WO2024066194A1 - 一种共聚酯及其制备方法 - Google Patents

一种共聚酯及其制备方法 Download PDF

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WO2024066194A1
WO2024066194A1 PCT/CN2023/078623 CN2023078623W WO2024066194A1 WO 2024066194 A1 WO2024066194 A1 WO 2024066194A1 CN 2023078623 W CN2023078623 W CN 2023078623W WO 2024066194 A1 WO2024066194 A1 WO 2024066194A1
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copolyester
ester
hydroxy acid
polymerization
cyclic
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PCT/CN2023/078623
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English (en)
French (fr)
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屠迎锋
杨木佳
李晓虹
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苏州大学
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Publication of WO2024066194A1 publication Critical patent/WO2024066194A1/zh

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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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • 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

Definitions

  • the invention belongs to the field of polymer material preparation, in particular to a copolyester and a preparation method thereof.
  • polyester has been widely used in fibers, packaging materials, films, engineering plastics, degradable plastics and medical materials due to its many advantages such as high cost performance, good biocompatibility and abundant sources.
  • polyester products mainly include aromatic polyesters such as polyethylene terephthalate (PET) and aliphatic polyesters such as polyethylene adipate (PEA), polylactic acid (PLA) and other products.
  • PET polyethylene terephthalate
  • PET polyethylene adipate
  • PLA polylactic acid
  • aliphatic polyesters have become a current research hotspot because they have biodegradable properties and can replace non-degradable polyolefin materials.
  • polyesters at present which are difficult to meet the ever-changing market demand, and functional groups need to be introduced therein to modify them.
  • polyesters with higher molecular weight need to be used.
  • the common synthesis methods of polyester are mainly condensation polymerization and ring-opening polymerization.
  • the ring-opening polymerization method obtains high molecular weight copolyester by increasing the ratio of monomer and initiator, but the introduction of its functional groups is relatively difficult.
  • the functional groups are introduced by initiators, and their content is very low, usually not exceeding 1% molar fraction, and it is difficult to obtain both high molecular weight and high functional groups. If the functional groups are introduced by monomers, it is necessary to obtain functional monomers through cumbersome synthesis steps, which increases the complexity of the polymerization method and increases the cost.
  • the condensation polymerization method can introduce high-content functional groups, but because its polymerization speed is relatively slow, esterification and pre-condensation take a long time, the reaction temperature is high, the polymerization time is long, and there are many side reactions, which is not suitable for preparing polyesters with higher molecular weight (generally less than 30 kilograms per mole). Therefore, the existing polyester synthesis technology has the problem of being difficult to synthesize functionalized polyesters with higher molecular weights, resulting in difficulty in modifying polyesters, limiting their further application.
  • Patent ZL201910245271.6 discloses a method for preparing a degradable aliphatic copolyester, which is prepared by ring-opening-condensation cascade polymerization of aliphatic macrocyclic diol ester and diol.
  • the copolyester has a high molecular weight and a high functional group content.
  • it uses small molecule diol or macromolecular diol as an initiator for copolymerization, and requires expensive macrocyclic diol esters such as musk T as monomers, which is costly.
  • the present invention provides a copolyester and a preparation method thereof.
  • the specific preparation method is: a compound containing both a hydroxyl group and a carboxyl group or a carboxyl group, such as hydroxypivalic acid, 10-hydroxydecanoic acid, mandelic acid, ricinoleic acid, 4-hydroxymethylbenzoic acid, methyl lactate, methyl hydroxypivalate, ethyl lactate, ethyl hydroxycaproate, etc., and a cyclic lactone such as ⁇ -valerolactone, caprolactone, hexadecanoic acid, etc. or a cyclic lactide such as glycolide, lactide, etc.
  • a cyclic oligomeric diacid diol ester such as musk T (ethylene 1,13-tridecanedioate), cyclic oligomeric ethylene terephthalate, cyclic oligomeric propylene terephthalate, cyclic oligomeric butylene terephthalate, etc.
  • musk T ethylene 1,13-tridecanedioate
  • cyclic oligomeric ethylene terephthalate cyclic oligomeric propylene terephthalate
  • cyclic oligomeric butylene terephthalate etc.
  • copolyesters having a higher functional group content and a higher molecular weight By copolymerizing hydroxy acids or hydroxy acid esters with cyclic esters having different structures, copolyesters having a higher functional group content and a higher molecular weight can be obtained, and the properties of the obtained copolyester materials can be regulated, so that they can be widely used in the fields of drug carriers, packaging materials, tissue engineering, and medical devices.
  • the first object of the present invention is to provide a copolyester, the chemical structural formula of the copolyester is as follows:
  • R is derived from a cyclic ester
  • R 5 is derived from a hydroxy acid or a hydroxy acid ester
  • R 4 is selected from CH 3 , CH 3 CH 2 or H
  • m is 2-40
  • n is 2-200.
  • the second object of the present invention is to provide a method for preparing a copolyester, comprising the following steps: using a cyclic ester and a hydroxy acid or a hydroxy acid ester to obtain the copolyester by ring-opening-condensation cascade polymerization under the action of a catalyst.
  • the hydroxy acid or the hydroxy acid ester first undergoes a ring-opening polymerization reaction with the cyclic ester to generate a copolyester with a lower molecular weight having a hydroxyl group at one end and a carboxyl group or a carboxylate structure at the other end, and then the terminal hydroxyl group undergoes condensation polymerization with the carboxyl group or the carboxylate to synthesize a copolyester with a higher molecular weight.
  • the present invention can regulate the content of the corresponding functional groups in the copolyester by regulating the ratio of the hydroxy acid or the hydroxy acid ester to the cyclic ester, and can prepare a copolyester with a high molecular weight.
  • the synthesized copolyester containing aliphatic polyester segments has excellent biocompatibility and biodegradability.
  • the cyclic ester is a lactone, a lactide or a cyclic oligomeric diacid diol ester, and the chemical structure of the cyclic ester is generally expressed as follows:
  • R is (CH 2 ) a CHR 1
  • the cyclic ester is a lactone
  • a is any integer from 2 to 14
  • R 1 is H or CH 3 ;
  • R is CHR 2 OCOCHR 2
  • the cyclic ester is lactide, and R 2 is H or CH 3 ;
  • R is [R 3 COO(CH 2 ) c OCO] p-1
  • R 3 COO(CH 2 ) c the cyclic ester is a cyclic oligomeric diacid diol ester
  • R 3 is Ph or (CH 2 ) d
  • c is any integer from 2 to 4
  • d is any integer from 2 to 12
  • p is any integer from 1 to 15.
  • the cyclic ester is selected from ⁇ -valerolactone, caprolactone, hexadecanoic acid lactone, glycolide, lactide, musk T (ethylene diethylene 1,13-tridecanedioate), cyclic oligoterephthalate, terephthalate, cyclic oligomeric propylene glycol terephthalate, cyclic oligomeric butylene terephthalate, and the like.
  • the cyclic ester when the cyclic ester is a cyclic lactone, it is preferably caprolactone, which is widely available, cheap and easy to obtain; when the cyclic ester is a cyclic lactide, it is preferably lactide, which is widely used; when the cyclic ester is a cyclic oligomeric diacid diol ester, it is preferably musk T (1,13-tridecane dioic acid ethylene ester) and cyclic oligomeric butylene terephthalate, which can be easily purchased on the market.
  • the obtained product is a copolyester, and when they are the same, the obtained product is a polyester homopolymer.
  • the copolyester is introduced with functional groups via hydroxy acid or hydroxy acid ester.
  • the functional group is selected from one or more of an alkyl chain, an aryl group and an alkenyl group.
  • the hydroxy acids and hydroxy acid esters are compounds containing both hydroxyl groups and carboxyl groups or carboxylates, such as hydroxypivalic acid, 10-hydroxydecanoic acid, mandelic acid, hydroxypivalic acid, ricinoleic acid, 4-hydroxymethylbenzoic acid, methyl lactate, methyl hydroxypivalate, ethyl lactate, ethyl hydroxycaproate, and the like.
  • the hydroxy acids and hydroxy acid esters are preferably 10-hydroxydecanoic acid, hydroxypivalic acid, ethyl hydroxycaproate, methyl lactate containing an aliphatic alkyl chain, 4-hydroxymethylbenzoic acid containing a benzene ring, ricinoleic acid containing a double bond, and the like.
  • the copolyester has a high molecular weight and a high content of functional groups, and the molar content of the functional groups in the structural units of the copolyester can reach 33%; the molecular weight of the copolyester can reach 40 to 60 kilograms per mole.
  • the catalyst is selected from titanate compounds.
  • the molar ratio of the cyclic ester to the hydroxy acid or hydroxy acid ester is 2-40:1.
  • the amount of the catalyst is 0.01% to 1%.
  • the ring-opening-condensation cascade polymerization reaction conditions are: reaction temperature is 180-260°C, and reaction time is 30-360 minutes.
  • the cascade polymerization reaction can be carried out at the same temperature or by gradually increasing the temperature.
  • the in-situ ring-opening-condensation cascade polymerization reaction is carried out under nitrogen atmosphere or vacuum conditions; after the reaction is completed, the product copolyester can be obtained without purification.
  • the third object of the present invention is to provide application of the copolyester in degradable polyester.
  • the copolyester structure of the present invention contains aliphatic polyester segments, it has biodegradability, and the degradation rate is controlled by conditions such as temperature and enzymes.
  • the polymerization mechanism of the present invention is an in-situ ring-opening-condensation cascade polymerization process, that is, the hydroxy acid or hydroxy acid ester first performs ring-opening polymerization on the cyclic ester monomer to obtain a copolyester with a hydroxyl group at one end and a carboxyl group or carboxylate at the other end.
  • the copolyester can continue to initiate the ring-opening polymerization of the cyclic ester, and can also perform condensation polymerization with each other to generate a copolyester with a higher molecular weight; the reaction product is the copolyester, and no purification and separation are required.
  • the molecular weight of the copolyester of the present invention can be adjusted by controlling the polymerization time and temperature, which can reach 54 kilograms per mole.
  • the molar content of the functional groups in the copolyester can reach 33%, which effectively solves the problems of low molecular weight, difficulty in introducing functional groups and single structure of the prior art polyester as a biomaterial.
  • the copolyester of the present invention uses an aliphatic cyclic ester as a monomer, or when the synthesized copolyester structure contains an aliphatic polyester fragment, it is biodegradable, and the degradation rate is controlled by temperature, enzymes and other conditions.
  • the mass and molecular weight decrease slowly over time in a phosphate buffered saline solution (pH 7.2-7.4) at 37°C, and the mass and molecular weight decrease rapidly in a phosphate buffered saline solution containing lipase (pH 7.2-7.4) at 37°C, and are basically completely degraded in 6 days.
  • the mass and molecular weight remain basically unchanged under refrigerated conditions at 4°C.
  • the in-situ ring-opening-condensation cascade polymerization method provided by the present invention aims to cascade the ring-opening polymerization reaction and the condensation polymerization reaction in the same system to prepare a copolyester with a high functional group content and a high molecular weight. While achieving high molecular weight, it has high functional group content.
  • the method has the advantages of simple reaction steps, high and controllable molecular weight, no need for post-treatment, and large-scale synthesis.
  • the polyester/copolyester prepared by the present invention using aliphatic cyclic ester as a monomer is biodegradable, and the degradation can be adjusted by temperature, enzyme content, etc. These technical effects are specifically shown in the examples.
  • the present invention discloses a method for preparing the above copolyester.
  • the invention synthesizes copolyester by in-situ ring-opening-condensation cascade polymerization of hydroxy acid or hydroxy acid ester and cyclic ester, thereby solving the problem that high molecular weight polyester with high functional group content is difficult to be synthesized by traditional polymerization method; a wide range of monomers can be used, and the copolyester can be widely applied to the synthesis of polyester, and the functional copolyester can be prepared simply and conveniently; and hydroxy acid or hydroxy acid ester is widely present in nature and of various kinds, and the functional copolyester can be conveniently prepared by introducing functional groups into hydroxy acid or hydroxy acid ester; the synthesized copolyester containing aliphatic polyester segments has biodegradable performance, is a kind of green and environmentally friendly material, and has great application value.
  • Fig. 1 is a synthetic route diagram of copolyester of the present invention
  • FIG2 is a size exclusion chromatogram of a copolyester (PHDACL) obtained by in-situ ring-opening-condensation cascade polymerization of 10-hydroxydecanoic acid and caprolactone at 220° C. under nitrogen for different reaction times;
  • PDACL copolyester
  • FIG3 is a size exclusion chromatogram of a copolyester (PHPACL) obtained by in situ ring-opening-condensation cascade polymerization of hydroxypivalic acid and caprolactone at 220° C. under nitrogen for different reaction times;
  • PPACL copolyester
  • FIG4 is a graph showing the molecular weight variation over time of a copolyester (PHPACL) obtained by in-situ ring-opening-condensation cascade polymerization of hydroxypivalic acid and caprolactone at 220° C. under nitrogen for different reaction times;
  • PPACL copolyester
  • FIG5 is a graph showing the molecular weight variation over time of a copolyester (PHBACL) obtained by in-situ ring-opening-condensation cascade polymerization of 4-hydroxymethylbenzoic acid and caprolactone at 220° C. under nitrogen for different reaction times;
  • PBACL copolyester
  • FIG6 is a size exclusion chromatogram of a copolyester (PRACL) obtained by in situ ring-opening-condensation cascade polymerization of ricinoleic acid and caprolactone at 220° C. under nitrogen;
  • PRACL copolyester
  • FIG7 is a graph showing the molecular weight variation over time of a copolyester (PMLACL) obtained by in-situ ring-opening-condensation cascade polymerization of methyl lactate and caprolactone at 210° C. under nitrogen for different reaction times;
  • PMLACL copolyester
  • FIG8 is a size exclusion chromatogram of a polyester (PCL) obtained by in-situ ring-opening-condensation cascade polymerization of ethyl hydroxycaproate and caprolactone at 210° C. under nitrogen;
  • PCL polyester
  • FIG9 is a size exclusion chromatogram of a polyester (PCL) obtained by in-situ ring-opening-condensation cascade polymerization of ethyl hydroxycaproate and caprolactone at 220° C. under vacuum;
  • PCL polyester
  • FIG10 is a size exclusion chromatogram of a copolyester (PHDAVL) obtained by in situ ring-opening-condensation cascade polymerization of 10-hydroxydecanoic acid and ⁇ -valerolactone at 210° C. under nitrogen for different reaction times;
  • PLDAVL copolyester
  • FIG11 is a size exclusion chromatogram of a copolyester (PHPADN) obtained by in-situ ring-opening-condensation cascade polymerization of hydroxypivalic acid and hexadecanoic acid lactone at 230° C. under nitrogen for different reaction times;
  • PHPADN copolyester
  • FIG12 is a size exclusion chromatogram of a copolyester (PHDALA) obtained by in-situ ring-opening-condensation cascade polymerization of 10-hydroxydecanoic acid and lactide at 200° C. under nitrogen for different reaction times;
  • PLDALA copolyester
  • FIG13 is a size exclusion chromatogram of a copolyester (PHPAEB) obtained by in-situ ring-opening-condensation cascade polymerization of hydroxypivalic acid and musk T at 230° C. under nitrogen for different reaction times;
  • PHPAEB copolyester
  • FIG14 is a degradation curve of the mass of copolyester (PHPACL) in 37° C. phosphate buffered saline solution without lipase and with lipase over time;
  • FIG15 is a scanning electron micrograph of the surface of copolyester (PHPACL) degraded in phosphate buffered saline at 37° C. in the absence of lipase for 3 days;
  • FIG. 16 is a scanning electron micrograph of the surface of copolyester (PHPACL) degraded in phosphate buffered saline at 37° C. in the presence of lipase for 3 days.
  • PPACL copolyester
  • the polymerization method for preparing copolyesters includes two processes: 1) hydroxy acid or hydroxy acid ester performs ring-opening polymerization on cyclic ester monomers to generate copolyester hydroxy acid or copolyester hydroxy acid ester; 2) copolyester hydroxy acid or copolyester hydroxy acid ester can continue to perform ring-opening polymerization on cyclic esters, or can perform condensation polymerization with each other to obtain a series of copolyesters.
  • 10-Hydroxydecanoic acid (14.4 g) and caprolactone (17.0 ml) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 32.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, the mixture was heated to 190°C, and in-situ ring-opening-condensation cascade polymerization was performed under a nitrogen atmosphere to synthesize the corresponding polymer. Samples were taken every 60 minutes during the reaction, and the reaction was stopped after 180 minutes.
  • Figure 2 is a size exclusion chromatogram of the copolyester obtained at the corresponding polymerization time.
  • the molecular weight measured after 60 minutes of polymerization is 21.1 kg/mol
  • the molecular weight measured after 120 minutes is 40.5 kg/mol
  • the molecular weight measured after 180 minutes is 54.4 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 0.4 kg/mol), proving the successful synthesis of the target product. It can be calculated that the molar content of the functional group in the copolyester is about 33%.
  • Hydroxypivalic acid (0.90 g) and caprolactone (17.0 ml) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 18.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, and the mixture was heated to 220° C. In a nitrogen atmosphere, an in-situ ring-opening-condensation cascade polymerization reaction was performed to synthesize the corresponding polymer. Samples were taken every 30 minutes during the reaction, and the reaction was stopped after 180 minutes.
  • Figure 3 is a size exclusion chromatogram of the copolyester obtained at the corresponding polymerization time.
  • Figure 4 is a graph showing the change in molecular weight of the copolyester over time.
  • the molecular weight of the copolyester is much greater than the theoretical molecular weight of the ring-opening polymerization (about 3.0 kg per mole), proving the successful synthesis of the target product.
  • its molecular weight can be controlled by controlling the polymerization time. It can be calculated that the molar content of the functional group in the copolyester is about 5%.
  • 4-Hydroxymethylbenzoic acid (1.17 g) and caprolactone (8.50 ml) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 10.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, and the mixture was heated to 220° C.
  • an in-situ ring-opening-condensation cascade polymerization reaction was performed to synthesize the corresponding polymer. Samples were taken every 60 minutes during the reaction, and the reaction was stopped after 180 minutes.
  • Figure 5 is a graph showing the molecular weight of the copolyester as a function of time.
  • the molecular weight is much greater than the theoretical molecular weight of ring-opening polymerization (about 1.3 kg/mol), proving the successful synthesis of the target product.
  • the molar content of the functional groups in the copolyester is about 9% by calculation.
  • ricinoleic acid (2.29 g) and caprolactone (8.50 ml) were added, nitrogen was passed to remove oxygen, 11.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, and the mixture was heated to 220° C.
  • an in-situ ring-opening-condensation cascade polymerization reaction was performed to synthesize the corresponding polymer. Samples were taken during the reaction, and the reaction was stopped after 200 minutes.
  • Figure 6 is a size exclusion chromatogram of the copolyester obtained after 200 minutes of polymerization.
  • the molecular weight measured after 200 minutes of polymerization is 20.6 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 1.4 kg/mol), proving the successful synthesis of the target product. It can be calculated that the molar content of the functional group in the copolyester is about 9%.
  • Methyl lactate (1.61 g) and caprolactone (17.0 ml) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 10.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, and the mixture was heated to 210° C.
  • an in-situ ring-opening-condensation cascade polymerization reaction was performed to synthesize the corresponding polymer. Samples were taken every 30 minutes during the reaction, and the reaction was stopped after 120 minutes.
  • Figure 7 is a graph showing the molecular weight of the copolyester as a function of time.
  • the molecular weight is much greater than the theoretical molecular weight of ring-opening polymerization (about 1.3 kg/mol), proving the successful synthesis of the target product.
  • the molar content of the functional groups in the copolyester is about 17% by calculation.
  • Ethyl hydroxycaproate (1.77 g) and caprolactone (8.5 ml) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 10.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, and the mixture was heated to 210° C.
  • In-situ ring-opening-condensation cascade polymerization was performed under nitrogen atmosphere to synthesize the corresponding polymer. The reaction was stopped after 30 minutes.
  • Figure 8 is a size exclusion chromatogram of the polyester obtained at the corresponding polymerization time.
  • the molecular weight measured after 30 minutes of polymerization is 49.4 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 0.7 kg/mol), proving the successful synthesis of the target product.
  • Ethyl hydroxycaproate (1.22 g) and caprolactone (8.5 ml) were added to a 100 ml single-necked flask, nitrogen was passed to remove oxygen, 5.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, the mixture was heated to 210°C, and the reaction was carried out under a nitrogen atmosphere for 15 minutes, and then vacuum polymerization was carried out for 90 minutes to finally produce the corresponding polymer.
  • Figure 9 is a size exclusion chromatogram of the polyester obtained at the corresponding polymerization time.
  • the molecular weight after 90 minutes of polymerization was measured to be 34.4 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 0.9 kg/mol), proving the successful synthesis of the target product.
  • Figure 10 is a size exclusion chromatogram of the copolyester obtained at the corresponding polymerization time.
  • the molecular weight after 300 minutes of reaction was 22.7 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 0.5 kg/mol).
  • the molar content of the functional groups in the copolyester is about 25%.
  • Figure 11 is a size exclusion chromatogram of the copolyester obtained at the corresponding polymerization time.
  • the molecular weight after 180 minutes of reaction was measured to be 9.48 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 0.9 kg/mol), proving the successful synthesis of the target product. It can be calculated that the molar content of the functional group in the copolyester is about 25%.
  • 10-Hydroxydecanoic acid (2.09 g) and lactide (8.00 g) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 10.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, the mixture was heated to 200°C, and an in-situ ring-opening-condensation cascade polymerization reaction was performed under a nitrogen atmosphere to synthesize the corresponding polymer. After 180 minutes of reaction, samples were taken every 60 minutes, and the reaction was stopped after 360 minutes.
  • Figure 12 is a size exclusion chromatogram of the copolyester obtained at the corresponding polymerization time.
  • the molecular weight after 360 minutes of reaction was measured to be 16.3 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 0.9 kg/mol), proving the successful synthesis of the target product. It can be calculated that the molar content of the functional group in the copolyester is about 17%.
  • Hydroxypivalic acid (1.13 g) and musk T (10.4 g) were added to a 100 ml three-necked flask, nitrogen was passed to remove oxygen, 14.0 ⁇ l of n-butyl titanate was added, mechanical stirring was performed, and the mixture was heated to 230°C.
  • In-situ ring-opening-condensation cascade polymerization was carried out under nitrogen atmosphere to synthesize the corresponding polymer. Samples were taken every 60 minutes during the reaction, and the reaction was stopped after 180 minutes.
  • Figure 13 is a size exclusion chromatogram of the copolyester obtained at the corresponding polymerization time.
  • the molecular weight after 180 minutes of reaction was measured to be 14.2 kg/mol, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 1.6 kg/mol), proving the successful synthesis of the target product. It can be calculated that the molar content of the functional group in the copolyester is about 20%.
  • Example 12 The copolyester PHPABT is synthesized by in-situ ring-opening-condensation cascade polymerization of hydroxypivalic acid and cyclic oligobutylene terephthalate.
  • Hydroxypivalic acid (0.71 g) and cyclic oligobutylene terephthalate (6.60 g) were added to a 100 ml three-necked flask, and 16.0 ⁇ l of n-butyl titanate was added. The mixture was mechanically stirred and heated to 250° C. The mixture was reacted for 10 minutes under a nitrogen atmosphere, and then vacuum polymerized for 45 minutes to finally synthesize the corresponding polymer.
  • the copolyester product was dissolved in a phenol/tetrachloroethane (3:2) mixed solvent, and the intrinsic viscosity of the sample was measured to be 0.55 deciliters per gram.
  • the corresponding viscosity-average molecular weight was calculated to be 14.3 kilograms per mole, which is much larger than the theoretical molecular weight of ring-opening polymerization (about 1.3 kilograms per mole), proving the successful synthesis of the target product.
  • the calculation shows that the molar content of the functional group in the copolyester is about 17%.
  • the pH value of the phosphate buffered saline solution is 7.2-7.4, wherein the components include 80.0 g/L of sodium chloride, 2.00 g/L of potassium chloride, 36.3 g/L of disodium hydrogen phosphate dodecahydrate, and 2.40 g/L of potassium dihydrogen phosphate; the phosphate buffered saline solution is divided into a group without lipase and a group with lipase (lipase name: Pseudomonas cepacia lipase, enzyme activity: 30.0 ⁇ 10 3 units per gram).
  • the PHPACL copolyester sample (molecular weight of 30.1 kg/mol) prepared in Example 2 was pressed into a 0.2 mm thick round slice. About 5.0 mg of the round slice was weighed and immersed in about 1.00 ml of phosphate buffered saline solution containing lipase (concentration: 1.00 mg/ml). The sample was placed at 37°C for degradation experiment. Another set of control experiments was set up in a phosphate buffered saline solution without lipase, and other conditions remained unchanged. When the predetermined number of days was reached, the sample was taken out. Rinse with distilled water, filter, dry, and use an electronic balance to measure the mass change. The experimental results are shown in Figures 14-16.
  • the degradation curve of the degradation mass of the copolyester (PHPACL) over time is shown in Figure 14.
  • the mass of the copolyester (PHPACL) in 37°C phosphate buffer solution does not decrease much in the absence of lipase; but its mass decreases rapidly under the action of lipase, and the remaining mass is about 68% (mass after degradation/initial mass ⁇ 100%) after 3 days of degradation, and it is almost completely degraded after 6 days, indicating that the copolyester (PHPACL) has good degradability.
  • the scanning electron micrograph of the copolyester degraded in phosphate buffered saline solution without lipase for 3 days is shown in Figure 15.
  • the surface is relatively smooth and no obvious etching is found.
  • the scanning electron micrograph of the copolyester degraded in phosphate buffered saline solution with lipase for 3 days is shown in Figure 16.
  • the surface of the copolyester is rough, with many voids and obvious erosion.

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Abstract

本发明公开了一种共聚酯及其制备方法，属于高分子材料制备领域。所述制备方法包括以下步骤：将羟基酸或羟基酸酯与环酯在催化剂存在下，升温到一定温度进行开环-缩合级联聚合，得到所述共聚酯；其中，所述环酯是具有环状结构的内酯、交酯或环状低聚二酸二醇酯。本发明的共聚酯的制备方法，可以一步合成具有高功能性基团含量的高分子量共聚酯。

Description

一种共聚酯及其制备方法 技术领域
本发明属于高分子材料制备领域，尤其是指一种共聚酯及其制备方法。
背景技术
近几十年来，聚酯由于其性价比高、生物相容性好、来源丰富等诸多优点，在纤维、包装材料、膜、工程塑料、可降解塑料及医用材料等方面得到了广泛应用。目前市售的聚酯产品主要包括芳香族聚酯如聚对苯二甲酸乙二醇酯(PET)和脂肪族聚酯如聚己二酸乙二醇酯(PEA)、聚乳酸(PLA)等产品。其中，脂肪族聚酯由于具有生物可降解性能，可替代不可降解的聚烯烃材料，成为目前的研究热点。但目前聚酯的品种较少，难以满足变化多端的市场需求，需要在其中引入功能性基团对其进行改性。此外，由于通常聚合物的性能与分子量具有正相关性，在某些方面，需要使用具有较高分子量的聚酯。
聚酯常见的合成方法主要是缩合聚合和开环聚合。开环聚合法通过提高单体和引发剂的比例来获得高分子量的共聚酯，但其功能性基团的引入比较困难，一般通过引发剂引入功能性基团，其含量很低，通常不超过1％摩尔分数，高分子量和高功能性基团难以兼得。若是通过单体来引入功能性基团，需要通过繁琐的合成步骤来获得功能性单体，增加了聚合方法的复杂性，并提高了成本。而缩合聚合法可以引入高含量功能性基团，但由于其聚合速度相对较慢，酯化和预缩聚占据较长时间，反应温度高、聚合时间长，存在较多副反应，不适合制备较高分子量的聚酯(一般分子量小于30千克每摩尔)。因此，现有的聚酯合成技术存在难以合成具有较高分子量的功能化聚酯的问题，导致难以对聚酯进行改性，限制了其进一步应用。
专利ZL201910245271.6公开了一种可降解脂肪族共聚酯的制备方法，通过以脂肪族大环二酸二醇酯和二醇进行开环-缩合级联聚合，制备得到可降解脂肪族共聚酯。共聚酯具有较高分子量的同时具有较高的功能性基团含量。但其使用小分子二醇或者大分子二醇作为引发剂进行共聚，并需要采用价格昂贵的大环二酸二醇酯如麝香T为单体，成本较高。
目前尚缺简单高效的制备具有较高功能性基团含量且具有较高分子量的低成本共聚酯的有效制备方法。为了适应社会的发展脚步，急需开发一种普适的在共聚酯中引入功能性基团的方法，使其满足更多应用领域的需求。
发明内容
为解决上述技术问题，本发明提供了一种共聚酯及其制备方法。具体制备方法：以羟基酸或羟基酸酯，如羟基特戊酸、10-羟基癸酸、扁桃酸、蓖麻油酸、4-羟甲基苯甲酸、乳酸甲酯、羟基特戊酸甲酯、乳酸乙酯、羟基己酸乙酯等同时含有羟基和羧基或羧酸酯的化合物，与环状内酯如γ-戊内酯、己内酯、十六内酯等或环状交酯如乙交酯、丙交酯等或环状低聚二酸二醇酯如麝香T(1,13-十三烷二酸乙二撑酯)、环状寡聚对苯二甲酸乙二醇酯、环状寡聚对苯二甲酸丙二醇酯、环状寡聚对苯二甲酸丁二醇酯等单体，在催化剂存在下通过开环-缩合级联聚合(PROP)合成共聚酯。通过采用开环-缩合级联聚合法，使得开环聚合反应和缩合聚合反应在同一个体系中级联进行，从而一步合成了共聚酯。本发明合成的含有脂肪族聚酯片段的共聚酯兼具良好的生物相容性和可生物降解性。
通过使用具有不同结构的羟基酸或羟基酸酯与环酯共聚，可以聚合得到具有较高功能性基团含量且具有较高分子量的共聚酯，进而调控所得共聚酯材料的性能，使其在药物载体、包装材料、组织工程以及医疗器械等领域得到广泛应用。
本发明的第一个目的在于提供一种共聚酯，所述共聚酯的化学结构式如下：
其中，R来自环酯，R5来自羟基酸或羟基酸酯，R4选自CH3、CH3CH2或H；m为2～40，n为2～200。
本发明的第二个目的在于提供一种共聚酯的制备方法，包括以下步骤：利用环酯与羟基酸或羟基酸酯在催化剂作用下，通过开环-缩合级联聚合得到所述共聚酯。其中，羟基酸或羟基酸酯先与环酯发生开环聚合反应，生成较低分子量的一端为羟基，一端为羧基或羧酸酯结构的共聚酯，然后末端的羟基与羧基或羧酸酯发生缩合聚合，合成较高分子量的共聚酯。本发明可通过调控羟基酸或羟基酸酯与环酯的比例调控相应功能性基团在共聚酯中的含量，并可制备具有高分子量的共聚酯。合成的含有脂肪族聚酯片段的共聚酯具有优异的生物相容性和可生物降解性。
在本发明的一个实施例中，所述环酯为内酯、交酯或环状低聚二酸二醇酯，所述环酯的化学结构通式为：
其中，R为(CH2)aCHR1时，所述环酯为内酯，a为2～14中的任一整数；R1为H或CH3；
R为CHR2OCOCHR2时，所述环酯为交酯，R2为H或CH3；
R为[R3COO(CH2)cOCO]p-1R3COO(CH2)c时，所述环酯为环状低聚二酸二醇酯，R3为Ph或(CH2)d；c为2～4中任一整数，d为2～12中任一整数，p为1～15中任一整数。
在本发明的一个实施例中，环酯选自γ-戊内酯、己内酯、十六内酯、乙交酯、丙交酯、麝香T(1,13-十三烷二酸乙二撑酯)、环状寡聚对苯二甲 酸乙二醇酯、环状寡聚对苯二甲酸丙二醇酯、环状寡聚对苯二甲酸丁二醇酯等。
进一步的，环酯为环状内酯时，优选为来源广泛廉价易得的己内酯；环酯为环状交酯时，优选为应用广泛的丙交酯；环酯为环状低聚二酸二醇酯时，优选为可以在市场上方便购得的麝香T(1,13-十三烷二酸乙二撑酯)和环状寡聚对苯二甲酸丁二醇酯。当使用的环酯的重复单元结构与羟基酸或羟基酸酯的相应结构不同时，得到的产物为共聚酯，当其相同时，得到的为聚酯均聚物。
在本发明的一个实施例中，所述共聚酯通过羟基酸或羟基酸酯引入功能性基团。
在本发明的一个实施例中，所述功能性基团选自烷基链、芳基和烯基中的一种或多种。
在本发明的一个实施例中，所述羟基酸和羟基酸酯为同时含有羟基和羧基或羧酸酯的化合物，如羟基特戊酸、10-羟基癸酸、扁桃酸、羟基特戊酸、蓖麻油酸、4-羟甲基苯甲酸、乳酸甲酯、羟基特戊酸甲酯、乳酸乙酯、羟基己酸乙酯等。
进一步的所述羟基酸和羟基酸酯优选含有脂肪族烷基链的10-羟基癸酸、羟基特戊酸、羟基己酸乙酯、乳酸甲酯、含有苯环的4-羟甲基苯甲酸、含有双键的蓖麻油酸等。
在本发明的一个实施例中，所述共聚酯具有高分子量的同时具有高的功能性基团含量，所述功能性基团在共聚酯中结构基元中的摩尔含量可达33％；所述共聚酯的分子量可达40～60千克每摩尔。
在本发明的一个实施例中，所述催化剂选自钛酸酯化合物。
在本发明的一个实施例中，所述环酯与羟基酸或羟基酸酯的摩尔比为2～40：1。
在本发明的一个实施例中，所述催化剂的用量为总投料质量的0.01％～ 1％。
在本发明的一个实施例中，所述开环-缩合级联聚合反应条件：反应温度为180～260℃，反应时间为30～360分钟。其中，所述级联聚合反应可在同一温度下进行，也可以通过逐步升温的方式进行。原位开环-缩合级联聚合反应在氮气氛围或真空条件下进行；反应结束后无需提纯，即可得到产物共聚酯。
本发明的第三个目的在于提供所述共聚酯在可降解聚酯中的应用。
本发明的共聚酯结构中含有脂肪族聚酯片段时，具有生物可降解性，并且降解速度受温度、酶等条件控制。
本发明聚合机理为原位开环-缩合级联聚合过程，即羟基酸或羟基酸酯先对环酯单体进行开环聚合得到一端为羟基一端为羧基或羧酸酯的共聚酯，共聚酯可继续引发环酯的开环聚合，也可相互之间进行缩合聚合，生成更高分子量的共聚酯；反应产物即为共聚酯，无需提纯分离。
本发明的上述技术方案相比现有技术具有以下优点：
本发明的共聚酯可通过控制聚合时间与温度来调控分子量，可达54千克每摩尔，功能性基团在共聚酯中摩尔含量可达33％，有效解决了现有技术聚酯作为生物材料分子量偏低、难以引入功能性基团且结构单一的问题。
本发明的共聚酯使用脂肪族环酯为单体时，或合成的共聚酯结构中含有脂肪族聚酯片段时，具有可生物降解性，并且降解速度受温度、酶等条件控制。在37℃下在磷酸缓冲盐溶液中(pH 7.2～7.4)质量、分子量随时间缓慢降低，在37℃下在含脂肪酶的磷酸缓冲盐溶液中(pH 7.2～7.4)质量、分子量迅速降低，6天便基本完全降解，在4℃冷藏条件下质量、分子量基本不变。
本发明提供的原位开环-缩合级联聚合法旨在将开环聚合反应和缩合聚合反应在同一个体系中级联进行，制备得到具有较高功能性基团含量且具有较高分子量的共聚酯。现有技术通过环酯开环聚合制备的聚酯/共聚酯无法 在实现高分子量的同时具备高功能性基团含量。并且本方法具有反应步骤简单，分子量高且可控，无需后处理，可以大量合成等优点。本发明使用脂肪族环酯为单体制备的聚酯/共聚酯具有可生物降解性，并且降解可通过温度、酶含量等调节，这些技术效果具体参见实施例。从而，本发明公开了上述共聚酯的制备方法。
本发明通过将羟基酸或羟基酸酯与环酯进行原位开环-缩合级联聚合方法合成了共聚酯，解决了传统聚合方法难以合成高功能性基团含量的高分子量聚酯的问题；可使用的单体范围广，可以广泛应用于聚酯的合成，简单方便地制备功能性共聚酯；并且羟基酸或羟基酸酯在自然界中广泛存在且种类繁多，通过在羟基酸或羟基酸酯中引入功能性基团，可以方便地制备功能性共聚酯；合成的含有脂肪族聚酯片段的共聚酯具有可生物降解性能，是一类绿色环境友好材料，具有较大的应用价值。
附图说明
为了使本发明的内容更容易被清楚的理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中
图1为本发明共聚酯的合成路线图；
图2为由10-羟基癸酸和己内酯进行原位开环-缩合级联聚合，氮气下在220℃反应不同时间得到的共聚酯(PHDACL)的体积排除色谱图；
图3为由羟基特戊酸和己内酯进行原位开环-缩合级联聚合，氮气下在220℃反应不同时间得到的共聚酯(PHPACL)的体积排除色谱图；
图4为由羟基特戊酸和己内酯进行原位开环-缩合级联聚合，氮气下在220℃反应不同时间得到的共聚酯(PHPACL)的分子量随时间变化图；
图5为由4-羟甲基苯甲酸和己内酯进行原位开环-缩合级联聚合，氮气下在220℃反应不同时间得到的共聚酯(PHBACL)的分子量随时间变化图；
图6为由蓖麻油酸和己内酯进行原位开环-缩合级联聚合，氮气下在220℃反应得到的共聚酯(PRACL)的体积排除色谱图；
图7为由乳酸甲酯和己内酯进行原位开环-缩合级联聚合，氮气下在210℃反应不同时间得到的共聚酯(PMLACL)的分子量随时间变化图；
图8为由羟基己酸乙酯和己内酯进行原位开环-缩合级联聚合，氮气下在210℃反应得到的聚酯(PCL)的体积排除色谱图；
图9为由羟基己酸乙酯和己内酯进行原位开环-缩合级联聚合，抽真空下在220℃反应得到的聚酯(PCL)的体积排除色谱图；
图10为由10-羟基癸酸和γ-戊内酯进行原位开环-缩合级联聚合，氮气下在210℃反应不同时间得到的共聚酯(PHDAVL)的体积排除色谱图；
图11为由羟基特戊酸和十六内酯进行原位开环-缩合级联聚合，氮气下在230℃反应不同时间得到的共聚酯(PHPADN)的体积排除色谱图；
图12为由10-羟基癸酸和丙交酯进行原位开环-缩合级联聚合，氮气下在200℃反应不同时间得到的共聚酯(PHDALA)的体积排除色谱图；
图13为由羟基特戊酸和麝香T进行原位开环-缩合级联聚合，氮气下在230℃反应不同时间得到的共聚酯(PHPAEB)的体积排除色谱图；
图14为共聚酯(PHPACL)在37℃磷酸缓冲盐溶液中，在不含脂肪酶和含脂肪酶条件下的质量随时间变化的降解曲线图；
图15为共聚酯(PHPACL)在37℃磷酸缓冲盐溶液中，在不含脂肪酶条件下的降解3天的表面的扫描电子显微镜图；
图16为共聚酯(PHPACL)在37℃磷酸缓冲盐溶液中，在含脂肪酶条件下降解3天的表面的扫描电子显微镜图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
参照图1所示：本发明共聚酯的制备方法，即通过原位开环-缩合级联 聚合方法制备共聚酯，包括两个过程，1)羟基酸或羟基酸酯对环酯单体进行开环聚合反应，生成共聚酯羟基酸或共聚酯羟基酸酯，2)共聚酯羟基酸或共聚酯羟基酸酯可以继续对环酯进行开环聚合反应，也可以相互之间进行缩合聚合，得到一系列共聚酯。
实施例1由10-羟基癸酸和己内酯进行原位开环-缩合级联聚合合成共聚酯PHDACL
在100毫升的三口烧瓶中加入10-羟基癸酸(14.4克)和己内酯(17.0毫升)，通氮气除去氧气，加入32.0微升的钛酸正丁酯，机械搅拌，加热至190℃，在氮气氛围下进行原位开环-缩合级联聚合，合成相应的聚合物。反应过程中每隔60分钟取样，180分钟后停止反应。
图2为聚合相应时间得到共聚酯的体积排除色谱图。聚合60分钟测得的分子量为21.1千克每摩尔，120分钟测得的分子量为40.5千克每摩尔，180分钟测得的分子量为54.4千克每摩尔，远大于开环聚合的理论分子量(约0.4千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中的摩尔含量约为33％。
实施例2由羟基特戊酸和己内酯进行原位开环-缩合级联聚合合成共聚酯PHPACL
在100毫升的三口烧瓶中加入羟基特戊酸(0.90克)和己内酯(17.0毫升)，通氮气除去氧气，加入18.0微升的钛酸正丁酯，机械搅拌，加热至220℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应过程中每隔30分钟取样，180分钟后停止反应。
图3为聚合相应时间得到共聚酯的体积排除色谱图。图4为测得的共聚酯分子量随时间变化图，共聚酯的分子量远大于开环聚合的理论分子量(约3.0千克每摩尔)，证明了目标产物的成功合成。并且其分子量可通过控制聚合时间而控制。由计算可得，功能性基团在共聚酯中摩尔含量约为5％。
实施例3由4-羟甲基苯甲酸和己内酯进行原位开环-缩合级联聚合合成共聚酯PHBACL
在100毫升的三口烧瓶中加入4-羟甲基苯甲酸(1.17克)和己内酯(8.50毫升)，通氮气除去氧气，加入10.0微升的钛酸正丁酯，机械搅拌，加热至220℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应过程中每隔60分钟取样，180分钟后停止反应。
图5为测得的共聚酯分子量随时间变化图，其分子量远大于开环聚合的理论分子量(约1.3千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为9％。
实施例4由蓖麻油酸和己内酯进行原位开环-缩合级联聚合合成共聚酯PRACL
在100毫升的三口烧瓶中加入蓖麻油酸(2.29克)和己内酯(8.50毫升)，通氮气除去氧气，加入11.0微升的钛酸正丁酯，机械搅拌，加热至220℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应过程中取样，200分钟后停止反应。
图6为聚合200分钟得到共聚酯的体积排除色谱图。聚合200分钟测得的分子量为20.6千克每摩尔，其分子量远大于开环聚合的理论分子量(约1.4千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为9％。
实施例5由乳酸甲酯和己内酯进行原位开环-缩合级联聚合合成共聚酯PMLACL
在100毫升的三口烧瓶中加入乳酸甲酯(1.61克)和己内酯(17.0毫升)，通氮气除去氧气，加入10.0微升的钛酸正丁酯，机械搅拌，加热至210℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应过程中每隔30分钟取样，120分钟后停止反应。
图7为测得的共聚酯分子量随时间变化图，其分子量远大于开环聚合的理论分子量(约1.3千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为17％。
实施例6由羟基己酸乙酯和己内酯进行原位开环-缩合级联聚合合成聚酯PCL
在100毫升的三口烧瓶中加入羟基己酸乙酯(1.77克)和己内酯(8.5毫升)，通氮气除去氧气，加入10.0微升的钛酸正丁酯，机械搅拌，加热至210℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应30分钟后停止。
图8为聚合相应时间得到聚酯的体积排除色谱图。聚合30分钟测得的分子量为49.4千克每摩尔，远大于开环聚合的理论分子量(约0.7千克每摩尔)，证明了目标产物的成功合成。
实施例7由羟基己酸乙酯和己内酯进行原位开环-缩合级联聚合合成聚酯PCL
在100毫升的单口烧瓶中加入羟基己酸乙酯(1.22克)和己内酯(8.5毫升)，通氮气除去氧气，加入5.0微升的钛酸正丁酯，机械搅拌，加热至210℃，在氮气氛围下反应15分钟，然后抽真空聚合90分钟，最终生合成相应的聚合物。
图9为聚合相应时间得到聚酯的体积排除色谱图。测得聚合90分钟的分子量为34.4千克每摩尔，远大于开环聚合的理论分子量(约0.9千克每摩尔)，证明了目标产物的成功合成。
实施例8由10-羟基癸酸和γ-戊内酯进行原位开环-缩合级联聚合合成共聚酯PHDAVL
在100毫升的三口烧瓶中加入10-羟基癸酸(2.61克)和γ-戊内酯(4.16克)，通氮气除去氧气，加入7.0微升的钛酸正丁酯，机械搅拌，加热至210℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应300分钟后停止。
图10为聚合相应时间得到共聚酯的体积排除色谱图。测得反应300分钟的分子量为22.7千克每摩尔，远大于开环聚合的理论分子量(约0.5千克 每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为25％。
实施例9由羟基特戊酸和十六内酯进行原位开环-缩合级联聚合合成共聚酯PHPADN
在100毫升的三口烧瓶中加入羟基特戊酸(0.46克)和十六内酯(3.00克)，通氮气除去氧气，加入7.0微升的钛酸正丁酯，机械搅拌，加热至230℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应180分钟后停止。
图11为聚合相应时间得到共聚酯的体积排除色谱图。测得反应180分钟的分子量为9.48千克每摩尔，远大于开环聚合的理论分子量(约0.9千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为25％。
实施例10由10-羟基癸酸和丙交酯进行原位开环-缩合级联聚合合成共聚酯PHDALA
在100毫升的三口烧瓶中加入10-羟基癸酸(2.09克)和丙交酯(8.00克)，通氮气除去氧气，加入10.0微升的钛酸正丁酯，机械搅拌，加热至200℃，在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应180分钟后，每隔60分钟取样，360分钟后停止反应。
图12为聚合相应时间得到共聚酯的体积排除色谱图。测得反应360分钟的分子量为16.3千克每摩尔，远大于开环聚合的理论分子量(约0.9千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为17％。
实施例11由羟基特戊酸和麝香T进行原位开环-缩合级联聚合合成共聚酯PHPAEB
在100毫升的三口烧瓶中加入羟基特戊酸(1.13克)和麝香T(10.4克)，通氮气除去氧气，加入14.0微升的钛酸正丁酯，机械搅拌，加热至230℃， 在氮气氛围下进行原位开环-缩合级联聚合反应，合成相应的聚合物。反应过程中每隔60分钟取样，180分钟后停止反应。
图13为聚合相应时间得到共聚酯的体积排除色谱图。测得反应180分钟的分子量为14.2千克每摩尔，远大于开环聚合的理论分子量(约1.6千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为20％。
实施例12由羟基特戊酸和环状寡聚对苯二甲酸丁二醇酯进行原位开环-缩合级联聚合合成共聚酯PHPABT。
在100毫升的三口烧瓶中加入羟基特戊酸(0.71克)和环状寡聚对苯二甲酸丁二醇酯(6.60克)，加入16.0微升的钛酸正丁酯，机械搅拌，加热至250℃，在氮气氛围下反应10分钟，然后抽真空聚合45分钟，最终合成相应的聚合物。
将共聚酯产物溶于苯酚/四氯乙烷(3:2)混合溶剂，测得样品的特性粘度为0.55分升每克，由此计算得到其相应粘均分子量为14.3千克每摩尔，远大于开环聚合的理论分子量(约1.3千克每摩尔)，证明了目标产物的成功合成。由计算可得，功能性基团在共聚酯中摩尔含量约为17％。
测试例1共聚酯(PHPACL)在37℃磷酸缓冲盐溶液中，不含脂肪酶和含脂肪酶条件下的降解测试
磷酸缓冲盐溶液pH 7.2～7.4，其中成分包括浓度为80.0克每升的氯化钠、2.00克每升的氯化钾、36.3克每升的十二水合磷酸氢二钠、2.40克每升的磷酸二氢钾；磷酸缓冲盐溶液分为不含脂肪酶组和含脂肪酶组(脂肪酶名称：洋葱假单胞菌脂肪酶，酶活：30.0×103单位每克)。
将实施例2制备的PHPACL共聚酯样品(分子量为30.1千克每摩尔)压成0.2毫米厚的圆形小薄片，称取5.0毫克左右的圆形小薄片浸没至1.00毫升左右含脂肪酶(浓度：1.00毫克每毫升)的磷酸缓冲盐溶液中，将试样放置在37℃的环境下进行降解实验。另设置一组对照实验，在不含脂肪酶的磷酸缓冲盐溶液中进行，其它条件不变。待其达到预定天数时，取出样品， 用蒸馏水淋洗、过滤、晾干，利用电子天平称量其质量变化。实验结果见图14-16。
共聚酯(PHPACL)降解的质量随时间变化的降解曲线图见图14。由图可知，共聚酯(PHPACL)在37℃磷酸缓冲盐溶液中，不含脂肪酶的条件下质量减少不大；而在脂肪酶的作用下其质量迅速下降，降解3天时剩余质量约68％(降解后质量/初始质量×100％)，6天后几乎完全降解，说明共聚酯(PHPACL)具有良好的可降解性。
共聚酯在不含脂肪酶条件下的磷酸缓冲盐溶液中降解3天的扫描电子显微镜图见图15，表面较为光滑，没有发现明显刻蚀。在含脂肪酶条件下的磷酸缓冲盐溶液中降解3天的扫描电子显微镜图见图16，共聚酯表面粗糙，有许多空洞，可见明显侵蚀。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种共聚酯，其特征在于，所述共聚酯的化学结构式如下：
    其中，R来自环酯，R5来自羟基酸或羟基酸酯，R4选自CH3、CH3CH2或H；m为2～40，n为2～200。
  2. 一种共聚酯的制备方法，其特征在于，包括以下步骤：利用环酯与羟基酸或羟基酸酯在催化剂作用下，通过开环-缩合级联聚合得到所述共聚酯。
  3. 根据权利要求2所述的制备方法，其特征在于，所述环酯为内酯、交酯或环状低聚二酸二醇酯，所述环酯化学结构通式为：
    其中，R为(CH2)aCHR1时，所述环酯为内酯，a为2～14中的任一整数；R1为H或CH3；
    R为CHR2OCOCHR2时，所述环酯为交酯，R2为H或CH3；
    R为[R3COO(CH2)cOCO]p-1R3COO(CH2)c时，所述环酯为环状低聚二酸二醇酯，R3为Ph或(CH2)d；c为2～4中任一整数，d为2～12中任一整数，p为1～15中任一整数。
  4. 根据权利要求2所述的制备方法，其特征在于，所述共聚酯通过羟基酸或羟基酸酯引入功能性基团。
  5. 根据权利要求2所述的制备方法，其特征在于，所述共聚酯具有高分子量的同时具有高的功能性基团含量，所述功能性基团在共聚酯中结构基元中的 摩尔含量可达33％；所述共聚酯的分子量可达40～60千克每摩尔。
  6. 根据权利要求2所述的制备方法，其特征在于，所述催化剂选自钛酸酯化合物。
  7. 根据权利要求2所述的制备方法，其特征在于，所述环酯与羟基酸或羟基酸酯的摩尔比为2～40：1。
  8. 根据权利要求2所述的制备方法，其特征在于，所述催化剂的用量为总投料质量的0.01％～1％。
  9. 根据权利要求2所述的制备方法，其特征在于，所述开环-缩合级联聚合反应条件：反应温度为180℃～260℃，反应时间为30分钟～360分钟。
  10. 权利要求1中所述共聚酯在可降解聚酯中的应用。
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