CN110218303B - Method for synthesizing aliphatic polyester by copolymerization of epoxide and cyclic anhydride under catalysis of metal-free catalyst - Google Patents
Method for synthesizing aliphatic polyester by copolymerization of epoxide and cyclic anhydride under catalysis of metal-free catalyst Download PDFInfo
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- CN110218303B CN110218303B CN201910563032.5A CN201910563032A CN110218303B CN 110218303 B CN110218303 B CN 110218303B CN 201910563032 A CN201910563032 A CN 201910563032A CN 110218303 B CN110218303 B CN 110218303B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- -1 cyclic anhydride Chemical class 0.000 title claims abstract description 22
- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 150000002118 epoxides Chemical class 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 77
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- 238000001291 vacuum drying Methods 0.000 claims description 32
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 29
- 229940014800 succinic anhydride Drugs 0.000 claims description 29
- 150000002924 oxiranes Chemical class 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229960001701 chloroform Drugs 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 6
- 150000004032 porphyrins Chemical class 0.000 claims description 6
- ANWXWWSYNQLVED-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-bromophenyl)-21,23-dihydroporphyrin Chemical compound Brc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(Br)cc2)c2ccc([nH]2)c(-c2ccc(Br)cc2)c2ccc(n2)c(-c2ccc(Br)cc2)c2ccc1[nH]2 ANWXWWSYNQLVED-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 description 90
- 235000014113 dietary fatty acids Nutrition 0.000 description 63
- 229930195729 fatty acid Natural products 0.000 description 63
- 239000000194 fatty acid Substances 0.000 description 63
- 150000004665 fatty acids Chemical class 0.000 description 63
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 33
- 238000010521 absorption reaction Methods 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 150000002148 esters Chemical group 0.000 description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 6
- 101100153331 Mus musculus Timp1 gene Proteins 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for synthesizing aliphatic polyester by copolymerization of epoxide and cyclic anhydride under the catalysis of a metal-free catalyst. The synthesis method takes epoxide and cyclic anhydride as monomers, initiates polymerization reaction by a metal-free catalyst under the conditions of drying and no oxygen, and obtains aliphatic polyester through post treatment; has the advantages of no metal residue, high catalytic efficiency, good selectivity, high yield, narrow molecular weight distribution and the like; has high practical application value.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and relates to a method for synthesizing aliphatic polyester by copolymerization of an epoxide and cyclic anhydride under the catalysis of a metal-free catalyst.
Background
With the development of social economy, plastic products have become indispensable articles in daily life. However, the common plastic itself is difficult to degrade, and the existing treatment methods of waste plastic products cause great pollution to water sources, soil, air, and the like, and cause white pollution. Therefore, people gradually focus on polyester macromolecule biodegradable materials, and substitute the materials for starch filling materials to overcome the defects of starch degradable materials. The polyester polymer material comprises aliphatic degradable polyester and aromatic polyester, and the aromatic polyester has a rigid benzene ring structure to influence the degradation performance of the aromatic polyester, so that the aliphatic polyester becomes a research hotspot. The copolymerization of epoxide and cyclic anhydride is one of the effective methods for generating aliphatic polyester, and the synthesized aliphatic polyester has high molecular weight and narrow molecular weight distribution, biodegradability, good biocompatibility and physical and mechanical properties, no toxicity, no pollution and a plurality of varieties. The performance of the material can be further improved by changing the chemical structure of the main chain and introducing functional groups, so that the material meets the requirements of various aspects and accords with the current trend of environmental protection. Therefore, the copolymerization synthesis of fatty acid polyester requires selecting a proper catalyst with higher catalytic activity.
Disclosure of Invention
The invention aims to provide a method for synthesizing aliphatic polyester by copolymerizing epoxide and cyclic anhydride under the catalysis of a metal-free catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for synthesizing aliphatic polyester by copolymerization of epoxide and cyclic anhydride under the catalysis of a metal-free catalyst specifically comprises the following steps:
respectively taking a metal-free catalyst and cyclic anhydride according to the mass ratio of 1: 200-600, dissolving 1g of the metal-free catalyst in 300mL of a solvent, taking the solvent, and taking an epoxide with the volume same as that of the solvent; placing a metal-free catalyst and cyclic anhydride in a reaction bottle, vacuumizing, sequentially adding an epoxide and a solvent into the reaction bottle, placing the reaction bottle in an environment with the temperature of 80-130 ℃, heating for 8-20 h, cooling to room temperature, dissolving out a polymer from the reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then carrying out vacuum drying at the temperature of 80-100 ℃ to obtain the aliphatic polyester.
The metal-free catalyst adopts small molecular porphyrin and derivatives thereof, and comprises the following components: tetraphenylporphyrin (TPP) CAS number: 917-23-7; 5,10,15, 20-tetrakis (4-bromophenyl) porphyrin (TBPP), CAS number: 29162-73-0;meso-tetrakis [4 (or 5) -imidazolyl]Porphyrin (TImp) porphyrin-like small molecule compounds. The metal-free catalyst has a structural formula shown in the following formula 1, formula 2, formula 3 or formula 4:
formula 1:
formula 2:
formula 3:
formula 4:
in the formula 4, R is various substituents, namely derivatives of small molecule porphyrins, and is selected from phenyl, bromophenyl or imidazolyl.
The cyclic anhydride is succinic anhydride or phthalic anhydride.
The epoxide is epichlorohydrin, propylene oxide, styrene oxide or cyclohexene oxide.
The solvent is at least one of tetrahydrofuran, toluene and dimethylformamide.
The synthesis method takes epoxide and cyclic anhydride as monomers, initiates polymerization reaction by a metal-free catalyst under the conditions of drying and no oxygen, and obtains aliphatic polyester through post treatment;
has the advantages of no metal residue, high catalytic efficiency, good selectivity, high yield, narrow molecular weight distribution and the like; has high practical application value. The highest catalytic efficiency in the synthesis process reaches 726.19g polymer/g catalyst, and the polyester content in the synthesized copolymer exceeds 90 percent.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 1 of the present invention (1HNMR， CDCl3) A drawing;
FIG. 2 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 2 of the present invention (see1HNMR， CDCl3) A drawing;
FIG. 3 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 3 of the present invention (see1HNMR， CDCl3) A drawing;
FIG. 4 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 4 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 5 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 5 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 6 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 6 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 7 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 7 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 8 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 8 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 9 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 9 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 10 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 10 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 11 is a nuclear magnetic hydrogen spectrum of fatty acid polyester prepared in example 11 of the present invention (1HNMR， CDCl3) A drawing;
FIG. 12 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 12 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 13 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 13 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 14 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 14 of the present invention (see1HNMR， CDCl3) A drawing;
FIG. 15 shows nuclear magnetic hydrogen spectra of fatty acid polyesters prepared in example 15 of the present invention (see below)1HNMR， CDCl3) A drawing;
FIG. 16 is a nuclear magnetic hydrogen spectrum of the reaction product of comparative example 1, which demonstrates the reaction of the catalyst with epoxide (1HNMR， CDCl3) A drawing;
FIG. 17 is a nuclear magnetic hydrogen spectrum of a reaction product of the catalyst of comparative example 2 after reaction with succinic anhydride (1HNMR， CDCl3) Figure (a).
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Example 1
Weighing 0.01g of TPP catalyst and 3.84g of succinic anhydride, putting into a reaction bottle, and vacuumizing; sequentially adding 3mL of epoxy chloropropane and 3mL of N, N-dimethylformamide into a reaction bottle, heating to 80 ℃, heating for 10h, and then cooling to room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, precipitating a product by using normal hexane as a settling agent, and placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 7.57g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 94%.
Example 2
Weighing 0.01g of TPP catalyst and 4.28g of succinic anhydride, placing the TPP catalyst and the succinic anhydride into a reaction bottle, and vacuumizing to replace air; 3mL of propylene oxide and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 4.96g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 60%.
Example 3
Weighing 0.01g of TPP catalyst and 2.63g of succinic anhydride, placing the TPP catalyst and the succinic anhydride into a reaction bottle, and vacuumizing to replace air; 3mL of styrene oxide and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.23g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 90%.
Example 4
Weighing 0.01g of TPP catalyst and 2.95g of succinic anhydride, placing the TPP catalyst and the succinic anhydride into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy cyclohexane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.03g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 85%.
Example 5
Weighing 0.01g of TPP catalyst and 5.67g of phthalic anhydride, placing the TPP catalyst and the phthalic anhydride into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy chloropropane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 9.01g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 97%.
Example 6
Weighing 0.01g of TBPP catalyst and 3.84g of succinic anhydride, putting into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy chloropropane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, precipitating a product by using normal hexane as a precipitating agent, and placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 7.26g of fatty acid polyester, wherein the content of polyester in the fatty acid polyester is 93%.
Example 7
Weighing 0.01g of TBPP catalyst and 4.28g of succinic anhydride, placing the TBPP catalyst and the succinic anhydride into a reaction bottle, and vacuumizing to replace air; 3mL of propylene oxide and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, precipitating a product by using normal hexane as a precipitating agent, and placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 6.45g of fatty acid polyester, wherein the content of polyester in the fatty acid polyester is 86%.
Example 8
Weighing 0.01g of TBPP catalyst and 2.63g of succinic anhydride, putting into a reaction bottle, and vacuumizing to replace air; 3mL of styrene oxide and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.49g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 94%.
Example 9
Weighing 0.01g of TBPP catalyst and 2.95g of succinic anhydride, putting into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy cyclohexane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.83g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 99%.
Example 10
Weighing 0.01g of TBPP catalyst and 5.67g of phthalic anhydride, placing the mixture into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy chloropropane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 8.62g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 94%.
Example 11
Weighing 0.01g of TIMp catalyst and 3.84g of succinic anhydride, placing the obtained mixture into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy chloropropane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, precipitating a product by using normal hexane as a settling agent, and placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 7.04g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 90%.
Example 12
Weighing 0.01g of TIMp catalyst and 4.28g of succinic anhydride, putting into a reaction bottle, and vacuumizing to replace air; 3mL of propylene oxide and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, precipitating a product by using normal hexane as a precipitating agent, and placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.58g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 57%.
Example 13
Weighing 0.01g of TIMp catalyst and 2.63g of succinic anhydride, putting into a reaction bottle, and vacuumizing to replace air; 3mL of styrene oxide and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.40g of fatty acid polyester, wherein the content of polyester in the fatty acid polyester is 93%.
Example 14
Weighing 0.01g of TIMp catalyst and 2.95g of succinic anhydride, placing the obtained mixture into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy cyclohexane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 5.30g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 90%.
Example 15
Weighing 0.01g of TIMp catalyst and 5.67g of phthalic anhydride, placing the obtained mixture into a reaction bottle, and vacuumizing to replace air; 3mL of epoxy chloropropane and 3mL of N, N-dimethylformamide are added into a reaction bottle, the temperature is increased to 80 ℃, the heating is carried out for 10 hours, and then the reaction bottle is cooled to the room temperature; dissolving the polymer out of a reaction bottle by using trichloromethane, taking normal hexane as a settling agent, settling out a product, and then placing the product in a vacuum drying oven for vacuum drying at 80 ℃ to obtain 6.05g of fatty acid polyester, wherein the polyester content in the fatty acid polyester is 66%.
Examples 1, 6 and 11 all use epichlorohydrin and succinic anhydride as the trans-isomerThe nuclear magnetic patterns of the fatty acid polyesters prepared in the three examples are shown in FIG. 1 (example 1), FIG. 6 (example 6) and FIG. 11 (example 11) (the abscissa in the figure is chemical shift, unit: ppm), and it can be seen that the chemical shifts of the prepared fatty acid polyesters are 5.0 to 5.5ppm and 4.0 to 4.4ppm, respectively corresponding to-CH-and-CH-in the ester chain2An absorption peak of an upper proton with a chemical shift of 1.0 to 1.5ppm being-CH in an ester chain3An absorption peak of-proton with a chemical shift of 3.4 to 3.7ppm being-CH-and-CH in polyether chain2The absorption peak of upper proton, 2.61ppm is the characteristic absorption peak of proton in polyester chain succinic anhydride, which shows that the synthetic method successfully synthesizes the polymer of epichlorohydrin and succinic anhydride.
Examples 2, 7 and 12 all synthesized fatty acid polyesters from propylene oxide and succinic anhydride as reaction monomers, and the nuclear magnetic patterns of the fatty acid polyesters obtained in the three examples are shown in FIG. 2 (example 2), FIG. 7 (example 7) and FIG. 12 (example 12) (the abscissa in the figure is chemical shift in ppm). As can be seen from the figure, the chemical shift of the fatty acid polyester is 1.0-1.3 ppm, which is-CH in the PO polyether chain3Absorption peaks of upper proton at 5.0-5.5 ppm and 4.0-4.4 ppm, corresponding to-CH-and-CH, respectively, in the ester chain2An absorption peak of an upper proton with a chemical shift of 1.0 to 1.5ppm being-CH in an ester chain3An absorption peak of-proton with a chemical shift of 3.4 to 3.7ppm being-CH-and-CH in polyether chain2The absorption peak of upper proton, 2.61ppm is the characteristic absorption peak of proton in polyester chain succinic anhydride, thus proving that the chain link structure of fatty acid polyester synthesized by the synthesis method of the invention is composed of chain links of anhydride and epoxide which are alternately copolymerized and a small amount of self-polymerization chain links of epoxide.
Examples 3, 8 and 13 each synthesized fatty acid polyester using styrene oxide and succinic anhydride as reaction monomers, and the nuclear magnetic patterns of the fatty acid polyester obtained in the three examples are shown in FIG. 3 (example 3), FIG. 8 (example 8) and FIG. 13 (example 13) (the abscissa in the figure is chemical shift in ppm). As can be seen from the figure, the fatty acid polyester is formedChemical shifts 4.7-5.0 ppm and 4.0-4.4 ppm, respectively corresponding to-CH-and-CH in the ester chain2An absorption peak of upper proton, chemical shift 7.0-7.5 ppm is an absorption peak of proton on benzene ring in ester chain, and chemical shift 3.4-3.7 ppm is-CH-and-CH in polyether chain2The absorption peak of upper proton, 2.61ppm is the characteristic absorption peak of proton in polyester chain succinic anhydride, thus proving that the chain link structure of fatty acid polyester synthesized by the synthesis method of the invention is composed of chain links of anhydride and epoxide which are alternately copolymerized and a small amount of self-polymerization chain links of epoxide.
Examples 4, 9 and 14 all synthesized fatty acid polyesters from epoxycyclohexane and succinic anhydride as reaction monomers, and the nuclear magnetic patterns of the fatty acid polyesters obtained in the three examples are shown in FIG. 4 (example 4), FIG. 9 (example 9) and FIG. 14 (example 14) (the abscissa in the figure is chemical shift in ppm). As can be seen from the figure, the chemical shifts of the fatty acid polyester are 4.5-5.0 ppm, which respectively correspond to the absorption peak of the proton on-CH-in the ester chain, and the chemical shifts of 1.2-1.7 ppm are-CH in the ester chain2An absorption peak of-proton with a chemical shift of 3.4 to 3.7ppm being-CH-and-CH in polyether chain2The absorption peak of upper proton, 2.61ppm is the characteristic absorption peak of proton in polyester chain succinic anhydride, thus proving that the chain link structure of fatty acid polyester synthesized by the synthesis method of the invention is composed of chain links of anhydride and epoxide which are alternately copolymerized and a small amount of self-polymerization chain links of epoxide.
Examples 5,10 and 15 all synthesized fatty acid polyesters from epichlorohydrin and phthalic anhydride as reaction monomers, and the nuclear magnetic patterns of the fatty acid polyesters obtained in the three examples are shown in FIG. 5 (example 5), FIG. 10 (example 10) and FIG. 15 (example 15) (the abscissa in the figure is chemical shift, unit: ppm). As can be seen from the figure, the chemical shifts of the prepared fatty acid polyester are 5.0-5.5 ppm and 4.0-4.4 ppm respectively corresponding to-CH-and-CH in the ester chain2An absorption peak of an upper proton with a chemical shift of 1.0 to 1.5ppm being-CH in an ester chain3An absorption peak of-proton with a chemical shift of 3.4 to 3.7ppm being-CH-and-CH in polyether chain2Absorption peak of upper proton, 7.5-7.8 ppm is polyester chain o-benzeneThe characteristic absorption peak of proton in the diformic anhydride shows that the synthetic method successfully synthesizes the polymer of the epichlorohydrin and the phthalic anhydride.
Comparative example 1
Weighing 0.005g of TBPP catalyst, placing the TBPP catalyst into a reaction bottle, and vacuumizing to replace air; adding 1.5mL of propylene oxide and 1.5mL of N, N-dimethylformamide into a reaction bottle, and stirring at room temperature for 24h to obtain a reaction product.
The reaction product obtained in comparative example 1 was dissolved in CDCl3And (5) performing nuclear magnetic hydrogen spectrum test.
Comparative example 2
Weighing 0.005g of TBPP catalyst and 2.14g of succinic anhydride, putting into a reaction bottle, and vacuumizing to replace air; 3mL of N, N-dimethylformamide is added into a reaction bottle, and the mixture is stirred for 24 hours at room temperature to obtain a reaction product.
The reaction product obtained in comparative example 2 was dissolved in CDCl3And (5) performing nuclear magnetic hydrogen spectrum test.
The synthesis method of the invention takes the micromolecular porphyrin and the derivatives thereof as a metal-free catalyst to catalyze the copolymerization of the epoxide and the cyclic anhydride to synthesize the aliphatic polyester, because the active hydrogen on the pyrrole nitrogen contained in the micromolecular porphyrin and the derivatives thereof and the oxygen of the epoxide easily form hydrogen bonds, the TBPP is taken as an example for researching the mechanism, as shown in figure 16, the peak of the epoxide is shifted, thereby activating the epoxide to promote the ring opening. And the small-molecular porphyrin and the derivatives thereof can not activate the acid anhydride to promote the ring opening, as shown in figure 17, so that after the epoxide is opened to form an active intermediate, the acid anhydride is continuously inserted to form the aliphatic polyester.
Claims (4)
1. A method for synthesizing aliphatic polyester by copolymerization of epoxide and cyclic anhydride under the catalysis of a metal-free catalyst is characterized by comprising the following steps:
respectively taking a metal-free catalyst and cyclic anhydride according to the mass ratio of 1: 200-400, dissolving 1g of the metal-free catalyst in 300mL of a solvent, taking the solvent, and taking an epoxide with the volume same as that of the solvent; placing a metal-free catalyst and cyclic anhydride into a reaction bottle, vacuumizing, sequentially adding an epoxide and a solvent into the reaction bottle, placing the reaction bottle in an environment with the temperature of 80-130 ℃, heating for 8-20 h, cooling to room temperature, dissolving out a polymer from the reaction bottle by using trichloromethane, taking normal hexane as a settling agent, precipitating a product, and then carrying out vacuum drying at the temperature of 80-100 ℃ to obtain aliphatic polyester;
the metal-free catalyst adopts tetraphenylporphyrin CAS number: 917-23-7; 5,10,15, 20-tetrakis (4-bromophenyl) porphyrin, CAS number: 29162-73-0 ormeso-tetrakis [4 (or 5) -imidazolyl]Porphyrins.
2. The method for synthesizing aliphatic polyester by the copolymerization of epoxide and cyclic anhydride catalyzed by the metal-free catalyst according to claim 1, wherein the cyclic anhydride is succinic anhydride or phthalic anhydride.
3. The method for synthesizing aliphatic polyester through the copolymerization of epoxide and cyclic anhydride under the catalysis of the metal-free catalyst according to claim 1, wherein the epoxide is epichlorohydrin, propylene oxide, cyclohexene oxide or styrene oxide.
4. The method for synthesizing aliphatic polyester by the copolymerization of epoxide and cyclic anhydride catalyzed by the metal-free catalyst according to claim 1, wherein the solvent is at least one of tetrahydrofuran, toluene and dimethylformamide.
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