner as described above in order to ensure high purity. And annealed at 300 캜 to obtain a transparent solution.
    [75] Table 2 shows the continuous process for the production of anhydrosugar alcohols (Atty. Docket No. 032358-019), filed by the same applicant as the present application (A-Isos) and commercially available isosorbide prepared by the method disclosed in US Pat. As can be seen from the above table, the best results are achieved by a combination of distillation followed by recrystallization from methanol or ethanol. These embodiments have the lowest saturation (10) and have a higher level of transmittance than commercially available products at each UV wavelength tested.
    [76] UV purity and purity of isosorbide by color measurement of polymer with purified isosorbide incorporated ExperimentIsosorbide UV transmittance%, 20 wt% solution, 5 cm cellPolymer * Color evaluation 224242276400HSB C-Isos (state as it is obtained)0.21.110.183.94530100 C-Isos &lt; / RTI &gt; 2xR (MeOH)29.460.169.393.85520100 C-Isos 1xR (MeOH) 1xD (NaBH 4)1.624.746.683.44510070C-Isos 1xD (NaBH 4) 1xR (MeOH)5.657.073.895.95010100 C-Isos &lt; / RTI &gt; 1xR (EtOAc) 1xD2.618.226.870.64040100 C-Isos &lt; / RTI &gt; 1xR (EtOAc) 1xD 1xR (MeOH)75.284.192.997.95010100 C-Isos &lt; 1 &gt; R (EtOAc) 1xD 1xR (EtOH)53.768.275.989.95510100 A-Isos 1xD 1xR (MeOH)23.641.259.693.35010100
    [77] * Polymers prepared by melt polymerization of ethylene glycol, isosorbide and terephthaloyl core.
    [78] Table 3 illustrates the effect of heating the purified isosorbide to the temperature required for polymer annealing. This indicates whether the purified monomers will develop color during the polymerization or remain transparent. As can be seen from the results in Table 3, the combination of recrystallization and distillation from methanol or ethanol provides a transparent monomer even at annealing, which gives good results when used to make polymers.
    [79] Color of refined isosorbide annealed at high temperature ExperimentEvaluation of annealed isosorbide color HSB C-Isos (state as it is obtained)5040100 C-Isos &lt; / RTI &gt; 1xR (MeOH)5510100 C-Isos &lt; 1 &gt; R (EtOH)5520100 C-Isos 1xD5520100 C-Isos 1xD (NaBH 4) 5510100 C-Isos 1xR (MeOH) 1xD-0100 C-Isos 1xR (MeOH) 1xD (NaBH 4)-0100 C-Isos &lt; / RTI &gt; 1xD 1xR (MeOH)-0100C-Isos 1xD (NaBH 4) 1xR (MeOH)-0100 A-Isos 1xD5520100 A-Isos 1xD 1xR (MeOH)-0100
    [80] It should be noted that the clear correlation between the analytical data relating to the purity of the purified isosorbide and the discoloration of the purified isosorbide observed on the HSB scale after annealing at 285 DEG C can not be established in all cases. This is probably due to the fact that trace amounts of impurities may cause discoloration.
    [81] As shown in the above table is only the purification of isophthalic sorbitan de performed by only the vacuum distillation comprises a preferably NaBH 4 was added in order to obtain good results. However, when a combination of distillation and recrystallization is applied, NaBH 4 is not required.
    [82] It has been found that the combination of distillation and subsequent recrystallization gives the best results with respect to purity and color of isosorbide.
    权利要求:
    Claims (39)
    [1" claim-type="Currently amended] Preparing a solution by dissolving an anhydrosugar alcohol in a lower aliphatic alcohol,
    Cooling the solution to a temperature sufficient to form crystals of purified anhydrosugar alcohol, and
    And separating the crystals of the purified anhydrosugar alcohol from the solution.
    [2" claim-type="Currently amended] The process according to claim 1, wherein the lower aliphatic alcohol is methanol, ethanol or ethylene glycol.
    [3" claim-type="Currently amended] The method of claim 1, further comprising distilling the free alcohol.
    [4" claim-type="Currently amended] 4. The method according to claim 3, wherein the anhydropoly alcohol is distilled in the presence of borohydride ions.
    [5" claim-type="Currently amended] 5. The method of claim 4, wherein the borohydride ion is sodium borohydride.
    [6" claim-type="Currently amended] 4. The process according to claim 3, wherein the anhydropoly alcohol is distilled and then recrystallized.
    [7" claim-type="Currently amended] A purified, free-sugar alcohol prepared by the process of claim 1 and having a purity of 99.8% or greater.
    [8" claim-type="Currently amended] Distilling the anhydrosugar alcohol, and
    And then melting and recrystallizing the alcohol with no anhydride to obtain an alcohol free alcohol having a purity of 99.0% or more.
    [9" claim-type="Currently amended] 9. The method of claim 8, wherein the anhydropoly alcohol is distilled in the presence of borohydride ions.
    [10" claim-type="Currently amended] 10. The method of claim 9, wherein the borohydride ion is sodium borohydride.
    [11" claim-type="Currently amended] 9. The process according to claim 8, wherein the anhydrosugar alcohol is distilled and subsequently subjected to melt recrystallization.
    [12" claim-type="Currently amended] A purified, free-sugar alcohol prepared by the process of claim 8 and having a purity of 99.8% or greater.
    [13" claim-type="Currently amended] Refined anhydrous alcohol with a purity of 99.0% or higher.
    [14" claim-type="Currently amended] The purified free-sugar alcohol according to claim 13, wherein the purity is 99.8% or more.
    [15" claim-type="Currently amended] 14. The purified free-sugar alcohol of claim 13, which is colorless after being annealed at a temperature of 260 DEG C or higher for 4 hours.
    [16" claim-type="Currently amended] A polymer comprising the purified anhydric alcohol of claim 13.
    [17" claim-type="Currently amended] 17. The polymer of claim 16, wherein the polymer is prepared by melt condensation.
    [18" claim-type="Currently amended] 17. The polymer of claim 16, further comprising a dicarboxylic acid and an aliphatic diol.
    [19" claim-type="Currently amended] 19. The polymer of claim 18, wherein the aliphatic diol is ethylene glycol.
    [20" claim-type="Currently amended] 19. The method of claim 18 wherein the dicarboxylic acid is a terephthaloyl precursor.
    [21" claim-type="Currently amended] An article made from the polymer of claim 16.
    [22" claim-type="Currently amended] 22. The article of claim 21, wherein the article is selected from the group consisting of fibers, optical disks, containers, sheets and films.
    [23" claim-type="Currently amended] Annealing an anhydrous alcohol at a temperature of 260 DEG C or higher for 4 hours or more,
    Cooling the annealed alcohol free alcohol to produce a sub-cooled melt, and
    And measuring the color of the subcooled melt as compared to a known color table. &Lt; Desc / Clms Page number 20 &gt;
    [24" claim-type="Currently amended] 24. The method of claim 23, wherein the annealed alcohol-free alcohol is colorless.
    [25" claim-type="Currently amended] Preparing an anhydrous alcohol solution in distilled water, and
    And measuring the ultraviolet transmittance of the solution.
    [26" claim-type="Currently amended] 26. The method of claim 25, wherein the solution is a 20% solution and the ultraviolet transmittance of the 20% solution measured over a cell path length of 5 cm at 224 nm is 50% or greater.
    [27" claim-type="Currently amended] 26. The method of claim 25, wherein the solution is a 20% solution and the ultraviolet transmittance of the 20% solution measured over a cell path length of 5 cm at 242 nm is 65% or greater.
    [28" claim-type="Currently amended] 26. The method of claim 25, wherein the solution is a 20% solution and the ultraviolet transmittance of the 20% solution measured over a cell path length of 5 cm at 276 nm is 75% or greater.
    [29" claim-type="Currently amended] 26. The method of claim 25, wherein the solution is a 20% solution and the ultraviolet transmittance of the 20% solution measured over a cell pathlength of 5 cm at 400 nm is greater than 85%.
    [30" claim-type="Currently amended] 14. An alcohol free alcohol according to claim 13, wherein the ultraviolet transmittance at 224 nm is at least 50% as measured over a cell path length of 5 cm with 20% aqueous solution.
    [31" claim-type="Currently amended] 14. An alcohol-free alcohol according to claim 13 wherein the ultraviolet transmittance at 242 nm is greater than or equal to 65% as measured over a cell path length of 5 cm with a 20% aqueous solution.
    [32" claim-type="Currently amended] 14. The free alcohol according to claim 13, wherein the ultraviolet transmittance at 276 nm is 75% or more as measured over a cell path length of 5 cm with a 20% aqueous solution.
    [33" claim-type="Currently amended] 14. The free alcohol of claim 13, wherein the ultraviolet transmittance at 400 nm is greater than or equal to 85% as measured over a cell path length of 5 cm with a 20% aqueous solution.
    [34" claim-type="Currently amended] (1) a monomer comprising a terephthaloyl macrolide, optionally one or more other monomers comprising an aromatic diacid base, a monomer comprising an ethylene glycol base, a monomer comprising a purified anhydride alcohol of claim 13 Optionally combining one or more other monomers comprising diol mother nuclei and optionally a monomer comprising diethylene glycol mother nuclei with a condensation catalyst suitable for the condensation reaction of aromatic diacids with glycols in a reactor,
    (2) heating the monomers and the catalyst to a temperature sufficient to polymerize the monomers with at least a polyester polymer having at least a terephthaloyl macromolecule, an ethylene glycol macromolecule and an isosorbide macromolecule,
    Here, for a time sufficient to obtain an isotropic polyester having an intrinsic viscosity of at least about 0.35 dL / g as measured at 25 DEG C for a 1% (weight / volume) polyester of polyester in o-chlorophenol, Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt;
    [35" claim-type="Currently amended] 35. The method of claim 34, wherein the refined anhydrosugar alcohol is isosorbide.
    [36" claim-type="Currently amended] Terephthaloyl, optionally aromatic dicarboxylic acid, ethylene glycol primary, diethylene glycol primary, purified anhydrosugar alcohol of claim 13, and optionally at least one other diol primary, wherein said polyester 1 in o-chlorophenol Isotropic polyester having an intrinsic viscosity of at least about 0.35 dL / g as measured at 25 DEG C for a% (weight / volume) solution.
    [37" claim-type="Currently amended] 38. The isotropic polyester of claim 36, wherein the refined anhydrosugar alcohol is isosorbide.
    [38" claim-type="Currently amended] Wherein the polyester comprises a terephthaloyl precursor, optionally a terephthaloyl precursor, optionally an aromatic dicaprate, an ethylene glycol precursor, optionally a diethylene glycol precursor, a purified free anhydride alcohol of claim 13 and optionally one or more other diol precursors, Isotropic polyester having an intrinsic viscosity of about 0.5 dL / g or greater as measured at 25 占 폚 for a 1% (weight / volume) solution.
    [39" claim-type="Currently amended] 39. The isotropic polyester of claim 38, wherein the refined anhydrosugar alcohol is isosorbide.
    类似技术:
    公开号 | 公开日 | 专利标题
    Jacquel et al.2015|Bio-based alternatives in the synthesis of aliphatic–aromatic polyesters dedicated to biodegradable film applications
    Calvez et al.2007|Selenium‐based glasses and glass ceramics transmitting light from the visible to the far‐IR
    AU737007B2|2001-08-09|Novel photochromic heterocyclic fused indenonaphthopyrans
    CA2164949C|1999-06-15|Photochromic naphthopyran compounds
    EP0662968B1|1998-12-02|Photochromic naphthopyran compounds
    EP0792468B1|2002-04-03|Novel photochromic indeno-fused naphthopyrans
    Girolamo et al.1976|Gelation‐crystallization in isotactic polystyrene solutions and its implications to crystal morphology, to the origin and structure of gels, and to the chemical homogeneity of polyolefins
    EP1500671B1|2010-03-31|Aromatic polycarbonate composition and hollow container therefrom
    TWI504633B|2015-10-21|Polycarbonate resin and transparent film made from the resin, and polarizing plate
    TWI432481B|2014-04-01|Production method of polycarbonate and polycarbonate molded product
    TWI417315B|2013-12-01|Optical film
    KR100212343B1|1999-08-02|Polymerizable organic resin compositions and articles prepared therefrom
    CA1335072C|1995-04-04|Method for determining the compositional distribution of a crystalline copolymer
    EP1375557B1|2006-08-02|Polymerization process using mono-and di-functional initiators to prepare fast crystallizing polylactone copolymers.
    US10308760B2|2019-06-04|Polycarbonate resin composition and molded article
    US5235027A|1993-08-10|Modified copolyethylene terephthalate
    US8455611B2|2013-06-04|Optical film
    KR100267064B1|2000-09-15|Novel photochromic indeno-fused naphthopyrans
    US7198830B2|2007-04-03|Polycarbonate resin composition and polarizing sheet used the same
    EP2513189B1|2015-10-14|Method for producing polyester polyols, polyester polyols produced by said method and polyurethanes obtained therefrom
    Barham et al.1976|A study on the achievement of high-modulus polyethylene fibres by drawing
    TWI428369B|2014-03-01|Production method of polycarbonate
    US6281366B1|2001-08-28|Photochromic [3H]naphtho[2,1-b]pyran compounds containing an acetylenic substituent, process for their manufacture, and photochromic materials and articles obtained
    TWI535755B|2016-06-01|Retardation film, and circular polarizing plate and image display device using the same
    US7569259B2|2009-08-04|Plasticizer, cellulose ester film, polarizing plate, and liquid crystal display
    同族专利:
    公开号 | 公开日
    EP1140733B1|2006-09-27|
    BR9917143A|2001-11-13|
    TR200102006T2|2002-02-21|
    CA2629484A1|2000-07-20|
    CA2359557A1|2000-07-20|
    EP1140733A1|2001-10-10|
    HK1043996B|2004-09-10|
    EP1580183A1|2005-09-28|
    DE69933390T2|2007-08-30|
    BR9917143B1|2011-04-19|
    WO2000041985A1|2000-07-20|
    DE69933390D1|2006-11-09|
    KR100591225B1|2006-06-19|
    MY121788A|2006-02-28|
    CN1333775A|2002-01-30|
    CN1128804C|2003-11-26|
    AU777446B2|2004-10-14|
    JP4681122B2|2011-05-11|
    EP1140733A4|2002-05-22|
    HK1043996A1|2004-09-10|
    AU2111499A|2000-08-01|
    CA2629496A1|2000-07-20|
    JP2002534486A|2002-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-01-11|Application filed by 메리 이. 보울러, 이 아이 듀폰 디 네모아 앤드 캄파니
    1999-01-11|Priority to PCT/US1999/000539
    2001-12-07|Publication of KR20010108084A
    2006-06-19|Application granted
    2006-06-19|Publication of KR100591225B1
    2011-09-27|First worldwide family litigation filed
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US1999/000539|WO2000041985A1|1999-01-11|1999-01-11|Process and products of purification of anhydrosugar alcohols|
    [返回顶部]