CN108558646A - A kind of crystal form of heneicosanedioic acid and preparation method thereof - Google Patents
A kind of crystal form of heneicosanedioic acid and preparation method thereof Download PDFInfo
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- CN108558646A CN108558646A CN201711331778.0A CN201711331778A CN108558646A CN 108558646 A CN108558646 A CN 108558646A CN 201711331778 A CN201711331778 A CN 201711331778A CN 108558646 A CN108558646 A CN 108558646A
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- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
The present invention relates to a kind of crystal forms of heneicosanedioic acid and preparation method thereof, indicate there is characteristic peak 7.6 ± 0.2,15.4 ± 0.2,18.8 ± 0.2,22.4 ± 0.2,27.4 ± 0.2,39.8 ± 0.2 with 2 θ of X-ray powder diffraction.The preparation method of the heneicosanedioic acid crystal form of the present invention：Heneicosanedioic acid crude product is added in specific solvent, 0.1 0.5g/ml of concentration, it is heated to 50~70 DEG C, stirring and dissolving is clarified, it is quickly cooled to 0~20 DEG C, it is no more than 20min in cooling terminal constant temperature growing the grain, magma obtains the heneicosanedioic acid crystal form crystal through being filtered, washed, drying to constant weight.The crystal product of preparation is white, and solubility property is good, and fusing point is low, is stablized, the subsequent solution for the product that is highly advantageous to and frit reaction, and a kind of new crystal and preparation method are provided for the efficient utilization of heneicosanedioic acid.
Description
Technical field
The invention belongs to industrial crystallization technical field, more particularly to a kind of crystal form of heneicosanedioic acid and preparation method thereof.
Background technology
Heneicosanedioic acid (English name：Undecanedioic acid), molecular formula：C11H20O4, molecular weight：216.27.Change
It is as follows to learn structural formula：
Long-chain biatomic acid refers to the straight chain saturated dicarboxylic acid containing ten or more carbon atoms, in being important in chemical process
Between raw material, be the primary raw material of the special articles for use such as musk ambrette-T, copolyamide hot melt adhesive, nylon engineering plastic.With long-chain two
First acid is basis raw material production synthesis fine perfumery Moschus, advanced nylon rubber, high-temperature electrolysis matter, high-grade hot melt adhesive, cold-resistant increasing
Mould agent, senior lubricant, advanced paint and the fine chemical products such as coating, be widely used in chemical industry, light industry, pesticide, medicine,
The fields such as liquid crystal material.There is very fast growth trend in its market demand, and heneicosanedioic acid is wherein important one kind.Hendecane
Diacid is mainly used for polyamide top grade engineering plastics, is the primary raw material of nylon 1011,611,1111, is alternatively arranged as high-grade hot melt
The important source material of glue, high-grade lubricant and musk ambrette.
Long-chain biatomic acid has such important and extensive industrial use, but they are not individualisms in nature
, mainly there are 3 kinds of catalysis grease method, chemical synthesis and biological fermentation process production methods at present.Heneicosanedioic acid mainly passes through
Biofermentation produces.
Exist in solid form under long-chain biatomic acid room temperature.Crystallization is the effective means that purifying refines solid matter.Fermentation
Liquid will obtain having the finished product of certain particle size distribution and crystal shape must also after preliminary pretreatment and isolating and purifying
Condensing crystallizing and recrystallization are carried out to it.This is also the key for determining end product quality.Heneicosanedioic acid is in subsequent reaction
In, there is very high requirement to the solubility property etc. of product.The raising of solubility can effectively increase the efficiency of subsequent reactions
And realize good reaction controlling, and reduce energy consumption, cost.
For heneicosanedioic acid product in production as intermediate in subsequent reactions, most of is that solution reaction or melting are anti-
It answers.Participating in solvent reaction then needs solvent to be dissolved, and such as generates nylon 11 11 with hendecane diamine reactant in ethanol, molten
Xie Du plays a key role reaction efficiency, and what is be associated with is energy consumption and cost；Frit reaction is participated in then to need reacting
Before melted, if frit reaction generates hendecane diamines, the height strong influence of fusing point energy consumption and cost.Object lineage
It is nucleated in polymorphic, i.e., in nucleation process, different crystal forms product mix can be obtained.Due to the difference of microcosmic upper crystal structure
Different, different crystal forms are apparent in macroscopically dissolubility difference.Heneicosanedioic acid crystal product industrial at present is in accompanying crystallization
In obtain so that its product is mixing crystal form, is showed in solubility barely satisfactory, and fusing point is inhomogenous, and melting range is long so that
Energy consumption is higher.So preparing single, high-dissolvability, the crystal form product of low melting point is extremely necessary.This aspect basis at present
Science is still in probing into and the hot spot of international research.It is nucleated mainly by solvent, temperature and degree of supersaturation etc. with polymorphic
The influence of operating condition.Different solvents is different from the molecular recognition of solute due to functional group's difference, influences polymorphic nucleation；
In most cases, the relatively low degree of supersaturation of high degree of supersaturation is more advantageous to obtaining for high-dissolvability crystal form.
Before this, since mechanism is unknown, and the crystal form problem for being not concerned with the substance is produced, has ignored crystallization process control
Combinations type is not subject to the crystallization processes such as solvent, temperature, degree of supersaturation parameter the importance of the subsequent reaction process of product
Grope and control, what is obtained is multiphase substance, i.e. the mixing crystal form of unstable product quality.
Invention content
The present invention provides a kind of crystal form and preparation method thereof of heneicosanedioic acid, sees attached drawing with X-ray powder diffraction pattern
1, it is indicated 7.6 ± 0.2,15.4 ± 0.2,18.8 ± 0.2,22.4 ± 0.2,27.4 ± 0.2,39.8 ± 0.2 with 2 θ of the angle of diffraction
There is characteristic peak.
The differential scanning calorimetry DSC figures of heneicosanedioic acid crystal form of the present invention are shown in that attached drawing 2, the fusing point that rises of crystal are
103±3℃。
It is probed into based on scientific experiment and mechanism of nucleation, the crystal form obtained for the first time in this patent is named as heneicosanedioic acid
Crystal habit II, uniform and have good stability, solubility significantly improves, and fusing point decreases, and is conducive in subsequent reactions
Reaction efficiency raising and energy consumption cost reduction.
A kind of preparation method of crystal form of heneicosanedioic acid of the present invention, including following method：Heneicosanedioic acid is thick
Product are added in alcohols or acids solvent, are heated to 50~70 DEG C, and stirring and dissolving clarification is cooled to 0~20 DEG C.In cooling terminal
Constant temperature growing the grain, magma obtain the hendecane binary acid crystal form crystal through being filtered, washed, drying to constant weight.
In the method, the one kind of organic solvent in ethyl alcohol, normal propyl alcohol, n-butanol, isobutanol, acetic acid, propionic acid.
In the method, solution concentration 0.1-0.5g/ml.
In the method, the type of cooling is quenching.
In the method, rearing crystal time is no more than 20min.
In the method, drying condition is 40~50 DEG C of constant pressure and dries of temperature, and drying time is 4~6h.
The preparation method of heneicosanedioic acid crystal form provided by the invention, the advantage is that：Operation is succinct, mild condition, effect
Rate is high, and energy consumption is low, reproducible, is easy to the implementation of commercial industries scale.The crystal product of preparation is white, solubility property pole
Good, fusing point is relatively low, while having preferable stability, is very beneficial for the subsequent solution of product and the reaction efficiency of frit reaction
It improves and energy consumption cost reduces.
The stability of the heneicosanedioic acid crystal form II is investigated, normal temperature condition produces the heneicosanedioic acid crystal form
Product are uniformly split in open culture dish, and thickness of sample is less than 5mm, and control temperature takes at 30 DEG C respectively at 50 days, 100 days
Sample carries out XRD detections, and is compareed with the 0th day result, judges the stable case of crystal.This experiment obtain about 11
The X-ray powder diffraction collection of docosandioic acid stability of crystal form experimental study, as shown in Fig. 3.The experimental results showed that：In room temperature
It is placed 100 days at 30 DEG C, crystal color keeps white powder, X-ray powder diffraction collection that significant change does not occur, the crystal form
Stablize.
The heneicosanedioic acid crystal form II and solid product in the market are compared, attached drawing 4 is shown in the comparison of PXRD spectrograms.
The solubility of the heneicosanedioic acid crystal form is investigated (by taking the alcohol solvent that subsequent reactions use as an example), and
(by taking producer three as an example) is compared with product in the market, as a result such as attached drawing 5, this patent product have apparent solubility performance excellent
Gesture significantly improves subsequent reactions workshop section efficiency, reduces energy consumption and cost.
Description of the drawings
The x-ray diffraction pattern of the crystal form of Fig. 1 heneicosanedioic acids of the present invention.
The differential scanning calorimetric DSC figures of the crystal form of Fig. 2 heneicosanedioic acids of the present invention.
The stability test trace analysis of the crystal form of Fig. 3 heneicosanedioic acids of the present invention.
The crystal form of Fig. 4 heneicosanedioic acids of the present invention and the PXRD comparison diagrams of other products.
The solubility performance of the crystal form of Fig. 5 heneicosanedioic acids of the present invention compares.
Specific implementation mode
It is below the specific implementation mode example of the heneicosanedioic acid crystal form II, but this should not be interpreted as to the present invention
The range of above-mentioned theme is only limitted to following embodiment.All technologies realized based on the above of the present invention belong to the present invention
Range.
Embodiment 1
The heneicosanedioic acid alcohol suspending liquid for preparing solid-liquid mass ratio 0.3g/ml is warming up to 50 DEG C of stirring dissolved clarifications, fast quickly cooling
But to 15 DEG C, constant temperature growing the grain 10min；After crystallization is complete, filtration washing, 40 DEG C of constant pressure and dry 5h to constant weight obtain described 11
Docosandioic acid crystal form product.The X-ray powder diffraction figure of product is in 2 θ=7.62,15.44,18.85,22.41,27.48,39.86
There is characteristic peak at place, and for solubility (25 DEG C in ethanol) up to 0.14g/ml, solubility property is good.
Embodiment 2
The heneicosanedioic acid acetic acid suspension for preparing solid-liquid mass ratio 0.1g/ml is warming up to 60 DEG C of stirring dissolved clarifications, fast quickly cooling
But to 10 DEG C, constant temperature growing the grain 5min；After crystallization is complete, filtration washing, 50 DEG C of constant pressure and dry 4h to constant weight obtain the hendecane
Diacid crystal form product.The X-ray powder diffraction figure of product has at 2 θ=7.61,15.4,18.8,22.39,27.41,39.83
Characteristic peak, for solubility (25 DEG C in ethanol) up to 0.11g/ml, solubility property is good.
Embodiment 3
The heneicosanedioic acid propionic acid suspension for preparing solid-liquid mass ratio 0.15g/ml is warming up to 70 DEG C of stirring dissolved clarifications, quickly
20 DEG C are cooled to, constant temperature growing the grain 20min；After crystallization is complete, filtration washing, 40 DEG C of constant pressure and dry 6h to constant weight obtain described ten
One docosandioic acid crystal form product.The X-ray powder diffraction figure of product 2 θ=7.55,15.38,18.74,22.35,27.37,
There is characteristic peak at 39.74, for solubility (25 DEG C in ethanol) up to 0.11g/ml, solubility property is good.
Embodiment 4
The heneicosanedioic acid normal propyl alcohol suspension for preparing solid-liquid mass ratio 0.5g/ml is warming up to 50 DEG C of stirring dissolved clarifications, quickly
5 DEG C are cooled to, constant temperature growing the grain 10min；After crystallization is complete, filtration washing, 45 DEG C of constant pressure and dry 5h to constant weight obtain described 11
Docosandioic acid crystal form product.The X-ray powder diffraction figure of product is at 2 θ=7.6,15.4,18.82,22.41,27.43,39.82
There is characteristic peak, for solubility (25 DEG C in ethanol) up to 0.11g/ml, solubility property is good.
Embodiment 5
The heneicosanedioic acid n-butanol suspension for preparing solid-liquid mass ratio 0.2g/ml is warming up to 55 DEG C of stirring dissolved clarifications, quickly
It is cooled to 0 DEG C, constant temperature growing the grain 10min；After crystallization is complete, filtration washing, 50 DEG C of constant pressure and dry 6h to constant weight obtain described 11
Docosandioic acid crystal form product.The X-ray powder diffraction figure of product is in 2 θ=7.58,15.35,18.76,22.34,27.36,39.73
There is characteristic peak at place, and for solubility (25 DEG C in ethanol) up to 0.11g/ml, solubility property is good.
Embodiment 6
The heneicosanedioic acid isobutanol suspension for preparing solid-liquid mass ratio 0.4g/ml is warming up to 60 DEG C of stirring dissolved clarifications, quickly
10 DEG C are cooled to, constant temperature growing the grain 5min；After crystallization is complete, filtration washing, 45 DEG C of constant pressure and dry 6h to constant weight obtain described 11
Docosandioic acid crystal form product.The X-ray powder diffraction figure of product is at 2 θ=7.6,15.39,18.8,22.39,27.38,39.78
There is characteristic peak, for solubility (25 DEG C in ethanol) up to 0.11g/ml, solubility property is good.
The heneicosanedioic acid crystal form and preparation method thereof that the present invention is disclosed and proposed, those skilled in the art can pass through reference
Present disclosure, under the guidance of polymorphic nucleation theory, the links such as appropriate feed change, technological parameter are realized.The method of the present invention
It has been described by preferred embodiment with product, related technical personnel can obviously not depart from the content of present invention, spirit
Method described herein and product are modified or are suitably changed and combined in range, to realize the technology of the present invention.Especially
It should be pointed out that all similar replacements and change it is apparent to those skilled in the art, they all by
It is considered as and is included in spirit of that invention, range and content.
Claims (9)
1. a kind of crystal of heneicosanedioic acid, it is characterised in that X-ray powder diffraction is in 2 θ=7.6 ± 0.2 of the angle of diffraction, 15.4
There is characteristic peak at ± 0.2,18.8 ± 0.2,22.4 ± 0.2,27.4 ± 0.2,39.8 ± 0.2 degree.
2. crystal as described in claim 1, which is characterized in that its differential scanning calorimetry measures the crystal form, starting heat absorption temperature
About 103 ± 3 DEG C of degree.
3. crystal as described in claim 1, it is characterised in that crystal form is named as the crystal habit II of heneicosanedioic acid.
4. the preparation method of crystal as described in claim 1, which is characterized in that by heneicosanedioic acid crude product be added to alcohols or
In acids solvent, 50~70 DEG C are heated to, stirring and dissolving clarification is cooled to 0~20 DEG C.In cooling terminal constant temperature growing the grain, magma
Through being filtered, washed, drying to constant weight, the hendecane binary acid crystal form crystal is obtained.
5. method as claimed in claim 4, which is characterized in that organic solvent is ethyl alcohol, normal propyl alcohol, n-butanol, isobutanol, second
One kind in acid, propionic acid.
6. method as claimed in claim 4, which is characterized in that initial concentration solution 0.1-0.5g/ml.
7. method as claimed in claim 4, which is characterized in that the type of cooling is quenching.
8. method as claimed in claim 4, which is characterized in that rearing crystal time is no more than 20min.
9. method as claimed in claim 4, which is characterized in that drying condition is 40~50 DEG C of constant pressure and dries, drying time 4
~6h.
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Application publication date: 20180921 |