CN108586265A - Pentanediamine sebacate and its crystal - Google Patents
Pentanediamine sebacate and its crystal Download PDFInfo
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- CN108586265A CN108586265A CN201810335906.7A CN201810335906A CN108586265A CN 108586265 A CN108586265 A CN 108586265A CN 201810335906 A CN201810335906 A CN 201810335906A CN 108586265 A CN108586265 A CN 108586265A
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- China
- Prior art keywords
- pentanediamine
- crystal
- decanedioic acid
- sebacate
- solution
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- 239000013078 crystal Substances 0.000 title claims abstract description 61
- YDCMTALHFLXJKA-UHFFFAOYSA-N C(CCCC)(N)N.C(CCCCCCCCC(=O)O)(=O)O Chemical compound C(CCCC)(N)N.C(CCCCCCCCC(=O)O)(=O)O YDCMTALHFLXJKA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 104
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920000305 Nylon 6,10 Polymers 0.000 claims abstract description 50
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- -1 pentanediamine cation Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002050 diffraction method Methods 0.000 claims description 2
- 230000005260 alpha ray Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 12
- 239000004677 Nylon Substances 0.000 description 11
- 229920001778 nylon Polymers 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 238000002447 crystallographic data Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IKIPCACNAHPXLR-UHFFFAOYSA-N CO.C(CCCC)(N)N Chemical compound CO.C(CCCC)(N)N IKIPCACNAHPXLR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ATXOMFZAMMBNFU-UHFFFAOYSA-N decanedioic acid ethanol Chemical compound C(C)O.C(CCCCCCCCC(=O)O)(=O)O ATXOMFZAMMBNFU-UHFFFAOYSA-N 0.000 description 2
- AARROMHWSQDDKO-UHFFFAOYSA-N decanedioic acid;pentane-1,5-diamine Chemical compound NCCCCCN.OC(=O)CCCCCCCCC(O)=O AARROMHWSQDDKO-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- OKMZYAZKTBCUNV-UHFFFAOYSA-N C(C)(=O)O.C(CCCC)(N)N Chemical compound C(C)(=O)O.C(CCCC)(N)N OKMZYAZKTBCUNV-UHFFFAOYSA-N 0.000 description 1
- ADGSRMQISKJODI-UHFFFAOYSA-N CC(CC)=O.C(CCCC)(N)N Chemical compound CC(CC)=O.C(CCCC)(N)N ADGSRMQISKJODI-UHFFFAOYSA-N 0.000 description 1
- XCPVUZPDYFWCHY-UHFFFAOYSA-N CO.C(CCCCCCCCC(=O)O)(=O)O Chemical compound CO.C(CCCCCCCCC(=O)O)(=O)O XCPVUZPDYFWCHY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/20—Sebacic acid
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses pentanediamine sebacate and its crystal, and preparation method thereof.The pentanediamine sebacate is the salt that solid state is presented under the room temperature that pentanediamine bivalent cation is combined into decanedioic acid dianion in such a way that molar ratio is 1: 1.Its crystal structure is C11H24N2O4, monoclinic system, C2 space groups, β=92.394 (2) °, unit cell volume
Description
Technical field
The invention belongs to crystallization technique fields, specifically, being the monomer pentanediamine decanedioic acid for being related to biology base nylon 510
Salt and its crystal structure and its crystalline powder, with and preparation method thereof.
Background technology
Polyamide is excellent due to having good mechanical property, heat resistance, wear resistance, chemical resistance, self-lubricating etc.
Point ranks first of five large-engineering plastics, is widely used in aviation field, packaging material, field of textiles, household electrical appliance, auto parts
The fields such as manufacture and medical treatment.Currently, principal item is polyamide 6 and polyamide 66.Wherein, the monomer of polyamide 6 is crystallization
Property powder caprolactam, the monomer of polyamide 66 is hexamethylene diamine crystalline adipic acid salt body.Polyamide 6 and polyamide 66 are with stone
Oil is that raw material is produced using chemical method.In recent years, the domestic bioanalysis technology of preparing about pentanediamine was increasingly ripe
(CN201610317272.3), the innovation (CN201420807159.X) of especially downstream separation purification technique is so that pentanediamine
Production cost significantly decline, come at present commercial running the popularization and application stage.Nylon 510 is by pentanediamine and decanedioic acid
It is polymerized under certain condition, there is excellent mechanical property.However, the polymerized monomer raw material about nylon 510 ---
Pentanediamine decanedioic acid crystal salt has not been reported, and the crystalline monomer salt of high-quality high-purity is the pass for obtaining high performance nylon 510
Key factor.
Invention content
Technical problem to be solved by the invention is to provide a kind of pentanediamine and decanedioic acid equimolar than high-purity penta
Diamines sebacate and its crystal, and one kind is provided, pentanediamine decanedioic acid is produced by pentanediamine and two component composition of decanedioic acid
The preparation process of crystal salt.Pentanediamine decanedioic acid crystalline salt produced by the present invention can be used as monomer, be directly used in nylon
510 polymerization.Polymerisation schematic diagram is as shown in formula III：
The invention is intended to provide a kind of monomer of 510 material of biology base nylon, pentanediamine sebacate and its crystal knot
Structure and its crystalline powder and preparation method.Need two components of pentanediamine and decanedioic acid that could carry out relative to traditional
510 polymerization technique of nylon, the product of this pentanediamine sebacate provided by the invention, is obtained by crystallization mode, product with
Pentanediamine and decanedioic acid equimolar than the mode of crystal present, be used directly for polymerizeing, there is stability in structure, change
It is good to learn purity height, graininess, it is advantageous in terms of transport, use, storage and quality.
The technical solution adopted by the present invention is as follows：
The invention discloses a kind of pentanediamine sebacate of solid state, also known as cadaverine sebacate, described penta 2
Amine sebacate is pentanediamine bivalent cation with decanedioic acid dianion be combined into such a way that molar ratio is 1: 1 it is normal
The lower salt that solid state is presented of temperature, molecular structure are shown in formula I：
The invention also discloses a kind of crystal of pentanediamine sebacate, the molecular formula is C15H32N2O4, without knot
Brilliant water, molecular structural formula is as shown in Formula II：
The detection method and instrument of the crystal structure of the pentanediamine sebacate of gained of the invention are as follows：
Monocrystalline X-ray diffraction measures crystal structure and analytic method：Take the preferable pentanediamine decanedioic acid of the quality turned out
Single-crystal of salt cuts into about 0.11 × 0.30 × 0.32mm3The bulk of size is put through Brooker APEX-II CCD diffractometer Mo K α
Penetrate source (graphite monochromator,) sample is irradiated, and collect diffraction data, diffraction data through SAINT into
Structure elucidation is carried out with SHELXL-97 softwares direct method after row reduction, and is based on F2Complete matrix least square method refine, own
Non-hydrogen atom pass through anisotropy refine.Final data is mapped by Mercury or Diamond softwares.It is of the present invention
The crystal structure of pentanediamine sebacate belongs to monoclinic system, C2 space groups, and cell parameter isβ=92.394 (2) °, unit cell volume Minimum asymmetric cell number Z=2 in structure cell contains 1 pentanediamine sun in its minimum asymmetric cell
Ion and 1 decanedioic acid anion.
Powder x-ray diffraction：Sample after grinding takes about 0.1g, passes through powder x-ray diffraction (Rigaku
Smartlab or Bruker D8 Advance) Diffraction Data Collection is carried out at room temperature, light source is CuK alpha rays Scanning step is 0.02 °, sets scanning voltage 40kV, electric current 40mA, and 0.2s/0.02 ° of sweep speed scans model
It is 5~50 ° to enclose 2 θ, and data are handled by JADE softwares and mapped.The crystal of pentanediamine sebacate of the present invention has such as
The diffracting spectrum shown in Fig. 4 for using CuK alpha rays to carry out diffraction analysis as characteristic X-ray.
The crystalline powder of above-mentioned pentanediamine sebacate, it is white.
The crystalline powder of above-mentioned Crystallization, have more than 0.22g/mL bulk density, preferably greater than 0.31g/mL, more
The preferably greater than bulk density of 0.41g/mL.
The crystalline powder of above-mentioned Crystallization, have more than 0.27g/mL tap density, preferably greater than 0.33g/mL, more
Preferably greater than 0.46g/mL.
The crystalline powder of above-mentioned Crystallization has the d more than 21 μm50, preferably greater than 30 μm, more preferably greater than 41 μm,
Most preferably greater than 55 μm of d50。
The crystalline powder of above-mentioned Crystallization has the d more than 8 μm10, preferably greater than 10 μm, more preferably greater than 12 μm,
Most preferably greater than 15 μm of d10。
D of the present invention50And d10It is used to indicate that the common amount of size distribution.The d50It is for granularity
Value so that the crystal of 50vol.% has the size less than this value.The d10It is the value for granularity so that 10vo1.%
Crystal have less than this value size.
The bulk density and tap density be and the relevant amount of the flow behavior of powder.Generally, it is desirable to high heap
Density and vibration density angle value.Heap density is pointed out to be expressed as usually with g/mL per the weight of volume unit powder in predefined conditions
The weight of every volume unit of meter.Tap density also shows the weight of every volume unit powder, in the retainer of the powder,
It is subjected to beating in predefined conditions or vibration.Tap density is expressed as the weight of every volume unit usually in terms of g/mL.It is logical
Crossing beating or vibration, more powder can be supplied in the retainer.Therefore, for same powder, tap density is higher than
Heap density.
Bulk density and the big powder of tap density, proportion is often larger, can reflect that crystal product is more thick and solid,
There are texture, stability also can relatively preferably；From another perspective, the mobility of the product of large bulk density, particle is general
Preferably, it also allows for storing and transport.
So specifically, the crystal powder particle size distribution, bulk density, the measurement method of tap density are as follows：
The particle size distribution of the sample from mixer is determined using Microtrac S3500 particle size analysis instrument
(including d10And d50), dry method measures；
The bulk density of particle is measured by USP methods II (page 1914)；
The tap density of particle is surveyed according to GB/T 5162-2006 by the economical tap density analyzers of FZS4-4
It is fixed.Specifically, determination condition is：The vibrating stroke for making real device is 3 ± 0.1MM, and vibration frequency is 250 ± 15 times per minute.
When above-mentioned crystal is configured to the aqueous solution that mass fraction is 5%, system pH is between 3.0~9.8, preferably
3.5~9.5, more preferable 5.0~8.5, most preferably 6.0~8.0.
Solid or solid powder of the present invention are a kind of coherent condition of substance, including amorphous and crystal.
Crystalline powder of the present invention refers to the powder with certain crystallinity, is for amorphous.
Crystal of the present invention is that the solid for having clear diffraction pattern to X-ray, atom or molecule press one in space
The set pattern rule period repeatedly arranges.
The invention also discloses a kind of compositions, including
(i) crystal of pentanediamine sebacate of the present invention and
(ii) (a) decanedioic acid solid；Or
(b) pentanediamine.
Above-mentioned composition so that the ratio between molal quantity of pentanediamine and decanedioic acid is not equal to 1: 1 in mixture.
The present invention finally discloses the preparation method of the crystal of above-mentioned pentanediamine sebacate, including, from containing dissolving
Pentanediamine sebacate is crystallized out in the solution of pentanediamine and decanedioic acid；Crystal is isolated from the solution；Drying is separated
Crystal.
Wherein, including in the drying process or after dry mechanical stamping is carried out to crystal.
Wherein, the solution of the pentanediamine containing dissolving and decanedioic acid is prepared according to following any modes：
(i) decanedioic acid solid and pentanediamine are added in solvent simultaneously；
(ii) decanedioic acid solid and pentanediamine are successively added in solvent；
(iii) pentanediamine is added in solvent and forms pentanediamine solution；Decanedioic acid solid is added in solvent and forms the last of the ten Heavenly stems two
Acid solution forms the decanedioic acid solution containing the undissolved decanedioic acid solid in part, then mixes the two；Wherein, penta 2 are dissolved
The solvent of amine and the solvent of dissolving decanedioic acid solid can be the same or different.
Wherein, the solvent include methanol, it is ethyl alcohol, water, normal propyl alcohol, ethyl acetate, Ethyl formate, methyl acetate, different
One kind or their mixed solvent of propyl alcohol, acetone, butanone, petroleum ether, tetrahydrofuran and DMSO, preferably methanol, ethyl alcohol, water,
The mixed solvent of one or more of acetone, normal propyl alcohol, isopropanol, butanone, DMSO.
Wherein, the feed postition of decanedioic acid can be varied, for example is disposably added directly into a manner of solid molten
Among agent, either repeatedly it is slowly added to dissolve among solvent or first by the decanedioic acid solvent in a manner of solid, then
It is added at one time or is added to several times among cadaverine solution.It is preferred that being then added to after first dissolving decanedioic acid with the solvent
Mode of operation among cadaverine solution.
Pentanediamine specifically, for example is added to organic solvent by the preparation method of the crystal of above-mentioned pentanediamine sebacate
In or the binary solvent of water and organic solvent in or the in the mixed solvent or water phase of water and a variety of organic solvents among, fill
After dividing mixing, decanedioic acid, within the scope of 10~50 DEG C of temperature, the slow crystallization under stirring, after 0.5~72h hours is added
There are white crystal precipitation, magma to be separated by solid-liquid separation by filtering or centrifuging, obtained solid is dried in vacuo at 35~70 DEG C, i.e.,
Obtain pentanediamine sebacate crystalline powder or composition of the present invention.
Wherein, the ratio of the volume mL of the weight g and solvent of pentanediamine can be 1: 0.5~30 in crystal preparation process；The last of the ten Heavenly stems
The addition of diacid, the molar ratio with pentanediamine can be 0.4~2.0, preferably equimolar ratio.
It should be pointed out that pentanediamine carries out reactive crystallization by equimolar with decanedioic acid than in the form of, then obtained
Solid product is easier to be formed and be crystallized with the pentanediamine sebacate of pentanediamine cation and decanedioic acid anion equimolar ratio
Body, the pH value of 5wt% aqueous solutions is between 6.0~8.0, between preferably 6.5~7.5.If added in crystal preparation process
The total mole number of the decanedioic acid entered is more than or less than the molal quantity for being initially added pentanediamine, then obtained solid product is easier to
Composition of the present invention is formed, the pH of the 5wt% aqueous solutions of product will show non-neutral.
Specifically, when the molal quantity for the decanedioic acid being added is more than the molal quantity of initial pentanediamine, gained powder will be shown
Give the impression of weakness acid or acid；When the molal quantity for the decanedioic acid being added is less than the molal quantity of initial pentanediamine, gained powder will be shown
Alkalinity of giving the impression of weakness or alkalinity.
It should be pointed out that in preparation method of the present invention, the crystallization process under organic solvent existence condition is
Reduction organic solvent volatilization, it may be considered that condensation reflux unit, difference of the condensation temperature according to refrigerant are installed on crystallizer
Different temperatures, such as -10~20 DEG C can be set.The refrigerant can use ethyl alcohol, ethylene glycol or water.
It should be pointed out that in preparation method of the present invention, after separation of solid and liquid, can be washed using detergent
Solid, the impurity in crystalline mother solution to remove surface of solids carrying, detergent can be to crystallize the institute that uses in preparation process
State solvent.
It should be pointed out that in preparation method of the present invention, dry process is to pentanediamine sebacate powder
Quality has certain influence, and lower drying temperature may cause dry insufficient to cause dissolvent residual exceeded or caking shows
As；Excessively high drying temperature is easy so that product jaundice.Under preparation method of the present invention, the preferred vacuum of drying mode is dry
Dry and microwave drying or combination, drying temperature can be from 30~70 DEG C, and preferably 45~60 DEG C, vacuum degree is less than
300mbar, preferably shorter than 100mbar, more preferably less than 50mbar.
It should be pointed out that in preparation method of the present invention, the source of pentanediamine in technique can be single group
Point pentanediamine, can also be that bioanalysis prepares during pentanediamine the solution containing pentanediamine of phase after isolation.
It should be pointed out that crystallization process can be carried out either intermittently or continuously.When the process is carried out batch wise, excellent
It selects and adds crystal seed into crystallizing system.It is continuously carried out it is preferred that crystallizing.
In addition, the more detailed information of cadaverine sebacate crystal structure according to the present invention, in Figure of description
In provide.
Advantageous effect：The invention discloses a kind of monomer pentanediamine sebacate of biology base nylon 510 and its crystal knots
Structure and its crystalline powder, with and preparation method thereof.It is as follows to have feature：(1) pentanediamine is at normal temperatures and pressures with colorless viscous
Fuming liquids form exists, and has the foul odour of similar ammonia, and the carbon dioxide easily absorbed in air generates pentanediamine carbon
Hydrochlorate, itself purity of extreme influence pentanediamine.The invention enables pentanediamines and decanedioic acid to bind directly to form solid salt, not only
Its existing forms is changed, the stability of product is improved, and significantly reduces original foul odour, is conducive to improve
The working environment of worker；(2) 510 crystalline salt of nylon provided by the invention, not only facilitates storage and transport, but also improves follow-up
The operability of polymerization technique；(3) 510 monomer salt of nylon provided by the invention exists with the state of highly crystalline, and purity is high,
It is used directly for the polymerization of nylon 510.
Description of the drawings
The minimum of Fig. 1 pentanediamine sebacates is not to the molecule ellipsoid figure at unit；
The cell configuration figure along c-axis direction of Fig. 2 pentanediamine sebacates；
The structure cell accumulation graph along c-axis direction of Fig. 3 pentanediamine sebacates；
The X-ray powder diffraction spectrums of Fig. 4 pentanediamine sebacates；
The characteristic spectral line of Fig. 5 pentanediamine sebacate X-ray powder diffractions；
Fig. 6 pentanediamine sebacate crystal and its structurally interrelated information；
Bond distance's information (Angstrom) in Fig. 7 pentanediamine sebacate structures；
Bond angle information (Deg) in Fig. 8 pentanediamine sebacate structures；
Dihedral angle information (Deg) in Fig. 9 pentanediamine sebacate structures；
Hydrogen bond information (Angstrom, Deg) in Figure 10 pentanediamine sebacate structures；
The characterization of Figure 11 products；
Figure 12 stability experiments.
Specific implementation mode
The preparation method of pentanediamine sebacate crystalline powder of the present invention and composition of the present invention is led to
It crosses non-limiting embodiment below will be evident from, following embodiment is descriptive, is not limiting, cannot be with
Limit protection scope of the present invention.
Embodiment 1：
The pentanediamine of 15.00g is added in 130g methanol solutions, is fully stirred evenly, pentanediamine methanol solution is formed.It will
The decanedioic acid of 29.69g is dissolved in 350g methanol, at 25 DEG C, is instilled in pentanediamine methanol solution with the flow velocity of 2mL/min,
It being crystallized under stirring, and monitoring process pH variations, in pH 10.5 or so, 0.15g crystal seeds is added, pause stream adds,
After growing the grain 3h, decanedioic acid methanol solution is instilled by crystallizing system with the flow velocity of 0.7mL/min, after waiting for that stream adds completely, is continued
2h is stirred, lower tank carries out the separation of solid and liquid of brilliant paddle by filtering, then washed with 80~100 mL methanol, then at 45 DEG C
Vacuum forced air drying 8h, its powder X-ray x ray diffraction collection of illustrative plates of acquisition pentanediamine sebacate crystalline powder is as shown in figure 4, with diffraction
2 θ ± 0.1 of angle is expressed as：9.62,11.06,17.54,19.96,21.08,22.24,27.28 etc..It is configured to quality point
When the aqueous solution that number is 5%, system pH 7.5.The powder has good graininess, mobility, stability.
Embodiment 2：
15.00g pentanediamines are added in 90% ethanol waters of 100mL (volume fraction of ethanol 90%), are fully stirred
It is even, form pentanediamine ethanol water.35g decanedioic acid solids are added in the ethanol water of 350mL 90% (ethyl alcohol body
Fraction is 90%), to form the ethanol water of decanedioic acid, and then the two is mixed in 500mL crystallizers, and control temperature exists
25 DEG C, 48h is stirred, white crystalline material, lower tank occurs, the mode of suction filtration is separated by solid-liquid separation, with the ethyl alcohol of 150mL 95%
Solid is washed, then microwave drying solid 8h, maintains 45~60 DEG C of temperature to get pentanediamine sebacate crystalline powder, product
X-ray powder collection of illustrative plates it is as shown in Fig. 4, be expressed as with 2 θ ± 0.1 of the angle of diffraction：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. 5.Its crystal structure as shown in fig. 6,
Belong to monoclinic system, C2 space groups, β=92.394 (2) °,
Unit cell volumeMinimum asymmetric cell number Z=2 in structure cell.In its minimum asymmetric cell, contain
1 pentanediamine cation and 1 decanedioic acid anion, the minimum asymmetric cell figure and structure cell accumulation graph of structure cell are respectively such as
Shown in attached drawing 1 and attached drawing 3, the detailed data of crystal structure --- bond distance's information as shown in fig. 7, bond angle information as shown in figure 8,
Dihedral angle information is as shown in figure 9, hydrogen bond information is as shown in Figure 10.During its crystal structure determination, diffraction data is in 298 (2) K
Under be collected.When being configured to the aqueous solution that mass fraction is 5%, system pH 5.6.The powder has good
Graininess, mobility, stability.
Embodiment 3：
Among 45.00g decanedioic acid is dissolved in the absolute ethyl alcohol of 500g, it is in uniform decanedioic acid ethanol solution, then moves
In the crystallizer for entering 1000mL.The pentanediamine of 30.00g is dissolved in the acetone water of 300mL 95% (acetone volume fraction accounts for 95%)
Among solution, pentanediamine aqueous acetone solution is formed.Then pentanediamine aqueous acetone solution is instilled in a manner of 3mL/min with pump
Among decanedioic acid ethanol solution, when the 20% of the amount that the amount of the substance of the pentanediamine of addition is decanedioic acid substance, 0.3g is added
Remaining pentanediamine aqueous acetone solution is added with 0.3mL/min in crystal seed, and whole process carries out under stirring, and temperature control exists
50 DEG C, at the end of complete stream adds, 15 DEG C are cooled to the rate of 2 DEG C/h, crystallization terminates, and lower tank is separated by solid-liquid separation, then
Filter cake is washed with 100mL absolute ethyl alcohols, is placed in micro-wave vacuum 8h at 35~45 DEG C, that is, obtains pentanediamine sebacate knot
Crystalline flour end, when being configured to the aqueous solution that mass fraction is 5%, system pH 8.8.The powder has good particle
Property, mobility, stability.
Embodiment 4：
In pentanediamine aqueous solution containing 50g/L, using thin film evaporator or concentrated by rotary evaporation device, this aqueous solution is concentrated
8 times, that is, volume is the 1/8 of original volume after concentrating, and is placed in crystallizer, and 15 DEG C are cooled under stirring, is then added
Enter the absolute ethyl alcohol at 15 DEG C of 2 times of material liquid volumes, after mixing well, decanedioic acid solid is added, in the amount and system of addition
The molal quantity of pentanediamine is suitable, stirred crystallization 48h, and lower tank is separated by solid-liquid separation, with 95% ethyl alcohol of 2 times of material liquid volumes into
Row washing, then vacuum drying 10h to get pentanediamine decanedioic acid crystalline powder, prepared by powder moisture 0 at 60 DEG C
At mass fraction be 5% aqueous solution when, system pH 7.1.The powder has good graininess, mobility, stability,
Ordorless smell.
Embodiment 5：
It is in uniform decanedioic acid normal propyl alcohol solution, then again among 50.00g decanedioic acid is dissolved in the normal propyl alcohol of 350g
The mixed liquor of one or more of addition ethyl acetate, Ethyl formate, methyl acetate, isopropanol, additive amount 250mL, and
It moves into the crystallizer of 1000mL afterwards.The pentanediamine of 20.00g is dissolved in the ethyl acetate of 350mL, pentanediamine acetic acid second is formed
Ester solution.Among pentanediamine ethyl acetate solution is then instilled decanedioic acid solution in a manner of 4mL/min with pump, when addition
When the amount of the substance of pentanediamine is the 10% of the amount of decanedioic acid substance, 0.2g crystal seeds are added, temperature is controlled at 10 DEG C, when complete stream
At the end of adding, continuing to stir 10h, crystallization terminates, and lower tank is separated by solid-liquid separation, and then washs filter cake with 100mL anhydrous propanones, and
It is placed at 70 DEG C and is dried in vacuo 6h, that is, obtain pentanediamine sebacate crystalline powder, be configured to the water that mass fraction is 5%
When solution, system pH is 3.0~6.5.
Embodiment 6：
50.00g decanedioic acid is dissolved among normal propyl alcohol-DMSO solution of 300g to (volume ratio of normal propyl alcohol and DMSO are 4
: 1), it is in uniform decanedioic acid solution, then adds the mixed liquor of one or more of butanone, petroleum ether, tetrahydrofuran,
Additive amount is 200mL, is then moved into the crystallizer of 1000mL.The pentanediamine of 50.00g is dissolved in the butanone of 250mL, forms penta
Diamines butanone solution.Then under stirring, among pentanediamine butanone solution is directly poured into decanedioic acid solution, maintenance system
25 DEG C, rotating speed 250r/min of temperature stirs 1.0h, and crystallization terminates, and lower tank is separated by solid-liquid separation, and is then washed with the anhydrous butanone of 80mL
Filter cake, and the micro-wave vacuum 5h at 50~70 DEG C are washed, that is, obtains pentanediamine sebacate crystalline powder, powder moisture is
0, when being configured to the aqueous solution that mass fraction is 5%, system pH is 7.0~9.8.
Embodiment 7：
The sample of gained, tests its d respectively in Example 1 to 610, d50, bulk density, tap density and solvent are residual
It stays, to illustrate that pentanediamine sebacate product obtained by technique of the present invention has good graininess and mobility, and produces
The organic solvent residual of product is nearly no detectable, as a result as shown in figure 11.
The sample of gained, is placed on carrying out stability experiment at 60 DEG C in Example 1 to 6, and interval 48h is surveyed respectively
Its light transmission at 430nm is tried, initial sample is used in combination to compare, as a result as shown in figure 12, finds gained sample in six kinds of embodiments
Product, color do not change, T430nmIt is not decreased obviously, illustrates that gained sample stability is good.
Claims (13)
1. a kind of pentanediamine sebacate, which is characterized in that the pentanediamine sebacate be pentanediamine bivalent cation with
The salt of solid state, molecule knot are presented under the room temperature that decanedioic acid dianion is combined into such a way that molar ratio is 1: 1
Structure is shown in formula I：
2. a kind of crystal of pentanediamine sebacate, which is characterized in that the molecular formula is C15H32N2O4, the crystallization water is free of,
Molecular structural formula is as shown in Formula II：
3. the crystal of pentanediamine sebacate according to claim 2, which is characterized in that its crystal structure belongs to monoclinic crystal
System, C2 space groups, cell parameter areB=92.394
(2) °, unit cell volumeMinimum asymmetric cell number Z=2 in structure cell, in its minimum asymmetric cell
In, contain 1 pentanediamine cation and 1 decanedioic acid anion.
4. the crystal of pentanediamine sebacate according to claim 2, which is characterized in that use CuK with as shown in Figure 4
Alpha ray carries out the diffracting spectrum of diffraction analysis as characteristic X-ray.
5. the crystal of the pentanediamine sebacate according to any one of claim 2~4, which is characterized in that crystal powder
End has the bulk density more than 0.22g/mL.
6. the crystal of the pentanediamine sebacate according to any one of claim 2~4, which is characterized in that crystal powder
End has the tap density more than 0.27g/mL.
7. the crystal of the pentanediamine sebacate according to any one of claim 2~4, which is characterized in that crystal powder
End has the d more than 21 μm50。
8. the crystal of the pentanediamine sebacate according to any one of claim 2~4, which is characterized in that crystal powder
End has the d more than 8 μm10。
9. the crystal of the pentanediamine sebacate according to any one of claim 2~4, which is characterized in that will be described
When crystal is configured to the aqueous solution that mass fraction is 5%, system pH is between 3.0~9.8.
10. a kind of composition, including
(i) crystal according to any one of claim 2~4, and
(ii) (a) decanedioic acid solid；Or
(b) pentanediamine.
11. the preparation method of the crystal of the pentanediamine sebacate described in any one of claim 2~4, which is characterized in that
From crystallizing out pentanediamine sebacate in the solution of the pentanediamine containing dissolving and decanedioic acid；Crystalline substance is isolated from the solution
Body；Dry separated crystal.
12. preparation method according to claim 11, which is characterized in that the pentanediamine and decanedioic acid containing dissolving
Solution be prepared according to following any modes：
(i) decanedioic acid solid and pentanediamine are added in solvent simultaneously；
(ii) decanedioic acid solid and pentanediamine are successively added in solvent；
(iii) pentanediamine is added in solvent and forms pentanediamine solution；It is molten that formation decanedioic acid in solvent is added in decanedioic acid solid
Liquid forms the solution containing the undissolved decanedioic acid solid in part；Then the two is mixed.
13. according to the method for claim 12, which is characterized in that the solvent include methanol, ethyl alcohol, water, normal propyl alcohol,
Ethyl acetate, Ethyl formate, methyl acetate, isopropanol, acetone, butanone, one kind of petroleum ether and DMSO or their mixing are molten
Agent.
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| CN110305022A (en) * | 2019-07-30 | 2019-10-08 | 南京工业大学 | A method of utilizing Microwave Extraction pentanediamine |
| CN115894250A (en) * | 2022-12-20 | 2023-04-04 | 南京工业大学 | Nylon 513 salt crystal and preparation method thereof |
| CN116003266A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Preparation method and application of long carbon chain nylon salt |
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| US10487176B2 (en) * | 2014-12-17 | 2019-11-26 | Cathay Biotech Inc. | Nylon salt and preparation method therefor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110305022A (en) * | 2019-07-30 | 2019-10-08 | 南京工业大学 | A method of utilizing Microwave Extraction pentanediamine |
| CN110305022B (en) * | 2019-07-30 | 2020-12-22 | 南京工业大学 | Method for extracting pentamethylene diamine by using microwave |
| CN116003266A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Preparation method and application of long carbon chain nylon salt |
| CN115894250A (en) * | 2022-12-20 | 2023-04-04 | 南京工业大学 | Nylon 513 salt crystal and preparation method thereof |
| CN115894250B (en) * | 2022-12-20 | 2024-04-19 | 南京工业大学 | Nylon 513 salt crystal and preparation method thereof |
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