CN111171296A - Preparation method and application of antibacterial antistatic flame-retardant polyester resin - Google Patents
Preparation method and application of antibacterial antistatic flame-retardant polyester resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- 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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- C08G63/183—Terephthalic acids
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
本发明公开了一种抗菌抗静电阻燃聚酯树脂的制备方法，是将羧基化氧化石墨烯与具有抗菌作用的金属氧化物前驱体进行螯合，再与烷基次膦酸金属盐进行原位聚合，即得所述抗菌抗静电阻燃聚酯树脂；本发明还公开了上述抗菌抗静电阻燃聚酯树脂的应用，它用于制备抗菌抗静电阻燃聚酯纤维。本发明利用羧基化的氧化石墨烯作为载体及协效阻燃部分，与烷基次膦酸金属盐通过原位聚合生成抗菌抗静电阻燃聚酯树脂，并进一步制成抗菌抗静电阻燃聚酯纤维。本发明属于抗菌抗静电阻燃材料制备技术领域，用于制备抗菌抗静电阻燃聚酯树脂，所得树脂进一步地应用于制备相应的纤维。
The invention discloses a preparation method of an antibacterial, antistatic and flame retardant polyester resin. The antibacterial and antistatic flame retardant polyester resin is obtained by in-situ polymerization; the invention also discloses the application of the above antibacterial and antistatic flame retardant polyester resin, which is used for preparing the antibacterial, antistatic and flame retardant polyester fiber. In the invention, the carboxylated graphene oxide is used as a carrier and a synergistic flame retardant part, and an antibacterial, antistatic and flame retardant polyester resin is produced by in-situ polymerization with a metal alkyl phosphinic acid salt, and the antibacterial, antistatic and flame retardant polyester resin is further prepared. Ester fiber. The invention belongs to the technical field of preparation of antibacterial, antistatic and flame retardant materials, and is used for preparing an antibacterial, antistatic and flame retardant polyester resin, and the obtained resin is further applied to prepare corresponding fibers.
Description
Technical Field
The invention belongs to the technical field of preparation of multifunctional polymer materials, relates to preparation of an antibacterial antistatic flame-retardant material, and particularly relates to a preparation method and application of an antibacterial antistatic flame-retardant polyester resin.
Background
Polyester fiber is widely applied to various fields due to excellent performance and low price, but has poor flame retardant property due to chemical structure and physical property, and is easy to breed bacteria due to loose porous structure after being woven into textile, and the antistatic ability of the polyester fiber is very weak.
Therefore, if the antibacterial, antistatic and flame-retardant modified polyester resin can be subjected to antibacterial, antistatic and flame-retardant modification, the application range of the polyester resin can be greatly widened, and the additional value of products is improved.
Disclosure of Invention
The invention aims to provide a preparation method of antibacterial antistatic flame-retardant polyester resin, which comprises the steps of utilizing carboxylated graphene oxide as a carrier and a synergistic flame-retardant part, and carrying out in-situ polymerization with alkyl phosphinate metal salt to generate the antibacterial antistatic flame-retardant polyester resin;
the invention also aims to provide the antibacterial antistatic flame-retardant polyester fiber prepared by applying the antibacterial antistatic flame-retardant polyester resin prepared by the preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of antibacterial antistatic flame-retardant polyester resin comprises the following steps:
chelating carboxylated graphene oxide with a metal oxide precursor with an antibacterial effect to obtain a material A;
and secondly, carrying out in-situ polymerization on the material A, the alkyl phosphinic acid metal salt, the ethylene glycol and the terephthalic acid to obtain the antibacterial antistatic flame-retardant polyester resin.
The carboxylated graphene oxide is limited to have a carboxylation ratio of 10-30%, a lamella size of 700-1200 nm, and a concentration of an aqueous dispersion of the graphene oxide of 0.5-3%.
As a second limitation, the metal oxide precursor having an antibacterial action is at least one of silver nitrate, copper sulfate, copper nitrate, copper chloride, and n-butyl titanate.
As a third limitation, the metal alkyl phosphinate is one or a combination of aluminum diethyl phosphinate and zinc diethyl phosphinate.
As a fourth limitation, in the second step, the esterification reaction temperature is 220-240 ℃, the reaction time is 1.5-2.5 hours, the polycondensation reaction temperature is 265-285 ℃, and the reaction time is 2-4 hours.
As a fifth limitation, in the antibacterial antistatic flame-retardant polyester resin, the mass fraction of the material A is 1-2%, and the mass fraction of the alkyl phosphinic acid metal salt is 5-8%.
The antibacterial antistatic flame-retardant polyester resin prepared by the preparation method is applied to preparing antibacterial antistatic flame-retardant polyester fibers.
By way of limitation, the antibacterial, antistatic and flame-retardant polyester resin is used for preparing the antibacterial, antistatic and flame-retardant polyester fiber by a melt spinning method.
As a second limitation, the spinning speed of the antibacterial, antistatic and flame-retardant polyester fiber prepared by the melt spinning method is 2800-4200 m/min.
As a third limitation, the limit oxygen index of the antibacterial antistatic flame-retardant polyester fiber is more than or equal to 30, the flame-retardant grade UL94 reaches V0 grade, and the resistivity is less than or equal to 109Omega ∙ cm, and the antibacterial rate to escherichia coli and staphylococcus aureus is more than 95%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) the invention prepares the multifunctional integrated functional fiber with antibacterial, antistatic and flame retardant functions by a one-step method;
(2) according to the invention, the metal oxide with antibacterial effect and the reduced graphene oxide with antistatic effect are generated by in-situ reduction of the reducing atmosphere and atmosphere in the polymerization system, and meanwhile, the metal oxide and the reduced graphene oxide can cooperate with the organic flame-retardant component, so that the flame-retardant capability of the functional resin is improved;
(3) the antibacterial antistatic flame-retardant polyester fiber prepared by the invention has the limiting oxygen index of more than or equal to 30, the flame-retardant grade UL94 reaching V0 grade, and the resistivity of less than or equal to 109Omega ∙ cm, and the antibacterial rate to escherichia coli and staphylococcus aureus is more than 95%.
The invention is suitable for preparing antibacterial antistatic flame-retardant polyester resin and corresponding fibers.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1a is a graph showing dilution 10 of the detection result of the antibacterial test of the existing polyester fiber against Staphylococcus aureus in example 2 of the present invention-2The picture of (2);
FIG. 1b is a diagram showing the result of the antibacterial test of Staphylococcus aureus using the antibacterial, antistatic, and flame retardant polyester fiber prepared in example 2 of the present invention;
FIG. 2a is a graph showing dilution 10 of the detection result of the antibacterial test of the conventional polyester fiber on Escherichia coli in example 2 of the present invention-2The picture of (2);
FIG. 2b is a diagram showing the results of the antibacterial test of Escherichia coli using the antibacterial, antistatic and flame retardant polyester fiber prepared in example 2 of the present invention;
FIG. 3 shows the results of testing the elongation at break of the antibacterial, antistatic and flame retardant polyester fiber prepared in example 2 of the present invention and the conventional polyester fiber;
FIG. 4a is a photograph of a burned carbon layer of a conventional polyester fiber according to example 2 of the present invention;
FIG. 4b is a picture of a burned carbon layer of the antibacterial, antistatic and flame retardant polyester fiber prepared in example 2 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1 preparation method of antibacterial, antistatic and flame retardant polyester resin
The present embodiment includes the following processes:
dispersing 0.5kg of graphene oxide with the lamella size of 700nm and the carboxylation proportion of 20% in 100kg of water, then adding 0.5kg of silver nitrate, stirring and reacting at 40 ℃ for 4h, cleaning with ultrapure water for 3 times, and then replacing for 2 times by using ethylene glycol to obtain a reduced graphene oxide composite material; the concentration of the aqueous dispersion of the graphene oxide is 0.5%;
adding 1kg of reduced graphene oxide composite material and 8kg of zinc alkyl phosphinate into 40kg of ethylene glycol, performing ultrasonic dispersion, esterifying the mixture with another 40kg of ethylene glycol and 80kg of terephthalic acid at 240 ℃ for 2.5 hours, and performing polycondensation at 280 ℃ for 2 hours to obtain the antibacterial antistatic flame-retardant polyester resin.
In the obtained antibacterial antistatic flame-retardant polyester resin, the mass fraction of the reduced graphene oxide composite material is 1%, and the mass fraction of the alkyl zinc phosphinate is 8%.
This example is an application of the antibacterial, antistatic and flame retardant polyester resin obtained in example 1. Specifically, the method comprises the following steps:
in this example, the particles of the antibacterial, antistatic and flame retardant polyester resin prepared in example 1 were dried and then melt-spun at 287 ℃ with a spinning speed of 3000 m/min to prepare the antibacterial, antistatic and flame retardant polyester fiber.
As shown in FIG. 1a, the test result of the antibacterial test of the existing polyester fiber to staphylococcus aureus is diluted 10-2The picture of (2); FIG. 1b is a diagram showing the result of the antibacterial test of the antibacterial antistatic flame-retardant polyester fiber prepared in this example on Staphylococcus aureus; as shown in FIG. 2a, it is dilution 10 of the test result of the antibacterial test of Escherichia coli by the existing polyester fiber-2The picture of (2); fig. 2b is a picture of the detection result of the antibacterial experiment of the antibacterial antistatic flame-retardant polyester fiber prepared in this example on escherichia coli. As can be seen from FIGS. 1 and 2, compared with the polyester fiber in the prior art, the antibacterial, antistatic and flame-retardant polyester fiber prepared in the embodiment has significantly improved antibacterial rate against Escherichia coli and Staphylococcus aureus, and the antibacterial rate is substantially improved>95%。
The antibacterial antistatic flame-retardant polyester fiber prepared in the embodiment has the fiber breaking strength of 3.6 cN/dtex and the fiber resistivity of 7.8 x 108Omega ∙ cm, the limiting oxygen index of the fiber is 31, and the flame retardant rating UL94 reaches V0. As shown in fig. 3, a curve a is a result of detecting the elongation at break of the conventional polyester fiber, and a curve b is a result of detecting the elongation at break of the antibacterial, antistatic and flame-retardant polyester fiber prepared in this example, and it can be seen from the graph that the elongation at break of the antibacterial, antistatic and flame-retardant polyester fiber prepared in this example reaches 14.2%, which is significantly higher than the elongation at break of the polyester fiber in the prior art.
If fig. 4a is a picture of a carbon layer after combustion of the existing polyester fiber, and fig. 4b is a picture of a carbon layer after combustion of the antibacterial antistatic flame-retardant polyester fiber prepared in the embodiment, the comparison of the two shows that the antibacterial rate of the antibacterial antistatic flame-retardant polyester fiber prepared in the embodiment is obviously improved and the mechanical property is not obviously reduced compared with the prior art, the carbon layer is loose and porous after combustion of the polyester fiber prepared in the prior art, and has no obvious flame-retardant effect, the carbon layer after combustion of the flame-retardant polyester fiber prepared in the embodiment is compact, the heat transfer amount and the air transfer amount are obviously reduced, and the flame-retardant effect.
Example 3 preparation method of antibacterial, antistatic and flame retardant polyester resin
The present embodiment includes the following processes:
dispersing 3kg of graphene oxide with the lamella size of 900nm and the carboxylation proportion of 20% in 97kg of water, then adding 0.5kg of silver nitrate and 0.5kg of copper nitrate, stirring and reacting at 40 ℃ for 6h, cleaning with ultrapure water for 3 times, and replacing for 2 times by using ethylene glycol to obtain a reduced graphene oxide composite material; the concentration of the aqueous dispersion of graphene oxide was 3%;
adding 2kg of reduced graphene oxide composite material and 8kg of alkyl zinc phosphinate into 40kg of ethylene glycol, performing ultrasonic dispersion, esterifying the mixture with another 40kg of ethylene glycol and 80kg of terephthalic acid at 220 ℃ for 1.5h, and performing polycondensation at 285 ℃ for 3h to obtain the antibacterial antistatic flame-retardant polyester resin.
In the obtained antibacterial antistatic flame-retardant polyester resin, the mass fraction of the reduced graphene oxide composite material is 2%, and the mass fraction of the alkyl zinc phosphinate is 8%.
Example 4 preparation method of antibacterial, antistatic and flame-retardant polyester fiber
This example is an application of the antibacterial, antistatic and flame retardant polyester resin obtained in example 3. Specifically, the method comprises the following steps:
in this example, the particles of the antibacterial, antistatic and flame retardant polyester resin prepared in example 3 were dried and then melt-spun at 285 ℃ and a spinning speed of 3200 m/min to prepare an antibacterial, antistatic and flame retardant polyester fiber.
Through detection, the breaking strength of the antibacterial antistatic flame-retardant polyester fiber prepared by the embodiment is 3.6 cN/dtex, the elongation at break reaches 13.7%, and the antibacterial rate on escherichia coli and staphylococcus aureus is high>95% and a fiber resistivity of 4.3 x 106Omega ∙ cm, the limiting oxygen index of the fiber is 30, and the flame retardant rating UL94 reaches V0.
Example 5 preparation method of antibacterial, antistatic and flame retardant polyester resin
The present embodiment includes the following processes:
dispersing 2kg of graphene oxide with the lamella size of 1000nm and the carboxylation proportion of 30% in 98kg of water, then adding 1kg of copper sulfate and 0.5kg of copper chloride, stirring and reacting at 40 ℃ for 5h, cleaning with ultrapure water for 3 times, and replacing for 2 times by using ethylene glycol to obtain a reduced graphene oxide composite material; the concentration of the aqueous dispersion of the graphene oxide is 2%;
adding 2kg of reduced graphene oxide composite material, 2kg of aluminum alkyl phosphinate and 3kg of zinc alkyl phosphinate into 40kg of ethylene glycol, performing ultrasonic dispersion, esterifying the mixture with another 40kg of ethylene glycol and 80kg of terephthalic acid at 240 ℃ for 2 hours, and performing polycondensation at 285 ℃ for 4 hours to obtain the antibacterial antistatic flame-retardant polyester resin.
In the obtained antibacterial antistatic flame-retardant polyester resin, the mass fraction of the reduced graphene oxide composite material is 2%, and the mass fraction of the alkyl phosphinate is 5%.
Example 6 preparation method of antibacterial, antistatic and flame-retardant polyester fiber
This example is an application of the antibacterial, antistatic and flame retardant polyester resin obtained in example 5. Specifically, the method comprises the following steps:
in this example, the particles of the antibacterial, antistatic and flame retardant polyester resin prepared in example 5 were dried and then melt-spun at 290 ℃ at a spinning speed of 4000 m/min to prepare an antibacterial, antistatic and flame retardant polyester fiber.
Through detection, the breaking strength of the antibacterial antistatic flame-retardant polyester fiber prepared by the embodiment is 3.9 cN/dtex, the elongation at break reaches 12.6%, and the antibacterial rate on escherichia coli and staphylococcus aureus is high>95% and a fiber resistivity of 5.8 x 107Omega ∙ cm, the limiting oxygen index of the fiber is 33, and the flame retardant rating UL94 reaches V0.
Example 7 preparation method of antibacterial, antistatic and flame retardant polyester resin
The present embodiment includes the following processes:
dispersing 1kg of graphene oxide with the sheet size of 1200nm and the carboxylation proportion of 10% in 99kg of water, then adding 1.0kg of n-butyl titanate, stirring and reacting at 40 ℃ for 3h, cleaning with ultrapure water for 3 times, and replacing for 2 times by using ethylene glycol to obtain a reduced graphene oxide composite material; the concentration of the aqueous dispersion of the graphene oxide is 1%;
adding 1kg of reduced graphene oxide composite material, 2kg of aluminum alkyl phosphinate and 5kg of zinc alkyl phosphinate into 40kg of ethylene glycol, performing ultrasonic dispersion, esterifying the mixture with another 40kg of ethylene glycol and 80kg of terephthalic acid at 240 ℃ for 1.5h, and performing polycondensation at 265 ℃ for 4h to obtain the antibacterial antistatic flame-retardant polyester resin.
In the obtained antibacterial antistatic flame-retardant polyester resin, the mass fraction of the reduced graphene oxide composite material is 1%, and the mass fraction of the alkyl phosphinate is 7%.
This example is an application of the antibacterial, antistatic and flame retardant polyester resin obtained in example 7. Specifically, the method comprises the following steps:
in this example, the particles of the antibacterial, antistatic and flame retardant polyester resin prepared in example 7 were dried and melt-spun at 287 ℃ and the spinning speed was 4200m/min, so as to prepare the antibacterial, antistatic and flame retardant polyester fiber.
Through detection, the antibacterial antistatic flame-retardant polyester fiber prepared in the embodiment has the breaking strength of 4.0 cN/dtex, the elongation at break of 10.5 percent and the antibacterial rate on escherichia coli and staphylococcus aureus>95% and a fiber resistivity of 5.7 x 108Omega ∙ cm, the limiting oxygen index of the fiber is 31, and the flame retardant rating UL94 reaches V0.
Example 9 preparation method of antibacterial, antistatic and flame retardant polyester resin
The present embodiment includes the following processes:
dispersing 1.5kg of graphene oxide with the lamella size of 1100nm and the carboxylation proportion of 30% in 88.5kg of water, then adding 3.0kg of copper chloride, stirring and reacting at 40 ℃ for 6h, cleaning with ultrapure water for 3 times, and replacing for 2 times by using ethylene glycol to obtain a reduced graphene oxide composite material; the concentration of the aqueous dispersion of the graphene oxide is 1.7%;
1.5kg of reduced graphene oxide composite material and 6kg of aluminum alkyl phosphinate are added into 40kg of ethylene glycol and subjected to ultrasonic dispersion, and then the mixture is esterified with another 40kg of ethylene glycol and 80kg of terephthalic acid at 230 ℃ for 2.5h and subjected to polycondensation at 275 ℃ for 3.5h to obtain the antibacterial antistatic flame-retardant polyester resin.
In the obtained antibacterial antistatic flame-retardant polyester resin, the mass fraction of the reduced graphene oxide composite material is 1.5%, and the mass fraction of the aluminum alkyl phosphinate is 6%.
Example 10 preparation method of antibacterial, antistatic and flame-retardant polyester fiber
This example is an application of the antibacterial, antistatic and flame retardant polyester resin obtained in example 9. Specifically, the method comprises the following steps:
in this example, the particles of the antibacterial, antistatic and flame retardant polyester resin prepared in example 9 were dried and then melt-spun at 287 ℃ at a spinning speed of 2800 m/min to prepare an antibacterial, antistatic and flame retardant polyester fiber.
Through detection, the breaking strength of the antibacterial antistatic flame-retardant polyester fiber prepared by the embodiment is 3.2 cN/dtex, the elongation at break reaches 13.8%, and the antibacterial rate on escherichia coli and staphylococcus aureus is high>95% and a fiber resistivity of 6.4 x 107Omega ∙ cm, the limiting oxygen index of the fiber is 34, and the flame retardant rating UL94 reaches V0.
The metal oxide precursor having antibacterial effect in examples 1, 3, 5, 7 and 9 may be one or a mixture of two or more of silver nitrate, copper sulfate, copper nitrate, copper chloride and n-butyl titanate, and the above examples only show five cases. The zinc alkylphosphinate in the above examples may be zinc diethylphosphinate, and the aluminum alkylphosphinate may be aluminum diethylphosphinate.
Claims (10)
1. The preparation method of the antibacterial antistatic flame-retardant polyester resin is characterized by comprising the following steps:
chelating carboxylated graphene oxide with a metal oxide precursor with an antibacterial effect to obtain a material A;
and secondly, carrying out in-situ polymerization on the material A and alkyl phosphinic acid metal salt to obtain the antibacterial antistatic flame-retardant polyester resin.
2. The method for preparing antibacterial, antistatic and flame retardant polyester resin according to claim 1,
the carboxylation proportion of the carboxylated graphene oxide is 10-30%, the size of the sheet layer is 700-1200 nm, and the concentration of the aqueous dispersion of the graphene oxide is 0.5-3%.
3. The method for preparing antibacterial, antistatic and flame retardant polyester resin according to claim 1 or 2, wherein the metal oxide precursor having antibacterial action is at least one of silver nitrate, copper sulfate, copper nitrate, copper chloride and n-butyl titanate.
4. The method for preparing antibacterial, antistatic and flame retardant polyester resin according to claim 1 or 2, wherein the metal alkyl phosphinate is one or a compound of aluminum diethyl phosphinate and zinc diethyl phosphinate.
5. The preparation method of the antibacterial, antistatic and flame retardant polyester resin according to claim 1 or 2, wherein in the second step, the esterification reaction temperature is 220-240 ℃, the reaction time is 1.5-2.5 hours, the polycondensation reaction temperature is 265-285 ℃, and the reaction time is 2-4 hours.
6. The method for preparing the antibacterial antistatic flame-retardant polyester resin according to claim 1 or 2, wherein the mass fraction of the material A in the antibacterial antistatic flame-retardant polyester resin is 1-2%, and the mass fraction of the metal alkyl phosphinate is 5-8%.
7. An application of the antibacterial antistatic flame-retardant polyester resin prepared by the preparation method of any one of claims 1 to 6, which is characterized in that the antibacterial antistatic flame-retardant polyester resin is used for preparing antibacterial antistatic flame-retardant polyester fibers.
8. The use of the antibacterial, antistatic and flame retardant polyester resin according to claim 7, wherein the antibacterial, antistatic and flame retardant polyester resin is used for preparing the antibacterial, antistatic and flame retardant polyester fiber by a melt spinning method.
9. The application of the antibacterial antistatic flame-retardant polyester resin as claimed in claim 8, wherein the spinning speed of the antibacterial antistatic flame-retardant polyester fiber prepared by the melt spinning method is 2800-4200 m/min.
10. The use of the polyester resin according to claim 8 or 9, wherein the antibacterial, antistatic and flame retardant polyester fiber has a limiting oxygen index of 30 or more, a flame retardant rating of UL94 up to V0, and a resistivity of 10 or less9Omega ∙ cm, and the antibacterial rate to escherichia coli and staphylococcus aureus is more than 95%.
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