CN108752643A - Preparation method based on cellulose derivative nano silicon dioxide hybridization material - Google Patents
Preparation method based on cellulose derivative nano silicon dioxide hybridization material Download PDFInfo
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- CN108752643A CN108752643A CN201810511828.1A CN201810511828A CN108752643A CN 108752643 A CN108752643 A CN 108752643A CN 201810511828 A CN201810511828 A CN 201810511828A CN 108752643 A CN108752643 A CN 108752643A
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- DYIJABPBKJCGJJ-UHFFFAOYSA-N CC(C1)=CC(C)=CC1C=[IH] Chemical compound CC(C1)=CC(C)=CC1C=[IH] DYIJABPBKJCGJJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention is to provide a kind of preparation methods based on cellulose derivative nano silicon dioxide hybridization material.The present invention is using microcrystalline cellulose as base starting material, 3 are introduced simultaneously in the sugar unit of microcrystalline cellulose, 5- dimethylphenylcarbamates and a small amount of 3- (triethoxysilylpropyl) carbamate, cellulose-three (3, the 5- dimethylphenylcarbamate) derivative of synthesis containing a small amount of 3- (triethoxysilylpropyl) group.Synthesized cellulose derivative is completely dissolved in tetrahydrofuran, copolymerzation with cross-linking is carried out by the precipitation method and ethyl orthosilicate, the cellulose derivative nano silicon dioxide hybridization material for having good spherical morphology is finally prepared.The condition that the clear feasible, technical maturity of the above synthetic route, easy to operate, needs control is few and is easily achieved, and can be used for producing in batches on a large scale.
Description
Technical field
The present invention relates to a kind of preparation method of functional material, specifically a kind of nano silicon dioxide hybridization material
The preparation method of material.
Background technology
Polysaccharide carbanilate derivative is widely used in efficiently due to outstanding chiral recognition
The preparation of liquid chromatogram chiral stationary phase.So far, chiral Recognition is had excellent performance by most of chiral stationary phase materials
Polysaccharide derivatives are combined with silica-gel carrier in a manner of coating or being bonded and are prepared, and silica gel itself is without chiral Recognition
Ability.Polysaccharide derivatives content in this kind of chiral stationary phase material is typically not greater than 20%, this feature constrains significantly
Further development with efficient chiral recognition performance chiral stationary phase.Therefore exploitation has high load capability and high chiral identification
The novel chiral separation material of performance has highly important theoretical and practical significance.
For the organic phase of hybrid polymeric material with inorganic phase size in nanometer range, the mixing of this precision makes these
Material shows simple organic polymer in optical transparence, tunable refractive index, mechanical property, high temperature resistant, wear-resistant etc.
Superior function not available for material or inorganic material.Organic phase and inorganic phase in hybrid polymeric material both can be with hydrogen bond knots
Close, and can covalently be keyed, to reach organic component and inorganic component on a molecular scale compound, can have both organic matter and
The advantage performance of inorganic matter.Currently, hybridized polymer has become the research hotspot of scientific workers as a cross discipline
One of.
Invention content
The purpose of the present invention is to provide a kind of technical maturity, simple, can be used for large-scale mass production based on fiber
The preparation method of plain derivates nanometer silicon dioxide hybrid materials.
The object of the present invention is achieved like this：
Step 1: microcrystalline cellulose is taken to be dried in vacuo 4h, then it is stirred at reflux in anhydrous n,N-dimethylacetamide
12h；Lithium chloride is added after being cooled to room temperature, continues after stirring 2-5h, heats up again, anhydrous pyridine is added, is added after the 6h that flows back
After being persistently stirred at reflux 8-10h, it is lasting that 3- (triethoxysilicane) propylisocyanate is added in 3,5- dimethylphenyl isocyanates
It is stirred at reflux 17-20h, then is handled with excessive 3,5- dimethylphenyl isocyanates, stops reaction after being persistently stirred at reflux 7h,
It is cooled to room temperature, methanol sedimentation filtration is added and washs, 60 DEG C are dried under vacuum to constant weight；
Step 2: step 1 products therefrom is dissolved in tetrahydrofuran, ethyl alcohol or isopropanol, water and diethyl is then added
Amine stirs evenly, and is eventually adding ethyl orthosilicate, stirs 4h at room temperature, stops reaction, and with ethyl alcohol centrifugation, washing, solid is produced
It is dried in vacuo under object room temperature.
The present invention can also include：
1, the heating amount of 3,5- dimethylphenyl isocyanates is the 83mol% of microcrystalline cellulose hydroxyl.
2, the stir speed (S.S.) in step 2 is 300rpm.
The present invention provides one kind to contain (the 3,5- 3,5-dimethylphenyls of cellulose-three of 2%3- (triethoxysilylpropyl)
Carbamate) derivative be template, diethylamine is catalyst, and tetraethyl orthosilicate is silicon source, prepare be based on cellulose derivative
The method of nano silicon dioxide hybridization material.And application scanning Electronic Speculum (SEM) characterizes its appearance, and utilize efficient liquid phase
Chromatography realizes the evaluation to its chiral recognition.
Fig. 4 is synthesized (the 3,5- dimethylphenylaminos of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl
Formic acid esters) nuclear magnetic resonance spectroscopy (1HNMR), it can be seen from figure 4 that the compound with regular structure of synthesized derivative, right1H H NMR spectroscopies
The integrated value for scheming each formant is analyzed, and the ratio of 3- (triethoxysilicane) propyl and (3,5) -3,5-dimethylphenyl is 98/2,
Meet expected structure target.And the chromatographic results in the table 1 of Fig. 7 show it is this kind of be based on cellulose derivative nano silicon dioxide
Hybrid material shows various racemic modifications outstanding chiral recognition, particularly with 7 kinds of enantiomers in the present invention, divides
It Wei not Te Luojie alkali (Fig. 3-1), trans- 2,3- hexichol hexadecyl ethylene oxide (Fig. 3-2), benzoin (Fig. 3-3), 2,2,2- fluoroforms
Base-1- (9- anthryls)-ethyl alcohol (Fig. 3-5), flavanones (Fig. 3-7), 2,2- dimethyl-1- phenyl-propanols (Fig. 3-8) and be dinaphthalene
Phenol (Fig. 3-9) can be achieved to efficiently separate.What is particularly worth mentioning is that for Te Luojie alkali (Fig. 3-1) and trans- 2,3- hexichol
The separating effect of two kinds of enantiomers of hexadecyl ethylene oxide (Fig. 3-2) has been more than excellent effect in presently commercially available commercialization chiral column
Bonding type ChiralcelIB columns, show prepared by the present invention based on the cellulose-containing a small amount of 3- (triethoxysilicane) propyl
There is the nano silicon dioxide hybridization material of three (3,5- dimethylphenylcarbamates) larger practical value and market to open
Send out potentiality.Wherein, Fig. 6 is the nano silicon dioxide hybridization material A prepared by the present invention for Te Luojie alkali enantiomers (Fig. 3-1)
Chromatographic resolution spectrogram.It will be seen from figure 6 that the hybrid material prepared by the present invention realizes Te Luojie alkali enantiomers
Complete baseline separation, and separating effect is considerably beyond chiral commodity column ChiralcelIB.
We are carried out to prepared based on cellulose derivative nano silicon dioxide hybridization material with scanning electron microscope simultaneously
Detailed structure and morphology characterization.Fig. 4 is the stereoscan photograph based on cellulose derivative nano silicon dioxide hybridization material,
From the figure, it can be seen that regular spherical morphology is presented in hybrid material prepared by the present invention, meet target, can be used for chirality
The preparation of stationary phase material.
The present invention introduces 3,5- diformazans simultaneously in the sugar unit of microcrystalline cellulose first using microcrystalline cellulose as base starting material
Base carbanilate and a small amount of 3- (triethoxysilylpropyl) carbamate, synthesis contain a small amount of 3- (triethoxies
Silicon propyl) group cellulose-three (3,5- dimethylphenylcarbamates) derivative.It on this basis, will be synthesized
Cellulose derivative is completely dissolved in tetrahydrofuran, and copolymerzation with cross-linking is carried out by the precipitation method and ethyl orthosilicate, final to prepare
Obtain the cellulose derivative nano silicon dioxide hybridization material for having good spherical morphology.The above synthetic route it is clear it is feasible,
The condition that technical maturity, easy to operate, needs control is few and is easily achieved, and can be used for producing in batches on a large scale.
The cellulose that the present invention uses derives from a wealth of sources with tetraethyl orthosilicate, is cheap and easy to get, and entire synthesis technology it is simple,
It is ripe, easily controllable.
Description of the drawings
It is (the 3,5- dimethylphenylamino formic acid of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl in Fig. 1
Ester) synthetic route.Wherein, R1For 3,5- 3,5-dimethylphenylsR2Position 3- (triethoxysilicane) propyl
For based on (the 3,5- dimethylphenylamino first of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl in Fig. 2
Acid esters) nano silicon dioxide hybridization material synthetic route.
It is listed in Fig. 3 for evaluating nine based on cellulose derivative nano silicon dioxide hybridization material chiral recognition
The structure of kind racemic modification.Wherein, Fig. 3-1 is Te Luojie alkali, and Fig. 3-2 is trans- 2,3- hexichol hexadecyl ethylene oxide, and Fig. 3-3 is benzene
Acyloin, Fig. 3-4 are 2- phenyl cyclohexanones, and Fig. 3-5 is 2,2,2- Trifluoromethyl-1s-(9- anthryls)-ethyl alcohol, and Fig. 3-6 is triacetyl
Benzylacetone acid cobalt, Fig. 3-7 are flavanones, and Fig. 3-8 is 2,2- dimethyl-1- phenyl-propanols, and Fig. 3-9 is dinaphthol.
Fig. 4 is synthesized (the 3,5- dimethylphenylaminos of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl
Formic acid esters) nuclear magnetic resonance spectroscopy (1HNMR)。
Fig. 5 is the stereoscan photograph based on cellulose derivative nano silicon dioxide hybridization material A.
Fig. 6 is based on (the 3,5- dimethylphenylamino formic acid of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl
Ester) nano silicon dioxide hybridization material A for Te Luojie alkali enantiomers Chromatographic resolution spectrogram.
Fig. 7 is chiral resolution result table 1 of 2 kinds of novel cellulose derivatives for nine kinds of racemic modifications.
Specific implementation mode
It illustrates below and the present invention is described in more detail.
Specific implementation mode one：
Step 1：It takes 1g microcrystalline celluloses in vacuum drying 4h, is then stirred in the anhydrous n,N-dimethylacetamide of 30mL
Mix reflux 12h；1.5g lithium chlorides are added after being cooled to room temperature；Continue after stirring 2h, be warming up to 80 DEG C again, it is anhydrous that 15mL is added
Appropriate 3,5- dimethylphenyl isocyanates (83mol% of microcrystalline cellulose hydroxyl) are added after the 6h that flows back in pyridine, lasting to stir
It flows back after 8-10h, quantitative 3- (triethoxysilicane) propylisocyanate is added according to the ratio of being introduced and is persistently stirred at reflux
17h, then handled with excessive 3,5- dimethylphenyl isocyanates, stop reaction after being persistently stirred at reflux 7h；It is cooled to room temperature,
Methanol sedimentation filtration is added simultaneously to wash, 60 DEG C are dried under vacuum to constant weight, yield 88%, 3,5- in synthesized cellulose derivative
The introducing ratio of dimethylphenylcarbamate and 3- (trimethoxy silicon) propyl carbamate is 98:2.
Step 2：It takes the above-mentioned products of 0.2g to be dissolved in 30mL tetrahydrofurans, ethyl alcohol, water and diethylamine, tetrahydrochysene is then added
The volume ratio of furans/ethanol/water/diethylamine stirs evenly for 30/15/3/8, is eventually adding 2mL ethyl orthosilicates, stirs at room temperature
Mix 4h, stir speed (S.S.) 300rpm.Stop reaction, with ethyl alcohol centrifugation, washing, will be dried in vacuo, obtain under solid product room temperature
Nano silicon dioxide hybridization material A.
The present invention obtains (the 3,5- dimethylphenylaminos of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl
Formic acid esters) compound with regular structure, yield is high.The regular appearance of prepared nano silicon dioxide hybridization material, uniform particle sizes, and have
There is excellent chiral recognition.
Specific implementation mode two：
Step 1：It takes 1g microcrystalline celluloses in vacuum drying 4h, is then stirred in the anhydrous n,N-dimethylacetamide of 30mL
Mix reflux 12h；1.5g lithium chlorides are added after being cooled to room temperature；Continue after stirring 2h, be warming up to 80 DEG C again, it is anhydrous that 15mL is added
Appropriate 3,5- dimethylphenyl isocyanates (83mol% of microcrystalline cellulose hydroxyl) are added after the 6h that flows back in pyridine, lasting to stir
It flows back after 8-10h, quantitative 3- (triethoxysilicane) propylisocyanate is added according to the ratio of being introduced and is persistently stirred at reflux
17h, then handled with excessive 3,5- dimethylphenyl isocyanates, stop reaction after being persistently stirred at reflux 7h；It is cooled to room temperature,
Methanol sedimentation filtration is added simultaneously to wash, 60 DEG C are dried under vacuum to constant weight, yield 88%, 3,5- in synthesized cellulose derivative
The introducing ratio of dimethylphenylcarbamate and 3- (trimethoxy silicon) propyl carbamate is 96:4.
Step 2：The above-mentioned products of 0.2g are taken to be dissolved in 30mL tetrahydrofurans, then addition isopropanol, water and diethylamine, four
The volume ratio of hydrogen furans/isopropanol/water/diethylamine stirs evenly for 30/15/3/8, is eventually adding 2mL ethyl orthosilicates, room temperature
Lower stirring 4h, stir speed (S.S.) 300rpm.Stop reaction, with ethyl alcohol centrifugation, washing, will be dried in vacuo under solid product room temperature,
Obtain nano silicon dioxide hybridization material B.
The present invention obtains (the 3,5- dimethylphenylaminos of cellulose-three containing a small amount of 3- (triethoxysilicane) propyl
Formic acid esters) compound with regular structure, yield is high.The regular appearance of prepared nano silicon dioxide hybridization material, uniform particle sizes, and have
There is excellent chiral recognition.
Claims (3)
1. a kind of preparation method based on cellulose derivative nano silicon dioxide hybridization material, it is characterized in that：
Step 1: microcrystalline cellulose is taken to be dried in vacuo 4h, then 12h is stirred at reflux in anhydrous n,N-dimethylacetamide；It is cold
But to lithium chloride is added after room temperature, continue after stirring 2-5h, heat up again, anhydrous pyridine is added, 3,5- bis- is added after the 6h that flows back
Methylphenyl isocyanate after being persistently stirred at reflux 8-10h, is added 3- (triethoxysilicane) propylisocyanate and persistently stirs back
17-20h is flowed, then is handled with excessive 3,5- dimethylphenyl isocyanates, stops reaction after being persistently stirred at reflux 7h, is cooled to
Room temperature is added methanol sedimentation filtration and washs, and 60 DEG C are dried under vacuum to constant weight；
Step 2: step 1 products therefrom is dissolved in tetrahydrofuran, ethyl alcohol or isopropanol, water and diethylamine is then added, stirs
It mixes uniformly, is eventually adding ethyl orthosilicate, stir 4h at room temperature, stop reaction, it is with ethyl alcohol centrifugation, washing, solid product is normal
The lower vacuum drying of temperature.
2. the preparation method according to claim 1 based on cellulose derivative nano silicon dioxide hybridization material, special
Sign is：The heating amount of 3,5- dimethylphenyl isocyanates is the 83mol% of microcrystalline cellulose hydroxyl.
3. the preparation method according to claim 1 or 2 based on cellulose derivative nano silicon dioxide hybridization material,
It is characterized in：Stir speed (S.S.) in step 2 is 300rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908813A (en) * | 2021-10-22 | 2022-01-11 | 浙江大学衢州研究院 | Cellulose derivative-silicon-based hybrid microsphere and preparation method thereof |
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Application publication date: 20181106 |