CN107141469B - Tartaric acid group optical activity polyamide and preparation method thereof - Google Patents
Tartaric acid group optical activity polyamide and preparation method thereof Download PDFInfo
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- CN107141469B CN107141469B CN201710485608.1A CN201710485608A CN107141469B CN 107141469 B CN107141469 B CN 107141469B CN 201710485608 A CN201710485608 A CN 201710485608A CN 107141469 B CN107141469 B CN 107141469B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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Abstract
The invention discloses tartaric acid optical rotation polyamide PAm L AT and a preparation method thereof, belonging to the technical field of functional polymer materials, wherein the structure general formula is as follows:
(m =4,5, 7-14). The polymer uses L-2, 3-diacetyl oxygen tartaric acid (L-ATA) as raw material, uses solid phosgene (BTC) as chlorination reagent, L-ATA is processed through acyl chlorination reaction to prepare L-2, 3-diacetyl oxygen succinyl chloride (L-ATC), then uses L-ATC and aliphatic diamine as monomers, and adopts interfacial polymerization method to prepare polyamide PAm L AT. with higher molecular weight and stronger optical activity.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials with optical activity, and particularly relates to tartaric acid polyamide with optical activity and a preparation method thereof.
Background
The optically active polymer material is a functional polymer material capable of deflecting plane polarized light. Like small chiral molecules, the presence of asymmetry in the molecular chain structure of a polymer is a prerequisite for the optically active nature of the polymer. Chirality is an important attribute of natural polymers in nature, such as proteins, DNA, amylopectin, etc., and plays an essential role in information transfer, equivalent storage, and structure construction of organisms. In recent years, artificially synthesized optically active polymers show good performance in the aspects of chiral stationary phase, asymmetric catalysis, selective crystallization of corresponding isomers and the like, and attract the attention of a large number of scientific researchers. Researches show that the optically active polyamide has good chiral recognition capability and can be used as a chiral stationary phase for chiral resolution of compounds. The optically active polyamide is usually prepared by taking a chiral monomer as a raw material by adopting a polycondensation method, and the expensive and unavailable chiral monomer greatly increases the preparation cost.
A series of optically active polyamides are prepared by using L-2, 3-dimethoxytartaric acid and 2, 3-diacetoxytartaric acid as monomers, wherein the carboxyl of diacid is esterified by pentachlorophenol, and the amino of diamine is activated by trimethyl silicon and then is subjected to high-temperature solution polycondensation to prepare the polyamide with high molecular weight, but the method has more reaction steps, harsh preparation conditions and longer polymerization time, and generally needs 3-5 days (see the document: 1: Macromolecules 1993,26:5664-5670.2.Polymer,2005,46: 2854-2861).
The method is mainly suitable for polycondensation reaction between monomers with high reaction activity, compared with a melt polymerization method, the interface polymerization method has the main advantages that the reaction conditions are mild, the method can be carried out at room temperature or low temperature, the reaction process is irreversible, even if one raw material is excessive, a high-molecular weight polymer can be produced, and the method is an efficient preparation method of polyamide.
Disclosure of Invention
The invention aims to develop a new tartaric acid-based polyamide variety with high optical activity and provide an efficient green preparation method of the optical activity polyamide.
In order to realize the purpose of the invention, firstly, L-2, 3-diacetyloxy tartaric acid (L-ATA) is used as a raw material, solid phosgene (BTC) is used as a chlorinating agent to prepare L-2, 3-diacetyloxy succinyl chloride (L-ATC), the solubility of aliphatic long carbon chain diamine (m is more than or equal to 10) in an aqueous phase is improved by adding a cosolvent, and finally, the aliphatic diamine in the aqueous phase and L-ATC in an organic phase (toluene) are subjected to interfacial polymerization to prepare the tartaric acid group optically active polyamide.
The invention discloses an optical activity polyamide PAm L AT, which has the following structural formula:
the preparation method of the optically active polyamide is characterized in that the optically active polyamide is prepared by interfacial polymerization of diamine dissolved in a water phase and L-2, 3-diacetyloxy succinyl chloride (L-ATC) dissolved in an organic solvent, and the synthesis steps are as follows:
(1) l-2, 3-diacetoxy tartaric acid and solid phosgene are added into a reaction bottle with a reflux condensing device, an organic solvent is taken and poured into the reaction bottle, the mixture is stirred for reaction at the temperature of 0-20 ℃, then a catalyst is added, the temperature is raised to 20-40 ℃, the mixture is continuously stirred for reaction, L-2, 3-diacetoxy succinyl chloride (L-ATC) prepared after the reaction is finished is dissolved in the organic solution, and a supernatant is taken for standby.
The organic solvent is selected from toluene and chloroform.
L-2, 3-diacetoxy tartaric acid and solid phosgene in a weight ratio of 1: 0.5-1.5.
The catalyst is N, N-dimethyl acetamide or N, N-dimethyl formamide.
(2) Stirring the aliphatic diamine and the distilled water uniformly at 30-60 ℃, then adding an acid-binding agent, and continuing stirring until the aliphatic diamine is completely dissolved.
The aliphatic diamine has a structural formula of H2N(CH2)mNH2Wherein m is 4,5, 7-14.
When m is 10-14, adding cosolvent, wherein the cosolvent is selected from one of methanol and ethanol or any mixture thereof; the acid-binding agent is one of sodium hydroxide, sodium carbonate, sodium bicarbonate or triethylamine.
(3) And (2) pouring the L-2, 3-diacetyloxy succinyl chloride (L-ATC) organic solution prepared in the step (1) into the aliphatic diamine aqueous solution in the step (2), reacting at the temperature of 10-50 ℃, forming an interface between an organic phase and a water phase, carrying out interfacial polymerization reaction on the aliphatic diamine and L-ATC at the interface, extracting a generated polyamide membrane, continuously carrying out the polymerization reaction until the polymerization reaction is finished, washing the product with distilled water, and drying to obtain the final product.
L-2, 3-diacetyloxy succinyl chloride and aliphatic diamine in the molar ratio of 1: 0.5-2.0.
The invention has the innovation points that L-2, 3-diacetyloxy succinyl chloride is prepared by Vilsmeier reaction of green environment-friendly acyl chlorination reagent solid phosgene (BTC) and L-2, 3-diacetoxy tartaric acid, and the BTC has the advantages of high melting point, low volatility, no corrosiveness and stable performance compared with phosphorus pentachloride, and is safe to use.
Compared with the prior art, the invention has the following obvious advantages:
(1) the binary acid L-2, 3-diacetyloxy tartaric acid (L-ATA) is prepared by taking L-tartaric acid as a natural product as a raw material.
(2) The invention adopts solid phosgene (BTC) to prepare L-2, 3-diacetyloxy succinyl chloride (L-ATC), the BTC as a raw material has the advantages of high melting point, low volatility, no corrosiveness and stable performance, the BTC is safe to use, can be dissolved in organic solvents such as diethyl ether, tetrahydrofuran, benzene, hexane, chloroform and the like, can be dropwise added for reaction and can be accurately metered, the BTC as an acyl chlorination reagent has high conversion efficiency, and conditions are provided for preparing high purity L-ATC.
(3) The solubility of aliphatic long carbon chain diamine (m is more than or equal to 10) in a water phase is improved by adding the cosolvent, so that the diamine can be fully contacted with acyl chloride in an interfacial polymerization process, the molecular weight and the reaction yield of the polyamide are further improved, the yield is more than 68 percent, and the number average molecular weight is between 1000 and 120,000 g/mol.
(4) The invention adopts an interfacial polymerization method, has low reaction temperature, high polymerization speed, low requirement on the molar ratio of the raw materials and easy control. Under mild reaction condition, the chiral compound is not easy to racemize, and the specific optical rotation [ DMSO [ a ] of the obtained polyamide]D 20,(°)]Between-13 and-18, optically active polyamides of high molecular weight with high optical activity can be prepared.
Drawings
FIG. 1 shows a solution of a polyamide PA 11L AT according to the invention in ethanol (c ═ 2.08 × 10 based on the structural units)-6mol/m L) CD-UV absorption spectrum at 20 ℃;
FIG. 2 is a diagram of the CD-UV absorption spectrum of the polyamide PA 11L AT of the invention in the solid state.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples, which are included by way of illustration and are not intended to limit the scope of the invention.
Example 1
(1) Adding 1g of L-ATA and 1g of BTC into a three-neck flask, pouring 20m of L of toluene into the three-neck flask, adding a reflux condenser on the three-neck flask, placing the reaction device in a water bath kettle, stirring at the speed of 100rmp for 30min at the temperature of 0 ℃, adding 0.5m of L N, N-dimethylacetamide catalyst, stirring at the speed of 50rmp for 20min, heating to 30 ℃, stirring for 1h, dissolving L-ATC prepared after the reaction is finished in the toluene solution, and taking the supernatant for later use.
(2) Adding 0.5g of 1, 4-butanediamine and 10m of L distilled water into a glass beaker, stirring for 20min at 50 ℃, dropwise adding 2g of sodium hydroxide acid-binding agent into the beaker, and continuously stirring for 30min until the 1, 4-butanediamine is completely dissolved.
(3) The aqueous solution of 1, 4-butanediamine was placed in a water bath and the temperature was controlled AT 50 ℃ and a toluene solution containing L-ATC was slowly poured into the aqueous solution of 1, 4-butanediamine, the polyamide PA 4L AT was polycondensed AT the interface, the interface was slowly stirred with a glass rod, the solid PA 4L AT was taken out and the polycondensation reaction continued for 10min, the obtained PA 4L AT was washed with 30m L distilled water AT 50 ℃ and filtered under reduced pressure, the process was repeated 3 times, and the solid PA 4L AT was dried in a vacuum oven AT 60 ℃ for 10h, the polymer yield, number average molecular weight and molecular weight distribution were as shown in Table 1.
Example 2
(1) Adding 1g of L-ATA and 1.5g of BTC into a three-neck flask, measuring 30m of L chloroform, pouring the chloroform into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring for 50min at the stirring speed of 200rmp, adding 1m of L N and N-dimethylformamide catalyst, continuously stirring for 40min at the stirring speed of 80rmp, heating to 20 ℃, continuously stirring for 1.5h, dissolving L-ATC prepared after the reaction is finished in a chloroform solution, and taking a supernatant for later use.
(2) 0.7g of 1, 5-pentanediamine and 10m of L distilled water are added into a glass beaker, stirred for 10min at 40 ℃, 1.5g of triethylamine acid-binding agent is dripped into the beaker, and stirred for 30min continuously until the 1, 5-pentanediamine is completely dissolved.
(3) Placing 1, 5-pentanediamine aqueous solution in a water bath kettle, controlling the temperature AT 30 ℃, slowly pouring L-ATC-containing chloroform solution into the 1, 5-pentanediamine aqueous solution, stirring for 40min AT 150rmp, washing the prepared PA 5L AT with 30m L distilled water AT 50 ℃, decompressing and filtering, repeating the process for 3 times, drying solid PA 5L AT in a vacuum oven AT 60 ℃ for 10h, wherein the polymer yield, the number average molecular weight and the molecular weight distribution are shown in Table 1.
Example 3
(1) Adding L-ATA (1 g) and BTC (0.7 g) into a three-neck flask, pouring 20m of L of toluene into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring at the temperature of 10 ℃ for 30min at the stirring speed of 150rmp, adding L N, N-dimethylformamide catalyst at the speed of 0.7m, continuing stirring at the stirring speed of 100rmp for 50min, heating to 40 ℃, continuing stirring for 2h, dissolving L-ATC (ethylene-vinyl acetate copolymer) prepared after the reaction is ended into a toluene solution, and taking a supernatant for later use.
(2) 1g of 1, 7-heptamethylenediamine and 20m of L distilled water are added into a glass beaker, stirred for 20min at 30 ℃, 2g of sodium bicarbonate acid-binding agent is added into the beaker in a dropwise manner, and stirring is continued for 30min until the 1, 7-heptamethylenediamine is completely dissolved.
(3) The preparation method comprises the steps of placing an aqueous solution of 1, 7-heptamethylenediamine in a water bath, controlling the temperature AT 50 ℃, slowly pouring a toluene solution containing L-ATC into the aqueous solution of 1, 7-heptamethylenediamine, carrying out polycondensation on polyamide PA 7L AT AT an interface, slowly stirring the interface with a glass rod, taking out solid PA 7L AT from the interface, continuing the process for 20min, then stirring a reaction system, continuing the reaction for 40min, carrying out vacuum filtration to obtain PA 7L AT, washing the obtained PA 7L AT with 30m L distilled water AT 50 ℃, carrying out vacuum filtration, repeating the process for 3 times, and drying a solid PA 7L AT in a vacuum oven AT 60 ℃ for 10h, wherein the yield, the number average molecular weight and the molecular weight distribution of the polymer are shown in Table 1.
Example 4
(1) Adding 1g of L-ATA and 1.5g of BTC into a three-neck flask, measuring 30m of L toluene, pouring the toluene into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring for 30min at a stirring speed of 200rmp, adding 2m of L N, N-dimethylacetamide catalyst, stirring for 40min at a stirring speed of 80rmp, heating to 20 ℃, stirring for 1.5h, dissolving L-ATC prepared after the reaction is finished in toluene solution, and taking supernatant for later use.
(2) 1g of 1, 8-octanediamine and 10m of L distilled water are added into a glass beaker, stirred for 15min at 60 ℃, 1.5g of sodium carbonate acid-binding agent is dripped into the beaker, and the stirring is continued for 30min until the 1, 8-octanediamine is completely dissolved.
(3) Placing the aqueous solution of 1, 8-octanediamine in a water bath kettle, controlling the temperature AT 30 ℃, slowly pouring L-ATC-containing toluene solution into the aqueous solution of 1, 8-octanediamine, slowly stirring the interface by using a glass rod to take out solid PA 8L AT, keeping the process for 10min, then stirring the reaction system AT the stirring speed of 150rmp, continuing to react for 40min, carrying out vacuum filtration, washing the combined prepared PA 8L AT by using 50m L distilled water AT 40 ℃, carrying out vacuum filtration for 3 times, and drying the solid PA 8L AT in a vacuum oven AT 90 ℃ for 8h, wherein the polymer yield, the number average molecular weight and the molecular weight distribution are shown in Table 1.
Example 5
(1) Adding 2g of L-ATA and 1.5g of BTC into a three-neck flask, measuring 50m of L of chloroform, pouring the chloroform into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring for 30min at the temperature of 0 ℃, the stirring speed is 200rmp, adding 3m of L N, N-dimethylacetamide catalyst, stirring for 40min, the stirring speed is 80rmp, heating to 20 ℃, stirring for 1.5h, dissolving L-ATC prepared after the reaction is finished in a chloroform solution, and taking a supernatant for later use.
(2) 2g of 1, 9-nonanediamine and 20m of L distilled water are added into a glass beaker and stirred for 20min at 50 ℃, 3g of a sodium carbonate acid-binding agent is added into the beaker in a dropwise manner, and stirring is continued for 30min until the 1, 9-nonanediamine is completely dissolved.
(3) Placing the aqueous solution of 1, 9-nonanediamine in a water bath, controlling the temperature AT 30 ℃, slowly pouring a chloroform solution containing L-ATC into the aqueous solution of 1, 9-nonanediamine, slowly stirring the mixture with a glass rod to take out solid PA 9L AT AT the interface, continuing the reaction for 15min, then stirring the reaction system AT a stirring speed of 150rmp, continuing the reaction for 40min, carrying out vacuum filtration, washing the combined PA 9L AT with 80m L of distilled water AT 40 ℃, carrying out vacuum filtration, repeating the process for 3 times, and drying the solid PA 9L AT in a vacuum oven AT 90 ℃ for 8h, wherein the yield, the number average molecular weight and the molecular weight distribution of the polymer are shown in Table 1.
Example 6
(1) Adding 1g of L-ATA and 1g of BTC into a three-neck flask, pouring 20m of L of chloroform into the three-neck flask, adding a reflux condenser on the three-neck flask, placing the reaction device in a water bath kettle, stirring at the speed of 100rmp for 30min at the temperature of 3 ℃, adding 0.5m of L N and N-dimethylformamide catalyst, stirring at the speed of 50rmp for 30min, heating to 30 ℃, stirring for 1h, dissolving L-ATC prepared after the reaction is finished in a chloroform solution, and taking a supernatant for later use.
(2) 1g of 1, 10-decamethylene diamine, 10m of L distilled water and 2m of L ethanol are added into a glass beaker and stirred for 20min at 30 ℃, 2g of triethylamine acid-binding agent is added into the beaker in a dropwise manner and stirred for 30min continuously until the 1, 10-decamethylene diamine is completely dissolved.
(3) Placing 1, 10-decamethylene diamine water solution in a water bath, controlling the temperature AT 50 ℃, slowly pouring L-ATC-containing chloroform solution into the 1, 10-decamethylene diamine water solution, carrying out polycondensation on polyamide PA 10L AT AT the interface, slowly stirring the interface by a glass rod, taking out solid PA 10L AT from the interface, continuously carrying out the polycondensation reaction for 10min, washing the obtained PA 10L AT by 30m L distilled water AT 50 ℃, carrying out vacuum filtration for 3 times, and drying solid PA 10L AT in a vacuum oven AT 60 ℃ for 10h, wherein the polymer yield, the number average molecular weight and the molecular weight distribution are shown in Table 1.
Example 7
(1) Adding 1g of L-ATA and 1.5g of BTC into a three-neck flask, measuring 30m of L toluene, pouring the toluene into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring for 30min at the stirring speed of 200rmp, adding 1m of L N and N-dimethylformamide catalyst, continuously stirring for 40min at 80rmp, heating to 20 ℃, continuously stirring for 1.5h, dissolving L-ATC prepared after the reaction is finished in the toluene solution, and taking the supernatant for later use.
(2) 1.5g of 1, 11-undecamethylene diamine, 10m of L distilled water and 2m of L methanol are added into a glass beaker and stirred for 20min at 60 ℃, 1.5g of triethylamine acid-binding agent is dripped into the beaker and stirred for 30min continuously until the 1, 11-undecamethylene diamine is completely dissolved.
(3) The aqueous solution of 1, 11-undecamide diamine was placed in a water bath AT 30 ℃ and L-ATC in toluene was slowly poured into the aqueous solution of 1, 11-undecamide diamine with stirring AT 150rmp for 40min, the resulting PA 11L AT was washed with 30m L distilled water AT 50 ℃ and vacuum filtered, this procedure was repeated 3 times, and the solid PA 11L AT was dried in a vacuum oven AT 60 ℃ for 10h, the polymer yield, number average molecular weight and molecular weight distribution are shown in Table 1.
Example 8
(1) Adding L-ATA (1 g) and BTC (0.7 g) into a three-neck flask, pouring 20m of L of toluene into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring at the temperature of 10 ℃ for 30min at the stirring speed of 150rmp, adding L N, N-dimethylformamide catalyst at the speed of 0.7m, continuing stirring at the stirring speed of 100rmp for 50min, heating to 40 ℃, continuing stirring for 2h, dissolving L-ATC (ethylene-vinyl acetate copolymer) prepared after the reaction is ended into a toluene solution, and taking a supernatant for later use.
(2) Adding 3g of 1, 12-dodecanediamine, 20m of L distilled water and 4m of L methanol into a glass beaker, stirring for 30min at 40 ℃, dropwise adding 2g of a sodium carbonate acid-binding agent into the beaker, and continuously stirring for 30min until the 1, 12-dodecanediamine is completely dissolved.
(3) Placing 1, 12-dodecaamine aqueous solution in a water bath kettle, controlling the temperature AT 50 ℃, slowly pouring L-ATC-containing toluene solution into the 1, 12-dodecaamine aqueous solution, carrying out polycondensation on polyamide PA 12L AT AT an interface, slowly stirring the interface by using a glass rod, taking out solid PA 12L AT from the interface, continuing the process for 20min, then stirring the reaction system, continuing the reaction for 40min, carrying out vacuum filtration to obtain PA 12L AT, washing the prepared PA 12L AT by using 30m L distilled water AT 50 ℃, carrying out vacuum filtration, repeating the process for 3 times, and drying a solid PA 12L in a vacuum oven AT 60 ℃ for 10h, wherein the polymer yield, the number average molecular weight and the molecular weight distribution are shown in Table 1.
Example 9
(1) Adding 1g of L-ATA and 1.5g of BTC into a three-neck flask, measuring 30m of L toluene, pouring the toluene into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring for 30min at a stirring speed of 200rmp, adding 2m of L N, N-dimethylformamide catalyst, stirring for 40min at a stirring speed of 80rmp, heating to 20 ℃, stirring for 1.5h, dissolving L-ATC prepared after the reaction is finished in the toluene solution, and taking the supernatant for later use.
(2) 1.8g of 1, 13-tridecyl diamine, 10m of L distilled water, 2m of L methanol and 2m of L ethanol are added into a glass beaker and stirred for 20min at the temperature of 60 ℃, 1.5g of sodium hydroxide acid-binding agent is dripped into the beaker and stirred for 30min continuously until the 1, 13-tridecyl diamine is completely dissolved.
(3) Placing an aqueous solution of 1, 13-tridecyl diamine in a water bath, controlling the temperature AT 30 ℃, slowly pouring a toluene solution containing L-ATC into the aqueous solution of 1, 13-tridecyl diamine, slowly stirring the interface by using a glass rod, taking out solid PA 13L AT, continuing the reaction for 10min, then stirring the reaction system AT a stirring speed of 150rmp, continuing the reaction for 40min, carrying out vacuum filtration, washing the combined PA 13L AT with 50m L distilled water AT 40 ℃, carrying out vacuum filtration, repeating the process for 3 times, and drying a solid PA 13L AT in a vacuum oven AT 90 ℃ for 8h, wherein the polymer yield, the number average molecular weight and the molecular weight distribution are shown in Table 1.
Example 10
(1) Adding 2g of L-ATA and 1.5g of BTC into a three-neck flask, measuring 50m of L toluene, pouring the toluene into the three-neck flask, adding a condensation reflux device on the three-neck flask, placing the reaction device in a water bath kettle, stirring for 30min at a stirring speed of 200rmp, adding 3m of L N, N-dimethylacetamide catalyst, stirring for 40min at a stirring speed of 80rmp, heating to 30 ℃, stirring for 1.5h, dissolving L-ATC prepared after the reaction is finished in toluene solution, and taking supernatant for later use.
(2) Adding 3g of 1, 14-tetradecyl diamine, 20m of L distilled water and 4m of L ethanol into a glass beaker, stirring for 20min at 60 ℃, dropwise adding 3g of sodium hydroxide acid-binding agent into the beaker, and continuously stirring for 30min until the 1, 14-tetradecyl diamine is completely dissolved.
(3) Placing an aqueous solution of 1, 14-tetradecane diamine in a water bath kettle, controlling the temperature AT 30 ℃, slowly pouring a toluene solution containing L-ATC into the aqueous solution of 1, 14-tetradecane diamine, slowly stirring the interface with a glass rod, taking out solid PA 14L AT, continuing to react for 40min, carrying out vacuum filtration, washing the combined PA 14L AT with 80m L of distilled water AT 40 ℃, carrying out vacuum filtration, repeating the process for 3 times, and drying a solid PA 14L AT in a vacuum oven AT 90 ℃ for 8h, wherein the polymer yield, the number average molecular weight and the molecular weight distribution are shown in Table 1.
TABLE 1 PA 11L AT yield and molecular weight
Claims (3)
1. An optically active polyamide based on tartaric acid, characterized in that it has the following general structural formula:
and is prepared by the following method:
(1) adding L-2, 3-diacetoxy tartaric acid and solid phosgene into a reaction bottle with a reflux condensing device, pouring an organic solvent into the reaction bottle, stirring for reaction at 0-20 ℃, then adding a catalyst, heating to 20-40 ℃, continuing stirring for reaction, dissolving prepared L-2, 3-diacetoxy succinyl chloride in the organic solution after the reaction is finished, and taking supernatant for later use;
the organic solvent is selected from toluene or chloroform;
the catalyst is N, N-dimethylacetamide or N, N-dimethylformamide;
(2) stirring aliphatic diamine and distilled water uniformly at 30-60 ℃, adding an acid-binding agent, and continuously stirring until the aliphatic diamine is completely dissolved;
the aliphatic diamine has a structural formula of H2N(CH2)mNH2Wherein m =4,5, 7-14;
when m =10-14, adding a cosolvent, wherein the cosolvent is selected from one of methanol and ethanol or a mixture of methanol and ethanol in any ratio; the acid-binding agent is one of sodium hydroxide, sodium carbonate, sodium bicarbonate or triethylamine;
(3) and (2) pouring the L-2, 3-diacetyloxy succinyl chloride organic solution prepared in the step (1) into the aliphatic diamine aqueous solution prepared in the step (2), reacting at the temperature of 10-50 ℃, extracting a generated polyamide membrane, continuously carrying out the polymerization reaction until the polymerization reaction is finished, washing the product with distilled water, and drying to obtain the final product.
2. A process for the preparation of an optically active polyamide according to claim 1, characterized in that it is obtained by:
(1) adding L-2, 3-diacetoxy tartaric acid and solid phosgene into a reaction bottle with a reflux condensing device, pouring an organic solvent into the reaction bottle, stirring for reaction at 0-20 ℃, then adding a catalyst, heating to 20-40 ℃, continuing stirring for reaction, dissolving prepared L-2, 3-diacetoxy succinyl chloride in the organic solution after the reaction is finished, and taking supernatant for later use;
the organic solvent is selected from toluene or chloroform;
the catalyst is N, N-dimethylacetamide or N, N-dimethylformamide;
(2) stirring aliphatic diamine and distilled water uniformly at 30-60 ℃, adding an acid-binding agent, and continuously stirring until the aliphatic diamine is completely dissolved;
the aliphatic diamine has a structural formula of H2N(CH2)mNH2Wherein m =4,5, 7-14;
when m =10-14, adding a cosolvent, wherein the cosolvent is selected from one of methanol and ethanol or a mixture of methanol and ethanol in any ratio; the acid-binding agent is one of sodium hydroxide, sodium carbonate, sodium bicarbonate or triethylamine;
(3) and (2) pouring the L-2, 3-diacetyloxy succinyl chloride organic solution prepared in the step (1) into the aliphatic diamine aqueous solution prepared in the step (2), reacting at the temperature of 10-50 ℃, extracting a generated polyamide membrane, continuously carrying out the polymerization reaction until the polymerization reaction is finished, washing the product with distilled water, and drying to obtain the final product.
3. The method of claim 2, wherein the weight ratio of L-2, 3-diacetoxy tartaric acid to phosgene solid in step (1) is 1: 0.5-1.5, and the molar ratio of L-2, 3-diacetoxy succinyl chloride to aliphatic diamine in step (3) is 1: 0.5-2.0.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4412059A (en) * | 1980-08-20 | 1983-10-25 | Duke University | High modulus cholesteric mesophase polymers |
| JPS6028430A (en) * | 1983-07-27 | 1985-02-13 | Masaki Hasegawa | Optically active polyamide |
| JPS61213220A (en) * | 1985-03-20 | 1986-09-22 | Masaki Hasegawa | Optically active polyamide |
| CN1702095A (en) * | 2005-07-01 | 2005-11-30 | 清华大学 | Polyamide containing isosorbide unit and process for preparing same |
| CN102167826A (en) * | 2011-01-21 | 2011-08-31 | 中山大学 | Optically active polyamide imide and preparation method as well as application thereof |
| JP2012131745A (en) * | 2010-12-22 | 2012-07-12 | Tokyo Univ Of Science | Material showing optical activity and method for producing the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4412059A (en) * | 1980-08-20 | 1983-10-25 | Duke University | High modulus cholesteric mesophase polymers |
| JPS6028430A (en) * | 1983-07-27 | 1985-02-13 | Masaki Hasegawa | Optically active polyamide |
| JPS61213220A (en) * | 1985-03-20 | 1986-09-22 | Masaki Hasegawa | Optically active polyamide |
| CN1702095A (en) * | 2005-07-01 | 2005-11-30 | 清华大学 | Polyamide containing isosorbide unit and process for preparing same |
| JP2012131745A (en) * | 2010-12-22 | 2012-07-12 | Tokyo Univ Of Science | Material showing optical activity and method for producing the same |
| CN102167826A (en) * | 2011-01-21 | 2011-08-31 | 中山大学 | Optically active polyamide imide and preparation method as well as application thereof |
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