A copolyester material and its preparation method

Abstract

The present invention relates to the field of polymer technology, and particularly relates to a copolyester material and a preparation method thereof. In the present invention, an antibacterial agent-containing copolyester and a POSS-containing copolyester are uniformly mixed and put into a twin-screw extruder for extrusion. By combining the respective characteristics of titanium-zinc composite nanofibers, POSS organic compounds, and copolyesters, the prepared copolyester material has excellent heat resistance, antibacterial properties, and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the field of polymer technology, and particularly to a copolyester material and a preparation method thereof. Background Art

[0002] Polyester is a general term for polymers obtained by polycondensation of polyols and polyacids. Copolyester materials have the advantages of good thermal stability, cold resistance, heat resistance, moisture resistance, chemical corrosion resistance, biodegradability, etc., and are widely used in industries such as fibers, clothing, packaging, binding, building materials, and automobiles. Polyester materials are widely used in food packaging. In the daily living environment, there are various bacteria and molds scattered, such as the most common Staphylococcus aureus, Escherichia coli, and Candida albicans, etc. These bacteria are easily attached to the plastic bottle body, especially on baby bottles, which may cause cross-infection and seriously endanger the health of infants. At the same time, conventional polyester materials have problems such as poor heat resistance and no antibacterial property in food packaging.

[0003] CN104804380A discloses a high-strength PET copolyester material for 3D printing and a preparation method thereof. The weight percentage composition of the raw materials is: 70 - 85% of PET, 15 - 30% of reinforcing fiber, 0.5 - 2.0% of coupling agent, 0.1 - 2.0% of stabilizer, 0.1 - 1.0% of antioxidant, and 0.1 - 1.0% of lubricant. The preparation method of the present invention is to weigh the materials in the raw material formula according to the weight ratio, dry the materials and mix them evenly, and then feed the mixed materials into the hopper of a twin-screw extruder, and perform high-speed shearing, extrusion, strand drawing, cooling, and pelletizing through the twin-screw. The 3D printing PET copolyester material prepared by the present invention has low price, high mechanical strength, low melting temperature, small shrinkage rate, and good dimensional stability, and can replace expensive 3D printing ABS materials and polylactic acid materials; however, the compatibility between the fiber and the PET resin is poor, and the fiber is prone to migration, which affects its mechanical properties.

[0004] CN104558551A discloses a method for preparing a copolyester material, a copolyester material and its application. The method includes: carrying out a first contact reaction and a second contact reaction on terephthalic acid, isophthalic acid and a diol in the presence of a catalyst in sequence to obtain the copolyester material, wherein the mass ratio of the amounts of terephthalic acid, isophthalic acid and the diol is 100:(50 - 110):(50 - 150), preferably 100:(55 - 100):(60 - 120). According to the copolyester material provided by the present invention, the foaming temperature range is relatively wide, which is suitable for realizing continuous extrusion foaming at a lower temperature. The obtained foamed product has a high closed-cell rate, a low processing temperature, and a high foaming ratio (the foaming ratio can reach 10 - 20 times). The foamed products prepared from the copolyester can be used for self-insulating sheets, packaging materials, etc.; however, the mechanical properties, antibacterial property, and heat resistance need to be further improved. Summary of the Invention

[0005] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a copolyester composite material with excellent heat resistance, antibacterial property and mechanical properties. In the present invention, the antibacterial agent-containing copolyester and the POSS-containing copolyester are uniformly mixed and put into a twin-screw extruder for extrusion. Combining the respective characteristics of titanium-zinc composite nanofibers, POSS organic compounds and copolyesters, the prepared copolyester material has excellent heat resistance, antibacterial property and mechanical properties.

[0006] To achieve the above object, the present invention provides a copolyester material, which is characterized in that it comprises an antibacterial agent-containing copolyester and a POSS-containing copolyester.

[0007] Among them, the antibacterial agent-containing copolyester and the POSS-containing copolyester are mixed in a mass ratio of (1 - 3):(1 - 3).

[0008] The preparation method of the antibacterial agent-containing copolyester comprises the following steps:

[0009] Mix the dibasic acid, carboxylated antibacterial agent, diol and polyol uniformly, heat to 200 - 210°C under a nitrogen atmosphere, add a catalyst, maintain 200 - 210°C to remove the water generated by the reaction through a shunt, judge the reaction degree by weighing the water generated by the reaction, when the esterification rate reaches 90 - 95%, continue the reaction at a vacuum of 50 - 100 Pa and 230 - 280°C for 3 - 5 h, after the reaction is completed, cool to room temperature, and obtain the antibacterial agent-containing copolyester through extraction with methanol and water, washing and drying.

[0010] Further, the preparation method of the antibacterial agent-containing copolyester comprises the following steps:

[0011] Mix 1 - 5 parts by weight of dibasic acid, 0.1 - 0.34 parts by weight of carboxylated antibacterial agent, 5 - 10 parts by weight of diol and 2 - 5 parts by weight of polyol uniformly, heat to 200 - 210°C under a nitrogen atmosphere, add 0.01 - 0.05 parts by weight of catalyst, maintain 200 - 210°C to remove the water generated by the reaction through a shunt, judge the reaction degree by weighing the water generated by the reaction, when the esterification rate reaches 90 - 95%, continue the reaction at a vacuum of 50 - 100 Pa and 230 - 280°C for 3 - 5 h, after the reaction is completed, cool to room temperature, and obtain the antibacterial agent-containing copolyester through extraction with methanol and water, washing and drying;

[0012] The present invention uses zinc gluconate and titanium dioxide as raw materials, and polyvinylpyrrolidone as a guiding agent to prepare titanium-zinc composite nanofibers. The combination between various substances is better, the mixing is more uniform, and the antibacterial performance in the lattice of zinc-doped titanium dioxide is improved. However, when the titanium-zinc composite nanofibers are added to copolyester in a conventional manner, their dispersion performance is poor and they are prone to migration, resulting in a significant reduction in their antibacterial performance. On this basis, the titanium-zinc composite nanofibers are modified to provide better dispersion with copolyester materials and a more stable system, making the antibacterial property and stability more persistent.

[0013] The present invention modifies the titanium-zinc composite nanofibers with an amino-silane coupling agent. At the same time, under the action of EDC and NHS, it is combined with citric acid and incorporated into copolyester as a monomer, providing better dispersion with copolyester materials and a more stable system, making the antibacterial property and stability more persistent. At the same time, the modified titanium-zinc composite nanofibers are distributed in all directions in the copolyester, intertwined with each other to form a network, improving their mechanical properties.

[0014] The preparation method of the carboxylated antibacterial agent includes the following steps:

[0015] Add 1-5 parts by weight of zinc gluconate to 100-200 parts by weight of a mixed solvent (volume ratio of ethylene glycol to water is 1:3), mix evenly, add 0.1-0.5 parts by weight of sodium hydroxide and perform ultrasonic treatment, then add 1-8 parts by weight of titanium dioxide and 2-5 parts by weight of polyvinylpyrrolidone and stir for 10-20 min. Transfer to a high-pressure hydrothermal autoclave (react at 1-3 MPa and 200-220 °C for 8-10 h), cool to room temperature, take out, filter, wash, and dry to obtain titanium-zinc composite nanofibers;

[0016] Add 5-15 parts by weight of titanium-zinc composite nanofibers and 0.01-0.8 parts by weight of amino-silane coupling agent to 100-200 parts by weight of a 70-90 wt% ethanol aqueous solution, perform ultrasonic treatment for 10-30 min (ultrasonic power 150-300 W, ultrasonic frequency 25-50 kHz), then heat to 75-90 °C and react for 1-2 h. After the reaction, centrifuge, wash, and dry to obtain the modified antibacterial agent;

[0017] Add 1-2 parts by weight of the modified antibacterial agent to 100-200 parts by weight of water for ultrasonic dispersion, add 0.1-0.5 parts by weight of citric acid and mix evenly, then add 1-2 parts by weight of an EDC / NHS mixed solution (where the final molar concentration of EDC is 1 mM and the final molar concentration of NHS is 0.5 mM), react at room temperature for 24 h. After the reaction, centrifuge, wash, and freeze-dry to obtain the carboxylated antibacterial agent.

[0018] Further, the amino-silane coupling agent is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)trimethoxysilane, and N-2-(aminoethyl)dimethoxysilane.

[0019] The preparation method of the POSS-containing copolyester comprises the following steps:

[0020] Mix the dibasic acid, diol, and polybasic acid evenly, heat to 200 - 210°C under a nitrogen atmosphere, add a catalyst, maintain at 200 - 210°C to remove the water generated by the reaction through distillation, judge the reaction degree by weighing the water generated by the reaction, when the esterification rate reaches 90 - 95%, add isobutylated cuboctasilsesquioxane of 1,2-propanediol and polylactic acid, continue the reaction for 1 - 2 h, and continue the reaction for 3 - 5 h under a vacuum of 50 - 100 Pa and at 230 - 280°C. After the reaction is completed, cool to room temperature, and obtain the POSS-containing copolyester through extraction with methanol and water, washing, and drying.

[0021] More preferably, the preparation method of the POSS-containing copolyester comprises the following steps:

[0022] Mix 1 - 3 parts by weight of dibasic acid, 5 - 10 parts by weight of diol, and 1 - 2 parts by weight of polybasic acid evenly, heat to 200 - 210°C under a nitrogen atmosphere, add 0.01 - 0.05 parts by weight of catalyst, maintain at 200 - 210°C to remove the water generated by the reaction through distillation, judge the reaction degree by weighing the water generated by the reaction, when the esterification rate reaches 90 - 95%, add 0.1 - 0.3 parts by weight of isobutylated cuboctasilsesquioxane of 1,2-propanediol and 1 - 5 parts by weight of polylactic acid, continue the reaction for 1 - 2 h, and continue the reaction for 3 - 5 h under a vacuum of 50 - 100 Pa and at 230 - 280°C. After the reaction is completed, cool to room temperature, and obtain the POSS-containing copolyester through extraction with methanol and water, washing, and drying.

[0023] Further, the dibasic acid is one or a mixture of more than one of terephthalic acid, sebacic acid, isophthalic acid, adipic acid, succinic acid, itaconic acid, fumaric acid, maleic acid, citric acid, tartaric acid, and 2,6-naphthalenedicarboxylic acid;

[0024] Further, the polybasic acid is trimesic acid;

[0025] Further, the diol is one or a mixture of more than one of 1,4-butanediol, hexanediol, neopentyl glycol, ethylene glycol, and propylene glycol;

[0026] Further, the polyol is one or a mixture of more than one of glycerol, trimethylolpropane, and pentaerythritol;

[0027] Further, the catalyst is one or a mixture of more of tetrabutyl titanate, dibutyltin dilaurate, and stannous chloride.

[0028] Further, the POSS is surrounded by eight organic substituents (R groups) connected to the Si vertices. The inorganic core endows the material with good heat resistance and mechanical properties, while the peripheral organic groups can improve the good chemical compatibility between POSS and copolyester. Introducing 1,2 - propanediol isobutylated cage - shaped sesquisiloxane into the copolyester can improve its dispersion performance, prevent agglomeration, change the internal arrangement rules of the copolyester molecular chain, and further improve its mechanical and heat resistance properties.

[0029] In the present invention, the antibacterial agent - containing copolyester and the POSS - containing copolyester are uniformly mixed and put into a twin - screw extruder for extrusion. Combining the respective characteristics of the titanium - zinc composite nanofibers, POSS organic matter, and copolyester, the prepared copolyester material has excellent heat resistance, antibacterial, and mechanical properties.

[0030] Auxiliary agents such as antioxidants, compatibilizers, lubricants, plasticizers, and heat stabilizers can also be added to the copolyester material provided by the present invention as needed.

[0031] The present invention also discloses a preparation method of a copolyester material.

[0032] A preparation method of a copolyester material includes the following steps:

[0033] The antibacterial agent - containing copolyester and the POSS - containing copolyester are uniformly mixed in a high - speed mixer, and then put into a twin - screw extruder, and melt - extruded and pelletized at 185 - 230 °C to obtain the copolyester material.

[0034] The beneficial effects of the present invention:

[0035] Compared with the prior art, in the present invention, the antibacterial agent - containing copolyester and the POSS - containing copolyester are uniformly mixed and put into a twin - screw extruder for extrusion. Combining the respective characteristics of the titanium - zinc composite nanofibers, POSS organic matter, and copolyester, the prepared copolyester material has excellent heat resistance, antibacterial, and mechanical properties. Specific embodiments

[0036] In the ranges disclosed in the present invention, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention.

[0037] Introduction to some raw materials used in the embodiments of the present invention:

[0038] 1,2-Propanediol isobutylated cage-shaped silsesquioxane, product number: Q-0000320, was purchased from Xi'an Qiyue Biotechnology Co., Ltd.

[0039] Titanium dioxide, 100 nm;

[0040] Polyvinyl pyrrolidone, product number: P274371, MW40000, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0041] Polylactic acid, molecular weight 60,000, was purchased from Shanghai Kanglang Biotechnology Co., Ltd.

[0042] Other raw materials not mentioned are common raw materials in the art. The above content is only to help illustrate the present invention and should not be construed as a strict limitation of the present invention. Those skilled in the art can directly purchase or prepare the same / similar raw materials from the market. These contents will not be repeated in the examples.

[0043] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0044] Example 1

[0045] A method for preparing a copolyester material comprises the following steps:

[0046] 3 parts by weight of terephthalic acid, 2 parts by weight of adipic acid, 0.35 parts by weight of carboxylated antibacterial agent, 5 parts by weight of neopentyl glycol, 5 parts by weight of 1,4-butanediol and 4 parts by weight of pentaerythritol were mixed uniformly, heated to 210°C under a nitrogen atmosphere, 0.05 parts by weight of tetrabutyl titanate were added, and the temperature was maintained at 210°C to remove water generated by the reaction by shunt. The degree of reaction was judged by weighing the water generated by the reaction. When the esterification rate reached 95%, the reaction was continued for 5 hours at a vacuum degree of 80Pa and 250°C. After the reaction was completed, it was cooled to room temperature, extracted with methanol and water, washed and dried to obtain a copolyester material.

[0047] The preparation method of the carboxylated antibacterial agent comprises the following steps:

[0048] S1 Add 5 parts by weight of zinc gluconate to 200 parts by weight of a mixed solvent (volume ratio of ethylene glycol to water is 1:3), mix evenly, add 0.5 part by weight of sodium hydroxide, and perform ultrasonic treatment. Then add 4 parts by weight of titanium dioxide and 2 parts by weight of polyvinylpyrrolidone, stir for 10 min, transfer to a high-pressure hydrothermal reactor, react at 2 MPa and 220 °C for 10 h, cool to room temperature, take out, filter, wash, and dry to obtain titanium-zinc composite nanofibers;

[0049] S2 Add 5 parts by weight of titanium-zinc composite nanofibers and 0.1 part by weight of 3-aminopropyltriethoxysilane to 100 parts by weight of a 90 wt% ethanol aqueous solution, perform ultrasonic treatment for 30 min, with an ultrasonic power of 300 W and an ultrasonic frequency of 25 kHz, then heat to 80 °C and react for 2 h. After the reaction, centrifuge, wash, and dry to obtain a modified antibacterial agent;

[0050] S3 Add 2 parts by weight of the modified antibacterial agent to 100 parts by weight of water, perform ultrasonic dispersion, add 0.5 part by weight of citric acid and mix evenly, then add 1 part by weight of an EDC / NHS mixture (where the final molar concentration of EDC is 1 mM and the final molar concentration of NHS is 0.5 mM), react at room temperature for 24 h. After the reaction, centrifuge, wash, and freeze-dry to obtain a carboxylated antibacterial agent.

[0051] Example 2

[0052] A method for preparing a copolyester material, comprising the following steps:

[0053] Mix 3 parts by weight of terephthalic acid, 5 parts by weight of neopentyl glycol, 5 parts by weight of 1,4-butanediol, and 2 parts by weight of trimellitic acid evenly, heat to 210 °C under a nitrogen atmosphere, add 0.05 part by weight of tetrabutyl titanate, maintain at 210 °C to remove the water generated by the reaction through distillation, judge the reaction degree by weighing the water generated by the reaction. When the esterification rate reaches 95%, add 0.2 part by weight of 1,2-propanediol isobutylated cage-like silsesquioxane and 5 parts by weight of polylactic acid, continue to react for 2 h, and then continue to react at a vacuum of 80 Pa and 250 °C for 5 h. After the reaction, cool to room temperature, extract with methanol and water, wash, and dry to obtain the copolyester material.

[0054] Example 3

[0055] A method for preparing a copolyester material, comprising the following steps:

[0056] Step 1: Mix 3 parts by weight of terephthalic acid, 2 parts by weight of adipic acid, 0.35 parts by weight of carboxylated antibacterial agent, 5 parts by weight of neopentyl glycol, 5 parts by weight of 1,4-butanediol, and 4 parts by weight of pentaerythritol evenly. Under a nitrogen atmosphere, heat to 210°C, add 0.05 parts by weight of tetrabutyl titanate, maintain 210°C to remove the water generated by the reaction through diversion, and judge the reaction degree by weighing the water generated by the reaction. When the esterification rate reaches 95%, continue the reaction at a vacuum of 80 Pa and 250°C for 5 h. After the reaction is completed, cool to room temperature, and obtain the antibacterial agent-containing copolyester through extraction, washing, and drying with methanol and water;

[0057] Step 2: Mix 3 parts by weight of terephthalic acid, 5 parts by weight of neopentyl glycol, 5 parts by weight of 1,4-butanediol, and 2 parts by weight of trimellitic acid evenly. Under a nitrogen atmosphere, heat to 210°C, add 0.05 parts by weight of tetrabutyl titanate, maintain 210°C to remove the water generated by the reaction through diversion, and judge the reaction degree by weighing the water generated by the reaction. When the esterification rate reaches 95%, add 0.2 parts by weight of 1,2-propanediol isobutylated cage-like silsesquioxane and 5 parts by weight of polylactic acid, and continue the reaction for 2 h. Then continue the reaction at a vacuum of 80 Pa and 250°C for 5 h. After the reaction is completed, cool to room temperature, and obtain the POSS-containing copolyester through extraction, washing, and drying with methanol and water;

[0058] Step 3: Mix the antibacterial agent-containing copolyester and the POSS-containing copolyester evenly in a high-speed mixer according to a mass ratio of 2:1, and then put them into a twin-screw extruder, melt extrude and pelletize at 210°C to obtain the copolyester material.

[0059] The preparation method of the carboxylated antibacterial agent is the same as that in Example 1.

[0060] Example 4

[0061] A preparation method of a copolyester material is basically the same as that in Example 1, except that: titanium-zinc composite nanofibers are used to replace the carboxylated antibacterial agent;

[0062] The preparation method of the titanium-zinc composite nanofibers includes the following steps:

[0063] Add 5 parts by weight of zinc gluconate to 200 parts by weight of a mixed solvent (volume ratio of ethylene glycol to water is 1:3) and mix evenly. Add 0.5 parts by weight of sodium hydroxide and perform ultrasonic treatment. Add 4 parts by weight of titanium dioxide and 2 parts by weight of polyvinylpyrrolidone and stir for 10 min. Transfer to a high-pressure hydrothermal reactor and react at 2 MPa and 220°C for 10 h. After cooling to room temperature, take out, filter, wash, and dry to obtain the titanium-zinc composite nanofibers.

[0064] Example 5

[0065] A preparation method of a copolyester material is basically the same as that of Example 3, except that in Step 3, the antibacterial agent-containing copolyester and the POSS-containing copolyester are mixed at a mass ratio of 1:1.

[0066] Example 6

[0067] A preparation method of a copolyester material is basically the same as that of Example 3, except that in Step 3, the antibacterial agent-containing copolyester and the POSS-containing copolyester are mixed at a mass ratio of 1:2.

[0068] Test Example

[0069] The antibacterial performance test was carried out with reference to GB / T 31402-2015 "Test Method for Antibacterial Properties of Plastics on the Surface of Plastics"; among them, the test bacteria were Escherichia coli ATCC8739 and Staphylococcus aureus ATCC6538P.

[0070] Experimental test results: The antibacterial rates of the copolyester materials obtained in Examples 1 and 3 against Escherichia coli were ≥99%, and the antibacterial rates against Staphylococcus aureus were ≥99%. The antibacterial rate of the copolyester material prepared in Example 4 against Escherichia coli was 87.8%, and the antibacterial rate against Staphylococcus aureus was 85.4%.

[0071] In Example 4, zinc gluconate and titanium dioxide were used as raw materials, and polyvinylpyrrolidone was used as a guiding agent to prepare titanium-zinc composite nanofibers. The combination between various substances was better, the mixing was more uniform, and the antibacterial performance in the lattice of zinc-doped titanium dioxide was improved. Therefore, the copolyester material prepared in this application has good antibacterial performance. However, its antibacterial performance is still inferior to that of Examples 1 and 3. On the basis of Example 4, Examples 1 and 3 modified the titanium-zinc composite nanofibers and introduced them into the copolyester block to improve its dispersion performance and avoid its migration, further improving the antibacterial performance. Therefore, the copolyester material prepared in this application has good antibacterial performance.

[0072] The tensile property test was carried out with reference to ASTM D638-91; the notched impact strength test was carried out with reference to GB / T 1843-2008 "Determination of Izod Impact Strength of Plastics".

[0073] Table 1 Test results of the mechanical properties of the copolyester material

[0074] Tensile strength / MPa <![CDATA[Notched impact strength (KJ / m 2 )]]> Example 1 35 23 Example 2 37 25 Example 3 43 31 Example 4 31 19 Example 5 40 28 Example 6 38 25

[0075] As can be seen from Table 1, the copolyester prepared in Example 3 has good mechanical properties. In Example 3, an amino-silane coupling agent was used to modify the titanium-zinc composite nanofibers. Meanwhile, under the action of EDC and NHS, it was combined with citric acid and used as a monomer to be incorporated into the copolyester, providing better dispersibility with the copolyester material and making the system more stable, so that the antibacterial property and stability are more persistent. At the same time, the modified titanium-zinc composite nanofibers are distributed in all directions in the copolyester, intertwined with each other to form a network, improving its mechanical properties. The periphery of POSS is surrounded by eight organic substituents (R groups) connected to the Si vertices. The inorganic core endows the material with good heat resistance and mechanical properties, while the peripheral organic groups can improve the good chemical compatibility between POSS and the copolyester. 1,2-Isobutylated propanediol caged silsesquioxane was introduced into the copolyester to improve its dispersion performance, prevent aggregation, change the internal arrangement rules of the copolyester molecular chain, and further improve its mechanical and heat resistance properties. In the present invention, the antibacterial agent-containing copolyester and the POSS-containing copolyester are uniformly mixed and fed into a twin-screw extruder for extrusion. By combining the respective characteristics of the titanium-zinc composite nanofibers, POSS organic matter, and copolyester, the prepared copolyester material has excellent heat resistance, antibacterial property, and mechanical properties.

[0076] The glass transition temperature was measured by a differential scanning calorimeter (DSC). The test conditions were as follows: nitrogen atmosphere, gas flow rate of 20 ml / min; the sample was heated from 30 °C to 250 °C at a heating rate of 20 °C / min.

[0077] Table 2 Test results of the glass transition temperature of the copolyester material

[0078]

[0079]

[0080] In the present invention, the antibacterial agent-containing copolyester and the POSS-containing copolyester are uniformly mixed and fed into a twin-screw extruder for extrusion. By combining the respective characteristics of the titanium-zinc composite nanofibers, POSS organic matter, and copolyester, the prepared copolyester material has excellent heat resistance, antibacterial property, and mechanical properties.

[0081] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative labor. Therefore, all technical solutions that can be obtained by those skilled in the art in the technical field of the present invention based on the concept of the present invention through logical analysis, reasoning, or limited experiments on the basis of the prior art should be within the protection scope determined by the claims.

Claims

1. A copolyester material, characterized in that: Including copolyesters containing antimicrobial agents and copolyesters containing POSS; The mass ratio of the copolyester containing antimicrobial agent and the copolyester containing POSS is (1-3): (1-3); The preparation method of the antibacterial agent-containing copolyester comprises the following steps: 1-5 parts by weight of a dibasic acid, 0.1-0.34 parts by weight of a carboxylated antibacterial agent, 5-10 parts by weight of a diol, and 2-5 parts by weight of a polyol are uniformly mixed, heated to 200-210° C. under a nitrogen atmosphere, 0.01-0.05 parts by weight of a catalyst are added, the temperature is maintained at 200-210° C. to remove water generated by the reaction by splitting, the degree of reaction is judged by weighing the water generated by the reaction, when the esterification rate reaches 90-95%, the reaction is continued for 3-5 hours at a vacuum degree of 50-100 Pa and 230-280° C., after the reaction is completed, the mixture is cooled to room temperature, extracted with methanol and water, washed, and dried to obtain a copolyester containing an antibacterial agent; The preparation method of the described POSS copolyester comprises the following steps: 1-3 parts by weight of a dibasic acid, 5-10 parts by weight of a diol, and 1-2 parts by weight of a polyacid are uniformly mixed, heated to 200-210° C. under a nitrogen atmosphere, 0.01-0.05 parts by weight of a catalyst are added, the temperature is maintained at 200-210° C. to remove water generated by the reaction by splitting, the degree of reaction is judged by weighing the water generated by the reaction, and when the esterification rate reaches 90-95%, 0.1-0.3 parts by weight of 1,2-propylene glycol isobutylated cage-shaped silsesquioxane and 1-5 parts by weight of polylactic acid are added, the reaction is continued for 1-2 hours, and the reaction is continued for 3-5 hours at a vacuum degree of 50-100 Pa and 230-280° C. After the reaction is completed, the mixture is cooled to room temperature, extracted with methanol and water, washed, and dried to obtain a POSS-containing copolyester; The preparation method of the carboxylated antibacterial agent comprises the following steps: 1-5 parts by weight of zinc gluconate are added to 100-200 parts by weight of a mixed solvent and mixed evenly, 0.1-0.5 parts by weight of sodium hydroxide are added for ultrasonic treatment, 1-8 parts by weight of titanium dioxide and 2-5 parts by weight of polyvinyl pyrrolidone are added and stirred for 10-20 minutes, and the mixture is transferred to a high-pressure hydrothermal autoclave at 1-3 MPa and 200-220° C. for reaction for 8-10 hours, and after cooling to room temperature, the mixture is taken out, filtered, washed, and dried to obtain titanium-zinc composite nanofibers; 5-15 parts by weight of titanium-zinc composite nanofibers and 0.01-0.8 parts by weight of aminosilane coupling agent are added to 100-200 parts by weight of 70-90wt% ethanol aqueous solution, and ultrasonically treated for 10-30 minutes at an ultrasonic power of 150-300W and an ultrasonic frequency of 25-50kHz, and then heated to 75-90°C for reaction for 1-2 hours. After the reaction is completed, centrifuge, wash, and dry to obtain a modified antibacterial agent; 1-2 parts by weight of the modified antibacterial agent are added to 100-200 parts by weight of water and ultrasonically dispersed, 0.1-0.5 parts by weight of citric acid are added and mixed evenly, and then 1-2 parts by weight of an EDC / NHS mixed solution is added, wherein the final molar concentration of EDC is 1 mM, and the final molar concentration of NHS is 0.5 mM. The mixture is reacted at room temperature for 24 hours. After the reaction is completed, the mixture is centrifuged, washed, and freeze-dried to obtain a carboxylated antibacterial agent.

2. The copolyester material according to claim 1, characterized in that: The dibasic acid is a mixture of one or more of terephthalic acid, sebacic acid, isophthalic acid, adipic acid, succinic acid, itaconic acid, fumaric acid, maleic acid, citric acid, tartaric acid and 2,6-naphthalene dicarboxylic acid.

3. The copolyester material according to claim 1, characterized in that: The polyacid is trimesic acid.

4. The copolyester material according to claim 1, characterized in that: The diol is a mixture of one or more of 1,4-butanediol, hexanediol, neopentyl glycol, ethylene glycol and propylene glycol.

5. The copolyester material according to claim 1, characterized in that: The polyol is a mixture of one or more of glycerol, trimethylolpropane and pentaerythritol.

6. The copolyester material according to claim 1, characterized in that: The catalyst is a mixture of one or more of tetrabutyl titanate, dibutyltin dilaurate and stannous chloride.

7. A method for preparing the copolyester material according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: uniformly mixing the antibacterial agent-containing copolyester and the POSS-containing copolyester in a high-speed mixer, and then putting them into a twin-screw extruder, melting and extruding at 185-230 DEG C, and pelletizing to obtain the copolyester material.

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