CN109320699B - Thermoplastic aliphatic-aromatic copolyester elastomer and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of synthesis of random copolyester elastomers, and particularly relates to a thermoplastic aliphatic-aromatic copolyester elastomer and a preparation method thereof. The copolyester is prepared by using 1, 4-butanediol, aliphatic dibasic acid and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl phthalate as raw materials and adopting a polymerization method of esterification and polycondensation. The invention can adopt a general polyester synthesis device to carry out polymerization, carries out continuous reaction in a one-time feeding mode, has simple operation and is easy for industrialized production. The copolyester prepared by the invention has good toughness and rebound resilience; meanwhile, the linear structure of the copolyester endows the material with good processing performance. Therefore, the process for preparing the copolyester is simple, and the copolyester has wide application prospect in the aspect of thermoplastic biodegradable elastomers.
Description
Technical Field
The invention belongs to the technical field of synthesis of random copolyester elastomers, and particularly relates to a thermoplastic aliphatic-aromatic copolyester elastomer and a preparation method thereof.
Background
Thermoplastic polyester elastomers are novel polymer materials having both rubber and plastic properties, and are favored for their excellent properties and easy processability. At present, thermoplastic polyester elastomers are mainly A-B type block polymer materials. Wherein amorphous polyester or polyether is used as a soft block, and crystalline or aromatic polyester is used as a hard block. Generally, a two-step process is adopted, i.e., a soft segment prepolymer and a hard segment prepolymer are prepared, and then a chain extender is adopted to react with the hard segment prepolymer and the soft segment prepolymer to form a block structure.
For example, patent CN 101768246B discloses that a multi-block copolyester is prepared by first preparing a hydroxyl-terminated aliphatic polyester and a hydroxyl-terminated aromatic polyester, and then using diisocyanate as a chain extender, and the tensile strength of the copolyester is 10-67MPa, and the elongation at break is 20-1080%. Patent CN 104610522B reports that prepolymer I (hydroxyl-terminated poly (propylene succinate)) and prepolymer II (hydroxyl-terminated aromatic polyester or another hydroxyl-terminated aliphatic polyester) are heated, melted and stirred uniformly under the protection of inert gas, and then diisocyanate is added to prepare the high-toughness segmented copolyester elastomer, wherein the elongation at break is 1112-2200%.
Compared with the two-step method for preparing the block copolyester elastomer, the one-step method for preparing the random copolyester elastomer is relatively simple and is easier for industrial production. The one-step method is to put the reaction monomer into the reactor in a one-step feeding mode for continuous reaction, and the operation steps are simple. Then, in order to impart the soft segment and the hard segment to the structure of the random copolyester, the present inventors have found that the random copolyester prepared by using 1, 4-butanediol as a diol monomer and aliphatic dibasic acid and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl dicarboxylate monomer as comonomers has good toughness and resilience. The reason is that the chain segment formed by the aliphatic dibasic acid monomer has certain flexibility; the benzene ring in the diphenyl ether dicarboxylic acid or dimethyl diphenyl ether dicarboxylate monomer structure is rigid structure, and the ether bond is good flexible structure. For example, patent CN102558519A discloses a liquid crystal polymer material, wherein 4, 4-diphenyl ether dicarboxylic acid contains ether bond, which reduces the rigidity of the chain, thereby improving the toughness or impact strength of LCP. The special design adopts aliphatic dibasic acid monomer and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl diformate monomer, and endows copolyester with good toughness and rebound resilience under random sequence by utilizing the comprehensive action on the structures of flexible monomer and rigid monomer.
Disclosure of Invention
Aiming at the problem that the existing method for preparing the polyester elastomer focuses on the synthesis of the block copolyester, the method is generally a two-step method and is relatively complex. An object of the present invention is to provide a simple method for preparing a thermoplastic aliphatic-aromatic copolyester elastomer, and a thermoplastic aliphatic-aromatic copolyester elastomer prepared by the method.
The invention also aims to endow the aliphatic-aromatic copolyester with good toughness and rebound property by adopting diphenyl ether dicarboxylic acid or diphenyl ether dimethyl dicarboxylate as a special aromatic comonomer from the aspect of molecular design, and the thermoplastic aliphatic-aromatic copolyester elastomer has the weight-average molecular weight of 20000-50000g/mol and the elongation at break of 800-1960%.
The technical scheme for realizing the purpose of the invention is as follows:
a thermoplastic aliphatic-aromatic copolyester elastomer has the following chemical structural formula:
wherein x is 1 or 4.
The synthetic route of the thermoplastic aliphatic-aromatic copolyester elastomer is as follows:
wherein x is 1 or 4.
The method comprises the following steps:
(1) adding 1, 4-butanediol, aliphatic dibasic acid and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl diformate into a reaction vessel with a stirring device, a condensing device and a nitrogen protection device; adding catalyst into the reaction container, opening condensed water, and introducing N2And then heating to ensure that the monomers are completely melted and fully and uniformly mixed, continuing heating to the esterification reaction temperature, then carrying out constant-temperature esterification reaction for 3-4h under the stirring condition, and considering that the esterification reaction is finished when the collection amount of water at least reaches 80% of a theoretical value.
(2) After the esterification reaction is finished, a polycondensation stage is carried out, specifically: removing the condensing device, replacing the condensing device with a vacuumizing device provided with a safety bottle, a wheat-type vacuum gauge and an oil pump, gradually heating to the polycondensation reaction temperature, carrying out constant-temperature polycondensation reaction for 3-4h under the stirring condition, simultaneously controlling the vacuum degree of the system to be 50-80Pa, cooling to room temperature after the polycondensation reaction is finished, collecting a product, dissolving the collected product with trichloromethane, adding methanol, fully stirring, filtering, collecting a precipitate, and drying to obtain the thermoplastic aliphatic-aromatic copolyester elastomer. The copolyester precipitate is obtained by adding methanol, and the purpose of purifying the polyester is achieved by utilizing the dissolution characteristics that the polyester and the impurities are dissolved in the trichloromethane, the polyester is not dissolved in the methanol, and the impurities are dissolved in the methanol.
In order to obtain better elasticity, the aliphatic dibasic acid in the step (1) is preferably any one of succinic acid and sebacic acid.
Preferably, the diphenyl ether dicarboxylic acid (ester) in the step (1) is any one of 4, 4-diphenyl ether dicarboxylic acid and dimethyl 4, 4-diphenyl ether dicarboxylate.
In order to make the prepared thermoplastic aliphatic-aromatic copolyester elastomer in a proper molecular weight range and avoid raw material waste, the 1, 4-butanediol, the aliphatic dibasic acid and the mixture are further optimized in the step (1)
The ratio of the total molar amount of diphenyl ether dicarboxylic acid or the total molar amount of aliphatic dibasic acid and diphenyl ether dicarboxylic acid dimethyl ester was 4: 1.
Preferably, the catalyst in the step (1) is any one or more of stannous chloride, stannous octoate, zinc acetate, tetrabutyl titanate and p-toluenesulfonic acid, and the dosage of the catalyst is 0.5-1.0% of the total molar amount of the aliphatic dibasic acid and the diphenyl ether dicarboxylic acid or the total molar amount of the aliphatic dibasic acid and the diphenyl ether dimethyl dicarboxylate.
To prevent the initial modulus (i.e., young's modulus) of the resultant thermoplastic aliphatic-aromatic copolyester elastomer from being high, the stress-strain curve exhibits significant yield, which is not characteristic of typical high-toughness materials, and the material exhibits the characteristics of general plastics (strong and tough), not the characteristics of high-resilience materials. Preferably, the ratio of the molar amount of the aliphatic dibasic acid to the molar amount of the diphenyl ether dicarboxylic acid or the diphenyl ether dimethyl dicarboxylate in step (1) is 40:60 to 70: 30.
Further optimally, the esterification reaction temperature in the step (1) is 180 ℃; the polycondensation reaction temperature in step (2) was 220 ℃.
The thermoplastic aliphatic-aromatic copolyester elastomer can be used for preparing high-molecular thermoplastic biodegradable elastomer products according to the structural characteristics (containing aliphatic monomers).
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation method provided by the invention adopts the mode of putting monomers into reaction equipment for continuous reaction at one time to prepare the high-molecular-weight random copolymerization thermoplastic aliphatic-aromatic copolyester elastomer, and has simple operation and strong process controllability, so that a new method is developed for preparing the thermoplastic copolyester elastomer, and the method is easy to realize the industrialization of products.
2) The invention adopts diphenyl ether dicarboxylic acid or dimethyl diphenyl ether dicarboxylate as a special aromatic comonomer to endow the aliphatic-aromatic copolyester with good toughness and rebound property.
3) The polyester of the present invention has a weight average molecular weight of 20000-50000g/mol and an elongation at break of 800-1960%. The mechanical elasticity of the thermoplastic aliphatic-aromatic copolyester elastomer can be adjusted by the proportion of aliphatic dibasic acid and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl diformate, so that the copolyester elastomer meeting different use requirements can be obtained, and the application space of the copolyester elastomer can be further expanded.
Drawings
FIG. 1 is a stress-strain curve of a thermoplastic aliphatic-aromatic copolyester elastomer prepared in examples 1-4 of the present invention;
FIG. 2 is a cyclic stretch curve of a thermoplastic aliphatic-aromatic copolyester elastomer prepared in example 2 of the present invention;
FIG. 3 is a melting curve in DSC spectrum of thermoplastic aliphatic-aromatic copolyester elastomer prepared in example 2 of the present invention;
fig. 4 is a DMA curve of a thermoplastic aliphatic-aromatic copolyester elastomer prepared in example 2 of the present invention.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1:
0.48mol (43.26g) of 1, 4-butanediol, 0.048mol (5.67g) of succinic acid and 0.072mol (18.59g) of diphenyl ether dicarboxylic acid are added into a 250ml three-neck flask with a stirring device, a condensing device and a nitrogen protection device according to the alkyd acid ratio of 4:1, wherein the molar ratio of the succinic acid to the diphenyl ether dicarboxylic acid is 40: 60. To a three-necked flask, tetrabutyl titanate as a catalyst was added dropwise in an amount of 0.5% (0.204g) based on the molar amount of the acid. Opening the condensed water and introducing N2Heating to 180 ℃, stirring at constant temperature for esterification reaction for 4 hours after the monomers are completely melted, and considering that the esterification reaction is finished when the collection amount of water reaches 80% of a theoretical value;
and (3) after the esterification reaction is finished, entering a polycondensation stage, removing a condensing device, replacing the condensing device with a vacuum pumping device provided with a safety bottle, a wheat-type vacuum meter and an oil pump, gradually heating to 220 ℃, continuously reacting for 4 hours, simultaneously controlling the vacuum degree of the system to be 50-80Pa, cooling to room temperature after the polycondensation reaction is finished, collecting a product, dissolving the collected product with trichloromethane, adding methanol, fully stirring, filtering and drying to obtain the purified thermoplastic aliphatic-aromatic copolyester elastomer.
Example 2
0.48mol (43.26g) of 1, 4-butanediol, 0.06mol (7.09g) of succinic acid and 0.06mol (17.17g) of diphenyl ether dimethyl dicarboxylate are added into a 250ml three-neck flask with a stirring device, a condensing device and a nitrogen protection device, wherein the molar ratio of the succinic acid to the diphenyl ether dimethyl dicarboxylate is 50: 50. To a three-necked flask, tetrabutyl titanate as a catalyst was added dropwise in an amount of 1.0% (0.4g) based on the molar amount of the acid. Opening the condensed water and introducing N2Heating to 180 ℃, stirring at constant temperature for esterification reaction for 3 hours after the monomers are completely melted, and considering that the esterification reaction is finished when the collection amount of water reaches 80% of a theoretical value;
and (3) after the esterification reaction is finished, entering a polycondensation stage, removing a condensing device, replacing the condensing device with a vacuum pumping device provided with a safety bottle, a wheat-type vacuum meter and an oil pump, gradually heating to 220 ℃, continuously reacting for 3 hours, simultaneously controlling the vacuum degree of the system to be 50-80Pa, cooling to room temperature after the polycondensation reaction is finished, collecting a product, dissolving the collected product with trichloromethane, adding methanol, fully stirring, filtering and drying to obtain the purified thermoplastic aliphatic-aromatic copolyester elastomer.
Example 3
0.48mol (43.26g) of 1, 4-butanediol, 0.072mol (14.56g) of sebacic acid and 0.048mol (12.40g) of diphenyl ether dicarboxylic acid are added to a 250ml three-neck flask with a stirring device, a condensing device and a nitrogen protection device according to an alkyd acid ratio of 4:1, wherein the molar ratio of sebacic acid to diphenyl ether dicarboxylic acid is 60: 40. To a three-necked flask, tetrabutyl titanate as a catalyst was added dropwise in an amount of 0.5% (0.2g) based on the molar amount of the acid. Opening the condensed water and introducing N2Heating to 180 ℃, stirring at constant temperature for esterification reaction for 4 hours after the monomers are completely melted, and considering that the esterification reaction is finished when the collection amount of water reaches 80% of a theoretical value;
and (3) after the esterification reaction is finished, entering a polycondensation stage, removing a condensing device, replacing the condensing device with a vacuum pumping device provided with a safety bottle, a wheat-type vacuum meter and an oil pump, gradually heating to 220 ℃, continuously reacting for 4 hours, keeping the system vacuum degree at 50-80Pa, cooling to room temperature after the polycondensation reaction is finished, collecting a product, dissolving the collected product with trichloromethane, adding methanol, fully stirring, filtering and drying to obtain the purified copolymer thermoplastic aliphatic-aromatic copolyester elastomer.
Example 4
0.48mol (43.26g) of 1, 4-butanediol, 0.084mol (16.99g) of sebacic acid and 0.036mol (10.30g) of diphenyl ether dimethyl dicarboxylate were added to a 250ml three-neck flask with a stirring device, a condensing device and a nitrogen protection device in an alkyd ratio of 4:1, wherein the molar ratio of sebacic acid to diphenyl ether dimethyl dicarboxylate was 70: 30. To a three-necked flask, tetrabutyl titanate as a catalyst was added dropwise in an amount of 0.5% (0.2g) based on the molar amount of the acid. Opening the condensed water and introducing N2Heating to 180 ℃, stirring at constant temperature for esterification reaction for 3 hours after the monomers are completely melted, and considering that the esterification reaction is finished when the collection amount of water reaches 80% of a theoretical value;
and (3) after the esterification reaction is finished, entering a polycondensation stage, removing a condensing device, replacing the condensing device with a vacuum pumping device provided with a safety bottle, a wheat-type vacuum meter and an oil pump, gradually heating to 220 ℃, continuously reacting for 3 hours, simultaneously controlling the vacuum degree of the system to be 50-80Pa, cooling to room temperature after the polycondensation reaction is finished, collecting a product, dissolving the collected product with trichloromethane, adding methanol, fully stirring, filtering and drying to obtain the purified thermoplastic aliphatic-aromatic copolyester elastomer.
The thermoplastic aliphatic-aromatic copolyester elastomers prepared in the examples were tested and evaluated by the following methods:
and (3) breaking and stretching: the WD-II 10 type electronic universal tester adopting Shenzhen Kelqiang force is used for measurement according to GB/T1040-.
And (3) cyclic stretching: and testing by adopting a WD-II 10 type electronic universal testing machine with Shenzhen Kenji strength, enabling the sample strip to reach the strain of 200% at the stretching speed of 50mm/min, then restoring the sample strip to the original length at the speed of-50 mm/min to form a cycle, and sequentially stretching back and forth until 10 cycles to obtain a stress-strain curve of cyclic stretching.
Melting curve: a Q200 differential scanning calorimeter of American TA company is adopted for testing, the temperature is increased from minus 40 ℃ to 120 ℃ at 10 ℃/min under the protection of nitrogen, the heat history is eliminated by melting at constant temperature for 3min, then the temperature is reduced by 10 ℃/min and scanned to the normal temperature, then the temperature is increased by 10 ℃/min and scanned to 120 ℃, and a second temperature-increasing curve is taken as a melting curve.
Dynamic mechanical analysis: a DMA 8000 instrument of PE company is adopted, the oscillation frequency is 1.0Hz, the amplitude is 50 μm under a stretching mode, the test temperature range is-90 ℃ to 60 ℃, the heating rate is 3 ℃/min, and a loss factor-temperature curve is obtained.
As is apparent from fig. 1, the stress-strain curves of the random copolymerized thermoplastic aliphatic-aromatic copolyester elastomers prepared in examples 1 to 4 have no yield point and exhibit elastomeric properties of high toughness, wherein the copolyester has the greatest tensile strength and elongation at break when the molar ratio of sebacic acid to dimethyl diphenyloxide dicarboxylate in example 2 is 50: 50. As is apparent from fig. 2, the random copolymerized thermoplastic aliphatic-aromatic copolyester elastomer prepared in example 2 exhibits high elastic recovery property. As is apparent from fig. 3, the random copolymerized thermoplastic aliphatic-aromatic copolyester elastomer prepared in example 2 has no melting peak and behaves as an amorphous polymer. As is apparent from fig. 4, the glass transition temperature of the random copolymerized thermoplastic aliphatic-aromatic copolyester elastomer prepared in example 2 is 19.7 ℃ < room temperature (25 ℃), so that the material exhibits good segmental motion ability at room temperature, thereby having good rebound characteristics.
Claims (6)
1. A thermoplastic aliphatic-aromatic copolyester elastomer characterized in that: the copolyester elastomer is a random copolymer of 1, 4-butanediol monomer, aliphatic dibasic acid monomer and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl dicarboxylate monomer, and the chemical structural formula of the random copolymer is as follows:
wherein x is 1 or 4;
the weight-average molecular weight of the copolyester elastomer is 20000-ion 50000g/mol, and the elongation at break is 800-ion 1960%;
the ratio of the molar weight of the 1, 4-butanediol monomer to the total molar weight of the aliphatic dibasic acid monomer and the diphenyl ether dicarboxylic acid or to the total molar weight of the aliphatic dibasic acid monomer and the diphenyl ether dicarboxylic acid dimethyl ester is 4: 1;
the ratio of the molar weight of the aliphatic dibasic acid monomer to the molar weight of the diphenyl ether dicarboxylic acid or the diphenyl ether dimethyl dicarboxylate is 40:60-70: 30.
2. A process for preparing a thermoplastic aliphatic-aromatic copolyester elastomer according to claim 1, wherein: the method comprises the following steps:
(1) adding monomer 1, 4-butanediol, aliphatic dibasic acid and diphenyl ether dicarboxylic acid or diphenyl ether dimethyl diformate into the beltA reaction vessel with a stirring device, a condensing device and a nitrogen protection device; adding catalyst into the reaction container, opening condensed water and introducing N2Heating to completely melt the monomers and fully and uniformly mixing, continuing heating to the esterification reaction temperature, then carrying out constant-temperature esterification reaction for 3-4h under the stirring condition, and considering that the esterification reaction is finished when the collection amount of water at least reaches 80% of a theoretical value;
(2) after the esterification reaction is finished, removing the condensing device, replacing the condensing device with a vacuumizing device provided with a safety bottle, a wheat-type vacuum meter and an oil pump, gradually heating to the polycondensation reaction temperature, carrying out constant-temperature polycondensation reaction for 3-4h under the stirring condition, simultaneously controlling the vacuum degree of the system to be 50-80Pa, cooling to room temperature after the polycondensation reaction is finished, collecting a product, dissolving the collected product with trichloromethane, adding methanol, fully stirring, filtering, collecting a precipitate, and drying to obtain the thermoplastic aliphatic-aromatic copolyester elastomer.
3. The process for preparing thermoplastic aliphatic-aromatic copolyester elastomer according to claim 2, characterized in that: the aliphatic dibasic acid in the step (1) is any one of succinic acid and sebacic acid.
4. The process for preparing thermoplastic aliphatic-aromatic copolyester elastomer according to claim 2, characterized in that: the esterification reaction temperature in the step (1) is 180 ℃; the polycondensation reaction temperature in the step (2) is 220 ℃.
5. The process for preparing thermoplastic aliphatic-aromatic copolyester elastomer according to claim 2, characterized in that: the catalyst in the step (1) is any one or more of stannous chloride, stannous octoate, zinc acetate, tetrabutyl titanate and p-toluenesulfonic acid, and the dosage of the catalyst is 0.5-1.0% of the total molar amount of the aliphatic dibasic acid and the diphenyl ether dicarboxylic acid or the total molar amount of the aliphatic dibasic acid and the diphenyl ether dimethyl phthalate.
6. Use of a thermoplastic aliphatic-aromatic copolyester elastomer according to claim 1 for preparing a polymeric thermoplastic biodegradable elastomer article.
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