CN101864055B - Optically active helical polyurethane material and preparation method thereof - Google Patents
Optically active helical polyurethane material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an optically active helical polyurethane material, which is prepared by the in-situ auto-polymerization of D- or L-tyrosine alcohol ester isocyanate monomer solution generated by reacting D- or L-tyrosine alcohol ester hydrochloride with triphosgene, and comprises the structural formula. The material has the characteristics of relatively higher specific rotatory power of +100 to +200 degrees, high thermal stability and film forming property and the polymerization degree n of 1 to 20,000.
Description
Technical field
The present invention relates to a kind of optically active helical polyurethane material and preparation method thereof, be applicable to that preparation has the optically activ material of high specific rotatory power, good thermal stability and film-forming properties.
Background technology
Optically active polymer is meant the family macromolecule compound that plane polarized light is deflected.The same with the opticity small molecules, the prerequisite that polymer has opticity is to have asymmetric factor in its structure, and spiral is a kind of very important chirality manifestation, and promptly left hand helix is the mirror that can not overlap with right-handed helix.In recent years; Receive the inspiration of natural macromolecular such as spirane structures such as DNA, protein; Have optically active polymkeric substance and received the extensive concern of scientists; Think that this spirane structure is that these molecules show bioactive important factor, thereby design and synthesized a large amount of spiropolymers, comprise polyacetylene class, polyolefins, polyacetals class and polymeric polyisocyanate class and gather isocyanide class etc.Usually; The synthetic of spiropolymer be to be raw material with the chiral monomer, obtains through monomer polymerization, also can be from the achirality monomer; Through adopting chiral catalyst/chiral additives or in the chirality applied field, monomer carries out the Asymmetric Polymerization reaction and prepares through inducing.CN1869013A and CN1865300A disclose Opticall activity N-propargyl sulfamide polymkeric substance and preparation method thereof and the alkynes third ureas monomer and opticity spiropolymer and preparation method thereof respectively; React through catalytic polycoordinations such as transition metal rhodium, tungsten, molybdenums and to obtain having stable helical conformation, the replaced acetylene base polymer that optical activity is stronger.CN101696260A discloses polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof, through in polymkeric substance, introducing 1, and 1 '-dinaphthalene-2, the monomeric axle of 2 '-diphenol chirality induces polymer to produce optical activity.
Amino acid is widely used as biomedical material because of its excellent biological compatibility makes its derived polymer, such as pharmaceutical carrier, and artificial organ etc.Because the effect of chiral carbon atom in its molecule; Helical conformation that often can inducing molecule chain formation compound with regular structure; Make with it to be that the polymkeric substance of feedstock production not only has general high molecular physical and chemical performance; And possessed such as electron transport information transmission, multiple performances such as photolytic activity and selectivity catalysis.Therefore, people hope to prepare the excellent more optical active polymer of performance through the particular functional group's structure in the amino acid derived polymkeric substance of accurate control.The present invention has prepared isocyanide ester-phenol monomer L-tyrosine alcohol ester isocyanide ester through safe and simple solid phosgene method, and adopts the original position auto-polymerization to obtain optically active helical polyurethane material.Owing to be present in the monomer molecule to isocyanide ester base and phenolic hydroxyl group equal proportion, thereby make its polymkeric substance have regular head-tail linear structure of joining.Simultaneously, can reach the purpose of regulating its helical conformation and stability through the structure that changes the polymer lateral chain alcohol ester.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of optically active polyurethanes material and preparation method thereof, this material has higher specific rotatory power, good thermostability and film-forming properties.
Technical scheme: a kind of optically active helical polyurethane material of the present invention is to be formed by the D or the auto-polymerization of L-tyrosine alcohol ester isocyanide ester monomer solution original position of D or L-tyrosine alcohol ester hydrochloride with solid phosgene reaction generation, and its general structure is:
Polymerization degree n is 1～20000,
Wherein, R1 is following structure:
The reaction equation of this optically active helical polyurethane material is:
The preparation method of this optically active helical polyurethane material is:
A kind of in following three kinds of methods adopted in the preparation of step a) D or L-tyrosine alcohol ester hydrochloride:
Method (1) adopts short chain fatty alcohol: the molar weight to add D or L-tyrosine is a standard, is 15～10: 1 by the mol ratio of short chain fatty alcohol and D or L-tyrosine, and short chain fatty alcohol is joined in the four-hole boiling flask; Mol ratio by sulfur oxychloride and D or L-tyrosine is 1.5～1.2: 1, sulfur oxychloride is slowly splashed in the short chain fatty alcohol that is chilled to-10～0 ℃, after dripping off;-10～0 ℃ is stirred 1～2h down, adds D or L-tyrosine and rises to 60～90 ℃ of reaction 5～10h, reduces to room temperature; Add the ether of 2～3 times of short chain fatty alcohol volumes, separate out solid, filter; Vacuum-drying 12～24h gets D or L-tyrosine alcohol ester hydrochloride;
Or method (2) adopts long chain aliphatic alcohol: the molar weight to add D or L-tyrosine is a standard, is 2～1.5: 1 by the mol ratio of long chain aliphatic alcohol and D or L-tyrosine, and long chain aliphatic alcohol is mixed with D or L-tyrosine; Feed the exsiccant hydrogen chloride gas and with mixture heating up to 100～120 ℃, stirring reaction 4～8h reduces to room temperature; Add the methylene dichloride of long chain aliphatic alcohol volume 5～8, suction filtration, gained solid are poured in the water of 2～5 times of long chain aliphatic alcohol volumes; Yellow soda ash is transferred pH to 9.0～10.0, extracts 2～3 times with the anhydrous diethyl ether of 3～5 times of long chain aliphatic alcohol volumes, and extracted with diethyl ether is spent the night with anhydrous sodium sulfate drying; The elimination siccative, filtrating feeds exsiccant hydrogen chloride gas, sedimentation and filtration; Vacuum-drying 12～24h gets D or L-tyrosine alcohol ester hydrochloride;
Or method (3) adopts aromatic alcohol: the molar weight to add D or L-tyrosine is a standard; Mol ratio by aromatic alcohol and D or L-tyrosine is 25～20: 1; Aromatic alcohol is joined in the four-hole boiling flask, is 1.5～1.2: 1 by the mol ratio of polyphosphoric acid and D or L-tyrosine, and polyphosphoric acid is added in the aromatic alcohol; Stirring at room 1～2h adds D or L-tyrosine and rises to 90～95 ℃ of reaction 4～10h.Reactant is poured in 10～20% the sulfuric acid of 4～6 times of aromatic alcohol volumes, with the anhydrous diethyl ether washing of 0.5～1 times of aromatic alcohol volume 2～3 times, water is regulated pH to 9.0～10.0 with yellow soda ash; Anhydrous diethyl ether with 3～5 times of aromatic alcohol volumes extracts 2～3 times, and organic phase is spent the night with anhydrous sodium sulfate drying, the elimination siccative; Filtrating feeds the exsiccant hydrogen chloride gas; Sedimentation and filtration, vacuum-drying 12～24h gets D or L-tyrosine alcohol ester hydrochloride;
Step b) is 0.34～0.36: 1 by the mol ratio of the D that makes in solid phosgene and the step a) or L-tyrosine alcohol ester hydrochloride under-5～0 ℃, and D or L-tyrosine alcohol ester hydrochloride are joined in the solid phosgene halohydrocarbon solution that concentration is 0.01～0.03g/mL; Slowly drip and the isopyknic saturated sodium bicarbonate solution of halohydrocarbon solution; After dripping off, room temperature reaction 2～5h, water washs 2～3 times with the halohydrocarbon of 0.1～0.2 times of its volume; Merge organic phase, anhydrous MgSO
4Dried overnight, the filtering siccative gets water white transparency D or L-tyrosine alcohol ester isocyanide ester monomer solution;
Step c) is in the anhydrous and oxygen-free sealing system; Mol ratio by D that adds in organic amine and the step b) or L-tyrosine alcohol ester hydrochloride is 0.03～0.05: 1, organic amine is added among the D or L-tyrosine alcohol ester isocyanide ester monomer solution that makes in the step b) room temperature reaction 12～24h; Pour in the anhydrous diethyl ether of 3～6 times of its volumes; Sedimentation and filtration, vacuum-drying 12～24h gets optically active helical polyurethane material.
What the described short chain fatty alcohol of method (1) was the backbone c atoms number in 2～8 straight chain or side chain saturated fatty alcohol in preparing method's step a) of above-mentioned materials is a kind of; What the described long chain aliphatic alcohol of method in preparing method's step a) (2) was the backbone c atoms number in 9～18 straight chain or side chain saturated fatty alcohol is a kind of; The described aromatic alcohol of method in preparing method's step a) (3) is a kind of in phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol, benzene butanols, Suidisin, the benzene hexanol; Halohydrocarbon described in the step b) is methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1, a kind of in the 2-ethylene dichloride; Organic amine described in the step c) is one or more the combination in triethylamine, triethylene diamine, tetramethyl butane diamine, the N-methylmorpholine.
Beneficial effect: optically active helical polyurethane material of the present invention and preparation method thereof, preparation technology is simple, and reaction conditions is gentle.This material has higher specific rotatory power, good thermostability and film-forming properties.
Characteristics of the present invention are:
(1) solid phosgene that adopts safety to be easy to get has prepared the auto-polymerization monomer that has hydroxyl and isocyanide ester base in the unit molecule simultaneously, and passes through the decomposition of mineral alkali catalytic solid phosgene, makes under relatively mild condition, promptly reaches in the short period of time and react completely;
(2) directly chiral carbon atom has been incorporated in the main chain of polymkeric substance, thereby has made polymkeric substance have higher specific rotatory power;
(3), can regulate hard and soft property and conformation with the controlling polymers chain, and then reach and regulate its optically active purpose through the alcohol of different molecular structures is introduced in the side chain of polymkeric substance.
Embodiment
Instance 1: get 78mL ethanol and join in the 250mL four-hole boiling flask, cryosel is bathed and is cooled to-5 ℃, slowly drips the 12.7g sulfur oxychloride, after dripping off, stirs 1h, adds 16.1g L-tyrosine, back flow reaction 8h.Reaction is reduced to room temperature after finishing, and adds the 160mL ether, sedimentation and filtration, and vacuum-drying 24h gets little yellow crystal L-TEE hydrochloride 19.2g.
Under-5～0 ℃, 1.24gL-TEE hydrochloride joins in the 50mL trichloromethane that is dissolved with the 0.5g solid phosgene.Slow Dropwise 5 0mL saturated sodium bicarbonate solution in this suspension-s, organic phase clear gradually in the dropping process.Drip and finish, room temperature reaction 2h tells organic phase, and water merges organic phase, anhydrous MgSO with 10mL trichloromethane washing secondary
4Dried overnight, the filtering siccative gets the monomeric chloroform soln of water white L-TEE isocyanide ester.
In the anhydrous and oxygen-free sealing system, add the above-mentioned monomeric chloroform soln of L-TEE isocyanide ester that obtains, add triethylamine 0.015g; Room temperature reaction 24h; Separate out white solid gradually, sedimentation and filtration, ether washing; Vacuum-drying 24h gets pale yellow powder shape optically active helical polyurethane material 0.96g.Productive rate: 81%;
IR (v/cm
-1): 3353,2953,1739 (C=O), 1716 (C (O) NH-), 1534,1502,1438,1358,1199,1017,841; 531;
1H-NMR (DMSO-d
6) δ: 1.05-1.25 (3H ,-CH
3), 2.77-3.08 (2H ,-PhCH
2-), 3.97-4.10 (2H ,-OCH
2), 4.15-4.34 (1H,＞CH-), 6.85-7.26 (4H ,-C
6H
4-), 8.18-8.28 (1H ,-NH-).
Instance 2: get the 75mL n-hexyl alcohol and join in the 250mL four-hole boiling flask, cryosel is bathed and is cooled to-5 ℃, slowly drips the 6.55g sulfur oxychloride, after dripping off, stirs 1h, adds 9.05g L-tyrosine, and rises to 80 ℃ of reaction 12h.Reaction is reduced to room temperature after finishing, and separates out a large amount of solids, filter, and the anhydrous diethyl ether washing, vacuum-drying 24h gets the own ester hydrochloride 13.6g of white needle-like crystals L-tyrosine.
Under-5～0 ℃, the own ester hydrochloride of 1.51gL-tyrosine joins in the 50mL methylene dichloride that is dissolved with the 0.5g solid phosgene.Slow Dropwise 5 0mL saturated sodium bicarbonate solution in this suspension-s, organic phase clear gradually in the dropping process.Drip and finish, room temperature reaction 2h tells organic phase, and water merges organic phase, anhydrous MgSO with 10mL washed with dichloromethane twice
4Dried overnight, the filtering siccative gets the monomeric dichloromethane solution of the own ester isocyanide ester of water white L-tyrosine.
In the anhydrous and oxygen-free sealing system; Add the monomeric dichloromethane solution of the own ester isocyanide ester of the above-mentioned L-tyrosine that obtains, add triethylamine 0.015g, room temperature reaction 24h; Reactant is poured in the 200mL ether; Sedimentation and filtration, vacuum-drying 18h gets white powder optically active helical polyurethane material 1.24g.Productive rate: 85%;
IR (v/cm
-1): 3330,2956,2930,1736 (C=O), 1711 (C (O) NH-), 1507,1217,1035,898;
1H-NMR (DMSO-d
6) δ: 0.82 (3H ,-CH
3), 1.22 (6H ,-(CH
2)
3-), 1.48-1.50 (2H ,-CH
2-), 2.78-3.06 (2H ,-PhCH
2-), 3.96-4.14 (2H ,-OCH
2-), 4.26-4.33 (1H,＞CH-), 6.86-7.26 (4H ,-C
6H
4-), 8.21-8.27 (1H ,-NH-).
Instance 3: under the room temperature, 6.0gL-tyrosine is joined in the 100mL four-hole boiling flask that the 10.5g decyl alcohol is housed, feed the exsiccant hydrogen chloride gas and with mixture heating up to 120 ℃, stirring reaction 5h; Reduce to room temperature, add the 100ml methylene dichloride, filter; The gained solid is poured in the 60ml water, and yellow soda ash is transferred pH to 9.0, with 50ml anhydrous diethyl ether extraction 2～3 times; Extracted with diethyl ether is spent the night with anhydrous sodium sulfate drying, removes siccative, feeds the exsiccant hydrogen chloride gas; Sedimentation and filtration, vacuum-drying 24h gets L-tyrosine ester hydrochloride in last of the ten Heavenly stems 2.78g.
Under-5～0 ℃, 0.9gL-tyrosine ester hydrochloride in the last of the ten Heavenly stems joins in the 25mL dichloromethane solution that is dissolved with the 0.25g solid phosgene.In this suspension-s, slowly drip the 25mL saturated sodium bicarbonate solution, organic phase clear gradually in the dropping process.After dripping off, stirring at room 2h tells organic phase, and water merges organic phase, anhydrous MgSO with 5mL washed with dichloromethane twice
4Dried overnight, the filtering siccative obtains the monomeric dichloromethane solution of water white L-tyrosine ester in last of the ten Heavenly stems isocyanide ester.
In the anhydrous and oxygen-free sealing system, add the monomeric dichloromethane solution of above-mentioned L-tyrosine ester in last of the ten Heavenly stems isocyanide ester, add triethylamine 0.008g; Room temperature reaction 20h pours reactant in the 90mL ether into sedimentation and filtration; Vacuum-drying 24h gets white powder optically active helical polyurethane material 0.68g.Productive rate: 77%;
IR (v/cm
-1): 3332,2958,1730 (C=O), 1709 (C (O) NH-), 1514,1199,841;
1H-NMR (DMSO-d
6) δ: 0.83 (3H ,-CH
3), 1.21-1.42 (14H ,-(CH
2)
7-), 1.49-1.52 (2H ,-CH
2-), 2.81-3.02 (2H ,-PhCH
2-), 3.92-4.05 (2H ,-OCH
2-), 4.23-4.41 (1H,＞CH-), 6.82-7.12 (4H ,-C
6H
4-), 8.18-8.23 (1H ,-NH-).
Instance 4: under the room temperature, 6gL-tyrosine is joined in the 100mL four-hole boiling flask that the 13.3g stearyl alcohol is housed, feed the exsiccant hydrogen chloride gas and with mixture heating up to 120 ℃, stirring reaction 4h; Reduce to room temperature, add the 100ml methylene dichloride, filter; The gained solid is poured in the 60ml water, and yellow soda ash is transferred pH to 9.0, with 50ml extracted with diethyl ether 2～3 times; Extracted with diethyl ether is spent the night with anhydrous sodium sulfate drying, removes siccative, feeds the exsiccant hydrogen chloride gas; Sedimentation and filtration, vacuum-drying 24h gets L-tyrosine stearyl alcohol ester hydrochloride 2.3g.
Under-5～0 ℃, 1.18gL-tyrosine stearyl alcohol ester hydrochloride joins in the 25mL dichloromethane solution that is dissolved with the 0.25g solid phosgene.In this suspension-s, slowly drip the 25mL saturated sodium bicarbonate solution, organic phase clear gradually in the dropping process.After dripping off, stirring at room 2h tells organic phase, and water merges organic phase, anhydrous MgSO with 5mL washed with dichloromethane twice
4Dried overnight, the filtering siccative obtains the monomeric dichloromethane solution of water white L-tyrosine stearyl alcohol ester isocyanide ester.
In the anhydrous and oxygen-free sealing system; Add the monomeric dichloromethane solution of above-mentioned L-tyrosine stearyl alcohol ester isocyanide ester, add triethylamine 0.008g, room temperature reaction 20h; Reactant is poured in the 90mL ether; Sedimentation and filtration, vacuum-drying 24h gets white powder optically active helical polyurethane material 0.81g.Productive rate: 70%;
IR (v/cm
-1): 3338,2987,2965,1733 (C=O), 1716 (C (O) NH-), 1501,1027,858;
1H-NMR (DMSO-d
6) δ: 0.86 (3H ,-CH
3), 1.01-1.43 (30H ,-(CH
2)
15-), 1.50-1.55 (2H ,-CH
2-), 2.76-3.02 (2H ,-PhCH
2-), 3.89-4.01 (2H ,-OCH
2-), 4.21-4.35 (1H,＞CH-), 6.70-7.12 (4H ,-C
6H
4-), 8.12-8.19 (1H ,-NH-).
Instance 5: the 10g polyphosphoric acid is joined in the four-hole boiling flask that the 52g phenylcarbinol is housed, and stirring at room 1h adds L-tyrosine 3.6g, is warming up to 92 ℃ of reaction 8h.After reaction finishes, pour 200mL concentration into and be in 10% the sulfuric acid, add 25mL ether washing 2～3 times; Tell water and regulate pH to 10.0 with yellow soda ash, with 200mL extracted with diethyl ether 2～3 times, organic phase is spent the night with anhydrous sodium sulfate drying; The filtering siccative, filtrating feeds exsiccant hydrogen chloride gas, sedimentation and filtration; Vacuum-drying 20h gets white powder L-tyrosine benzyl ester hydrochloride 3.1g.
Under-5～0 ℃, 1.54gL-tyrosine benzyl ester hydrochloride joins in the 50mL chloroform soln that is dissolved with the 0.5g solid phosgene.Slow Dropwise 5 0mL saturated sodium bicarbonate solution in this suspension-s, organic phase clear gradually in the dropping process.After dripping off, stirring at room 2h tells organic phase, and water merges organic phase, anhydrous MgSO with 10mL trichloromethane washed twice
4Dried overnight, the filtering siccative gets the monomeric chloroform soln of water white L-tyrosine benzyl ester isocyanide ester.
In the anhydrous and oxygen-free sealing system, add the monomeric chloroform soln of above-mentioned L-tyrosine benzyl ester isocyanide ester, add triethylamine 0.015g; Room temperature reaction 24h pours reactant in the 150mL ether into sedimentation and filtration; Vacuum-drying 24h gets pale yellow powder shape optically active helical polyurethane material 1.08g.Productive rate: 73%;
IR (v/cm
-1): 3331,2987,2958,1730 (C=O), 1706 (C (O) NH-), 1507,1127,1033,858;
1H-NMR (DMSO-d
6) δ: 2.89-3.15 (2H ,-PhCH
2-), 4.34-4.41 (1H,＞CH-), 5.03-5.22 (2H, PhCH
2-) 6.83-6.90 (4H ,-C
6H
4-), 7.07-7.38 (5H, C
6H
5-), 8.36-8.39 (1H ,-NH-).
Instance 6: under the room temperature, the 10g polyphosphoric acid is joined in the four-hole boiling flask that the 65g Suidisin is housed, stir 1h, add L-tyrosine 3.6g, be warming up to 95 ℃ of reaction 8h.After reaction finishes, pour 200mL concentration into and be in 10% the sulfuric acid, add 25mL ether washing 2～3 times; Tell water and regulate pH to 10.0 with yellow soda ash, with 200mL extracted with diethyl ether 2～3 times, organic phase is spent the night with anhydrous sodium sulfate drying; Remove siccative, feed the exsiccant hydrogen chloride gas, sedimentation and filtration; Vacuum-drying 24h gets white powder L-tyrosine benzene pentyl ester hydrochloride 3.4g.
Under-5～0 ℃, 1.83gL-tyrosine benzene pentyl ester hydrochloride joins in the 50mL chloroform soln that is dissolved with the 0.5g solid phosgene.Slow Dropwise 5 0mL saturated sodium bicarbonate solution in this suspension-s, organic phase clear gradually in the dropping process.After dripping off, stirring at room 2h tells organic phase, and water merges organic phase, anhydrous MgSO with 10mL trichloromethane washed twice
4Dried overnight, the filtering siccative gets the monomeric chloroform soln of water white L-tyrosine benzene pentyl ester isocyanide ester.
In the anhydrous and oxygen-free sealing system; Add the monomeric chloroform soln of above-mentioned L-tyrosine benzene pentyl ester isocyanide ester, add triethylamine 0.015g, room temperature reaction 24h; Reactant is poured in the 150mL ether; Sedimentation and filtration, vacuum-drying 24h gets pale yellow powder shape optically active helical polyurethane material 1.35g.Productive rate: 76%;
IR (v/cm
-1): 3331,2985,2960,1728 (C=O), 1705 (C (O) NH-), 1513,1231,1109,832;
1H-NMR (DMSO-d
6) δ: 1.29-1.62 (6H ,-(CH
2)
3-), 2.64-2.66 (2H ,-CH
2-), 2.98-3.15 (2H ,-PhCH
2-), 3.98-4.11 (2H ,-OCH
2-), 4.24-4.32 (1H,＞CH-), 6.68-6.95 (4H ,-C
6H
4-), 7.17-7.26 (5H, C
6H
5-), 8.21-8.26 (1H ,-NH-).
Claims (7)
1. optically active helical polyurethane material is characterized in that this material is to be formed by D or the auto-polymerization of L-tyrosine alcohol ester isocyanate-monomer solution original position with solid phosgene reaction generation of D or L-tyrosine alcohol ester hydrochloride, and its general structure is:
Polymerization degree n is greater than 1, less than 20000,
Wherein, R1 is following structure:
2. the preparation method of an optically active helical polyurethane material as claimed in claim 1 is characterized in that its preparation method is:
The preparation method of step a) D or L-tyrosine alcohol ester hydrochloride:
Method 1): adopt short chain fatty alcohol: the molar weight to add D or L-tyrosine is a standard, is 15～10: 1 by the mol ratio of short chain fatty alcohol and D or L-tyrosine, and short chain fatty alcohol is joined in the reaction kettle; Mol ratio by sulfur oxychloride and D or L-tyrosine is 1.5～1.2: 1, sulfur oxychloride is slowly splashed in the short chain fatty alcohol that is chilled to-10～0 ℃, after dripping off;-10～0 ℃ is stirred 1～2h down, adds D or L-tyrosine and rises to 60～90 ℃ of reaction 5～10h, reduces to room temperature; Add the ether of 2～3 times of short chain fatty alcohol volumes, separate out solid, filter; Vacuum-drying 12～24h gets D or L-tyrosine alcohol ester hydrochloride; What above-mentioned short chain fatty alcohol was the backbone c atoms number in 2～8 straight chain or side chain saturated fatty alcohol is a kind of;
Step b) is 0.34～0.36: 1 by the mol ratio of the D that makes in solid phosgene and the step a) or L-tyrosine alcohol ester hydrochloride under-5～0 ℃, and D or L-tyrosine alcohol ester hydrochloride are joined in the solid phosgene halohydrocarbon solution that concentration is 0.01～0.03g/mL; Slowly drip and the isopyknic saturated sodium bicarbonate solution of halohydrocarbon solution; After dripping off, room temperature reaction 2～5h, water washs 2～3 times with the halohydrocarbon of 0.1～0.2 times of its volume; Merge organic phase, anhydrous MgSO
4Dried overnight, the filtering siccative gets water white transparency D or L-tyrosine alcohol ester isocyanate-monomer solution;
Step c) is in the anhydrous and oxygen-free sealing system; Mol ratio by D that adds in organic amine and the step b) or L-tyrosine alcohol ester hydrochloride is 0.03～0.05: 1, organic amine is added among the D or L-tyrosine alcohol ester isocyanate-monomer solution that makes in the step b) room temperature reaction 12～24h; Pour in the anhydrous diethyl ether of 3～6 times of its volumes; Sedimentation and filtration, vacuum-drying 12～24h gets optically active helical polyurethane material.
3. the preparation method of optically active helical polyurethane material according to claim 2, it is characterized in that the preparation method of step a) D or L-tyrosine alcohol ester hydrochloride also can be: adopt long chain aliphatic alcohol: the molar weight to add D or L-tyrosine is a standard, is 2～1.5: 1 by the mol ratio of long chain aliphatic alcohol and D or L-tyrosine; Long chain aliphatic alcohol is mixed with D or L-tyrosine, feed the exsiccant hydrogen chloride gas and mixture heating up to 100～120 ℃, stirring reaction 4～8h; Reduce to room temperature, add the methylene dichloride of long chain aliphatic alcohol volume 5～8, suction filtration; The gained solid is poured in the water of 2～5 times of long chain aliphatic alcohol volumes; Yellow soda ash is transferred pH to 9.0～10.0, extracts 2～3 times with the anhydrous diethyl ether of 3～5 times of long chain aliphatic alcohol volumes, and extracted with diethyl ether is spent the night with anhydrous sodium sulfate drying; The elimination siccative; Filtrating feeds exsiccant hydrogen chloride gas, sedimentation and filtration, vacuum-drying 12～24h; D or L-tyrosine alcohol ester hydrochloride, what above-mentioned long chain aliphatic alcohol was the backbone c atoms number in 9～18 straight chain or side chain saturated fatty alcohol is a kind of.
4. the preparation method of optically active helical polyurethane material according to claim 2; The preparation employing method that it is characterized in that D or L-tyrosine alcohol ester hydrochloride also can be: adopt aromatic alcohol: the molar weight to add D or L-tyrosine is a standard; Mol ratio by aromatic alcohol and D or L-tyrosine is 25～20: 1; Aromatic alcohol is joined in the reaction kettle, is 1.5～1.2: 1 by the mol ratio of polyphosphoric acid and D or L-tyrosine, and polyphosphoric acid is added in the aromatic alcohol; Stirring at room 1～2h adds D or L-tyrosine and rises to 90～95 ℃ of reaction 4～10h.Reactant is poured in 10～20% the sulfuric acid of 4～6 times of aromatic alcohol volumes, with the anhydrous diethyl ether washing of 0.5～1 times of aromatic alcohol volume 2～3 times, water is regulated pH to 9.0～10.0 with yellow soda ash; Anhydrous diethyl ether with 3～5 times of aromatic alcohol volumes extracts 2～3 times, and organic phase is spent the night with anhydrous sodium sulfate drying, the elimination siccative; Filtrating feeds the exsiccant hydrogen chloride gas; Sedimentation and filtration, vacuum-drying 12～24h gets D or L-tyrosine alcohol ester hydrochloride.
5. the preparation method of optically active helical polyurethane material according to claim 4; It is characterized in that described aromatic alcohol is a kind of in phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol, benzene butanols, Suidisin, the benzene hexanol among the preparation method of D or L-tyrosine alcohol ester hydrochloride.
6. the preparation method of optically active helical polyurethane material according to claim 2 is characterized in that the halohydrocarbon described in this preparing method's step b) is methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1, a kind of in the 2-ethylene dichloride.
7. the preparation method of optically active helical polyurethane material according to claim 2 is characterized in that the organic amine described in this preparing method's step c) is one or more the combination in triethylamine, triethylene diamine, tetramethyl butane diamine, the N-methylmorpholine.
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| CN102060968B (en) * | 2010-12-09 | 2012-11-14 | 东南大学 | Optically active polyurethane-amide material and preparation method thereof |
| CN103923243B (en) * | 2014-04-11 | 2016-06-01 | 东南大学 | A kind of optically-active polyacetylene infrared low-emissivity material and its preparation method |
| CN105440189B (en) * | 2015-11-27 | 2017-09-12 | 湘潭大学 | It is a kind of to trigger the method that achiral monomers polymerization prepares chiral polymer as radical initiator by the use of qinghaosu and its derivative |
| CN106075572B (en) * | 2016-07-05 | 2019-03-22 | 河南理工大学 | Nanometer hydroxyapatite, poly- (the own ester of desaminotyrosyl tyrosine) carbonic ester composite bone repairing material and preparation method thereof |
| CN108395523B (en) * | 2018-03-29 | 2020-05-01 | 湖北科技学院 | Oxidation helix conformation-reversed isonitrile helical polymer containing thioether side chain and preparation method thereof |
| CN113534316B (en) * | 2020-04-15 | 2023-10-31 | 中国科学院宁波材料技术与工程研究所 | Optical film, preparation method thereof and photoelectric device |
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| JP2002322144A (en) * | 2001-04-27 | 2002-11-08 | Jsr Corp | Method for producing isocyanate compound having optical activity and method for producing polyurethane having optical activity |
| CN100471918C (en) * | 2003-07-08 | 2009-03-25 | 树脂核动力工业有限公司 | Carbon-substituted methyl amine derivatives and their use as a rheology control agent |
| CN101696260A (en) * | 2009-10-12 | 2010-04-21 | 东南大学 | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof |
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| JP2002322144A (en) * | 2001-04-27 | 2002-11-08 | Jsr Corp | Method for producing isocyanate compound having optical activity and method for producing polyurethane having optical activity |
| CN100471918C (en) * | 2003-07-08 | 2009-03-25 | 树脂核动力工业有限公司 | Carbon-substituted methyl amine derivatives and their use as a rheology control agent |
| CN101696260A (en) * | 2009-10-12 | 2010-04-21 | 东南大学 | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof |
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