CN111303390A - Biodegradable polyester-carbonate elastomer and preparation method thereof - Google Patents

Biodegradable polyester-carbonate elastomer and preparation method thereof Download PDF

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CN111303390A
CN111303390A CN202010217260.XA CN202010217260A CN111303390A CN 111303390 A CN111303390 A CN 111303390A CN 202010217260 A CN202010217260 A CN 202010217260A CN 111303390 A CN111303390 A CN 111303390A
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carbonate
polyester
elastomer
acetate
biodegradable polyester
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吴林波
谢鸿洲
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Zhejiang University ZJU
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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

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Abstract

The invention provides a biodegradable polyester-carbonate elastomer and a preparation method thereof, wherein the elastomer is a multi-component random copolymer prepared by reacting 20-70 wt% of aromatic polyester component, 30-80 wt% of aliphatic polycarbonate component and 0-5 wt% of cross-linking agent. The polyester-carbonate elastomer prepared by the invention has the structural characteristics of rigidity, flexibility, symmetry, asymmetry, aroma, fat, short carbon chain and long carbon chain matching, so that the polyester-carbonate elastomer has excellent elasticity and mechanical strength, and also has excellent biodegradability and higher gas barrier property than the traditional airtight rubber. The biodegradable polyester-carbonate elastomer provided by the invention is prepared by melt polycondensation, has a simple and convenient preparation process, is environment-friendly, and is easy to realize industrialization.

Description

Biodegradable polyester-carbonate elastomer and preparation method thereof
Technical Field
The invention relates to the field of biodegradable elastomers, in particular to a biodegradable polyester-carbonate elastomer and a preparation method thereof, and more particularly relates to a biodegradable high-gas-barrier polyester-carbonate elastomer and a preparation method thereof.
Background
The elastomer is generally a high polymer material which has a glass transition temperature lower than room temperature, an elongation at break of not less than 50%, is easily subjected to large deformation under the action of an external force, and has good deformation recovery after the external force is removed. Elastomers are largely classified into thermosetting elastomers, i.e., chemically crosslinked vulcanized rubbers, and thermoplastic elastomers, depending on whether they are plasticized or not. As one of the three synthetic materials, the elastomer is widely applied to the fields of tires, sealing elements, shock-absorbing elements, rubber tubes, adhesive tapes, rubber rollers, linings, sealing gaskets, shock-absorbing products, brake cups, printing rubber rollers, cable jackets and the like, and makes important contribution to improving the production and living standard of people.
At present, most elastomers, such as polyolefin elastomers, polystyrene elastomers, polyurethane elastomers, silicone rubbers, fluororubbers, natural rubbers, butadiene rubbers, styrene butadiene rubbers, butyl rubbers, chloroprene rubbers and the like, do not have biodegradability, and the elastomers discarded after the service life is over cause serious environmental pollution problems, so that the sustainable development is not facilitated. In order to solve this problem, some biodegradable elastomers have been reported in recent years, for example, CN105330828A and CN104497318A disclose a biodegradable aliphatic polyester elastomer, CN105524259A discloses a biodegradable aliphatic-aromatic copolyester elastomer, CN107312165A discloses a biodegradable aliphatic-aromatic copolyester elastomer with pendant groups, and CN102115529A discloses a biodegradable aliphatic-aromatic copolyester-polyether elastomer. Among them, CN105330828A, CN107312165A, CN104497318A, CN102115529A disclose biodegradable elastomers having a block copolymerization structure, and CN105524259a discloses biodegradable elastomers having a random copolymerization structure.
On the other hand, elastomers are commonly used as air-tight or gas barrier materials, such as tires, seals, sealants, stoppers, rubber films, hoses, tapes, sealing gaskets, and the like. As the gas-tight material, high gas barrier properties or gas tightness are required. However, the elastomer material has low glass transition temperature, strong molecular chain mobility and generally low gas barrier property. Among the rubbers for tires, butyl rubber is most preferred for its air impermeability, generally having an oxygen permeability coefficient of about 1.5barrer and a carbon dioxide permeability coefficient of about 2barrer at ambient temperature. As a sealant, epichlorohydrin rubber has better air impermeability than butyl rubber, and has an oxygen permeability coefficient of about 0.3barrer and a carbon dioxide permeability coefficient of about 3 barrer. However, these elastomers still have gas barrier properties inferior to those of common plastics, such as PET, and are also lacking in biodegradability. There has been no report of an elastomer having a gas barrier property or gas impermeability higher than that of butyl rubber or chlorohydrin rubber, particularly no report of a biodegradable elastomer having a high gas barrier property.
Disclosure of Invention
The invention provides a biodegradable polyester-carbonate elastomer and a preparation method thereof, aiming at the problems that the existing elastomer is insufficient in gas barrier property and the elastomer with higher gas barrier property is lack of biodegradability, and the obtained polyester-carbonate elastomer has excellent elasticity, biodegradability and gas barrier property.
The technical scheme adopted by the invention is as follows:
a biodegradable polyester-carbonate elastomer is a multicomponent random copolymer prepared by the reaction of 20-70 wt% of aromatic polyester component, 30-80 wt% of aliphatic polycarbonate component and 0-5 wt% of cross-linking agent;
the aromatic polyester component consists of (A) asymmetric aromatic dibasic acid, (B) short-chain dihydric alcohol or alicyclic dihydric alcohol with the main chain carbon atom number not more than 4 and optionally (C) short-chain polyhydric alcohol;
the aliphatic polycarbonate component is composed of (D) carbonic diester and (E) C5-C12α, omega-straight chain diol is subjected to ester exchange reaction to prepare aliphatic polycarbonate oligomer;
or, the aliphatic polycarbonate component is composed of (D) carbonic acid diester and (E) C5-C12α, an aliphatic polycarbonate oligomer having a number average molecular weight of not more than 5000g/mol, which is obtained by subjecting an omega-linear diol to transesterification and polycondensation.
The biodegradable polyester-carbonate elastomer has biodegradability and high gas barrier property, and has an oxygen permeability coefficient of not higher than 1.5barrer and a carbon dioxide permeability coefficient of not higher than 2.0 barrer. Preferably, it has an oxygen permeability coefficient of not higher than 0.3barrer and a carbon dioxide permeability coefficient of not higher than 0.2 barrer.
The aromatic dibasic acid with the asymmetric structure is selected from one or more of furan dicarboxylic acid or diester thereof, isophthalic acid or diester thereof, and phthalic acid or diester thereof.
The short-chain dihydric alcohol with the main chain carbon atom number not more than 4 is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2-methyl-1, 3-propanediol and neopentyl glycol.
The alicyclic diol is selected from one or two of 1, 4-cyclohexanedimethanol and 1, 4-cyclohexanediol.
The short-chain polyol is selected from one or more of glycerol, trimethylolpropane and pentaerythritol.
The carbonic diester is selected from dimethyl carbonate, diethyl carbonate and diphenyl carbonate.
Said C5-C12The α, omega-linear diol of (1) is selected from one or more of 1, 5-pentanediol, 1, 6-hexanediol, and 1, 10-decanediol.
Preferably, the aliphatic polycarbonate oligomer is selected from one or more of 1, 5-pentanediol polycarbonate, 1, 6-hexanediol polycarbonate, and 1, 5-pentanediol-co-1, 6-hexanediol polycarbonate.
The number average molecular weight of the aliphatic polycarbonate oligomer is not more than 2000 g/mol.
The cross-linking agent is diisocyanate or polyisocyanate.
The invention further discloses a preparation method of the biodegradable polyester-carbonate elastomer, which comprises the following steps:
(1) uniformly mixing the aromatic polyester component, a catalyst X and the aliphatic polycarbonate component according to the molar ratio of A to B to C of 1: 1.05-2: 0-0.05, and carrying out esterification or ester exchange reaction at the temperature of 170-230 ℃ for 2-4 hours;
or, the aromatic polyester component and the catalyst X are uniformly mixed according to the molar ratio of A to B to C of 1: 1.05-2: 0-0.05, the aromatic polyester oligomer is prepared by esterification or ester exchange reaction for 2-4 hours at the temperature of 230 ℃ of 170-;
(2) the product prepared in the step (1) is subjected to reduced pressure copolycondensation at the temperature of 180 ℃ and 240 ℃ under high vacuum, and the reaction is carried out for 2 to 6 hours.
The above preparation method further comprises the step (3): and (3) mixing the product prepared in the step (2) with a cross-linking agent, and then carrying out cross-linking reaction.
The catalyst X is one or more of n-butyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silicon dioxide/titanium dioxide compound, a silicon dioxide/titanium dioxide/nitrogen-containing compound and a silicon dioxide/titanium dioxide/phosphorus-containing compound.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the biodegradable polyester-carbonate elastomer provided by the invention contains ester bonds and carbonate bonds simultaneously, and has the structural characteristics of rigidity, flexibility, symmetry, asymmetry, aroma, fat, short carbon chain and long carbon chain matching, so that the biodegradable polyester-carbonate elastomer has excellent elasticity and also keeps excellent mechanical strength; the random rather than block copolymeric structure makes it less expensive to prepare elastomers than block copolymeric structures.
(2) The biodegradable polyester-carbonate elastomer provided by the invention has excellent biodegradability due to the specific random copolymerization structure and composition.
(3) The biodegradable polyester-carbonate elastomer provided by the invention has higher gas barrier property or air tightness than traditional airtight rubbers such as butyl rubber, chlorohydrin rubber and the like, and the oxygen permeability coefficient is not higher than 1.5barrer and the carbon dioxide permeability coefficient is not higher than 2.0 barrer.
(4) The biodegradable polyester-carbonate elastomer provided by the invention can be a thermoplastic elastomer or a thermosetting elastomer, and the performance of the biodegradable polyester-carbonate elastomer can be adjusted in a wide range.
(5) The biodegradable polyester-carbonate elastomer provided by the invention has the advantages of simple and convenient preparation process, environment-friendly process and easy realization of industrialization.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a sample prepared in example 6;
figure 2 is a tensile curve for the samples prepared in example 4 and example 6.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Conventional elastomers are mostly triblock or multiblock copolymers, such as polystyrene elastomers and polyurethane elastomers. Common polyester elastomers (actually polyester-ether elastomers) are also segmented copolymers, wherein polyester is a hard segment, polyether is a soft segment, and the segmented copolymer is prepared by directly participating in copolycondensation reaction by using polyether glycol macromonomer as the soft segment. However, unlike polyester-ether elastomers, polyester-ester or polyester-carbonate elastomers having a multiblock structure are often difficult to obtain by direct participation in a copolycondensation reaction of aliphatic polyester diols or polycarbonate diols as soft segments. This is because an exchange reaction easily occurs between an ester bond and an ester bond or an ester bond and a carbonate bond, and thus a copolymer having a random copolymerization structure is often obtained, and it is difficult to obtain a desired multiblock copolymer. The synthesis of polyester-ester or polyester-carbonate segmented copolymer elastomers often requires the synthesis of hydroxyl-terminated polyester oligomers and hydroxyl-terminated polycarbonate oligomers, which are then chain extended/coupled with diisocyanates, or the use of high molecular weight polyesters and high molecular weight polycarbonates as starting materials, by controlling the reaction temperature and time, to produce segmented copolymers by a moderate exchange process but avoiding excessive exchange reactions, such as the polyester-carbonate elastomers disclosed in CN 101605833B, CN 101341186B. Both of these processes are obviously more complex, especially the latter requiring the initial preparation of high molecular weight polyesters and polycarbonates, the more costly procedure, and the difficulty of obtaining pure multiblock copolymers, the product being in fact a mixture of multiblock copolymers and homopolymers.
On the other hand, if one segment of the multi-block copolymer is not biodegradable, the whole multi-block copolymer cannot be completely biodegradable, for example, the multi-block copolymer composed of PBT segment and aliphatic polyester or polycarbonate segment, because the PBT segment cannot be biodegradable, the whole multi-block copolymer can be only partially biodegradable, but not completely biodegradable. While random copolymers are not, as in PBAT copolyesters, fully biodegradable in a suitable composition range. Furthermore, the gas barrier properties of the conventional elastomers are generally low, and it is difficult to meet practical application requirements.
Accordingly, the present invention is directed to a random copolyester-carbonate elastomeric material that is simple in synthesis process, completely biodegradable, and has high gas barrier or gas impermeability.
The invention provides a biodegradable polyester-carbonate elastomer, which is a multi-component random copolymer prepared by reacting 20-70 wt% of aromatic polyester component, 30-80 wt% of aliphatic polycarbonate component and 0-5 wt% of cross-linking agent;
the aromatic polyester component consists of (A) asymmetric aromatic dibasic acid, (B) short-chain dihydric alcohol or alicyclic dihydric alcohol with the main chain carbon atom number not more than 4 and optionally (C) short-chain polyhydric alcohol;
the aliphatic polycarbonate component is composed of (D) carbonic diester and (E) C5-C12α, omega-straight chain diol is subjected to ester exchange reaction to prepare aliphatic polycarbonate oligomer;
or, the aliphatic polycarbonate component is composed of (D) carbonic acid diester and (E) C5-C12α, an aliphatic polycarbonate oligomer having a number average molecular weight of not more than 5000g/mol, which is obtained by subjecting an omega-linear diol to transesterification and polycondensation.
In the invention, the aromatic polyester component refers to a monomer mixture capable of synthesizing aromatic polyester, and specifically comprises (A) asymmetric aromatic dibasic acid, (B) short-chain dihydric alcohol or alicyclic dihydric alcohol with the main chain carbon atom number not more than 4, and optionally (C) short-chain polyhydric alcohol.
Wherein, the aromatic dibasic acid monomer (A) with asymmetric structure is selected from the group known by the technical personnel in the field, for example, one or more of furan dicarboxylic acid or diester thereof, isophthalic acid or diester thereof, and phthalic acid or diester thereof can be selected. Preferably, the aromatic dibasic acid monomer with the asymmetric structure is selected from furan dicarboxylic acid or diester thereof, isophthalic acid or diester thereof. More preferably, the aromatic dibasic acid monomer with asymmetric structure is selected from furan dicarboxylic acid or diester thereof.
Wherein, the short-chain diol monomer (B) is selected from diols with the main chain carbon atom number not more than 4, which are well known by the technical personnel in the field, and ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2-methyl-1, 3-propylene glycol or neopentyl glycol can be used. Preferably, the short-chain diol monomer is selected from ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
Wherein, the alicyclic diol component monomer (B) is selected from those known in the art, for example, 1, 4-cyclohexanedimethanol or 1, 4-cyclohexanediol, etc.
Wherein, the short-chain polyol monomer (C) is selected from the group known to those skilled in the art, and can be selected from glycerol, trimethylolpropane or pentaerythritol.
In the present invention, the aliphatic polycarbonate component is composed of (D) a carbonic acid diester and (E) C5-C12α, omega-straight chain diol is prepared into aliphatic polycarbonate oligomer through ester exchange reaction.
Specifically, the aliphatic polycarbonate oligomer is prepared from (D) carbonic acid diester and (E) C5-C12α, the omega-straight chain diol is prepared by uniformly mixing the omega-straight chain diol with the mol ratio D: E being 1: 0.5-2, and carrying out transesterification reaction for 2-8 hours at the temperature of 195 ℃ under the action of the catalyst Y, preferably, the omega-straight chain diol is uniformly mixed with the mol ratio D: E being 1:0.5-1.5 and then is reacted.
Alternatively, in the present invention, the aliphatic polycarbonate component is composed of (D) a carbonic acid diester and (E) C5-C12α, omega-linear diols, by transesterification and polycondensation, to obtain aliphatic polycarbon compounds having a number average molecular weight of not more than 5000g/molAn acid ester oligomer.
Specifically, the aliphatic polycarbonate oligomer is prepared from (D) carbonic acid diester and (E) C5-C12α, omega-straight chain diol is prepared by uniformly mixing the components according to the mol ratio D: E of 1: 0.5-2, carrying out ester exchange reaction at 100-205 ℃ for 2-8 hours under the action of a catalyst Y, and then continuously carrying out polycondensation reaction at 195-230 ℃ for 1-4 hours under vacuum, preferably, carrying out reaction after uniformly mixing the components according to the mol ratio D: E of 1: 0.5-1.5.
Wherein, the carbonic acid diester monomer is selected from the group known to those skilled in the art, such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate; preferably, the carbonic acid diester monomer is dimethyl carbonate.
Wherein, said C5-C12The α, omega-linear diol monomer is selected from those known to those skilled in the art, such as 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, and the like, preferably C5-C12The α, omega-linear diol of (1) is selected from the group consisting of 1, 5-pentanediol and 1, 6-hexanediol.
Wherein the catalyst Y is selected from the group known to those skilled in the art, and can be selected from the group consisting of n-butyl titanate, isopropyl titanate, titanium glycol, titanium acetylacetonate, lithium acetylacetonate, antimony glycol, antimony trioxide, dibutyltin oxide, stannous oxalate, stannous octoate, antimony acetate, zinc acetate, manganese acetate, lead acetate, calcium acetate, cobalt acetate, potassium acetate, magnesium acetate, barium acetate, lithium acetate, potassium carbonate, lithium carbonate, magnesium carbonate, sodium carbonate, a silica/titanium dioxide complex, a silica/titanium dioxide/nitrogen-containing compound complex, and a silica/titanium dioxide/phosphorus-containing compound complex, for example. Preferably, the catalyst Y is selected from n-butyl titanate, lithium acetylacetonate, zinc acetate, potassium carbonate, lithium carbonate, and silicon dioxide/titanium dioxide/nitrogen-containing compound complex.
In the present invention, the aliphatic polycarbonate oligomer may be a commercially available aliphatic polycarbonate having a number average molecular weight of not more than 5000g/mol, preferably a commercially available 1, 5-pentanediol polycarbonate, 1, 6-hexanediol polycarbonate, 1, 5-pentanediol-co-1, 6-hexanediol polycarbonate having a number average molecular weight of not more than 2000 g/mol; more preferably, commercially available 1, 5-pentanediol polycarbonate, 1, 6-hexanediol polycarbonate, 1, 5-pentanediol polycarbonate-co-1, 6-hexanediol carbonate diol having a number average molecular weight of not more than 1000g/mol are used.
Since ester-carbonate exchange reaction between ester bonds and carbonate bonds is likely to occur, even if aliphatic polycarbonate oligomers having a molecular weight of several thousands are used to participate in copolycondensation reaction, a polyester-carbonate elastomer having a random copolymerization structure rather than a block copolymerization structure is obtained.
In some embodiments of the present invention, the hydroxyl terminated linear polyester-polycarbonate elastomer may be further crosslinked with a crosslinking agent to produce a chemically crosslinked polyester-polycarbonate elastomer.
In some embodiments of the present invention, the branched polyester-polycarbonate elastomer is prepared by introducing a small amount of short-chain polyol into the reaction, and the branched polyester-polycarbonate elastomer can be further subjected to a crosslinking reaction with a crosslinking agent to prepare a chemically crosslinked polyester-carbonate elastomer.
Wherein the cross-linking agent is selected from diisocyanate or polyisocyanate. Further, the diisocyanate may be selected from Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, lysine diisocyanate, and the like. The polyisocyanate can be selected from TDI trimer, HDI trimer, IPDI trimer, TDI-TMP adduct, HDI biuret, etc.
The invention also provides a preparation method of the biodegradable polyester-carbonate elastomer, which comprises the following steps:
(1) uniformly mixing the aromatic polyester component, a catalyst X and the aliphatic polycarbonate component according to the molar ratio of A to B to C of 1: 1.05-2: 0-0.05, and carrying out esterification or ester exchange reaction at the temperature of 170-230 ℃ for 2-4 hours;
or, the aromatic polyester component and the catalyst X are uniformly mixed according to the molar ratio of A to B to C of 1: 1.05-2: 0-0.05, the aromatic polyester oligomer is prepared by esterification or ester exchange reaction for 2-4 hours at the temperature of 230 ℃ of 170-;
(2) the product prepared in the step (1) is subjected to reduced pressure copolycondensation at the temperature of 180 ℃ and 240 ℃ under high vacuum, and the reaction is carried out for 2 to 6 hours.
In certain embodiments, the method of preparation further comprises step (3): and (3) mixing the product prepared in the step (2) with a cross-linking agent, and then carrying out cross-linking reaction.
Preferably, in the step (1), the reaction is carried out after the components are uniformly mixed in a molar ratio of a: B: C of 1:1.1 to 1.3:0 to 0.05.
Wherein, the catalyst X can be one or more of tetrabutyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silicon dioxide/titanium dioxide compound, a silicon dioxide/titanium dioxide/nitrogen-containing compound and a silicon dioxide/titanium dioxide/phosphorus-containing compound. Preferably, the catalyst X is selected from n-butyl titanate, isopropyl titanate, dibutyl tin oxide, stannous oxalate, zinc acetate, silicon dioxide/titanium dioxide/nitrogen-containing compound and silicon dioxide/titanium dioxide/phosphorus-containing compound.
The biodegradable polyester-carbonate elastomer provided by the invention has an ester-carbonate exchange reaction in the synthesis process to generate a plurality of aromatic dibasic acid glycol ester repeating units and carbonic acid glycol ester repeating units with asymmetric structures. Wherein the asymmetric structure aromatic dibasic acid short chain dihydric alcohol ester repeating unit and the carbonic acid short chain dihydric alcohol ester repeating unit endow the copolymer with high gas barrier property, the oxygen permeability coefficient is not higher than 1.5barrer, the carbon dioxide permeability coefficient is not higher than 2.0barrer, and the copolymer is superior to butyl rubber (P)O21.5barrer，PCO22.2 barrer). Preferably, it has an oxygen permeability coefficient of not highAt 0.3barrer, the carbon dioxide permeability coefficient is not higher than 0.2barrer, and is superior to chlorohydrin rubber (P)O20.33barrer，PCO23.4barrer)。
In the biodegradable polyester-carbonate elastomer provided by the invention, the asymmetric structure aromatic dibasic acid short chain dihydric alcohol ester repeating unit or the asymmetric structure aromatic dibasic acid alicyclic dihydric alcohol ester repeating unit provides high strength, and the asymmetric structure aromatic dibasic acid long chain dihydric alcohol ester repeating unit and the asymmetric structure carbonic acid dihydric alcohol ester repeating unit, especially the carbonic acid long chain dihydric alcohol ester repeating unit, provide flexibility and elasticity, so that the elastomer provided by the invention has excellent elasticity and strength and good comprehensive mechanical property.
It is well known that aliphatic polycarbonates generally have good biodegradability, whereas aromatic homopolyesters such as PET are difficult to biodegrade. The biodegradable polyester-carbonate elastomer provided by the invention is composed of a plurality of aromatic dibasic acid glycol ester repeating units with asymmetric structures and a plurality of carbonic acid glycol ester repeating units, although the homopolymer composed of the aromatic dibasic acid glycol ester repeating units is not easy to biodegrade, the homopolymer has a random copolymerization structure, and the sequence length of the aromatic dibasic acid glycol ester is very short, so that the biodegradable polyester-carbonate elastomer provided by the invention has biodegradability similar to that of common fat-aromatic copolyesters PBAT and PBAF.
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to these examples. The test analysis methods used in the following examples are as follows:
1h NMR measurement: the samples were dissolved in 0.5mL of deuterated trifluoroacetic acid (TFA-d1) as a solvent with TMS as an internal standard and tested using an AC-80 NMR spectrometer (400M) from Bruker, Germany.
Intrinsic Viscosity (IV) measurement: the test was carried out using an automatic viscosity measuring instrument model IVS 3000. Phenol-tetrachloroethane was used as a solvent and the test temperature was 25 ℃.
Number average molecular weight:1h NMR results were calculated.
And (3) testing mechanical properties: a thin plate with the thickness of about 1mm is prepared by adopting a hot-press forming method, and after the thin plate is kept at the constant temperature of 50 ℃ for 24 hours, a dumbbell-shaped sample bar of a type 2 cutter is used. The specimens were subjected to tensile testing at 25 ℃ and a tensile rate of 20mm/min using a Roell Z020 model universal materials tester from Zwick. 5 bars were tested per sample and averaged.
The tensile elasticity of the material is characterized by a tensile recovery rate. A Zwick/Roell Z020 type electronic universal material testing machine is adopted to stretch a dumbbell type tensile sample bar to a set tensile strain at the stretching speed of 100mm/min, pause for 1min, then return to an initial position and stand for 1min, finally the length of the sample bar is measured, and the tensile recovery rate is calculated according to the following formula.
Figure BDA0002424904960000111
Gas barrier property test: the sample was hot-pressed into a film with a thickness of about 200 μm on a press vulcanizer. The permeability coefficients of oxygen (99.9% purity) and carbon dioxide (99% purity) of the sample were measured at 1atm and 23 ℃ using a BSG-33E gas permeability tester from west down electromechanical technologies, ltd. Each sample was tested for 3 films, and the average was taken as the test result. The lower the gas permeability coefficient, the better the gas barrier or gas tightness.
Biodegradability test: the sample was hot-pressed into a film on a press vulcanizer using a mold having a size of 100X 0.2mm, and the film was buried in ordinary horticultural soil, and the change in appearance of the sample film after four months was observed. After four months of soil burying, if the sample film has obvious phenomena of thinning, breakage, film layer peeling and the like, the sample has biodegradability; if the sample film had a substantially intact shape and no breakage occurred, the sample was not completely biodegradable.
EXAMPLE 1 preparation of PPeC oligomer
Adding 180g (2mol) of dimethyl carbonate, 104g (1mol) of 1, 5-pentanediol and 0.78g of potassium carbonate into a reactor protected by nitrogen, uniformly mixing, starting reaction at 90 ℃, then gradually heating to 190 ℃, reacting for about 8 hours until no distillate exists, and stopping the reaction to obtain the 1, 5-pentanediol polycarbonate (PPeC) oligomer.
Example 2 preparation of PPeC4800 oligomer
150g (1.67mol) of dimethyl carbonate, 208g (2mol) of 1, 5-pentanediol and 0.6g of potassium carbonate are added into a reactor protected by nitrogen and mixed uniformly; starting the reaction at 90 ℃, then gradually heating to 190 ℃, and reacting for 7 hours until no distillate exists; the polycondensation was continued at 210 ℃ under a pressure of 100Pa for 4 hours to obtain a PPeC oligomer having a number average molecular weight of 4800 g/mol.
Example 3 preparation of PHC2100 oligomer
160g (1.78mol) of dimethyl carbonate, 250g (2.12mol) of 1, 6-hexanediol and 0.8g of lithium carbonate are added into a reactor protected by nitrogen, the mixture is uniformly mixed, the reaction is started at 90 ℃, then the temperature is gradually increased to 190 ℃, and the reaction is carried out for 7 hours until no distillate exists; the polycondensation reaction was continued at 210 ℃ under a pressure of 100Pa for 3 hours to obtain a 1, 6-hexanediol polycarbonate diol (PHC) oligomer having a number-average molecular weight of 2100 g/mol.
EXAMPLE 4 addition of PPeC oligomer to PEF polyester monomer mixture
(1) 70g (0.45mol) of 2, 5-furandicarboxylic acid, 55.6g (0.9mol) of ethylene glycol and 0.08g (0.39mmol) of stannous oxalate were charged into a reactor protected with nitrogen, 350g (73.6 wt%) of the PPeC oligomer prepared in example 1 was further added, and after uniform mixing, the mixture was reacted at 180 ℃ for 4 hours.
(2) The product obtained in step (1) was polycondensed at 200 ℃ for 1 hour and at 210 ℃ for 2 hours under a pressure of 100Pa to obtain a polyester-carbonate elastomer having a tensile curve as shown in FIG. 2.
The intrinsic viscosity of the obtained elastomer is detected to be 1.28 dL/g; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 1MPa, and the elongation at break is 268 percent; the elastic recovery at 100% strain was 97%. At room temperature, the oxygen permeability coefficient is 0.17barrer, the carbon dioxide permeability coefficient is 1.6barrer, the gas barrier property is better than that of the chlorohydrin rubber, and the rubber is biodegradable.
EXAMPLE 5 addition of PPeC oligomer Mn 4800 to PEF polyester monomer mixture
(1) 60.7g (0.33mol) of dimethyl 2, 5-furandicarboxylate, 40.9g (0.66mol) of ethylene glycol and 0.1g of n-butyl titanate were charged into a reactor protected with nitrogen, and after mixing them well, 140g (57.9 wt%) of the PPeC oligomer prepared in example 2 was added and reacted at 180 ℃ for 4 hours to obtain a transesterification product;
(2) and (2) carrying out reduced pressure copolycondensation on the product obtained in the step (1) at 240 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 3 hours to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is detected to be 1.03 dL/g; the material shows typical elastomer tensile behavior in a tensile test, the tensile strength is 16MPa, and the elongation at break is 339%; the elastic recovery at 100% strain was 92%. At room temperature, the permeability coefficient of oxygen is 0.096barrer, the permeability coefficient of carbon dioxide is 1.02barrer, the gas barrier property is better than that of chlorohydrin rubber, and the rubber is biodegradable.
Example 6 PEF polyester monomer mixture 40% commercial PPeHC oligomer Mn2000 was added
(1) Adding 60.7g (0.33mol) of dimethyl 2, 5-furandicarboxylate, 40.9g (0.66mol) of ethylene glycol, 0.3g of silicon dioxide/titanium dioxide/nitrogen-containing compound and 45g (30.8 wt%) of commercial copolycarbonate diol PPeHC-diol (hydroxyl-terminated copolyester carbonate synthesized by 1, 5-pentanediol, 1, 6-hexanediol and dimethyl carbonate, the content of hexanediol carbonate repeating units is 55 mol%, and the number average molecular weight is 2000g/mol) into a reactor protected by nitrogen, and uniformly mixing; reacting for 4 hours at 180 ℃ to obtain an ester exchange product;
(2) and (2) carrying out reduced pressure copolycondensation on the product obtained in the step (1) at 230 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 3 hours to obtain the polyester-carbonate elastomer, wherein the nuclear magnetic resonance hydrogen spectrum of the polyester-carbonate elastomer is shown in figure 1, and the tensile curve of the polyester-carbonate elastomer is shown in figure 2.
The intrinsic viscosity of the obtained elastomer is detected to be 0.81 dL/g; the material shows typical elastomer tensile behavior in a tensile test, the tensile strength is 23MPa, and the elongation at break is 203 percent; the elastic recovery at 100% strain was 91%. At room temperature, the oxygen permeability coefficient is 0.053barrer, the carbon dioxide permeability coefficient is 0.20barrer, the gas barrier property is better than that of the chlorohydrin rubber and the rubber is biodegradable.
EXAMPLE 7 addition of PPeC oligomer to PEF polyester oligomer
(1) Adding 60.7g (0.33mol) of dimethyl 2, 5-furandicarboxylate, 40.9g (0.66mol) of ethylene glycol and 0.1g of n-butyl titanate into a reactor protected by nitrogen, reacting at 170 ℃ for 1 hour, at 180 ℃ for 1 hour, at 190 ℃ for 1 hour, and at 200 ℃ for 2 hours to obtain poly (ethylene 2, 5-furandicarboxylate) (PEF) oligomer; 58g (36.3%) of the PPeC oligomer prepared in example 1 were added and mixed homogeneously.
(2) And (2) carrying out polycondensation on the product obtained in the step (1) at the temperature of 200 ℃ for 1 hour and at the temperature of 210 ℃ for 1 hour under high vacuum (less than or equal to 133Pa) to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is detected to be 1.27 dL/g; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 5MPa, and the elongation at break is 223%; the elastic recovery at 100% strain was 94%. At room temperature, the permeability coefficient of oxygen is 0.07barrer, the permeability coefficient of carbon dioxide is 0.41barrer, the gas barrier property is better than that of chlorohydrin rubber and the rubber is biodegradable.
EXAMPLE 8 addition of PHC oligomer to PBF polyester oligomer
(1) 60.7g (0.33mol) of dimethyl 2, 5-furandicarboxylate, 55g (0.611mol) of 1, 4-butanediol and 0.3g of zinc acetate are added into a reactor protected by nitrogen and reacted at 180 ℃ for 4 hours to obtain a poly (butylene 2, 5-furandicarboxylate) (PBF) oligomer, 88g (43.2 wt%) of the PHC oligomer prepared in example 3 is added and mixed uniformly;
(2) and (2) carrying out reduced pressure copolycondensation on the product obtained in the step (1) at 240 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 4 hours to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is detected to be 0.93 dL/g; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 18MPa, and the elongation at break is 210 percent; the elastic recovery at 100% strain was 93%. The gas barrier property is superior to that of epichlorohydrin rubber and is biodegradable, and the permeability coefficient of oxygen is 0.078barrer and the permeability coefficient of carbon dioxide is 0.62barrer at room temperature.
EXAMPLE 9 addition of PHC oligomer to PEI polyester oligomer
(1) Adding 70g (0.422mol) of isophthalic acid, 43.4g (0.70mol) of ethylene glycol and 0.3g of isopropyl titanate into a reactor protected by nitrogen, reacting at 170 ℃ for 4 hours to obtain polyethylene isophthalate (PEI) oligomer, adding 195g (63.2 wt%) of the PHC oligomer prepared in example 3, and uniformly mixing;
(2) and (2) carrying out reduced pressure copolycondensation on the product prepared in the step (1) at 200 ℃ under high vacuum, and reacting for 4 hours to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is 1.19dL/g through detection; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 9MPa, and the elongation at break is 370 percent; the elastic recovery at 100% strain was 95%. At room temperature, the permeability coefficient of oxygen is 0.13barrer, the permeability coefficient of carbon dioxide is 1.3barrer, the gas barrier property is better than that of chlorohydrin rubber and the rubber is biodegradable.
EXAMPLE 10 branched PEF polyester oligomer with addition of commercial PPeHC oligomer Mn2000
(1) Adding 60.7g (0.33mol) of 2, 5-furandicarboxylic acid dimethyl ester, 40.9g (0.66mol) of ethylene glycol, 0.45g (3.3mmol) of pentaerythritol and 0.2g of silicon dioxide/titanium dioxide/nitrogen-containing compound into a reactor protected by nitrogen, uniformly mixing, and reacting at 180 ℃ for 4 hours to obtain an ester exchange product; then adding 45g (30.5 wt%) of commercial copolycarbonate dihydric alcohol PPeHC-diol (hydroxyl-terminated copolyestercarbonate synthesized by 1, 5-pentanediol, 1, 6-hexanediol and dimethyl carbonate, wherein the content of a repeating unit of the hexanediol carbonate is 55 mol%, and the number average molecular weight is 2000g/mol), and uniformly mixing;
(2) and (2) carrying out reduced pressure copolycondensation on the product obtained in the step (1) at 240 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 2 hours to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is detected to be 0.91 dL/g; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 21MPa, and the elongation at break is 298%; the elastic recovery at 100% strain was 93%. At room temperature, the oxygen permeability coefficient is 0.064barrer, the carbon dioxide permeability coefficient is 0.32barrer, the gas barrier property is better than that of the chlorohydrin rubber, and the rubber is biodegradable.
EXAMPLE 11 in the same manner as in example 10, diisocyanate crosslinking
To the product obtained in example 10, in a nitrogen-blanketed reactor, a crosslinker hexamethylene diisocyanate was added in a molar ratio of isocyanate groups to hydroxyl groups of 1.05: 1, uniformly mixing, and reacting at 160 ℃ for 15 minutes to obtain the crosslinked polyester-carbonate elastomer.
The product shows typical elastomer tensile behavior in a tensile test, the tensile strength is 26MPa, and the elongation at break is 285%; the elastic recovery at 100% strain was 96%. At room temperature, the permeability coefficient of oxygen is 0.061barrer, the permeability coefficient of carbon dioxide is 0.29barrer, the gas barrier property is better than that of chlorohydrin rubber and the rubber is biodegradable.
EXAMPLE 12 same as in example 6, polyisocyanate crosslinking
To the product obtained in example 6, in a nitrogen-blanketed reactor, a crosslinker hexamethylene diisocyanate trimer was added in a molar ratio of isocyanate groups to hydroxyl groups of 1.1: 1, uniformly mixing, and reacting at 150 ℃ for 30 minutes to obtain the crosslinked polyester-carbonate elastomer.
The product shows typical elastomer tensile behavior in a tensile test, the tensile strength is 27MPa, and the elongation at break is 187%; the elastic recovery at 100% strain was 94%. At room temperature, the oxygen permeability coefficient is 0.051barrer, the carbon dioxide permeability coefficient is 0.16barrer, the gas barrier property is better than that of chlorohydrin rubber, and the rubber is biodegradable.
Comparative example 1 PET polyester monomer mixture 40% commercial PPeHC oligomer Mn2000 was added
(1) Adding 70g (0.42mol) of terephthalic acid, 50g (0.81mol) of ethylene glycol, 0.3g of silicon dioxide/titanium dioxide/nitrogen-containing compound composite and 54g (31 wt%) of commercial copolycarbonate diol PPeHC-diol (hydroxyl-terminated copolyestercarbonate synthesized by 1, 5-pentanediol, 1, 6-hexanediol and dimethyl carbonate, wherein the content of a repeating unit of the hexanediol carbonate is 55 mol%, and the number average molecular weight is 2000g/mol) into a reactor protected by nitrogen, and uniformly mixing; reacting for 4 hours at 220 ℃ to obtain an ester exchange product;
(2) and (2) carrying out reduced pressure copolycondensation on the product obtained in the step (1) at 270 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 3 hours to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is detected to be 0.86 dL/g; the material shows typical elastomer tensile behavior in a tensile test, the tensile strength is 16MPa, and the elongation at break is 248 percent; the elastic recovery at 100% strain was 68%. At room temperature, the permeability coefficient for oxygen is 0.29barrer and the permeability coefficient for carbon dioxide is 2.8 barrer. The elastomer is also biodegradable, but its elastic recovery and gas barrier properties are significantly lower than those of examples 4-12.
This is because terephthalic acid (TPA) is a symmetric aromatic dibasic acid, and comparative example 1 shows that elastomer containing a symmetric dibasic acid (PET-PPeHC) in the aromatic polyester component has significantly lower elastic recovery and gas barrier properties than elastomer containing an asymmetric dibasic acid (PEF-PPeHC) in the polyester component.
Comparative example 2 transesterification of PEI Polymer with PHC diol Polymer
(1) Adding 73g of isophthalic acid, 48g of ethylene glycol and 0.28g of isopropyl titanate into a reactor protected by nitrogen, and reacting at 170 ℃ for 5 hours to obtain a polyethylene isophthalate (PEI) oligomer; carrying out reduced pressure copolycondensation on the product at 200 ℃ under high vacuum, and reacting for 4 hours to obtain polyethylene isophthalate with the number average molecular weight of 15000 g/mol;
(2) adding 170g of dimethyl carbonate, 280g of 1, 6-hexanediol and 0.7g of potassium carbonate into a reactor protected by nitrogen, uniformly mixing, starting reaction at 90 ℃, then gradually heating to 190 ℃, and reacting for 8 hours until no distillate exists; continuously carrying out polycondensation reaction for 3 hours at 210 ℃ and under the pressure of 100Pa to prepare polycarbonate 1, 6-hexanediol diol (PHC) oligomer with the molecular weight of 2500 g/mol; to this product was added hexamethylene diisocyanate in a molar ratio of isocyanate groups to hydroxyl groups of 0.95: 1, reacting for 0.5 hour at 160 ℃ in a nitrogen atmosphere to prepare a polycarbonate 1, 6-hexanediol diol high polymer with the molecular weight of 20000 g/mol;
(3) adding 60g of polyethylene isophthalate with the molecular weight of 15000g/mol prepared in the step (1) and 90g of polycarbonate 1, 6-hexanediol high polymer with the molecular weight of 20000g/mol prepared in the step (2) into a reactor protected by nitrogen, and uniformly mixing under the stirring condition of 190 ℃;
(4) and (3) carrying out reduced pressure copolycondensation on the product obtained in the step (3) at 200 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 0.5 hour to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is 1.06dL/g through detection; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 8MPa, and the elongation at break is 416 percent; the elastic recovery at 100% strain was 97%. At room temperature, the permeability coefficient of oxygen is 0.11barrer, the permeability coefficient of carbon dioxide is 1.2barrer, and the gas barrier property is better than that of chlorohydrin rubber. However, since the molecular weights of the polyethylene isophthalate and the polycarbonate diol used are too high, a multiblock copolymer is produced by the reaction, in which the length of the polyethylene isophthalate hard segment is too long to be biodegradable, and the elastomer is not completely biodegradable.
Comparative example 3 transesterification of PEI Polymer with PHC Polymer
(1) Adding 73g of isophthalic acid, 48g of ethylene glycol and 0.28g of isopropyl titanate into a reactor protected by nitrogen, and reacting at 170 ℃ for 5 hours to obtain a polyethylene isophthalate (PEI) oligomer; carrying out reduced pressure copolycondensation on the product at 200 ℃ under high vacuum, and reacting for 4 hours to obtain polyethylene isophthalate with the number average molecular weight of 15000 g/mol;
(2) adding 180g (2mol) of dimethyl carbonate, 104g (1mol) of 1, 5-pentanediol and 0.78g of potassium carbonate into a reactor protected by nitrogen, uniformly mixing, starting reaction at 90 ℃, then gradually heating to 180 ℃, reacting for about 8 hours until no distillate exists, and stopping the reaction to obtain 1, 5-pentanediol polycarbonate (PPeC) oligomer; continuously carrying out polycondensation reaction for 4 hours at 200 ℃ and under the pressure of 100Pa to prepare polycarbonate 1, 5-pentanediol ester high polymer with the molecular weight of 25000 g/mol;
(3) adding 60g of polyethylene isophthalate with the molecular weight of 15000g/mol prepared in the step (1) and 90g of 1, 5-pentanediol polycarbonate high polymer with the molecular weight of 25000g/mol prepared in the step (2) into a reactor protected by nitrogen, and uniformly mixing under the stirring condition of 190 ℃;
(4) and (3) carrying out reduced pressure copolycondensation on the product obtained in the step (3) at 200 ℃ under high vacuum (less than or equal to 133Pa), and reacting for 0.5 hour to obtain the polyester-carbonate elastomer.
The intrinsic viscosity of the obtained elastomer is 1.08dL/g through detection; the material shows typical elastomer tensile behavior in a tensile test, wherein the tensile strength is 11MPa, and the elongation at break is 401%; the elastic recovery at 100% strain was 96%. At room temperature, the permeability coefficient of oxygen is 0.1barrer, the permeability coefficient of carbon dioxide is 1.14barrer, and the gas barrier property is better than that of chlorohydrin rubber. However, since the molecular weights of the polyethylene isophthalate and the polycarbonate used are too high, a multiblock copolymer is produced by the reaction, in which the length of the polyethylene isophthalate hard segment is too long to be biodegradable, and the elastomer is not completely biodegradable.
The compositions and measured properties of the elastomers obtained in examples 4 to 12 and comparative examples 1 to 3 are shown in table 1 below, and it can be seen from table 1 that the polyester-carbonate elastomer prepared by the present invention has excellent elasticity, biodegradability and gas barrier property.
TABLE 1
Figure BDA0002424904960000201

Claims (10)

1. A biodegradable polyester-carbonate elastomer is characterized in that the elastomer is a multicomponent random copolymer prepared by the reaction of 20-70 wt% of aromatic polyester component, 30-80 wt% of aliphatic polycarbonate component and 0-5 wt% of cross-linking agent;
the aromatic polyester component consists of (A) asymmetric aromatic dibasic acid, (B) short-chain dihydric alcohol or alicyclic dihydric alcohol with the main chain carbon atom number not more than 4 and optionally (C) short-chain polyhydric alcohol;
the above-mentionedThe aliphatic polycarbonate component (A) is composed of (D) a carbonic acid diester and (E) C5-C12α, omega-straight chain diol is subjected to ester exchange reaction to prepare aliphatic polycarbonate oligomer;
or, the aliphatic polycarbonate component is composed of (D) carbonic acid diester and (E) C5-C12α, an aliphatic polycarbonate oligomer having a number average molecular weight of not more than 5000g/mol, which is obtained by subjecting an omega-linear diol to transesterification and polycondensation.
2. The biodegradable polyester-carbonate elastomer according to claim 1, characterized by biodegradability and high gas barrier properties, having an oxygen permeability coefficient not higher than 1.5barrer and a carbon dioxide permeability coefficient not higher than 2.0 barrer;
preferably, it has an oxygen permeability coefficient of not higher than 0.3barrer and a carbon dioxide permeability coefficient of not higher than 0.2 barrer.
3. The biodegradable polyester-carbonate elastomer according to claim 1, characterized in that the aromatic dibasic acid of asymmetric structure is selected from one or more of furan dicarboxylic acid or its diester, isophthalic acid or its diester, phthalic acid or its diester;
the short-chain dihydric alcohol with the main chain carbon atom number not more than 4 is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2-methyl-1, 3-propanediol and neopentyl glycol;
the alicyclic diol is selected from one or two of 1, 4-cyclohexanedimethanol and 1, 4-cyclohexanediol;
the short-chain polyol is selected from one or more of glycerol, trimethylolpropane and pentaerythritol.
4. The biodegradable polyester-carbonate elastomer according to claim 1, wherein the carbonic acid diester is selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate;
said C5-C12α, the omega-linear diol of (A) is selected from 1, 5-pentanediol, 16-hexanediol and 1, 10-decanediol.
5. The biodegradable polyester-carbonate elastomer according to claim 1, wherein the aliphatic polycarbonate oligomer is selected from one or more of 1, 5-pentanediol polycarbonate, 1, 6-hexanediol polycarbonate, and 1, 5-pentanediol-co-1, 6-hexanediol polycarbonate.
6. The biodegradable polyester-carbonate elastomer according to claim 5, characterized in that the aliphatic polycarbonate oligomer has a number average molecular weight of not more than 2000 g/mol.
7. The biodegradable polyester-carbonate elastomer according to claim 1, wherein the cross-linking agent is a diisocyanate or a polyisocyanate.
8. A method for preparing a biodegradable polyester-carbonate elastomer according to any one of claims 1 to 7, comprising the steps of:
(1) uniformly mixing the aromatic polyester component, a catalyst X and the aliphatic polycarbonate component according to the molar ratio of A to B to C of 1: 1.05-2: 0-0.05, and carrying out esterification or ester exchange reaction at the temperature of 170-230 ℃ for 2-4 hours;
or, the aromatic polyester component and the catalyst X are uniformly mixed according to the molar ratio of A to B to C of 1: 1.05-2: 0-0.05, the aromatic polyester oligomer is prepared by esterification or ester exchange reaction for 2-4 hours at the temperature of 230 ℃ of 170-;
(2) the product prepared in the step (1) is subjected to reduced pressure copolycondensation at the temperature of 180 ℃ and 240 ℃ under high vacuum, and the reaction is carried out for 2 to 6 hours.
9. The method for preparing a biodegradable polyester-carbonate elastomer according to claim 8, further comprising the step (3): and (3) mixing the product prepared in the step (2) with a cross-linking agent, and then carrying out cross-linking reaction.
10. The method for preparing biodegradable polyester-carbonate elastomer according to claim 8, wherein the catalyst X is one or more of n-butyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyl tin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silicon dioxide/titanium dioxide composite, a silicon dioxide/titanium dioxide/nitrogen-containing compound composite and a silicon dioxide/titanium dioxide/phosphorus-containing compound composite.
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