CN113185678A - Preparation method of aliphatic polycarbonate polyester copolymer with zero catalyst addition - Google Patents
Preparation method of aliphatic polycarbonate polyester copolymer with zero catalyst addition Download PDFInfo
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- CN113185678A CN113185678A CN202110468017.XA CN202110468017A CN113185678A CN 113185678 A CN113185678 A CN 113185678A CN 202110468017 A CN202110468017 A CN 202110468017A CN 113185678 A CN113185678 A CN 113185678A
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 122
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 116
- 229920000728 polyester Polymers 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
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- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000000376 reactant Substances 0.000 claims abstract description 5
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- 238000006116 polymerization reaction Methods 0.000 claims description 21
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
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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 relates to a preparation method of an aliphatic polycarbonate polyester copolymer, wherein the structural formula of the aliphatic polycarbonate polyester copolymer comprises a structural unit shown as a formula 4:
in the preparation process of the aliphatic polycarbonate polyester copolymer, when the structural unit shown in the formula 4 is coupled, a compound shown in a formula 1 and a compound shown in a formula 2 are used as reactants for preparation, wherein the structural formula of the compound shown in the formula 1 is shown as follows:
the structural formula of the compound shown in the formula 2 is shown as follows:
the preparation method has the advantages of no catalyst in the preparation process, completely avoiding potential toxic and side effects of catalyst residues, simple preparation steps, high yield, low cost, suitability for large-scale production, simplicity, convenience and high efficiency, and huge application and transformation potentials.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a preparation method of an aliphatic polycarbonate polyester copolymer with zero catalyst addition.
Background
Biodegradable polymer materials are polymer materials that can be degraded in a microbial environment, and they have wide applications as environment-friendly materials and biomedical materials. Compared with non-biodegradable materials, the medical material has the advantages in the medical field: after the specific function is finished, the material is finally degraded into non-toxic small molecules in vivo which are absorbed or metabolized by organisms, no residue is left in vivo, and the potential suffering of long-term toxic and side effects of the material and the pain of patients who need to take out the material after the material is implanted in a secondary operation are avoided.
Biodegradable polymer materials are classified into natural and synthetic biodegradable polymer materials. The natural biodegradable high molecular material is natural active high molecular extracted from animal and plant bodies in nature, and mainly comprises protein (such as collagen and gelatin), polysaccharide (such as cellulose, chitosan and starch), sodium alginate, hyaluronic acid and the like. The material has good biocompatibility and rich sources, but has the obvious defects of poor mechanical property, difficult processing, poor stability, larger difference of properties along with different sources and the like. The synthesized biodegradable high polymer material can be produced in large scale, and has high performance reproducibility, so the biodegradable high polymer material becomes an important pillar material in the fields of modern medicine and degradable plastics. Among them, biodegradable aliphatic polyesters represented by poly-epsilon-caprolactone (PCL), polyglycolic acid (PGA), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), and the like are a class of biodegradable polymers which are most widely studied and applied at present. The polymer is easy to crystallize, so that the polymer has high mechanical strength and is a mainstream source of the biomedical absorbable material at present. However, the degradation products of aliphatic polyesters cause a local slightly acidic environment, cause non-infectious inflammation when applied as an implant material, easily inactivate/inactivate the loaded protein or DNA as a drug carrier, and have problems of excessively high degradation rate in vivo, easily thermally degraded by melt processing, excessively high degradation rate, and the like.
Aliphatic polycarbonates are an important class of degradable polymeric materials for polyesters, and have received considerable attention in recent years due to their unique properties relative to polyesters. The aliphatic polycarbonate degradation products are micromolecular diol and carbon dioxide, so that no acid product is retained, and the biocompatibility is excellent; the processing stability is much higher than that of polyester, the degradation speed is slower than that of polyester, and the bidirectional requirements of longer-term use and final degradation are met. In addition, the biodegradable material is an amorphous polymer, has excellent ductility and flexibility and high film forming property, the current biodegradable material mostly utilizes the copolymer of aliphatic polycarbonate and polyester to adjust the important properties of the absorbable biomaterial, such as mechanical strength, processability, degradation rate and the like, and various copolymers have been approved by the Food and Drug Administration (FDA) and are applied to the fields of surgical sutures, drug controlled release, gene transfection, tissue engineering and the like.
Aliphatic polyesters can be polymerized by polycondensation and ring opening to give high molecular weight products. In contrast, aliphatic polycarbonate polycondensation can only yield oligomers, but can only yield higher molecular weight products by ring-opening polymerization. Among the ring-opening polymerization methods, bulk polymerization is undoubtedly more preferable for practical use because it does not generate any by-products, and it is easier to control the molecular weight, the polymerization does not require a solvent, and there is no environmental pollution and harsh solvent treatment requirements, and it is now the first preparation method for medical grade polycarbonate and polyester materials. The six-membered cyclic carbonate is easy to carry out ring-opening polymerization due to larger ring tension, so that the six-membered cyclic carbonate becomes a representative material of aliphatic polycarbonate meeting the requirements of the medical field at present, and particularly a non-crystalline amorphous linear polycarbonate material prepared by the ring-opening of trimethylene carbonate.
It should be noted that, for biomedical field and food packaging degradable plastic field, the metal catalyst residue used in ring-opening polymerization is a very important potential source of safety, and although the current exploration work of replacing metal catalyst with organic small molecule catalyst, the toxicity of the catalyst is still large in general, and the safety of small molecule organic matter itself cannot be evaluated.
Therefore, how to prepare the aliphatic polycarbonate polyester copolymer in a green way is a great challenge related to biodegradable aliphatic polycarbonate materials in the fields of medical use and food packaging. It is known that cyclic six-membered cyclic carbonates can spontaneously polymerize thermally, and although the mechanism is not clear at present, the catalyst has high similarity to the ring-opening polymerization mechanism catalyzed by most cyclic lactones and carbonates, and it is believed that the active end in the thermal polymerization of polycarbonate can also induce ring-opening of cyclic lactone, thereby obtaining a copolymer of the two. The green preparation method has great application and transformation potential and great social and economic significance.
Disclosure of Invention
The present invention has been made to solve at least some of the technical problems occurring in the prior art, and in a first aspect of the present invention, the present invention provides a method for preparing an aliphatic polycarbonate polyester copolymer having a structural formula including the following structural units:
in the preparation process of the aliphatic polycarbonate polyester copolymer, when the structural unit shown in the formula 4 is used, the aliphatic polycarbonate polyester copolymer is prepared by polymerizing two or more compounds shown in the formula 1 and the formula 2 as reactant monomers, wherein the structural formula of the compound shown in the formula 1 is shown as follows:
the structural formula of the compound shown in the formula 2 is shown as follows:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from various substituent groups; preferably, R1、R2、R3、R4、R5、R6Are respectively provided withIndependently selected from alkyl, alkyl derivatives, halogen, hydrogen, esters, ethers; r is selected from (CH)2)n、(CH2)n1O(CH2)n2One of COO and COO; r7、R8Each independently selected from various substituent groups; preferably, R7、R8Each independently selected from alkyl, alkyl derivatives, hydrogen; preferably, R7、R8Each independently selected from methyl, hydrogen, n1、n2Each independently selected from any integer from 0 to 10. When R is COO, the carbon of the carbonyl group of the ester group and R8Substituted carbons are linked.
In one or more embodiments of the present invention, the present invention provides a method for preparing an aliphatic polycarbonate polyester copolymer, the aliphatic polycarbonate polyester copolymer has a structural formula as shown in formula 3, and the aliphatic polycarbonate polyester copolymer is prepared from
The compound shown in the formula 1 and the compound shown in the formula 2 are prepared, and the reaction formula is shown as follows:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from various substituent groups; preferably, R1、R2、R3、R4、R5、R6Each independently selected from alkyl, alkyl derivatives, halogen, hydrogen, esters, ethers; r is selected from (CH)2)n、(CH2)n1O(CH2)n2One of COO and COO; r7、R8Each independently selected from various substituent groups; preferably, R7、R8Each independently selected from alkyl, alkyl derivatives, hydrogen; preferably, R7、R8Each independently selected from methyl, hydrogen, n1、n2Each independently selected from any integer from 0 to 10. When R is COO, the carbon of the carbonyl group of the ester group and R8Substituted carbons are linked.
In one or more embodiments of the present invention, the compound of formula 1 is trimethylene carbonate having the following structural formula:
in one or more embodiments of the invention, the compound of formula 2 is epsilon-caprolactone or lactide;
the structural formula of the epsilon-caprolactone is shown as follows:
the structural formula of the lactide is shown as follows:
in one or more embodiments of the present invention, the compound represented by formula 1 and the compound represented by formula 2 do not require an addition of a catalyst during the preparation of the aliphatic polycarbonate polyester copolymer.
In one or more embodiments of the present invention, the compound represented by formula 1 and the compound represented by formula 2 are polymerized to obtain the compound represented by formula 3, and the polymerization temperature is controlled to be 100-140 ℃.
In one or more embodiments of the present invention, the polymerization reaction is performed under vacuum or under inert gas protection in a dry environment.
In one or more embodiments of the present invention, the method for preparing an aliphatic polycarbonate polyester copolymer further comprises purifying the aliphatic polycarbonate polyester copolymer, the purifying comprising dissolving the aliphatic polycarbonate polyester copolymer with a good solvent for the aliphatic polycarbonate polyester copolymer, and separating the aliphatic polycarbonate polyester copolymer by precipitation in a poor solvent for the aliphatic polycarbonate polyester copolymer.
In one or more embodiments of the present invention, the good solvent of the aliphatic polycarbonate polyester copolymer is selected from one or more of methylene chloride and chloroform; the poor solvent of the aliphatic polycarbonate polyester copolymer is methanol.
In a second aspect of the present invention, the present invention provides an application of an aliphatic polycarbonate polyester copolymer in pharmaceutical excipients, tissue engineering materials, plasticizers, and 3D printing materials, wherein a structural formula of the aliphatic polycarbonate polyester copolymer comprises a structural unit represented by formula 4:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from various substituent groups; preferably, R1、R2、R3、R4、R5、R6Each independently selected from alkyl, alkyl derivatives, halogen, hydrogen, esters, ethers; r is selected from (CH)2)n、(CH2)n1O(CH2)n2One of COO and COO; r7、R8Each independently selected from various substituent groups; preferably, R7、R8Each independently selected from alkyl, alkyl derivatives, hydrogen; preferably, R7、R8Each independently selected from methyl, hydrogen, n1、n2Each independently selected from any integer from 0 to 10. When R is COO, the carbon of the carbonyl group of the ester group and R8Substituted carbons are linked.
Preferably, the aliphatic polycarbonate polyester copolymer has a structural formula shown in formula 3:
more preferably, the aliphatic polycarbonate polyester copolymer has a structural formula shown in the following formula:
compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a preparation method of an aliphatic polycarbonate polyester copolymer, which is characterized in that a heating melting body is subjected to ring-opening copolymerization to polymerize a cyclic carbonate monomer and a cyclic lactone, and the high-safety-level degradable aliphatic polycarbonate polyester copolymer is prepared in an environment-friendly manner.
2. The invention provides a preparation method of an aliphatic polycarbonate polyester copolymer, which does not add a catalyst in the preparation process and completely avoids the potential toxic and side effects of catalyst residues.
3. The aliphatic polycarbonate polyester copolymer prepared by the preparation method can be used for biomedical application, degradable plastics, material additives and other multiple applications, and has great social and economic significance.
Drawings
FIG. 1 is a GPC chart of an aliphatic polycarbonate polyester copolymer produced in example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of an aliphatic polycarbonate polyester copolymer prepared in example 5 of the present invention;
FIG. 3 is a GPC chart of an aliphatic polycarbonate polyester copolymer produced in example 9 of the present invention;
FIG. 4 is a GPC chart of an aliphatic polycarbonate polyester copolymer produced in example 10 of the present invention.
FIG. 5 is a nuclear magnetic spectrum of an aliphatic polycarbonate polyester copolymer prepared in example 10 of the present invention.
Detailed Description
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Example 1
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is shown below:
the preparation method of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps: 0.15 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.15 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in a 100 ℃ oil bath with magnetic stirring for 7 hours to complete the polymerization. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain the aliphatic polycarbonate polyester copolymer with the structural formula
Weighing, calculating the yield, and the yield is 47%. The aliphatic polycarbonate polyester copolymer obtained had a number average molecular weight of 2.49X 10 as determined by GPC (THF as mobile phase, polystyrene as standard)4Daltons, dispersity of 1.66, GPC profile showed the product to be unimodal, indicating that the product is not a mixture of homopolymers, but rather a copolymer (the GPC profile of the resulting aliphatic polycarbonate polyester copolymer is shown in figure 1). Nuclear magnetic analysis showed that the aliphatic polycarbonate polyester copolymer obtained had a composition molar ratio of CL: TMC 23: 77.Namely, the aliphatic polycarbonate polyester copolymer obtained has the structural formula wherein x: y is 23: 77.
in contrast, when 0.3g of ε -caprolactone was used as a reactant and the reaction was carried out under the other conditions as described above, no product could be precipitated. This is because the thermal polymerization of trimethylene carbonate can induce the polymerization of epsilon-caprolactone, and thus a copolymer can be obtained.
Example 2
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.15 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.15 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in a 120 ℃ oil bath with magnetic stirring for 7 hours to complete the polymerization. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain aliphatic polycarbonate with the structural formula
Weighing, calculating the yield, and the yield is 38%. GPC (THF as mobile phase, polystyrene as standard) determined a number average molecular weight of 4.18X 104Daltons, dispersion 1.53, GPC pattern showed the product to be unimodal, indicating that the product is not a mixture of homopolymers, but rather a copolymer. Nuclear magnetic analysis shows that the molar ratio of the polymer product composition is CL: TMC 7: 93. Namely, the aliphatic polycarbonate obtained has the structural formula in which x: y is 7: 93.
example 3
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.15 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.15 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a pressure-reducing sealed container, and vacuum dryingDrying for 0.5 hour, and sealing under negative pressure. The reaction vessel was placed in an oil bath at 140 ℃ for 7 hours with magnetic stirring, and the polymerization was completed. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain aliphatic polycarbonate with the structural formula
Weighing, calculating the yield, and the yield is 41%. GPC (THF as the mobile phase, polystyrene as the standard) determined a number average molecular weight of 5.41X 104Daltons, dispersion 1.48, GPC pattern showed the product to be a single peak, indicating that the product is not a mixture of homopolymers, but rather a copolymer. Nuclear magnetic analysis shows that the molar ratio of the polymer product composition CL: TMC 6: 94. Namely, the aliphatic polycarbonate obtained has the structural formula in which x: y is 6: 94.
as shown by comparing examples 1, 2 and 3, the molecular weight of the obtained aliphatic polycarbonate is increased by increasing the temperature, but the TMC content in the copolymer is remarkably increased. The method shows that the ring opening of the carbonic ester is more facilitated at high temperature, and the advantage of the ring opening activity of the carbonic ester at high temperature is more obvious.
Example 4
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.25 g of six-membered cyclic carbonate [ particularly trimethylene carbonate (abbreviated as TMC) ]was weighed]And 0.05 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in an oil bath at 140 ℃ for 25 hours with magnetic stirring, and the polymerization was completed. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain aliphatic polycarbonate with the structural formula
Weighing, calculating the yield, and the yield is 92%. GPC (THF as the mobile phase,polystyrene as a standard) was determined to obtain an aliphatic polycarbonate having a number average molecular weight of 4.38X 104Daltons, dispersity 1.61, GPC pattern showed the resulting aliphatic polycarbonate product to be a single peak, indicating that the product is not a mixture of homopolymers, but rather a copolymer. Nuclear magnetic analysis shows that the molar ratio of the polymer product composition CL: TMC 14: 86. Namely, the aliphatic polycarbonate obtained has the structural formula in which x: y is 14: 86.
Example 5
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.05 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.25 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in an oil bath at 140 ℃ for 25 hours with magnetic stirring, and the polymerization was completed. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain the aliphatic polyester polycarbonate copolymer with the structural formula
Weighing, calculating the yield, and the yield is 79%. The number average molecular weight of the obtained aliphatic polyester polycarbonate copolymer was determined by GPC (THF as a mobile phase, polystyrene as a standard) and found to be 3.04X 104Daltons, dispersion 1.81. The high conversion and GPC chart of this example, single peak, further demonstrates that thermal polymerization of trimethylene carbonate can induce epsilon caprolactone polymerization, and thus copolymers. Nuclear magnetic analysis shows that the molar ratio of the polymer product composition CL: TMC 81: 19. Namely, the structural formula of the obtained aliphatic polyester polycarbonate copolymer, x: y is 81: 19. Random copolymer was indicated by random peaks near 4.0 in the nmr. The nuclear magnetic spectrum of the prepared aliphatic polycarbonate polyester copolymer is shown in figure 2.
Example 6
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.1 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.2 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in an oil bath at 140 ℃ for 25 hours with magnetic stirring, and the polymerization was completed. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain the aliphatic polycarbonate polyester copolymer with the structural formula
Weighing, calculating the yield, and the yield is 79%. The aliphatic polycarbonate polyester copolymer obtained had a number average molecular weight of 3.46X 10 as measured by GPC (THF as mobile phase, polystyrene as standard)4Daltons, dispersity 1.68. The high conversion and GPC chart of this example, single peak, further demonstrates that thermal polymerization of trimethylene carbonate can induce epsilon caprolactone polymerization, and thus copolymers. Nuclear magnetic analysis showed that the resulting aliphatic polycarbonate polyester copolymer product had a composition molar ratio CL: TMC 78: 22. Namely, the aliphatic polycarbonate polyester copolymer obtained has the structural formula wherein x: y is 78: 22.
Example 7
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.2 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.1 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in an oil bath at 140 ℃ for 25 hours with magnetic stirring, and the polymerization was completed. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain the aliphatic polycarbonate polyester copolymer with the structural formula
Weighing, calculating the yield, and the yield is 86%. The aliphatic polycarbonate polyester copolymer obtained had a number average molecular weight of 3.74X 10 as measured by GPC (THF as mobile phase, polystyrene as standard)4Daltons, dispersity 1.67. The high conversion and GPC chart of this example, single peak, further demonstrates that thermal polymerization of trimethylene carbonate can induce epsilon caprolactone polymerization, and thus copolymers. Nuclear magnetic analysis showed that the resulting aliphatic polycarbonate polyester copolymer product had a composition molar ratio CL: TMC 32: 68. Namely, the aliphatic polycarbonate polyester copolymer obtained has the structural formula wherein x: y is 32: 68.
Comparative examples 4 to 7, it is easy to conclude that: during copolymerization, the higher the feeding proportion of the trimethylene carbonate is, the higher the molecular weight of the obtained product is, the higher the proportion of the carbonate is, the higher the yield is and the lower the dispersity is.
Example 8
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.1 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.2 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in a 120 ℃ oil bath with magnetic stirring for 25 hours to complete the polymerization. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain the aliphatic polycarbonate polyester copolymer with the structural formula
Weighing, calculating the yield, wherein the yield is 75%. The aliphatic polycarbonate polyester copolymer obtained had a number average molecular weight of 4.34X 10 as determined by GPC (THF as the mobile phase, polystyrene as the standard)4Daltons, dispersity was 1.70. The high conversion and GPC chart of this example unimodal further demonstrates the thermal polymerization of trimethylene carbonateThe polymerization of epsilon-caprolactone can be induced, and then the copolymer can be obtained. Nuclear magnetic analysis showed that the resulting aliphatic polycarbonate polyester copolymer product had a composition molar ratio CL: TMC 52: 48. Namely, the aliphatic polycarbonate polyester copolymer obtained has the structural formula wherein x: y is 52: 48.
Example 9
The reaction formula for the preparation of the aliphatic polycarbonate polyester copolymer is the same as that of example 1, and the preparation of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.25 g of six-membered cyclic carbonate [ particularly trimethylene carbonate (abbreviated as TMC) ]was weighed]And 0.05 Cyclic lactone [ particularly, ε -caprolactone (abbreviated as CL)]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in a 120 ℃ oil bath with magnetic stirring for 25 hours to complete the polymerization. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain the aliphatic polycarbonate polyester copolymer with the structural formula
Weighing, calculating the yield, wherein the yield is 85%. The number average molecular weight of the obtained aliphatic polycarbonate polyester copolymer was measured by GPC (THF as a mobile phase, polystyrene as a standard) and found to be 6.48X 104Dalton, dispersity 1.52 (GPC chart of the obtained aliphatic polycarbonate polyester copolymer is shown in FIG. 3). The high conversion and GPC chart of this example, single peak, further demonstrates that thermal polymerization of trimethylene carbonate can induce epsilon caprolactone polymerization, and thus copolymers. Nuclear magnetic analysis shows that the molar ratio of the polymer product composition CL: TMC 7: 93. Namely, the aliphatic polycarbonate polyester copolymer obtained has the structural formula wherein x: y is 7: 93.
In addition, 120 ℃ shows the same trend as 140 ℃, and the higher the charge proportion of trimethylene carbonate, the higher the molecular weight of the obtained product, the higher the yield and the lower the dispersity. But under the condition of the same charge ratio and the same reaction time, the CL content of the product obtained at 120 ℃ is lower, which shows that the high temperature is favorable for inducing the CL ring opening.
Example 10
The preparation method of the aliphatic polycarbonate polyester copolymer specifically comprises the following steps:
0.20 g of six-membered cyclic carbonate [ in particular trimethylene carbonate (referred to as TMC for short)]And 0.10 Cyclic lactone [ specifically, lactide (abbreviated as LA) ]]Adding into a container capable of being sealed under reduced pressure, vacuum drying for 0.5 hr, and sealing under negative pressure. The reaction vessel was placed in a 140 ℃ oil bath with magnetic stirring for 24 hours to complete the polymerization. The product was dissolved in 2mL of dichloromethane and dropped into 40mL of methanol to obtain a white precipitate. The methanol was poured off while the product was washed 2 times with clean methanol. Drying to obtain aliphatic polycarbonate polyester copolymer with the structural formula
The yield was 88% by weight. The number average molecular weight of the obtained aliphatic polycarbonate polyester copolymer was measured by GPC (THF as a mobile phase, polystyrene as a standard) and found to be 1.51X 104Daltons, dispersity 1.57, GPC pattern showed the product to be a single peak, indicating that the product is not a mixture of homopolymers, but rather a copolymer. The GPC chart of the obtained aliphatic polycarbonate polyester copolymer is shown in FIG. 4. It is clear that the copolymer with LA is more susceptible to thermal decomposition than the copolymerization with CL, resulting in a significantly lower molecular weight. Nuclear magnetic analysis shows that the polymer product has a molar ratio of TMC to LA 88: 12. the nuclear magnetic spectrum of the prepared aliphatic polycarbonate polyester copolymer is shown in figure 5.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of an aliphatic polycarbonate polyester copolymer is characterized in that the structural formula of the aliphatic polycarbonate polyester copolymer comprises a structural unit shown as a formula 4:
in the preparation process of the aliphatic polycarbonate polyester copolymer, when the structural unit shown in the formula 4 is used, the preparation method comprises the step of preparing the compound shown in the formula 1 and the compound shown in the formula 2 as reactants, wherein the structural formula of the compound shown in the formula 1 is shown as follows:
the structural formula of the compound shown in the formula 2 is shown as follows:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from various substituent groups; preferably, R1、R2、R3、R4、R5、R6Each independently selected from alkyl, alkyl derivatives, halogen, hydrogen, esters, ethers; r is selected from (CH)2)n、(CH2)n1O(CH2)n2One of COO and COO; r7、R8Each independently selected from various substituent groups; preferably, R7、R8Each independently selected from alkyl, alkyl derivatives, hydrogen; n, n1、n2Each independently selected from any integer from 0 to 10.
2. The preparation method of the aliphatic polycarbonate polyester copolymer is characterized in that the structural formula of the aliphatic polycarbonate polyester copolymer is shown as a formula 3, the aliphatic polycarbonate polyester copolymer is prepared by polymerizing a compound shown as a formula 1 and a compound shown as a formula 2 as reactant monomers, and the reaction formula is shown as follows:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from various substituent groups; preferably, R1、R2、R3、R4、R5、R6Each independently selected from alkyl, alkyl derivatives, halogen, hydrogen, esters, ethers; r is selected from (CH)2)n、(CH2)n1O(CH2)n2One of COO and COO; r7、R8Each independently selected from various substituent groups; preferably, R7、R8Each independently selected from alkyl, alkyl derivatives, hydrogen; n, n1、n2Each independently selected from any integer from 0 to 10.
3. The method for producing an aliphatic polycarbonate polyester copolymer according to claim 2, wherein the compound represented by formula 1 is trimethylene carbonate.
4. The method for producing an aliphatic polycarbonate polyester copolymer according to claim 2, wherein the compound represented by formula 2 is epsilon-caprolactone or lactide.
5. The method of claim 2, wherein the aliphatic polycarbonate polyester copolymer is prepared without adding a catalyst to the compound represented by formula 1 and the compound represented by formula 2.
6. The method for preparing an aliphatic polycarbonate polyester copolymer as defined in claim 2, wherein the compound represented by formula 1 and the compound represented by formula 2 are polymerized to obtain the compound represented by formula 3, and the polymerization temperature is controlled to be 100-140 ℃.
7. The method of claim 6, wherein the polymerization reaction is carried out under vacuum or under inert gas atmosphere in a dry environment.
8. The method of claim 2, further comprising purifying the aliphatic polycarbonate polyester copolymer, wherein the purifying comprises dissolving the aliphatic polycarbonate polyester copolymer in a good solvent for the aliphatic polycarbonate polyester copolymer, and separating the aliphatic polycarbonate polyester copolymer by precipitation in a poor solvent for the aliphatic polycarbonate polyester copolymer.
9. The method of producing an aliphatic polycarbonate polyester copolymer according to claim 8, wherein the good solvent for the aliphatic polycarbonate polyester copolymer is one or more selected from methylene chloride and chloroform; the poor solvent of the aliphatic polycarbonate polyester copolymer is methanol.
10. The application of the aliphatic polycarbonate polyester copolymer in pharmaceutic adjuvants, tissue engineering materials, plasticizers and 3D printing materials is characterized in that the structural formula of the aliphatic polycarbonate polyester copolymer comprises the following structural units:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from various substituent groups; preferably, R1、R2、R3、R4、R5、R6Each independently selected from alkyl, alkyl derivatives, halogen, hydrogen, esters, ethers; r is selected from (CH)2)n、(CH2)n1O(CH2)n2COO (cooling agent)；R7、R8Each independently selected from various substituent groups; preferably, R7、R8Each independently selected from alkyl, alkyl derivatives, hydrogen; n, n1、n2Each independently selected from any integer from 0 to 10;
preferably, the aliphatic polycarbonate polyester copolymer has a structural formula shown in formula 3:
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