CN102060968B - Optically active polyurethane-amide material and preparation method thereof - Google Patents

Optically active polyurethane-amide material and preparation method thereof Download PDF

Info

Publication number
CN102060968B
CN102060968B CN2010105791947A CN201010579194A CN102060968B CN 102060968 B CN102060968 B CN 102060968B CN 2010105791947 A CN2010105791947 A CN 2010105791947A CN 201010579194 A CN201010579194 A CN 201010579194A CN 102060968 B CN102060968 B CN 102060968B
Authority
CN
China
Prior art keywords
tyrosine
acid
solution
ester
methyl
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.)
Expired - Fee Related
Application number
CN2010105791947A
Other languages
Chinese (zh)
Other versions
CN102060968A (en
Inventor
周钰明
杨勇
葛建华
王泳娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southeast University
Original Assignee
Southeast University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Southeast University filed Critical Southeast University
Priority to CN2010105791947A priority Critical patent/CN102060968B/en
Publication of CN102060968A publication Critical patent/CN102060968A/en
Application granted granted Critical
Publication of CN102060968B publication Critical patent/CN102060968B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention aims to provide an optically active polyurethane-amide material and a preparation method thereof. The material is obtained by copolymerization of L or D-tyrosine derivative bisphenol monomer, diisocyanate and organic diacid monomer and has the structural formula in the specification. The glass transition temperature of the material is 150-200 DEG C, the thermal decomposition temperature is 300-350 DEG C and the specific rotation absolute value at room temperature is 30-100 degrees.

Description

Optically active polyurethanes-acid amides material and preparation method thereof
Technical field
The present invention relates to a kind of optically active polyurethanes-acid amides material and preparation method thereof, belong to the preparation category of organic functions polymer materials.
Background technology
Polyurethane material has excellent abrasive, oil-proofness and elastic plastics characteristic and is widely used in fields such as automobile, building, machinery, aerospace, electronics.Yet the thermotolerance of conventional polyurethanes material is relatively poor, and mechanical propertys such as its tensile strength, Young's modulus can obviously descend at 80-90 ℃, make its range of application receive certain limitation.Thereby the research and development of high heat stability based polyurethane have received people's generally attention.It is one of important means that improves material property that the polymers functionality that will have a different qualities is introduced in the polymer chain structure.For example; It is the high-performance polymer of constitutional features with the imide ring that polyimide is one type; It still can keep excellent mechanical property in the pyritous environment; Polymeric amide then has chemicalstabilities such as good acid and alkali-resistance, organic solvent-resistant, and the two is used for the modification of polyurethane material, can significantly improve its application performance.And the existence of polymeric amide, imide functionality can produce a large amount of interchain hydrogen bond effects, has material impact for flexible polyurethane, the compatibility of hard section and even the higher structure of macromolecular chain.
In addition, being applied to polymkeric substance amino acid molecular synthetic is a very significant research direction, and this base polymer is considered to the most promising one type of material.Natural amino acid and derived polymer safety non-toxic thereof are easy to degraded and have good biocompatibility.Patent CN200810045884 discloses a kind of tissue renovation material that is polymerized by epsilon-amino caproic acid and at least two kinds of other amino acid and preparation method thereof; Patent CN02134373 discloses a kind of amino acid modified polysiloxane organism; Under phase-transfer catalyst or ion exchange resin inducing action; Is that amino acid or its salt of amino link together with the covalent linkage form with organo-siloxane performed polymer and end group through silane coupling agent, and patent CN01132179 discloses a kind of containing in active medicine, the main chain and had amino acid whose polyester and preparation method thereof, and this invention is randomly introduced natural multifunctional amino acid in the biodegradation type polyester; Avoided the antigenicity of degraded product; Degraded product can be can be used as the coating of medicine equipment by complete bio-absorbable simultaneously, also can be made into implant or other preparations.Simultaneously; The effect of the chiral atom higher structure that the induced polymer chain formation is regular in the amino acid molecular; Except producing better crystallinity and solvability, also given its unique optical property, have important use value aspect chiral separation, chiral catalysis and the asymmetric synthesis.It is monomeric synthetic that the present invention is applied to dihydroxyl with chirality tyrosine; Obtain the end capped prepolymer of isocyanate groups through itself and di-isocyanate reaction; And further prepared a series of novel optical active polyurethanes-acid amides material with the organic diacid monomer copolymerization; This material has higher thermostability, and adjustable chain structure and stable conformation have wide research and application prospect.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of optically active polyurethanes-acid amides material and preparation method thereof.This material has adjustable chain structure, good thermostability and higher optical activity.
Technical scheme: a kind of optically active polyurethanes of the present invention-acid amides material, obtain by L or D-tyrosine-derived biphenol monomer, vulcabond and organic diacid monomer copolymerization, its general structure is:
Figure BDA0000036957580000021
Polymerization degree n is 1～40000,
Wherein, R 1Be following structure:
A kind of in ; M is 1～5, and p is 1～5;
R 2Be following structure:
A kind of in , k is 0～5;
R 3Be following structure:
A kind of in
Figure BDA0000036957580000024
;
R 4Be following structure:
A kind of in .
Optically active polyurethanes of the present invention-acid amides preparation methods is:
Under the step a)-5～0 ℃; With concentration is that the L of 0.5～2mol/L or the tetrahydrofuran solution of D-tyrosine alcohol ester add reaction kettle; The p-hydroxybenzoic acid that adds: the mol ratio of L or D-tyrosine alcohol ester is 1: 1～1.2: 1, stirs 0.5～1h, and add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate again: the mol ratio of L or D-tyrosine alcohol ester is 1: 1～1.2: 1; Reaction 1～3h; Rise to room temperature and continue reaction 18～24h, above reactant is poured in the deionized water of tetrahydrofuran solution volume of 5～10 times of L or D-tyrosine alcohol ester, with the CH of 2～4 times of L or D-tyrosine alcohol ester tetrahydrofuran solution volume 2Cl 2Extract, and use the Na of the tetrahydrofuran solution volume of 3～5 times of L or D-tyrosine ester successively 2CO 3The aqueous solution, the saturated NaCl aqueous solution, aqueous citric acid solution, the saturated NaCl aqueous solution and deionized water are to this CH 2Cl 2Extraction liquid washs, Na 2CO 3Concentration of aqueous solution is 0.1～0.2mol/L, and aqueous citric acid solution concentration is 0.1～0.2mol/L; CH after the washing 2Cl 2Extraction liquid is used anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets L or D-chirality biphenol monomer;
Under the step b) condition of nitrogen gas, L or D-chirality biphenol monomer that step a) is made join in the reaction kettle, and adding N-N-methyl-2-2-pyrrolidone N-compound concentration is the N-N-methyl-2-2-pyrrolidone N-solution of 1～3mol/L; Being warming up to 90～110 ℃, is 2: 1 by the mol ratio of vulcabond and L or D-chirality biphenol monomer, adds the N-N-methyl-2-2-pyrrolidone N-solution of 1～3mol/L vulcabond; Reaction 5～10h obtains the end capped polyurethane prepolymer of isocyanate groups, is cooled to room temperature; Mol ratio by organic diacid monomer and L or D-chirality biphenol monomer is 1: 1, adds the monomeric N-N-methyl-2-2-pyrrolidone N-of 0.5～2mol/L organic diacid solution, stirring at room 1～3h post-heating to 120～150 ℃ of reaction 2～5h; Be cooled to room temperature; Pour in the methyl alcohol of N-N-methyl-2-2-pyrrolidone N-liquor capacity of 10～50 times of L or D-chirality biphenol monomer, separate out deposition, filter; 60～80 ℃ of vacuum-drying 10～20h get optically active polyurethanes-acid amides material.
L described in this preparing method's step a) or D-tyrosine alcohol ester are L or D-tyrosine C 2～C 6A kind of in straight chain saturated fatty alcohol ester, L or D-tyrosine phenylcarbinol ester, L or D-tyrosine phenylglycollic ester, L or D-tyrosine phenylpropyl alcohol alcohol ester, L or D-tyrosine benzene butyl alcohol ester, L or D-tyrosine Suidisin ester, L or the D-tyrosine benzene hexanol ester.
P-hydroxybenzoic acid described in this preparing method's step a) is a kind of in PHB, p-hydroxyphenylaceticacid, para hydroxybenzene propionic acid, para hydroxybenzene butyric acid, para hydroxybenzene valeric acid, para hydroxybenzene caproic acid or the p-Coumaric Acid.
Vulcabond described in this preparing method's step b) is 2; 4-tolylene diisocyanate, 4; A kind of in 4 '-'-diphenylmethane diisocyanate or the dimethyl diphenyl vulcabond; Described organic diacid monomer is a terephthalic acid, 4,4 '-biphenyl dicarboxylic acid or 4, a kind of in 4 '-phenyl ether dioctyl phthalate.
The second-order transition temperature of the above-mentioned optically active polyurethanes for preparing-acid amides material is that 150 ℃～200 ℃, heat decomposition temperature are that specific rotatory power absolute value under 300 ℃～350 ℃, room temperature is 30 °～100 °.
Beneficial effect: the present invention provides a kind of optically active polyurethanes-acid amides material and preparation method thereof, and this material has higher optical activity, good solvent resistance, high thermal stability and good conformational stability.
Characteristics of the present invention are:
(1) the chiral amino acid molecule is introduced in the main polymer chain, prepared and have optically active urethane-acid amides material, this material has percent crystallinity and higher optical activity preferably.
(2) the amino acid alcohol ester of employing different molecular structures, the side chain steric hindrance size of adjustable polymkeric substance, and then regulate its optical activity stability.
(3) select the 3rd monomer organic diacid to carry out copolymerization, the amide group of generation has been given key propertys such as the anti-solvent of polymkeric substance, acid and alkali-resistance, helps producing a large amount of intermolecular ydrogen bondings simultaneously, has significantly improved the thermostability of polymkeric substance.
Embodiment
Optically active polyurethanes of the present invention-acid amides material is obtained by L or D-tyrosine-derived biphenol monomer, vulcabond and organic diacid monomer copolymerization, and its general structure is:
Figure BDA0000036957580000041
Polymerization degree n is 1～40000,
Wherein, R 1Be following structure:
A kind of in
Figure BDA0000036957580000042
; M is 1～5, and p is 1～5;
R 2Be following structure:
A kind of in
Figure BDA0000036957580000043
, k is 0～5;
R 3Be following structure:
A kind of in
Figure BDA0000036957580000044
;
R 4Be following structure:
A kind of in
Figure BDA0000036957580000045
.
Embodiment 1:
Under 0 ℃, 1.05g L-TEE is dissolved in the 5mL THF, adds the 0.84g p-hydroxyphenylaceticacid, stir 30min, add 1.06g1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, 0 ℃ of reaction 1h rises to room temperature and continues reaction 20h.Reactant is poured the 50mL deionized water into, produces the oily deposition, uses 20mLCH 2Cl 2Extraction uses 20mL concentration to be 0.1mol/LNa more successively 2CO 3Solution, the saturated NaCl aqueous solution of 20mL, 20mL concentration is the 0.1mol/L citric acid solution, the saturated NaCl aqueous solution of 20mL and 20mL deionized water are to this CH 2Cl 2Extraction liquid washs, and uses anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets L-TEE phenylacetamide biphenol monomer 0.86g.
N 2Protection is dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-with 0.5g L-TEE phenylacetamide bis-phenol down, is heated to 100 ℃; Get 0.73g 4; 4 '-diphenylmethanediisocyanate is dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-, and slowly drops to above-mentioned biphenol monomer solution, prepolymerization reaction 5h.Be cooled to room temperature, add the N-N-methyl-2-2-pyrrolidone N-solution that 1mL is dissolved with the 0.25g terephthalic acid, stirring at room 2h; Be heated to 120 ℃ of reaction 3h, be cooled to room temperature, pour in the 50mL methyl alcohol; Separate out deposition; Filter, 60 ℃ of following vacuum-drying 12h get L type optically active polyurethanes-acid amides material 1.0g.The specific rotatory power of this material is that 175 ℃, heat decomposition temperature are 325 ℃ for-49.3 °, second-order transition temperature.
Embodiment 2:
Under 0 ℃, the own ester of 1.33g L-tyrosine is dissolved in the 5mL THF, adds the 0.76g PHB, stir 30min, add 1.06g1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, 0 ℃ of reaction 1h rises to room temperature and continues reaction 24h.Reactant is poured the 50mL deionized water into, produces the oily deposition, uses 20mLCH 2Cl 2Extraction uses 20mL concentration to be 0.1mol/LNa more successively 2CO 3Solution, the saturated NaCl aqueous solution of 20mL, 20mL concentration is the 0.1mol/L citric acid solution, the saturated NaCl aqueous solution of 20mL and 20mL deionized water are to this CH 2Cl 2Extraction liquid washs, and uses anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets the own ester BM of L-tyrosine biphenol monomer 1.35g.
N 2Protection is dissolved in the 1mLN-N-methyl-2-2-pyrrolidone N-with the own ester BM of 0.5g L-tyrosine bis-phenol down, is heated to 90 ℃; Get 0.46g 2; The 4-tolylene diisocyanate is dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-, and slowly drops to above-mentioned biphenol monomer solution, prepolymerization reaction 8h.Be cooled to room temperature, add 1mL and be dissolved with 0.32g 4, the N-N-methyl-2-2-pyrrolidone N-solution of 4 '-biphenyl dicarboxylic acid; Stirring at room 1h is heated to 120 ℃ of reaction 3h, is cooled to room temperature; Pour in the 50mL methyl alcohol, separate out deposition, filter; 60 ℃ of following vacuum-drying 12h get L type optically active polyurethanes-acid amides material 0.87g.The specific rotatory power of this material is that 163 ℃, heat decomposition temperature are 312 ℃ for-45 °, second-order transition temperature.
Embodiment 3:
Under 0 ℃, 1.2g L-tyrosine phenylcarbinol ester is dissolved in the 5mL THF, adds the 0.68g p-hydroxyphenylaceticacid, stir 30min, add 0.95g1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, 0 ℃ of reaction 1h rises to room temperature and continues reaction 20h.Reactant is poured the 50mL deionized water into, produces the oily deposition, uses 20mLCH 2Cl 2Extraction uses 20mL concentration to be 0.1mol/LNa more successively 2CO 3Solution, the saturated NaCl aqueous solution of 20mL, 20mL concentration is the 0.1mol/L citric acid solution, the saturated NaCl aqueous solution of 20mL and 20mL deionized water are to this CH 2Cl 2Extraction liquid washs, and uses anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets L-tyrosine phenylcarbinol ester phenylacetamide biphenol monomer 0.9g.
N 2Protection down; 0.5g L-tyrosine phenylcarbinol ester phenylacetamide bis-phenol is dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-; Be heated to 100 ℃, get 0.62g 4,4 '-diphenylmethanediisocyanate is dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-; And slowly drop to above-mentioned biphenol monomer solution, prepolymerization reaction 5h.Be cooled to room temperature, add the N-N-methyl-2-2-pyrrolidone N-solution that 1mL is dissolved with the 0.21g terephthalic acid, stirring at room 2h; Be heated to 120 ℃ of reaction 3h, be cooled to room temperature, pour in the 50mL methyl alcohol; Separate out deposition; Filter, 60 ℃ of following vacuum-drying 12h get L type optically active polyurethanes-acid amides material 0.8g.The specific rotatory power of this material is that 198 ℃, heat decomposition temperature are 351 ℃ for-67.3 °, second-order transition temperature.
Embodiment 4:
Under 0 ℃, 1.43g D-tyrosine pentyl ester is dissolved in the 5mL THF, adds the 0.87g PHB, stir 1h, add 1.2g1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, 0 ℃ of reaction 2h rises to room temperature and continues reaction 24h.Reactant is poured the 50mL deionized water into, produces the oily deposition, uses 20mLCH 2Cl 2Extraction uses 20mL concentration to be 0.1mol/LNa more successively 2CO 3Solution, the saturated NaCl aqueous solution of 20mL, 20mL concentration is the 0.1mol/L citric acid solution, the saturated NaCl aqueous solution of 20mL and 20mL deionized water are to this CH 2Cl 2Extraction liquid washs, and uses anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets D-tyrosine pentyl ester BM biphenol monomer 1.38g.
N 2Protection is dissolved in the 1mLN-N-methyl-2-2-pyrrolidone N-with 0.5g D-tyrosine pentyl ester BM bis-phenol down, is heated to 100 ℃; Get 0.47g 2; The 4-tolylene diisocyanate is dissolved in the 1mLN-N-methyl-2-2-pyrrolidone N-, and slowly drops to above-mentioned biphenol monomer solution, prepolymerization reaction 8h.Be cooled to room temperature, add 1mL and be dissolved with 0.35g 4, the N-N-methyl-2-2-pyrrolidone N-solution of 4 '-phenyl ether dioctyl phthalate; Stirring at room 2h is heated to 150 ℃ of reaction 5h, is cooled to room temperature; Pour in the 50mL methyl alcohol, separate out deposition, filter; 80 ℃ of following vacuum-drying 20h get D type optically active polyurethanes-acid amides material 0.78g.The specific rotatory power of this material is that 153 ℃, heat decomposition temperature are 308 ℃ for+55 °, second-order transition temperature.
Embodiment 5:
Under 0 ℃, 1.42g D-tyrosine monooctyl ester is dissolved in the 5mL THF, adds the 0.74g PHB, stir 30min, add 1g 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, 0 ℃ of reaction 1h rises to room temperature and continues reaction 24h.Reactant is poured the 50mL deionized water into, produces the oily deposition, uses 20mLCH 2Cl 2Extraction uses 20mL concentration to be 0.1mol/LNa more successively 2CO 3Solution, the saturated NaCl aqueous solution of 20mL, 20mL concentration is the 0.1mol/L citric acid solution, the saturated NaCl aqueous solution of 20mL and 20mL deionized water are to this CH 2Cl 2Extraction liquid washs, anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets D-tyrosine monooctyl ester BM biphenol monomer 1.32g.
N 2Protection down; 0.5g D-tyrosine monooctyl ester BM bis-phenol is dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-, is heated to 100 ℃, get 0.64g dimethyl diphenyl vulcabond and be dissolved in 1mL N-N-methyl-2-2-pyrrolidone N-; And slowly drop to above-mentioned biphenol monomer solution, prepolymerization reaction 8h.Be cooled to room temperature, add the N-N-methyl-2-2-pyrrolidone N-solution that 1mL is dissolved with the 0.2g terephthalic acid, stirring at room 1h; Be heated to 150 ℃ of reaction 5h, be cooled to room temperature, pour in the 50mL methyl alcohol; Separate out deposition; Filter, 80 ℃ of following vacuum-drying 20h get D type optically active polyurethanes-acid amides material 0.88g.The specific rotatory power of this material is that 165 ℃, heat decomposition temperature are 322 ℃ for+38 °, second-order transition temperature.

Claims (4)

1. optically active polyurethanes-acid amides material is characterized in that this material is obtained by L or D-tyrosine-derived biphenol monomer, vulcabond and organic diacid monomer copolymerization, and its general structure is:
Figure FDA00001672182400011
Polymerization degree n is 1～40000,
Wherein, R 1Be following structure:
A kind of in
Figure FDA00001672182400012
; M is 1～5, and p is 1～5;
R 2Be following structure:
A kind of in
Figure FDA00001672182400013
, k is 0～5;
R 3Be following structure:
A kind of in
Figure FDA00001672182400014
;
R 4Be following structure:
A kind of in .
2. optically active polyurethanes as claimed in claim 1-acid amides preparation methods is characterized in that its preparation method is:
Under the step a)-5～0 ℃; With concentration is that the L of 0.5～2mol/L or the tetrahydrofuran solution of D-tyrosine alcohol ester add reaction kettle; The p-hydroxybenzoic acid that adds: the mol ratio of L or D-tyrosine alcohol ester is 1: 1～1.2: 1, stirs 0.5 ~ 1h, and add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate again: the mol ratio of L or D-tyrosine alcohol ester is 1: 1～1.2: 1; Reaction 1～3h; Rise to room temperature and continue reaction 18～24h, above reactant is poured in the deionized water of tetrahydrofuran solution volume of 5～10 times of L or D-tyrosine alcohol ester, with the CH of 2～4 times of L or D-tyrosine alcohol ester tetrahydrofuran solution volume 2Cl 2Extract, and use the Na of the tetrahydrofuran solution volume of 3～5 times of L or D-tyrosine ester successively 2CO 3The aqueous solution, the saturated NaCl aqueous solution, aqueous citric acid solution, the saturated NaCl aqueous solution and deionized water are to this CH 2Cl 2Extraction liquid washs, Na 2CO 3Concentration of aqueous solution is 0.1～0.2mol/L, and aqueous citric acid solution concentration is 0.1～0.2mol/L; CH after the washing 2Cl 2Extraction liquid is used anhydrous MgSO 4Drying is filtered the back and is steamed except that CH 2Cl 2Solvent gets L or D-chirality biphenol monomer;
Under the step b) condition of nitrogen gas, L or D-chirality biphenol monomer that step a) is made join in the reaction kettle, and adding N-N-methyl-2-2-pyrrolidone N-compound concentration is the N-N-methyl-2-2-pyrrolidone N-solution of 1～3mol/L; Being warming up to 90 ~ 110 ℃, is 2: 1 by the mol ratio of vulcabond and L or D-chirality biphenol monomer, adds the N-N-methyl-2-2-pyrrolidone N-solution of 1～3mol/L vulcabond; Reaction 5～10h obtains the end capped polyurethane prepolymer of isocyanate groups, is cooled to room temperature; Mol ratio by organic diacid monomer and L or D-chirality biphenol monomer is 1: 1, adds the monomeric N-N-methyl-2-2-pyrrolidone N-of 0.5～2mol/L organic diacid solution, stirring at room 1～3h post-heating to 120 ~ 150 ℃ of reaction 2 ~ 5h; Be cooled to room temperature; Pour in the methyl alcohol of N-N-methyl-2-2-pyrrolidone N-liquor capacity of 10～50 times of L or D-chirality biphenol monomer, separate out deposition, filter; 60～80 ℃ of vacuum-drying 10～20h get optically active polyurethanes-acid amides material;
L described in this preparing method's step a) or D-tyrosine alcohol ester are L or D-tyrosine C 2~ C 6A kind of in straight chain saturated fatty alcohol ester, L or D-tyrosine phenylcarbinol ester, L or D-tyrosine phenylglycollic ester, L or D-tyrosine phenylpropyl alcohol alcohol ester, L or D-tyrosine benzene butyl alcohol ester, L or the D-tyrosine Suidisin ester.
3. optically active polyurethanes according to claim 2-acid amides preparation methods is characterized in that the p-hydroxybenzoic acid described in this preparing method's step a) is a kind of in PHB, p-hydroxyphenylaceticacid, para hydroxybenzene propionic acid, para hydroxybenzene butyric acid, para hydroxybenzene valeric acid, para hydroxybenzene caproic acid or the p-Coumaric Acid.
4. optically active polyurethanes according to claim 2-acid amides preparation methods; It is characterized in that the vulcabond described in this preparing method's step b) is 2; 4-tolylene diisocyanate, 4, a kind of in 4 '-'-diphenylmethane diisocyanate or the dimethyl diphenyl vulcabond, described organic diacid monomer is a terephthalic acid, 4; 4 '-biphenyl dicarboxylic acid or 4, a kind of in 4 '-phenyl ether dioctyl phthalate.
CN2010105791947A 2010-12-09 2010-12-09 Optically active polyurethane-amide material and preparation method thereof Expired - Fee Related CN102060968B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010105791947A CN102060968B (en) 2010-12-09 2010-12-09 Optically active polyurethane-amide material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010105791947A CN102060968B (en) 2010-12-09 2010-12-09 Optically active polyurethane-amide material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102060968A CN102060968A (en) 2011-05-18
CN102060968B true CN102060968B (en) 2012-11-14

Family

ID=43996486

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010105791947A Expired - Fee Related CN102060968B (en) 2010-12-09 2010-12-09 Optically active polyurethane-amide material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102060968B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104059208A (en) * 2014-01-02 2014-09-24 南京理工大学 Optical-activity polyurethane material and preparation method thereof
CN109999009B (en) * 2019-03-14 2020-06-23 重庆医药高等专科学校 Oral sustained-release preparation of antitumor drug and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864055A (en) * 2010-06-13 2010-10-20 东南大学 Optically active helical polyurethane material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7935843B2 (en) * 2005-12-09 2011-05-03 Bezwada Biomedical, Llc Functionalized diphenolics and absorbable polymers therefrom

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864055A (en) * 2010-06-13 2010-10-20 东南大学 Optically active helical polyurethane material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘引烽等.旋光性高分子的合成(上).《高分子通报》.1994,(第2期),72-79. *

Also Published As

Publication number Publication date
CN102060968A (en) 2011-05-18

Similar Documents

Publication Publication Date Title
CN103687723A (en) Polymer compositions and methods
CN101817924A (en) Method for preparing novel polyaspartic ester and application thereof
CN101889039A (en) Shape memory resin, shaped article using the same and method of using the shaped article
Qu et al. High toughness polyurethane toward artificial muscles, tuned by mixing dynamic hard domains
US7919656B2 (en) Linear amine functionalized poly(trimethylene ether) compositions
EP2547744A2 (en) Silane moisture curable hot melts
CA2417679C (en) Dendritic macromolecule with improved polyether polyol solubility and process for production thereof
JP2011503272A (en) NCO functional prepolymer composed of dicyclohexylmethane diisocyanate, isophorone diisocyanate and polyether polyol and having a tendency for reduced crystallization
CN102060968B (en) Optically active polyurethane-amide material and preparation method thereof
CN107602867B (en) Polyolefin-polyarylate copolymer containing fluorine and/or silicon, preparation method and application thereof
Cui et al. Sustainable approach for the synthesis of biopolycarbonates from carbon dioxide and soybean oil
Huang et al. Cross-linked networks in poly (propylene carbonate) by incorporating (maleic anhydride/cis-1, 2, 3, 6-tetrahydrophthalic anhydride) oligomer in CO2/propylene oxide copolymerization: improving and tailoring thermal, mechanical, and dimensional properties
CN102167826B (en) Optically active polyamide imide and preparation method as well as application thereof
CN110467726B (en) High-melting-point bio-based polyesteramide and preparation method thereof
Kausar et al. Studies on novel thermally stable segmented polyurethanes based on thiourea-derivative diols
JP2008531790A (en) Process using α, ω-bifunctional aldaramide as monomer and crosslinker
CN103936994A (en) Active-amino-terminated hyperbranched polysiloxane liquid crystalline and preparation method thereof
JP2016501925A (en) Polydiorganosiloxane polyurethane
CN101328267B (en) Biodegradable polyamideimide and preparation thereof
CN105482124B (en) A kind of helix poly silane material and preparation method thereof
Mallakpour et al. Direct polycondensations of N, N′‐(4, 4′‐oxydiphthaloyl)‐bis‐L‐leucine diacid by use of tosyl chloride in the presence of N, N‐dimethylformamide
CN1120164C (en) 5-benzyloxy-trimethylene carbonate and its prepn.
Zhou et al. A novel rosin-based non-isocyanate polyurethane with high-strength, self-healing, and recyclable properties for wood adhesives
CN103554449A (en) Thermotropic liquid crystal multi-component copolyester and preparation method thereof
CN109535417A (en) The preparation method of biology base thermoplastic poly oxamides urea

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent for invention or patent application
CB02 Change of applicant information

Address after: 211300 Gaochun County of Jiangsu Province Economic Development Zone Branch Center Building Room 405

Applicant after: Southeast University

Address before: 210096 Jiangsu city Nanjing Province four pailou No. 2

Applicant before: Southeast University

C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20121114

Termination date: 20151209

EXPY Termination of patent right or utility model