CN114716798A - Environment-friendly flame-retardant transparent polyester material and preparation method thereof - Google Patents
Environment-friendly flame-retardant transparent polyester material and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention provides an environment-friendly flame-retardant transparent polyester material, which comprises thermoplastic polyester resin and a flame retardant, wherein each 100 parts of the thermoplastic polyester resin corresponds to 0.5-2 parts of the flame retardant in parts by mass; the flame retardant is a montmorillonite-silicon-fluorine modified polypropylene ester material with a core-shell structure, montmorillonite and fluorine-silicon elements are both positioned in the core, and the proportion of hard monomers in the shell layer is greater than that of the hard monomers in the core. The transparent polyester material has excellent flame retardant property. Meanwhile, the invention also provides a preparation method of the material.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an environment-friendly flame-retardant transparent polyester material and a preparation method thereof.
Background
The polyester material is widely applied to the fields of packaging industry, electronic and electric appliances, medical treatment and health, buildings, automobiles and the like, and is an engineering plastic with excellent performance and wide application. Along with the increasing safety awareness of people, the flame-retardant and fireproof performance of polyester materials is more and more important. The existing polyester flame retardant can be generally divided into an additive type and a reactive type, the additive type mainly comprises the step of directly mixing a polyester material and a flame retardant to improve the flame retardant property of the polyester material, and common additive type flame retardants mainly comprise phosphorus-containing inorganic flame retardants, halogen-containing organic flame retardants and the like, but the phosphorus-containing inorganic flame retardants include, for example: most of red phosphorus flame retardants, ammonium dihydrogen phosphate and the like are bright in color, and the application range of the flame retardants is greatly limited, and halogen-containing organic flame retardants such as: tetrabromophthalic anhydride, pentabromotoluene and the like have great influence on the mechanical property of the polymer, so that the dosage of the halogen flame retardant in the polymer is limited, and meanwhile, a halogen-containing gas phase is formed during the decomposition of the halogen flame retardant and is a flame-retardant gas, and the halogen-containing gas phase is covered on the surface of an object and can play a role in isolating oxygen to play a role in flame retardance, but the gases are easy to cause pollution and even influence the fire fighting process; moreover, the halogen flame retardant is commonly applied with antimony oxides in a synergistic manner, so that heavy metal pollution is easily caused, and the overall treatment difficulty is high.
In order to solve the above problems, people are always seeking an ideal technical solution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an environment-friendly flame-retardant transparent polyester material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
an environment-friendly flame-retardant transparent polyester material comprises thermoplastic polyester resin and a flame retardant, wherein each 100 parts of the thermoplastic polyester resin corresponds to 0.5-2 parts of the flame retardant in parts by mass; the flame retardant is a montmorillonite-silicon fluorine modified polypropylene ester material with a core-shell structure, montmorillonite and fluorine-silicon elements are positioned in the core, and the proportion of hard monomers in the shell layer is greater than that of the hard monomers in the core.
Based on the above, the flame retardant comprises the following raw materials in parts by mass: 50-60 parts of deionized water, 1-2 parts of initiator, 0.5-1.0 part of buffering agent, 3.5-4.5 parts of emulsifier, 2-3 parts of silane coupling agent, 4-5 parts of nano montmorillonite, 2-3 parts of fluoroolefin and 30-60 parts of acrylic monomer; wherein, the acrylic monomer comprises 20-40 parts of hard monomer and 10-20 parts of soft monomer; the glass transition temperature of the hard monomer is more than 25 ℃, and the glass transition temperature of the soft monomer is less than 0 ℃.
Based on the above, the particle size range of the nano montmorillonite is 10-30 nm.
Based on the above, the emulsifier comprises an anionic surfactant and a reactive surfactant in a mass ratio of (2-3): 1.5, or a cationic surfactant and a reactive surfactant in a mass ratio of (2-3): 1.5.
Based on the above, the anionic surfactant is sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate, sulfonate of ethoxylated fatty acid methyl ester or sodium alkenyl sulfonate; the cationic surfactant is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, octadecyl amine polyoxyethylene ether biquaternary ammonium salt or cetyl polyoxyethylene ether dimethyl octane ammonium chloride; the reactive surfactant is allyloxy nonyl phenol polyethenoxy ether ammonium sulfate.
Based on the above, the soft monomer is one or a combination of at least two of ethyl acrylate, butyl acrylate, isooctyl acrylate and hexyl methacrylate; the hard monomer is one or the combination of at least two of vinyl acetate, tert-butyl methacrylate, acrylamide, styrene, methyl methacrylate and isobutyl methacrylate; the flame retardant adopts the theoretical glass transition temperature of acrylic monomers according to the fox equation of 1/Tg = W1/Tg1+ W2/Tg2+ … … + Wn/Tgn, and the Tg is calculated to be more than 45 ℃, wherein n is a natural number, and W1, W2, … … and Wn are the mass fractions of each soft monomer or hard monomer respectively; w1+ W2 + … … + Wn = 100%.
Based on the above, the fluoroolefin is vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene or trifluorostyrene.
Based on the above, the silane coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, or vinyltriisopropenoxysilane.
A preparation method of the environment-friendly flame-retardant transparent polyester material comprises the following steps:
1) mixing nano montmorillonite and deionized water according to the proportion of (4-5) g/200 ml, performing ultrasonic treatment for 10-20 min, adjusting pH, adding anionic surfactant/cationic surfactant, performing ultrasonic treatment for 2-3 h, performing solid-liquid separation, repeatedly cleaning the solid with deionized water, and drying;
2) uniformly mixing a silane coupling agent and an ethanol aqueous solution according to the proportion of (3-4) g/100 ml, adjusting ph, adding the montmorillonite particles obtained in the step (1), and carrying out heat preservation at 40-50 ℃ for 4-6 h by ultrasonic treatment; cooling, carrying out solid-liquid separation and drying;
3) 1/3 parts by mass of reactive surfactant, 1/10 parts by mass of deionized water and the montmorillonite particles obtained in the step (2) are uniformly mixed, 1/2 parts by mass of soft monomer and fluoroolefin are slowly added, and the mixture is stirred at a high speed for 10-20 min to obtain a first pre-emulsion for later use;
4) 1/3 parts by mass of reactive surfactant and 2/5 parts by mass of deionized water are uniformly mixed, and a hard monomer and the rest soft monomer are slowly added and stirred at a high speed for 10-20 min to obtain a second pre-emulsion for later use;
5) 3/4 parts by mass of an initiator and 1/5 parts by mass of deionized water are uniformly mixed to obtain a priming solution for later use;
6) adding 3/10 parts by mass of deionized water, 1/3 parts by mass of reactive surfactant, 1/4 parts by mass of initiator and buffer into a reaction kettle, stirring and heating, raising the temperature to 50-60 ℃, synchronously adding 1/5 parts by mass of initiating solution and first pre-emulsion, and reacting for 20-40 min; 4/5 parts by mass of the priming solution and the second pre-emulsion are synchronously added and react for 2 to 3 hours; then filtering, performing Soxhlet extraction and vacuum drying to prepare the flame retardant;
7) and melting and mixing the flame retardant and the thermoplastic polyester resin, extruding and granulating to obtain the flame retardant. Specifically, a double-screw extruder is adopted, the screw rotating speed is 100-.
Compared with the prior art, the material has the following beneficial effects that the flame retardant property test of the material can reach V-0 level, and the flame retardant property is good. The environment-friendly flame-retardant transparent polyester material combines the polymer with the montmorillonite and the fluorosilicone element, so that the flame retardant property of the material can be effectively improved, and the material is more environment-friendly compared with halogen flame retardant modes such as chlorine, bromine and the like; meanwhile, low-polarity fluorine silicon and the like are positioned in the inner core of the colloidal particle, the proportion of hard monomers in the inner core is smaller than that of hard monomers in the outer shell, an inner soft and outer hard structure is formed, and the polarity of the shell layer of the material is larger.
In addition, the invention also provides a preparation method of the material, wherein in the preparation process, the montmorillonite is modified by adopting the anionic/cationic surfactant and the silane coupling agent in sequence, particularly the silane coupling agent with carbon-carbon double bonds is adopted, and the emulsifying agent is a reactive emulsifying agent, so that the silane coupling agent, the emulsifying agent and other organic monomers jointly participate in polymerization reaction; in the polymerization process, firstly, fluorine-containing monomers and partial monomers are added to carry out polymerization reaction on the surface of the montmorillonite to form a core layer containing fluorine silicon, and the fluorine silicon has low polarity, so that the fluorine silicon is not easy to migrate to the outside in the subsequent shell polymerization process, and finally, an external hard and internal soft structure is formed and is easier to be wetted.
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FIG. 1 is a SEM image of example 1.
Fig. 2 is a scanning electron microscope image measured in comparative experiment 2.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
Example 1
The embodiment provides an environment-friendly flame-retardant transparent polyester material, which comprises, by mass, 1 part of a flame retardant per 100 parts of a thermoplastic polyester resin (PET); the flame retardant is a montmorillonite-silicon-fluorine modified polypropylene ester material with a core-shell structure, and montmorillonite and fluorine-silicon elements are both positioned in the inner core.
The flame retardant comprises the following raw materials in parts by mass: 50 parts of deionized water, 1 part of initiator, 0.5 part of buffering agent, 3.5 parts of emulsifier, 2 parts of silane coupling agent, 4 parts of nano montmorillonite and 2 parts of fluoroolefin; 40 parts of hard monomer and 10 parts of soft monomer; the particle size range of the nano montmorillonite is 10-30 nm; the emulsifier comprises cetyl trimethyl ammonium bromide and allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate, and the proportion is 2: 1.5; the fluoroolefin is vinylidene fluoride; the silane coupling agent is vinyl triethoxysilane; the soft monomer comprises 3 parts of isooctyl acrylate and 7 parts of butyl acrylate; the hard monomer comprises 12 parts of methyl methacrylate, 15 parts of styrene and 13 parts of acrylamide.
A preparation method of the environment-friendly flame-retardant transparent polyester material comprises the following steps:
weighing the deionized water according to the proportion for later use, wherein the deionized water in the steps 1 and 2 does not account for the mass fraction of the deionized water;
1) mixing nano montmorillonite and deionized water at a ratio of 4.3 g/200 ml, performing ultrasonic treatment for 10-20 min, adjusting pH (adjusted by common acid such as citric acid), adding cetyl trimethyl ammonium bromide, performing ultrasonic treatment for 2-3 h, performing solid-liquid separation, repeatedly cleaning the solid with deionized water, and oven drying;
2) uniformly mixing a silane coupling agent and an ethanol aqueous solution according to the proportion of 3.7 g/100 ml, adjusting ph, adding the montmorillonite particles obtained in the step (1), and carrying out heat preservation at 40-50 ℃ for 4-6 h by ultrasonic treatment; cooling, carrying out solid-liquid separation and drying;
3) 1/3 parts by mass of allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate salt and 1/10 parts by mass of deionized water are uniformly mixed with the montmorillonite particles obtained in the step (2), 1/2 parts by mass of soft monomer and fluoroolefin are slowly added, and the mixture is stirred at a high speed for 10-20 min to obtain a first pre-emulsion for later use;
4) 1/3 parts by mass of allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate salt and 2/5 parts by mass of deionized water are uniformly mixed, a hard monomer and the rest soft monomer are slowly added, and the mixture is stirred at a high speed for 10-20 min to obtain a second pre-emulsion for later use;
5) 3/4 parts by mass of an initiator and 1/5 parts by mass of deionized water are uniformly mixed to obtain a priming solution for later use;
6) adding a buffering agent, the rest of deionized water, the rest of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate and the rest of an initiator into a reaction kettle (a four-neck flask with a stirring thermometer), heating while stirring, heating to 50-60 ℃, synchronously adding 1/5 serving as a trigger and a first pre-emulsion in parts by mass, reacting for 20-40 min, and raising the temperature in the reaction process without cooling; synchronously adding the second pre-emulsion and the rest priming solution, and reacting for 2-3 h; cooling, filtering, performing Soxhlet extraction, and vacuum drying to obtain the flame retardant; in the step, after cooling and filtering, sampling, coating, drying at 60 ℃, and then carrying out contact angle test, wherein the measured static water contact angle is 75.2 degrees; meanwhile, sampling and carrying out scanning electron microscope test, wherein the scanning electron microscope picture is shown in figure 1;
7) and melting and mixing the flame retardant and the thermoplastic polyester resin, extruding and granulating to obtain the flame retardant.
Preparing combustion test samples with the thickness of 12.5mm multiplied by 125mm multiplied by 0.75mm and 0.38mm by adopting an injection molding machine; the tests were conducted in accordance with Underwriters Laboratories Subject 94(UL94) for flame retardancy and were classified as V-0, V-1, V-2 or NR (not classified) for each test, with each test in this example achieving a V-0 rating.
Comparative experiment 1
The comparative experiment 1 and the above examples have the same raw material ratio and are prepared by the following method.
A preparation method of the environment-friendly flame-retardant transparent polyester material comprises the following steps:
1) mixing nano montmorillonite and deionized water at a ratio of 4.3 g/200 ml, performing ultrasonic treatment for 10-20 min, adjusting pH (which can be adjusted by common acid such as citric acid), adding cetyl trimethyl ammonium bromide, performing ultrasonic treatment for 2-3 h, performing solid-liquid separation, repeatedly cleaning the solid with deionized water, and oven drying;
2) uniformly mixing a silane coupling agent and an ethanol aqueous solution according to the proportion of 3.7 g/100 ml, adjusting ph, adding the montmorillonite particles obtained in the step (1), keeping the temperature at 40-50 ℃, and performing ultrasonic treatment for 4-6 h; cooling, carrying out solid-liquid separation and drying;
3) 2/3 parts by mass of allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate salt and 1/2 parts by mass of deionized water are uniformly mixed with the montmorillonite particles obtained in the step (2), hard monomers, soft monomers and fluoroolefin are slowly added, and the mixture is stirred at a high speed for 10-20 min to obtain pre-emulsion for later use;
4) 3/4 parts by mass of an initiator and 1/5 parts by mass of deionized water are uniformly mixed to obtain a priming solution for later use;
5) adding a buffering agent, the rest of deionized water, the rest of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate and the rest of an initiator into a reaction kettle (a four-neck flask with a stirring thermometer), heating while stirring, heating to 50-60 ℃, synchronously adding 1/5 parts by mass of a priming solution and 1/5 parts by mass of a pre-emulsion, reacting for 20-40 min, and raising the temperature in the reaction process without cooling; synchronously adding the rest pre-emulsion and the rest priming solution, and reacting for 2-3 h; cooling, filtering, performing Soxhlet extraction, and vacuum drying to obtain the flame retardant; in the step, after cooling and filtering, sampling, coating, drying at 60 ℃, and then carrying out contact angle test to obtain a static water contact angle of 110.7 degrees;
6) and melting and mixing the flame retardant and the thermoplastic polyester resin, extruding and granulating to obtain the flame retardant.
Comparative experiment 2
Comparative experiment 2 and the above examples were prepared using the same raw material ratios and using the following method.
Weighing the deionized water according to the proportion for later use, wherein the deionized water in the steps 1 and 2 does not account for the mass fraction of the deionized water;
1) mixing nano montmorillonite and deionized water at a ratio of 4.3 g/200 ml, performing ultrasonic treatment for 10-20 min, adjusting pH (adjusted by common acid such as citric acid), adding cetyl trimethyl ammonium bromide, performing ultrasonic treatment for 2-3 h, performing solid-liquid separation, repeatedly cleaning the solid with deionized water, and oven drying;
2) uniformly mixing a silane coupling agent and an ethanol aqueous solution according to the proportion of 3.7 g/100 ml, adjusting ph, adding the montmorillonite particles obtained in the step (1), keeping the temperature at 40-50 ℃, and performing ultrasonic treatment for 4-6 h; cooling, carrying out solid-liquid separation and drying;
3) 1/3 parts by mass of allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate salt and 1/10 parts by mass of deionized water are uniformly mixed, 1/2 parts by mass of soft monomer is slowly added, and the mixture is stirred at a high speed for 10-20 min to obtain a first pre-emulsion for later use;
4) 1/3 parts by mass of allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate salt, 2/5 parts by mass of deionized water and montmorillonite particles obtained in the step (2) are uniformly mixed, fluoroolefin, hard monomer and residual soft monomer are slowly added, and high-speed stirring is carried out for 10-20 min to obtain a second pre-emulsion for later use;
5) 3/4 parts by mass of an initiator and 1/5 parts by mass of deionized water are uniformly mixed to obtain a priming solution for later use;
6) adding a buffering agent, the rest of deionized water, the rest of allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate and the rest of an initiator into a reaction kettle (a four-neck flask with a stirring thermometer), heating while stirring, heating to 50-60 ℃, synchronously adding 1/5 and a first pre-emulsion in parts by mass of an initiating solution, reacting for 20-40 min, and raising the temperature in the reaction process without cooling; synchronously adding the second pre-emulsion and the rest priming solution, and reacting for 2-3 h; cooling, filtering, performing Soxhlet extraction, and vacuum drying to obtain the flame retardant; in the step, after cooling and filtering, sampling, coating, drying at 60 ℃, and then carrying out contact angle test, wherein the static water contact angle measured in a comparative experiment 2 is 113.9 degrees; in addition, sampling is carried out for scanning electron microscope test, and a scanning electron microscope picture is shown in figure 2;
7) and melting and mixing the flame retardant and the thermoplastic polyester resin, extruding and granulating to obtain the flame retardant.
FIG. 1 is a SEM picture of example 1, and FIG. 2 is a SEM picture of comparative experiment 2; the static water contact angle measured in example 1 was 75.2 °, the static water contact angle measured in comparative experiment 1 was 110.7 °, and the static water contact angle measured in comparative experiment 2 was 113.9 °; as can be seen from the scanning electron microscope picture and the contact angle test data, the scanning electron microscope picture (shown in figure 1) in example 1 has an obvious core-shell structure, the static water contact angle measured in example 1 is smaller, which indicates that the flame retardant in example 1 is easier to be wetted, the static water contact angle measured in the comparative experiment 1 is larger, which may be caused by that various monomers are uniformly applied and part of fluorine silicon is located on the surface of the colloidal particles during polymerization, so that the polarity of the colloidal particles is reduced and the hydrophilicity is deteriorated, and at the same time, in comparative experiment 2, although the core shell was designed using different monomers, the measured static water contact angle was also larger, probably because the fluorosilicone polymerization occurred only in the shell layer during the experimental design, but the fluorine silicon has smaller polarity and is easy to migrate to the inner core, so that the core shell contains the fluorine silicon, the boundary of the core shell is fuzzy, an outer hard and inner soft structure cannot be formed, and the core shell is not easy to be wetted; the scanning electron micrograph of comparative experiment 2 also demonstrates that the core-shell structure is not evident in FIG. 2.
Example 2
This example is substantially the same as example 1, with the differences including: the flame retardant comprises the following raw materials in parts by mass: 60 parts of deionized water, 2 parts of initiator, 1.0 part of buffering agent, 4.5 parts of emulsifier, 3 parts of silane coupling agent, 5 parts of nano-montmorillonite and 3 parts of fluoroolefin; 30 parts of hard monomer and 20 parts of soft monomer; the emulsifier comprises sodium dodecyl benzene sulfonate and allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate, and the proportion is 3: 1.5; the fluoroolefin is fluorinated ethylene; the silane coupling agent is vinyl trimethoxy silane; the soft monomer comprises 6 parts of hexyl methacrylate and 9 parts of ethyl acrylate; 5 parts of butyl acrylate; the hard monomer comprises 10 parts of tert-butyl methacrylate, 10 parts of styrene and 10 parts of acrylamide; 0.8 parts of a flame retardant per 100 parts of the thermoplastic polyester resin.
The flame retardant property test method is the same as that of example 1, and the flame retardant property test of each test in the implementation reaches V-0 level.
Example 3
This example is substantially the same as example 1, with the differences including: the flame retardant comprises the following raw materials in parts by mass: 60 parts of deionized water, 1 part of initiator, 0.7 part of buffering agent, 4.5 parts of emulsifier, 3 parts of silane coupling agent, 5 parts of nano montmorillonite and 3 parts of fluoroolefin; 40 parts of hard monomer and 10 parts of soft monomer; the fluoroolefin is tetrafluoroethylene; the silane coupling agent is vinyl triethoxysilane; the soft monomer comprises 3 parts of hexyl methacrylate and 7 parts of butyl acrylate; the hard monomer comprises 11 parts of vinyl acetate, 16 parts of methyl methacrylate and 13 parts of styrene; 0.8 parts of a flame retardant per 100 parts of the thermoplastic polyester resin.
The flame retardant property test method is the same as that of example 1, and the flame retardant property test of each test in the implementation reaches V-0 level.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (9)
1. An environment-friendly flame-retardant transparent polyester material is characterized in that: the flame retardant comprises thermoplastic polyester resin and a flame retardant, wherein the mass portion of the flame retardant is 0.5-2 parts per 100 parts of the thermoplastic polyester resin; the flame retardant is a montmorillonite-silicon-fluorine modified polypropylene ester material with a core-shell structure, montmorillonite and fluorine-silicon elements are both positioned in the core, and the proportion of hard monomers in the shell layer is greater than that of the hard monomers in the core.
2. The environmentally friendly, flame retardant, transparent polyester material of claim 1, wherein: the flame retardant comprises the following raw materials in parts by mass: 50-60 parts of deionized water, 1-2 parts of initiator, 0.5-1.0 part of buffering agent, 3.5-4.5 parts of emulsifier, 2-3 parts of silane coupling agent, 4-5 parts of nano montmorillonite, 2-3 parts of fluoroolefin and 30-60 parts of acrylic monomer; wherein, the acrylic monomer comprises 20 to 40 parts of hard monomer and 10 to 20 parts of soft monomer; the glass transition temperature of the hard monomer is more than 25 ℃, and the glass transition temperature of the soft monomer is less than 0 ℃.
3. The environmentally friendly flame retardant transparent polyester material of claim 2, wherein: the particle size range of the nano montmorillonite is 10-30 nm.
4. The environmentally friendly flame retardant transparent polyester material of claim 2, wherein: the emulsifier comprises an anionic surfactant and a reactive surfactant in a mass ratio of (2-3) to 1.5, or a cationic surfactant and a reactive surfactant in a mass ratio of (2-3) to 1.5.
5. The environmentally friendly flame retardant transparent polyester material of claim 4, wherein: the anionic surfactant is sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate, sulfonate of ethoxylated fatty acid methyl ester or sodium alkenyl sulfonate; the cationic surfactant is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, octadecyl amine polyoxyethylene ether biquaternary ammonium salt or cetyl polyoxyethylene ether dimethyl octane ammonium chloride; the reactive surfactant is allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate.
6. The environmentally friendly flame retardant transparent polyester material of claim 2, wherein: the soft monomer is one or the combination of at least two of ethyl acrylate, butyl acrylate, isooctyl acrylate and hexyl methacrylate; the hard monomer is one or the combination of at least two of vinyl acetate, tert-butyl methacrylate, acrylamide, styrene, methyl methacrylate and isobutyl methacrylate; the theoretical glass transition temperature of acrylic monomers adopted by the flame retardant is calculated according to a fox equation of 1/Tg = W1/Tg1+ W2/Tg2+ … … + Wn/Tgn, wherein Tg is more than 45 ℃, n is a natural number, and W1, W2, … … and Wn are mass fractions of soft monomers or hard monomers respectively; w1+ W2 + … … + Wn = 100%.
7. The environmentally friendly flame retardant transparent polyester material of claim 2, wherein: the fluoroolefin is vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene or trifluorostyrene.
8. The environmentally friendly flame retardant transparent polyester material of claim 2, wherein: the silane coupling agent is vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane or vinyl triisopropenoxysilane.
9. A method for preparing the environment-friendly flame-retardant transparent polyester material as claimed in claims 1 to 8, which comprises the following steps:
1) mixing nano montmorillonite and deionized water according to the proportion of (4-5) g/200 ml, performing ultrasonic treatment for 10-20 min, adjusting pH, adding anionic surfactant/cationic surfactant, performing ultrasonic treatment for 2-3 h, performing solid-liquid separation, repeatedly cleaning the solid with deionized water, and drying;
2) uniformly mixing a silane coupling agent and an ethanol aqueous solution according to the proportion of (3-4) g/100 ml, adjusting ph, adding the montmorillonite particles obtained in the step (1), and carrying out heat preservation at 40-50 ℃ for 4-6 h by ultrasonic treatment; cooling, carrying out solid-liquid separation and drying;
3) 1/3 parts by mass of reactive surfactant, 1/10 parts by mass of deionized water and the montmorillonite particles obtained in the step (2) are uniformly mixed, 1/2 parts by mass of soft monomer and fluoroolefin are slowly added, and the mixture is stirred at a high speed for 10-20 min to obtain a first pre-emulsion for later use;
4) 1/3 parts by mass of reactive surfactant and 2/5 parts by mass of deionized water are uniformly mixed, and a hard monomer and the rest soft monomer are slowly added and stirred at a high speed for 10-20 min to obtain a second pre-emulsion for later use;
5) 3/4 parts by mass of an initiator and 1/5 parts by mass of deionized water are uniformly mixed to obtain a priming solution for later use;
6) adding 3/10 parts by mass of deionized water, 1/3 parts by mass of reactive surfactant, 1/4 parts by mass of initiator and buffer into a reaction kettle, stirring and heating, raising the temperature to 50-60 ℃, synchronously adding 1/5 parts by mass of initiating solution and first pre-emulsion, and reacting for 20-40 min; 4/5 parts by mass of the priming solution and the second pre-emulsion are synchronously added and react for 2 to 3 hours; then filtering, performing Soxhlet extraction and vacuum drying to prepare the flame retardant;
7) and melting and mixing the flame retardant and the thermoplastic polyester resin, extruding and granulating to obtain the flame retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210639959.4A CN114716798B (en) | 2022-06-08 | 2022-06-08 | Environment-friendly flame-retardant transparent polyester material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210639959.4A CN114716798B (en) | 2022-06-08 | 2022-06-08 | Environment-friendly flame-retardant transparent polyester material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN114716798A true CN114716798A (en) | 2022-07-08 |
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