WO2019037438A1 - 戊二胺己二酸盐及其晶体 - Google Patents

戊二胺己二酸盐及其晶体 Download PDF

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WO2019037438A1
WO2019037438A1 PCT/CN2018/082438 CN2018082438W WO2019037438A1 WO 2019037438 A1 WO2019037438 A1 WO 2019037438A1 CN 2018082438 W CN2018082438 W CN 2018082438W WO 2019037438 A1 WO2019037438 A1 WO 2019037438A1
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pentamethylenediamine
crystal
adipic acid
adipate
solution
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PCT/CN2018/082438
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French (fr)
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应汉杰
杨朋朋
王森
吴菁岚
朱晨杰
许晟
陈可泉
陈勇
欧阳平凯
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南京工业大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/14—Adipic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the invention belongs to the technical field of bio-based materials, in particular to a monomeric pentanediamine adipate of bio-based nylon 56, a crystal structure thereof, a crystalline powder thereof, and a preparation method thereof.
  • Nylon polyamide, PA
  • PA polyamide
  • the global PA production is about 6 million tons, and it is growing at a rate of 5.4% per year. It is estimated that by 2020, the global nylon market will reach 43.7 billion US dollars. Consumption accounts for 30% of global nylon production.
  • the textile industry has problems such as heavy pollution and low profits, which is in urgent need of transformation and upgrading.
  • the monomers used in the production of nylon are mainly obtained by chemical processing, which are derivatives of fossil resources. With the depletion of fossil resources and the enhancement of people's environmental awareness, the development of biomass-based fibers, from resources and environment Aspects are in line with the trend of social development.
  • Bio-based nylon 56 (polypentanediamine adipate) is a synthetic material obtained by polymerizing 1-5-Diaminopentane (also known as Cadaverine and petroleum-based adipic acid). Absorbency, dyeability, comfort, elasticity, abrasion resistance and flame retardancy all show excellent performance, and its performance is comparable to that of the classic petroleum-based nylon-66 and nylon-6, so it is in parachute , aircraft tire cord fabrics, military uniforms and other fields have a good application prospects (Zhang Chen, Journal of Donghua University, 2016). The synthesis principle of bio-based nylon-56 is shown in Formula III:
  • bio-based nylon 56 The current preparation idea of bio-based nylon 56 is basically: firstly prepare pentanediamine, then purchase adipic acid, put the two components together, and carry out polymerization by a special polymerization company, and then perform spinning application (CN201610428399.2) ).
  • Toray the current cooperation between Toray and Ajinomoto, Ajinomoto's first production of pentamethylenediamine by fermentation and enzymatic catalysis, Toray is responsible for the reaction of adipic acid purchased from the market with pentaamine produced by Ajinomoto. The material is then spun to produce bio-based nylon 56 fibers.
  • the properties of the polymeric material directly affect the effect of the spinning product, and the properties of the polymeric material are affected by the purity of the polymerized monomer, and are sensitive to some impurities, such as lysine, alcohols, and hydroxyl-containing pigments.
  • the preparation method of pentamethylenediamine is basically based on lysine as a substrate, starting from lysine fermentation broth or direct lysine hydrochloride, in lysine decarboxylase (EC 4.1.1.18) or It can be prepared by the action of a lysine decarboxylase-producing bacterium (such as Hafni's bacterium), and then purified and purified to obtain pure pentanediamine as shown in Formula IV (CN201180010538.5, CN201310755027.7).
  • the separation and purification method here is basically a distillation or a method of first extracting and then distilling, and it is relatively easy to introduce an impurity such as an alcohol (CN201380075176.7).
  • pentamethylenediamine is liquid at room temperature, has a rot odor, and is highly volatile, which is inconvenient in transportation and use compared with solid raw materials; further, pentamethylenediamine is required in the polymerization process.
  • the molar ratio to adipic acid is preferably 1:1.
  • liquid pentane diamine containing a small amount of impurities and industrial grade adipic acid it is difficult to maintain an equimolar ratio during the process operation.
  • the technical problem to be solved by the present invention is to provide a high purity pentamethyleneamine adipate crystal powder having an equimolar ratio of pentamethyleneamine to adipic acid, and to provide a two-component compound of pentamethylenediamine and adipic acid.
  • the schematic formula V of the polymerization reaction is as follows:
  • the present invention is intended to provide a monomer of bio-based nylon 56 material, pentamethyleneamine adipate, and its crystal structure, and crystalline powder thereof, and a preparation method.
  • the product of the pentamethylenediamine adipate provided by the present invention is obtained by crystallization, and the product is pentanediamine and Adipic acid is expressed in the form of a molar ratio of crystals, can be directly used for polymerization, has structural stability, and has good product purity and particle size, and has advantages in transportation, use, storage and quality.
  • the invention discloses a pentamethyleneamine adipate in a solid state, also known as cadaverine adipate.
  • the pentamethylenediamine adipate is a divalent cation of pentamethylenediamine and a divalent anion of adipic acid.
  • a salt which exhibits a solid state at a normal temperature in a molar ratio of 1:1, and its molecular structure is as shown in Formula I:
  • the crystal form contains crystal water, and the molecular structural formula is as shown in formula II:
  • n is preferably 1 or 2, most preferably 2.
  • the stacked graphs are respectively shown in Fig. 1 and Fig. 2, and the detailed data of the crystal structure, the key length information is as shown in Fig. 7, the key angle information is as shown in Fig. 8, and the dihedral angle information is as shown in Fig. 9.
  • the hydrogen bond information is as shown in FIG. During the measurement of the crystal structure, the diffraction data was collected at 298 (2) K.
  • the diffraction pattern having the diffraction analysis using CuK ⁇ ray as the characteristic X-ray as shown in FIG. 3 is expressed as diffraction angle 2 ⁇ 0.1: 19.96, 24.06, 9.62, 27.28, 25.42, 21.08, 24.48, 11.06, 26.14, 23.68, 30.52, etc., as shown in Figure 5.
  • a diffraction pattern having diffraction analysis using CuK ⁇ rays as characteristic X-rays as shown in FIG. 4 is expressed as diffraction angles 2 ⁇ 0.1: 9.59, 10.94, 19.78, 20.75, 21.83, 22.20, 27.81, and the like. ,As shown in Figure 6.
  • the method and apparatus for detecting the crystal structure of the pentamethylenediamine adipate of the present invention are as follows:
  • Crystal structure and analytical method for single crystal X-ray diffraction a single crystal of pentamethylenediamine adipate with good quality was cut and cut into a block of about 0.22 ⁇ 0.24 ⁇ 0.26 mm 3 by Bruker APEX- II CCD diffractometer Mo K ⁇ radioactive source (graphite monochromator, The sample is irradiated and the diffraction data is collected. The diffraction data is reduced by SAINT, and then structurally analyzed by SHELXTL software direct method, and refined based on F 2 full matrix least squares method, all non-hydrogen atoms pass through anisotropic fine repair. The final data is plotted by Mercury or Diamond software.
  • Powder X-ray Diffraction The sample after grinding was taken to be about 0.1 g, and the diffraction data was collected by a powder X-ray diffractometer (Japanese physics Smartlab or Bruker D8 Advance) at room temperature, and the light source was Cu K ⁇ ray.
  • the scanning step is 0.02°, the scanning voltage is set to 40 kV, the current is 40 mA, the scanning rate is 0.2 s/0.02°, and the scanning range is 2 to 50°.
  • the data is processed by JADE software.
  • the crystalline powder of the above pentamethylenediamine adipate is white or yellowish.
  • the crystalline powder formed by the above crystals has a bulk density of more than 0.20 g/mL, preferably more than 0.30 g/mL, more preferably a bulk density of more than 0.40 g/mL.
  • the crystalline powder formed by the above crystals has a tap density L of more than 0.23 g/mL, preferably more than 0.33 g/mL, more preferably a tap density of more than 0.44 g/mL.
  • Crystals formed above crystalline powder having a d 50 of greater than 10 ⁇ m, preferably greater than of 30 m, and more preferably greater than 50 m, most preferably greater than 50 d of 60 ⁇ m.
  • the crystalline powder formed by the above crystals has d 10 of more than 3 ⁇ m, preferably more than 6 ⁇ m, more preferably more than 10 ⁇ m, and most preferably d 10 of more than 15 ⁇ m.
  • the d 50 and d 10 described in the present invention are the usual amounts for indicating the particle size distribution.
  • the d 50 is a value for the particle size such that 50 vol.% of the crystal has a size smaller than this.
  • the d 10 is a value for the particle size such that 10 vol.% of the crystal has a size lower than this value.
  • the bulk density and tap density are amounts related to the flow characteristics of the powder. In general, high packing densities and tap density values are desirable.
  • the bulk density indicates the weight per unit volume of powder under predetermined conditions. In other words, how many grams of powder can be supplied to a sample holder having a specific volume under predetermined conditions. For this reason, the bulk density is expressed as the weight per unit of volume, usually in g/mL.
  • the tap density also indicates the weight of the powder per volume unit, in which case the holder of the powder is subjected to flapping or vibration under predetermined conditions. The tap density is expressed as the weight per unit of volume, usually in g/mL. More powder can be supplied to the holder by tapping or vibrating. Therefore, for the same powder, the tap density is higher than the bulk density.
  • Powders with large bulk density and high tap density tend to have a large specific gravity, which can reflect that the crystal product is thicker and has a texture, and its stability is relatively better. From another point of view, the product with high bulk density, the particle The fluidity is generally good, it is also easy to store and transport, and it is more convenient to mix with other components.
  • the particle size distribution, bulk density, and tap density are measured as follows:
  • the particle size distribution (including d 10 and d 50 ) of the sample from the mixer was determined using a Microtrac S3500 particle size analyzer, dry assay;
  • the bulk density of the particles is determined by USP Method II (page 1914);
  • the tap density of the particles was measured by the FZS4-4 economical tap density meter according to GB/T 5162-2006. Specifically, the measurement conditions were as follows: the vibration stroke of the tapping device was 3 ⁇ 0.1 MM, and the vibration frequency was 250 ⁇ 15 times per minute.
  • the above crystalline powder may exhibit different apparent water contents (including free water and bound water) due to differences in preparation methods, or different drying methods, or different storage environment humidity, and therefore, the crystalline powder May have a water content of 0 to 23 wt%, preferably 4 to 7% and 10 to 14%
  • the method for measuring the water content of the crystalline powder is a Karl Fischer method, which can be measured by a Metrohm 870 Titrino plus practical volumetric Karl Fischer moisture analyzer.
  • the pH of the system is between 2.5 and 10, preferably between 3.5 and 9.5, more preferably between 5.0 and 8.5, most preferably between 6.0 and 8.0.
  • the solid or solid powder of the present invention is an aggregated state of the substance, including amorphous and crystalline.
  • the crystalline powder according to the present invention refers to a powder having a certain degree of crystallinity, which is relative to amorphous.
  • the crystal according to the present invention is a solid having a clear diffraction pattern for X-rays, and its atoms or molecules are repeatedly arranged in a regular cycle in space.
  • the invention also discloses a composition
  • a composition comprising
  • the above composition makes the ratio of the moles of pentanediamine to adipic acid in the mixture not equal to 1:1.
  • the invention finally discloses a method for preparing crystals of the above pentamethyleneamine adipate, comprising: crystallizing pentamethylenediamine adipate from a solution containing dissolved pentamethylenediamine and adipic acid; separating from the solution Crystals are removed; and the separated crystals are washed and dried.
  • solution containing dissolved pentamethylenediamine and adipic acid is prepared according to any of the following methods:
  • the solvent comprises methanol, ethanol, water, acetonitrile, ethyl acetate, ethyl formate, methyl acetate, butyl acetate, acetone, methyl ethyl ketone, petroleum ether, tetrahydrofuran and DMSO or a mixed solvent thereof.
  • a mixed solvent of several of methanol, ethanol, water, acetone, methyl ethyl ketone, and DMSO is preferred.
  • the adipic acid can be added in various ways, for example, directly into the solvent in a solid manner, or slowly added to the solvent in a solid manner, or the adipic acid can be used first. Dissolved and then added in one portion or added to the cadaverine solution in multiple portions. Preferably, the adipic acid is first dissolved in the solvent and then added to the cadaverine solution.
  • a method for preparing a crystal of the above pentamethyleneamine adipate specifically, for example, adding pentamethylenediamine to an organic solvent, or a binary solvent of water and an organic solvent, or a mixed solvent of water and a plurality of organic solvents.
  • adding adipic acid slowly crystallize under stirring at a temperature of 10 to 50 ° C, and white crystals precipitate after 0.5 to 72 hours, and the crystal paddle is subjected to suction filtration or The solid-liquid separation is carried out by centrifugation, and the obtained solid is dried under vacuum at 35 to 70 ° C to obtain a pentanediamine adipate crystal powder or the composition of the present invention.
  • the ratio of the weight g of pentanediamine to the volume mL of the solvent in the preparation of the crystal may be 1:0.5-30; the amount of adipic acid added may be 0.4-2.0 in molar ratio to pentanediamine, preferably etc. The molar ratio of.
  • the acid salt crystal powder has a pH of 5 wt% aqueous solution of between 6.0 and 8.0, preferably between 6.5 and 7.5. If the total moles of adipic acid added during crystal preparation is greater or less than the number of moles of pentanediamine initially added, then the resulting solid product is more likely to form the composition of the present invention, a 5 wt% aqueous solution of the product.
  • the pH will show non-neutral.
  • the resulting powder when the number of moles of adipic acid added is greater than the number of moles of the initial pentamethylenediamine, the resulting powder will exhibit weak acidity or acidity; when the number of moles of adipic acid added is less than the number of moles of the initial pentamethylenediamine, The resulting powder will show weakly alkaline or basic.
  • the condensation temperature can be set according to the difference of the refrigerant. Different temperatures, such as -10 to 20 °C.
  • the refrigerant may be ethanol, ethylene glycol or water.
  • the drying process has a certain influence on the stability and water content of the pentamethylenediamine adipate powder, and the lower drying temperature tends to lower the drying efficiency, which may cause drying. It can cause the solvent residue to exceed the standard or agglomerate; too high drying temperature will easily cause the product to lose crystal water, and the crystalline powder which loses crystal water will be easily absorbed in the indoor environment.
  • the drying method is preferably blast drying, the drying temperature may be from 30 to 70 ° C, preferably from 35 to 45 ° C, and the humidity of the drying gas stream is preferably from 30% to 65%. To the loss of crystal water, the air flow with excessive humidity tends to make the product absorb more free water and even deliquesce.
  • the source of the pentamethylenediamine in the process may be a single component of pentamethylenediamine or a biological process for preparing pentamethylenediamine in the late stage of separation.
  • the crystallization process can be carried out batchwise or continuously. When the process is carried out intermittently, it is preferred to add seed crystals to the crystallization system. Preferably, the crystallization is carried out continuously.
  • Figure 2 is a diagram showing the cell packing in the b-axis direction of pentamethyleneamine adipate dihydrate
  • Figure 5 is a characteristic line of the divalent X-ray powder diffraction of pentamethyleneamine adipate dihydrate
  • Figure 6 is a characteristic line of the divalent X-ray powder diffraction of pentamethyleneamine adipate monohydrate
  • Figure 8 key angle information (Deg) in the structure of pentamethyleneamine adipate dihydrate
  • Figure 11 is a representation of the product
  • Figure 12 shows the stability experiment.
  • the crystal powder of pentamethylenediamine adipate according to the present invention and the preparation method of the composition of the present invention are further clarified by the following non-limiting examples.
  • the following examples are merely illustrative and not limiting. It is not intended to limit the scope of the invention.
  • the solid was washed with 150 mL of 95% ethanol, and then placed in an environment of 45 ° C, and dried with a hot air having a relative humidity of RH of 50% for 8 hours.
  • RH relative humidity of 50% for 8 hours.
  • Fig. 3 is a crystalline powder of pentamethyleneamine adipate containing two crystal waters with a water content of (12.6 ⁇ 0.2)%.
  • the powder X-ray spectrum of the product is shown in Fig. 3, and is represented by a diffraction angle of 2 ⁇ 0.1. They are: 19.96, 24.06, 9.62, 27.28, 25.42, 21.08, 24.48, 11.06, 26.14, 23.68, 30.52, etc., as shown in FIG.
  • the stacked graphs are respectively shown in Fig. 1 and Fig. 2, and the detailed data of the crystal structure, the key length information is as shown in Fig. 7, the key angle information is as shown in Fig. 8, and the dihedral angle information is as shown in Fig. 9.
  • the hydrogen bond information is as shown in FIG.
  • the diffraction data was collected at 298 (2) K.
  • the pH of the system was 8.0.
  • the powder has good particle properties, fluidity and stability.
  • adipic acid 50.00 g was dissolved in 550 g of absolute ethanol to give a uniform ethanolic solution of adipic acid, which was then transferred to a 1000 mL crystallizer.
  • 32.00 g of pentamethylenediamine was dissolved in 250 mL of 95% acetone water (acetone volume fraction 95%) solution to form an aqueous solution of pentamethylenediamine.
  • the aqueous solution of pentamethylenediamineacetate was dropped into the adipic acid ethanol solution by means of a pump at a rate of 2 mL/min.
  • the amount of the substance of the pentamethylenediamine added was 20% of the amount of the adipic acid substance, 0.2 g was added.
  • aqueous solution of pentamethylenediamine was concentrated 8 times using a thin film evaporator or a rotary concentrator, that is, the volume after concentration was 1/8 of the original volume, and then placed in a crystallizer, stirred.
  • the diamine adipate crystal powder has a water content of 14.6 ⁇ 0.5%, and when it is formulated into an aqueous solution having a mass fraction of 5%, the pH of the system is 9.0.
  • the powder has good particle properties, fluidity and stability.
  • adipic acid Dissolving 50.00 g of adipic acid in 300 g of acetonitrile as a homogeneous solution of adipic acid in acetonitrile, followed by addition of one or more of ethyl acetate, ethyl formate, methyl acetate and butyl acetate The solution was added in an amount of 200 mL and then transferred to a 1000 mL crystallizer. 25.00 g of pentamethylenediamine was dissolved in 250 mL of ethyl acetate to form a solution of ethyl pentaamine.
  • the ethyl pentamamine solution was dropped into the adipic acid solution by a pump at a rate of 1 mL/min, and when the amount of the substance of the pentamethylenediamine added was 10% of the amount of the adipic acid substance, 0.2 was added.
  • the temperature is controlled at 10 ° C, when the end of the complete addition, stirring is continued for 10 h, the crystallization is finished, the lower tank is subjected to solid-liquid separation, and then the filter cake is washed with 100 mL of absolute ethanol and placed at 70 ° C for relative humidity.
  • a crystalline powder of pentamethylenediamine adipate is obtained, and the water content of the powder is (0 to 4.5)%.
  • the pH of the system is 2.5. ⁇ 5.5.
  • adipic acid Dissolving 50.00 g of adipic acid in 300 g of acetonitrile-DMSO solution (volume ratio of acetonitrile to DMSO of 4:1), forming a uniform adipic acid solution, and then adding one of methyl ethyl ketone, petroleum ether and tetrahydrofuran. The mixture or mixtures were added in an amount of 200 mL and then transferred to a 1000 mL crystallizer. 50.00 g of pentamethylenediamine was dissolved in 250 mL of methyl ethyl ketone to form a pentanediamine solution.
  • the pentanediamine butanone solution was directly poured into the adipic acid solution, the system temperature was maintained at 30 ° C, the rotation speed was 300 r / min, and the mixture was stirred for 0.5 h, the crystallization was completed, and the lower tank was subjected to solid-liquid separation, and then 100 mL was used.
  • the filter cake was washed with anhydrous ethanol and dried under a flowing atmosphere of 40% relative humidity of 40% at 40 ° C for 4 hours to obtain a pentanediamine adipate crystal powder having a water content of (4.0 ⁇ 1.5)%.
  • the pH of the system is 8.0 to 10.0.

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Abstract

本发明涉及一种生物基材料尼龙56的单体戊二胺己二酸盐，及其晶体结构，及其结晶粉末，及其制备方法。所述的戊二胺己二酸盐是戊二胺二价阳离子与己二酸二价阴离子以摩尔比为1:1的方式结合而成的常温下呈现固体状态的盐。其晶体结构为C 11H 24N 2O 4·nH 2O，单斜晶系，C2/c空间群，a=20.2977（18）Å，b=4.6957（3）Å，c=17.8233（16）Å，β=116.121（3）° ，晶胞体积V=1525.3（2）A3 ，晶胞内分子数Z＝4。其结晶粉末的堆积密度大于0.20g/mL，所述制备方法包括：从含有溶解的戊二胺和己二酸的溶液中结晶出含有结晶水的戊二胺己二酸盐，从所述溶液中分离出晶体，和干燥所分离的晶体，得到堆积密度大于0.20g/mL的结晶粉末。

Description

戊二胺己二酸盐及其晶体 技术领域
本发明属于生物基材料技术领域，具体地说，是涉及生物基尼龙56的单体戊二胺己二酸盐，及其晶体结构、及其结晶粉末，以及其制备方法。
背景技术
尼龙(聚酰胺，PA)是一种重要的纺织化学纤维材料，全球PA产量在600万吨左右，并以每年5.4％的速度增长，预计到2020年全球尼龙市场将达到437亿美元，中国的消费量占全球尼龙产量的30％，然而纺织行业存在污染重、利润低等问题，亟待转型升级。目前，用于生产尼龙的单体主要通过化学加工获得，是化石资源的衍生物，随着化石资源的日渐枯竭以及人们环保意识的加强，开发以生物质为原料的纤维，从资源和环境两方面都符合社会发展的趋势。
生物基尼龙56(聚戊二胺己二酸)是由生物基戊二胺(1-5-Diaminopentane，又名尸胺(Cadaverine)和石油基己二酸聚合而成的合成材料，其纤维在吸湿性、可染性、舒适度、弹性、耐磨性和阻燃性等方面均展示了极其优异的性能，其性能媲美甚至超越了经典的石油基尼龙-66和尼龙-6，因此在降落伞、飞机轮胎帘子布、军服等领域都有较好应用前景(张晨，东华大学学报，2016)。生物基尼龙-56的合成原理如式III所示：
Figure PCTCN2018082438-appb-000001
生物基尼龙56当前的制备思路基本是：先制得戊二胺，而后购买己二酸，将两种组分放在一起，由专门的聚合公司负责聚合，而后再进行纺丝应用(CN201610428399.2)。比如，当前Toray与Ajinomoto的合作方式，Ajinomoto公司通过发酵和酶催化技术先制的戊二胺，Toray公司则负责将从市场上买来的己二酸与Ajinomoto制得的戊二胺反应生成高聚物，而后再纺丝制造出生物基尼龙56纤维。
聚合材料的性能直接影响到纺丝产品的效果，而聚合材料的性能又受到聚合单体纯度的影响，对部分杂质十分敏感，比如赖氨酸，醇类，含有羟基的色素等。而戊二胺的 制备方法基本上是以赖氨酸为底物，以赖氨酸发酵液或者直接的成品赖氨酸盐酸盐为出发点，在赖氨酸脱羧酶(E.C.4.1.1.18)或者可以产赖氨酸脱羧酶的菌(比如蜂房哈夫尼菌)的作用下制得，而后经过分离纯化获得纯品戊二胺，如式IV所示(CN201180010538.5，CN201310755027.7)。这里的分离纯化方式基本上为蒸馏或先萃取后蒸馏的方式，比较容易引入醇类等杂质(CN201380075176.7)。
Figure PCTCN2018082438-appb-000002
另一方面，戊二胺在常温下呈液态，具有尸腐气味，挥发性较强，相对于固体原料而言，在运输和使用过程中带来不便；再者，聚合过程中要求戊二胺和己二酸的摩尔比优选1:1，对于含有少量杂质的液体戊二胺以及工业级的己二酸而言，在工艺操作过程中保持等摩尔比有一定的困难。
发明内容
本发明所要解决的技术问题是提供一种戊二胺与己二酸等摩尔比的高纯度的戊二胺己二酸盐结晶粉末，并提供一种由戊二胺和己二酸两组分化合物来生产戊二胺己二酸结晶盐的制备工艺，和一种盐的晶体结构。如此一来，既改变了产品形态，消除了产品气味，使其便于运输和使用，也改善了产品纯度和稳定性，保证了戊二胺和己二酸在等摩尔比的条件下参与反应，使其可以直接用于聚合。聚合反应示意公式V如下：
Figure PCTCN2018082438-appb-000003
本发明意在提供一种生物基尼龙56材料的单体，戊二胺己二酸盐，及其晶体结构，及其结晶粉末，以及制备方法。相对于传统的需要戊二胺和己二酸两个组分才能进行的尼龙56聚合工艺，本发明提供的这种戊二胺己二酸盐的产品，通过结晶方式获得，产品以戊二胺与己二酸等摩尔比的晶体的方式呈现，可以直接用于聚合，在结构上具有稳定性，且具备较好的产品纯度与颗粒度，在运输、使用、储存及质量方面均有优势。
为解决上述技术问题，本发明采用的技术方案如下：
本发明公开了一种固体状态的戊二胺己二酸盐，又称尸胺己二酸盐，所述的戊二胺己二酸盐是戊二胺二价阳离子与己二酸二价阴离子以摩尔比为1:1的方式结合而成的常温下呈现固体状态的盐，其分子结构如式I所示：
Figure PCTCN2018082438-appb-000004
本发明还公开了一种戊二胺己二酸盐的晶体，所述的分子式为C 11H 24N 2O 4·nH 2O,n＝0～4，可能含有结晶水或不含结晶水，优选含有结晶水的晶型，分子结构式如式II所示：
Figure PCTCN2018082438-appb-000005
具体来说，n优选为1或2，最优选2。
当n＝2时，其晶体结构属于单斜晶系，C2/c空间群，晶胞参数为
Figure PCTCN2018082438-appb-000006
Figure PCTCN2018082438-appb-000007
β＝116.121(3)°,晶胞体积
Figure PCTCN2018082438-appb-000008
晶胞内分子数Z＝4，在其最小不对称单元中，含有1个戊二胺阳离子和1个己二酸阴离子，和两分子结晶水，其晶胞的最小不对称单元图以及晶胞堆积图分别如附图1和附图2所示，其晶体结构的详细数据——键长信息如附图7所示，键角信息如附图8所示，二面角信息如附图9所示，氢键信息如附图10所示。其晶体结构测定过程中，衍射数据在298(2)K下进行收集。
当n＝2时，具有如图3所示的用CuKα射线作为特征X射线进行衍射分析的衍射图 谱，以衍射角2θ±0.1表示为：19.96，24.06，9.62，27.28，25.42，21.08，24.48，11.06，26.14，23.68，30.52等，如附图5所示。
当n＝1时，具有如图4所示的用CuKα射线作为特征X射线进行衍射分析的衍射图谱，以衍射角2θ±0.1表示为：9.59,10.94,19.78,20.75,21.83,22.20,27.81等，如图6所示。
本发明戊二胺己二酸盐的晶体结构的检测方法及仪器如下：
单晶X-ray衍射测定晶体结构与解析方法：取培养出的质量较好的戊二胺己二酸盐单晶，切割成约0.22×0.24×0.26mm 3大小的块状，经布鲁克APEX-II CCD衍射仪Mo Kα放射源(石墨单色器，
Figure PCTCN2018082438-appb-000009
)对样品进行照射，并收集衍射数据，衍射数据经SAINT进行还原后用SHELXTL软件直接法进行结构解析，并基于F 2的全矩阵最小二乘法精修，所有的非氢原子通过各向异性精修。最终数据通过Mercury或Diamond软件作图。
粉末X-ray衍射：研磨后的样品，取约0.1g，通过粉末X射线衍射仪(日本理学Smartlab或Bruker D8Advance)在室温下进行衍射数据收集，光源为Cu Kα射线
Figure PCTCN2018082438-appb-000010
Figure PCTCN2018082438-appb-000011
扫描步长为0.02°，设定扫描电压40kV，电流40mA，扫描速率0.2s/0.02°，扫描范围2θ为5～50°，数据通过JADE软件处理作图。
上述戊二胺己二酸盐的结晶粉末，呈白色或微黄色。
上述晶体形成的结晶粉末，具有大于0.20g/mL的堆积密度，优选大于0.30g/mL，更优选大于0.40g/mL的堆积密度。
上述晶体形成的结晶粉末，具有大于0.23g/mL的振实密度L，优选大于0.33g/mL，更优选大于0.44g/mL的振实密度。
上述晶体形成的结晶粉末，具有大于10μm的d 50，优选大于30μm，更优选大于50μm，最优选大于60μm的d 50。
上述晶体形成的结晶粉末，具有大于3μm的d 10，优选大于6μm，更优选大于10μm，最优选大于15μm的d 10。
本发明所述的d 50和d 10是用于表明粒度分布的通常的量。所述的d 50是用于粒度的值，使得50vol.％的晶体具有小于这个值得尺寸。所述的d 10是用于粒度的值，使得10vol.％的晶体具有低于这个值的尺寸。
所述的堆积密度和振实密度是与粉末的流动特性相关的量。总体上，希望高的堆密 度和振实密度值。简而言之，堆密度指出在预定条件下每体积单位粉末的重量。换言之，在预定条件下多少克粉末可以供给到具有特定容积的样品保持器中。因为这个原因，堆密度表示为通常以g/mL计的每体积单位的重量。振实密度也表明了每体积单位粉末的重量，在这种情况下，在该粉末的保持器经受在预定条件下的拍打或振动的情况下。振实密度表示为通常以g/mL计的每体积单位的重量。通过拍打或振动，更多的粉末可以供给到该保持器中。因此，对于同一粉末，其振实密度高于堆密度。
堆积密度与振实密度大的粉末，其比重往往较大，可以反映出晶体产品比较厚实，有质感，其稳定性也会相对较好；从另一个角度讲，堆积密度大的产品，颗粒的流动性一般较好，也便于储存和运输，更便于与其他组分高效混合。
那么具体地，所述颗粒尺寸分布、堆积密度、振实密度的测量方法如下：
使用Microtrac S3500颗粒粒度分析仪确定来自混合器的样品的颗粒尺寸分布(包括d 10和d 50)，干法测定；
颗粒的堆积密度按USP方法II(第1914页)来测定；
颗粒的振实密度通过，依据GB/T 5162-2006，通过FZS4-4经济型振实密度测定仪进行测定。具体地，测定条件为：拍实装置的振动冲程为3±0.1MM，振动频率为每分钟250±15次。
需要指出的是，上述结晶粉末会因为制备方法的差异，或干燥方式的不同，或储存环境湿度的不同而展现出不同的表观水含量(包含自由水和结合水)，因此，该结晶粉末可能具有0～23wt％的水含量，优选4～7％和10～14％
具体地，所述结晶粉末水含量的测定方法为卡尔费休法，可以通过瑞士万通的870Titrino plus实用型容量法卡尔费休水分测定仪进行测定。
将上述晶体配制成质量分数为5％的水溶液时，体系pH值在2.5～10之间，优选3.5～9.5，更优选5.0～8.5，最优选6.0～8.0。
本发明所述的固体或固体粉末是物质的一种聚集状态，包括无定形和晶体。
本发明所述的结晶粉末，指具有一定结晶度的粉末，是相对于无定形而言。
本发明所述的晶体是对X射线有明确衍射图案的固体，其原子或分子在空间按一定规律周期重复地排列。
本发明还公开了一种组合物，包含
(i)根据权利要求2～6中任一项所述的晶体，和
(ii)(a)己二酸固体；或
(b)戊二胺。
上述组合物使得混合物中戊二胺与己二酸的摩尔数之比不等于1:1。
本发明最后公开了上述戊二胺己二酸盐的晶体的制备方法，包括，从含有溶解的戊二胺和己二酸的溶液中结晶出戊二胺己二酸盐；从所述溶液中分离出晶体；和洗涤、干燥所分离的晶体。
其中，包括在干燥过程中或干燥后对晶体进行机械冲压。
其中，所述的含有溶解的戊二胺和己二酸的溶液按照下述任一种方式制备得到：
(i)将己二酸固体和戊二胺同时加入溶剂中；
(ii)将己二酸固体和戊二胺先后加入溶剂中；
(iii)将戊二胺加入溶剂中形成戊二胺溶液；将己二酸固体加入溶剂中形成己二酸溶液或含有部分未溶解己二酸固体的己二酸溶液，而后将两者混合；其中，溶解戊二胺的溶剂和溶解己二酸固体的溶剂可以相同也可以不同。
其中，所述的溶剂包括甲醇、乙醇、水、乙腈、乙酸乙酯、甲酸乙酯、乙酸甲酯、乙酸丁酯、丙酮、丁酮、石油醚、四氢呋喃和DMSO的一种或它们的混合溶剂，优选甲醇、乙醇、水、丙酮、丁酮、DMSO中的一种几种的混合溶剂。
其中，己二酸的加入方式可以多种多样，比如以固体的方式一次性直接加入到溶剂之中，或者以固体的方式多次缓慢加入溶剂之中，或者先将己二酸用所述溶剂溶解，而后一次性加入或者分多次加入到尸胺溶液之中。优选先将己二酸用所述溶剂溶解后再加入到尸胺溶液之中的操作方式。
上述戊二胺己二酸盐的晶体的制备方法，具体地，比如将戊二胺加入到有机溶剂中，或水与有机溶剂的二元溶剂中，或水与多种有机溶剂的混合溶剂中，或者水相之中，充分混匀后，加入己二酸，在温度10～50℃范围内，在搅拌状态下缓慢析晶，0.5～72h小时后有白色晶体析出，晶桨经过抽滤或离心进行固液分离，所得固体在35～70℃下真空干燥，即得戊二胺己二酸盐结晶粉末，或本发明所述的组合物。
其中，晶体制备过程中戊二胺的重量g与溶剂的体积mL的比可以为1:0.5～30；己二酸的加入量，其与戊二胺的摩尔比可以为0.4～2.0，优选等摩尔比。
需要指出的是，戊二胺与己二酸以等摩尔比的形式进行反应结晶，那么所获得的固体产品就更容易形成以戊二胺阳离子和己二酸阴离子等摩尔比的戊二胺己二酸盐结晶粉末，其5wt％水溶液的pH值在6.0～8.0之间，优选6.5～7.5之间。如果晶体制备过程中所加入的己二酸的总摩尔数，大于或小于初始加入戊二胺的摩尔数，那么所得固体产品就更容易形成本发明所述的组合物，其产品的5wt％水溶液的pH将显示非中性。
具体地，当所加入的己二酸的摩尔数大于初始戊二胺的摩尔数时，所得粉末将显示弱酸性或酸性；当所加入的己二酸的摩尔数小于初始戊二胺的摩尔数时，所得粉末将显示弱碱性或碱性。
需要指出的是，在本发明所述制备方法里，在有机溶剂存在条件下的结晶过程，为了减少有机溶剂挥发，可以考虑在结晶器上安装冷凝回流装置，冷凝温度依据冷媒的不同可以设定不同温度，比如-10～20℃。所述的冷媒可以使用乙醇，乙二醇或水。
需要指出的是，在本发明所述的制备方法里，在固液分离后，需要用到洗涤剂洗涤固体，以除去固体表面携带的结晶母液中的杂质，洗涤剂可以为结晶制备过程中使用的所述溶剂。
需要指出的是，在本发明所述制备方法里，干燥的过程对戊二胺己二酸盐粉末的稳定性和水含量有一定影响，较低的干燥温度容易降低干燥效率，可能引起干燥不充分导致溶剂残留超标或者结块的现象；过高的干燥温度容易使得产品失去结晶水，而失去结晶水的结晶粉末，放置在室内环境下容易吸潮。在本发明所述的制备方法下，干燥方式优选鼓风干燥，干燥温度可以从30～70℃，优选35～45℃，干燥气流的湿度优选30％～65％，过低湿度的气流容易带来结晶水的损失，过高湿度的气流容易使产品吸收更多的自由水，甚至发生潮解。
需要指出的是，在本发明所述的制备方法里，工艺中戊二胺的来源，可以是单一组分的戊二胺，也可以是生物法制备戊二胺过程中在分离后期的含有戊二胺的溶液。
需要指出的是，结晶过程可以间歇或者连续地进行。当该工艺过程间歇进行时，优选向结晶体系中添加晶种。优选地，结晶连续地进行。
另外，本发明所涉及的尸胺己二酸盐晶体结构的更加详细的信息，在附图中一并给出。
附图说明
图1戊二胺己二酸盐的最小不对成单元的分子椭球图；
图2戊二胺己二酸盐二水合物的沿b轴方向的晶胞堆积图；
图3戊二胺己二酸盐二水合物的X-ray粉末衍射图谱；
图4戊二胺己二酸盐单水合物的X-ray粉末衍射图谱；
图5戊二胺己二酸盐二水合物X-ray粉末衍射的特征谱线；
图6戊二胺己二酸盐单水合物X-ray粉末衍射的特征谱线；
图7戊二胺己二酸盐二水合物结构中的键长信息(Angstrom)；
图8戊二胺己二酸盐二水合物结构中的键角信息(Deg)；
图9戊二胺己二酸盐二水合物结构中的二面角信息(Deg)；
图10戊二胺己二酸盐二水合物结构中的氢键信息(Angstrom,Deg)；
图11产品的表征；
图12稳定性实验。
具体实施方式
本发明涉及的戊二胺己二酸盐结晶粉末以及本发明所述的组合物的制备方法，通过下面非限制性的实施例将进一步阐明，以下实施例只是描述性的，不是限制性的，不能以限定本发明的保护范围。
实施例1：
将15.00g的戊二胺加入到150g甲醇溶液中，充分搅匀，形成戊二胺甲醇溶液。将21.45g的己二酸溶解于240g甲醇中，在25℃下，以2mL/min的流速滴入戊二胺甲醇溶液中，在搅拌状态下进行结晶，并监测过程pH变化，在pH 10.5左右，加入0.1g晶种，暂停流加，养晶4h后，以0.5mL/min的流速将己二酸甲醇溶液滴入结晶体系，待完全流加结束后，继续搅拌2h，下罐，抽滤进行晶桨的固液分离，而后用60～80mL甲醇洗涤，而后于40℃下鼓风干燥10h，获得戊二胺己二酸盐结晶粉末，含水量为(6.7±0.2)％，1个结晶水，其粉末X射线衍射图谱如图4所示，以衍射角2θ±0.1表示为：9.59,10.94,19.78,20.75,21.83,22.20,27.81等，如附图6所示，将其配制成质量分数为5％的水溶液时，体系pH值为7.5。该粉末具有良好的颗粒性、流动性、稳定性。
实施例2：
将10.00g戊二胺加入到100mL 90％乙醇水溶液中(乙醇体积分数为90％)，充分搅匀，形成戊二胺乙醇水溶液。将14.30g己二酸固体加入到160mL 90％的乙醇水溶液中(乙醇体积分数为90％)，形成己二酸的乙醇水溶液，而后将二者混合于500mL结晶器中，控制温度在25℃，搅拌48h，出现白色晶体物质，下罐，抽滤的方式进行固液分离，用150mL 95％的乙醇洗涤固体，而后放入45℃的环境中，用相对湿度RH为50％的热风干燥固体8h，即得戊二胺己二酸盐结晶粉末，含有两个结晶水，含水量在(12.6±0.2)％，产品的粉末X射线图谱如附图3所示，，以衍射角2θ±0.1表示为：19.96，24.06，9.62，27.28，25.42，21.08，24.48，11.06，26.14，23.68，30.52等，如图5所示。其晶体结构属于单斜晶系，C2/c空间群，晶胞参数为
Figure PCTCN2018082438-appb-000012
Figure PCTCN2018082438-appb-000013
β＝116.121(3)°,晶胞体积
Figure PCTCN2018082438-appb-000014
晶胞内分子数Z＝4，在其最小不对称单元中，含有1个戊二胺阳离子和1个己二酸阴离子，和两分子结晶水，其晶胞的最小不对称单元图以及晶胞堆积图分别如附图1和附图2所示，其晶体结构的详细数据——键长信息如附图7所示，键角信息如附图8所示，二面角信息如附图9所示，氢键信息如附图10所示。其晶体结构测定过程中，衍射数据在298(2)K下进行收集。将其配制成质量分数为5％的水溶液时，体系pH值为8.0。该粉末具有良好的颗粒性、流动性、稳定性。
实施例3：
将50.00g己二酸溶解于550g的无水乙醇之中，呈均一的己二酸乙醇溶液，而后移入1000mL的结晶器中。将32.00g的戊二胺溶于250mL 95％的丙酮水(丙酮体积分数占95％)溶液之中，形成戊二胺丙酮水溶液。而后用泵将戊二胺丙酮水溶液以2mL/min的方式滴入己二酸乙醇溶液之中，当加入的戊二胺的物质的量为己二酸物质的量的20％时，加入0.2g晶种，以0.2mL/min加入剩余戊二胺丙酮水溶液，整个过程在搅拌状态下进行，温度控制在50℃，当完全流加结束时，以2℃/h的速率降温至15℃，结晶结束，下罐进行固液分离，而后用100mL无水乙醇洗涤滤饼，并置于35℃下相对湿度为65％的流动气氛下干燥10h，即获得戊二胺己二酸盐结晶粉末，粉末含水量为(21.4±1.6)％，将其配制成质量分数为5％的水溶液时，体系pH值为9.0。该粉末具有良好的颗粒性、流动性、稳定性。
实施例4：
含有40g/L的戊二胺水溶液中，使用薄膜蒸发器或者旋蒸浓缩器，将此水溶液浓缩8倍，即浓缩后体积为原有体积的1/8，而后置于结晶器中，搅拌状态下降温至15℃，而后加入1倍于料液体积的15℃下的无水乙醇，充分混匀后，加入己二酸固体，加入的量与体系中戊二胺的摩尔数相当，搅拌结晶48h，下罐进行固液分离，用1倍于料液体积的90％的乙醇进行洗涤，而后用相对湿度RH为55％的流动空气流，温度控制在45℃下进行干燥10h，即得戊二胺己二酸结晶粉末，粉末含水量为14.6±0.5％，将其配制成质量分数为5％的水溶液时，体系pH值为9.0。该粉末具有良好的颗粒性、流动性、稳定性。
实施例5：
将50.00g己二酸溶解于300g的乙腈之中，呈均一的己二酸乙腈溶液，然后再加入乙酸乙酯、甲酸乙酯、乙酸甲酯、乙酸丁酯中的一种或几种的混合液，添加量为200mL，而后移入1000mL的结晶器中。将25.00g的戊二胺溶于250mL的乙酸乙酯中，形成戊二胺乙酸乙酯溶液。而后用泵将戊二胺乙酸乙酯溶液以1mL/min的方式滴入己二酸溶液之中，当加入的戊二胺的物质的量为己二酸物质的量的10％时，加入0.2g晶种，温度控制在10℃，当完全流加结束时，继续搅拌10h，结晶结束，下罐进行固液分离，而后用100mL无水乙醇洗涤滤饼，并置于70℃下相对湿度为30％的流动气氛下干燥6h，即获得戊二胺己二酸盐结晶粉末，粉末含水量为(0～4.5)％，将其配制成质量分数为5％的水溶液时，体系pH值为2.5～5.5。
实施例6：
将50.00g己二酸溶解于300g的乙腈-DMSO溶液之中(乙腈与DMSO的体积比为4：1)，呈均一的己二酸溶液，然后再加入丁酮、石油醚、四氢呋喃中的一种或几种的混合液，添加量为200mL，而后移入1000mL的结晶器中。将50.00g的戊二胺溶于250mL的丁酮，形成戊二胺丁酮溶液。而后搅拌状态下，将戊二胺丁酮溶液直接倒入己二酸溶液之中，维持体系温度30℃，转速300r/min，搅拌0.5h，结晶结束，下罐进行固液分离，而后用100mL无水乙醇洗涤滤饼，并置于40℃下相对湿度为40％的流动气 氛下干燥4h，即获得戊二胺己二酸盐结晶粉末，粉末含水量为(4.0±1.5)％，将其配制成质量分数为5％的水溶液时，体系pH值为8.0～10.0。
实施例7：
取实施例1至4中所得的样品，分别测试其d 10，d 50，堆积密度，振实密度，以说明本发明所述工艺所得尸胺己二酸盐产品具有良好的颗粒性和流动性，而且产品的有机溶剂残留几乎检测不到，结果如图11所示。
取实施例1至4中所得的样品，将其放置于60℃下进行稳定性实验，间隔24h分别测试其在430nm下的透光，并用初始样品做对照，结果如图12所示，发现四种实施例中所得样品，颜色均没有发生变化，T 430nm没有明显下降，说明所得样品稳定性良好。

Claims (17)

  1. 一种戊二胺己二酸盐，其特征在于，所述的戊二胺己二酸盐是戊二胺二价阳离子与己二酸二价阴离子以摩尔比为1:1的方式结合而成的常温下呈现固体状态的盐，其分子结构如式I所示：
    Figure PCTCN2018082438-appb-100001
  2. 一种戊二胺己二酸盐的晶体，其特征在于，所述的分子式为C 11H 24N 2O 4·nH 2O,n＝0～4，分子结构式如式II所示：
    Figure PCTCN2018082438-appb-100002
  3. 根据权利要求2所述的戊二胺己二酸盐的晶体，其特征在于，n为1或2。
  4. 根据权利要求3所述的戊二胺己二酸盐的晶体，其特征在于，当n＝2时，其晶体结构属于单斜晶系，C2/c空间群，晶胞参数为
    Figure PCTCN2018082438-appb-100003
    Figure PCTCN2018082438-appb-100004
    β＝116.121(3)°,晶胞体积
    Figure PCTCN2018082438-appb-100005
    晶胞内分子数Z＝4，在其最小不对称单元中，含有1个戊二胺阳离子和1个己二酸阴离子，和两分子结晶水。
  5. 根据权利要求4所述的戊二胺己二酸盐的晶体，其特征在于，当n＝2时，具有如附图3所示的用CuKα射线作为特征X射线进行衍射分析的衍射图谱。
  6. 根据权利要求3所述的戊二胺己二酸盐的晶体，其特征在于，当n＝1时，具有如附图4所示的用CuKα射线作为特征X射线进行衍射分析的衍射图谱。
  7. 根据权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体，其特征在于，结晶粉末具有大于0.20g/mL的堆积密度。
  8. 根据权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体，其特征在于，结晶粉末具有大于0.23g/mL的振实密度。
  9. 根据权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体，其特征在于，结晶粉末具有大于10μm的d 50。
  10. 根据权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体，其特征在于，结晶粉 末具有大于3μm的d 10。
  11. 根据权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体，其特征在于，结晶粉末具有0～23wt％的水含量。
  12. 根据权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体，其特征在于，将所述晶体配制成质量分数为5％的水溶液时，体系pH值在2.5～10之间。
  13. 一种组合物，包含
    (i)根据权利要求2～6中任一项所述的晶体，和
    (ii)(a)己二酸固体；或
    (b)戊二胺。
  14. 权利要求2～6中任意一项所述的戊二胺己二酸盐的晶体的制备方法，其特征在于，包括，从含有溶解的戊二胺和己二酸的溶液中结晶出戊二胺己二酸盐；从所述溶液中分离出晶体；和干燥所分离的晶体。
  15. 根据权利要求14所述的制备方法，其特征在于，包括在干燥过程中或干燥后对晶体进行机械冲压。
  16. 根据权利要求14所述的制备方法，其特征在于，所述的含有溶解的戊二胺和己二酸的溶液按照下述任一种方式制备得到：
    (i)将己二酸固体和戊二胺同时加入溶剂中；
    (ii)将己二酸固体和戊二胺先后加入溶剂中；
    (iii)将戊二胺加入溶剂中形成戊二胺溶液；将己二酸固体加入溶剂中形成己二酸溶液或含有部分未溶解己二酸固体的己二酸溶液；而后将两者混合。
  17. 根据权利要求16所述的方法，其特征在于，所述的溶剂包括甲醇、乙醇、水、乙腈、乙酸乙酯、甲酸乙酯、乙酸甲酯、乙酸丁酯、丙酮、丁酮、石油醚、四氢呋喃和DMSO的一种或它们的混合溶剂。
PCT/CN2018/082438 2017-08-25 2018-04-10 戊二胺己二酸盐及其晶体 WO2019037438A1 (zh)

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