CN101935395A - Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof - Google Patents
Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof Download PDFInfo
- Publication number
- CN101935395A CN101935395A CN2010101014357A CN201010101435A CN101935395A CN 101935395 A CN101935395 A CN 101935395A CN 2010101014357 A CN2010101014357 A CN 2010101014357A CN 201010101435 A CN201010101435 A CN 201010101435A CN 101935395 A CN101935395 A CN 101935395A
- Authority
- CN
- China
- Prior art keywords
- fluorenes
- alkyl
- unidextrality
- skeleton structure
- spiral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *C1(CC2OC2)c2c(*)c(*)c(*)c(*)c2-c2c(*)c(*)c(*)c(*)c12 Chemical compound *C1(CC2OC2)c2c(*)c(*)c(*)c(*)c2-c2c(*)c(*)c(*)c(*)c12 0.000 description 2
Images
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention discloses poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and a preparation method thereof. The unidextrality spiral polyether is formed by performing ring-opening polymerization on a 3-(9-alkyl fluorene-9-group)-1,2-epoxypropane skeleton structure-containing rotatory epoxy compound by using anions. The rotatory epoxy compound is prepared by reacting a 9-alkyl-9-metal fluorene compound with rotatory epoxypropane. The poly[3-(9-alkyl fluorine-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether prepared by the method has narrowly distributed molecular weight, wherein Mw/Mn is about 1.04 to 1.1. A polymer exists in solution in a mode of a unidextrality spiral structure; the rotatory direction of the polymer is opposite to that of a monomer; the absolute value of specific rotation is more than 44 times that of the monomer; and the CD signal intensity is more than 40 times that of the monomer.
Description
Technical field
The present invention relates to 3-(the 9-alkyl fluorenes-9-yl) propylene oxide of optically-active and unidextrality helix poly (3-(9-alkyl fluorenes-9-yl) propylene oxide) and preparation method thereof.
Background technology
The complex compound that Okamoto in 1979 form with n-Butyl Lithium and (-)-spartiodine causes the polymerization of methacrylic triphenyl phosphate methyl esters, has obtained keeping in solution the polymkeric substance (J.Am.Chem.Soc.1979,101,4763) of unidextrality spirane structure first.The polymethyl triphenyl phosphate methyl esters of finding the unidextrality spiral afterwards again has good chiral recognition function, make high performance liquid chromatography (HPLC) chiral stationary phase with this unidextrality spiropolymer, can separate many racemic modifications (J.Am.Chem.Soc.1980,102,6358; J.Am.Chem.Soc., 1981,103,6971.).This chiral stationary phase has been successfully used to industrial production now.
At present in China with chiral polymer as many achievement patent applied fors of high performance liquid chromatography (HPLC) chiral stationary phase, as: CN 200410013305.2.
The unidextrality spiropolymer also finds can be used for preparing chiral catalyst recently except having the application aspect the HPLC chiral stationary phase.People such as Reggelin report loads to precious metal palladium and rhodium on the polymethyl acrylic acid triaryl methyl esters of the spiral that contains nitrogen-atoms or phosphorus atom on the aromatic ring, hydrogenation to allylation and two keys has good enantioselectivity katalysis [Natl.Acad.Sci.U.S.A.2004,101,5461].In asymmetry catalysis, chiral catalyst is quite expensive, and the recovery of chiral catalyst is very difficult again.And the recovery of polymer chiral catalyst is very easy, as long as reaction is filtered just can reclaim.
Because the unidextrality spiropolymer has important use in chiral chromatography stationary phase and asymmetry catalysis, in recent years, many synthetic chemistries man was devoted to the design and the synthetic research of unidextrality spiropolymer.Up to the present, the polymkeric substance that keeps stablizing the unidextrality spirane structure in solution of report has polyacetals class (J.Polym.Sci., Part A:Polym.Chem.2000,38,2623), poly-isonitrile class (Angew.Chem., Int.Ed.Engl.1996,35,1554), polymeric polyisocyanate class (Polym.J.1993,25,391), polyacetylene class (Macromolecules 2000,33,3978), poly-aryne class (Angew.Chem., Int.Ed.Engl.1996,35,2111) etc.The patent that occurred the application of many novel unidextrality spiropolymers recently.Poly-isonitrile as the unidextrality spiral has obtained United States Patent (USP) in 2009.US7619109B2。
The above-mentioned unidextrality spiropolymer of hitherto reported all is the polymkeric substance of unsaturated compound, but does not almost have design and synthetic report about unidextrality helix poly epoxy compounds.This mainly be because polyepoxides and poly-unsaturated compound to compare main chain submissiveer, thereby be not easy to form spirane structure.
Before state, unidextrality helix poly methyl three benzene methyls are as the chiral stationary phase of high performance liquid chromatography, thereby but this spiropolymer easily and the common solvent methyl alcohol generation alcoholysis of high performance liquid chromatography and lose the bulky group trityl and lose chiral helical character.Anti-alcoholysis ability for the strongest this chiral helical polymkeric substance, poly-methyl three benzene methyls of people have been done many modifications and transformation, though these modifications and transformation reach some effects, the ester group of finally not breaking away from side chain connects character, thereby can not thoroughly solve the predicament of alcoholysis.
And the helix poly epoxy compounds does not have ester bond fully, thereby has thoroughly eliminated alcoholysis.
We had successfully synthesized unidextrality helix poly (4,4,4-triphenyl butylene oxide ring) in the past.But the polymerization degree of unidextrality helix poly (4,4,4-triphenyl butylene oxide ring) is too low, and mean polymerisation degree has only about 7-9, and the too wide (M of molecular weight distribution
n/ M
w=1.7-1.8), very restricted (Polym.Int., 2008,57,530 on using; Polym.Bull., 2007,59,481.).
Summary of the invention
The purpose of this invention is to provide a class polymerization degree high with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] the unidextrality spiral polyethers of skeleton structure of having of narrow molecular weight distribution and the preparation method of this class unidextrality spiral polyethers.
A kind of unidextrality spiral polyethers with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure has the skeleton structure shown in the formula I:
In the formula:
R can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl; Other position of fluorenes ring can also have other substituting group.Being with the configuration of * number carbon atom is R type or S type, and polymkeric substance has the unidextrality spirane structure.
A kind of preparation method with unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure:
1), the optically-active epoxy compounds that has 3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane skeleton structure with 9-alkyl-9-metal compound of fluorene class and the preparation of optically-active epichlorohydrin reaction;
2), has 3-(9-alkyl fluorenes-9-yl)-1 with the initiator initiation, the optically-active epoxy compounds of 2-propylene oxide skeleton structure heated polymerizable in body or solution, obtain having the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
The initiator that uses in the polymerization process of the optically-active epoxy compounds with 3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane skeleton structure is alkali metal hydroxide, metal-alcoholates thing or alkide.
Using solvent in solution polymerization is the cyclic ethers class, as tetrahydrofuran (THF), also can be hydro carbons, as hexanaphthene, toluene.
The temperature of mass polymerization is 100-250 ℃.
The temperature of solution polymerization is 70-200 ℃.
Obtain polymerization degree unidextrality spiral polyethers high and narrow molecular weight distribution, its core is exactly to introduce a suitable substituting group on the methyl of propylene oxide.The present invention has designed and synthesized the structure chiral epoxy compound that has shown in II and the III for this reason:
R in II and the III formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other substituting group.II is the R configuration, and III is the S configuration.
The constructional feature of the structure chiral epoxy compound shown in II and the III is to introduce the substituting group of a 9-alkyl fluorenes-9-base skeleton on the methyl of propylene oxide, and this substituent skeleton is shown in IV.
R is CH in the formula
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl.
After introducing the substituting group of such skeleton, the skeleton of II and III is respectively V and VI.
In the formula:
R can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl.
Just can form molecular weight unidextrality spiral polyethers high and narrow molecular weight distribution after having the epoxy compounds of skeleton shown in the V or having the synthesis of epoxy compounds of skeleton shown in the VI.
The epoxy compounds synthetic method of this optically-active is to have the reaction of the 9-of structure shown in VII alkyl fluorenes metallic compound and chiral epichlorohydrin, the chiral epoxy compound that obtains having structure shown in II and the III formula.
R in the VII formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other alkyl.M is an atoms metal.
The synthetic of 3-(9-alkyl fluorenes-9-yl) propylene oxide realized by following method:
Earlier 9-alkyl fluorenes is made 9-alkyl fluorenes metallic compound VII, VII obtains the optically-active epoxy compounds with the chiral epichlorohydrin reaction again, and reaction is shown in reaction formula one:
Reaction formula one
R in the formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other alkyl; M is alkali metal atom, magnesium atom, zinc atom or copper atom;
The configuration of gained epoxy compounds determines that by the enough of epoxy chloropropane its e.e. value (being polarimetry purity) is consistent with epoxy chloropropane, and its reaction mechanism is shown in reaction formula two:
Reaction formula two
The configuration of chiral carbon does not change in the reaction process.Chlorine atom in the epoxy chloropropane also can replace with bromine and iodo.
Optically-active epoxy compounds II (or III) with 3-(9-alkyl fluorenes-9-yl) propylene oxide skeleton structure uses the anionic initiator initiated polymerization, obtains the unidextrality spiral polyethers VIII that the unidextrality spiral has poly-[3-(9-alkyl fluorenes-9-yl) propylene oxide] skeleton structure.Polyreaction is shown in reaction formula three:
Reaction formula three
VIII is unidextrality spiral (left hand helix or right-handed helix) structure in solution.The direction of spirane structure is determined by the configuration of cyclosiloxane monomer oxygen compound.Obtaining the optically-active symbol after the II polymerization is positive spiral polyethers, obtains the optically-active symbol after the III polymerization and is negative spiral polyethers.
Anionic initiator can be alkali-metal oxyhydroxide MOH (M is a basic metal), also can be the metallic compound ROM (M is a metal) of alcohol, also can be other organometallic compound RM (R is an alkyl, and M is a metal).
Polyreaction can be mass polymerization, also can be solution polymerization.Polymerization temperature is preferably between 90-130 ℃ between 60-250 ℃.
The molecular weight distribution of the unidextrality spiral polyethers with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure that makes with this method is very narrow, M
w/ M
nFor about 1.04-1.1, polymkeric substance exists with the unidextrality spirane structure in solution, and the optical direction of polymkeric substance is opposite with monomeric direction, and the absolute value of specific rotation is monomeric more than 44 times, and the CD strength of signal is monomeric more than 40 times.
Description of drawings
Fig. 1 is the CD spectrogram of monomer of the present invention and polymkeric substance, a:3-among the figure (9-methyl fluorenes-9-yl) propylene oxide; B:3-(9-ethyl fluorenes-9-yl) propylene oxide; C:3-(9-propyl group fluorenes-9-yl) propylene oxide; D:3-(9-butyl fluorenes-9-yl) propylene oxide; E:3-(9-amyl group fluorenes-9-yl) propylene oxide.
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:(R)-(-)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Get 9-ethyl fluorenes 9.8g (0.05mol); join in the 100mL there-necked flask; use nitrogen protection; inject the 40mL tetrahydrofuran (THF) and make solvent; slowly add n-butyllithium solution 20mL (2.5mol/L) under the magnetic agitation; be reflected under the condition of ice bath and carry out; finally obtain blood red solution. after dropwising; stirring at room 3h; then reaction mixture is cooled to-70 ℃; slowly add 3.5g (R)-(+)-epoxy chloropropane (e.e. is 99%); this moment blood red taking off. dropwise the back and continue to stir 15min at-70 ℃; and then at room temperature stir 3h; obtain orange solution. wash orange solution with water (10mL * 3) three times; again with the water extracting twice of ether with washing; merge organic phase. with concentrating under reduced pressure after the organic phase usefulness Calcium Chloride Powder Anhydrous drying; obtaining orange-yellow thick liquid. yellow thick liquid is separated out crystal (crude product) after placing gradually. with the crude product ethyl alcohol recrystallization; the gained white solid is after 35 ℃ of vacuum-drying; obtain 9.6g (R)-(-)-3-(9-ethyl fluorenes-9-yl)-1; 2-propylene oxide, productive rate are 80.2%, m.p.:79-80 ℃; e.e.:98.8%
(c=0.0100g/mL, THF).Anal.Calcd?for?C
18H
18O：C，86.36；H，7.25；Found?C，86.34；H，7.27.
1H-NMR(CCl
3D，TMS)δ(ppm)：7.73(d，J＝5.6Hz，2H，Ar)，7.44(d，J＝7.2，1H，Ar-H)，7.29-7.39(m，5H，Ar-H)，2.41-2.45(m，1H，CH)，2.25-2.28(m，2H，CH
2)，1.99-2.12(m，4H，2CH
2)，0.33(t，J＝7.4Hz，3H，Me).
13C-NMR(CDCl
3，TMS?D)δ(ppm)：149.20，148.96，141.12，140.94，127.30，127.26，127.17，127.12，123.29，123.00，119.93，119.90，54.05，49.01，47.21，42.87，32.60，8.02。
Example 2:(S)-(+)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Except replacing 3.5g (R)-(+)-epoxy chloropropane (e.e. is 99%) with 3.5g (S)-(-)-epoxy chloropropane (e.e. is 99%), all the other are all undertaken by example 1.The product that obtains is (S)-(+)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane.
Productive rate is 80.2%, e.e.:98.8%,
(c=0.0100g/mL, THF).
Example 3:(R)-(-)-3-(9-methyl fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (R)-(+)-3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Except using 9-methyl base fluorenes (0.05mol), 9-propyl group base fluorenes (0.05mol), 9-butyl base fluorenes (0.05mol), 9-amyl group base fluorenes (0.05mol) or 9-phenyl base base fluorenes (0.05mol) to replace the 9-ethyl fluorenes (0.05mol), all the other are all undertaken by example 1.Obtain (R)-(-)-3-(9-methyl fluorenes-9-yl)-1 respectively, 2-propylene oxide, (R)-(-)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (R)-(-)-3-(9-phenyl fluorenes-9-yl)-1,2-propylene oxide (R)-(-)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane.
(R)-(-)-and 3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane: productive rate white solid, m.p.:41-42 ℃.
(c=0.0100g/mL, THF), e.e.:98.8%, Anal.Calcdfor C
17H
16O:C, 86.40; H, 6.82; 0,6.77; Found C, 86.34; H, 6.85.
1H-NMR (CCl
3D, TMS) δ (ppm): 7.73 (d, J=6.8Hz, 2H, Ar-H), 7.48 (d, 1H, Ar-H), 7.32-7.40 (m, 5H, Ar-H), 2.38-2.41 (m, 1H, CH), 2.30-2.33 (m, 2H, CH
2), 2.11-2.13 (m, 1H, CHH), 1.97-2.02 (m, 1H, CHH), 1.55 (s, 3H, Me).
13C-NMR (CDCl
3, TMS) δ: 151.18,150.92,139.94,139.79,127.39,127.38,127.35,127.27,123.20,122.90,120.11,120.09,49.46,49.17,47.09,43.36,26.34.
(R)-(-)-and 3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane: productive rate 77.3%; White solid, m.p.:87-88 ℃;
(c=0.0100g/mL, THF); E.e.:98.6%; Anal.Calcd for C
19H
20O:C, 86.32; H, 7.63; 0,6.05; Found C, 86.27; H, 7.65.
1H-NMR (CCl
3D, TMS) δ (ppm): 7.72 (d, J=7.2Hz, 2H, Ar-H), 7.45 (d, J=6.8Hz, 1H, Ar-H), 7.30-7.37 (m, 5H, Ar-H), 2.402.45 (m, 1H, CH), 2.25-2.27 (m, 2H, CH
2), 1.97-2.10 (m, 4H, 2CH
2), 0.65-0.67 (m, 5H, Et).
13C-NMR (CCl
3D, TMS) δ (ppm): 149.62,149.38,140.90,140.72,127.26,127.25,127.22,127.11,123.28,122.98,119.93,119.90,53.68,48.94,47.19,43.10,42.25,16.89,14.32.
(R)-(-)-and 3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane: productive rate 69.4%, white solid, m.p.:46-47 ℃;
(c=0.0100g/mL, THF); E.e:98.3%; Anal.Calcd for C
20H
22O:C, 86.29; H, 7.97; 0,5.75; Found C, 86.29; H, 7.99.
1H-NMR (CCl
3D, TMS) δ (ppm): 7.73 (d, J=6.4Hz, 2H, Ar-H), 7.45 (d, J=6.8Hz, 1H, Ar-H), 7.30-7.37 (m, 5H, Ar-H), 2.39-2.44 (m, 1H, CH), 2.24-2.26 (m, 2H, CH
2), 2.01-2.09 (m, 4H, CH
2CH
2), 1.041.12 (m, 2H, CH
2), 0.59-0.69 (m, 5H, Et).
13C-NMR (CCl
3D, TMS) δ (ppm): 149.62,149.37,140.92,140.74,127.26,127.25,127.21,127.11,123.27,122.97,119.93,119.90,53.56,48.94,47.18,43.21,39.58,25.62,22.92,13.75.
(R)-(-)-and 3-(9-amyl group fluorenes-9-yl)-1,2 epoxy prapane: colorless oil, productive rate 61.4%,
(c=0.0100g/mL, THF); E.e:98.1%; Calcd for C
21H
24O:C, 86.26; H, 8.27; 0,5.47; Found C, 86.21; H, 8.28.1H NMR (CCl3D, TMS) δ (ppm): 7.72 (d, J=6.2Hz, 2H, Ar-H), 7.45 (d, J=6.2Hz, 1H, Ar-H), 7.29-7.39 (m, 5H, Ar-H), 2.42-2.43 (m, 1H, CH), and 2.25-2.26 (m, 2H, CH2), 2.00-2.10 (m, 4H, CH2CH2), 1.06-1.12 (m, 2H, CH2), 0.59-0.69 (m, 5H, Et) .13C NMR (CDCl3, TMS) δ (ppm): 149.64,149.30,140.94,140.76,127.28,127.26,127.23,127.14,123.28,122.99,119.96,119.93,53.60,48.96,47.20,43.20,39.77,32.09,23.09,22.24,13.93.
(R)-(+)-and 3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane: white solid, productive rate 80.4%.m.p.:151-152 ℃;
(c=0.0100g/mL, THF); E.e:98.3%;
1H-NMR (CDCl
3, TMS) δ (ppm): 7.76-7.79 (m, 2H, Ar), 7.34-7.40 (m, 2H, Ar), 7.14-7.32 (m, 9H, Ar), 2.99-3.03 (m, 1H, CH
2O), and 2.45-2.49 (m, 1H, CH), 2.26-2.27 (m, 2H, CH
2), 2.08-2.10 (m, 1H, CH-O).
13C NMR (CDCl
3, TMS) δ (ppm): 151.12,150.86,144.12,140.56,140.46,128.52,12.46,127.81,127.66,127.60,126.71,124.73,124.44,120.14,120.10,57.32,49.04,47.38,40.85.Anal.Calcd for C
22H
18O:C, 88.56; H, 6.08; Found C, 88.51; H, 6.10.
Example 4:(S)-(+)-3-(9-methyl fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (S)-(-)--3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Except replacing 3.5g (R)-(+)-epoxy chloropropane (e.e. is 99%) with (S)-(-)-epoxy chloropropane (e.e. is 99%), all the other are all undertaken by example 3.Obtain (S)-(+)-3-(9-methyl fluorenes-9-yl)-1 respectively, 2-propylene oxide, (S)-(+)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (S)-(-)--3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane.
(S)-(+)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF), e.e.:98.8%.
(S)-(+)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF); E.e.:98.6%
(S)-(+)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF); E.e:98.3%;
(S)-(+)-3-(9-amyl group fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF), e.e:98.1%;
(S)-(-)--3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF); E.e:98.3%;
Example 5: mass polymerization
Magnetic stir bar and 10.00 mmole 3-(9-alkyl base fluorenes-9-yl)-1 are being housed; in the glass test tube of 2-propylene oxide epoxy monomer; under the atmosphere of nitrogen protection; the KOH that adds 0.4 mmole rapidly; and with behind the gas in the nitrogen replacement test tube three times, tube sealing reduces pressure on the flame of alcohol blast burner.The test tube of sealing is placed in the oil bath pan of band magnetic agitation, under design temperature, stirs polymerization.
3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane, 3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane, 3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane and 3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane are at 130 ℃ of polymerization 4-6h.3-(9-amyl group fluorenes-9-yl)-1,2 epoxy prapane is at 130 ℃ of polymerization 12-16h.After polymerization finishes, glass test tube is opened, added the 10mL tetrahydrofuran (THF), under the ultrasonic wave effect, solid is dissolved fully. polymers soln is added drop-wise in the beaker that 100mL methyl alcohol is housed, separates out with precipitation mode after making polymerization. suction filtration, the white solid that obtains.The white solid of gained is dissolved in the 10mL tetrahydrofuran (THF) again, tetrahydrofuran solution is added drop-wise in the beaker that 100mL methyl alcohol is housed, polymkeric substance is repeated precipitation once.The white polymer that suction filtration obtains.With the resulting polymers drying, weigh, carry out every test.The resulting polymers parameter is listed in table one, and the CD spectrogram of monomer and polymkeric substance is seen Fig. 1.
Table one, mass polymerization resulting polymers parameter
Example 6: use KOH to cause with 3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane polymerization.
3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane polymerization is undertaken by example 5, and just polymerization temperature is at 150 ℃, and separation and purification is also undertaken by example 5.
Example 7: solution polymerization
In being housed, the magnetic stir bar glass test tube adds 10.00 mmole 3-(9-ethyl fluorenes-9-yl) propylene oxide or 3-(9-propyl group fluorenes-9-yl) propylene oxide; under the atmosphere of nitrogen protection; inject 5 milliliters of exsiccant tetrahydrofuran (THF)s (perhaps 5 milliliters of exsiccant toluene); inject the t-BuOK solution of 0.4 mmole rapidly; and with nitrogen with invisible spectro gas displacement three times after, on the flame of alcohol blast burner, test tube is sealed.The test tube that to seal then mouthful is placed in the oil bath pan of band magnetic agitation, 70 ℃ of polymerizations 2 days.After polymerization finishes, glass test tube is opened, polymers soln is added drop-wise in the beaker that 100 ml methanol are housed, polymer precipitation is come out.Suction filtration, the white solid polymkeric substance that obtains.The white solid polymkeric substance that obtains is dissolved in 5 milliliters of tetrahydrofuran (THF)s again, and then tetrahydrofuran solution is poured in 100 ml methanol polymkeric substance is precipitated out again.Suction filtration is collected solid polymer, with polymkeric substance 50 ℃ of dried overnight.The productive rate of polymkeric substance is 63.4%.The polymerization degree is 13-14, and the optical direction of polymkeric substance is opposite with monomer.When R=was methyl, the specific rotatory power of polymkeric substance was monomeric 52 times; The specific rotatory power of polymkeric substance is monomeric 62 times during for propyl group.
The present invention obtains National Natural Science Foundation of China (NSFC) and subsidizes and (to subsidize number: 20972131).
Claims (5)
1. unidextrality spiral polyethers with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure is characterized in that: have the skeleton structure shown in the formula I,
In the formula:
R can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl; Other position of fluorenes ring can also have other substituting group; Being with the configuration of * number carbon atom is R type or S type, and polymkeric substance has the unidextrality spirane structure.
2. a kind of preparation method with unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure according to claim 1 is characterized in that:
1), with optically-active epoxy compounds II and III that 9-alkyl fluorenes metallic compound VII and optically-active epoxy chloropropane have 3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane skeleton structure-70 ℃ of following prepared in reaction, reaction formula is:
Reaction formula one
R in the formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other alkyl; M is alkali metal atom, magnesium atom, zinc atom or copper atom;
2), has 3-(9-alkyl fluorenes-9-yl)-1 with the initiator initiation, the optically-active epoxy compounds II of 2-propylene oxide skeleton structure or III heated polymerizable in body or solution, the unidextrality spiral polyethers I that must have poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
3. a kind of poly-[3-(9-alkyl fluorenes-9-yl)-1 that has according to claim 2, the 2-propylene oxide] preparation method of unidextrality spiral polyethers of skeleton structure, it is characterized in that: the initiator that uses in the polymerization process of the optically-active epoxy compounds with 3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane skeleton structure is alkali metal hydroxide, metal-alcoholates thing or alkide.
4. a kind of preparation method with unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure according to claim 2, it is characterized in that: the employed solvent of solution polymerization is cyclic ethers class or hydro carbons.
5. a kind of preparation method with unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure according to claim 2, it is characterized in that: polymerization temperature is 70-250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101014357A CN101935395B (en) | 2010-01-27 | 2010-01-27 | Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101014357A CN101935395B (en) | 2010-01-27 | 2010-01-27 | Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101935395A true CN101935395A (en) | 2011-01-05 |
| CN101935395B CN101935395B (en) | 2012-01-25 |
Family
ID=43388982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101014357A Expired - Fee Related CN101935395B (en) | 2010-01-27 | 2010-01-27 | Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101935395B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212190A (en) * | 2011-03-31 | 2011-10-12 | 湘潭大学 | 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 |
| CN103787897A (en) * | 2014-02-13 | 2014-05-14 | 湘潭大学 | Uni-dextral spiral polyether with poly-(3-diarylamine-1, 2-epoxypropane) framework structure and preparation method of uni-dextral spiral polyether |
| CN104031182A (en) * | 2014-06-10 | 2014-09-10 | 湘潭大学 | Method for preparing chiral carbon anion composite initiator |
| CN108395536A (en) * | 2018-03-17 | 2018-08-14 | 湖南城市学院 | A kind of preparation method of epithio monomer and the unidextrality polythiaether with skeleton structure |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002201222A (en) * | 2000-09-19 | 2002-07-19 | Merck Patent Gmbh | Polymer bead, method of using polymer bead, reflective film, security mark, securities, security device |
| CN1594397A (en) * | 2004-06-17 | 2005-03-16 | 武汉化工学院 | Heterochain polymer chiral stationary phase and process for preparing same |
-
2010
- 2010-01-27 CN CN2010101014357A patent/CN101935395B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212190A (en) * | 2011-03-31 | 2011-10-12 | 湘潭大学 | 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 |
| CN103787897A (en) * | 2014-02-13 | 2014-05-14 | 湘潭大学 | Uni-dextral spiral polyether with poly-(3-diarylamine-1, 2-epoxypropane) framework structure and preparation method of uni-dextral spiral polyether |
| CN103787897B (en) * | 2014-02-13 | 2016-05-04 | 湘潭大学 | The preparation method of the unidextrality spiral polyethers of skeleton structure that one has poly-[3-diaryl-amine base-1,2-expoxy propane] |
| CN104031182A (en) * | 2014-06-10 | 2014-09-10 | 湘潭大学 | Method for preparing chiral carbon anion composite initiator |
| CN108395536A (en) * | 2018-03-17 | 2018-08-14 | 湖南城市学院 | A kind of preparation method of epithio monomer and the unidextrality polythiaether with skeleton structure |
| CN108395536B (en) * | 2018-03-17 | 2020-10-27 | 湖南城市学院 | Preparation method of episulfide monomer and single-chiral polythioether with skeleton structure |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101935395B (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101935395B (en) | Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof | |
| JP2010001443A (en) | Stereoselective alternating copolymerization of epoxide and carbon dioxide | |
| CN110483748B (en) | Bipyridyl bisphenol-aluminum catalyst for preparing unsaturated polyester and preparation method thereof | |
| CN101906195B (en) | Star polymer and method for producing the same | |
| CN105646741B (en) | A kind of preparation method of luxuriant zirconium type olefin polymerization catalysis | |
| CN111848669A (en) | Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof | |
| CN102212190A (en) | 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 | |
| CN114653404B (en) | Ruthenium compound catalyst and application thereof in olefin metathesis | |
| US5889134A (en) | Chiral organozinc species for use in asymmetric reactions | |
| CN108395536B (en) | Preparation method of episulfide monomer and single-chiral polythioether with skeleton structure | |
| JPH05170705A (en) | Radically polymerizable bifunctional (meth)acrylate | |
| Cortial et al. | Neutral ansa-bis (fluorenyl) silane neodymium borohydrides: synthesis, structural study and behaviour as catalysts in butadiene–ethylene copolymerisation | |
| CN114149537A (en) | Disulfide synergistic photoresponse coumarin-based self-repairing material and preparation method thereof | |
| CN111499524B (en) | Method for preparing amino alcohol compound by using halogenated intermediate | |
| CN111875534B (en) | Safe and efficient preparation method of 1, 8-diformylcarbazole | |
| CN103787897A (en) | Uni-dextral spiral polyether with poly-(3-diarylamine-1, 2-epoxypropane) framework structure and preparation method of uni-dextral spiral polyether | |
| CN108218901B (en) | Indeno [1,2-b ] indolyl rare earth metal complex and preparation method thereof | |
| CN110423297B (en) | [ C ^ N ^ O ] tridentate chelated asymmetric transition metal catalyst and preparation method thereof | |
| CN114163474B (en) | Polyketone catalyst ligand and synthesis method thereof | |
| CN117924173B (en) | Aniline quaternary ammonium salt chiral phase transfer catalyst and application thereof in asymmetric alkylation catalysis of amino acid derivatives | |
| CN114874105B (en) | Preparation method of visible light and water promoted homoallylic amine compound | |
| CN108383862B (en) | Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof | |
| JP4325097B2 (en) | Optically active poly (N-methylbenzylmaleimide) and process for producing the same | |
| JP2017203053A (en) | Substituted polyacetylene having optically active group and method for producing the same | |
| CN116554443A (en) | Non-conjugated polymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120125 Termination date: 20140127 |