CN111592521A - Amino acid group S-carboxyl internal cyclic anhydride and functionalized poly-thioester and preparation method thereof - Google Patents
Amino acid group S-carboxyl internal cyclic anhydride and functionalized poly-thioester and preparation method thereof Download PDFInfo
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Abstract
The invention relates to amino acid group S-carboxyl internal cyclic anhydride and functionalized thioester and a preparation method thereof, belonging to the technical field of polymer preparation. The invention designs and synthesizes amino acid group S-carboxyl internal cyclic anhydride monomer by taking renewable amino acid as a source, the monomer can be rapidly and controllably polymerized in a room temperature open system to obtain functional thioester with a structure shown in a formula (VII), and the polymer is prepared by taking renewable resource amino acid as a starting material. The polymer is a typical semi-crystalline material with a high refractive index, chemical resistance and heavy metal recognition capability. The invention also provides a preparation method of the amino acid group S-carboxyl internal cyclic anhydride and the functionalized thioester, which is a new method for synthesizing the functionalized thioester by taking renewable amino acid as a source, and has the advantages of simple preparation method and cheap raw materials.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to amino acid group S-carboxyl intra-cyclic anhydride and functionalized thioester and a preparation method thereof.
Background
With the development and progress of the human society, the demand for polymer materials such as plastics, fibers, rubbers, etc. is increasing year by year. However, with the continuous consumption of petroleum resources, the utilization of renewable resources has been brought forward. The great significance of using renewable resources for the synthesis of polymeric materials is self evident.
Polythioester has high refractive index, chemical resistance and heavy metal recognition capability, and is widely applied to the fields of optics, photoelectric materials and sewage treatment. Thioesters are generally obtained by ring-opening polymerization of thiolactones. However, polythioesters obtained by this method require stronger bases as catalysts due to lower ring tensions, so that the thioester exchange reaction is very severe and polymerization is not controllable, and polythioesters obtained by this method often lack functional side groups and are not easy to improve their physicochemical properties by post-modification.
Amino acids are constituent units of proteins. The synthesis of polymers having a precise structure from natural amino acids is an important research topic in the field of polymer chemistry. The yield of amino acid from biomass in China is rich, and the problem of excess production of part of amino acid even exists. Therefore, the preparation of high value-added polymer materials from cheap and renewable natural amino acid monomers is of great significance.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, polythioester obtained by ring-opening polymerization of thiolactone requires stronger base as a catalyst due to smaller ring tension, so that thioester exchange reaction is very serious and polymerization is uncontrollable, and polythioester obtained by the method often lacks functional side groups and is not easy to improve the physical and chemical properties of the polythioester by post-modification, and provides amino acid-based S-carboxyanhydride and functional polythioester and a preparation method thereof. Their physicochemical properties are easily improved by post-modification.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides amino acid group S-carboxyl cyclic internal anhydride, which has the following structural formula:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection position.
The invention also provides a preparation method of the amino acid group S-carboxyanhydride, which comprises the following steps:
the method comprises the following steps: carrying out diazotization bromination reaction on amino acid to obtain alpha-amino brominated amino acid;
step two: reacting the alpha-amino brominated amino acid obtained in the step one with a thionizing agent to obtain alpha-amino thionized amino acid;
step three: reacting the alpha-amino sulfo amino acid obtained in the step two with a reagent under the action of a catalyst to obtain amino acid group S-carboxyanhydride;
the synthetic route is as follows:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection position.
In the above technical solution, it is preferable that: the reagent used in the diazotization bromination reaction in the step one is selected from sodium nitrite and hydrobromic acid, or sodium nitrite, sulfuric acid and potassium bromide.
In the above technical solution, it is preferable that: and the thionizing agent in the second step is sodium hydrosulfide or sodium trithiocarbonate.
In the above technical solution, it is preferable that: the reagent in the third step is selected from one or more of phosgene, diphosgene and triphosgene.
In the above technical solution, it is preferable that: the catalyst in the third step is one or more selected from activated carbon, pyridine and triethylamine.
The invention also provides a functionalized thioester, which is characterized by having the following structural formula:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection location;
r' is chlorine, bromine or any one of the following substituent groups:
wherein R is1Is alkyl or aryl, "-" represents the attachment position;
n is 20 to 400.
The invention also provides a preparation method of the functionalized thioester, which is characterized by comprising the following steps:
dissolving amino acid group S-carboxyl internal anhydride in an organic solvent, and carrying out ring-opening polymerization reaction under the action of a catalyst to obtain the functionalized thioester shown as the formula (VII);
the synthetic route is as follows:
in which case R' is chlorine, bromine, or
Wherein R is1Is alkyl or aryl, "-" represents the attachment position;
or comprises the following steps:
dissolving amino acid group S-carboxyl internal anhydride in an organic solvent, and carrying out ring-opening polymerization reaction under the action of an initiator and a catalyst to obtain the functionalized thioester shown as the formula (VII);
the synthetic route is as follows:
in the above synthetic route, the amino acid group S-carboxyanhydride is selected from any of the following structures:
the initiator R' OOH is one of benzoic acid, 3-diphenyl propionic acid and 4-tert-butyl benzene propionic acid;
n is 20 to 400;
the catalyst is any one of the following structures:
wherein R is1Is an alkyl or aryl group.
In the above technical solution, it is preferable that: the mass ratio of the catalyst to the initiator is 0.001-1; the mass ratio of the catalyst to the amino acid group S-carboxyanhydride is 10-600: 1.
in the above technical solution, it is preferable that: the polymerization reaction is carried out at the temperature of-20-30 ℃ for 0.01-24 hours, and the organic solvent is one of chloroform, toluene, dichloromethane and tetrahydrofuran.
The invention has the beneficial effects that:
the invention designs and synthesizes a novel amino acid group S-carboxyl internal cyclic anhydride monomer by taking reproducible amino acid as a source, and the ring-opening polymerization of the monomer has the characteristic of active polymerization. The amino acid group S-carboxyl internal cyclic anhydride (SCA) monomer is driven by released carbon dioxide entropy due to large ring tension, the monomer is rapidly polymerized at room temperature, the thioester exchange reaction is inhibited, and the obtained polythioester has high molecular weight and narrow distribution. The molecular weight is adjusted by carboxylic acid, so that the controllable polymerization of the OCAs monomer is realized, and finally the polythioester with the molecular weight of up to 15 ten thousand is obtained.
The functionalized thioester synthesized by amino acid group S-carboxyl internal cyclic anhydride monomer has the structure shown in formula (VII), and the polymer is prepared by using amino acid which is renewable resource as starting material. The polymer is a typical semi-crystalline material with a high refractive index, chemical resistance and heavy metal recognition capability.
The invention provides a novel method for synthesizing functional poly-thioester by taking renewable amino acid as a source. The synthesis method is simple and the raw materials are cheap. The amino acid group S-carboxyl internal cyclic anhydride monomer can be rapidly and controllably polymerized in a room temperature open system to obtain functional poly-thioester, and the polymerization is not sensitive to water and oxygen, so the invention provides a novel method for synthesizing polythioester.
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The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a nuclear magnetic spectrum of a functionalized thioester prepared according to application example 3 of the present invention.
Detailed Description
The invention provides amino acid group S-carboxyl cyclic internal anhydride, which has the following structural formula:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection location;
that is, the amino acid based S-carboxyanhydride of the present invention is selected from any of the following structures:
the invention also provides a preparation method of the amino acid group S-carboxyanhydride, which comprises the following steps:
the method comprises the following steps: carrying out diazotization bromination reaction on amino acid, sodium nitrite and hydrobromic acid or on the amino acid, sodium nitrite, sulfuric acid and potassium bromide to obtain alpha-amino brominated amino acid;
wherein, the adding sequence of the sodium nitrite and the hydrobromic acid is as follows: hydrobromic acid is added firstly, and then sodium nitrite is added dropwise in an ice bath; the order of addition of sodium nitrite, sulfuric acid and potassium bromide is: firstly, adding sulfuric acid and potassium bromide, and then dropwise adding sodium nitrite in an ice bath;
step two: reacting the alpha-amino brominated amino acid obtained in the step one with a thioreagent sodium hydrosulfide or sodium trithiocarbonate to obtain alpha-amino thio amino acid;
step three: mixing the alpha-amino sulfo amino acid obtained in the step two with phosgene, diphosgene or triphosgene in dry dichloromethane under the action of catalyst carbon, pyridine or triethylamine, reacting for 96 hours at room temperature, filtering after the reaction is finished, drying the solvent, and recrystallizing to obtain amino acid group S-carboxyl ring internal anhydride;
the synthetic route is as follows:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection position.
The invention also provides a functionalized thioester, which has the following structural formula:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection location;
r' is chlorine, bromine or any one of the following substituent groups:
wherein R is1Is alkyl or aryl, "-" represents the attachment position;
n is 20 to 400.
The invention also provides a preparation method of the functionalized thioester, which comprises the following steps:
the functionalized thioester has the following structural formula:
when R' in the formula VII is chlorine, bromine or
The preparation method of the functionalized thioester comprises the following steps:
dissolving amino acid group S-carboxyl internal anhydride in an organic solvent, and carrying out ring-opening polymerization reaction under the action of a catalyst to obtain the functionalized thioester shown as the formula (VII);
the synthetic route is as follows:
cl in the catalyst in the above reaction-、Br-Or is or
Is used as an initiator, and the molecular weight of the prepared functional poly-thioester can reach more than 12.1 ten thousand.
When R' in the formula VII is any one of the following structures,
the preparation method of the functionalized thioester comprises the following steps:
firstly, recrystallizing a pre-prepared amino acid group S-carboxyl internal cyclic anhydride monomer by using solvents such as dichloromethane, diethyl ether, tetrahydrofuran and the like, removing the solvents, and storing in an anhydrous and oxygen-free low-temperature environment for later use;
dissolving amino acid group S-carboxyanhydride in chloroform or toluene or dichloromethane or tetrahydrofuran, wherein the concentration of the amino acid group S-carboxyanhydride monomer is 0.1M, carrying out ring-opening polymerization reaction under the action of an initiator and a catalyst, wherein the polymerization reaction temperature is-20-30 ℃, the reaction time is 0.01-24 hours, quenching the reaction by using a trifluoroacetic acid/dichloromethane mixed solution after the reaction is finished, and settling a polymer by using methanol to obtain the functionalized thioester shown in the formula (VII). The molecular weight of the polyester was determined by gel permeation chromatography (Waters 2414) and the structure was determined by nuclear magnetic resonance spectroscopy (Bruker AV-500).
The synthetic route is as follows:
wherein the amino acid group S-carboxyanhydride is selected from any of the following structures:
the initiator R' OOH is one of benzoic acid, 3-diphenyl propionic acid and 4-tert-butyl benzene propionic acid;
n is 20 to 400;
the catalyst is any one of the following structures:
wherein R is1Is an alkyl or aryl group.
The mass ratio of the catalyst to the initiator is 0.001-1; the mass ratio of the catalyst to the amino acid group S-carboxyanhydride is 10-600: 1;
in the preparation method, the molecular weight of the obtained functionalized thioester can be regulated by additionally adding an initiator R' OOH which is one of benzoic acid, 3-diphenylpropionic acid and 4-tert-butyl-phenylpropionic acid, and for example, the molecular weight of the functionalized thioester can be regulated to be 0.52-1.86 ten thousand.
Preparation example 1 preparation of monomer 1
The method comprises the following specific steps:
(1) HBr 40mL of water 36mL and benzyl protected serine 7.8g were added to a 500mL round bottom flask for ice bath, an aqueous solution of sodium nitrite was slowly added dropwise at 0 deg.C, added dropwise for 1h, stirred for 2.5h, quenched three times with 20mL diethyl ether, washed once with saturated brine, dried over anhydrous sodium sulfate, filtered and spun dry. A yellow oily liquid was obtained. The yield was 85%. The next step was carried out without purification.
(2) Dissolving 6.21g of sodium hydrosulfide in 60mL of water, carrying out ice bath to 0 ℃, dissolving 9.57g of the product obtained in the previous step in water, dropwise adding at 0 ℃ overnight at room temperature, heating to 70 ℃, reacting for 2h, acidifying with 30% sulfuric acid at 0 ℃, extracting with diethyl ether for three times, drying with anhydrous sodium sulfate, and spin-drying. The column was chromatographed with DCM: MeOH 100: 1. A yellow liquid is obtained. Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product.1H NMR(300MHz,CDCl3):11.156(1H),7.36(5H),4.61(2H),3.77(2H),3.63(1H),2.17(1H).
4.8g of the product obtained in the previous step is pumped out under vacuum for 2h, activated by active carbon at 120 ℃ for 2h, 480mg of active carbon is added into a reaction bottle, and 50mL of THF is added. Triphosgene (3.36 g) was added and the reaction was carried out for 4 days. Filtering to remove the active carbon, pumping the solvent, and recrystallizing with diethyl ether petroleum ether to obtain white solid product. Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1HNMR) characterizes the structure of ser (bn) SCA.1H NMR(500MHz,CDCl3):7.26-7.41(m,5H),4.69(m,1H),4.62(m,2H,),3.90(m,2H,).13C NMR(CDCl3,125MHz):167.02,164.41,136.58,128.77,128.40,127.90,73.86,68.57,52.51.
The other monomers were prepared in the same manner as monomer 1.
Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product GlySCA1H NMR(500MHz,CDCl3):4.30(1H).
Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product LaSCA1H NMR(500MHz,CDCl3):4.61(1H),1.84(3H).
Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product PheSCA1H NMR(500MHz,CDCl3):7.22-7.38(m,5H),4.81(t,1H),3.22-3.58(m,2H).13C NMR(CDCl3,125MHz):168.18,163.89,134.89,129.29,129.20,128.29,53.81,39.00.
Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product LySCA1H NMR(500MHz,CDCl3):7.38-7.26(m,5H),5.09(s,2H),4.84(m,1H),4.53(s,1H),3.18(m,2H),2.02(m,2H),1.41-1.57(m,4H).13C NMR(CDCl3,125MHz):168.68,164.10,156.56,136.58,128.68,128.25,128.07,68.86,51.77,40.45,32.78,29.38,24.10.
Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product TyrSCA1H NMR(500MHz,CDCl3):7.34-7.44(m,5H),7.14(m,2H),6.95(m,2H),5.06(s,2H),4.77(m,2H),3.18-3.49(m,2H).13C NMR(CDCl3,125MHz):168.19,163.93,158.78,136.81,130.45,128.78,127.64,126.99,115.57,70.21,54.15,38.23.
Deuterated chloroform (CDCl)3) A 300 mhz nmr (hydrogen spectrum,1h NMR) characterized the structure of the product GluSCA1H NMR(500MHz,CDCl3):7.33-7.40(m,5H),5.15(s,2H),4.71(m,1H),2.62(m,2H),2.50(m,2H).13C NMR(CDCl3,125MHz):171.37,168.38,163.71,135.39,128.81,128.69,128.53,67.68,67.11,50.35,30.85,28.38.
Application example 1 approximately 5.7mg (0.1mmol) of the catalyst PPNCl were weighed or metered in separately in a glove box as stock solutions in 1mL of anhydrous dichloromethane. Weighing about 60mg (0.25mmol) of serine SCAs monomer, placing the monomer into a reaction bottle, dissolving the monomer in 2.4mL of toluene (the reaction bottle is subjected to evacuation, fire baking, cooling and nitrogen charging treatment in advance, and the process is repeated three times), then weighing 50 microliters of catalyst solution and dichloromethane solution into the reaction bottle, wherein the molar ratio of the monomer to the catalyst is 250: the reaction was carried out at 1, 25 ℃ for 2 min. When the polymerization was complete, it was diluted with chloroform, quenched with trifluoroacetic acid/dichloro solution (1mL/10mL), settled with about 10mL of methanol, and centrifuged to give a white solid. After drying for 24 hours, the molecular weight of the polymer was analyzed by GPC to obtain Mn12.1 ten thousand, Mw/Mn1.31 nuclear magnetism: (1HNMR,300MHz,CDCl3) The monomer conversion was analyzed to be greater than 99%.
Application example 2
Respectively weighing or measuring the catalyst in a glove boxThe dose PPNCl was about 5.7mg (0.1mmol) and benzoic acid 6.1mg (0.05mol) was dissolved in 1mL of anhydrous dichloromethane as a stock solution. Weighing about 60mg (0.25mmol) of serine SCAs monomer, placing the monomer into a reaction bottle, dissolving the monomer in 2.4mL of toluene (the reaction bottle is subjected to evacuation, fire baking, cooling and nitrogen charging treatment in advance, and the process is repeated three times), then weighing 50 microliters of catalyst solution and 100 microliters of benzoic acid solution into the reaction bottle, wherein the molar ratio of the monomer, the initiator and the catalyst is 250: 10: the reaction was carried out at 1, 25 ℃ for 2 min. When the polymerization was complete, it was diluted with chloroform, quenched with trifluoroacetic acid/dichloro solution (1mL/10mL), settled with about 10mL of methanol, and centrifuged to give a white solid. After drying for 24 hours, the molecular weight of the polymer was analyzed by GPC to obtain Mn0.52 ten thousand, Mw/Mn1.24 nuclear magnetism: (1H NMR,300MHz,CDCl3) The monomer conversion was analyzed to be greater than 99%.
Application example 3
Approximately 5.7mg (0.1mmol) of the catalyst PPNCl and 6.1mg (0.05mol) of benzoic acid were weighed or measured in a glove box and dissolved in 1mL of anhydrous dichloromethane as stock solutions. Weighing about 60mg (0.25mmol) of serine SCAs monomer, placing the monomer into a reaction bottle, dissolving the monomer in 2.4mL of toluene (the reaction bottle is subjected to evacuation, fire baking, cooling and nitrogen charging treatment in advance, and the process is repeated three times), then weighing 50 microliters of catalyst solution and 100 microliters of benzoic acid solution into the reaction bottle, wherein the molar ratio of the monomer, the initiator and the catalyst is 250: 2.5: reaction at 1, 25 deg.C for 3 min. When the polymerization was complete, it was diluted with chloroform, quenched with trifluoroacetic acid/dichloro solution (1mL/10mL), settled with about 10mL of methanol, and centrifuged to give a white solid. After drying for 24 hours, the molecular weight of the polymer was analyzed by GPC to obtain Mn1.86 ten thousand, Mw/Mn1.26 nuclear magnetism: (1H NMR,300MHz,CDCl3) The monomer conversion was analyzed to be greater than 99%. The GPC curve is shown in FIG. 1.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An amino acid based S-carboxyanhydride characterized by the following structural formula:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection position.
2. A process for the preparation of amino acid based S-carboxyanhydrides of claim 1 comprising the steps of:
the method comprises the following steps: carrying out diazotization bromination reaction on amino acid to obtain alpha-amino brominated amino acid;
step two: reacting the alpha-amino brominated amino acid obtained in the step one with a thionizing agent to obtain alpha-amino thionized amino acid;
step three: reacting the alpha-amino sulfo amino acid obtained in the step two with a reagent under the action of a catalyst to obtain amino acid group S-carboxyanhydride;
the synthetic route is as follows:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection position.
3. The method for preparing amino acid based S-carboxyanhydrides as claimed in claim 2, wherein the reagent used in the diazotization bromination reaction in step one is selected from the group consisting of sodium nitrite and hydrobromic acid, or sodium nitrite, sulfuric acid and potassium bromide.
4. The method for producing an amino acid based S-carboxyanhydride according to claim 2, wherein the thioting agent in step two is sodium hydrosulfide or sodium trisulfide.
5. The method for preparing amino acid based S-carboxyanhydrides as claimed in claim 2, wherein the reagent in step three is selected from one or more of phosgene, diphosgene and triphosgene.
6. The method for preparing amino acid based S-carboxyanhydrides as claimed in claim 2, wherein the catalyst in step three is selected from one or more of activated carbon, pyridine, and triethylamine.
7. A functionalized thioester of the formula:
wherein R is hydrogen or any one of the following substituent groups:
wherein "+" represents a connection location;
r' is chlorine, bromine or any one of the following substituent groups:
wherein R is1Is alkyl or aryl, "-" represents the attachment position;
n is 20 to 400.
8. A method of preparing the functionalized thioester of claim 7, comprising the steps of:
dissolving amino acid group S-carboxyl internal anhydride in an organic solvent, and carrying out ring-opening polymerization reaction under the action of a catalyst to obtain the functionalized thioester shown as the formula (VII);
the synthetic route is as follows:
in which case R' is chlorine, bromine, or
Wherein R is1Is alkyl or aryl, "-" represents the attachment position;
or comprises the following steps:
dissolving amino acid group S-carboxyl internal anhydride in an organic solvent, and carrying out ring-opening polymerization reaction under the action of an initiator and a catalyst to obtain the functionalized thioester shown as the formula (VII);
the synthetic route is as follows:
in the above synthetic route, the amino acid group S-carboxyanhydride is selected from any of the following structures:
the initiator R' OOH is one of benzoic acid, 3-diphenyl propionic acid and 4-tert-butyl benzene propionic acid;
n is 20 to 400;
the catalyst is any one of the following structures:
wherein R is1Is an alkyl or aryl group.
9. The method for preparing a functionalized thioester according to claim 8, wherein the mass ratio of the catalyst to the initiator is 0.001-1; the mass ratio of the catalyst to the amino acid group S-carboxyanhydride is 10-600: 1.
10. the method for preparing a functionalized thioester according to claim 8, wherein the polymerization temperature is-20 to 30 ℃ and the time is 0.01 to 24 hours, and the organic solvent is one of chloroform, toluene, dichloromethane and tetrahydrofuran.
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| CN113943485A (en) * | 2021-10-27 | 2022-01-18 | 中国科学院长春应用化学研究所 | Application of polythioester material in recyclable plastic product |
| CN115703756A (en) * | 2021-08-17 | 2023-02-17 | 四川大学 | Recoverable poly (p-dithio-cyclohexanone) and derivatives and preparation method thereof |
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