CN114213709A - Antibacterial flame retardant, multifunctional antibacterial flame-retardant master batch, and preparation method and application thereof - Google Patents
Antibacterial flame retardant, multifunctional antibacterial flame-retardant master batch, and preparation method and application thereof Download PDFInfo
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- CN114213709A CN114213709A CN202111606676.1A CN202111606676A CN114213709A CN 114213709 A CN114213709 A CN 114213709A CN 202111606676 A CN202111606676 A CN 202111606676A CN 114213709 A CN114213709 A CN 114213709A
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
An antibacterial flame retardant, its preparation method and application, zinc diethylphosphinate, cuprous salt are dissolved in water to form the first mixed solution; adding organic acid into the first mixed solution, and dissolving to form a second mixed solution; adjusting the second mixed solution until the solution is neutral; evaporating water to form gel, and calcining the gel to obtain the antibacterial flame retardant. In the antibacterial flame retardant prepared by the gel method, cuprous serves as a capping agent, so that the increase of zinc diethylphosphinate can be inhibited, and the phenomenon that the melting point is too high due to too high molecular weight of the zinc diethylphosphinate is avoided, so that the zinc diethylphosphinate is difficult to process and apply is avoided. This application adopts the gel method, can also prepare out more homogeneous antibacterial flame retardant, moreover, can also full play cuprous and zinc diethylphosphinate compound antibacterial effect.
Description
Technical Field
The invention relates to the technical field of flame retardants and applications thereof, and particularly relates to a migration-free and thermostable flame retardant, a multifunctional antibacterial flame-retardant master batch, and preparation methods and applications thereof.
Background
At present, the products with antibacterial and mildew-proof properties are recognized by all countries in the world as century-spanning green environment-friendly healthy products, and the application of the products with antibacterial and mildew-proof properties can fundamentally prevent the bacteria cross infection among people, people and objects, so that the research on the products with antibacterial properties is significant.
Polyester is a widely used polymer, and belongs to flammable materials due to the chemical structure and the combustion characteristic of the polyester, and because fire caused by the polyester is very easy to cause huge personal injury and property loss, the polyester fiber is subjected to flame retardant treatment to reduce the danger of polyester fabric in the fire, and the polyester fiber is also a research direction with wide attention.
The polyester fiber flame-retardant master batch can increase the flame-retardant function of the product without reducing the processing performance of the product, and has the advantages of simple and convenient use, low cost and good production environment-friendly condition, thus being gradually and widely adopted at present.
There are many flame retardants for imparting flame retardancy to polyester fibers, and they are classified into two main groups, namely halogen and non-halogen based flame retardants, which are represented by bromine-based and phosphorus-based flame retardants, respectively, according to the classification of flame retardant elements. Generally, the brominated flame retardant has a good flame retardant effect, the dosage is relatively small, but the toxicity of hydrogen halide generated during combustion is high, and the use of the brominated flame retardant is forbidden in many occasions; the phosphorus flame retardant is halogen-free flame retardant (non-halogen), and in terms of comprehensive performance of the flame-retardant polyester fiber, the phosphorus flame retardant can overcome influences of reduction of light fastness, color deterioration, increase of brittleness and the like of the fiber caused by the halogen flame retardant, and can generally improve color and dyeing performance of the fiber.
The diethyl phosphate metal salt serving as a novel phosphorus flame retardant has high thermal stability, chemical stability and environmental friendliness, can be used as an excellent high-molecular material flame retardant to replace halogen flame retardants harmful to the environment, and has the characteristics of serving as excellent flame retardants, so that the diethyl phosphate metal salt is widely applied to the fields of engineering plastics flame retardance such as high processing temperature, high shear strength, high CTI value and the like, particularly the fields of glass fiber reinforced nylon, polyester and the like. Aluminum diethylphosphinate is frequently studied.
TW200632080A discloses the use of zinc diethylphosphinate, which has limited antimicrobial activity, although having some antimicrobial activity, and its use in polyesters results in some degradation of the polyester. CN112195531A also discloses that zinc diethylphosphinate and cuprous oxide are subjected to chelating action and blended to form a compound flame retardant, and the quick antibacterial property is provided by the chelating action of zinc and cuprous oxide, but the problem of degradation of polyester by zinc ions still exists. Further, zinc diethylphosphinate tends to have an excessively high melting temperature due to the molecular chain growth during use, and is close to its decomposition temperature, and thus cannot be melt-processed and used.
In addition, the powder flame retardant generates a large amount of dust and dirt in the production and use processes, and is not used for clean production and seriously harms the body health of operators.
Disclosure of Invention
The application provides an antibacterial flame retardant and a preparation method thereof. On one hand, the antibacterial property of zinc diethylphosphinate is improved, and the problem that the melting temperature is too high due to the fact that the molecular chain of zinc diethylphosphinate is easy to grow is solved, and the problem of degradation of the polyester by zinc ions is also solved.
The application also provides a multifunctional compound antibacterial flame-retardant master batch and a preparation method thereof, and solves the problem that more dust bodies are generated in the production process of powder flame retardants and the like.
The first aspect of the application provides a preparation method of an antibacterial flame retardant, which comprises the following steps:
providing zinc diethylphosphinate, and a cuprous salt;
dissolving zinc diethylphosphinate and cuprous salt in water to form a first mixed solution;
adding organic acid into the first mixed solution, and dissolving to form a second mixed solution; adjusting the second mixed solution until the solution is neutral;
evaporating water to form gel, and calcining the gel to obtain the antibacterial flame retardant.
In a second aspect, the present application provides an antibacterial flame retardant obtained by the above method.
In a preferred embodiment, the cuprous salt is preferably a water-soluble cuprous salt, and may be any one or more of cuprous nitrate, cuprous chloride, cuprous sulfate, cuprous acetate, and cuprous oxalate, for example.
In a preferred embodiment, zinc diethylphosphinate, and cuprous; the ionic molar ratio is preferably 1:0.01 to 0.1, more preferably 1:0.02 to 0.08, and still more preferably 1:0.04 to 0.06.
In a preferred embodiment, the organic acid may be one or more of citric acid, malic acid, oxalic acid.
In a preferred embodiment, the "adjusting the second mixed solution to be neutral" is performed using an alkaline compound, preferably, the alkaline compound is one or more of ammonia, a water-soluble hydroxide, and an organic amine compound.
In a preferred embodiment, the calcination is carried out in air.
In a preferred embodiment, the calcination temperature is 500-800 deg.C, more preferably 600-650 deg.C.
In a preferred embodiment, the calcination time is preferably at least 0.5h, more preferably 0.5-4h, more preferably 1-3h, more preferably 2-2.5 h.
In a preferred embodiment, the zinc diethylphosphinate is prepared by the following method: dissolving sodium diethylhypophosphite and deionized water in a mass ratio of 1:4, adding the mixture into a reactor with a reflux condenser tube, adding a proper amount of formaldehyde solution, heating to 80 ℃, and stirring. Adding zinc sulfate solution, heating to 85-95 ℃, stirring for reaction, cooling to room temperature after the reaction is finished, filtering, washing twice with deionized water, and drying to obtain white powder namely zinc diethylphosphinate.
The third aspect of the application provides a multifunctional compound antibacterial flame-retardant master batch, which comprises a resin matrix, the antibacterial flame retardant of the second aspect of the application, a coupling agent and a grafted elastomer. In a more preferred embodiment, the multifunctional compound antibacterial and flame-retardant master batch further comprises any one or more of a dispersing agent and an antistatic agent.
The fourth aspect of the application provides a method for preparing the multifunctional compound antibacterial flame-retardant master batch, which comprises the following steps: and mixing the antibacterial flame retardant and the coupling agent, then adding a polyester matrix and a grafted elastomer, or further adding an antistatic agent and a dispersing agent, mixing, and then performing melt extrusion granulation to obtain the multifunctional compound anti-flame master batch.
In a preferred embodiment, the method for preparing the multifunctional compound antibacterial and flame-retardant master batch comprises the following steps: the antibacterial flame retardant is mixed with a coupling agent, then a polyester substrate and a grafted elastomer (or an antistatic agent and a dispersing agent) are added, and after mixing, extrusion granulation is carried out at the temperature of 200 ℃ and 280 ℃.
More preferably, the method for preparing the multifunctional compound antibacterial flame-retardant master batch comprises the following steps:
placing the polyester in a forced air circulation oven to dry for 6-8 hours at the temperature of 100-120 ℃, and respectively placing the high-efficiency halogen-free flame-retardant antibacterial agents at the temperature of 50-90 ℃ to dry for 1-2 hours;
adding the dry high-efficiency halogen-free flame-retardant antibacterial agent into a high-speed mixer with a charging barrel at the temperature of 80-100 ℃, adding a coupling agent, stirring at the rotating speed of 3000-4500r/min for 10-45 minutes, then adding the dry polyester, adding the graft elastomer, the antistatic agent and the dispersing agent, stirring together for 3-5 minutes until the materials are uniformly mixed, and discharging;
adding the mixture into a double-screw extruder, performing melt mixing at the temperature of between 200 and 280 ℃, extruding and granulating the mixture, and then drying the mixture.
In a preferred embodiment, the multifunctional compound antibacterial flame-retardant master batch comprises the following components in parts by weight: 20-40% of resin matrix, 30-60% of antibacterial flame retardant, 0.5-2% of coupling agent, 10-20% of grafted elastomer, 0-15% of antistatic agent and 0-5% of dispersing agent.
More preferably, the multifunctional compound antibacterial flame-retardant master batch comprises the following components in parts by weight: 20-40% of resin matrix, 30-60% of antibacterial flame retardant, 0.5-2% of coupling agent, 10-20% of grafted elastomer, 5-15% of antistatic agent and 1-5% of dispersing agent.
In a preferred embodiment, the resin matrix may preferably be a polyester, such as one of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT).
In a preferred embodiment, the resin matrix intrinsic viscosity is preferably from 0.3 to 2dL/g, more preferably from 0.5 to 1.8dL/g, more preferably from 0.6 to 1.6 dL/g.
In a preferred embodiment, the grafted elastomer may be a maleic anhydride grafted polymer, particularly a maleic anhydride grafted polyolefin, such as any one or more of a maleic anhydride grafted monoolefin-nonconjugated diolefin copolymer, a maleic anhydride grafted monoolefin-butadiene copolymer. More preferably, the grafted elastomer may be one or more of a maleic anhydride grafted ethylene-propylene-non-conjugated diene copolymer, a maleic anhydride grafted ethylene-octene copolymer, a maleic anhydride grafted styrene-butadiene-styrene copolymer.
In a preferred embodiment, the antistatic agent may be any one or more of sulfonic acid, sulfonate, metal oxide, glyceryl stearate, such as: one or more of ammonium bis (2-hydroxyethyl) octylmethyl bis-p-toluenesulfonate, an alkylsulfonate, glycerol monostearate, and nano antimony-doped tin oxide.
In a preferred embodiment, the dispersant may be one or more of calcium stearate, ultra-fine TAS-2A powder, modified ethylene bis fatty acid amide.
In a preferred embodiment, the coupling agent may be one or more of a silane coupling agent, a titanate coupling agent, an aluminum titanium composite coupling agent.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
in the antibacterial flame retardant prepared by the gel method, cuprous serves as a capping agent, so that the increase of zinc diethylphosphinate can be inhibited, and the phenomenon that the melting point is too high due to too high molecular weight of the zinc diethylphosphinate is avoided, so that the zinc diethylphosphinate is difficult to process and apply is avoided. This application adopts the gel method, can also prepare out more homogeneous antibacterial flame retardant, moreover, can also full play cuprous and zinc diethylphosphinate compound antibacterial effect.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 preparation of a formulation of Zinc diethylphosphinate and cuprous nitrate
Preparation of high-purity zinc diethylphosphinate: dissolving sodium diethylhypophosphite and deionized water in a mass ratio of 1:4, adding the mixture into a reactor with a reflux condenser tube, adding a proper amount of formaldehyde solution, heating to 80 ℃, and stirring. Dropwise adding a zinc sulfate solution (n zinc sulfate: n diethyl sodium hypophosphite is 0.23:0.25), heating to 90 ℃ after the dropwise adding is finished, stirring for reaction, cooling to room temperature after the reaction is finished, filtering, washing with deionized water twice, and drying to obtain white powder, namely zinc diethyl hypophosphite.
Preparing a compound of zinc diethylphosphinate and cuprous nitrate by a sol-gel method: respectively weighing zinc diethylphosphinate and cuprous nitrate with the molar ratio of 1:0.03, dissolving the zinc diethylphosphinate and the cuprous nitrate in distilled water, and placing the mixture in a three-neck flask for magnetic stirring until a transparent solution is obtained; adding citric acid, and magnetically stirring until the citric acid is fully dissolved; dropwise adding ammonia water by using a constant-pressure titration funnel to adjust the solution to be neutral; evaporating water in a constant-temperature water bath at a certain temperature to form wet gel, and drying in a vacuum drying oven at a specific temperature until the weight is constant to obtain dry gel; and calcining the xerogel in air atmosphere at 600 ℃ for 2h, and naturally cooling to room temperature to obtain the flame-retardant antibacterial composite material of zinc diethylphosphinate and cuprous nitrate.
Example 2 preparation of a Compound of Zinc diethylphosphinate and cuprous nitrate
Preparation of high-purity zinc diethylphosphinate: dissolving sodium diethylhypophosphite and deionized water in a mass ratio of 1:4, adding the mixture into a reactor with a reflux condenser tube, adding a proper amount of formaldehyde solution, heating to 80 ℃, and stirring. Dropwise adding a zinc sulfate solution (n zinc sulfate: n diethyl sodium hypophosphite is 0.23:0.25), heating to 86 ℃ after the dropwise adding is finished, stirring for reaction, cooling to room temperature after the reaction is finished, filtering, washing with deionized water twice, and drying to obtain white powder, namely zinc diethyl hypophosphite.
Preparing a compound of zinc diethylphosphinate and cuprous nitrate by a sol-gel method: respectively weighing zinc diethylphosphinate and cuprous nitrate with the molar ratio of 1:0.06, dissolving the zinc diethylphosphinate and the cuprous nitrate in distilled water, and placing the mixture in a three-neck flask for magnetic stirring until a transparent solution is obtained; adding citric acid, and magnetically stirring until the citric acid is fully dissolved; dropwise adding ammonia water by using a constant-pressure titration funnel to adjust the solution to be neutral; evaporating water in a constant-temperature water bath at a certain temperature to form wet gel, and drying in a vacuum drying oven at a specific temperature until the weight is constant to obtain dry gel; and calcining the xerogel in air atmosphere at 600 ℃ for 2h, and naturally cooling to room temperature to obtain the flame-retardant antibacterial composite material of zinc diethylphosphinate and cuprous nitrate.
Example 3 preparation of a Compound of Zinc diethylphosphinate and cuprous nitrate
Preparation of high-purity zinc diethylphosphinate: dissolving sodium diethylhypophosphite and deionized water in a mass ratio of 1:4, adding the mixture into a reactor with a reflux condenser tube, adding a proper amount of formaldehyde solution, heating to 80 ℃, and stirring. Dropwise adding a zinc sulfate solution (n zinc sulfate: n diethyl sodium hypophosphite is 0.23:0.25), heating to 93 ℃ after the dropwise adding is finished, stirring for reaction, cooling to room temperature after the reaction is finished, filtering, washing with deionized water twice, and drying to obtain white powder, namely zinc diethyl hypophosphite.
Preparing a compound of zinc diethylphosphinate and cuprous nitrate by a sol-gel method: respectively weighing zinc diethylphosphinate and cuprous nitrate with the molar ratio of 1:0.09, dissolving the zinc diethylphosphinate and the cuprous nitrate in distilled water, and placing the mixture in a three-neck flask for magnetic stirring until a transparent solution is obtained; adding citric acid, and magnetically stirring until the citric acid is fully dissolved; dropwise adding ammonia water by using a constant-pressure titration funnel to adjust the solution to be neutral; evaporating water in a constant-temperature water bath at a certain temperature to form wet gel, and drying in a vacuum drying oven at a specific temperature until the weight is constant to obtain dry gel; and calcining the xerogel in air atmosphere at 600 ℃ for 2h, and naturally cooling to room temperature to obtain the flame-retardant antibacterial composite material of zinc diethylphosphinate and cuprous nitrate.
Example 4 preparation of antibacterial toughening halogen-free flame retardant masterbatch
20kg of resin matrix, 50kg of efficient halogen-free flame-retardant antibacterial agent in example 1, 15kg of grafted elastomer, 10kg of antistatic agent, 4kg of dispersing agent and 1kg of coupling agent.
(1) The polyester is placed in a forced air circulation oven to be dried for 6 to 8 hours at the temperature of 110 ℃, and the high-efficiency halogen-free flame-retardant antibacterial agent is placed at the temperature of 50 ℃ to be dried for 1 to 2 hours for standby.
(2) Weighing dry high-efficiency halogen-free flame-retardant antibacterial agent according to the weight ratio, adding the dry high-efficiency halogen-free flame-retardant antibacterial agent into a high-speed mixer with a charging barrel temperature of 80-100 ℃, adding a coupling agent according to the weight ratio, stirring for 30 minutes at a rotating speed of 3000-.
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, performing melt mixing at the temperature of 260 ℃, extruding and granulating, and then drying and packaging to obtain the polyester antibacterial toughening halogen-free flame retardant master batch.
Example 5 preparation of antibacterial toughening halogen-free flame retardant masterbatch
30kg of resin matrix, 45kg of the high-efficiency halogen-free flame-retardant antibacterial agent in the embodiment 1, 12kg of grafted elastomer, 8kg of antistatic agent, 4kg of dispersing agent and 1kg of coupling agent.
(1) The polyester is placed in a forced air circulation oven to be dried for 6 to 8 hours at the temperature of 110 ℃, and the high-efficiency halogen-free flame-retardant antibacterial agent is placed at the temperature of 50 ℃ to be dried for 1 to 2 hours for standby.
(2) Weighing dry high-efficiency halogen-free flame-retardant antibacterial agent according to the weight ratio, adding the dry high-efficiency halogen-free flame-retardant antibacterial agent into a high-speed mixer with a charging barrel temperature of 80-100 ℃, adding a coupling agent according to the weight ratio, stirring for 30 minutes at a rotating speed of 3000-.
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, performing melt mixing at the temperature of 260 ℃, extruding and granulating, and then drying and packaging to obtain the polyester antibacterial toughening halogen-free flame retardant master batch.
Example 6 preparation of antibacterial toughening halogen-free flame retardant masterbatch
20kg of resin matrix, 60kg of the high-efficiency halogen-free flame-retardant antibacterial agent in the embodiment 1, 10kg of grafted elastomer, 5kg of antistatic agent, 3kg of dispersing agent and 2kg of coupling agent.
(1) The polyester is placed in a forced air circulation oven to be dried for 6 to 8 hours at the temperature of 110 ℃, and the high-efficiency halogen-free flame-retardant antibacterial agent is placed at the temperature of 50 ℃ to be dried for 1 to 2 hours for standby.
(2) Weighing dry high-efficiency halogen-free flame-retardant antibacterial agent according to the weight ratio, adding the dry high-efficiency halogen-free flame-retardant antibacterial agent into a high-speed mixer with a charging barrel temperature of 80-100 ℃, adding a coupling agent according to the weight ratio, stirring for 30 minutes at a rotating speed of 3000-.
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, performing melt mixing at the temperature of 260 ℃, extruding and granulating, and then drying and packaging to obtain the polyester antibacterial toughening halogen-free flame retardant master batch.
Example 7 preparation of antibacterial toughening halogen-free flame retardant masterbatch
40kg of resin matrix, 30kg of the efficient halogen-free flame-retardant antibacterial agent in the embodiment 1, 15kg of grafted elastomer, 12kg of antistatic agent, 2kg of dispersing agent and 1kg of coupling agent.
(1) The polyester is placed in a forced air circulation oven to be dried for 6 to 8 hours at the temperature of 110 ℃, and the high-efficiency halogen-free flame-retardant antibacterial agent is placed at the temperature of 50 ℃ to be dried for 1 to 2 hours for standby.
(2) Weighing dry high-efficiency halogen-free flame-retardant antibacterial agent according to the weight ratio, adding the dry high-efficiency halogen-free flame-retardant antibacterial agent into a high-speed mixer with a charging barrel temperature of 80-100 ℃, adding a coupling agent according to the weight ratio, stirring for 30 minutes at a rotating speed of 3000-.
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, performing melt mixing at the temperature of 260 ℃, extruding and granulating, and then drying and packaging to obtain the polyester antibacterial toughening halogen-free flame retardant master batch.
Comparative example 2
Zinc diethylphosphinate and cuprous nitrate were physically blended at a 1:0.03 molar ratio, and master batches were prepared without preparing a gel, otherwise with reference to example 4.
Comparative example 2
Instead of cuprous oxide, cuprous nitrate was physically blended with zinc diethylphosphinate at a molar ratio of 1:0.03, and master batches were prepared without preparing a gel, otherwise with reference to example 4.
Master batches of examples 4-7, according to 1: 10, and the fiber obtained by melt spinning with polyester has the following properties:
in the embodiments of the application, the multifunctional antibacterial toughening flame-retardant master batch is prepared by adopting a gel method, the flame retardant, the antibacterial agent and the toughening agent are more uniformly distributed, and the flame retardance, the bacteriostasis rate and the breaking strength are all improved compared with those of the comparison document 2 of physical blending.
In addition, if cuprous oxide is adopted for physical blending, cuprous oxide cannot generate dissociative cuprous ions and cannot inhibit the molecular chain growth of zinc diethylphosphinate, and during melt spinning, macromolecular zinc diethylphosphinate cannot be melted and cannot be well blended with polyester, so that the antibacterial and flame-retardant effects of the zinc diethylphosphinate are reduced.
In addition, in the application, after the cuprous ions are blocked, the problem of degradation of the polyester by zinc ions is solved, and the mechanical property of the polyester is further maintained.
The embodiments of the present invention have been described in detail, but the present invention is only by way of example and is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, it is intended that all equivalent alterations and modifications be included within the invention, without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of an antibacterial flame retardant is characterized by comprising the following steps:
providing zinc diethylphosphinate, and a cuprous salt;
dissolving zinc diethylphosphinate and cuprous salt in water to form a first mixed solution;
adding organic acid into the first mixed solution, and dissolving to form a second mixed solution; adjusting the second mixed solution until the solution is neutral;
evaporating water to form gel, and calcining the gel to obtain the antibacterial flame retardant.
2. The method for preparing antibacterial flame retardant according to claim 1, wherein the cuprous salt is a water-soluble cuprous salt, and for example, can be any one or more of cuprous nitrate, cuprous chloride, cuprous sulfate, cuprous acetate, and cuprous oxalate;
the organic acid is one or more of citric acid, malic acid and oxalic acid.
3. The method for preparing an antibacterial flame retardant according to claim 1, wherein zinc diethylphosphinate, and cuprous; the ion molar ratio is 1:0.01 to 0.1, more preferably 1:0.02 to 0.08, and still more preferably 1:0.04 to 0.06.
4. The method for preparing the antibacterial flame retardant according to claim 1, wherein the calcining temperature is 500-800 ℃, more preferably 600-650 ℃; the calcination time is preferably at least 0.5h, more preferably 0.5 to 4h, more preferably 1 to 3h, more preferably 2 to 2.5 h.
5. An antimicrobial flame retardant prepared by the process of claim 1.
6. A multifunctional compound antibacterial flame-retardant master batch is characterized by comprising a resin matrix, the antibacterial flame retardant of claim 6, a coupling agent and a grafted elastomer; or, any one or more of a dispersant and an antistatic agent is also included.
7. The multifunctional compound antibacterial flame-retardant master batch according to claim 6, wherein the multifunctional compound antibacterial flame-retardant master batch comprises the following components in parts by weight: 20-40% of resin matrix, 30-60% of antibacterial flame retardant, 0.5-2% of coupling agent, 10-20% of grafted elastomer, 0-15% of antistatic agent and 0-5% of dispersing agent.
8. The multifunctional compounded antibacterial and flame-retardant masterbatch according to claim 6, wherein the grafted elastomer is maleic anhydride grafted polymer, especially maleic anhydride grafted polyolefin, such as one or more of maleic anhydride grafted mono-olefin-non-conjugated diene copolymer, maleic anhydride grafted mono-olefin copolymer, and maleic anhydride grafted mono-olefin-butadiene copolymer. More preferably, the grafted elastomer may be one or more of a maleic anhydride grafted ethylene-propylene-non-conjugated diene copolymer, a maleic anhydride grafted ethylene-octene copolymer, a maleic anhydride grafted styrene-butadiene-styrene copolymer;
the antistatic agent is any one or more of sulfonic acid, sulfonate, metal oxide and glycerol stearate, and specifically comprises the following components: one or more of ammonium bis (2-hydroxyethyl) octylmethyl bis-p-toluenesulfonate, an alkylsulfonate, glycerol monostearate, and nano antimony-doped tin oxide;
the dispersing agent is one or more of calcium stearate, superfine TAS-2A powder and modified ethylene bis fatty acid amide;
the coupling agent may be one or more of a silane coupling agent, a titanate coupling agent, an aluminum titanium composite coupling agent.
9. The method for preparing the multifunctional compound antibacterial flame-retardant master batch of claim 7 is characterized by comprising the following steps: and mixing the antibacterial flame retardant and the coupling agent, then adding a polyester matrix and a grafted elastomer, or further adding an antistatic agent and a dispersing agent, mixing, and then performing melt extrusion granulation to obtain the multifunctional compound anti-flame master batch.
10. The method of claim 9, wherein the resin matrix has an intrinsic viscosity of 0.3 to 2dL/g, more preferably 0.5 to 1.8dL/g, more preferably 0.6 to 1.6 dL/g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111606676.1A CN114213709A (en) | 2021-12-26 | 2021-12-26 | Antibacterial flame retardant, multifunctional antibacterial flame-retardant master batch, and preparation method and application thereof |
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| CN202111606676.1A CN114213709A (en) | 2021-12-26 | 2021-12-26 | Antibacterial flame retardant, multifunctional antibacterial flame-retardant master batch, and preparation method and application thereof |
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