CN116874451A - Aliphatic diamine furan diformate and crystal thereof - Google Patents

Aliphatic diamine furan diformate and crystal thereof Download PDF

Info

Publication number
CN116874451A
CN116874451A CN202310873748.1A CN202310873748A CN116874451A CN 116874451 A CN116874451 A CN 116874451A CN 202310873748 A CN202310873748 A CN 202310873748A CN 116874451 A CN116874451 A CN 116874451A
Authority
CN
China
Prior art keywords
salt
furandicarboxylic acid
aliphatic diamine
furandicarboxylate
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310873748.1A
Other languages
Chinese (zh)
Inventor
杨朋朋
张珂珂
石裕中
张啸涵
王莹莹
庄伟�
李明
柳东
沈涛
应汉杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Nanjing Tech University
Original Assignee
Zhengzhou University
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University, Nanjing Tech University filed Critical Zhengzhou University
Priority to CN202310873748.1A priority Critical patent/CN116874451A/en
Publication of CN116874451A publication Critical patent/CN116874451A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation
    • 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
    • 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

Abstract

The invention discloses aliphatic diamine furan diformate and crystals thereof, including pentanediamine furan diformate (PA 5F salt), hexanediamine furan diformate (PA 6F salt), heptanediamine furan diformate (PA 7F salt), octanediamine furan diformate (PA 8F salt), nonanediamine furan diformate (PA 9F salt), decanediamine furan diformate (PA 10F salt) and crystals thereof. The crystal provided by the invention eliminates the odor of aliphatic diamine by a specific method, has higher bulk density, is convenient to transport, improves the stability of a polymerization monomer, meets the requirement of nylon polymerization on molar ratio, and can be directly used for polymerization.

Description

Aliphatic diamine furan diformate and crystal thereof
Technical Field
The invention belongs to the field of raw material refining of bio-based polymers, and particularly relates to a monomer (raw material) aliphatic diamine furan diformate of bio-based nylon nF, a crystal structure thereof and a preparation method thereof.
Background
As one of five engineering plastics, nylon (polyamide) has the advantages of good mechanical property, wear resistance, corrosion resistance and the like, and has wide application range. With the increasing shortage of global petroleum resources, nylon materials derived from petroleum raw materials are severely restricted in the face of an unprecedented energy crisis. On the other hand, excessive industrial utilization of fossil resources causes problems such as environmental pollution and ecological deterioration. Serious resource, energy and environmental crisis have prompted worldwide innovation of replacing fossil resources with biorenewable resources, and therefore bio-based nylon materials derived from renewable raw materials are receiving widespread attention.
Aliphatic diamines, which are one of nylon nF monomers, can be produced from biomass feedstock while furandicarboxylic acid is a bio-based aromatic diacid similar to terephthalic acid, can be produced from biomass-derived 5-hydroxymethylfurfural, and have been used for commercial production. Therefore, biobased nylon nF is a high performance material with great commercial value.
The aliphatic diamine is an odorous aliphatic diamine, has strong volatility, is easy to absorb acidic carbon dioxide in air, and brings a lot of difficulties for transportation and storage. Nylon synthesis is a polycondensation reaction, and if a polymer with a larger molecular weight is to be synthesized, equimolar reaction of dibasic acid and diamine needs to be strictly controlled, so that a high-quality polymer material is obtained. However, it is difficult to maintain an equimolar ratio during the polymerization process for liquid aliphatic diamines containing small amounts of impurities and technical grade furandicarboxylic acids. The first step in the preparation of polyamides is generally the synthesis of the corresponding diamine diacid salt, a particular ionic compound formed by proton exchange between diacid and diamine, ensuring a stoichiometric ratio of acid and amine end groups of 1:1, to obtain a high molecular weight polymer. Nylon salts are generally very stable in nature because they are in a solid, neutral state. The salification not only improves the purity and stability of the monomer, ensures the molar ratio to ensure that the monomer can be directly used for polymerization, but also changes the product form, eliminates the smell of raw material amine, ensures that the raw material amine is convenient to transport and use, and has lower storage and transportation cost. Therefore, most of the polycondensation reaction is carried out by the form of nylon salt
The existing nylon salt is prepared by dissolving acid and amine in water respectively through a heating mode, and then crystallizing by adding an organic solvent or cooling and crystallizing. For example, after salt is formed by using water as solvent solution method according to Chinese invention CN105777553A, adding organic solvents such as alcohols and lipids to perform anti-solvent crystallization, for example, after diamine diacid is dissolved at high temperature according to Chinese invention CN1887841A, cooling to crystallize, for example, after Chinese invention CN112111058A is dissolved into solvent under the protection of inert gas, reacting to generate nylon salt, for example, heating to react under the action of catalyst according to Chinese invention CN111925521A to obtain nylon salt. This process consumes a large amount of reagents and energy, ultimately resulting in an increase in production costs.
Mechanochemical milling is a green, sustainable and efficient method that can achieve controlled crystallization results in the pharmaceutical co-crystal building field with no or little solvent. Thus, mechanochemistry follows the principles of green chemistry, promotes benign reactions, limits solvent use, and optimizes all resources involved. It clearly has a higher yield and is more controllable than typical solution crystallization. In addition, the resulting product is easy to dry.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing aliphatic diamine furan diformate (PAnF salt) and crystals thereof, aiming at the defects of the prior art.
The invention also solves the technical problem of providing a green sustainable and efficient method for preparing the aliphatic diamine furan diformate (PAnF salt) and the crystals thereof.
In order to solve the technical problems, the invention discloses an aliphatic diamine furan diformate shown in a formula I;
n is selected from any integer of 5-10, and the information of each crystal structure is shown in table 1.
When n is selected from any one integer of 6 to 9, the tap density/bulk density of the aliphatic diamine furan diformate is 1.0 to 1.25, preferably 1.05 to 1.20.
TABLE 1 six crystal structure information for aliphatic diamine furandicarboxylic acid salts
Wherein when n=5, the diamine furandicarboxylic acid salt is a solid-state pentanediamine furandicarboxylic acid salt (PA 5F salt), and the PA5F salt is a specific temperature at which a pentanediamine divalent cation and a furandicarboxylic acid divalent anion are combined in a molar ratio of 1:1Salts in solid form of formula C 11 H 18 N 2 O 5 。
The crystal structure of the pentanediamine furan diformate belongs to a monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter is α＝90°，/>β＝100.022(2)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, in its smallest asymmetric unit, contains 1 pentanediamine cation and 1 furandicarboxylic acid anion.
The minimum asymmetric unit diagram and the unit cell stacking diagram of the glutarimfuran diformate are shown in the accompanying figures 1 and 2 respectively. It has a diffraction pattern for diffraction analysis using the cukα ray as a characteristic X-ray as shown in the PA5F salt curve in fig. 3, with the following X-ray powder diffraction characteristic lines expressed in terms of 2θ±0.1 diffraction angle and i% relative intensity measured after milling, measured using the Cu-kα ray:
the bulk density of the crystal powder of the PA5F salt crystal is more than 0.49g/cm 3 Preferably 0.49-0.52g/cm 3 。
The PA5F salt crystal has a tap density of more than 0.64g/cm 3 Preferably 0.66-0.71g/cm 3 。
Wherein when n=6, the diamine furandicarboxylic acid salt is hexamethylenediamine furandicarboxylic acid salt (PA 6F salt) in a solid state, the PA6F salt is hexamethylenediamine divalent cation with furanA salt of dicarboxylic acid dianion which is combined in a molar ratio of 1:1 and is in a solid state at a specific temperature, and has a molecular formula of C 12 H 20 N 2 O 5 。
The crystal structure of the hexamethylenediamine furandicarboxylic acid salt belongs to a monoclinic system, and P2 1 Space group/c, unit cell parameters areα＝90°，/>β＝108.538(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 hexamethylenediamine cation and 1 furandicarboxylic acid anion.
The minimum asymmetric unit diagram and the unit cell stacking diagram of the hexamethylenediamine furandicarboxylic acid salt are shown in the accompanying figures 1 and 2 respectively. It has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA6F salt curve in fig. 3, with the following X-ray powder diffraction characteristic lines expressed in terms of 2θ±0.1 diffraction angle and i% relative intensity measured after milling, measured using cu—kα rays:
the bulk density of the crystal powder of the PA6F salt crystal is more than 0.77g/cm 3 Preferably 0.82-0.84g/cm 3 。
The PA6F salt crystal has the tap density of crystal powder larger than 0.81g/cm 3 Preferably 0.88-0.89g/cm 3 。
Wherein when n=7, the diamine furandicarboxylic acid salt is in solid formA salt of pimediamine furandicarboxylic acid (PA 7F salt) in a solid state at a specific temperature, wherein the salt of PA7F is a salt formed by combining a pimediamine divalent cation and a furandicarboxylic acid divalent anion in a molar ratio of 1:1, and has a molecular formula of C 13 H 22 N 2 O 5 。
The crystal structure of the pimediamine furan diformate belongs to monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，/>β＝105.896(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 heptadiamine cation and 1 furandicarboxylic acid anion.
The minimum asymmetric unit diagram and the unit cell stacking diagram of the pimediamine furandicarboxylic acid salt are shown in the accompanying figures 1 and 2 respectively. It has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA7F salt curve in fig. 3, with the following X-ray powder diffraction characteristic lines expressed in terms of 2θ±0.1 diffraction angle and i% relative intensity measured after milling, measured using Cu-kα rays:
the bulk density of the crystal powder of the PA7F salt crystal is more than 0.44g/cm 3 Preferably 0.47-0.58g/cm 3 。
The PA7F salt crystal has a tap density of more than 0.50g/cm 3 Preferably 0.53-0.62g/cm 3 。
Wherein when n=8, the diamine furandicarboxylic acid salt is a solid state octanediamine furandicarboxylic acid salt (PA 8F salt), and the PA8F salt is a salt in which a divalent cation of octanediamine and a divalent anion of furandicarboxylic acid are combined in a molar ratio of 1:1, and has a molecular formula of C 14 H 24 N 2 O 5 。
The crystal structure of the octanediamine furandicarboxylic acid salt belongs to a monoclinic system, and the space group C2/C has the unit cell parameters of α＝90°，/>β＝127.238(6)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 0.5 octanediamine cations and 0.5 furandicarboxylic acid anions.
The minimum asymmetric unit diagram and the unit cell stacking diagram of the octanediamine furandicarboxylic acid salt are shown in the accompanying figures 1 and 2 respectively. It has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA8F salt curve in fig. 3, with the following X-ray powder diffraction characteristic lines expressed in terms of 2θ±0.1 diffraction angle and i% relative intensity measured after milling, measured using cu—kα rays:
the bulk density of the crystal powder of the PA8F salt crystal is more than 0.25g/cm 3 Preferably 0.25-0.38g/cm 3 。
The PA8F salt crystal and the crystal powderTap density of greater than 0.28g/cm 3 Preferably 0.30-0.44g/cm 3 。
Wherein when n=9, the diamine furandicarboxylic acid salt is a solid state nonanediamine furandicarboxylic acid salt (PA 9F salt), and the PA9F salt is a salt which is formed by combining a nonanediamine divalent cation and a furandicarboxylic acid divalent anion in a molar ratio of 1:1 and shows a solid state at a specific temperature, and has a molecular formula of C 15 H 26 N 2 O 5 。
The crystal structure of the nonanediamine furan diformate belongs to a monoclinic system, cc space group and unit cell parameters are as follows α＝90°，/>β＝108.924(3)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, in its smallest asymmetric unit, contains 4 nonanediamine cations and 4 furandicarboxylic acid anions.
The minimum asymmetric unit diagram and the unit cell stacking diagram of the nonanediamine furan diformate are shown in the accompanying figures 1 and 2 respectively. It has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA9F salt curve in fig. 3, with the following X-ray powder diffraction characteristic lines expressed in terms of 2θ±0.1 diffraction angle and i% relative intensity measured after milling, measured using cu—kα rays:
the bulk density of the crystal powder of the PA9F salt crystal is more than 0.45g/cm 3 Preferably 0.49-0.6g/cm 3 。
The PA9F salt crystal has a tap density of more than 0.50g/cm 3 Preferably 0.65-0.66g/cm 3 。
Wherein when n=10, the diamine furandicarboxylic acid salt is decadiamine furandicarboxylic acid salt (PA 10F salt) in a solid state, and the PA10F salt is a salt which is formed by combining decadiamine divalent cations and furandicarboxylic acid divalent anions in a molar ratio of 1:1 and shows a solid state at a specific temperature, and has a molecular formula of C 16 H 28 N 2 O 5 。
The minimum asymmetric unit diagram and the unit cell stacking diagram of the decamethylene diamine furandicarboxylic acid salt are shown in the accompanying figures 1 and 2 respectively. It has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA10F salt curve in fig. 3, with the following X-ray powder diffraction characteristic lines expressed in terms of 2θ±0.1 diffraction angle and i% relative intensity measured after milling, measured using Cu-kα rays:
The bulk density of the crystal powder of the PA10F salt crystal is more than 0.52g/cm 3 Preferably 0.53-0.6g/cm 3 。
The PA10F salt crystal has a tap density of more than 0.72g/cm 3 Preferably 0.74-0.78g/cm 3 。
In order to solve the second technical problem, the invention discloses a preparation method-grinding method of aliphatic diamine furan diformate shown in a formula I.
The grinding method specifically comprises the steps of grinding a mixture containing aliphatic diamine and furandicarboxylic acid, and grinding and crystallizing to obtain aliphatic diamine furandicarboxylic acid salt; separating salt from the mixture, and drying to obtain the product;
n is selected from any integer from 5 to 10.
Wherein the molar ratio of the aliphatic diamine to the furandicarboxylic acid is 1:0.5-1.5. It should be noted that when the crystallization is carried out in an equimolar ratio of aliphatic diamine to furandicarboxylic acid, the solid product obtained is more apt to form an aliphatic diamine furandicarboxylic acid salt crystalline powder in an equimolar ratio of aliphatic diamine cation to furandicarboxylic acid anion. If the total moles of furandicarboxylic acid added during the crystal production process is greater or less than the moles of aliphatic diamine initially added, the resulting solid product is more readily formed into the composition of the present invention. Specifically, when the mole number of furandicarboxylic acid added is greater than the mole number of the initial aliphatic diamine, the resulting powder will exhibit weak acidity or acidity; when the moles of furandicarboxylic acid added are less than the moles of the initial aliphatic diamine, the resulting powder will exhibit weak or basic properties.
Wherein the grinding temperature is 0-45 ℃.
Wherein, in the preparation of the glutarimfuran diformate, the grinding temperature is 30-40 ℃.
Wherein, in the preparation of hexamethylenediamine furandicarboxylic acid salt, the grinding temperature is 35-45 ℃.
Wherein, in the preparation of the pimediamine furan diformate, the grinding temperature is 10-20 ℃.
Wherein, in the preparation of the octanediamine furandicarboxylic acid salt, the grinding temperature is 0-10 ℃.
Wherein, in the preparation of the nonanediamine furan diformate, the grinding temperature is 25-35 ℃.
Wherein, in the preparation of the decanediamine furandicarboxylic acid salt, the grinding temperature is 5-15 ℃.
Wherein the grinding is performed in any of the following ways:
(i) Directly grinding furan dicarboxylic acid and aliphatic diamine;
(ii) The furandicarboxylic acid, aliphatic diamine and solvent are milled.
In the mode (ii), the solvent is added in various ways, such as being added directly to the mixture in a liquid form at a time before grinding, or being added slowly to the mortar in a liquid form multiple times during grinding, or being added slowly to the mortar in a liquid form multiple times before grinding and during grinding, and may be added in any one of the following ways, preferably being added slowly to the mixture of aliphatic diamine and furandicarboxylic acid multiple times in a liquid form, as the solvent is added in the mode described in (ii-2) or (ii-3);
(ii-1) adding a solvent to a mixture of furandicarboxylic acid and an aliphatic diamine at one time before milling;
(ii-2) adding a solvent during milling of the furandicarboxylic acid and the aliphatic diamine;
(ii-3) adding a part of the solvent to the mixture of furandicarboxylic acid and aliphatic diamine for grinding before grinding, and adding the rest of the solvent during grinding.
Wherein the dosage ratio of the aliphatic diamine to the solvent is 10-20mmol:0-3mL, preferably 10-20mmol:0.5-3mL.
Wherein the solvent is any one or more of methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, ethyl formate, methyl acetate, butyl acetate, acetone, butanone, petroleum ether, tetrahydrofuran and dimethyl sulfoxide, or a mixed solvent of any one or more of the above solvents and water; preferably, any one or more of methanol, ethanol, ethyl acetate, acetone, dimethyl sulfoxide, isopropanol and acetonitrile, or a mixed solvent of any one of the above and water, or a mixed solvent of any of the above and water; wherein, different solvents can be slowly added for a plurality of times in the grinding process.
In the preparation of the glutarimide furandicarboxylate, the solvent is a mixed solution of water and ethanol, preferably the volume ratio of water to ethanol is 1:0.5-1.5, preferably 1:1.
Wherein, in the preparation of hexamethylenediamine furandicarboxylic acid salt, the solvent is ethyl acetate.
Wherein, in the preparation of the pimediamine furandicarboxylic acid salt, the solvent is a ketone compound, preferably acetone.
Wherein, in the preparation of the octanediamine furandicarboxylic acid salt, the solvent is an alcohol compound, preferably isopropanol.
Wherein, in the preparation of the nonanediamine furan diformate, the solvent is dimethyl sulfoxide.
Wherein, in the preparation of the decanediamine furandicarboxylic acid salt, the solvent is ethyl acetate.
It should be noted that in the preparation method of the present invention, the operation of preparing different PAnF salts is mainly based on the difference of the auxiliary solvent and the grinding time. Such as:
when the aliphatic diamine furan diformate crystal is PA5F salt, the preparation method adopts a wet grinding crystallization method, and comprises the following steps: adding the pentanediamine and the furandicarboxylic acid into a mortar, adding a small amount of solvent before or during grinding, and grinding for 5-2 h to obtain the PA5F salt, wherein the preferable grinding time is 18-29 min.
When the aliphatic diamine furan diformate crystal is PA6F salt, the preparation method adopts a dry or wet grinding crystallization method, and comprises the following steps: adding hexamethylenediamine and furandicarboxylic acid into a mortar, adding no solvent in the grinding process or adding the solvent before or during grinding, and grinding for 10-4 h to obtain PA6F salt, wherein the grinding is preferably carried out for 10-50 min.
When the aliphatic diamine furan diformate crystal is PA7F salt, the preparation method adopts a wet grinding crystallization method, and comprises the following steps: the pimelin and the furandicarboxylic acid are added into a mortar, a small amount of solvent is added before or during grinding, and the grinding is carried out for 10min to 3h, so that the PA7F salt is obtained, and the grinding is preferably carried out for 13 min to 25min.
When the aliphatic diamine furan diformate crystal is PA8F salt, the preparation method adopts a wet grinding crystallization method, and comprises the following steps: adding the octanediamine and the furandicarboxylic acid into a mortar, adding a small amount of solvent before or during grinding, and grinding for 5-2 hours to obtain the PA8F salt, wherein the grinding is preferably 8-18 minutes.
When the aliphatic diamine furan diformate crystal is PA9F salt, the preparation method adopts a wet grinding crystallization method, and comprises the following steps: adding the pentanediamine and the furandicarboxylic acid into a mortar, adding a small amount of solvent before or during grinding, and grinding for 10-3 hours to obtain the PA9F salt, wherein the grinding is preferably 15-30 minutes.
When the aliphatic diamine furan diformate crystal is PA10F salt, the preparation method adopts a wet grinding crystallization method, and comprises the following steps: adding decanediamine and furandicarboxylic acid into a mortar, adding a small amount of solvent before or during grinding, and grinding for 10 min-2 h to obtain PA10F salt, preferably grinding for 15-25 min.
It should be noted that in the preparation method of the present invention, the crystallization process in the presence of the organic solvent may be performed under a low temperature environment, for example, -10 to 30 ℃, in order to reduce volatilization of the organic solvent.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the invention provides a PAnF salt crystal structure with high purity and equal molar ratio of aliphatic diamine and furandicarboxylic acid, and provides a green, sustainable and efficient mechanochemical grinding method, which can realize a controlled crystallization result in the field of pharmaceutical eutectic construction under the condition of no solvent or a small amount of solvent. Therefore, the product form is changed, the odor of aliphatic diamine is eliminated, the aliphatic diamine is convenient to transport, the purity and stability of the polymerized monomer are improved, the requirement of nylon polymerization on the molar ratio is met, and the aliphatic diamine can be directly used for polymerization. Meanwhile, the grinding time can be shortened by grinding under a specific solvent.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a molecular ellipsograph of a minimum asymmetric unit of six crystal structures of aliphatic diamine furandicarboxylic acid salt.
FIG. 2 is a diagram showing the packing of the six crystal structure unit cells of aliphatic diamine furandicarboxylic acid salt.
FIG. 3 is an X-ray powder diffraction pattern of an aliphatic diamine furandicarboxylic acid salt six crystal structure.
FIG. 4 is a six TGA-DSC plot of aliphatic diamine furandicarboxylic acid salts.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The detection method and instrument of the PAnF salt crystal structure are as follows:
single crystal X-ray diffraction measurement crystal structure and analytical method: taking the cultured aliphatic diamine furan diformate monocrystal with better quality, cutting into blocks, passing through a Bruker SMART APEX monocrystal diffractometer Mo K alpha radioactive source (graphite monochromator,the sample was irradiated and diffraction data collected. The single crystal data was resolved by direct method in SHELXL and at F by full matrix least squares 2 And finishing. Data were processed using PLATON, MERCURY 3.6 for crystal structure visualization.
Powder X-ray diffraction: grinding the sample with agate mortar for about two minutes, collecting diffraction data at room temperature by powder X-ray diffractometer (Bruker D8 Advance), and collecting diffraction data with light source of Cu K alpha ray wavelength of Tube pressure 50kV, tube flow 50mA, scanning speed 10 DEG/min, scanning range 2 theta: 5 DEG to 40 DEG, the data are processed by JADE software and the origin software is plotted.
Thermogravimetric analysis and differential scanning calorimetry (TGA-DSC): thermodynamic performance analysis was performed on the resulting crystal product of biobased nylon nF salt monomer using the Mettler TGA/DSC 3+ combination in switzerland. The testing method comprises the following steps: accurately weighing 5-10mg of the sample, placing in a sealed crucible tray, selecting nitrogen as atmosphere, heating to 350 ℃ from room temperature under the condition of 5 ℃/min heating rate under nitrogen purging (the rate is 50 ml/min), and plotting by origin software.
The bulk density and tap density are amounts related to the powder properties. In general, it is desirable that the tap/bulk density is close to 1. Bulk density refers to the weight per volume of powder under predetermined conditions, expressed as weight per volume unit, typically in g/mL. Tap density also indicates the weight per volume of powder, in the holder of which the powder is subjected to beating or vibration under predetermined conditions. Thus, for the same powder, its tap density is higher than the bulk density. The crystal with large bulk density and tap density has larger specific gravity, can reflect that the crystal product is thicker and has texture, and has relatively better stability; from another point of view, products with a high bulk density generally have better flowability of the granules and are also easy to store and transport.
Specifically, the method for measuring the bulk density and the tap density of the crystalline powder is as follows:
bulk density of particles was measured according to USP method II (page 1914);
the tap density of the particles was determined by means of an FZS4-4 economical tap densitometer according to GB/T5162-2006. Specifically, the test conditions were: the vibration stroke of the beating device was 3.+ -. 0.1MM and the vibration frequency was 250.+ -.15 times per minute.
Wherein the crystalline powder of the aliphatic diamine furan diformate is white or yellowish.
The solid or solid powder according to the present invention is an aggregated state of matter, including amorphous and crystalline.
The crystalline powder according to the present invention means a powder having a certain crystallinity, as opposed to an amorphous form.
The crystal is solid with definite diffraction pattern for X-ray, and its atoms or molecules are repeatedly arranged in space according to a certain regular period.
Example 1:
1.0g (10 mmol) of pentanediamine and 1.6g of furandicarboxylic acid (10 mmol) were weighed and placed in an agate mortar, 1ml of methanol was added before grinding, grinding was performed at 30℃to 40℃for 20 minutes, and then standing and drying were performed in an oven at 40℃for 24 hours, whereby 1.5g of PA5F salt powder was obtained.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter is α＝90°，β＝100.022(2)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, and in its smallest asymmetric unit, contains 1 pentanediamine cation and 1 furandicarboxylic acid anion, and the crystal structure information is shown in table 1 below. The results of TGA and DSC analysis are shown in fig. 4, and there is an endothermic characteristic peak at 186.8 ℃ on the DSC curve, corresponding to the melting point of PA5F salt crystal, and an endothermic characteristic peak at 262.2 ℃ corresponding to the decomposition point of the crystal, indicating that the crystal has good stability. The bulk density of the obtained PA5F salt crystals was 0.49g/cm 3 Tap density of 0.66g/cm 3 . The powder X-ray diffraction pattern is shown in figure 3, and is expressed as diffraction angle 2 theta + -0.1.
TABLE 2X-ray powder diffraction characteristic lines of PA5F salt crystals
Example 2:
2.6g (25 mmol) of pentanediamine and 3.1g (20 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSPRP-24L), 0.5ml of water is added before grinding, 70HZ of power is carried out at 30-40 ℃, 70S is operated, 20S is stopped, the steps are repeated for 25 times, and then the mixture is placed in a baking oven at 40 ℃ for standing and drying for 24 hours, so that 3.9g of PA5F salt powder is obtained.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter isα＝90°，β＝100.022(2)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, in its smallest asymmetric unit, contains 1 pentanediamine cation and 1 furandicarboxylic acid anion. The bulk density of the obtained PA5F salt crystals was 0.52g/cm 3 Tap density of 0.71g/cm 3 。
Example 3:
2.6g (25 mmol) of pentanediamine and 3.1g (20 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSPRP-24L), 0.5ml of water and 0.5ml of ethanol are added before grinding, the operation is carried out at the power of 70HZ at the temperature of 30-40 ℃, the operation is carried out for 70S, the operation is stopped for 20S, the operation is repeated for 15 times, and then the operation is carried out for 24h in a baking oven at the temperature of 40 ℃ to obtain 4g of PA5F salt powder.
Example 4:
1.7g (15 mmol) of hexamethylenediamine and 2.6g (17 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSPRP-24L), 1ml of ethanol is added before grinding, the operation is carried out for 60S under the condition of 35-45 ℃ and the power is 60HZ, the operation is stopped for 15S, the operation is repeated for 20 times, and then the mixture is placed in a baking oven at 40 ℃ for 12h for standing and drying, so that 3.4g of PA6F salt powder is obtained.
The crystal structure belongs to monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝108.538(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, and in its smallest asymmetric unit, contains 1 hexamethylenediamine cation and 1 furandicarboxylic acid anion, and the crystal structure information is shown in the attached table 1. The TGA and DSC analysis results are shown in fig. 4, and there is a step of weight loss at 264.2 ℃, corresponding to the decomposition point of the crystal, indicating that the crystal has good stability. The bulk density of the obtained PA6F salt crystals was 0.82g/cm 3 Tap density of 0.89g/cm 3 . The powder X-ray diffraction pattern is shown in figure 3, and is expressed as diffraction angle 2 theta + -0.1.
TABLE 3X-ray powder diffraction characteristic lines of PA6F salt crystals
Example 5:
1.2g (10 mmol) of hexamethylenediamine and 1.6g (10 mmol) of furandicarboxylic acid were weighed and placed in an agate mortar, and the mixture was ground for 50min at 35℃to 45℃without adding a solvent during the grinding to obtain 1.4g of PA6F salt powder.
The crystal structure belongs to monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝108.538(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 hexamethylenediamine cation and 1 furandicarboxylic acid anion. The obtained PA6F salt crystalBulk density of the body was 0.84g/cm 3 Tap density of 0.88g/cm 3 。
Example 6:
1.7g (15 mmol) of hexamethylenediamine and 2.6g (17 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSPRP-24L), 0.8ml of ethyl acetate is added before grinding, the operation is carried out for 60S under the condition of 35-45 ℃ and the power is 60HZ, the operation is stopped for 15S, the operation is repeated for 10 times, and then the mixture is placed in a baking oven at 40 ℃ for 12h for standing and drying, so as to obtain 3.7g of PA6F salt powder.
The crystal structure belongs to monoclinic system, P2 1 Space group/c, unit cell parameters are α＝90°，β＝108.538(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, and in its smallest asymmetric unit, contains 1 hexamethylenediamine cation and 1 furandicarboxylic acid anion, and the crystal structure information is shown in the attached table 1.
Example 6-1
As in example 6, after the milling temperature was modified to 0-10deg.C, other conditions were identical and no PA6F salt material was found after comparison of the PXRD patterns of the resulting product.
Example 7:
1.6g (12 mmol) of pimelin and 1.9g (12 mmol) of furandicarboxylic acid were weighed, placed in an agate mortar, 1ml of DMSO was added before grinding, grinding was performed at 10℃to 20℃for 25 minutes, and then, standing and drying were performed in a vacuum drying oven at 40℃for 24 hours, whereby 2.1g of PA7F salt powder was obtained.
The crystal structure belongs to monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝105.896(3)°，/>Gamma=90°, unit cell volume->The number of molecules in the unit cell z=4, and in its smallest asymmetric unit, it contains 1 heptadiamine cation and 1 furandicarboxylic acid anion, and the information of the crystal structure is shown in the attached table 1. The results of TGA and DSC analysis are shown in fig. 4, and there is an endothermic characteristic peak at 203 ℃ on the DSC curve, corresponding to the melting point of PA7F salt crystal, and an endothermic characteristic peak at 270.8 ℃ corresponding to the decomposition point of the crystal, indicating that the crystal has good stability. The bulk density of the obtained PA7F salt crystals was 0.47g/cm 3 Tap density of 0.53g/cm 3 . The powder X-ray diffraction pattern is shown in figure 3, and is expressed as diffraction angle 2 theta + -0.1.
TABLE 4X-ray powder diffraction characteristic lines of PA7F salt crystals
Example 8:
1.6g (12 mmol) of pimelin and 2.5g (16 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSTPRP-24L), 1.2ml of methanol is added in the grinding process, the operation is carried out for 40S under the condition of 10-20 ℃ and 65HZ of power, the operation is stopped for 10S, the operation is repeated for 30 times, and then the mixture is placed in a vacuum drying oven at 40 ℃ for standing and drying for 24 hours, so as to obtain 3g of PA7F salt powder.
The crystal structure belongs to monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝105.896(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 heptadiamine cation and 1 furandicarboxylic acid anion. The bulk density of the obtained PA7F salt crystals was 0.58g/cm 3 Tap density of 0.62g/cm 3 。
Example 9:
1.6g (12 mmol) of pimelin and 2.5g (16 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSTPRP-24L), 1ml of acetone is added in the grinding process, the operation is carried out for 40S under the condition of 10-20 ℃ and the power is 65HZ, the operation is stopped for 10S, the operation is repeated for 20 times, and then the mixture is placed in a vacuum drying oven at 40 ℃ for standing and drying for 24 hours, so that 3.2g of PA7F salt powder is obtained.
The crystal structure belongs to monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝105.896(3)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 heptadiamine cation and 1 furandicarboxylic acid anion.
Example 9-1
As in example 9, the grinding temperature was modified to 30-40℃and the other conditions were identical, and the PXRD patterns of the resulting product were compared and no PA7F salt species were found.
Example 10:
1.9g (13 mmol) of octanediamine and 2g (13 mmol) of furandicarboxylic acid were weighed and placed in an agate mortar, 1ml of acetonitrile was added before grinding, grinding was performed at 0℃to 10℃for 18 minutes, and then standing and drying were performed in an oven at 40℃for 12 hours, whereby 1.9g of PA8F salt powder was obtained.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter isα＝90°，β＝127.238(6)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, and in its smallest asymmetric unit, contains 0.5 octanediamine cations and 0.5 furandicarboxylic acid anions, and the crystal structure information is shown in table 1 below. The TGA and DSC analysis results are shown in fig. 4, where two endothermic peaks appear consecutively from 243.1 ℃ on the DSC curve with a loss of weight phenomenon on the TGA curve, indicating that melting and decomposition simultaneously occur at this time. The bulk density of the obtained PA8F salt crystals was 0.25g/cm 3 Tap density of 0.3g/cm 3 . The powder X-ray diffraction pattern is shown in figure 3, and is expressed as diffraction angle 2 theta + -0.1.
TABLE 5X-ray powder diffraction characteristic lines of PA8F salt crystals
Example 11:
2g (14 mmol) of subelamine and 1.6g (10 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSTPRP-24L), 1ml of isopropanol is added in the grinding process, the operation is carried out for 50S at the power of 50HZ at the temperature of 0-10 ℃, the operation is stopped for 15S, the operation is repeated for 10 times, and then the mixture is placed in a baking oven at the temperature of 40 ℃ for 12h for drying, so that 2.5g of PA8F salt is obtained.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter isα＝90°，β＝127.238(6)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 0.5 octanediamine cations and 0.5 furandicarboxylic acid anions. The bulk density of the obtained PA8F salt crystals was 0.38g/cm 3 Tap density of 0.44g/cm 3 。
Example 12:
2g (14 mmol) of subelamine and 1.6g (10 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSTPRP-24L), 1ml of petroleum ether is added in the grinding process, the operation is carried out for 50S at the power of 50HZ under the condition of 0-10 ℃, the operation is stopped for 15S, the operation is repeated for 15 times, and then the mixture is placed in a baking oven at the temperature of 40 ℃ for 12h for drying, so that 2.6g of PA8F salt powder is obtained.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter isα＝90°，β＝127.238(6)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 0.5 octanediamine cations and 0.5 furandicarboxylic acid anions.
Example 12-1
As in example 12, the milling temperature was modified to 15-25℃and the other conditions were identical, and the PXRD patterns of the resulting product were compared and no PA8F salt species were found.
Example 13:
2.4g (15 mmol) of nonylenediamine and 2.3g (15 mmol) of furandicarboxylic acid are weighed, placed in an agate mortar, 2ml of acetonitrile is added before grinding, grinding is carried out for 30min at 25-35 ℃, and then standing and drying are carried out for 24h in a vacuum drying oven at 40 ℃ to obtain 3g of PA9F salt powder.
The crystal structure belongs to monoclinic system, cc space group and unit cell parameter isα＝90°， β＝108.924(3)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, and in its smallest asymmetric unit, contains 4 nonanediamine cations and 4 furandicarboxylic acid anions, and the crystal structure information is shown in table 1 below. The TGA and DSC analysis results are shown in fig. 4, and there is an endothermic characteristic peak at 212.5 ℃ on the DSC curve, corresponding to the melting point of PA9F salt crystal, and an endothermic characteristic peak at 281.9 ℃ corresponding to the decomposition point of the crystal, and the crystal has good stability. The bulk density of the obtained PA9F salt crystals was 0.49g/cm 3 Tap density of 0.55g/cm 3 . The powder X-ray diffraction pattern is shown in figure 3, and comprises diffraction angles2θ±0.1 is expressed as follows.
TABLE 6X-ray powder diffraction characteristic lines of PA9F salt crystals
Example 14:
2.4g (15 mmol) of nonanediamine and 1.9g (12 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSTPRP-24L), 1ml of ethanol is added in the grinding process, the operation is carried out for 60S under the condition of 25-35 ℃ and 70HZ of power, 10S is stopped, the operation is repeated for 25 times, and then the mixture is placed in a vacuum drying oven at 40 ℃ for standing and drying for 24 hours, so that 3.5g of PA9F salt powder is obtained.
The crystal structure belongs to monoclinic system, cc space group and unit cell parameter isα＝90°，/>/>β＝108.924(3)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, in its smallest asymmetric unit, contains 4 nonanediamine cations and 4 furandicarboxylic acid anions. The bulk density of the obtained PA9F salt crystals was 0.60g/cm 3 Tap density of 0.66g/cm 3 。
Example 15:
2.4g (15 mmol) of nonanediamine and 1.9g (12 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSTPRP-24L), 0.5ml of dimethyl sulfoxide is added in the grinding process, the operation is carried out for 60 seconds under the condition of 25-35 ℃ and 70HZ of power, 10 seconds are stopped, 15 times are repeated, and then the mixture is placed in a vacuum drying oven at 40 ℃ for standing and drying for 24 hours, so that 3.7g of PA9F salt powder is obtained.
The crystal structure belongs to monoclinic system, cc space group and unit cell parameter isα＝90°，/> β＝108.924(3)°，/>Gamma=90°, unit cell volume->Z=1 in the unit cell, in its smallest asymmetric unit, contains 4 nonanediamine cations and 4 furandicarboxylic acid anions.
Example 15-1
As in example 15, the milling temperature was modified to 0-20deg.C, the other conditions were identical, and no PA9F salt species were found after comparison of the PXRD patterns of the resulting product.
Example 16:
2.7g (16 mmol) of decamethylene diamine and 2.5g (16 mmol) of furandicarboxylic acid are weighed, placed in an agate mortar, 1.5ml of acetonitrile is added in the grinding process, the mixture is ground for 30min at the temperature of 5-15 ℃, and then the mixture is kept stand and dried for 12h in a baking oven at the temperature of 40 ℃ to obtain 3.6g of PA10F salt powder.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter isα＝90°，/> β＝124.338(6)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, and in its smallest asymmetric unit, contains 0.5 decamethylene diamine cations and 0.5 furandicarboxylic acid anions, and the crystal structure information is shown in table 1 below. The TGA and DSC analysis results are shown in fig. 4, and on the DSC curve, there is an endothermic characteristic peak at 235.3 ℃, corresponding to the melting point of PA10F salt crystal, and there is an endothermic characteristic peak at 270.4 ℃, corresponding to the decomposition point of the crystal, indicating that the crystal has good stability. The bulk density of the obtained PA10F salt crystals was 0.53g/cm 3 Tap density of 0.74g/cm 3 . The powder X-ray diffraction pattern is shown in figure 3, and is expressed as diffraction angle 2 theta + -0.1.
TABLE 7X-ray powder diffraction characteristic lines of PA10F salt crystals
Example 17:
1.7g (10 mmol) of decamethylene diamine and 2.0g (13 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSPRP-24L), 1.5ml of ethanol is put before grinding, the operation is carried out for 60S under the condition of 5-15 ℃ and 70HZ of power, the operation is stopped for 20S and repeated for 25 times, and then the mixture is placed in a baking oven at 40 ℃ for 12h for standing and drying, so as to obtain 2.5g of PA10F salt powder.
The crystal structure belongs to monoclinic system, the space group of C2/C is C2/C, and the unit cell parameter isα＝90°，/> β＝124.338(6)°，/>Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 0.5 decamethylene diamine cations and 0.5 furandicarboxylic acid anions. The bulk density of the obtained PA10F salt crystals was 0.6g/cm 3 Tap density of 0.78g/cm 3 。
Example 18:
1.7g (10 mmol) of decamethylene diamine and 2.0g (13 mmol) of furandicarboxylic acid are weighed and placed in a full-automatic sample rapid grinding instrument-24L (Jingxin JXFSPRP-24L), 0.5ml of ethyl acetate is used before grinding, the operation is carried out for 60S under the condition of 5-15 ℃ and 70HZ of power, the operation is stopped for 20S, the operation is repeated for 19 times, and then the mixture is placed in a baking oven at 40 ℃ for 12h for standing and drying, so that 2.7g of PA10F salt powder is obtained.
Comparative example 1:
the preparation method refers to example 1 in patent CN112111058A, 2, 5-furandicarboxylic acid and 1, 6-hexamethylenediamine are respectively dissolved in absolute ethanol according to the mol ratio of 1:1, then 1, 6-hexamethylenediamine solution is slowly poured into 2, 5-furandicarboxylic acid solution, the reaction temperature is 50 ℃ under the condition of nitrogen protection and magnetic stirring, precipitation is generated in water bath reaction for 12 hours, and the precipitate is cooled, filtered and dried in vacuum for 12 hours to obtain composite salt; the resulting complex salt was white powder. Tested to have a bulk density of 0.51g/cm 3 Tap density of 0.64g/cm 3 The whole crystal has finer particles and weak texture.
Comparative example 2:
preparation method referring to example 2 in patent CN111925521a, air in a stainless steel salifying reaction kettle is replaced three times by vacuumizing and introducing nitrogen, 1mol of bio-based monomer 2, 5-furandicarboxylic acid, 1.10mol of bio-based monomer 1, 5-pentanediamine, 536mg of phosphorous acid catalyst and 500mL of ethanol are added into the salifying reaction kettle under the protection of nitrogen to obtain a mixture; stirring to mix the above mixtureThe stirring speed was set at 350rpm, the mixture was heated to 72℃under normal pressure, and reacted for 75 minutes, after the completion of the reaction, the pH of the solution was 7.4, thereby obtaining a solution of pentamethylenediamine furandicarboxylic acid salt having a mass fraction of 38%. Evaporating and crystallizing in a 40 deg.C oven to obtain solid powder, and testing the bulk density of the material to be 0.23g/cm 3 Tap density of 0.39g/cm 3 。
Comparative example 3:
preparation method referring to example 7 in patent CN111925521a, air in a stainless steel salifying reaction kettle is replaced three times by vacuumizing and introducing nitrogen, 1mol of bio-based monomer 2, 5-furandicarboxylic acid, 1.0mol of bio-based monomer 1, 10-decanediamine, 32.8mg of phosphorous acid catalyst and 400mL of dimethylformamide are added into the salifying reaction kettle under the protection of nitrogen to obtain a mixture; stirring is started to uniformly mix the mixture, the stirring rotating speed is set to 500rpm, the mixture is heated to 120 ℃ under normal pressure, the reaction is carried out for 140min, cooling precipitation is carried out after the reaction is finished, centrifugal separation is carried out, and the obtained precipitate is washed with dimethylformamide and deionized water for several times, so that the furandicarboxylic acid sebacamide salt is obtained. Tested to have a bulk density of 0.29g/cm 3 Tap density of 0.37g/cm 3 The particles of the whole crystal are finer.
The results of experiments were carried out to test the humidity stability of PA5F salt, PA6F salt, PA7F salt, PA8F salt, PA9F salt and PA10F salt and the products of comparative examples 1, 2, 3 under conditions that the relative humidity was 98%, 76%, 67%, 43%, 32% and 0%, respectively, and are shown in table 8. Under the high humidity condition with the relative humidity of 98%, a plurality of crystals show certain moisture absorption behavior, and compared with the comparative example product, the three crystal products prepared by the method have better humidity stability.
TABLE 8 humidity stability experiment
0％ 32％ 43％ 67％ 76％ 98％
PA5F salt 0％ 0％ 0％ 0％ 48.5％ 250.1％
PA6F salt 0％ 0％ 0％ 13％ - -
PA7F salt 0％ 0％ 0％ 0％ 0％ 117.4％
PA8F salt 0％ 0％ 0％ 0％ 0％ 148.7％
PA9F salt 0％ 0％ 0％ 0％ 0％ 151.5％
PA10F salt 0％ 0％ 0％ 0％ 20.8％ 180.1％
Comparative example 1 0％ 0％ 0％ 18％ - -
Comparative example 2 0％ 0％ 0％ 16.5％ 70.3％ 294.5％
Comparative example 3 0％ 0％ 0％ 0％ 6.1％ 205.4％
The invention provides a green and environment-friendly method for preparing a bio-based nylon nF material monomer, a series of aliphatic diamine furan diformate and a crystal structure thereof. Compared with the traditional anti-solvent and cooling crystallization method, the method prepares the diamine and the diacid into salt form in a grinding mode, the product is presented in a crystal mode with the same mole ratio of aliphatic diamine to furandicarboxylic acid, the volatilization loss of amine in the polymerization process is reduced, and the mole ratio of raw materials is ensured. The product is more stable, can be directly used for polymerization, and has advantages in transportation, use, storage and quality.
The method and means for implementing the technical solution are numerous, the above description is only a preferred embodiment of the present invention, it should be noted that, for a person skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. The components not explicitly described in this embodiment can be implemented by using the prior art.

Claims (15)

1. An aliphatic diamine furan diformate is characterized by having a structure shown in a formula I;
n is selected from any integer from 6 to 9;
the tap density/bulk density of the aliphatic diamine furan diformate is 1.0-1.25, preferably 1.05-1.20.
2. Aliphatic diamine furandicarboxylate according to claim 1, characterized in that when n=6, the diamine furandicarboxylate is hexamethylenediamine furandicarboxylate, the crystal structure of which belongs to the monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，/>β＝108.538(3)°，Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 hexamethylenediamine cation and 1 furandicarboxylic acid anion.
3. Aliphatic diamine furandicarboxylic acid salt according to claim 2, characterized in that it has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA6F salt curve in fig. 3.
4. Aliphatic diamine furandicarboxylate according to claim 1, characterized in that when n=7, the diamine furandicarboxylate is pimediamine furandicarboxylate, the crystal structure of which belongs to the monoclinic system, P2 1 Space group/c, unit cell parameters are α＝90°，/>β＝105.896(3)°，Gamma=90°, unit cell volume->Z=4 in the unit cell, in its smallest asymmetric unit, contains 1 heptadiamine cation and 1 furandicarboxylic acid anion.
5. The aliphatic diamine furandicarboxylic acid salt according to claim 4, wherein the pimediamine furandicarboxylic acid salt has a diffraction pattern which is obtained by diffraction analysis using cukα rays as characteristic X-rays as shown in PA7F salt curve in fig. 3.
6. Aliphatic diamine furandicarboxylate according to claim 1, characterized in that when n=8, the diamine furandicarboxylate is octanediamine furandicarboxylate, the crystal structure of which belongs to the monoclinic system, the C2/C space group, the unit cell parameters areα＝90°，/>β＝127.238(6)°，Gamma=90°, unit cell volume->Z=4 in unit cell, at its minimumThe symmetrical units contained 0.5 octanediamine cations and 0.5 furandicarboxylic acid anions.
7. The aliphatic diamine furandicarboxylic acid salt according to claim 6, wherein the octanediamine furandicarboxylic acid salt has a diffraction pattern which is diffraction-analyzed using cukα rays as characteristic X-rays as shown in the PA8F salt curve of fig. 3.
8. Aliphatic diamine furandicarboxylate according to claim 1, characterized in that when n=9, the diamine furandicarboxylate is nonanediamine furandicarboxylate, the crystal structure of which belongs to the monoclinic system, the Cc space group, the unit cell parameters are α＝90°，/>β＝108.924(3)°，Gamma=90°, unit cell volume->Z=1 in the unit cell, in its smallest asymmetric unit, contains 4 nonanediamine cations and 4 furandicarboxylic acid anions.
9. Aliphatic diamine furandicarboxylic acid salt according to claim 10, characterized in that it has a diffraction pattern for diffraction analysis using cukα rays as characteristic X-rays as shown in the PA9F salt curve in fig. 3.
10. The preparation method of the aliphatic diamine furandicarboxylic acid shown in the formula I is characterized by comprising the steps of grinding a mixture containing aliphatic diamine and furandicarboxylic acid, and grinding and crystallizing the mixture to obtain the aliphatic diamine furandicarboxylic acid;
separating salt from the mixture, and drying to obtain the product;
n is selected from any integer from 5 to 10.
11. The method of claim 10, wherein the milling is performed at a temperature of 0-45 ℃; preferably, in the preparation of the glutarimfuran diformate, the milling temperature is 30-40 ℃; preferably, in the preparation of hexamethylenediamine furandicarboxylate, the milling temperature is between 35 and 45 ℃; preferably, in the preparation of pimediamine furandicarboxylate, the milling temperature is 10-20 ℃; preferably, in the preparation of the octanediamine furandicarboxylate, the milling temperature is 0-10 ℃; preferably, in the preparation of the nonanediamine furandicarboxylate, the milling temperature is 25-35 ℃; preferably, the milling temperature is 5-15 ℃ when preparing decamethylene diamine furandicarboxylic acid salt.
12. The method of claim 10, wherein the grinding is performed in any of the following ways:
(i) Directly grinding furan dicarboxylic acid and aliphatic diamine;
(ii) Grinding furan dicarboxylic acid, aliphatic diamine and a solvent;
preferably, in the mode (ii), the solvent is added according to any one of the following modes:
(ii-1) adding a solvent to a mixture of furandicarboxylic acid and an aliphatic diamine at one time before milling; (ii-2) adding a solvent during milling of the furandicarboxylic acid and the aliphatic diamine;
(ii-3) adding a part of the solvent to the mixture of furandicarboxylic acid and aliphatic diamine for grinding before grinding, and adding the rest of the solvent during grinding;
further preferably, in the mode (ii), the solvent is added in the mode described in (ii-2) or (ii-3).
13. The process according to claim 12, wherein the ratio of aliphatic diamine to solvent is from 10 to 20mmol:0-3mL, preferably 10-20mmol:0.5-3mL.
14. The preparation method according to claim 12, wherein the solvent is any one or more of methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, ethyl formate, methyl acetate, butyl acetate, acetone, butanone, petroleum ether, tetrahydrofuran and dimethyl sulfoxide, or a mixed solvent of any one or more of the foregoing with water.
15. The process according to claim 14, wherein in the preparation of the glutarimfuran diformate, the solvent is a mixed solution of water and ethanol, preferably the volume ratio of water to ethanol is 1:0.5-1.5, preferably 1:1; preferably, in the preparation of hexamethylenediamine furandicarboxylate, the solvent is ethyl acetate; preferably, in the preparation of pimediamine furandicarboxylate, the solvent is a ketone compound, preferably acetone; preferably, in the preparation of the octanediamine furandicarboxylate, the solvent is an alcohol compound, preferably isopropanol; preferably, in the preparation of the nonanediamine furandicarboxylate, the solvent is dimethyl sulfoxide; preferably, in the preparation of decamethylene diamine furandicarboxylate, the solvent is ethyl acetate.
CN202310873748.1A 2023-07-17 2023-07-17 Aliphatic diamine furan diformate and crystal thereof Pending CN116874451A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310873748.1A CN116874451A (en) 2023-07-17 2023-07-17 Aliphatic diamine furan diformate and crystal thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310873748.1A CN116874451A (en) 2023-07-17 2023-07-17 Aliphatic diamine furan diformate and crystal thereof

Publications (1)

Publication Number Publication Date
CN116874451A true CN116874451A (en) 2023-10-13

Family

ID=88258306

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310873748.1A Pending CN116874451A (en) 2023-07-17 2023-07-17 Aliphatic diamine furan diformate and crystal thereof

Country Status (1)

Country Link
CN (1) CN116874451A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456804A (en) * 2007-12-14 2009-06-17 金发科技股份有限公司 Method for preparing semi-aromatic nylon salt
CN109575276A (en) * 2018-12-06 2019-04-05 浙江新力新材料股份有限公司 A kind of preparation method of high temperature resistant nylon
CN111925521A (en) * 2019-05-13 2020-11-13 中国石油天然气股份有限公司 Full-bio-based polyamide and preparation method thereof
CN112111058A (en) * 2020-10-16 2020-12-22 天津工业大学 Preparation method of furan dicarboxylic acid diamine high polymer
CN114437005A (en) * 2022-03-14 2022-05-06 郑州大学 Butanediamine furan diformate and crystal thereof
CN116622065A (en) * 2023-06-05 2023-08-22 中科国生(泰兴)新材料科技有限公司 Bio-based nylon containing furan ring structure and preparation method thereof
CN116693477A (en) * 2023-06-05 2023-09-05 中科国生(泰兴)新材料科技有限公司 Furanyl nylon salt and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456804A (en) * 2007-12-14 2009-06-17 金发科技股份有限公司 Method for preparing semi-aromatic nylon salt
CN109575276A (en) * 2018-12-06 2019-04-05 浙江新力新材料股份有限公司 A kind of preparation method of high temperature resistant nylon
CN111925521A (en) * 2019-05-13 2020-11-13 中国石油天然气股份有限公司 Full-bio-based polyamide and preparation method thereof
CN112111058A (en) * 2020-10-16 2020-12-22 天津工业大学 Preparation method of furan dicarboxylic acid diamine high polymer
CN114437005A (en) * 2022-03-14 2022-05-06 郑州大学 Butanediamine furan diformate and crystal thereof
CN116622065A (en) * 2023-06-05 2023-08-22 中科国生(泰兴)新材料科技有限公司 Bio-based nylon containing furan ring structure and preparation method thereof
CN116693477A (en) * 2023-06-05 2023-09-05 中科国生(泰兴)新材料科技有限公司 Furanyl nylon salt and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王莹莹: "生物基呋喃二甲酸系列尼龙盐晶体结构、结晶热力学及晶型转化研究", 《郑州大学专业硕士学位论文》, 17 May 2023 (2023-05-17), pages 15 - 16 *

Similar Documents

Publication Publication Date Title
CN109265353B (en) Pentanediamine dodecanedioic acid salt and crystal thereof
Yang et al. Crystal structure, thermodynamics, and crystallization of bio-based polyamide 56 salt
WO2019196132A1 (en) Pentanediamine sebacate salt and crystal thereof
Al Abbas et al. Bolaamphiphilic liquid crystals based on bis-imidazolium cations
CN107353198B (en) Pentanediamine adipate and crystal thereof
CN104003926B (en) Based on the side chain type magnetic monomer of alkylammonium salt, polymer and its preparation method and application
CN116874451A (en) Aliphatic diamine furan diformate and crystal thereof
CN114437005B (en) Butanediamine furan diformate and crystal thereof
CN110950977B (en) Acylphosphine oxide photoinitiator and synthesis method thereof
CN109180494B (en) Pentanediamine succinate and crystal thereof
TW201900721A (en) Polyester production method
CN100374448C (en) Diene silicoxyane linking disbenzocyclobutylene monomer and process for preparing prepolymer
CN111087295B (en) Pentanediamine succinic acid terephthalic acid eutectic salt and preparation method thereof
CN109265354B (en) Pentanediamine oxalate and crystal thereof
CN111138423B (en) Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof
CN114479112B (en) Dendritic eosin B-iodonium salt visible light initiator and preparation method and application thereof
CN114478845B (en) Dendritic fluorescein sodium-iodonium salt visible light initiator and preparation method and application thereof
CN115894250B (en) Nylon 513 salt crystal and preparation method thereof
CN100506857C (en) Process for preparing diene radical siloxane bridge-linked double benzocyclobutene prepolymer
CN109384805A (en) A kind of cadmium (II) Inorganic-Organic Hybrid Material and preparation method thereof
JP6021002B2 (en) Polyetherketone and method for producing the same
JP4109127B2 (en) Polymer compound having highly branched structure and monomer compound thereof
JP2004262822A (en) Carix resorcinol arene derivative, its production method, refractive index conversion material, and light and heat energy conversion and storage material
CN110724276B (en) Preparation method of acid-alkali difunctional MOFs material and method for synthesizing 3, 4-dimethylfurazan by using acid-alkali difunctional MOFs material as catalyst
Shahni Synthesis Of A Gemini Monomer And Cyclobutane-Containing Bifunctional Building Blocks For Novel Materials

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination