CN105669396B - A kind of preparation of industrialization chromatographic separation and purification method of Z6148 liquid crystal molecules - Google Patents
A kind of preparation of industrialization chromatographic separation and purification method of Z6148 liquid crystal molecules Download PDFInfo
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- CN105669396B CN105669396B CN201610091994.1A CN201610091994A CN105669396B CN 105669396 B CN105669396 B CN 105669396B CN 201610091994 A CN201610091994 A CN 201610091994A CN 105669396 B CN105669396 B CN 105669396B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
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Abstract
The present invention relates to a kind of preparation of industrialization chromatographic separation and purification methods of Z6148 liquid crystal molecules, belong to liquid crystal material technical field.This method comprises the following steps：(1) by Z6148 liquid crystal molecule synthesis reaction solution preliminary purifications；(2) the Z6148 liquid crystal after preliminary purification is dissolved in solvent, is configured to solution, is filtered to remove insoluble matter；(3) above-mentioned Z6148 liquid crystal solutions are pumped into dynamic axial compression column preparing chromatography system, it is eluted through eluent gradient, the New UV Spectrophotometric detector for being 254nm with Detection wavelength, distillate of the retention time in 30~50min is collected, solvent for use of the present invention is cheap, safety, isolates and purifies the completion of one step of process, it and can on-line real time monitoring, security is substantially increased, has saved raw material and time cost, suitable for large-scale industrial production.
Description
Technical field
The invention belongs to liquid crystal material technical fields, relate generally to the purifying of liquid crystal material, and particularly the present invention is to be related to
A kind of preparation of industrialization chromatographic separation and purification method of fluorine-containing phenyl ring class Z6148 liquid crystal molecules.
Background technology
Liquid crystal is in the organic substance between solid-state and liquid with certain ordered, has photoelectricity dynamic scattering spy
Property；There are many liquid crystal phase, such as cholesteric phase, various smectic phases, nematic phases etc. for it.Most successful, market is wherein developed to occupy
Amount is maximum, it is with fastest developing speed be nematic liquid crystal.Display is made of with liquid crystal material a variety of small molecular organic compounds, this
The key structural feature of a little small molecules is bar-like molecular structure.Developed into many types, for example, various biphenyl nitriles, esters,
Cyclohexyl (connection) benzene class, oxygen heterocycle benzene class, pyrimidine ring class, diphenyl acetylene class, ethyl bridged bond class and alkene end group class and various
Fluorine-containing phenyl ring class etc..China's liquid crystal material production from scratch, has gradually formed considerable scale by the effort of more than ten years
Industry.The new display professional income in China in 2013 breaks through 100,000,000,000 yuan, continues within 2014 to keep 50% or so growth rate,
Close to 150,000,000,000 yuan.
The Chinese patent " manufacturing method of liquid crystal material " of Application No. 201110417782.5 is described to be tied again with multistep
The method that crystallization purifies liquid crystal molecule can remove most of impurity molecule after recrystallization, but for some structures and liquid crystal molecule
Be difficult then removal by recrystallization method for more similar impurity molecule itself, and multistep recrystallizing technology to yield and
Cost is totally unfavorable；The Chinese patent " purification process of liquid crystal monomer or liquid-crystal composition " of Application No. 200810155843.3
The method to be cleaned with macroporous resin adsorption is described, this method can substantially remove the polar impurity contained in liquid crystal, but still be difficult to
Control the content of the other impurity in part in liquid crystal molecule.
The content of the invention
In order to solve the above technical problems, present invention aims in current Z6148 liquid crystal molecules subtractive process for being deposited
Purification step it is more, the cycle is long, and single miscellaneous content is difficult to control, and organic solvent consumption is big, and product fractional dose is limited, and is difficult to
In real time the problems such as monitoring separation progress；A kind of isolation and purification method of the preparation of industrialization chromatography of Z6148 liquid crystal molecules is provided, it should
Method can quickly, a large amount of, controllable isolated high-purity in real time Z6148 liquid crystal molecules.
In order to solve the above-mentioned technical problem technical solution is：A kind of preparation of industrialization chromatography point of Z6148 liquid crystal molecules
From purification process, the purification process comprises the following steps：
The molecular formula of the Z6148 liquid crystal molecules is as follows：
(1) by Z6148 liquid crystal molecule synthesis reaction solution preliminary purifications；
(2) the Z6148 liquid crystal after preliminary purification is dissolved in solvent, is configured to solution, is filtered to remove insoluble matter；
(3) above-mentioned Z6148 liquid crystal solutions are pumped into dynamic axial compression column preparing chromatography system, are washed through eluent gradient
De-, the New UV Spectrophotometric detector for being 254nm with Detection wavelength collects distillate of the retention time in 30~50min；
Wherein dynamic axial compression column preparing chromatography system, column dimension are described in step (3)Filler
For 10~50 μm of reverse phase spherical silica gels, mobile phase is the aqueous solution of organic solvent, and concentration is 5~95wt%.
Preferably, mobile phase described in step (3) be acetonitrile and water, gradient 90:10, flow velocity 100mL/min, elution
Time is 55min.
Preferably, mobile phase described in step (3) be first alcohol and water, gradient 80:20, flow velocity 80mL/min, elution
Time is 40min.
Preferably, mobile phase described in step (3) is acetonitrile and water, and a gradient is 90:10, flow velocity 80mL/
Min, elution time 40min；Secondary gradient is 95:5, flow velocity 100mL/min, elution time 10min.
Preferably, reverse phase spherical silica gel described in step (3) is reverse phase n-octadecane base silica gel.
Preferably, reverse phase n-octadecane base silica gel grain size described in step (3) is 10 μm or 22 μm.
Preferably, solvent described in step (2) is water, organic solvent or water and the mixture of organic solvent.
Preferably, preliminary purification described in step (1) is distillation or extraction and recrystallization.
The beneficial effects of the invention are as follows directly prepare high-purity using the Z6148 liquid crystal crude product solution after preliminary purification
Z6148, the pretreatment process cumbersome without large amount of complex, solvent for use is cheap, safety, isolates and purifies the completion of one step of process, and
Can on-line real time monitoring, substantially increase security, saved raw material and time cost, suitable for large-scale industrial production.
High performance liquid chromatography finally measures display, and Z6148 purity is always miscellaneous to be less than 0.3% more than 99.5%.
Description of the drawings
The present invention is described further below in conjunction with the accompanying drawings.
Fig. 1 is Z6148 liquid crystal molecule formulas.
Fig. 2 is Z6148 synthesis of liquid crystal chemical formulas.Wherein R is the straight chained alkyl or alkoxy of 1-5 carbon atom；Ring A and B
It is identical or different, be each independently selected from byM and n it is identical or
Difference each represents 0 or 1 independently of one another；
Fig. 3 is that the high performance liquid chromatography of Z6148 crude products measures collection of illustrative plates.
Fig. 4 is to isolate and purify Z6148 with the dynamic axial compression column for being filled with 10 μm of n-octadecane base reverse phase silica gel fillers
Prepare collection of illustrative plates, sample introduction 400mg.
Fig. 5 is to isolate and purify Z6148 with the dynamic axial compression column for being filled with 10 μm of n-octadecane base reverse phase silica gel fillers
Prepare collection of illustrative plates, sample introduction 1g.
Fig. 6 is to isolate and purify Z6148 with the dynamic axial compression column for being filled with 10 μm of n-octadecane base reverse phase silica gel fillers
Prepare collection of illustrative plates, sample introduction 2g.
Fig. 7 is to isolate and purify Z6148 with the dynamic axial compression column for being filled with 10 μm of n-octadecane base reverse phase silica gel fillers
Prepare collection of illustrative plates, sample introduction 3g.
Specific embodiment
Below by specific embodiment, the present invention will be further described.
The optimal separation purification condition of Z6148 is studied and optimized using high performance liquid chromatography (HPLC).Thereafter by its grade ratio
Example amplification, is separated in the dynamic axial compression column (DAC) filled with reverse phase n-octadecane base silica filler, online to collect
Z6148 corresponds to the eluent of chromatographic peak, and yield is between 60%~80%.It is pure again that low-purity component can be incorporated to material liquid again
Change, final total recovery is up to more than 95%.
Using filler 10-50 micron reverse phase spherical silica gels, preferably 10 or 22 microns of C18 reverse phase spherical silica gels.
Mobile phase is the aqueous solution of organic solvent, and organic solvent includes but not limited to methanol, acetonitrile etc., and concentration is in 10-
Between 90wt%, for cost consideration, preferably methanol.
Embodiment 1
1. 400mgZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, positive ten
Eight alkyl reverse phase silica gel packing material sizes be 10 μm, applied sample amount 400mg, mobile phase be methanol and water, gradient 80:20, flow velocity
For 80ml/min, elution time 40min.Continued to elute 10min with 100% methanol afterwards, a separation cycle terminates.Using
New UV Spectrophotometric detector Detection wavelength for 254nm, collect distillate of the retention time in 30~40min.As shown in figure 3,
It is 99.8% through HPLC purity assays.
Embodiment 2
1. 1gZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, positive ten
Eight alkyl reverse phase silica gel packing material sizes be 10 μm, applied sample amount 1g, mobile phase be methanol and water, gradient 80:20, flow velocity is
80ml/min, elution time 40min.Continued to elute 10min with 100% methanol afterwards, a separation cycle terminates.It uses
The Detection wavelength of New UV Spectrophotometric detector is 254nm, collects distillate of the retention time in 30~40min.As shown in figure 3, through
HPLC purity assays are 99.7%.
Embodiment 3
1. 2gZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, positive ten
Eight alkyl reverse phase silica gel packing material sizes be 10 μm, applied sample amount 2g, mobile phase be methanol and water, gradient 80:20, flow velocity is
80ml/min, elution time 40min.Continued to elute 10min with 100% methanol afterwards, a separation cycle terminates.It uses
The Detection wavelength of New UV Spectrophotometric detector is 254nm, collects distillate of the retention time in 30~40min.As shown in figure 3, through
HPLC purity assays are 99.5%.
Embodiment 4
1. 2gZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, positive ten
Eight alkyl reverse phase silica gel packing material sizes be 10 μm, applied sample amount 2g, mobile phase be acetonitrile and water, gradient 90:10, flow velocity is
80ml/min, elution time 40min.Continued to elute 10min with 100% acetonitrile afterwards, a separation cycle terminates.It uses
The Detection wavelength of New UV Spectrophotometric detector is 254nm, collects distillate of the retention time in 35~45min.As shown in figure 3, through
HPLC purity assays are 99.8%.
Embodiment 5
1. 3gZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, positive ten
Eight alkyl reverse phase silica gel packing material sizes be 10 μm, applied sample amount 3g, mobile phase be methanol and water, gradient 80:20, flow velocity is
80ml/min, elution time 40min.Continued to elute 10min with 100% methanol afterwards, a separation cycle terminates.It uses
The Detection wavelength of New UV Spectrophotometric detector is 254nm, collects distillate of the retention time in 30~40min.As shown in figure 3, through
HPLC purity assays are 99.6%.
Embodiment 6
1. 3gZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, filler
Using 22 micron reverse phase spherical silica gels, applied sample amount 3g, mobile phase is methanol and water, gradient 80:20, flow velocity 80ml/
Min, elution time 40min.Continued to elute 10min with 100% methanol afterwards, a separation cycle terminates.What is used is ultraviolet
The Detection wavelength of photometric detector is 254nm, collects distillate of the retention time in 30~40min.As shown in figure 3, through HPLC
Purity assay is 99.5%.
Embodiment 7
1. 108gZ6148 crude products is taken to be configured to solution, insoluble matter is filtered to remove；
2. Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 300 × 250mm of Φ, positive ten
Eight alkyl reverse phase silica gel packing material sizes be 10 μm, applied sample amount 3g, mobile phase be methanol and water, gradient 80:20, flow velocity is
2880ml/min, elution time 40min.Continued to elute 10min with 100% methanol afterwards, a separation cycle terminates.Using
New UV Spectrophotometric detector Detection wavelength for 254nm, collect distillate of the retention time in 30~40min.As shown in figure 3,
It is 99.5% through HPLC purity assays.
The specific technical solution being not limited to described in above-described embodiment of the present invention, all technologies formed using equivalent substitution
Scheme be the present invention claims protection domain.
Claims (1)
1. a kind of preparation of industrialization chromatographic separation and purification method of Z6148 liquid crystal molecules, which is characterized in that the purification process,
Comprise the following steps：
The molecular formula of the Z6148 liquid crystal molecules is as follows：
(1) 2gZ6148 crude products is taken to be configured to solution, are filtered to remove insoluble matter；
(2) Z6148 solution is pumped into dynamic axial compression column preparing chromatography system, column dimension is 50 × 250mm of Φ, n-octadecane
Base reverse phase silica gel packing material size be 10 μm, applied sample amount 2g, mobile phase be acetonitrile and water, gradient 90:10, flow velocity 80ml/
Min, elution time 40min；Continued to elute 10min with 100% acetonitrile afterwards, a separation cycle terminates；What is used is ultraviolet
The Detection wavelength of photometric detector is 254nm, collects distillate of the retention time in 35~45min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565343A (en) * | 2009-05-14 | 2009-10-28 | 浙江永太科技股份有限公司 | Preparation method of difluoro methoxy bridge bond compound |
| CN102675062A (en) * | 2012-04-27 | 2012-09-19 | 石家庄诚志永华显示材料有限公司 | Method for preparing difluoromethoxy bridge type liquid crystal |
| CN104513115A (en) * | 2013-09-30 | 2015-04-15 | 大金工业株式会社 | Process for producing fluorine-containing biaryl compound |
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- 2016-02-19 CN CN201610091994.1A patent/CN105669396B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565343A (en) * | 2009-05-14 | 2009-10-28 | 浙江永太科技股份有限公司 | Preparation method of difluoro methoxy bridge bond compound |
| CN102675062A (en) * | 2012-04-27 | 2012-09-19 | 石家庄诚志永华显示材料有限公司 | Method for preparing difluoromethoxy bridge type liquid crystal |
| CN104513115A (en) * | 2013-09-30 | 2015-04-15 | 大金工业株式会社 | Process for producing fluorine-containing biaryl compound |
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