CN114381097A - Flame-retardant thermoplastic PET composite material and preparation method thereof - Google Patents
Flame-retardant thermoplastic PET composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant thermoplastic PET composite material and a preparation method thereof, wherein purified diatomite is used as a flame retardant carrier, sodium molybdate dihydrate is used as a molybdenum source, and molybdenum disulfide is loaded on the surface of the diatomite through hydrothermal reaction to synthesize a low-cost, green and efficient flame retardant; and the diatomite is rich in active silicon, the silicon can increase the thermal stability of the carbon layer to generate a better flame-retardant effect, and the two flame-retardant elements of molybdenum disulfide, Mo and S are combined to isolate the conduction and the transportation of oxygen, heat and volatile inflammable micromolecules at the same time, so that the release rate and the combustion rate of combustible gas are reduced, and the residual carbon rate is increased.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a flame-retardant thermoplastic PET composite material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is a thermoplastic resin with excellent combination properties of high strength, good chemical stability, easy processing success and dimensional stability. The method is widely applied to the fields of containers, packaging materials, films, engineering plastics and the like, and has good development prospect and potential research value. However, the PET macromolecular chain has regular structure, higher crystallinity and no strong polar group in the molecule, so the surface affinity is poor, and the surface performance of the PET material is greatly influenced. PET is easy to burn like many high molecular materials, and generates molten drops, toxic gas, black smoke and the like when being burnt under a high temperature condition, so that a more serious fire is induced, the processing and the application of the PET are influenced, and the immeasurable loss is caused, so that the PET needs to be subjected to flame retardant modification, and the melting point of a flame retardant is required to be adapted to the PET so as to ensure that the PET plays a stable role in processing. The processing method of PET mainly comprises the methods of melt blending, in-situ polymerization and the like to prepare the flame-retardant thermoplastic PET composite material, and has good development prospect and potential research value.
Two-dimensional molybdenum disulfide is one of typical representatives of transition metal chalcogenide, and due to the unique monomolecular layered structure and a plurality of excellent properties, a research hot tide is raised in the field of materials. Two-dimensional MoS2The material has an electronic band gap of 1.9eV, excellent mechanical, thermal stability, catalysis and photoelectric properties, and is widely concerned and researched in the fields of sensing, catalysis, electronic information and material modification.
Diatomite is a fine-particle, low-density natural material, is mostly gray or white, and belongs to a porous structure. The chemical components of the diatomite are mainly amorphous water and SiO2And trace metal oxide and organic impurities, so that the surface of the diatomite has a plurality of free hydrogen bonds and silicon hydroxyl groups, and the diatomite has dielectricity and low reactivity, so that the diatomite is convenient to be grafted or combined with other functional groups, the performance and the chemical activity of the diatomite are improved, and the diatomite has the advantages of high stability, high stability and the likeWhen the soil is used as a filler, the mechanical property of the composite material can be obviously improved.
According to the method, firstly, concentrated acid is used for purifying diatomite to be used as a carrier, and then molybdenum disulfide is loaded on the surface of the diatomite through a hydrothermal reaction to synthesize MoS2The flame retardant is added into PET through an in-situ polymerization method to synthesize the PET/MoS2The composite material can fully utilize the advantages of each component of the composite material, so that the flame retardant property of the composite material is more excellent, and compared with pure PET, the composite material has more efficient flame retardant property. Due to the characteristics of light weight, porosity, rich active silicon and the like of the diatomite, the molybdenum disulfide is well dispersed on the surface of the diatomite, and the silicon, the molybdenum and the sulfur flame retardant elements in the diatomite have a synergistic effect to promote the generation of carbon at high temperature. The diatomite is used as a silicon-containing substance, can promote the carbon formation effect, plays a role of a framework, increases the stability of a carbon layer, improves the LOI value of a polymer, has the capability of providing a stronger and larger protective carbon barrier layer for PET, and simultaneously easily shows the nanometer barrier effect to block heat, oxygen transportation and escape of volatile inflammable micromolecules due to the large specific surface area structure of molybdenum disulfide. The diatomite has the silicon carbonization effect and the molybdenum disulfide blocking effect, so that the combustion efficiency is delayed, a good blocking effect is achieved, the degradation is blocked, the diatomite and the molybdenum disulfide respectively play different roles and promote each other, the combustible gas is diluted in a gas phase, the flame is inhibited, a flame retardant system is formed, and an excellent flame retardant effect is achieved.
Disclosure of Invention
The invention aims to provide a flame-retardant thermoplastic PET composite material and a preparation method thereof. The invention has scientific and reasonable formula and simple and practical process flow, and synthesizes the novel flame retardant MoS2the/f-DE ensures that the produced PET composite material has excellent flame retardant property and can generate great social and economic benefits.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps: drying and dredging the PET modified master batchPerforming injection molding by using an injection molding machine to obtain the flame-retardant thermoplastic PET composite material; wherein, the PET modified master batch is prepared by adding a flame retardant MoS in the in-situ polymerization of PET2and/f-DE, granulating the obtained product by a crusher to obtain the PET modified master batch.
The preparation method of the flame-retardant thermoplastic PET composite material specifically comprises the following steps:
1) flame retardant MoS2The preparation process of/f-DE comprises the following steps:
(1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
(2) Preparing molybdenum disulfide-loaded diatomite: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, dissolving 1g of the product f-DE obtained in the step (1) in 40ml of deionized water, stirring for 30min, slowly adding the sodium molybdate solution, continuously stirring for 10min, dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly dripping the mixed solution, continuously stirring for 1h, finally pouring the solution into a 100ml of polytetrafluoroethylene inner container, filling the mixture into a reaction kettle, carrying out hydrothermal reaction for 12h at 190 ℃, centrifuging, washing, freeze-drying and calcining at 500 ℃ for 2h after the reaction is finished to obtain the flame retardant MoS2/f-DE。
2) The preparation method of the PET modified master batch comprises the following steps: the flame retardant MoS prepared by the steps2Adding the/f-DE into 60g of ethylene glycol solution (EG) according to different proportions (accounting for 1-5% of the total mass of the synthesized PET raw materials, wherein the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), and uniformly mixing the solution by ultrasonic stirring for a period of time to obtain MoS2a/f-DE/ethylene glycol complex for use; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and 60g of MoS were added2Adding the/f-DE/ethylene glycol complex into a high-pressure reaction kettle, adding 0.1g of condensation polymerization catalyst ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa, and controlling the temperature at 22Esterification reaction is carried out for 2h at the temperature of 0-240 ℃, and the pressure in the kettle is regulated and controlled within a certain pressure range (0.3 MPa) through continuous air release in the reaction process. When the temperature of a thermometer on the reflux column is increased to 270-290 ℃, condensation polymerization is carried out, and water discharge is started, wherein the water discharge time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET modified master batch with different flame retardant contents.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
The invention has the beneficial effects that:
according to the method, firstly, concentrated acid is used for purifying diatomite to be used as a carrier, and then molybdenum disulfide is loaded on the surface of the diatomite through a hydrothermal reaction to synthesize MoS2The flame retardant is added into PET through an in-situ polymerization method to synthesize the PET/MoS2The composite material can fully utilize the advantages of each component of the composite material, so that the flame retardant property of the composite material is more excellent, and compared with pure PET, the composite material has more efficient flame retardant property. Due to the characteristics of light weight, porosity, rich active silicon and the like of the diatomite, the molybdenum disulfide is well dispersed on the surface of the diatomite, the diatomite has the capability of providing a stronger and larger protective carbon barrier layer for PET, the silicon, molybdenum and sulfur flame retardant elements in the two substances have a synergistic effect, the generation of carbon is promoted at high temperature, a good blocking effect is achieved, the degradation is blocked, the silicon, molybdenum and sulfur flame retardant elements respectively play different roles and mutually promote, a flame retardant system is formed by diluting combustible gas and inhibiting flame in a gas phase, and an excellent flame retardant effect is achieved.
Drawings
FIG. 1 is an SEM image of f-DE prepared according to the present invention.
FIG. 2 is a MoS prepared according to the present invention2SEM image of/f-DE.
Detailed Description
The present invention will be further understood from the following examples, which are not intended to limit the scope of the invention.
Example 1
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) flame retardant MoS2The preparation process of/f-DE comprises the following steps:
(1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
(2) Preparing molybdenum disulfide-loaded diatomite: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, dissolving 1g of the product f-DE obtained in the step (1) in 40ml of deionized water, stirring for 30min, slowly adding the sodium molybdate solution, continuously stirring for 10min, dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly dripping the mixed solution, continuously stirring for 1h, finally pouring the solution into a 100ml of polytetrafluoroethylene inner container, filling the mixture into a reaction kettle, carrying out hydrothermal reaction for 12h at 190 ℃, centrifuging, washing, freeze-drying and calcining at 500 ℃ for 2h after the reaction is finished to obtain the flame retardant MoS2/f-DE。
2) The preparation method of the PET modified master batch comprises the following steps: 1g of the flame retardant MoS2the/f-DE was added to a glycol solution (concentration 98% by weight) containing 60g of glycol (flame retardant MoS)2the/f-DE accounts for 1 percent of the total mass of the synthesized PET raw materials, the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), and the solution is uniformly mixed by ultrasonic stirring for a period of time to obtain MoS2a/f-DE/ethylene glycol complex for use; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and MoS were added2Adding the/f-DE/glycol complex into a high-pressure reaction kettle, adding 0.1g of condensation polymerization catalyst ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa,the temperature is controlled at 240 ℃ for esterification reaction for 2h, and the pressure in the kettle is regulated and controlled at 0.3MPa through continuous air release in the reaction process. When the temperature of a thermometer on the reflux column is increased to 280 ℃, condensation polymerization is carried out, and water begins to be discharged, wherein the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET modified master batch with different flame retardant contents.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Example 2
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) flame retardant MoS2The preparation process of/f-DE comprises the following steps:
(1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
(2) Preparing molybdenum disulfide-loaded diatomite: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, dissolving 1g of the product f-DE obtained in the step (1) in 40ml of deionized water, stirring for 30min, slowly adding the sodium molybdate solution, continuously stirring for 10min, dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly dripping the mixed solution, continuously stirring for 1h, finally pouring the solution into a 100ml of polytetrafluoroethylene inner container, filling the mixture into a reaction kettle, carrying out hydrothermal reaction for 12h at 190 ℃, centrifuging, washing, freeze-drying and calcining at 500 ℃ for 2h after the reaction is finished to obtain the flame retardant MoS2/f-DE。
2) The preparation method of the PET modified master batch comprises the following steps: 2g of the flame retardant MoS2the/f-DE was added to a glycol solution (concentration 98% by weight) containing 60g of glycol (flame retardant MoS)2the/f-DE accounts for 2 percent of the total mass of the synthesized PET raw materials, the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), and the solution is uniformly mixed by ultrasonic stirring for a period of time to obtain MoS2a/f-DE/ethylene glycol complex for use; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and MoS were added2Adding the/f-DE/ethylene glycol complex into a high-pressure reaction kettle, adding 0.1g of condensation polymerization catalyst ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa, controlling the temperature at 240 ℃ to perform esterification reaction for 2 hours, and controlling the pressure in the kettle to be 0.3MPa through continuous gas release regulation in the reaction process. When the temperature of a thermometer on the reflux column is increased to 280 ℃, condensation polymerization is carried out, and water begins to be discharged, wherein the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET modified master batch with different flame retardant contents.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Example 3
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) flame retardant MoS2The preparation process of/f-DE comprises the following steps:
(1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
(2) Preparing molybdenum disulfide-loaded diatomite: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, and taking a certain mass of product f obtained in the step (1)Dissolving 1g of DE in 40ml of deionized water, stirring for 30min, slowly adding a sodium molybdate solution, continuously stirring for 10min, dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly and dropwise adding the mixed solution, continuously stirring for 1h, finally pouring the solution into a 100ml polytetrafluoroethylene inner container, filling the solution into a reaction kettle, carrying out hydrothermal treatment at 190 ℃ for 12h, centrifuging, washing, freeze-drying and calcining at 500 ℃ for 2h after the reaction is finished to obtain a flame retardant MoS2/f-DE。
2) The preparation method of the PET modified master batch comprises the following steps: 3g of the flame retardant MoS2the/f-DE was added to a glycol solution (concentration 98% by weight) containing 60g of glycol (flame retardant MoS)2the/f-DE accounts for 3 percent of the total mass of the synthesized PET raw materials, the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), and the solution is uniformly mixed by ultrasonic stirring for a period of time to obtain MoS2a/f-DE/ethylene glycol complex for use; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and MoS were added2Adding the/f-DE/ethylene glycol complex into a high-pressure reaction kettle, adding 0.1g of condensation polymerization catalyst ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa, controlling the temperature at 240 ℃ to perform esterification reaction for 2 hours, and controlling the pressure in the kettle to be 0.3MPa through continuous gas release regulation in the reaction process. When the temperature of a thermometer on the reflux column is increased to 280 ℃, condensation polymerization is carried out, and water begins to be discharged, wherein the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET modified master batch with different flame retardant contents.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Example 4
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) flame retardant MoS2Preparation of/f-DEThe process is as follows:
(1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
(2) Preparing molybdenum disulfide-loaded diatomite: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, dissolving 1g of the product f-DE obtained in the step (1) in 40ml of deionized water, stirring for 30min, slowly adding the sodium molybdate solution, continuously stirring for 10min, dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly dripping the mixed solution, continuously stirring for 1h, finally pouring the solution into a 100ml of polytetrafluoroethylene inner container, filling the mixture into a reaction kettle, carrying out hydrothermal reaction for 12h at 190 ℃, centrifuging, washing, freeze-drying and calcining at 500 ℃ for 2h after the reaction is finished to obtain the flame retardant MoS2/f-DE。
2) The preparation method of the PET modified master batch comprises the following steps: 4g of the flame retardant MoS2the/f-DE was added to a glycol solution (concentration 98% by weight) containing 60g of glycol (flame retardant MoS)2the/f-DE accounts for 4 percent of the total mass of the synthesized PET raw materials, the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), and the solution is uniformly mixed by ultrasonic stirring for a period of time to obtain MoS2a/f-DE/ethylene glycol complex for use; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and MoS were added2Adding the/f-DE/ethylene glycol complex into a high-pressure reaction kettle, adding 0.1g of condensation polymerization catalyst ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa, controlling the temperature at 240 ℃ to perform esterification reaction for 2 hours, and controlling the pressure in the kettle to be 0.3MPa through continuous gas release regulation in the reaction process. When the temperature of a thermometer on the reflux column is increased to 280 ℃, condensation polymerization is carried out, and water begins to be discharged, wherein the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET modified master batch with different flame retardant contents.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Example 5
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) flame retardant MoS2The preparation process of/f-DE comprises the following steps:
(1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
(2) Preparing molybdenum disulfide-loaded diatomite: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, dissolving 1g of the product f-DE obtained in the step (1) in 40ml of deionized water, stirring for 30min, slowly adding the sodium molybdate solution, continuously stirring for 10min, dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly dripping the mixed solution, continuously stirring for 1h, finally pouring the solution into a 100ml of polytetrafluoroethylene inner container, filling the mixture into a reaction kettle, carrying out hydrothermal reaction for 12h at 190 ℃, centrifuging, washing, freeze-drying and calcining at 500 ℃ for 2h after the reaction is finished to obtain the flame retardant MoS2/f-DE。
2) The preparation method of the PET modified master batch comprises the following steps: 5g of the flame retardant MoS2the/f-DE was added to a glycol solution (concentration 98% by weight) containing 60g of glycol (flame retardant MoS)2the/f-DE accounts for 5 percent of the total mass of the synthesized PET raw materials, the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), and the solution is uniformly mixed by ultrasonic stirring for a period of time to obtain MoS2a/f-DE/ethylene glycol complex for use; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and MoS were added2Addition of the/f-DE/ethylene glycol Complex to high pressure0.1g of condensation polymerization catalyst of ethylene glycol aluminum is added into a reaction kettle in advance, nitrogen is introduced, the pressure is maintained at 0.3MPa, the temperature is controlled at 240 ℃ for esterification reaction for 2 hours, and the pressure in the kettle is controlled at 0.3MPa through continuous gas release regulation in the reaction process. When the temperature of a thermometer on the reflux column is increased to 280 ℃, condensation polymerization is carried out, and water begins to be discharged, wherein the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET modified master batch with different flame retardant contents.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Comparative example 1 (without diatomaceous earth and molybdenum disulfide)
A preparation method of a thermoplastic PET composite material comprises the following steps:
1) the preparation method of the PET master batch comprises the following steps: after nitrogen is replaced by the high-pressure reaction kettle, 40g of Purified Terephthalic Acid (PTA) and 98wt% ethylene glycol solution containing 60g of ethylene glycol are added into the high-pressure reaction kettle, 0.1g of condensation polymerization catalyst aluminum ethylene glycol is added in advance, nitrogen is introduced, the pressure is maintained at 0.3MPa, the temperature is controlled at 240 ℃ for esterification reaction for 2h, when the temperature of a thermometer on a reflux column is raised to 280 ℃ for polycondensation, water begins to be discharged, and the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and then cutting the obtained product into particles to obtain the PET master batch.
2) The preparation method of the thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the thermoplastic PET composite material.
COMPARATIVE EXAMPLE 2 (containing only diatomaceous earth)
A preparation method of a thermoplastic PET composite material comprises the following steps:
1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
2) The preparation method of the PET modified master batch comprises the following steps: adding 5g of f-DE prepared in the step into 98wt% ethylene glycol solution (EG) containing 60g of ethylene glycol (the f-DE accounts for 5% of the total mass of the synthesized PET raw materials, and the PET raw materials specifically refer to ethylene glycol and purified terephthalic acid), so that the flame retardant is better dispersed in the in-situ polymerization process, and uniformly mixing the solution by ultrasonic stirring for 30min to obtain f-DE/ethylene glycol complex for later use; after nitrogen is replaced by the high-pressure reaction kettle, 40g of Purified Terephthalic Acid (PTA) and 5% f-DE/ethylene glycol complex are added into the high-pressure reaction kettle, 0.1g of condensation polymerization catalyst aluminum glycol is added in advance, nitrogen is introduced, the pressure is maintained at 0.3MPa, the temperature is controlled at 240 ℃ for esterification reaction for 2 hours, when the temperature of a thermometer on a reflux column is raised to 280 ℃ for condensation polymerization, water begins to be discharged, and the water discharging time is about 90 minutes; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and cutting the obtained product into particles to obtain the PET modified master batch.
3) The preparation method of the thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the thermoplastic PET composite material.
Comparative example 3 (containing molybdenum disulfide only)
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) the preparation process of the flame retardant molybdenum disulfide comprises the following steps: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, then dissolving 0.5g of L-cysteine in 10ml of deionized water, and slowly dissolvingDropwise adding the solution, continuously stirring for 1h, finally pouring the solution into a 100ml polytetrafluoroethylene inner container, filling the solution into a reaction kettle, carrying out hydrothermal treatment at 190 ℃ for 12h, centrifuging, washing and freeze-drying the product after the reaction is finished to obtain the flame retardant MoS2。
2) The preparation method of the PET modified master batch comprises the following steps: 5g of the flame retardant MoS prepared in the above step2Added to a 98% strength by weight ethylene glycol solution (EG) containing 60g of ethylene glycol (flame retardant MoS)25% of the total mass of the synthesized PET raw materials, specifically ethylene glycol and purified terephthalic acid), and ultrasonically stirring for 30min to uniformly mix the solution to obtain MoS2The ethylene glycol complex is used for standby; after the nitrogen gas was replaced in the autoclave, 40g of Purified Terephthalic Acid (PTA) and 5% MoS were added2Adding the ethylene glycol complex into a high-pressure reaction kettle, adding 0.1g of condensation polymerization catalyst ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa, controlling the temperature at 240 ℃ to perform esterification reaction for 2 hours, and when the temperature of a thermometer on a reflux column is raised to 280 ℃ to perform condensation polymerization, beginning to discharge water, wherein the water discharge time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and cutting the obtained product into particles to obtain the PET modified master batch.
3) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Comparative example 4 (adding diatomaceous earth and molybdenum disulfide, respectively)
A preparation method of a flame-retardant thermoplastic PET composite material comprises the following steps:
1) and (3) purifying and treating diatomite: 2g of diatomaceous earth were dispersed in 65% strength by weight nitric acid and then sonicated for 30 min. Slowly stirring the diatomite subjected to ultrasonic treatment for 2 hours in a water bath condition at 60 ℃, then performing suction filtration, washing with deionized water to be neutral, and drying in an oven at 60 ℃ for later use, wherein the name of the diatomite is f-DE.
2) The preparation process of the flame retardant molybdenum disulfide comprises the following steps: dissolving 1g of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, then dissolving 0.5g of L-cysteine in 10ml of deionized water, slowly dropwise adding the solution, continuously stirring for 1h, finally pouring the solution into a 100ml polytetrafluoroethylene inner container, filling the solution into a reaction kettle, carrying out hydrothermal treatment at 190 ℃ for 12h, and after the reaction is finished, centrifuging, washing and freeze-drying the product to obtain the flame retardant MoS2。
3) The preparation method of the PET modified master batch comprises the following steps: 2.5g of f-DE and 2.5g of MoS obtained in the preceding step2Added to a 98wt% ethylene glycol solution (EG) containing 60g of ethylene glycol (f-DE and MoS)2The total mass of the raw materials accounts for 5 percent of the total mass of the synthesized PET raw materials, the raw materials of the PET are ethylene glycol and purified terephthalic acid), so that the flame retardant is better dispersed in the in-situ polymerization process, and the solution is uniformly mixed by ultrasonic stirring for 30min to obtain an ethylene glycol complex for later use; after nitrogen is replaced by the high-pressure reaction kettle, 40g of Purified Terephthalic Acid (PTA) and ethylene glycol complex are added into the high-pressure reaction kettle, 0.1g of condensation polymerization catalyst ethylene glycol aluminum is added in advance, nitrogen is introduced, the pressure is maintained at 0.3MPa, the temperature is controlled at 240 ℃ for esterification reaction for 2h, when the temperature of a thermometer on a reflux column is raised to 280 ℃ for condensation polymerization, water begins to be discharged, and the water discharging time is about 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and cutting the obtained product into particles to obtain the PET modified master batch.
4) The preparation method of the flame-retardant thermoplastic PET composite material comprises the following steps: drying the obtained PET modified master batch at the temperature of 120 ℃ for 10h, and performing injection molding by an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are 260 ℃, 255 ℃, 250 ℃, the injection molding pressure is 120MPa, and the pressure maintaining pressure is 60MPa, so as to obtain the flame-retardant thermoplastic PET composite material.
Performance testing
As can be seen from the results in the above table, Mo is present as a flame retardantS2The tensile strength of the composite material is obviously improved by increasing the dosage of the/f-DE; in connection with the data of comparative examples 2 and 3, f-DE and MoS2The use of the molybdenum disulfide is beneficial to increasing the tensile strength of the composite material, and the dispersibility of the molybdenum disulfide in a matrix is increased after the two are compositely modified, so that MoS is added2The tensile strength of the composite material after the/f-DE is in an increasing trend; the elongation at break is continuously decreased because the structure of PET is affected by the addition of the flame retardant. It can also be seen that the limiting oxygen index of the material increases with the increase of the amount of the flame retardant, and the flame retardant grade is gradually improved, which indicates that the flame retardant performance of the composite material is slowly enhanced.
The data of example 5 and comparative example 4 show that the flame retardant MoS is added2(f-DE) and MoS2And f-DE, synthetic flame retardants MoS2In the/f-DE, diatomite plays a role of a framework, molybdenum disulfide is loaded on the surface of the diatomite, and MoS is added in a compounding manner2The tensile strength and the flame retardant property of the mixture f-DE are improved, because the two substances are added in a compounding way, agglomeration is easy to occur in a matrix material, the flame retardant effect is not obvious, and the description shows that MoS2The flame retardant property can be improved by loading the diatomite.
From fig. 1, it can be seen that the surface of the diatomite has a porous structure, and fig. 2 shows that molybdenum disulfide is successfully loaded on the surface of the diatomite.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a flame-retardant thermoplastic PET composite material is characterized by comprising the following steps: drying the PET modified master batch, and performing injection molding through an injection molding machine to obtain the flame-retardant thermoplastic PET composite material; wherein, the PET modified master batch is prepared by adding a flame retardant MoS in the in-situ polymerization of PET2and/f-DE, granulating the obtained product by a crusher to obtain the PET modified master batch.
2. The method of claim 1, wherein: the flame retardant MoS2The preparation method of the/f-DE comprises the following steps:
(1) and (3) purifying and treating diatomite: dispersing diatomite in nitric acid, performing ultrasonic treatment for 30min, slowly stirring the diatomite subjected to ultrasonic treatment under the condition of water bath, performing suction filtration, washing with deionized water to be neutral, and drying in a 60 ℃ drying oven for later use, wherein the name of the drying oven is f-DE;
(2) preparing molybdenum disulfide-loaded diatomite: dissolving a certain mass of sodium molybdate dihydrate in 20ml of deionized water, fully stirring for 30min for later use, dissolving a certain mass of the product f-DE obtained in the step (1) in 40ml of deionized water, stirring for 30min, slowly adding a sodium molybdate solution, continuously stirring for 10min, dissolving a certain mass of L-cysteine in 10ml of deionized water, slowly dripping the mixed solution, continuously stirring for 1h, pouring the solution into a 100ml of polytetrafluoroethylene inner container, filling the solution into a reaction kettle, carrying out hydrothermal reaction, and centrifuging, washing, freeze-drying and calcining the product after the reaction is finished to obtain the flame retardant MoS2/f-DE。
3. The method of claim 2, wherein: the concentration of nitric acid in the step (1) is 65wt%, and the water bath condition is as follows: 60 ℃ and 2 h.
4. The method of claim 2, wherein: in the step (2), the mass of the sodium molybdate dihydrate is 1g, the mass ratio of the diatomite f-DE to the sodium molybdate dihydrate is 1:1, and the mass of the L-cysteine is 0.5 g.
5. The method of claim 2, wherein: the hydrothermal reaction condition in the step (2) is 190 ℃ for 12 h; calcining conditions are as follows: 500 ℃ for 2 h.
6. The method of claim 1, wherein: the preparation method of the PET modified master batch comprises the following specific steps: mixing the flame retardant MoS2Adding the/f-DE into the ethylene glycol aqueous solution, and uniformly mixing the solution by ultrasonic stirring to obtain MoS2(f-DE/Ether II)Alcohol complex for later use; after the nitrogen is replaced by the high-pressure reaction kettle, the purified terephthalic acid and the MoS are added2Adding the/f-DE/ethylene glycol complex into a high-pressure reaction kettle, adding a condensation polymerization catalyst of ethylene glycol aluminum in advance, introducing nitrogen, maintaining the pressure at 0.3MPa, controlling the temperature at 220-240 ℃ for esterification reaction for 2h, and controlling the pressure in the kettle at 0.3MPa through continuous gas release regulation in the reaction process; when the temperature of a thermometer on the reflux column is increased to 270-290 ℃, carrying out polycondensation, and beginning to discharge water, wherein the water discharge time is 90 min; and finally pouring the mixture into a mold, curing the mixture in a vacuum drying oven at 160 ℃ for 12 hours, and cutting the obtained product into particles to obtain the PET modified master batch.
7. The method of claim 6, wherein: flame retardant MoS2The addition amount of the/f-DE accounts for 1-5% of the total mass of the raw materials for synthesizing the PET.
8. The method of claim 1, wherein: the preparation method of the flame-retardant thermoplastic PET composite material comprises the steps of drying PET modified master batches at the temperature of 120 ℃ for 10 hours, and carrying out injection molding through an injection molding machine, wherein the injection molding temperatures of five sections from a feed inlet to a discharge outlet of the injection molding machine are respectively 260 ℃, 255 ℃, 250 ℃ and 250 ℃, the injection molding pressure is 120MPa, and the holding pressure is 60MPa, so that the flame-retardant thermoplastic PET composite material is obtained.
9. A flame retardant thermoplastic PET composite material obtained by the method of any one of claims 1 to 8.
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