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

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

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CN102060968B
CN102060968B CN 201010579194 CN201010579194A CN102060968B CN 102060968 B CN102060968 B CN 102060968B CN 201010579194 CN201010579194 CN 201010579194 CN 201010579194 A CN201010579194 A CN 201010579194A CN 102060968 B CN102060968 B CN 102060968B
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tyrosine
acid
solution
optically active
ester
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CN102060968A (en )
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周钰明
杨勇
王泳娟
葛建华
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东南大学
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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

光学活性聚氨酯-酰胺材料及其制备方法 Optically active polyurethane - amide material and method

技术领域 FIELD

[0001] 本发明涉及一种光学活性聚氨酯-酰胺材料及其制备方法,属于有机功能聚合物材料的制备范畴。 [0001] The present invention relates to an optically active polyurethane - amide material and preparation method, the organic category belongs preparing functional polymer material.

背景技术 Background technique

[0002] 聚氨酯材料具有优异的耐磨性、耐油性以及弹塑性能而被广泛应用于汽车、建筑、机械、航空航天、电子等领域。 [0002] The polyurethane material has excellent abrasion resistance, oil resistance and elastoplastic can be widely used in automotive, construction, machinery, aerospace, electronics and other fields. 然而,普通聚氨酯材料的耐热性较差,其抗拉强度、弹性模量等机械性能在80-90°C会明显下降,使其应用范围受到了一定限制。 However, poor heat resistance general polyurethane materials, the tensile strength, elastic modulus and other mechanical properties decrease significantly at 80-90 ° C will make the application range has been limited. 因而,高热稳定性聚氨酯的研发受到了人们的普遍重视。 Thus, the high thermal stability of polyurethane research and development has been widespread attention. 将具有不同特性的聚合物官能团引入高分子链结构中是提高材料性能的重要手段之一。 The polymer having functional group introduced into a polymer having different characteristics in the chain structure is an important means of improving material properties. 例如,聚酰亚胺是一类以酰亚胺环为结构特征的高性能聚合物,其在高温的环境中仍能保持优异的力学性能,聚酰胺则具有很好的耐酸碱、耐有机溶剂等化学稳定性,将二者用于聚氨酯材料的改性中,可以显著提高其应用性能。 For example, polyimide is a class of imide ring structural features of high-performance polymers, which can maintain excellent mechanical properties in a high temperature environment, the polyamide has good acid resistance, organic solvents and other chemical stability, both for the modified polyurethane material, can significantly improve their application performance. 并且聚酰胺、酰亚胺官能团的存在会产生大量的链间氢键作用,对于聚氨酯软、硬段的混容性乃至大分子链的高级结构具有重要影响。 And polyamide imide functional group will generate a lot of inter-chain hydrogen bonds, the polyurethane soft, miscibility higher order structure of macromolecular chains and the hard segment has a significant impact.

[0003] 此外,将氨基酸分子应用于聚合物合成是一个非常有意义的研究方向,该类聚合物被认为是最有前景的一类材料。 [0003] Further, the amino acid molecule is a synthetic polymer applied very meaningful research, such polymers are considered the most promising class of materials. 天然氨基酸及其衍生聚合物安全无毒,易于降解且具有很好的生物相容性。 Natural amino acids and derivatives thereof safe non-toxic polymer, susceptible to degradation and has good biocompatibility. 专利CN200810045884公开了一种由e -氨基己酸与至少两种其它氨基酸聚合而成的组织修复材料及其制备方法,专利CN02134373公开了一种氨基酸改性聚有机硅氧烷,在相转移催化剂或离子交换树脂诱导作用下,通过硅烷偶联剂以共价键形式将有机硅氧烷预聚体与端基为氨基的氨基酸或其盐连接在一起,专利CN01132179公开了一种含有活性药物、主链中具有氨基酸的聚酯及其制备方法,该发明将天然多官能团氨基酸无规地引入生物降解型聚酯中,避免了降解产物的抗原性,同时降解产物可被完全生物吸收,可作为医疗器械的涂层,也可制成植入体或其他制剂。 Patent CN200810045884 discloses a e - aminocaproic acid polymerized with at least two other amino acid formed tissue repair material and its preparation method, a patent CN02134373 discloses amino modified polyorganosiloxane, or a phase transfer catalyst the ion exchange resin induced by a silane coupling agent to form a covalent bond organosiloxane prepolymer with terminal amino groups together is an amino acid or a salt thereof, Patent No. CN01132179 discloses a medicament containing an active primary polyesters and their method of preparation having an amino acid chain, the invention is a polyfunctional natural amino acids randomly incorporated biodegradable polyesters, avoiding the antigenicity of degradation products, degradation products can be absorbed while completely biological, medical as coating equipment, or other formulations may also be made implantation. 同时,氨基酸分子中手性原子的作用将诱导聚合物链形成规整的高级结构,除了产生更好结晶性以及溶解性外,还赋予了其独特的光学性能,在手性分离、手性催化和不对称合成方面具有重要的应用价值。 Meanwhile, the role of amino acids in the molecule chiral atom of the polymer chain will induce regular higher-order structure is formed, in addition to producing a better crystallinity and solubility, but also gives the unique optical properties, the chiral separation, chiral catalysis and asymmetric synthesis has important application value. 本发明将手性酪氨酸应用于二羟基单体的合成,通过其与二异氰酸酯反应得到异氰酸酯基团封端的预聚物,并进一步与有机二酸单体共聚制备了一系列新型光学活性聚氨酯-酰胺材料,该材料具有较高的热稳定性,可调的链结构和稳定的构象,具有广阔的研究和应用前景。 The present invention will be applied to the synthesis of chiral dihydroxy tyrosine monomers, ester groups to give a prepolymer terminated by an isocyanate which is reacted with a diisocyanate, and further copolymerized with an organic diacid monomer a series of novel optically active polyurethanes - amide materials, the material having a high thermal stability, adjustable chain structure and a stable conformation, and research has broad application prospect.

发明内容 SUMMARY

[0004] 技术问题:本发明的目的是提供一种光学活性聚氨酯-酰胺材料及其制备方法。 [0004] The technical problem: The purpose of the present invention is to provide an optically active polyurethane - amide material and its preparation method. 该材料具有可调的链结构,良好的热稳定性和较高的光学活性。 This material has an adjustable chain structure, good thermal stability and high optical activity.

[0005] 技术方案:本发明的一种光学活性聚氨酯-酰胺材料,由L或D-酪氨酸衍生双酚单体、二异氰酸酯和有机二酸单体共聚得到,其结构通式为: [0005] Technical Solution: an optically active polyurethane according to the present invention - amide materials, D- or L-tyrosine derived from the bisphenol monomer, a diisocyanate monomer and an organic diacid obtained, which is the structural formula:

[0006] [0006]

Figure CN102060968BD00051

[0007] 聚合度n为I〜40000, [0007] The polymerization degree n is I~40000,

[0008] 其中,R1为以下结构: [0008] wherein, R1 is the following structure:

[0009] [0009]

Figure CN102060968BD00052

中的一种,m为I 〜5,p为I 〜5; Of one, m is I ~5, p is I ~5;

[0010] R2为以下结构: [0010] R2 is the following structure:

[0011] [0011]

Figure CN102060968BD00053

中的一种,k 为0 〜5 ; Of one, k is 0 ~ 5;

[0012] R3为以下结构: [0012] R3 is the structure:

Figure CN102060968BD00054

中的一种; In one;

[0014] R4为以下结构: [0014] R4 is the following structure:

Figure CN102060968BD00055

中的一种。 In kind.

[0016] 本发明的光学活性聚氨酯-酰胺材料的制备方法为: [0016] The optically active polyurethane according to the invention - preparation of amide materials are:

[0017] 步骤a)_5〜0°C下,将浓度为0. 5〜2mol/L的L或D-酪氨酸醇酯的四氢呋喃溶液加入反应釜,加入的对羟基苯酸:L或D-酪氨酸醇酯的摩尔比为I : I〜I. 2 : 1,搅拌0. 5〜lh,再加入I-乙基-(3- 二甲基氨基丙基)碳酰二亚胺盐酸盐:L或D-酪氨酸醇酯的摩尔比为I : I〜I. 2 : 1,反应I〜3h,升至室温继续反应18〜24h,将以上反应物倒入5〜10倍L或D-酪氨酸醇酯的四氢呋喃溶液体积的去离子水中,用2〜4倍L或D-酪氨酸醇酯四氢呋喃溶液体积的CH2Cl2萃取,并依次用3〜5倍L或D-酪氨酸酯的四氢呋喃溶液体积的Na2CO3水溶液、饱和NaCl水溶液、柠檬酸水溶液、饱和NaCl水溶液和去离子水对该CH2Cl2萃取液进行洗涤,Na2CO3水溶液浓度为0. I〜0. 2mol/L,柠檬酸水溶液浓度为0. I〜0. 2mol/L ;洗涤后的CH2Cl2萃取液用无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得L或D-手性双酚单体; The [0017] Step a) _5~0 ° C, at a concentration of 0. 5~2mol / L tetrahydrofuran solution of D- or L-tyrosine ester added to the reaction vessel, was added p-hydroxybenzoate acid: L or D - molar ratio of tyrosine esters are I: I~I 2: 1, stirring 0. 5~lh, was added ethyl I- - (3-dimethylaminopropyl) carbodiimide salts. acid: L-tyrosine or D- molar ratio of alcohol to ester I: I~I 2:. 1, the reaction I~3h, warmed to room temperature the reaction was continued 18~24h, the reaction was poured into 5 to 10 times more tetrahydrofuran solution of D- or L-tyrosine volume of alcohol esters of deionized water, CH2Cl2 and extracted with a tetrahydrofuran solution of 2 ~ 4 times the volume of the D- or L-tyrosine esters, and washed successively with 3 to 5 times the D- or L aqueous Na2CO3 solution volume tyrosine ester in tetrahydrofuran, saturated aqueous NaCl solution, aqueous citric acid solution, saturated aqueous NaCl and deionized water, the extract was washed with CH2Cl2, aqueous Na2CO3 concentration of 0. I~0. 2mol / L, lemon aqueous acid solution at a concentration of 0. I~0 2mol / L;. CH2Cl2 extracts were washed dried over anhydrous MgSO4, the solvent was distilled off to obtain CH2Cl2 D- or L chiral filtered bisphenol monomer;

[0018] 步骤b)氮气条件下,将步骤a)制得的L或D-手性双酚单体加入到反应釜中,力口A N-甲基-2-吡咯烷酮配制浓度为I〜3mol/L的N-甲基-2-吡咯烷酮溶液,升温至90〜110°C,按二异氰酸酯与L或D-手性双酚单体的摩尔比为2 : 1,加入I〜3mol/L 二异氰酸酯的N-甲基-2-吡咯烷酮溶液,反应5〜10h,得到异氰酸酯基团封端的聚氨酯预聚物,冷却至室温,按有机二酸单体与L或D-手性双酚单体的摩尔比为I : 1,加入0.5〜2mol/L有机二酸单体的N-甲基-2-吡咯烷酮溶液,室温搅拌I〜3h后加热到120〜150°C反应2〜5h,冷却至室温,倒入10〜50倍L或D-手性双酚单体的N-甲基-2-吡咯烷酮溶液体积的甲醇中,析出沉淀,过滤,60〜80°C真空干燥10〜20h,得光学活性聚氨酯-酰胺材料。 The [0018] Step b) nitrogen conditions, step a) obtained in chiral D- or L bisphenol monomer is added to the reaction kettle, power port A N- methyl-prepared at a concentration I~3mol / L solution of N- methyl-2-pyrrolidone was heated to 90~110 ° C, a molar ratio diisocyanate D- or L chirality with a bisphenol monomer is 2: 1, was added I~3mol / L two isocyanate-N- methyl-2-pyrrolidone solution, the reaction 5~10h, to give a polyurethane prepolymer isocyanate group terminated, cooled to room temperature, according to the organic diacid monomers with D- or L chiral bisphenol monomer molar ratio of I: 1, was added N- methyl-2-pyrrolidone solution 0.5~2mol / L organic diacid monomers, was stirred at room temperature I~3h reaction was heated to 120~150 ° C 2~5h, cooled to room temperature , D- or L poured 10~50 times bisphenol monomer chiral N- methyl-2-pyrrolidone solution volume of methanol, a precipitate was filtered, 60~80 ° C and dried in vacuo 10~20h, to obtain an optical reactive polyurethane - amide material. [0019] 该制备方法步骤a)中所述的L或D-酪氨酸醇酯为L或D-酪氨酸C2〜C6直链饱和脂肪醇酯、L或D-酪氨酸苯甲醇酯、L或D-酪氨酸苯乙醇酯、L或D-酪氨酸苯丙醇酯、L或D-酪氨酸苯丁醇酯、L或D-酪氨酸苯戊醇酯、L或D-酪氨酸苯己醇酯中的一种。 [0019] The preparation method step a) of the D- or L-tyrosine esters of D- or L-tyrosine C2~C6 straight chain saturated alcohol esters, L-tyrosine benzyl ester of methanol or D- , L or D- tyrosine phenylethyl alcohol ester, L-tyrosine phenyl propanol acetate, or D-, L or D- tyrosine butanol phenyl ester, L-tyrosine or D- pentanol phenyl ester, L, or D- tyrosine one kind of phenyl-hexyl ester.

[0020] 该制备方法步骤a)中所述的对羟基苯酸为对羟基苯甲酸、对羟基苯乙酸、对羟基苯丙酸、对轻基苯丁酸、对轻基苯戍酸、对轻基苯己酸或对轻基苯丙烯酸中的一种。 [0020] The preparation method step a) of the p-hydroxybenzoic acid, p-hydroxyphenyl acetic acid, p-hydroxyphenyl propionic acid, butyric mild benzene, benzene light Shu acid, p-hydroxyphenyl light Acid benzene hexanoic acid, phenyl acrylic acid or one of the light.

[0021] 该制备方法步骤b)中所述的二异氰酸酯为2,4_甲苯二异氰酸酯、4,4' - 二苯甲烷二异氰酸酯或二甲基联苯二异氰酸酯中的一种,所述的有机二酸单体为对苯二甲酸、4,4' -联苯二甲酸或4,4' - 二苯醚二甲酸中的一种。 [0021] The preparation method step b) according to 2,4_ diisocyanate toluene diisocyanate, 4,4 '- one kind of diphenylmethane diisocyanate or dimethyl-biphenyl diisocyanate in the said the organic diacid monomer is terephthalic acid, 4,4 '- biphenyl dicarboxylic acid or 4,4' - diphenyl ether dicarboxylic acid of one kind.

[0022] 上述制备得到的光学活性聚氨酯-酰胺材料的玻璃化温度为150°C〜200°C、热分解温度为300°C〜350°C、室温下的比旋光度绝对值为30°〜100°。 [0022] Preparation of optically active polyurethane were obtained - a glass transition temperature amide material is 150 ° C~200 ° C, a thermal decomposition temperature of 300 ° C~350 ° C, than the absolute value of rotation at room temperature to 30 ° 100 °.

[0023] 有益效果:本发明提供一种光学活性聚氨酯-酰胺材料及其制备方法,该材料具有较高的光学活性,良好的耐溶剂性能、高热稳定性和优良的构象稳定性。 [0023] Advantageous Effects: The present invention provides an optically active polyurethane - amide material and its preparation method, the material having a high optical activity, good solvent resistance, excellent thermal stability and conformational stability.

[0024] 本发明的特点为: [0024] The features of the present invention are:

[0025] (I)将手性氨基酸分子引入聚合物主链中,制备了具有光学活性的聚氨酯-酰胺材料,该材料具有较好的结晶度和较高的光学活性。 [0025] (I) chiral amino acid molecules into the polymer main chain, polyurethane having preparing optically active - amide material that has good crystallinity and high optical activity.

[0026] (2)采用不同分子结构的氨基酸醇酯,可调节聚合物的侧链位阻大小,进而调节其光学活性稳定性。 [0026] (2) with different molecular structures amino alcohol esters, hindered adjustable size of the polymer side chains, thereby regulating an optically active stability.

[0027] (3)选择第三单体有机二酸进行共聚,生成的酰胺基团赋予了聚合物耐溶剂、耐酸碱等重要性能,同时有利于产生大量分子间氢键,显著提高了聚合物的热稳定性。 [0027] (3) selecting a third copolymerized monomeric organic diacid, an amide group resulting polymer impart solvent resistance, acid and other important properties, while facilitating the generation of hydrogen bonds between a large number of molecules, significantly improving the polymerisation thermal stability thereof.

具体实施方式 detailed description

[0028] 本发明的光学活性聚氨酯-酰胺材料,由L或D-酪氨酸衍生双酚单体、二异氰酸酯和有机二酸单体共聚得到,其结构通式为: [0028] The optically active polyurethane according to the present invention - amide materials, D- or L-tyrosine derived from the bisphenol monomer, a diisocyanate monomer and an organic diacid obtained, which is the structural formula:

[0029] [0029]

Figure CN102060968BD00061

[0030] 聚合度n为I〜40000, [0030] The polymerization degree n is I~40000,

[0031] 其中,R1为以下结构: [0031] wherein, R1 is the following structure:

[0032 ]- [0032] -

Figure CN102060968BD00062

中的一种,m为I 〜5,p为I 〜5; Of one, m is I ~5, p is I ~5;

[0033] R2为以下结构: [0033] R2 is the following structure:

[0034] [0034]

Figure CN102060968BD00063

中的一种,k 为0 〜5 ; Of one, k is 0 ~ 5;

[0035] R3为以下结构: [0035] R3 is the structure:

Figure CN102060968BD00071

中的一种; In one;

[0037] R4为以下结构: [0037] R4 is the following structure:

Figure CN102060968BD00072

中的一种。 In kind.

[0039] 实施例I : [0039] Example I:

[0040] (TC下,将1.05g L-酪氨酸乙酯溶于5mL四氢呋喃,加入0.84g对羟基苯乙酸,搅拌30min,加入I. 06gl-乙基-(3- 二甲基氨基丙基)碳酰二亚胺盐酸盐,0°C反应Ih,升至室温继续反应20h。反应物倒入50mL去离子水,产生油状沉淀,用20mLCH2Cl2萃取,再依次用20mL浓度为0. ImoVLNa2CO3溶液,20mL饱和NaCl水溶液,20mL浓度为0. lmol/L柠檬酸溶液,20mL饱和NaCl水溶液和20mL去离子水对该CH2Cl2萃取液进行洗涤,并用无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得L-酪氨酸乙酯苯乙酰胺双酚单体0. 86g。 [0040] (lower TC, the 1.05g L- tyrosine ethyl ester was dissolved in 5mL of tetrahydrofuran was added 0.84g of p-hydroxyphenylacetic acid, stirred for 30min, added I. 06gl- ethyl - (3-dimethylaminopropyl ) carbodiimide hydrochloride, 0 ° C the reaction Ih is, warmed to room temperature the reaction was continued 20h. The reaction was poured into 50mL of deionized water, give an oily precipitate was extracted with 20mLCH2Cl2, then washed with 20mL solution of a concentration of 0. ImoVLNa2CO3 , 20mL saturated aqueous NaCl solution, 20mL concentration of 0. lmol / L citric acid solution, saturated aqueous NaCl 20mL 20mL deionized water and the CH2Cl2 extract was washed and dried over anhydrous MgSO4, filtered and the solvent evaporated to give CH2Cl2 L- tyrosine ethyl ester benzeneacetamide bisphenol monomers 0. 86g.

[0041] N2保护下,将0. 5g L-酪氨酸乙酯苯乙酰胺双酚溶于ImL N-甲基_2_吡咯烷酮,加热至100°c,取0. 73g 4,4'- 二苯基甲烷二异氰酸酯溶于ImL N-甲基-2-吡咯烷酮,并缓慢滴加至上述双酚单体溶液,预聚反应5h。 [0041] Under N2 protection, the 0. 5g L- tyrosine ethyl ester was dissolved in ImL N- phenylacetamide bisphenol _2_ methyl pyrrolidone and heated to 100 ° c, takes 0. 73g 4,4'- diphenylmethane diisocyanate was dissolved in ImL N- methyl-2-pyrrolidone, and slowly added dropwise to the monomer solution bisphenols, prepolymerization 5h. 冷却至室温,加入ImL溶有0. 25g对苯二甲酸的N-甲基-2-吡咯烷酮溶液,室温搅拌2h,加热到120°C反应3h,冷却至室温,倒入50mL甲醇中,析出沉淀,过滤,60°C下真空干燥12h,得L型光学活性聚氨酯-酰胺材料I. 0g。 Cooled to room temperature, a solution of 0. 25g N- ImL-methyl-2-pyrrolidone solution of terephthalic acid, stirred at room temperature 2h, the reaction was heated to 120 ° C 3h, cooled to room temperature, poured into 50mL of methanol, a precipitate , filtered, and dried in vacuo 60 ° C for 12h, to give optically active L-form polyurethane - amide materials I. 0g. 该材料的比旋光度为-49. 3°、玻璃化温度为175°C、热分解温度为325°C。 Specific rotation of this material was -49. 3 °, a glass transition temperature of 175 ° C, the thermal decomposition temperature of 325 ° C.

[0042] 实施例2 : [0042] Example 2:

[0043] (TC下,将1.33g L-酪氨酸己酯溶于5mL四氢呋喃,加入0. 76g对轻基苯甲酸,搅拌30min,加入I. 06gl-乙基-(3- 二甲基氨基丙基)碳酰二亚胺盐酸盐,0°C反应Ih,升至室温继续反应24h。反应物倒入50mL去离子水,产生油状沉淀,用20mLCH2Cl2萃取,再依次用20mL浓度为0. ImoVLNa2CO3溶液,20mL饱和NaCl水溶液,20mL浓度为0. lmol/L柠檬酸溶液,20mL饱和NaCl水溶液和20mL去离子水对该CH2Cl2萃取液进行洗涤,并用无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得L-酪氨酸己酯苯甲酰胺双酚单体I. 35g。 [0043] (lower TC, the 1.33g L- tyrosine hexyl ester was dissolved in 5mL of tetrahydrofuran was added 0. 76g mild acid, stirred for 30min, added I. 06gl- ethyl - (3-dimethylaminopropyl propyl) carbodiimide hydrochloride, 0 ° C the reaction Ih is, warmed to room temperature the reaction was continued 24h. The reaction was poured into 50mL of deionized water to produce an oily precipitate was extracted with 20mLCH2Cl2, then washed with 20mL concentration of 0. ImoVLNa2CO3 solution, 20mL saturated aqueous NaCl solution, 20mL concentration of 0. lmol / L citric acid solution, saturated aqueous NaCl 20mL 20mL deionized water and the CH2Cl2 extract was washed and dried over anhydrous MgSO4, solvent was distilled CH2Cl2 and filtered to give L- tyrosine hexyl ester monomers bisphenol benzamide I. 35g.

[0044] N2保护下,将0. 5g L-酪氨酸己酯苯甲酰胺双酚溶于ImLN-甲基_2_吡咯烷酮,力口热至90°C,取0. 46g 2,4-甲苯二异氰酸酯溶于ImL N-甲基-2-吡咯烷酮,并缓慢滴加至上述双酚单体溶液,预聚反应8h。 Under [0044] N2 protection, the 0. 5g L- tyrosine hexyl ester was dissolved ImLN- methyl benzamide bisphenol _2_ pyrrolidone, thermal power port to 90 ° C, taking 0. 46g 2,4- tolylene diisocyanate were dissolved in ImL N- methyl-2-pyrrolidone, and slowly added dropwise to the monomer solution bisphenols, prepolymerization 8h. 冷却至室温,加入ImL溶有0. 32g 4,4'-联苯二甲酸的N-甲基-2-吡咯烷酮溶液,室温搅拌lh,加热到120°C反应3h,冷却至室温,倒入50mL甲醇中,析出沉淀,过滤,60°C下真空干燥12h,得L型光学活性聚氨酯-酰胺材料0. 87g。 Cooled to room temperature, a solution of 0. 32g 4,4'- ImL acid with a solution of N- methyl-2-pyrrolidone, LH was stirred at room temperature, the reaction was heated to 120 ° C 3h, cooled to room temperature, poured into 50mL methanol, a precipitate was filtered and dried in vacuo 60 ° C for 12h, to give optically active L-form polyurethane - amide materials 0. 87g. 该材料的比旋光度为-45°、玻璃化温度为163°C、热分解温度为312°C。 Specific rotation of this material was -45 °, a glass transition temperature of 163 ° C, the thermal decomposition temperature of 312 ° C.

[0045] 实施例3 : [0045] Example 3:

[0046] 0°C下,将1.2g L-酪氨酸苯甲醇酯溶于5mL四氢呋喃,加入0. 68g对轻基苯乙酸,搅拌30min,加入0. 95gl-乙基-(3- 二甲基氨基丙基)碳酰二亚胺盐酸盐,(TC反应lh,升至室温继续反应20h。反应物倒入50mL去离子水,产生油状沉淀,用20mLCH2Cl2萃取,再依次用20mL浓度为0. ImoVLNa2CO3溶液,20mL饱和NaCl水溶液,20mL浓度为0. lmol/L柠檬酸溶液,20mL饱和NaCl水溶液和20mL去离子水对该CH2Cl2萃取液进行洗涤,并用无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得L-酪氨酸苯甲醇酯苯乙酰胺双酚单体0. 9g。 The [0046] 0 ° C, the benzyl alcohol 1.2g L- tyrosine ester was dissolved in 5mL of tetrahydrofuran was added 0. 68g of the light phenylacetic acid, stirred for 30min, added 0. 95gl- ethyl - (3-dimethylaminopropyl yl amino propyl) carbodiimide hydrochloride, (the TC LH reaction, warmed to room temperature the reaction was continued 20h. The reaction was poured into 50mL of deionized water, give an oily precipitate was extracted with 20mLCH2Cl2, then washed with 20mL concentrations of 0 . ImoVLNa2CO3 solution, 20mL saturated aqueous NaCl solution, 20mL concentration of 0. lmol / L citric acid solution, saturated aqueous NaCl 20mL 20mL deionized water and the CH2Cl2 extract was washed and dried over anhydrous MgSO4, filtered and the solvent was distilled off CH2Cl2 L- tyrosine benzyl alcohol to give an ester monomers bisphenol phenylacetamide 0. 9g.

[0047] N2保护下,将0. 5g L-酪氨酸苯甲醇酯苯乙酰胺双酚溶于ImL N-甲基_2_吡咯烷酮,加热至100°C,取0.62g 4,4'-二苯基甲烷二异氰酸酯溶于ImL N-甲基-2-吡咯烷酮,并缓慢滴加至上述双酚单体溶液,预聚反应5h。 [0047] Under N2 protection, the 0. 5g L- tyrosine benzyl ester of methanol was dissolved in ImL N- phenylacetamide bisphenol _2_ methyl pyrrolidone and heated to 100 ° C, taking 0.62g 4,4'- diphenylmethane diisocyanate was dissolved in ImL N- methyl-2-pyrrolidone, and slowly added dropwise to the monomer solution bisphenols, prepolymerization 5h. 冷却至室温,加入ImL溶有0. 21g对苯二甲酸的N-甲基-2-吡咯烷酮溶液,室温搅拌2h,加热到120°C反应3h,冷却至室温,倒入50mL甲醇中,析出沉淀,过滤,60°C下真空干燥12h,得L型光学活性聚氨酯-酰胺材料0. Sg。 Cooled to room temperature, a solution of 0. 21g N- ImL-methyl-2-pyrrolidone solution of terephthalic acid, stirred at room temperature 2h, the reaction was heated to 120 ° C 3h, cooled to room temperature, poured into 50mL of methanol, a precipitate , filtered, and dried in vacuo 60 ° C for 12h, to give optically active L-form polyurethane - amide materials 0. Sg. 该材料的比旋光度为-67. 3°、玻璃化温度为198°C、热分解温度为351°C。 Specific rotation of this material was -67. 3 °, a glass transition temperature of 198 ° C, the thermal decomposition temperature of 351 ° C.

[0048] 实施例4 : [0048] Example 4:

[0049] 0°C下,将1.43g D-酪氨酸戍酯溶于5mL四氢呋喃,加入0. 87g对轻基苯甲酸,搅拌Ih,加入I. 2gl-乙基-(3- 二甲基氨基丙基)碳酰二亚胺盐酸盐,(TC反应2h,升至室温继续反应24h。反应物倒入50mL去离子水,产生油状沉淀,用20mLCH2Cl2萃取,再依次用20mL浓度为0. ImoVLNa2CO3溶液,20mL饱和NaCl水溶液,20mL浓度为0. lmol/L柠檬酸溶液,20mL饱和NaCl水溶液和20mL去离子水对该CH2Cl2萃取液进行洗涤,并用无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得D-酪氨酸戊酯苯甲酰胺双酚单体I. 38g。 The [0049] 0 ° C, the ester was dissolved in 1.43g D- tyrosine Shu 5mL of tetrahydrofuran was added 0. 87g mild acid, stirred Ih is added I. 2gl- ethyl - (3-dimethylaminopropyl aminopropyl) carbodiimide hydrochloride, (the TC reaction 2h, warmed to room temperature the reaction was continued 24h. The reaction was poured into 50mL of deionized water, give an oily precipitate was extracted with 20mLCH2Cl2, then washed with 20mL concentration of 0. ImoVLNa2CO3 solution, 20mL saturated aqueous NaCl solution, 20mL concentration of 0. lmol / L citric acid solution, saturated aqueous NaCl 20mL 20mL deionized water and the CH2Cl2 extract was washed and dried over anhydrous MgSO4, solvent was distilled CH2Cl2 and filtered to give D- tyrosine pentyl ester monomers bisphenol benzamide I. 38g.

[0050] N2保护下,将0. 5g D-酪氨酸戊酯苯甲酰胺双酚溶于ImLN-甲基_2_吡咯烷酮,力口热至100°C,取0. 47g 2,4-甲苯二异氰酸酯溶于ImLN-甲基-2-吡咯烷酮,并缓慢滴加至上述双酚单体溶液,预聚反应8h。 [0050] Under N2 protection, the 0. 5g D- tyrosine amyl methyl benzamide bisphenol dissolved ImLN- _2_ methylpyrrolidone, heated to force the mouth 100 ° C, taking 0. 47g 2,4- tolylene diisocyanate was dissolved in methyl-2-pyrrolidone ImLN-, and slowly added dropwise to the monomer solution bisphenols, prepolymerization 8h. 冷却至室温,加入ImL溶有0. 35g 4,4'-二苯醚二甲酸的N-甲基-2-吡咯烷酮溶液,室温搅拌2h,加热到150°C反应5h,冷却至室温,倒入50mL甲醇中,析出沉淀,过滤,80°C下真空干燥20h,得D型光学活性聚氨酯-酰胺材料0. 78g。 Cooled to room temperature, was added ImL solution of 0. 35g 4,4'- diphenylether dicarboxylic acid N- methyl-2-pyrrolidinone was stirred at room temperature 2h, the reaction was heated to 150 ° C 5h, cooled to room temperature, poured 50mL of methanol, a precipitate was filtered, dried in vacuo 80 ° C for 20h to give the optically active D-type polyurethane - amide materials 0. 78g. 该材料的比旋光度为+55°、玻璃化温度为153°C、热分解温度为308°C。 Specific rotation of this material was + 55 °, the glass transition temperature of 153 ° C, the thermal decomposition temperature of 308 ° C.

[0051] 实施例5: [0051] Example 5:

[0052] 0°C下,将1.42g D-酪氨酸辛酯溶于5mL四氢呋喃,加入0. 74g对轻基苯甲酸,搅拌30min,加入Ig 1_乙基_ (3-二甲基氨基丙基)碳酰二亚胺盐酸盐,0°C反应Ih,升至室温继续反应24h。 The [0052] 0 ° C, the tyrosine octyl ester was dissolved in 1.42g D- 5mL of tetrahydrofuran was added 0. 74g mild acid, stirred for 30min, added ethyl Ig 1_ _ (3-dimethylaminopropyl yl) carbodiimide hydrochloride, 0 ° C the reaction Ih, warmed to room temperature the reaction was continued 24h. 反应物倒入50mL去离子水,产生油状沉淀,用20mLCH2Cl2萃取,再依次用20mL浓度为0. ImoVLNa2CO3溶液,20mL饱和NaCl水溶液,20mL浓度为0. lmol/L柠檬酸溶液,20mL饱和NaCl水溶液和20mL去离子水对该CH2Cl2萃取液进行洗涤,无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得D-酪氨酸辛酯苯甲酰胺双酚单体I. 32g。 The reaction was poured into 50mL of deionized water, give an oily precipitate was extracted with 20mLCH2Cl2, then washed with a concentration of 0. ImoVLNa2CO3 solution 20mL, 20mL saturated aqueous NaCl solution, 20mL concentration of 0. lmol / L citric acid solution, and 20mL saturated aqueous NaCl 20mL deionized water from the CH2Cl2 extract was washed, dried over anhydrous MgSO4, filtered and the solvent evaporated to give CH2Cl2 D- tyrosine octyl benzamide bisphenol monomer I. 32g.

[0053] N2保护下,将0. 5g D-酪氨酸辛酯苯甲酰胺双酚溶于ImL N-甲基_2_吡咯烷酮,加热至100°c,取0. 64g 二甲基联苯二异氰酸酯溶于ImL N-甲基-2-吡咯烷酮,并缓慢滴加至上述双酚单体溶液,预聚反应8h。 [0053] N2 is protected under the 0. 5g D- tyrosine octyl benzamide were dissolved in ImL N- bisphenol _2_ methyl pyrrolidone and heated to 100 ° c, to take two methylene diphenyl 0. 64g isocyanate was dissolved in ImL N- methyl-2-pyrrolidone, and slowly added dropwise to the monomer solution bisphenols, prepolymerization 8h. 冷却至室温,加入ImL溶有0. 2g对苯二甲酸的N-甲基-2-吡咯烷酮溶液,室温搅拌lh,加热到150°C反应5h,冷却至室温,倒入50mL甲醇中,析出沉淀,过滤,80°C下真空干燥20h,得D型光学活性聚氨酯-酰胺材料0. 88g。 Cooled to room temperature, a solution of 0. 2g ImL terephthalic acid N- methyl-2-pyrrolidone solution, LH was stirred at room temperature, the reaction was heated to 150 ° C 5h, cooled to room temperature, poured into 50mL of methanol, a precipitate , filtered, and dried in vacuo 80 ° C for for 20 h, to give the optically active D-type polyurethane - amide materials 0. 88g. 该材料的比旋光度为+38°、玻璃化温度为165°C、热分解温度为322°C。 Specific rotation of this material was + 38 °, the glass transition temperature of 165 ° C, the thermal decomposition temperature of 322 ° C.

Claims (4)

  1. 1. 一种光学活性聚氨酯-酰胺材料,其特征在于该材料由L或D-酪氨酸衍生双酚单体、二异氰酸酯和有机二酸单体共聚得到,其结构通式为: An optically active polyurethane - amide materials, characterized in that the material consists of D- or L-tyrosine-derived diphenolic monomers, diisocyanates, and organic diacid monomers obtained, which is the structural formula:
    Figure CN102060968BC00021
    聚合度η为I〜40000, 其中,R1为以下结构: Η is the degree of polymerization I~40000, wherein, R1 is the following structure:
    Figure CN102060968BC00022
    中的一种,m为I 〜5,ρ为I 〜5; R2为以下结构: —C=C— 中的一种,k 为O 〜5 ; HH η κ R3为以下结构: Of one, m is I ~5, ρ is I ~5; R2 is the structure: -C = C- in one kind, k is O ~5; HH η κ R3 is the structure:
    Figure CN102060968BC00023
    兮3 丨分中的一种; Xi points in a 3-Shu;
    Figure CN102060968BC00024
    R4为以下结构: R4 is the following structure:
    Figure CN102060968BC00025
    中的一种。 In kind.
  2. 2. 一种如权利要求I所述的光学活性聚氨酯-酰胺材料的制备方法,其特征在于其制备方法为: 步骤a) -5〜(TC下,将浓度为O. 5〜2mol/L的L或D-酪氨酸醇酯的四氢呋喃溶液加入反应釜,加入的对羟基苯酸:L或D-酪氨酸醇酯的摩尔比为I : I〜1.2 : 1,搅拌0.5〜lh,再加入I-乙基-(3- 二甲基氨基丙基)碳酰二亚胺盐酸盐:L或D-酪氨酸醇酯的摩尔比为I : I〜I. 2 : 1,反应I〜3h,升至室温继续反应18〜24h,将以上反应物倒入5〜10倍L或D-酪氨酸醇酯的四氢呋喃溶液体积的去离子水中,用2〜4倍L或D-酪氨酸醇酯四氢呋喃溶液体积的CH2Cl2萃取,并依次用3〜5倍L或D-酪氨酸酯的四氢呋喃溶液体积的Na2CO3水溶液、饱和NaCl水溶液、柠檬酸水溶液、饱和NaCl水溶液和去离子水对该CH2Cl2萃取液进行洗涤,Na2CO3水溶液浓度为O. I〜O. 2mol/L,柠檬酸水溶液浓度为O. I〜O. 2mol/L ;洗涤后的CH2Cl2萃 As claimed in claim I 2. The optically active polyurethane - preparation of amides material, characterized in that it is a preparation method: Step a) -5~ (lower TC, a concentration of O. 5~2mol / L of D- or L-tyrosine tetrahydrofuran was added to the reaction kettle alcohol esters, acid p-hydroxybenzoate was added: L-tyrosine or D- molar ratio of alcohol to ester I: I~1.2: 1, stirring 0.5~lh, then was added ethyl I- - (3-dimethylaminopropyl) carbodiimide hydrochloride: molar ratio of D- or L-tyrosine esters are I: I~I 2: 1, the reaction I. ~3h, warmed to room temperature the reaction was continued 18~24h, the above reaction was poured into a tetrahydrofuran solution of 5 to 10 times the volume of the D- or L-tyrosine esters of deionized water, 2 ~ 4 times with D- or L casein acid alcohol esters tetrahydrofuran volume extracted with CH2Cl2, and washed successively with aqueous Na2CO3 3 to 5 times the volume of tetrahydrofuran D- or L-tyrosine ester, saturated aqueous NaCl solution, aqueous citric acid solution, saturated aqueous NaCl and deionized water the extract was washed with CH2Cl2, Na2CO3 aqueous solution at a concentration of O. I~O 2mol, aqueous solution of citric acid / L to O. I~O 2mol / L;.. CH2Cl2 extracts washed 液用无水MgSO4干燥,过滤后蒸除CH2Cl2溶剂得L或D-手性双酚单体; 步骤b)氮气条件下,将步骤a)制得的L或D-手性双酚单体加入到反应釜中,力口AN-甲基-2-吡咯烷酮配制浓度为I〜3mol/L的N-甲基-2-吡咯烷酮溶液,升温至9(TllO°C,按二异氰酸酯与L或D-手性双酚单体的摩尔比为2 : 1,加入I〜3mol/L二异氰酸酯的N-甲基-2-吡咯烷酮溶液,反应5〜10h,得到异氰酸酯基团封端的聚氨酯预聚物,冷却至室温,按有机二酸单体与L或D-手性双酚单体的摩尔比为I : 1,加入O. 5〜2mol/L有机二酸单体的N-甲基-2-吡咯烷酮溶液,室温搅拌I〜3h后加热到12(Tl50°C反应2飞h,冷却至室温,倒入10〜50倍L或D-手性双酚单体的N-甲基-2-吡咯烷酮溶液体积的甲醇中,析出沉淀,过滤,60〜80°C真空干燥10〜20h,得光学活性聚氨酯-酰胺材料; 该制备方法步骤a)中所述的L或D-酪氨酸醇酯为L或D-酪氨酸CfC6 Was dried over anhydrous MgSO4, the solvent was distilled off to obtain CH2Cl2 D- or L chiral bisphenol monomer after filtration; in step b) nitrogen conditions, step a) obtained in chiral D- or L bisphenol monomer is added into the autoclave, opening force AN- methyl-prepared at a concentration I~3mol / L solution of N- methyl-2-pyrrolidone, was warmed to 9 (TllO ° C, according to the diisocyanate with D- or L the molar ratio of the bisphenol monomers chiral 2: 1, N- methyl-2-pyrrolidone was added I~3mol / L diisocyanate reaction 5~10h, to give a polyurethane prepolymer isocyanate group terminated, cooled to room temperature, the organic diacid molar ratio of monomer to chiral D- or L bisphenol monomers I: 1, was added O. 5~2mol / L organic diacid monomers methyl-N- solution, heated to room temperature with stirring I~3h 12 (Tl50 ° C for 2 fly H, cooled to room temperature, poured into 10~50 times D- or L chiral bisphenol monomer solution of N- methyl-2-pyrrolidone volume of methanol, a precipitate was filtered, 60~80 ° C and dried in vacuo 10~20h, to give optically active polyurethane - amide materials; a) prepared in this method step a L-tyrosine ester of D- or L D- or tyrosine CfC6 链饱和脂肪醇酯、L或D-酪氨酸苯甲醇酯、L或D-酪氨酸苯乙醇酯、L或D-酪氨酸苯丙醇酯、L或D-酪氨酸苯丁醇酯、L或D-酪氨酸苯戊醇酯中的一种。 Chain saturated fatty alcohol esters, L-tyrosine benzyl alcohol ester or D-, L or D- tyrosine phenylethyl alcohol ester, L-tyrosine phenyl propanol acetate, or D-, L-tyrosine benzyl alcohol or D- ester, L-tyrosine or D- phenyl amyl alcohol esters of one.
  3. 3.根据权利要求2所述的光学活性聚氨酯-酰胺材料的制备方法,其特征在于该制备方法步骤a)中所述的对羟基苯酸为对羟基苯甲酸、对羟基苯乙酸、对羟基苯丙酸、对羟基苯丁酸、对羟基苯戊酸、对羟基苯己酸或对羟基苯丙烯酸中的一种。 The optically active polyurethane according to claim 2 - Preparation of amides material, wherein the production method step a) of hydroxy acid is p-hydroxybenzoic acid, p-hydroxyphenyl acetic acid, p-hydroxyphenyl said propionic acid, butyric acid p-hydroxyphenyl, p-hydroxyphenyl valeric acid, caproic acid or one of hydroxy p-hydroxybenzoate acrylic acid.
  4. 4.根据权利要求2所述的光学活性聚氨酯-酰胺材料的制备方法,其特征在于该制备方法步骤b)中所述的二异氰酸酯为2,4-甲苯二异氰酸酯、4,4' - 二苯甲烷二异氰酸酯或二甲基联苯二异氰酸酯中的一种,所述的有机二酸单体为对苯二甲酸、4,4'-联苯二甲酸或4,4' -二苯醚二甲酸中的一种。 The optically active polyurethane according to claim 2 - Preparation of amides material, wherein the preparation process in step b) said diisocyanate is 2,4-toluene diisocyanate, 4,4 '- diphenyl one of methane diisocyanate or dimethyl-biphenyl diisocyanate, said organic diacid monomer is terephthalic acid, 4,4'-biphenyl dicarboxylic acid or 4,4 '- diphenyl ether dicarboxylic acid in kind.
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