CN105903456A - Preparation method of amylose type derivative functional inorganic-silicon-based chiral micro-sphere fixed-phase material - Google Patents
Preparation method of amylose type derivative functional inorganic-silicon-based chiral micro-sphere fixed-phase material Download PDFInfo
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Abstract
The invention provides a preparation method of an amylose type derivative functional inorganic-silicon-based chiral micro-sphere fixed-phase material. The preparation method comprises the following steps: (1) stirring and reflowing dried mirco-crystalline amylose in anhydrous N,N-dimethylacetamide; cooling to a room temperature and then adding lithium chloride; after raising the temperature, adding anhydrous pyridine; after reflowing, adding 3,5-dimethylphenyl isocyanate; continuously stirring and reflowing and adding 3-(trimethoxysilicon) propyl isocyanate and continuously stirring and reflowing; treating with excessive amount of the 3,5-dimethylphenyl isocyanate; (2) dissolving into tetrahydrofuran and adding n-heptanol, ethyl orthosilicate, water and trimethylsilyl chloride; (3) adding into a sodium dodecyl sulfate water solution; (4) adding trimethylsilyl chloride and anhydrous toluene and reacting under a nitrogen gas atmosphere. A synthesis route is clear and feasible, developed in process, simple to operate and easy to realize and has a few of conditions needing to be controlled; the preparation method can be used for large-scale batch production.
Description
Technical field
The present invention relates to the preparation method of a kind of chirality microsphere stationary phase material, based on amylose-three
(3,5-dimethylphenylcarbamate) derivant functionalization inorganic silica-based chirality microsphere stationary phase material
Preparation method.
Background technology
In recent years, developing rapidly, for the hands of chiral stationary phase material along with chiral separation and analysis field
Property recognition efficiency and fractionation scope are had higher requirement, and therefore design and develop and novel have broad-spectrum high efficacy
The chiral stationary phase of chiral recognition has become one of this field problem demanding prompt solution.In existing chirality
In fixing mutually, polysaccharide derivatives chiral stationary phase is good by chiral separation performance, chiral Recognition scope is wide
Advantage is widely used in chromatograph.But current all commercialization chiral stationary phases are typically all by coating or key
The means closed obtain, and the content of polysaccharide derivates is relatively low, and bearing capacity is limited, significantly limit fixing phase
Application in extensive preparative separation field.Until 2008, Okamoto seminar is prepared for having height first
The organic inorganic hybridization microsphere of fibres in amounts element-three (3,5-dimethylphenylcarbamate) derivant, greatly
Improve greatly the bearing capacity of material, and the mechanical strength of material also can substantially meet the requirement of chromatographic isolation.But
Being that the course of reaction of this material is wayward causes its productivity relatively low, and poor repeatability.Additionally, due to this is miscellaneous
Change microsphere and the most do not carry out respective handling, cause material surface to there is a large amount of silanol so that
This material occurs more significantly conditions of streaking when for chromatographic isolation, is substantially reduced its separation efficiency.Directly
Extremely currently for novel preparation method and the research of tailing problem thereof of this kind of organic-inorganic hybrid material, and
Grinding of such organic-inorganic hybrid material is prepared based on other type (such as amylose analog derivative) polymer
Study carefully all that there is not been reported.Early-stage Study shows, amylose analog derivative has outstanding chiral Recognition equally
With split performance, and the identification of its recognition performance for a lot of enantiomeric compounds and cellulose derivative
Performance complement.If amylose class organic-inorganic hybrid material can be prepared, will develop and novel have
The chiral stationary phase material of high-efficiency broad spectrum separating property, and to development enantiomer analytical separation and preparative separation skill
Art has important using value.
Summary of the invention
It is an object of the invention to provide a kind of organic nothing that can obtain there is high-load straight chain starch derivative
Machine hybrid silicon ball, it is possible to solve the amylose class of the tailing problem occurred during Chromatographic resolution well
The preparation method of derivant functionalization inorganic silica-based chirality microsphere stationary phase material.
The object of the present invention is achieved like this:
1, by dry crystallite amylose in anhydrous DMAC N,N' dimethyl acetamide, 70～80 DEG C of temperature stirrings
Backflow 8-16h, is cooled to after room temperature to add the lithium chloride of 2 times of amylose quality, continues stirring 2-5h
After, again it is warming up to 70～80 DEG C, adds anhydrous pyridine, after backflow 2～4h, add amylose hydroxyl
The 3 of 77mol%, 5-dimethylphenyl isocyanate, after continuously stirred backflow 8～10h, according to ratio to be introduced
Example adds 3-(trimethoxy silicon) the continuously stirred backflow of propylisocyanate 12～16h, then with excessive 3,5-
Dimethylphenyl isocyanate processes, continuously stirred backflow 8～10h, is cooled to room temperature, adds methanol sedimentation
Filtering and wash, 40～60 DEG C are dried under vacuum to constant weight；
2, the product synthesized by step 1 is completely dissolved in oxolane and is added thereto to n-heptanol, just
Silester, water and trim,ethylchlorosilane, react 8～10h at 80～100 DEG C；
3, the reactant that step 2 obtained add in the lauryl sodium sulfate aqueous solution of 80～100 DEG C with
1000～1200rpm speed stirring ageings 0.5～1h, product carries out sucking filtration, successively with hot water, ethanol and just
Hexane washs and is dried；
4, add trim,ethylchlorosilane and dry toluene, react under the conditions of 80～100 DEG C under nitrogen atmosphere 1～
5h, sucking filtration separation product, wash with absolute methanol, 40～60 DEG C are dried under vacuum to constant weight.
The present invention can also include:
1, crystallite amylose is vacuum dried 2～8h at 80 DEG C.
2, addition is amylose hydroxyl the 3～7mol% of 3-(trimethoxy silicon) propylisocyanate.
3, the 3 of described excess, 5-dimethylphenyl isocyanate processes, 3,5-dimethylphenyl isocyanates
90mol% for amylose hydroxyl.
The present invention is with amylose as initial raw material, and the first sugar unit at amylose is simultaneously introduced 3,5-bis-
Methyl phenyl carbamate and a small amount of 3-(trimethoxy silicon) propyl carbamate, synthesis is containing few
The amylose-three (3,5-dimethylphenylcarbamate) of amount 3-(trimethoxy silicon) propyl group spreads out
Biological.On this basis, synthesized straight chain starch derivative is completely dissolved in oxolane, passes through
Sol-gel process and tetraethyl orthosilicate carry out copolymerzation with cross-linking, then disperse in lauryl sodium sulfate aqueous solution
Aging, finally prepare the organic inorganic hybridization silicon ball with high-load straight chain starch derivative.And to institute
Obtain material surface and carry out termination process, solve the tailing problem occurred during Chromatographic resolution very well,
Above synthetic route is the most feasible, technical maturity, simple to operate, need the condition controlled few and be prone to
Realize, can be used for producing in batches on a large scale.
The amylose wide material sources, cheap and easy to get that the present invention uses, productivity is high.
It Fig. 1 is the synthetic route of this straight chain starch derivative.Fig. 2 is amylose-three (3,5-dimethyl
Carbanilate) syntheti c route of the derivant organic inorganic hybridization ball stationary phase material of chirality silicon.Fig. 3
For synthesized containing a small amount of 3-(trimethoxy silicon) propyl carbamate amylose-three (3,5-diformazan
Base carbanilate) proton nmr spectra (1H-NMR).From the figure, it can be seen that it is synthesized derivative
The compound with regular structure of thing, and the substitution value of introduced 3-(trimethoxy silicon) propyl carbamate meets expection
Composite structure target.Fig. 4 is the SEM figure of synthesized organic inorganic hybridization silicon ball.From the figure, it can be seen that
The spherical morphology of prepared organic inorganic hybridization silicon ball is uniform, reaches desired design target.
Accompanying drawing explanation
Fig. 1 contains a small amount of 3-(trimethoxy silicon) propyl group amylose-three (3,5-dimethylphenylamino first
Acid esters) synthetic route of derivant.
Fig. 2 is based on amylose-three (3,5-dimethylphenylcarbamate) derivant functionalization inorganic silicon
The preparation method of base chirality microsphere.
Fig. 3 contains amylose-three (the 3,5-diformazan of a small amount of 3-(trimethoxy silicon) propyl carbamate
Base carbanilate) derivant proton nmr spectra (1H-NMR) (500MHz, deuterated pyridine, 80 DEG C).
Fig. 4 has high-load amylose-three (3,5-dimethylphenylcarbamate) derivant functionalization
The SEM figure of inorganic silicon-based chirality microsphere.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Detailed description of the invention one:
1. take 0.2g crystallite amylose under high temperature, be vacuum dried 4h, then at anhydrous N, N-dimethylacetamide
Amine is stirred at reflux 12h；(quality is the 2 of amylose quality to add lithium chloride after being cooled to room temperature
Times)；After continuing stirring 3h, again heat up, add anhydrous pyridine, after backflow 2h, add appropriate 3,5-
Dimethylphenyl isocyanate (77mol% of amylose hydroxyl), adds after continuously stirred backflow 8h
Enter a small amount of 3-(trimethoxy silicon) propylisocyanate (3.1mol% of amylose hydroxyl),
(amylose is processed with the 3,5-dimethylphenyl isocyanate of excess after continuously stirred backflow 12h
The 90mol% of hydroxyl), stopped reaction after continuously stirred backflow 8h；It is cooled to room temperature, adds methanol
Sedimentation filtration is also washed, and 60 DEG C are dried under vacuum to constant weight, and productivity is 87%.Synthesized amylose
3,5-dimethylphenylcarbamate and 3-(trimethoxy silicon) propyl carbamic acid in derivant
The introducing ratio of ester is 98:2.
2. take the product 0.25g synthesized by previous step, be completely dissolved in oxolane, and be added thereto to 6mL
N-heptanol, 2ml tetraethyl orthosilicate, 1mL water and 0.5mL trim,ethylchlorosilane, react at 80 DEG C
9h。
3. during reactant is dropwise instilled the lauryl sodium sulfate aqueous solution of 80 DEG C by reaction after terminating with
1100rpm speed stirring ageing 1h, stopped reaction.Will obtain product sucking filtration, successively with hot water,
The washing of ethanol, normal hexane completely and is dried.
4. take prepared organic inorganic hybridization silicon ball 0.85g, add 5mL trim,ethylchlorosilane and 20mL
Dry toluene, reacts 1h at nitrogen atmosphere 80 DEG C, stopped reaction, sucking filtration separation product, with anhydrous
Completely, 60 DEG C are dried under vacuum to constant weight in methanol washing.
Detailed description of the invention two:
1. take 0.2g crystallite amylose under high temperature, be vacuum dried 4h, then at anhydrous N, N-dimethylacetamide
Amine is stirred at reflux 12h；(quality is the 2 of amylose quality to add lithium chloride after being cooled to room temperature
Times)；After continuing stirring 3h, again heat up, add anhydrous pyridine, after backflow 2h, add appropriate 3,5-
Dimethylphenyl isocyanate (77mol% of amylose hydroxyl), adds after continuously stirred backflow 8h
Enter a small amount of 3-(trimethoxy silicon) propylisocyanate (6.9mol% of amylose hydroxyl) to hold
Continue and process (amylose hydroxyl with the 3,5-dimethylphenyl isocyanate of excess after being stirred at reflux 12h
The 90mol% of base), stopped reaction after continuously stirred backflow 8h；It is cooled to room temperature, adds methanol
Sedimentation filtration is also washed, and 60 DEG C are dried under vacuum to constant weight, and productivity is 85%.Synthesized amylose
3,5-dimethylphenylcarbamate and 3-(trimethoxy silicon) propyl carbamic acid in derivant
The introducing ratio of ester is 95:5.
2. take the product 0.25g synthesized by previous step, be completely dissolved in oxolane, and be added thereto to 6mL
N-heptanol, 2ml tetraethyl orthosilicate, 1mL water and 0.5mL trim,ethylchlorosilane react at 80 DEG C
9h。
3. during reactant is dropwise instilled the lauryl sodium sulfate aqueous solution of 80 DEG C by reaction after terminating with
1100rpm speed stirring ageing 1h, stopped reaction.Will obtain product sucking filtration, successively with hot water,
The washing of ethanol, normal hexane completely and is dried.
4. take prepared organic inorganic hybridization silicon ball 0.85g, add 5mL trim,ethylchlorosilane and 20mL
Dry toluene, reacts 1h at nitrogen atmosphere 80 DEG C, stopped reaction, sucking filtration separation product, with anhydrous
Completely, 60 DEG C are dried under vacuum to constant weight in methanol washing.
The high-load amylose-three (3,5-dimethylphenylcarbamate) that has prepared by the present invention spreads out
The productivity of biologic organic, inorganic hybrid silicon ball is high, and reproducible.
Claims (5)
1. the preparation side of an amylose analog derivative functionalization inorganic silica-based chirality microsphere stationary phase material
Method, is characterized in that:
(1), by dry crystallite amylose in anhydrous DMAC N,N' dimethyl acetamide, 70～80 DEG C of temperature
It is stirred at reflux 8-16h, is cooled to after room temperature to add the lithium chloride of 2 times of amylose quality, continues stirring
After 2-5h, again it is warming up to 70～80 DEG C, adds anhydrous pyridine, after backflow 2～4h, add amylose hydroxyl
The 3 of the 77mol% of base, 5-dimethylphenyl isocyanate, after continuously stirred backflow 8～10h, according to being wanted
Introducing ratio adds 3-(trimethoxy silicon) the continuously stirred backflow of propylisocyanate 12～16h, then uses
The 3 of amount, 5-dimethylphenyl isocyanate processes, and continuously stirred backflow 8～10h is cooled to room temperature, adds
Methanol sedimentation filtration is also washed, and 40～60 DEG C are dried under vacuum to constant weight；
(2), the product synthesized by step (1) is completely dissolved in oxolane and is just added thereto to
Enanthol, tetraethyl orthosilicate, water and trim,ethylchlorosilane, react 8～10h at 80～100 DEG C；
(3) sodium lauryl sulphate that the reactant, step (2) obtained adds 80～100 DEG C is water-soluble
With 1000～1200rpm speed stirring ageings 0.5～1h in liquid, product carries out sucking filtration, successively by hot water, second
Alcohol and normal hexane wash and are dried；
(4), trim,ethylchlorosilane and dry toluene are added, anti-under the conditions of 80～100 DEG C under nitrogen atmosphere
Answering 1～5h, sucking filtration separation product, with absolute methanol washing, 40～60 DEG C are dried under vacuum to constant weight.
Amylose analog derivative functionalization inorganic the most according to claim 1 silica-based chirality microsphere is fixed
The preparation method of phase material, is characterized in that: crystallite amylose is vacuum dried 2～8h at 80 DEG C.
Amylose analog derivative functionalization inorganic the most according to claim 1 and 2 silica-based chirality microsphere
The preparation method of stationary phase material, is characterized in that: the addition of 3-(trimethoxy silicon) propylisocyanate
For amylose hydroxyl 3～7mol%.
Amylose analog derivative functionalization inorganic the most according to claim 1 and 2 silica-based chirality microsphere
The preparation method of stationary phase material, is characterized in that: the 3 of described excess, at 5-dimethylphenyl isocyanate
Reason, 3,5-dimethylphenyl isocyanates are the 90mol% of amylose hydroxyl.
Amylose analog derivative functionalization inorganic the most according to claim 3 silica-based chirality microsphere is fixed
The preparation method of phase material, is characterized in that: the 3 of described excess, and 5-dimethylphenyl isocyanate processes,
3,5-dimethylphenyl isocyanate is the 90mol% of amylose hydroxyl.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268716A (en) * | 2016-10-21 | 2017-01-04 | 哈尔滨工程大学 | The preparation method of functionalization inorganic based on straight chain starch derivative silica-based chirality microsphere stationary phase material |
| CN108752643A (en) * | 2018-04-10 | 2018-11-06 | 哈尔滨工程大学 | Preparation method based on cellulose derivative nano silicon dioxide hybridization material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104741102A (en) * | 2013-12-30 | 2015-07-01 | 中国科学院兰州化学物理研究所 | A preparing method of a surface organic-inorganic hybrid core-shell type polysaccharide chiral stationary phase |
| CN105017437A (en) * | 2015-07-24 | 2015-11-04 | 哈尔滨工程大学 | Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups |
-
2016
- 2016-05-06 CN CN201610297892.5A patent/CN105903456B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104741102A (en) * | 2013-12-30 | 2015-07-01 | 中国科学院兰州化学物理研究所 | A preparing method of a surface organic-inorganic hybrid core-shell type polysaccharide chiral stationary phase |
| CN105017437A (en) * | 2015-07-24 | 2015-11-04 | 哈尔滨工程大学 | Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268716A (en) * | 2016-10-21 | 2017-01-04 | 哈尔滨工程大学 | The preparation method of functionalization inorganic based on straight chain starch derivative silica-based chirality microsphere stationary phase material |
| CN108752643A (en) * | 2018-04-10 | 2018-11-06 | 哈尔滨工程大学 | Preparation method based on cellulose derivative nano silicon dioxide hybridization material |
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