CN111978522B - Preparation method of hydrophilic antistatic antibacterial copolyester master batch - Google Patents
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Abstract
The invention belongs to the field of new materials, and particularly relates to a preparation method of hydrophilic antistatic antibacterial copolyester master batch, which takes triethylene glycol diacetate as a solvent and a nanoparticle stabilizer, adopts a non-hydrolytic sol-gel method to prepare nano ZnO, and can be used for polycondensation reaction of polyethylene terephthalate (PET) without separation; in the polycondensation reaction of PET, triethylene glycol is used as a hydrophilic modification monomer to participate in the polycondensation reaction of PET. The method has the advantages of simple preparation process, uniform dispersion of the nanoparticles in the PET, good antibacterial property and good moisture absorption of the obtained polyester.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a preparation method of hydrophilic antistatic antibacterial copolyester master batch.
Background
The polyethylene terephthalate (PET) fiber has high strength and good stiffness and smoothness, and is widely applied to the fields of textile clothing, decoration and industrial textiles. However, the conventional polyester fiber has high crystallinity, regular molecular structure arrangement, and the macromolecule lacks polar hydrophilic groups, the official moisture regain of the conventional polyester fiber is only 0.4%, the conventional polyester fiber is poor in hygroscopicity, static electricity is easy to generate, and the wearing comfort is affected. In the fabric after-finishing stage, the moisture absorption of the polyester fiber can be improved through hydrophilic finishing, but the finishing effect is not durable to water washing.
Antibacterial agents can be classified into natural, organic and inorganic antibacterial agents. The inorganic antibacterial agent has wide antibacterial spectrum, high safety, good heat resistance, and good plasticityThe method has wide application in the fields of materials, papermaking, building materials and the like. According to the action mechanism, the inorganic antibacterial agent can be divided into two categories of metal ion type and photocatalysis type, zinc oxide is taken as the representative of the photocatalysis type inorganic antibacterial agent, the antibacterial mechanism is that under the irradiation of ultraviolet light, photoproduction electrons and cavities are formed, and the cavities can lead OH-and H-in the air 2 O is oxidized to OH, and simultaneously, high-activity electrons formed on a conduction band can reduce oxygen in the air to O 2- These OH and O 2- Not only can oxidize and degrade organic matters, but also can penetrate cell membranes to cause the rupture and decomposition of bacterial cells, thereby playing a role in sterilization. Although the advantages of the inorganic antibacterial agent are obvious, when the inorganic antibacterial agent is used as an antibacterial component to prepare antibacterial master batches, the particle size, the dispersibility and the compatibility with matrix resin of the inorganic antibacterial agent directly influence the performance of a final product.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the problems of poor moisture absorption of conventional PET fibers and poor compatibility and dispersibility of the existing zinc oxide antibacterial agent and PET are solved, and the method for preparing the hydrophilic antistatic antibacterial copolyester master batch is provided.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of hydrophilic antistatic antibacterial copolyester master batch is characterized in that triethylene glycol and zinc acetate are used as raw materials to prepare nano ZnO dispersion liquid, and then the dispersion liquid is directly used for preparing PET to obtain the hydrophilic antistatic antibacterial copolyester master batch. Triethylene glycol is a solvent and a nanoparticle stabilizer; in the polymerization process of PET, triethylene glycol is used as a hydrophilic monomer to participate in the modification of PET, nano ZnO is uniformly dispersed in matrix resin, the antibacterial property is good, and the obtained polyester has good hygroscopicity.
The invention provides a preparation method of hydrophilic antistatic antibacterial copolyester master batch, which comprises the following steps:
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, fully stirring and uniformly mixing, heating to 120 ℃, stirring until the zinc acetate is completely dissolved, slowly heating to 180-220 ℃, preserving heat for 30-60min, and cooling to room temperature after heat preservation is finished to obtain nano ZnO dispersion liquid;
wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol is 0.02-0.1g/mL;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle, adding ethylene glycol antimony as a catalyst and triphenyl phosphate as a heat stabilizer, introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 230-250 ℃ and 0.1-0.3 MPa, controlling the temperature at the top of the kettle to be 110-135 ℃, adding the nano ZnO dispersion liquid obtained in the step (1) when the esterification water yield reaches 95% of a theoretical value after finishing esterification, continuously esterifying for 40-60min at 230-250 ℃ and 0.1-0.3 MPa, and then entering a polycondensation stage; and (3) carrying out polycondensation reaction at 260-285 ℃ under the condition of vacuum degree of 20-60Pa, adjusting the rotating speed to 60r/min when the ethylene glycol distillation amount is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurization, extruding a reaction product and pelletizing.
Wherein the molar ratio of terephthalic acid to ethylene glycol is 1.0-1.4; the mass ratio of the nano ZnO dispersion liquid to the terephthalic acid is 80-120; the mass fraction of the ethylene glycol antimony relative to the terephthalic acid is 0.05-0.1%; the mass fraction of triphenyl phosphate relative to terephthalic acid is 0.05% -0.1%.
The method takes triethylene glycol diacetate as a solvent and a nano particle stabilizer, adopts a non-hydrolytic sol-gel method to prepare nano ZnO, and the obtained product does not need to be separated; in the polycondensation reaction of PET, triethylene glycol is used as a hydrophilic modification monomer to participate in the polycondensation reaction of PET. The preparation process is simple, the nano particles are uniformly dispersed in the PET, the antibacterial property is good, and the moisture absorption property of the obtained polyester is good.
The invention has the beneficial effects that:
(1) The triethylene glycol diacetate is used as a solvent and a nanoparticle stabilizer, the nano ZnO is prepared by a non-hydrolytic sol-gel method, and the obtained product can be used for modifying PET without separation, so that the process flow is shortened, and the agglomeration in the nanoparticle separation process is avoided.
(2) Triethylene glycol diacetate can be condensed with terephthalic acid, so that the moisture absorption performance of PET is improved, and the uniform dispersion of nano ZnO in the PET is ensured.
Drawings
FIG. 1 XRD of the product obtained in the first step of example 1;
figure 2 XRD of the product obtained in the first step of comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It will be understood that these examples are for the purpose of illustrating the invention and are not intended to limit the scope of the invention in any way.
Example 1
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol is 0.02g/mL; stirring thoroughly, mixing, heating to 120 deg.C, stirring until zinc acetate is completely dissolved, slowly heating to 180 deg.C, maintaining the temperature for 60min, and cooling to room temperature to obtain nanometer ZnO dispersion;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle according to the mol ratio of 1.0; the mass fraction of triphenyl phosphate relative to the terephthalic acid is 0.05%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 230 ℃ and 0.3MPa, controlling the temperature of the top of the kettle to be 110 ℃, and adding the nano ZnO dispersion liquid obtained in the step (1) when the esterification water yield reaches 95% of a theoretical value, wherein the mass ratio of the nano ZnO dispersion liquid to the terephthalic acid is 80; then, continuously esterifying for 40min at 230 ℃ and under the condition of 0.3MPa, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 260 ℃ under the vacuum degree of 20Pa, adjusting the rotating speed to 60r/min when the ethylene glycol distilled amount is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurization, extruding a reaction product, and pelletizing.
Comparative example 1
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol is 0.02g/mL; fully stirring and uniformly mixing, heating to 120 ℃, stirring until zinc acetate is completely dissolved, slowly heating to 180 ℃, preserving heat for 60min, and cooling to room temperature after heat preservation is finished to obtain nano ZnO dispersion liquid; and (4) performing high-speed centrifugal separation, washing the solid with deionized water for 3 times, drying and grinding to obtain the nano ZnO.
(2) Re-dispersing the nano ZnO prepared in the step (1) in triethylene glycol to obtain nano ZnO dispersion liquid, wherein the mass-volume ratio of the nano ZnO (calculated by anhydrous zinc acetate) to the triethylene glycol is 0.02g/mL; putting terephthalic acid and ethylene glycol into a polymerization reaction kettle according to the mol ratio of 1.0; the mass fraction of triphenyl phosphate relative to the terephthalic acid is 0.05%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 230 ℃ and 0.3MPa, controlling the temperature of the top of the kettle to be 110 ℃, and adding nano ZnO dispersion liquid when the esterification water yield reaches 95% of a theoretical value, wherein the mass ratio of the nano ZnO dispersion liquid to terephthalic acid is 80; then, continuously esterifying for 40min at 230 ℃ and under the condition of 0.3MPa, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 260 ℃ under the vacuum degree of 20Pa, adjusting the rotating speed to 60r/min when the ethylene glycol distilled amount is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurization, extruding a reaction product, and pelletizing.
Comparative example 2
(1) Adding anhydrous zinc acetate and 1,3-propylene glycol into a reaction kettle, wherein the mass-volume ratio of the anhydrous zinc acetate to 1,3-propylene glycol is 0.02g/mL; stirring thoroughly, mixing, heating to 120 deg.C, stirring until zinc acetate is completely dissolved, slowly heating to 180 deg.C, maintaining the temperature for 60min, and cooling to room temperature to obtain nanometer ZnO dispersion;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle according to the mol ratio of 1.0; the mass fraction of triphenyl phosphate relative to the terephthalic acid is 0.05%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 230 ℃ under the condition of 0.3MPa, controlling the temperature at the top of the kettle to be 110 ℃, finishing esterification when the esterification water yield reaches 95% of a theoretical value, and adding the nano ZnO dispersion liquid obtained in the step (1), wherein the mass ratio of the nano ZnO dispersion liquid to the terephthalic acid is 80; then, under the conditions of 230 ℃ and 0.3MPa, continuously esterifying for 40min, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 260 ℃ under the vacuum degree of 20Pa, adjusting the rotating speed to 60r/min when the ethylene glycol distilled amount is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurization, extruding a reaction product, and pelletizing.
Comparative example 3
(1) Adding anhydrous zinc acetate and ethylene glycol into a reaction kettle, wherein the mass volume ratio of the anhydrous zinc acetate to the ethylene glycol is 0.02g/mL; stirring thoroughly and mixing uniformly, heating to 120 deg.C, stirring until zinc acetate is completely dissolved, slowly heating to 180 deg.C, keeping the temperature for 60min, and cooling to room temperature after keeping the temperature;
(2) Putting terephthalic acid and triethylene glycol into a polymerization reaction kettle, wherein the mass ratio of the triethylene glycol to the terephthalic acid is 80; then adding catalyst ethylene glycol antimony and heat stabilizer triphenyl phosphate, wherein the mass fraction of the ethylene glycol antimony relative to the terephthalic acid is 0.05 percent; the mass fraction of triphenyl phosphate relative to the terephthalic acid is 0.05%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 230 ℃ and 0.3MPa, controlling the temperature of the top of the kettle to be 110 ℃, and adding the dispersion liquid obtained in the step (1) when the esterification water yield reaches 95% of a theoretical value, wherein the mass ratio of the dispersion liquid to terephthalic acid is 80; then, continuously esterifying for 40min at 230 ℃ and under the condition of 0.3MPa, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 260 ℃ under the vacuum degree of 20Pa, adjusting the rotating speed to 60r/min when the distilled amount of the ethylene glycol is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurizing, extruding a reaction product, and pelletizing.
Example 2
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol is 0.1g/mL; fully stirring and uniformly mixing, heating to 120 ℃, stirring until zinc acetate is completely dissolved, slowly heating to 220 ℃, preserving heat for 30min, and cooling to room temperature after heat preservation is finished to obtain nano ZnO dispersion liquid;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle according to the mol ratio of 1.0; the mass fraction of triphenyl phosphate relative to the terephthalic acid is 0.1%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 250 ℃ and 0.3MPa, controlling the temperature of the top of the kettle to be 135 ℃, and adding the nano ZnO dispersion liquid obtained in the step (1) when the esterification water yield reaches 95% of a theoretical value, wherein the mass ratio of the nano ZnO dispersion liquid to the terephthalic acid is 120; then, under the conditions of 250 ℃ and 0.3MPa, continuously esterifying for 60min, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 285 ℃ under the vacuum degree of 60Pa, adjusting the rotating speed to 60r/min when the ethylene glycol distilled amount is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurizing, extruding a reaction product, and pelletizing.
Example 3
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol is 0.05g/mL; fully stirring and uniformly mixing, heating to 120 ℃, stirring until zinc acetate is completely dissolved, slowly heating to 200 ℃, preserving heat for 45min, and cooling to room temperature after heat preservation is finished to obtain nano ZnO dispersion liquid;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle according to the mol ratio of 1.0; the mass fraction of triphenyl phosphate relative to terephthalic acid is 0.08%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 240 ℃ and 0.2MPa, controlling the temperature of the top of the kettle to be 120 ℃, and adding the nano ZnO dispersion liquid obtained in the step (1) when the esterification water yield reaches 95% of a theoretical value, wherein the mass ratio of the nano ZnO dispersion liquid to the terephthalic acid is 100; then, continuously esterifying for 50min at the temperature of 240 ℃ and under the pressure of 0.2MPa, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 270 ℃ and under the vacuum degree of 30Pa, adjusting the rotating speed to 60r/min when the ethylene glycol distilled amount is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurizing, extruding a reaction product, and pelletizing.
Example 4
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol is 0.06g/mL; stirring thoroughly, mixing, heating to 120 deg.C, stirring until zinc acetate is completely dissolved, slowly heating to 190 deg.C, maintaining the temperature for 40min, and cooling to room temperature to obtain nanometer ZnO dispersion;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle according to the mol ratio of 1.0; the mass fraction of triphenyl phosphate relative to the terephthalic acid is 0.06%; introducing nitrogen to discharge air in the kettle, carrying out esterification reaction at 245 ℃ under the condition of 0.25MPa, controlling the temperature of the top of the kettle to be 125 ℃, and adding the nano ZnO dispersion liquid obtained in the step (1) when the esterification water yield reaches 95% of a theoretical value, wherein the mass ratio of the nano ZnO dispersion liquid to the terephthalic acid is 110; then, under the conditions of 245 ℃ and 0.25MPa, continuing esterification for 45min, and entering a polycondensation stage; and (3) carrying out polycondensation reaction at 275 ℃ under the vacuum degree of 30Pa, adjusting the rotating speed to 60r/min when the distilled amount of the ethylene glycol is more than 92% of the theoretical amount, stopping the reaction when the power is 30W, filling nitrogen for pressurizing, extruding a reaction product, and pelletizing.
Example 5
Preparing antibacterial polyester fibers: the polyester chip and nano ZnO hydrophilic antistatic antibacterial copolyester master batch accounting for 10 percent of the total mass of the raw materials are uniformly mixed, the mixture is fully dried and then is subjected to melt spinning at the spinning temperature of 260-270 ℃, POY fiber is spun, and the fiber is woven into a band-shaped fabric for antibacterial performance test.
And (3) testing antibacterial performance: the antibacterial performance of the fabric is tested according to a GB/T20944.3-2008 test method, and the bacteriostasis rate is calculated according to the following formula:
in the formula: a-the average number of bacterial colonies on the polyester fiber fabric without the added antibacterial master batch; b-average number of bacterial colonies on the polyester fiber fabric added with the antibacterial master batch.
Antibacterial effect wash resistance test: the test of the washing resistance of the fabric against the antibacterial effect is carried out in a colorfastness to washing machine, the washing procedure is as follows (this washing procedure corresponds to 5 washes): washing for 45min at room temperature with 0.2% detergent, 150mL solution and 10 steel balls. After washing, the sample was removed and washed 2 times for 1min in 100mL of water.
Fiber moisture absorption test: fully washing 50g of fiber, removing oil on the surface of the fiber, putting the fiber into an oven to be dried to constant weight, putting the fiber into an environment with the temperature of 20 ℃ and the relative humidity of 65 percent to absorb moisture and balance for 48 hours, putting the fiber with the moisture and balance in an eight-basket oven, weighing the fiber by a balance, and recording the mass M at the moment 0 Drying at 105 ℃ to constant weight, weighing the mass M at that time, and calculating the moisture regain according to the following formula:
moisture regain (%) = (M) 0 -M)/M×100％
In the formula: m 0 The mass (g) of the fiber after moisture absorption equilibrium; m is the completely dry mass of the fiber.
Fiber specific resistance test: each sample was measured 3 times by using YG321 fiber specific resistance meter under the environment of 20 ℃ and 65% relative humidity, and the average value was obtained.
The antibacterial property test result of the fabric is as follows:
TABLE 1 antibacterial Properties of the fabrics
As can be seen from the above table, the polyester fiber obtained by the present invention is excellent in hygroscopicity, antibacterial property and antistatic property. In the comparative example 1, the agglomeration of zinc oxide is caused in the separation process of nano ZnO, so that the antibacterial performance of the final product is poor; the master batch obtained in comparative example 2 has poor hydrophilicity, so that the polyester obtained therefrom has poor hygroscopicity and antistatic property; comparative example 3 in the process of preparing nano ZnO, the product obtained is not pure ZnO with ethylene glycol as the raw material, and therefore, the antibacterial performance of the product obtained is also poor.
Claims (8)
1. The hydrophilic antistatic antibacterial copolyester master batch is characterized in that the copolyester master batch takes triethylene glycol and zinc acetate as raw materials to prepare nano ZnO dispersion, and then the dispersion is directly used for preparing PET to obtain the hydrophilic antistatic antibacterial copolyester master batch;
the preparation method of the hydrophilic antistatic antibacterial copolyester master batch comprises the following specific steps:
(1) Adding anhydrous zinc acetate and triethylene glycol into a reaction kettle, fully stirring and uniformly mixing, heating to 120 ℃, stirring until the zinc acetate is completely dissolved, heating for reaction, and cooling to room temperature to obtain a nano ZnO dispersion liquid;
(2) Putting terephthalic acid and ethylene glycol into a polymerization reaction kettle, adding catalyst ethylene glycol antimony and heat stabilizer triphenyl phosphate, introducing nitrogen to discharge air in the kettle for esterification reaction, controlling the temperature of the top of the kettle to be 110-135 ℃, when the esterification water yield reaches 95% of a theoretical value, finishing esterification, adding the nano ZnO dispersion liquid obtained in the step (1), continuing esterification for 40-60min under the same condition, carrying out polycondensation reaction, when the ethylene glycol distillation amount is more than 92% of the theoretical amount, adjusting the rotating speed to be 60r/min, stopping the reaction when the power is 30W, filling nitrogen for pressurization, extruding a reaction product and pelletizing.
2. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the mass volume ratio of the anhydrous zinc acetate to the triethylene glycol in the step (1) is 0.02-0.1g/mL.
3. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the reaction temperature in the step (1) is 180-220 ℃ and the reaction time is 30-60min.
4. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the molar ratio of terephthalic acid to ethylene glycol in step (2) is 1.0.
5. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the mass fraction of the ethylene glycol antimony to the terephthalic acid in the step (2) is 0.05-0.1%; the mass fraction of triphenyl phosphate relative to terephthalic acid is 0.05% -0.1%.
6. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the mass ratio of the nano ZnO dispersion liquid in the step (2) to the terephthalic acid is 80-120.
7. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the esterification reaction temperature in the step (2) is 230-250 ℃ and the esterification reaction pressure is 0.1-0.3 MPa.
8. The hydrophilic antistatic antibacterial copolyester master batch as claimed in claim 1, wherein the polycondensation reaction temperature in the step (2) is 260-285 ℃ and the vacuum degree is 20-60 Pa.
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| CN114775279B (en) * | 2022-06-20 | 2022-09-09 | 河南源宏高分子新材料有限公司 | Antistatic flame-retardant polyester material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1565977A (en) * | 2003-07-08 | 2005-01-19 | 中国科学院过程工程研究所 | Process for preparing nano zinc oxide |
| CN107201567A (en) * | 2017-06-22 | 2017-09-26 | 江苏三房巷集团有限公司 | A kind of preparation method of the super imitative cotton polyester fiber of continuous polymerization fused mass directly spinning |
| CN108976400A (en) * | 2018-08-07 | 2018-12-11 | 日华化学（中国）有限公司 | A kind of synthesis preparation method of the polyether high molecular compound of polyester containing zinc |
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| EP2089467A2 (en) * | 2006-11-07 | 2009-08-19 | Basf Se | Method for producing nanoscale metal oxide-filled polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565977A (en) * | 2003-07-08 | 2005-01-19 | 中国科学院过程工程研究所 | Process for preparing nano zinc oxide |
| CN107201567A (en) * | 2017-06-22 | 2017-09-26 | 江苏三房巷集团有限公司 | A kind of preparation method of the super imitative cotton polyester fiber of continuous polymerization fused mass directly spinning |
| CN108976400A (en) * | 2018-08-07 | 2018-12-11 | 日华化学（中国）有限公司 | A kind of synthesis preparation method of the polyether high molecular compound of polyester containing zinc |
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