CN102212190A - Silica gel bonded with single-chiral spiral polyether, preparation method thereof, and application thereof used as chiral immobile phase of high-performance liquid chromatographic column - Google Patents
Silica gel bonded with single-chiral spiral polyether, preparation method thereof, and application thereof used as chiral immobile phase of high-performance liquid chromatographic column Download PDFInfo
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Abstract
The invention discloses silica gel bonded with a single-chiral spiral polyether which has a frame structure of poly[3-(9-alkylfluoren-9-yl)-1,2-epoxy propane], a preparation method thereof, and application thereof used as a chiral immobile phase of a high-performance liquid chromatographic column. The invention has the following technical effects that: the silica gel bonded with a single-chiral spiral polyether which has the frame structure of poly[3-(9-alkylfluoren-9-yl)-1,2-epoxy propane] is used as the chiral immobile phase of the high-performance liquid chromatographic column, which can separate and analyze a plurality of racemes such as alcohols, ketones, esters, carboxylic acids and amines.
Description
Technical field
The present invention relates to bonding poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure unidextrality spiral polyethers silica gel preparation and as the high performance liquid chromatography chiral stationary phase to analyze and the separation of racemic body.
Background technology
Okamoto adopted the polymerization of spiral selectivity polymerization process with methacrylic triphenyl phosphate methyl esters in 1979, had obtained keeping in solution the polymethyl triphenyl phosphate methyl esters (J.Am.Chem.Soc.1979,101,4763) of unidextrality spirane structure first.Okamoto finds that the polymethyl triphenyl phosphate methyl esters of this unidextrality spiral can be used as high performance liquid chromatography (HPLC) chiral stationary phase subsequently, in order to separation of racemic body (J.Am.Chem.Soc.1980,102,6358; J.Am.Chem.Soc., 1981,103,6971).This chiral stationary phase is successfully made commercial HPLC chiral chromatographic column now.
Though unidextrality helix poly methacrylic triphenyl phosphate methyl esters is as the chiral stationary phase of HPLC, can separate many racemic modifications, thereby but this spiropolymer easily and the common solvent methyl alcohol generation alcoholysis of HPLC and lose the bulky group trityl and lose chiral helical character.In order to strengthen the anti-alcoholysis ability of this chiral helical polymkeric substance, chemists have done many modifications and transformation to poly-methyl three benzene methyls, for example introduce nitrogen-atoms or other electron-withdrawing substituent (J.Polym.Sci., Part A:Polym.Chem.1993 on aromatic ring, 31,2721-2728; J.Polym.Sci., Part A:2001 39,1610-1614; J.Polym.Sci., Part A:Polym.Chem., 199836,2013-2019), or two phenyl are coupled together (polymer Journal, 1996,28 330-336) with ethylene group.Though these modifications and transformation can reach the effect that suppresses alcoholysis, do not break away from the ester group character of side chain all the time, thereby can not thoroughly solve the problem of alcoholysis.
In order thoroughly to solve the alcoholysis problem, in recent years, people had designed the chiral helical polymkeric substance of many types.Up to the present, the polymkeric substance that keeps stablizing the unidextrality spirane structure in solution of report has: polyacrylamide (J.Polym.Sci.:Part A:Polymer Chemistry, 2010,48,5411-5418), (Macromolecules 2010 for the polycarbodiimide class, 43,1867-1873), polyacetals class (J.Polym.Sci., Part A:Polym.Chem.2000,38,2623), polymeric polyisocyanate class (Polym.J.1993,25,391), polyacetylene class (Macromolecules, 200740, No.19; Macromolecules 2000,33,3978), poly-isonitrile class (Angew.Chem., Int.Ed.Engl.1996,35,1554), poly-aryne class (Angew.Chem., Int.Ed.Engl.1996,35,2111) etc.The application of many novel unidextrality spiropolymers has been arranged patent.As: the poly-isonitrile of unidextrality spiral in 2009 has obtained United States Patent (USP), US7619109B2.Also applied for patent with chiral polymer as many achievements of high performance liquid chromatography (HPLC) chiral stationary phase in China, as: CN200410013305.2.
About the applied research of chiral helical polymkeric substance as the chiral chromatography stationary phase, people such as Eiji Yashima and YOSHIO OKAMOTO have done recently and have summarized (Chem.Rev.2009,109,6102-6211, J.Polym.Sci:Part A:Polymer Chemistry, 200947,1731-1739).
The above-mentioned unidextrality spiropolymer as the HPLC chiral stationary phase of hitherto reported all is the polymkeric substance of unsaturated compound, but almost not about the report of unidextrality helix poly epoxy compounds as the HPLC chiral stationary phase.This be because polyethylene oxide derivant and poly-unsaturated compound to compare main chain submissiveer, be not easy to form the unidextrality spirane structure.
We have successfully obtained unidextrality helix poly (4,4,4-triphenyl butylene oxide ring) (Polym.Int., 2008,57,530 by introduce large volume side chain radical triphenyl ethyl on the main chain of polyethylene oxide; Polym.Bull., 2007,59,481.).But the polymerization degree of this polymkeric substance has only about 7-9, and is very restricted on using.We have and have synthesized a kind of polyethers with fluorenyl recently, shown in following 1 formula of its structural formula:
In the formula, R is alkyl, aryl or other alkyl; Substituting group can also be with in other position of fluorenes ring; R
1Be alkyl or hydrogen atom; M is an integer.
We find that this class polyethers has stable unidextrality spirane structure in solution, and the polymerization degree of resultant unidextrality spiral polyethers reaches more than 18, molecular weight distribution also very narrow (Polymer, 2010515712-5718).We have applied for patent (2010101014357) in China the structure of this unidextrality spiral polyethers and synthetic method thereof.Unidextrality spiral polyethers does not have ester bond fully, has thoroughly eliminated alcoholysis.Recently, studied the chiral recognition function of this class unidextrality spiral polyethers, found that this class unidextrality spiral polyethers can be used as the chiral stationary phase of HPLC, separates many racemic modifications.The present invention makes the chiral stationary phase of HPLC with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] the unidextrality spiral polyethers of skeleton structure that has that patent 2010101014357 is invented, and the analysis that chiral stationary phase is used for raceme with separate.
Summary of the invention
The purpose of this invention is to provide bonding and had a poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] skeleton structure unidextrality spiral polyethers silica gel, use this bonding have poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure the silica gel of unidextrality spiral polyethers as the chiral stationary phase of high performance liquid chromatography to separate and to analyze the synthetic method of the chiral stationary phase of racemic modification and this high performance liquid chromatography.
A kind of bonding have the silica gel of the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure, this silica gel has the skeleton structure shown in the formula 2:
In the formula: R is CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl; R
1It is alkyl; R
2And R
3Be alkyl, R
2And R
3Can be identical, also can be inequality; X is the coupling agent residue; Being with the configuration of * number carbon atom all is the S type, or all is the R configuration; M is an integer.
Bonding have a preparation method of silica gel of the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Bonding have the unidextrality spiral polyethers silica gel of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure the preparation method have 4 kinds.
Method one:
The epoxy compounds that will have skeleton structure shown in 3 formulas is used the anionic initiator initiated polymerization in body, obtain polymkeric substance 4; Reaction is shown in reaction formula one, in the formula: R is identical with the front, and M is an atoms metal, R
1Be alkyl.Polymkeric substance 4 and coupling agent 5 (as 3-glycidyl propyl trimethoxy silicane) reaction obtain being connected with 6 of coupling agent residue then; Reaction is shown in reaction formula two, in the formula: R
2, R
3And R
3Be alkyl, R
2, R
3And R
3Can be identical, also can be different, Y is a substituting group, this substituting group has and O is connected to functional group on the Y after can reacting with the M-O key.6 slough alcohol with the hydroxyl generation condensation reaction on silica gel particle surface has more promptly obtained bonding and has had the unidextrality spiral polyethers silica gel 2 of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure; Reaction is shown in reaction formula three.
Reaction formula one
Reaction formula two
Reaction formula three
Method two:
The epoxy compounds that will have skeleton structure shown in 3 formulas is used the anionic initiator initiated polymerization in solution, obtain polymkeric substance 4; Reaction is shown in reaction formula four, in the formula: R is identical with the front, and M is an atoms metal, R
1Be alkyl).And then carry out the reaction of back by method one, obtain bonding and had the silica gel 2 of the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Reaction formula four
Method three:
Silica gel particle generates the silica gel particle 7 of silanization earlier with coupling agent 5 reactions; Reaction is shown in reaction formula five.7 again with 4 reactions that obtain by mass polymerization, obtained bonding and had the silica gel 2 of the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure; Reaction is shown in reaction formula six.
Reaction formula five
Reaction formula six
Method four:
Silica gel particle generates the silica gel particle 7 of silanization earlier with coupling agent 5 reactions; 7 again with 4 reactions that obtain by solution polymerization, obtained bonding and had the silica gel 2 of the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
The 2nd, bonding have a representative structure formula of the unidextrality spiral polyethers silica gel of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.X in the formula is the group that forms by behind the M-O radical reaction in the Y in the coupling agent 5 and 4, and we claim that this group is the coupling agent residue.As: when coupling agent was 3-glycidyl propyl trimethoxy silicane (8), 8 epoxy group(ing) and 4 reactions generated 9 (seeing reaction formula seven).9 have generated bonding with the hydroxyl reaction on silica gel particle surface has the unidextrality spiral polyethers silica gel 10 (seeing reaction formula eight) of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Reaction formula seven
Reaction formula eight
At this moment, the structure of coupling agent residue X is 11:
9 can also polymerizations take place with other 8 generates 12 (seeing reaction formula nine).CH in 12
3The unidextrality spiral polyethers silica gel 13 (seeing reaction formula ten) that the hydroxyl on O and silica gel surface reacts and makes silica gel particle and polyethers bonding get up to form bonding to have poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Reaction formula nine
Reaction formula ten
At this moment, the structure of coupling agent residue X is 14:
OR in 2 formulas
2And OR
3Can also slough the structure of alcohol generation shown in 15 and 16 with the hydroxyl reaction on silica gel surface.
If as also having SiOR among the coupling agent residue X
2Group, SiOR
2In OR
2Can also slough alcohol with the hydroxyl generation condensation reaction on silica gel surface and generate the Si-O-Si key, make it to link up with silica gel particle again.As also having three CH in the coupling agent residue 14
3The O-Si key, these three CH
3The O-Si key can also be sloughed methyl alcohol with the hydroxyl condensation reaction on silica gel surface and generate the Si-O-Si key.
Technique effect of the present invention: use the present invention poly-[3-(9-alkyl fluorenes-9-yl)-1 that prepared bonding, the 2-propylene oxide] silica gel of unidextrality spiral polyethers of skeleton structure can the many racemic modifications of compartment analysis as the high performance liquid chromatography chiral stationary phase, and these racemic modifications have alcohols, ketone, lipid, carboxylic-acid, amine etc.
Embodiment
Following is to further specify of the present invention in conjunction with example, but the present invention does not limit to following example.
Example 1: the activation of silica gel
60g ball-type silica gel is put into the 2000mL there-necked flask, add the hydrochloric acid of 1500mL 10%, reflux 10h.Cooled and filtered.After filter cake is washed with distilled water to the water that washes out and is neutrality, more repeatedly with washing with acetone.After treating the acetone volatilization on surface, place baking oven at 160 ℃ of dry 8h filter cake, it is standby to be kept in the moisture eliminator cooling then.
Example 2: the preparation bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.Method one.
In being housed, the reaction flask of magnetic stir bar adds 8 mmoles (S)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane and 0.020g KOH.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.Reaction flask is placed 100-110 ℃ of oil bath, under magnetic agitation, react.When reactant solidifies, after stirrer can not stir, oil bath temperature is reduced to 80 ℃, add the 3mL dry toluene with syringe.After treating that solid piece dissolves fully, add 0.4 mmole (0.095 gram) 3-glycidyl propyl trimethoxy silicane, in 80 ℃ of oil bath stirring reactions 4 hours.With syringe reaction solution is taken out then, be injected into rapidly in the there-necked flask that 60mL dry toluene and 4.00g activatory silica gel are housed, and add the 0.1mL triethylamine.Under the high-purity argon gas protection, there-necked flask is placed 100-110 ℃ of oil bath back flow reaction 48h.Reaction mixture is chilled to the room temperature after-filtration, and filter cake is used toluene, methyl alcohol and washing with acetone successively, and the acetone extracting is 48 hours then.The gained solid carries out end-blocking with trimethylchlorosilane.Solid behind the end-blocking is 60 ℃ of following vacuum-dryings 8 hours, the 4.622g white solid, promptly bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Example 3: the preparation bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.Method two.
In being housed, the reaction flask of magnetic stir bar adds 8 mmoles (S)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.Inject the tetrahydrofuran solution of the potassium tert.-butoxide of 3mL dry toluene and 0.2 mmole with syringe.Reaction flask is placed 100-110 ℃ of oil bath, and reaction is 12 hours under magnetic agitation.Oil bath temperature is reduced to 80 ℃, add 0.4 mmole (0.095 gram) 3-glycidyl propyl trimethoxy silicane, in 80 ℃ of oil bath stirring reactions 4 hours.With syringe reaction solution is taken out then, be injected into rapidly in the there-necked flask that 60mL dry toluene and 4.00g activatory silica gel are housed, and add the 0.1mL triethylamine.Reaction mixture under the high-purity argon gas protection, was placed 100-110 ℃ of oil bath back flow reaction 48 hours.Reaction mixture is chilled to the room temperature after-filtration, and filter cake is used toluene, methyl alcohol and washing with acetone successively, and the acetone extracting is 48 hours then.The gained solid carries out end-blocking with trimethylchlorosilane.Solid behind the end-blocking is 60 ℃ of following vacuum-dryings 8 hours, the 4.724g white solid, promptly bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Example 4: the preparation bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.Method three.
Earlier silica gel is used 3-glycidyl propyl trimethoxy silicane silanization: in there-necked flask, add 4.00g activatory silica gel.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.In there-necked flask, inject 50mL dry toluene, 0.5 mmole (0.118 gram) 3-glycidyl propyl trimethoxy silicane and 0.1mL triethylamine with syringe.There-necked flask was placed 100-110 ℃ of oil bath back flow reaction 48 hours.Cooled and filtered is isolated solid, and solid is put into the moisture eliminator drying for standby after washing with dry toluene.
In the reaction flask that magnetic stir bar is housed, add 8 mmoles (S)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane and 0.020g KOH.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.Reaction flask is placed 100-110 ℃ of oil bath, under magnetic agitation, react.When reactant solidifies, after stirrer can not stir, oil bath temperature is reduced to 80 ℃, add the 60mL dry toluene with syringe solid is dissolved fully, must gather the unidextrality helix poly ethereal solution of [3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
The silica gel that adds above-mentioned silanization in three mouthfuls of reaction flasks.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.The unidextrality helix poly ethereal solution that will gather [3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure with syringe is injected in the reaction flask.Reaction flask is placed 100-110 ℃ of oil bath reaction 5 hours.Reaction mixture is chilled to the room temperature after-filtration, and filter cake is used toluene, methyl alcohol and washing with acetone successively, and the acetone extracting is 48 hours then.The gained solid carries out end-blocking with trimethylchlorosilane.Solid behind the end-blocking is 60 ℃ of following vacuum-dryings 8 hours, the 4.511g white solid, promptly bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Example 5: the preparation bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.Method four.
In being housed, the reaction flask of magnetic stir bar adds 8 mmoles (S)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.Inject the tetrahydrofuran solution of the potassium tert.-butoxide of 3mL dry toluene and 0.2 mmole with syringe.Reaction flask is placed 100-110 ℃ of oil bath, and reaction is 12 hours under magnetic agitation.Cooling is gathered the solution of the unidextrality spiral polyethers of [(S)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
In three mouthfuls of reaction flasks, add the silica gel of pressing example 4 silanizations.Charge into high-purity argon gas after reaction flask vacuumized, repeatedly pumping applying argon gas operation 2 times.The unidextrality helix poly ethereal solution that will gather [(S)-3-(9-gathers basic fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure with syringe is injected in the reaction flask.Reaction flask was placed 100-110 ℃ of oil bath back flow reaction 5 hours.Reaction mixture is chilled to the room temperature after-filtration, and filter cake is used toluene, methyl alcohol and washing with acetone successively, and the acetone extracting is 48 hours then.The gained solid carries out end-blocking with trimethylchlorosilane.Solid behind the end-blocking is 60 ℃ of following vacuum-dryings 8 hours, the 4.531g white solid, promptly bonding have the silica gel of the unidextrality spiral polyethers of poly-[(S)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Example 6: the preparation bonding have the silica gel of the unidextrality spiral polyethers of poly-[(R)-3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure
In example 2, example 3, example 4 and example 5, with (S)-3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide changes (R)-3-(9-alkyl fluorenes-9-yl)-1 into, the 2-propylene oxide has obtained corresponding bonding equally and has had the silica gel of the unidextrality spiral polyethers of poly-[(R)-3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
Example 7: with bonding have a unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure silica gel fix and prepare chirality HPLC post and external mesotomy ability assessment thereof mutually.
With packing column machine will be by the bonding of examples preparation have a unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure silica gel pack the stainless steel column jecket into (in 250 * 4.6mm.i.d.) with the homogenate method.Stuffing pressure is 30-50MPa during the dress post.The rust steel column that installs is the HPLC chiral chromatographic column with moving phase balance repeatedly.Carrying out racemic modification on this chromatographic column splits.Filter through the G4 sand core funnel before all moving phases are used, and use ultrasonic degas, flow velocity is 0.8mL/min, and column temperature is room temperature (25 ℃).The detection wavelength is 254nm.By 1,3, the 5-tri-butyl benzene is measured the dead time t of pillar
0The retention time that goes out the isomer at peak earlier is designated as t
1, its capacity factor is designated as k
1, k
1=(t
1-t
0)/t
0After go out the isomer at peak retention time be designated as t
2, its capacity factor is designated as k
2, k
, 2=(t
2-t
0)/t
0Enantioselectivity α is defined as: α=k
2/ k
1
Example 8: bonding have the silica gel of unidextrality spiral polyethers of poly-[(S)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure to the fractionation of racemic modification.
By example 2 described methods prepare bonding poly-[(S)-3-(9-ethyl fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers, fix by example 7 making HPLC chiral columns and the chromatographic separation of carrying out racemic modification with this silica gel, the results are shown in table one.
The fractionation effect of table one, chiral helical poly-[(S)-3-(9-ethyl fluorenes-9-yl)-1,2-oxyethane] post
Example 9: bonding have the silica gel of unidextrality spiral polyethers of poly-[(R)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure to the fractionation of racemic modification
By example 4 described methods prepare bonding poly-[(R)-3-(9-propyl group fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers, fix by example 7 making HPLC chiral columns and the chromatographic separation of carrying out racemic modification with this silica gel, the results are shown in table two.
The fractionation effect of table two, chiral helical poly-[(R)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane] post
Example 9: bonding have the silica gel of unidextrality spiral polyethers of poly-[(S)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure to the fractionation of racemic modification
By example 3 described methods prepare bonding poly-[(S)-3-(9-butyl fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers, fix by example 7 making HPLC chiral columns and the chromatographic separation of carrying out racemic modification with this silica gel, the results are shown in table three.
The fractionation effect of table three, chiral helical poly-[(S)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane] post
The present invention obtain National Natural Science Foundation of China (NSFC) (subsidize number: 20972131) and University Of Xiangtan's natural science fund (subsidize number: 06KZ/KZ033008) subsidy.
Claims (8)
- A bonding poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers of skeleton structure, it is characterized in that bonding the silica gel of unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure have the structure shown in the formula I;
In the formula: R is an alkyl; R 2And R 3Be alkyl, R 2And R 3Can be identical, also can be inequality; X is the coupling agent residue; Being with the configuration of * number carbon atom all is the S type, or all is the R configuration. - Bonding according to claim 1 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] the silica gel I of unidextrality spiral polyethers of skeleton structure, it is characterized in that the silica gel particle surface is connected with the chiral helical polyether chain with poly-[3-(the 9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure shown in the formula III by coupling agent (II);
In the II formula: Y is a substituting group, and this substituting group has and O is connected to functional group on the Y after can reacting with the M-O key in the HI formula; R 2, R 3And R 4Be alkyl, R 2, R 3And R 4Can be identical, also can be different; In the HI formula: R 1Be alkyl, M is atoms metal or hydrogen atom, and R is an alkyl. - Bonding according to claim 1 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] preparation method of silica gel of unidextrality spiral polyethers of skeleton structure, it is characterized in that silica gel particle and have the poly-[3-(9-alkyl fluorenes-9-yl)-1 shown in the formula III, the 2-propylene oxide] the chiral helical polyether chain of skeleton structure connects the silica gel of unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure that obtained bonding by coupling agent.
- Bonding according to claim 3 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] preparation method of silica gel of unidextrality spiral polyethers of skeleton structure, it is characterized in that general formula is that the linking agent of II and spiral polyether reactant that general formula is III obtain the poly-[3-(9-alkyl fluorenes-9-yl)-1 that general formula is the silanization of IV, the 2-propylene oxide] the unidextrality spiral polyethers of skeleton structure, general formula is the poly-[3-(9-alkyl fluorenes-9-yl)-1 of the silanization of IV then, the 2-propylene oxide] the unidextrality spiral polyethers of skeleton structure and silica gel particle reaction the have obtained bonding silica gel of unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure;
R in the IV formula, R 1, R 2And R 3Be alkyl, X is the coupling agent residue, and m is an integer. - Bonding according to claim 3 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] preparation method of silica gel of unidextrality spiral polyethers of skeleton structure, it is characterized in that silica gel particle is that the coupling agent of II reacts with silica gel particle and obtains the silica gel particle that general formula is the V silanization with general formula earlier, general formula is that the silica gel particle of V silanization is the spiral polyether reactant of the III silica gel of unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure that obtained bonding with general formula again;
R in the V formula 2And R 3Be alkyl, Y has O to be connected to functional group on the Y after can reacting with the M-O key in the III formula. - A kind of bonding according to claim 1 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers of skeleton structure, the silica gel that it is characterized in that with bonding the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure is used as the chiral chromatography stationary phase.
- A kind of bonding according to claim 6 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers of skeleton structure, it is characterized in that unidextrality spiral polyethers chiral chromatography stationary phase is made the high performance liquid chromatography chiral column.
- A kind of bonding according to claim 7 poly-[3-(9-alkyl fluorenes-9-yl)-1, the 2-propylene oxide] silica gel of unidextrality spiral polyethers of skeleton structure, it is characterized in that the high performance liquid chromatography chiral column that will be made by unidextrality spiral polyethers chiral chromatography stationary phase is used for the compartment analysis racemic modification.
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| WO2015145871A1 (en) * | 2014-03-25 | 2015-10-01 | 住友化学株式会社 | Polymer compound, and light-emitting element using same |
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| WO2015145871A1 (en) * | 2014-03-25 | 2015-10-01 | 住友化学株式会社 | Polymer compound, and light-emitting element using same |
| CN106103537A (en) * | 2014-03-25 | 2016-11-09 | 住友化学株式会社 | Macromolecular compound and use the light-emitting component of this macromolecular compound |
| JPWO2015145871A1 (en) * | 2014-03-25 | 2017-04-13 | 住友化学株式会社 | Polymer compound and light emitting device using the same |
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| CN109280118A (en) * | 2018-07-26 | 2019-01-29 | 湘潭大学 | A kind of unidextrality spiropolymer and preparation method thereof of the bis- propinyl fluorene skeleton structure of poly- 9,9- with high stereoregularity |
| WO2023243651A1 (en) * | 2022-06-15 | 2023-12-21 | 大阪ガスケミカル株式会社 | Polyether-based resin, method for producing same, and application thereof |
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