CN109666147B - Linear random biodegradable copolyester and preparation method thereof - Google Patents
Linear random biodegradable copolyester and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- 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
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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Abstract
The invention relates to the field of high polymer materials, and discloses linear random biodegradable copolyester and a preparation method thereof. The copolyester has an aliphatic ester structural unit and an aromatic ester structural unit, the melt index of the copolyester is 2.5-4g/10min measured by adopting an ISO 1133 & lt- & gt 2005 & lt- & gt method at 150 ℃ under a load of 2.16kg, and the melt index of the copolyester is 8-15g/10min measured by adopting the ISO 1133 & lt- & gt 2005 & lt- & gt method at 190 ℃ under a load of 2.16 kg. The copolyester has the advantages of low melt index, high molecular weight and good tensile mechanical property.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to linear random biodegradable copolyester and a preparation method thereof.
Background
The thermoplastic aromatic polyester widely used in industry and daily life has excellent thermal stability and mechanical property, convenient processing and low price. For example, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have been widely used in the manufacture of fibers, films and containers. However, these aromatic polyesters are difficult to degrade after disposal, and no microbial para-aromatic polyesters such as PE have been observed to dateT, PBT has any significant direct degradation. In order to combine the excellent properties of aromatic polyesters, the skilled person in the art has been working on the synthesis of aliphatic-aromatic copolyesters since the 80 th century, i.e. the introduction of aromatic segments into aliphatic polyesters ensures that the copolyesters have both the excellent properties of aromatic polyesters and the biodegradability of the copolyesters. For example, biodegradable aliphatic-aromatic copolyesters can be prepared from aliphatic dibasic acids or derivatives thereof, aliphatic dihydric alcohols, aromatic dibasic acids or derivatives thereof. The copolyester being produced by BASF company of Germany
For representation, the raw materials are 1, 6-Adipic Acid (AA), 1, 4-Butanediol (BDO) and dimethyl terephthalate (DMT), and the production process comprises the following steps: AA and BDO are subjected to esterification reaction, DMT and BDO are subjected to ester exchange reaction, and then the esterification product and the ester exchange product are subjected to copolycondensation together.
Chinese patent application CN1807485A discloses that linear random aliphatic/aromatic copolyester is prepared from aromatic dibasic acid or ester, aliphatic dibasic alcohol, aliphatic dibasic acid or its derivative system, and rare earth catalytic system is added during the preparation process, so that the prepared aliphatic/aromatic copolyester has high molecular weight. However, as processing applications develop, the linear random aliphatic/aromatic copolyester also has some performance defects, such as higher melt index, which is difficult to meet the processing requirements, so that the preparation of the biodegradable copolyester with low melt index is very necessary without changing the product structure.
Disclosure of Invention
The invention aims to overcome the defect that the melt index of biodegradable copolyester prepared by the existing method is higher, and provides linear random biodegradable copolyester and a preparation method thereof.
In order to achieve the above objects, the present invention provides, in one aspect, a linear random biodegradable copolyester having an aliphatic ester structural unit represented by formula (1) and an aromatic ester structural unit represented by formula (2),
wherein R is1' and R3' are the same or different and are each independently selected from alkylene; r2' is selected from the group consisting of alkylene and cycloalkylene; r4' is an arylene group; the melt index of the copolyester is 2.5-4g/10min measured by adopting the ISO 1133 & 2005 method at 150 ℃ and under the load of 2.16kg, and the melt index is 8-15g/10min measured by adopting the ISO 1133 & 2005 method at 190 ℃ and under the load of 2.16 kg.
The invention also provides a preparation method of the linear random biodegradable copolyester, which comprises the following steps:
(1) carrying out esterification reaction on the component a and the component b in the presence of a first catalyst, a second catalyst and a third catalyst, starting vacuumizing until the esterification reaction is finished, carrying out pre-polycondensation under a first low vacuum, and then carrying out polycondensation under a first high vacuum to obtain a polymer P1, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum;
(2) carrying out esterification reaction on the component b and the component c in the presence of a first catalyst, a second catalyst and a third catalyst, starting vacuumizing until the esterification reaction is finished, carrying out pre-polycondensation under a second low vacuum, and then carrying out polycondensation under a second high vacuum to obtain a polymer P2, wherein the absolute pressure under the second low vacuum is greater than the absolute pressure under the second high vacuum;
(3) mixing the polymer P1 and the polymer P2 and carrying out a polycondensation reaction;
wherein the component a is at least one of aliphatic dibasic acid, anhydride of aliphatic dibasic acid, alicyclic dibasic acid and anhydride of alicyclic dibasic acid; the component b is aliphatic dihydric alcohol; the component c is at least one of aromatic dibasic acid and anhydride of the aromatic dibasic acid;
the first catalyst is selected from the oxides of M, M (OR)1)nAnd M (-OOCR)2)nWherein M is titanium, antimony or zinc, n is the valence of M, R is1Is C1-C10Alkyl of R2Is C1-C30Alkyl groups of (a);
the second catalyst is at least one organotin compound;
the third catalyst is at least one catalyst with a chemical formula of RE (R)3)3Wherein RE is a rare earth metal element, R3Is selected from halogen, alkoxy, aryloxy, acetylacetonate and R4At least one of COO-groups, R4Is C1-C30Alkyl group of (1).
The invention also provides linear random biodegradable copolyester prepared by the method.
The linear random biodegradable copolyester prepared by the method has a low melt index and excellent physical and mechanical properties, and can meet the requirements of processing.
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.
The linear random biodegradable copolyester disclosed by the invention has an aliphatic ester structural unit shown in a formula (1) and an aromatic ester structural unit shown in a formula (2).
In the formulae (1) and (2), R1' and R3' are the same or different and are each independently selected from alkylene groups, which may be, for example, C2-C10 alkylene groups. The alkylene group of C2-C10 may be a linear alkylene group or an alkylene group having a branched chain. Preferably, R1' and R3' each is independently selected from C2-C8 alkylene groups, more preferably C2-C6 alkylene groups.
In the formulae (1) and (2), R2' is selected from the group consisting of alkylene and cycloalkylene, and may be, for example, C1-C12 alkylene or C3-C12 cycloalkylene. The alkylene group of C1-C12 may be a linear alkylene group or an alkylene group having a branched chain. Preferably, R2' is an alkylene group of C1 to C8, more preferably C2 to C6.
In the formulae (1) and (2), R4' is an arylene group, preferably a C6-C12 arylene group. The arylene group may be a group having at least one benzene ring, naphthalene ring and anthracene ring. Preferably, R4' is an arylene group as follows:
wherein R is5、R6、R7、R8、R9And R10Each independently is hydrogen, C1-C4Alkyl group of F, Cl, -NO2-CN OR-OR11Wherein R is11Is C1-C4Alkyl group of (1).
In the present invention, the linear random biodegradable copolyester has a melt index of 2.5 to 4g/10min, specifically, for example, 2.5g/10min, 2.8g/10min, 3.0g/10min, 3.1g/10min, 3.2g/10min, 3.4g/10min, 3.5g/10min, 3.6g/10min, 3.8g/10min, 4g/10min and any value in the range of any two of these values, as measured by ISO 1133-2005 method at 150 ℃ under a load of 2.16 kg.
In the present invention, the linear random biodegradable copolyester has a melt index of 8-15g/10min, specifically, 8g/10min, 8.5g/10min, 9g/10min, 9.5g/10min, 10g/10min, 10.5g/10min, 11g/10min, 11.5g/10min, 12g/10min, 12.5g/10min, 13g/10min, 13.5g/10min, 14g/10min, 14.5g/10min, 15g/10min and any value within a range of any two of these values, as measured by ISO 1133-2005 method at 190 ℃ under a load of 2.16 kg.
In the present invention, the linear random biodegradable copolyester may have a number average molecular weight of 5 to 7 ten thousand. In the present invention, the number average molecular weight of the polymer is measured by a Gel Permeation Chromatography (GPC) method.
In the present invention, the linear random biodegradable copolyester may have a weight average molecular weight of 10.5 to 14 ten thousand. In the present invention, the weight average molecular weight of the polymer is measured according to a Gel Permeation Chromatography (GPC) method.
In the present invention, the linear random biodegradable copolyester may have an elongation at break of 500-. In the present invention, the elongation at break of the copolyester is measured according to the method of ASTM D638-03.
In the present invention, the linear random biodegradable copolyester may have a tensile strength at break of 8 to 35MPa, preferably 10 to 25 MPa. In the present invention, the tensile strength at break of the copolyester is measured according to the method of ASTM D638-03.
In the present invention, the linear random biodegradable copolyester may have a glass transition temperature of-32 ℃ to 30 ℃. In the present invention, the glass transition temperature of the copolyester is measured according to Differential Scanning Calorimetry (DSC) measurement.
The preparation method of the linear random biodegradable copolyester comprises the following steps:
(1) carrying out esterification reaction on the component a and the component b in the presence of a first catalyst, a second catalyst and a third catalyst, starting vacuumizing until the esterification reaction is finished, carrying out pre-polycondensation under a first low vacuum, and then carrying out polycondensation under a first high vacuum to obtain a polymer P1, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum;
(2) carrying out esterification reaction on the component b and the component c in the presence of a first catalyst, a second catalyst and a third catalyst, starting vacuumizing until the esterification reaction is finished, carrying out pre-polycondensation under a second low vacuum, and then carrying out polycondensation under a second high vacuum to obtain a polymer P2, wherein the absolute pressure under the second low vacuum is greater than the absolute pressure under the second high vacuum;
(3) the polymer P1 and the polymer P2 were mixed and subjected to polycondensation.
In the method of the present invention, the component a is at least one of an aliphatic dibasic acid, an anhydride of an aliphatic dibasic acid, an alicyclic dibasic acid, and an anhydride of an alicyclic dibasic acid. The aliphatic dibasic acid has a chemical formula of HOOC-R13-COOH, wherein R13May be a C1-C12 alkylene group, and the C1-C12 alkylene group may be a straight chain alkyl group or an alkylene group with a branched chain. Preferably, R13Is alkylene of C1-C8, namely the aliphatic dibasic acid is aliphatic dibasic acid of C3-C10, and more preferably aliphatic dibasic acid of C3-C7. The cycloaliphatic diacid may be a diacid having at least one aliphatic ring. Preferably, the alicyclic dibasic acid is an alicyclic dibasic acid of C5-C10.
In the method of the invention, the component b is aliphatic diol, preferably C2-C6 aliphatic diol. The chemical general formula of the aliphatic diol can be HO-R12-OH, wherein R12Can be C2-10And R is alkylene of12May be a straight chain alkyl group or an alkyl group with a branched chain. Preferably, the component b is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, and octylene glycol.
In the method of the present invention, the component c is at least one of an aromatic dibasic acid and an acid anhydride of the aromatic dibasic acid. The chemical formula of the aromatic dibasic acid can be HOOC-Ar-COOH, wherein Ar can be a group with at least one benzene ring, naphthalene ring and anthracene ring, and preferably Ar is the following aryl:
wherein R is5、R6、R7、R8、R9And R10Each independently is hydrogen, C1-C4Alkyl group of F, Cl, -NO2-CN OR-OR11Wherein R is11Is C1-C4Alkyl group of (1).
According to a preferred embodiment of the invention, said component a is selected from C3-C10Aliphatic dibasic acid of (1), C3-C10Acid anhydride of aliphatic dibasic acid, C5-C10And C is a cycloaliphatic dibasic acid5-C10At least one of anhydrides of the alicyclic dibasic acids of (a); the component b is 1, 4-butanediol; the component c is terephthalic acid and/or terephthalic anhydride. The linear random biodegradable copolyester prepared according to the preferred embodiment has a higher molecular weight and good tensile mechanical properties.
In the process of the invention, the first catalyst is an oxide selected from M, M (OR)1)nAnd M (-OOCR)2)nWherein M is titanium, antimony or zinc, n is the valence of M, R is1Is C1-C10Alkyl of R2Is C1-C30Alkyl group of (1). In order to provide the finally prepared biodegradable polyester with a further increased molecular weight and a smaller molecular weight distribution coefficient while improving the tensile mechanical properties of the finally prepared biodegradable polyester, the first catalyst is preferably at least one selected from the group consisting of titanium alkoxide, antimony acetate, zinc acetate, an oxide of zinc, an oxide of antimony, and an oxide of titanium. More preferably, the first catalyst is selected from tetrabutyl titanate (Ti (OC)4H9)4) At least one of titanium isopropoxide, titanium dioxide, antimony trioxide, antimony acetate and zinc acetate.
In the process of the present invention, the second catalyst is at least one organotin compound. In order to provide the finally produced biodegradable polyester with a further increased molecular weight and a smaller molecular weight distribution coefficient while improving the tensile mechanical properties of the finally produced biodegradable polyester, the second catalyst is preferably at least one selected from the group consisting of dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyltin oxide, hexacyclohexylditin oxide, didodecyltin oxide, triethylhydroxytin, triphenylhydroxytin, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutylthiotin, butylhydroxytin oxide, methylstannoic acid, ethylstannoic acid and butylstannoic acid. Further preferably, the second catalyst is a mixture of at least two selected from the group consisting of dibutyltin oxide, tetraethyltin, triphenylhydroxytin, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannoic acid, ethylstannoic acid and butylstannoic acid. In this case, each component of the third catalyst may be contained in an amount of 10 to 90 mol%, preferably 30 to 70 mol%.
In the process of the present invention, the third catalyst is at least one catalyst of the formula RE (R)3)3Wherein RE is a rare earth metal element, R3Is selected from halogen, alkoxy, aryloxy, acetylacetonate and R4At least one of COO-groups, R4Is C1-C30Alkyl group of (1). In order to make the finally prepared biodegradable polyester have further increased molecular weight and smaller molecular weight distribution coefficient, and simultaneously improve the tensile mechanical property of the finally prepared biodegradable polyester, in the third catalyst, the catalyst has the chemical formula RE (R)3)3In the compound of (1), RE is preferably lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium or scandium; the halogen is chlorine or bromine, and the alkoxy is C3-C6An aryloxy group being an aryloxy group comprising at least one benzene ring and/or naphthalene ring, R4Is C1-C20Alkyl group of (1). More preferably, RE is selected from lanthanum, cerium, praseodymium, neodymium or scandium, the halogen is chlorine or bromine, the alkyl group in the alkoxy group is isopropyl, n-butyl or isoamyl, the aryl group in the aryloxy group is 2, 6-di-tert-butyl-4-methylphenyl or 4-butylphenyl, and R is4Is C3-C18Alkyl group of (1). More preferably, the third catalyst is lanthanum acetylacetonate, neodymium isopropoxide, lanthanum isopropoxide, scandium isopropoxide, lanthanum stearate, neodymium stearate, lanthanum chloride, lanthanum oxide,one or more of lanthanum tris (2, 6-di-tert-butyl-4-methylphenoxy) and hydrates thereof.
In the process of the present invention, the esterification reaction conditions in step (1) may be appropriately selected among conventional esterification reaction conditions. Preferably, the esterification reaction temperature is 180-220 ℃. In the esterification reaction, when the amount of water produced by the reaction is greater than 98% of the theoretical amount of water produced, it can be judged that the esterification reaction is completed.
In the method of the present invention, in step (1), the absolute pressure under the first low vacuum is preferably higher than the absolute pressure under the first high vacuum by 300-600Pa, more preferably by 400-500 Pa. Preferably, the absolute pressure under the first low vacuum is 500-600Pa, and the absolute pressure under the first high vacuum is 200Pa or less (e.g., 10-200 Pa).
In the method of the present invention, in the step (1), the reaction conditions of the prepolycondensation may include: the temperature is 240 ℃ and 260 ℃ and the time is 0.5-2 hours.
In the method of the present invention, in step (1), the reaction conditions of the polycondensation may include: the temperature is 250 ℃ and 270 ℃ and the time is 2-3 hours.
In the method of the present invention, in the step (1), the molar ratio of the amount of the component a to the amount of the component b is 1: 0.8 to 6, preferably 1: 0.8-3.
In the process of the present invention, the esterification reaction conditions in step (2) may be appropriately selected among conventional esterification reaction conditions. Preferably, the esterification reaction temperature is 150-200 ℃. In the esterification reaction, when the amount of water produced by the reaction is greater than 98% of the theoretical amount of water produced, it can be judged that the esterification reaction is completed.
In the method of the present invention, in the step (2), the absolute pressure at the second low vacuum is preferably higher than the absolute pressure at the second high vacuum by 300-600Pa, more preferably by 400-500 Pa. Preferably, the absolute pressure under the second low vacuum is 500-600Pa, and the absolute pressure under the second high vacuum is 200Pa or less (e.g., 10-200 Pa).
In the method of the present invention, in the step (2), the reaction conditions of the prepolycondensation may include: the temperature is 240 ℃ and 260 ℃ and the time is 0.5-2 hours.
In the method of the present invention, in the step (2), the reaction conditions of the polycondensation may include: the temperature is 250 ℃ and 270 ℃ and the time is 2-3 hours.
In the method of the present invention, in the step (2), the molar ratio of the component c to the amount of the component b is 1: 0.8 to 6, preferably 1: 0.8-3.
In the method of the present invention, in the step (3), the conditions of the polycondensation reaction may include: the temperature is 250-270 ℃, and the absolute pressure is below 200Pa (such as 10-200 Pa).
According to a preferred embodiment of the present invention, the preparation method of the linear random biodegradable copolyester comprises:
(1) subjecting component a and component b to an esterification reaction in the presence of a first catalyst, a second catalyst and a third catalyst; the component a is at least one of aliphatic dibasic acid, anhydride of aliphatic dibasic acid, alicyclic dibasic acid and anhydride of alicyclic dibasic acid; the component b is aliphatic dihydric alcohol; the molar ratio of the added amount of the component a to the added amount of the component b is 1: 0.8 to 6, preferably 1: 0.8 to 3; when the esterification reaction is finished, vacuumizing is started, pre-polycondensation is carried out under low vacuum (the vacuum degree is 600-300Pa) and at the temperature of 240-260 ℃, then high vacuum (the vacuum degree is less than 200Pa) polycondensation reaction is carried out, the reaction temperature is 250-270 ℃, the reaction is carried out for 2-3 hours, and the reaction is finished, so that the polymer P1 is prepared, and optionally, crushing and grain-sized dicing are carried out.
(2) In the presence of a first catalyst, a second catalyst and a third catalyst, carrying out an esterification reaction on a component b and a component c, wherein the component c is at least one of aromatic dibasic acid and anhydride of the aromatic dibasic acid; the molar ratio of the added amount of the component c to the added amount of the component b is 1: 0.8 to 6; when the esterification reaction is finished, vacuumizing is started, pre-polycondensation is carried out under low vacuum (the vacuum degree is 600-300Pa) and at the temperature of 240-260 ℃, then high vacuum (the vacuum degree is less than 200Pa) polycondensation reaction is carried out, the reaction temperature is 250-270 ℃, the reaction is carried out for 2-3 hours, and the reaction is finished, so that the polymer P2 is prepared, and optionally, crushing and grain-sized dicing are carried out.
(3) Adding the polymer P1 and the polymer P2 into a reaction kettle, reheating to the polycondensation reaction temperature, and carrying out polycondensation reaction until the reaction is finished.
In the method of the present invention, the step (1) and the step (2) are not sequentially divided, either one of them may be performed first and then the other one may be performed, or both of them may be performed simultaneously.
The invention also provides linear random biodegradable copolyester prepared by the method. The copolyester has a low melt index, specifically, the melt index of the copolyester is 2.5-4g/10min measured by adopting the method of ISO 1133 & lt- & gt 2005 & lt- & gt at 150 ℃ and under the load of 2.16kg, and the melt index of the copolyester is 8-15g/10min measured by adopting the method of ISO 1133 & lt- & gt 2005 & lt- & gt at 190 ℃ and under the load of 2.16 kg.
The invention is further described below by way of examples, without restricting its scope.
In the following examples and comparative examples, lanthanum stearate was prepared according to the method of example a5 in CN 1807485A.
Example 1
A2.5L reaction kettle was charged with 202.6g of 1, 4-succinic acid, 200g of 1, 4-butanediol, 0.245g of tetrabutyl titanate (purchased from Beijing Chemicals), 0.1g of dibutyltin oxide (purchased from Beijing chemical three factories), 0.14g of triphenylhydroxytin (purchased from Beijing Chemicals) and 0.31g of lanthanum stearate, stirred and heated to reflux under a nitrogen atmosphere, the temperature was adjusted to 220 ℃, when the amount of water produced by the reaction was more than 98% of the theoretical amount, the absolute pressure in the reaction kettle was adjusted to 550Pa, the temperature in the reaction kettle was 255 ℃, pre-polycondensation was carried out for 1 hour, the degree of vacuum was further adjusted to 150Pa, the temperature was adjusted to 260 ℃, and polycondensation was carried out at the temperature and the pressure for about 2 hours to the end point, to obtain a pale yellow polymer P11.
285g of terephthalic acid, 200g of 1, 4-butanediol, 0.245g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.2g of dibutyltin oxide (purchased from Beijing chemical three factories) and 0.31g of lanthanum stearate are added into a 2.5L reaction kettle, the mixture is heated and stirred to reflux under the nitrogen atmosphere, the temperature is adjusted to 200 ℃, when the water generated by the reaction is more than 98 percent of the theoretical generation amount, the absolute pressure in the reaction kettle is adjusted to 550Pa, the temperature of the reaction kettle is 255 ℃, pre-polycondensation is carried out for 1 hour, the vacuum degree is continuously adjusted to 150Pa, the temperature is adjusted to 260 ℃, and the polycondensation is carried out for about 2 hours to the end point under the temperature and the pressure, so that a light yellow polymer P12 is obtained.
Adding the copolymer P11 and P12 together, continuing to heat to 260 ℃, adjusting the vacuum degree to 150Pa, and continuing to react until the reaction end to obtain the copolymer SP 1.
Comparative example 1
Adding 285g of terephthalic acid, 200g of 1, 4-butanediol, 0.245g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.1g of dibutyltin oxide (purchased from Beijing chemical three factories company) and 0.14g of triphenylhydroxytin (purchased from Beijing chemical reagent company) into a 2.5L reaction kettle, stirring and heating to reflux under a nitrogen atmosphere, adjusting the temperature to 220 ℃, adding 202.6g of 1, 4-succinic acid, 200 of 1, 4-butanediol and 0.62g of lanthanum stearate when the water generated by the reaction is more than 98% of the theoretical generation amount, continuously heating and stirring to reflux, adjusting the temperature to 200 ℃, adjusting the absolute pressure in the reaction kettle to 550Pa when the water generated by the reaction is completely evaporated, adjusting the temperature of the reaction kettle to 255 ℃, carrying out pre-polycondensation for 1 hour, continuously adjusting the vacuum degree to 150Pa, adjusting the temperature to 260 ℃, and polycondensed at that temperature and pressure for 7 hours to give a pale yellow copolymer DP 1.
Example 2
269g of 1, 4-succinic acid, 266g of 1, 4-butanediol, 0.3g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.13g of dibutyltin oxide (purchased from Beijing chemical three factories) and 0.4g of lanthanum stearate are added into a 2.5L reaction kettle, stirred and heated to reflux in a nitrogen atmosphere, the temperature is adjusted to 220 ℃, the absolute pressure in the reaction kettle is adjusted to 550Pa when the water generated by the reaction is more than 98% of the theoretical generation amount, the temperature in the reaction kettle is 255 ℃, pre-polycondensation is carried out for 1 hour, the vacuum degree is continuously adjusted to 150Pa, the temperature is adjusted to 260 ℃, and polycondensation is carried out for 3 hours to the end point under the temperature and the pressure, so that a light yellow polymer P21 is obtained.
204g of terephthalic acid, 144g of 1, 4-butanediol, 0.174g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.071g of dibutyltin oxide (purchased from Beijing chemical three factories), 0.099g of triphenylhydroxytin (purchased from Beijing chemical reagent company) and 0.22g of lanthanum stearate are added into a 2.5L reaction kettle, the mixture is heated and stirred under a nitrogen atmosphere until the reflux, the temperature is adjusted to 200 ℃, when the water generated by the reaction is more than 98% of the theoretical generation amount, the absolute pressure in the reaction kettle is adjusted to 550Pa, the temperature of the reaction kettle is 255 ℃, the pre-polycondensation is carried out for 1 hour, the vacuum degree is continuously adjusted to 150Pa, the temperature is adjusted to 260 ℃, and the polycondensation is carried out for 3 hours under the temperature and the pressure until the end point, so as to obtain a light yellow polymer P22.
Adding the polymers P21 and P22 together, continuing to heat to 260 ℃, adjusting the vacuum degree to 150Pa, and continuing to react until the reaction end to obtain the copolymer SP 2.
Comparative example 2
204g of terephthalic acid, 144g of 1, 4-butanediol, 0.174g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.071g of dibutyltin oxide (purchased from Beijing chemical three-plant company) and 0.099g of triphenylhydroxytin (purchased from Beijing chemical reagent company) were added to a 2.5L reaction vessel, stirred and heated to reflux under a nitrogen atmosphere, the temperature was adjusted to 220 ℃, when the amount of water produced by the reaction was more than 98% of the theoretical amount, 269g of 1, 4-succinic acid, 266g of 1, 4-butanediol and 0.62g of lanthanum stearate were added thereto, the heating and stirring were continued to reflux, the temperature was adjusted to 200 ℃, when the water produced by the reaction was completely distilled off, the absolute pressure in the reaction vessel was adjusted to 550Pa, the reaction vessel temperature was 255 ℃, the pre-polycondensation was carried out for 1 hour, the degree of vacuum was further adjusted to 150Pa, the temperature was adjusted to 260 ℃ and polycondensation was carried out at this temperature and pressure for 7 hours to give a pale yellow copolymer DP 2.
Example 3
82.8g of 1, 4-succinic acid, 76.0g of 1, 4-butanediol, 0.3g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.13g of dibutyltin oxide (purchased from Beijing chemical three factories) and 0.4g of lanthanum stearate are added into a 2.5L reaction kettle, stirred and heated to reflux under a nitrogen atmosphere, the temperature is adjusted to 200 ℃, when the water generated by the reaction is more than 98 percent of the theoretical generation amount, the absolute pressure in the reaction kettle is adjusted to 600Pa, the temperature of the reaction kettle is 255 ℃, pre-polycondensation is carried out for 1 hour, the vacuum degree is continuously adjusted to 150Pa, the temperature is adjusted to 260 ℃, and polycondensation is carried out for 2 hours under the temperature and the pressure to the end point, so that the light yellow polymer P31 is obtained.
466g of terephthalic acid, 303g of 1, 4-butanediol, 0.174g of tetrabutyl titanate (purchased from Beijing chemical reagent company), 0.071g of dibutyltin oxide (purchased from Beijing chemical three factories), 0.099g of triphenylhydroxytin (purchased from Beijing chemical reagent company) and 0.22g of lanthanum stearate are added into a 2.5L reaction kettle, the mixture is heated and stirred under a nitrogen atmosphere until the reflux, the temperature is adjusted to 200 ℃, when the water generated by the reaction is more than 98% of the theoretical generation amount, the absolute pressure in the reaction kettle is adjusted to 600Pa, the temperature of the reaction kettle is 255 ℃, the pre-polycondensation is carried out for 1 hour, the vacuum degree is continuously adjusted to 150Pa, the temperature is adjusted to 260 ℃, and the polycondensation is carried out for 2 hours under the temperature and the pressure until the end point, so as to obtain the light yellow polymer P32.
Adding the polymers P31 and P32 together, continuing to heat to 260 ℃, adjusting the vacuum degree to 100Pa, and continuing to react until the reaction end to obtain the copolymer SP 3.
Test example
The number average molecular weight and the weight average molecular weight of the copolymers SP1-SP3 and DP1-DP2 were determined according to a Gel Permeation Chromatography (GPC) method;
detecting and calculating the molecular weight distribution coefficient of the copolymer according to a GPC method;
detecting the glass transition temperature of the copolymer according to Differential Scanning Calorimeter (DSC) measurement;
the tensile mechanical properties such as elongation at break and tensile strength at break of the copolymers SP1-SP3 and DP1-DP2 were examined according to the method of ASTM D638-03;
determination of melt index: the melt flow rate (MI) of the copolymer was measured using a melt index apparatus model CS-127, scientific instruments, USA, under a load of 2.16kg at 190 deg.C (or 150 deg.C) using ISO 1133-2005 Standard "determination of melt mass flow rate and melt volume flow rate of thermoplastics".
The results are shown in Table 1 below.
TABLE 1
As can be seen from the data in Table 1 above, the copolyester prepared by the method of the present invention has a lower melt index, a higher molecular weight and better tensile mechanical properties.
Claims (11)
1. A linear random biodegradable copolyester having an aliphatic ester structural unit represented by formula (1) and an aromatic ester structural unit represented by formula (2),
wherein R is1' and R3' are the same or different and are each independently selected from alkylene; r2' is selected from the group consisting of alkylene and cycloalkylene; r4' is an arylene group;
the melt index of the copolyester is 2.5-4g/10min measured by adopting the ISO 1133 & 2005 method at 150 ℃ and under the load of 2.16kg, and the melt index is 8-15g/10min measured by adopting the ISO 1133 & 2005 method at 190 ℃ and under the load of 2.16 kg.
2. The copolyester of claim 1, wherein R1' and R3' are the same and are selected from C2-C6 alkylene; r2' is C2-C6 alkylene; r4' is an arylene group having from C6 to C12.
3. A process for the preparation of a linear random biodegradable copolyester according to claim 1 or 2, which comprises:
(1) carrying out esterification reaction on the component a and the component b in the presence of a first catalyst, a second catalyst and a third catalyst, starting vacuumizing until the esterification reaction is finished, carrying out pre-polycondensation under a first low vacuum, and then carrying out polycondensation under a first high vacuum to obtain a polymer P1, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum;
(2) carrying out esterification reaction on the component b and the component c in the presence of a first catalyst, a second catalyst and a third catalyst, starting vacuumizing until the esterification reaction is finished, carrying out pre-polycondensation under a second low vacuum, and then carrying out polycondensation under a second high vacuum to obtain a polymer P2, wherein the absolute pressure under the second low vacuum is greater than the absolute pressure under the second high vacuum;
(3) mixing the polymer P1 and the polymer P2 and carrying out a polycondensation reaction;
wherein the component a is at least one of aliphatic dibasic acid, anhydride of aliphatic dibasic acid, alicyclic dibasic acid and anhydride of alicyclic dibasic acid; the component b is aliphatic dihydric alcohol; the component c is at least one of aromatic dibasic acid and anhydride of the aromatic dibasic acid;
the first catalyst is selected from the oxides of M, M (OR)1)nAnd M (-OOCR)2)nWherein M is titanium, antimony or zinc, n is the valence of M, R is1Is C1-C10Alkyl of R2Is C1-C30Alkyl groups of (a);
the second catalyst is at least one organotin compound;
the third catalyst is at least one catalyst with a chemical formula of RE (R)3)3Wherein RE is a rare earth metal element, R3Is selected from halogen, alkoxy, aryloxy, acetylacetonate and R4At least one of COO-groups, R4Is C1-C30Alkyl group of (1).
4. The method as claimed in claim 3, wherein the esterification reaction temperature in step (1) is 180-220 ℃ and the esterification reaction temperature in step (2) is 150-200 ℃.
5. The method as claimed in claim 3, wherein, in the step (1), the absolute pressure at the first low vacuum is 500-600Pa, and the absolute pressure at the first high vacuum is 200Pa or less.
6. The process according to claim 3 or 5, wherein, in step (1), the reaction conditions of the prepolycondensation comprise: the temperature is 240 ℃ and 260 ℃, and the time is 0.5-2 hours; the reaction conditions of the polycondensation include: the temperature is 250 ℃ and 270 ℃ and the time is 2-3 hours.
7. The method as claimed in claim 3, wherein, in the step (2), the absolute pressure at the second low vacuum is 500-600Pa, and the absolute pressure at the second high vacuum is 200Pa or less.
8. The process according to claim 3 or 7, wherein, in step (2), the reaction conditions of the prepolycondensation comprise: the temperature is 240 ℃ and 260 ℃, and the time is 0.5-2 hours; the reaction conditions of the polycondensation include: the temperature is 250 ℃ and 270 ℃ and the time is 2-3 hours.
9. The process of any one of claims 3-5 and 7, wherein in step (3), the conditions of the polycondensation reaction comprise: the temperature is 250-270 ℃, and the absolute pressure is below 200 Pa.
10. The method of claim 3, wherein the component a is at least one of an anhydride of an aliphatic dibasic acid of C3-C7 and an aliphatic dibasic acid of C3-C7; the component b is aliphatic dihydric alcohol of C2-C6; the component C is at least one of C8-C14 aromatic dibasic acid and C8-C14 aromatic dibasic acid anhydride.
11. A linear random biodegradable copolyester prepared by the process of any one of claims 3-10.
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