CN111808444A

CN111808444A - Preparation method of PET modified filler, PET composite material and preparation method thereof

Info

Publication number: CN111808444A
Application number: CN202010740826.7A
Authority: CN
Inventors: 姜永胜; 刘凯; 吴先立
Original assignee: Anhui Jianghuai Automobile Group Corp
Current assignee: Anhui Jianghuai Automobile Group Corp
Priority date: 2020-07-24
Filing date: 2020-07-24
Publication date: 2020-10-23
Anticipated expiration: 2040-07-24
Also published as: CN111808444B

Abstract

The invention discloses a preparation method of a PET modified filler, a PET composite material and a preparation method thereof, wherein the preparation method of the PET modified filler comprises the following steps: modifying the fullerene to enable the surface of the fullerene to be modified with dimercapto to obtain modified fullerene; mixing the modified fullerene with poly glycidyl methacrylate and acetone, reacting at 40-60 ℃ for 6-12 h, separating out solid substances after the reaction is finished, and drying to obtain microspheres; and calcining the microspheres at 600-800 ℃ for 4-6 h to obtain the PET modified filler. The PET modified filler prepared by the method provided by the invention has higher porosity and specific surface area, and the VOC performance of the PET material can be well improved when the PET modified filler is used for modifying the PET material.

Description

Preparation method of PET modified filler, PET composite material and preparation method thereof

Technical Field

The invention relates to the technical field of polymer modification, and particularly relates to a preparation method of a PET modified filler, a PET composite material and a preparation method of the PET composite material.

Background

VOC refers to volatile organic compounds (alkanes), aromatic hydrocarbons, olefins, halocarbons, esters, aldehydes, ketones and other organic compounds, most of which have unpleasant special odor and certain toxicity, irritation, teratogenicity and carcinogenicity, especially benzene, toluene and formaldehyde, which cause great harm to human health. Common sources of VOCs include plastic products prepared from synthetic resins, and the sources of VOCs in the plastic products are complex and wide, for example, in the preparation process of raw material resins, catalysts, monomers, solvents, generated impurities, oligomers and the like added in the synthesis reaction remain in the resins and cannot be effectively removed through subsequent treatment; for example, in order to improve the application properties of plastic products, when a raw resin is molded into a plastic product, an auxiliary agent for improving the aging resistance, the oxidation resistance, and the like is usually added, and these auxiliary agents are easily decomposed to generate aldehydes, ketones, and the like during high-temperature processing or during long storage and transportation.

Polyethylene terephthalate (PET) has the advantages of good fatigue resistance, good heat resistance, excellent dimensional stability and the like as a widely-used high-molecular polyester resin, but the VOC performance of PET generally limits the application of PET composite materials in some specific fields.

Disclosure of Invention

The invention mainly aims to provide a preparation method of a PET modified filler, a PET composite material and a preparation method thereof, and aims to provide a modified filler capable of obviously improving the VOC (volatile organic compounds) performance of PET.

In order to achieve the purpose, the invention provides a preparation method of a PET modified filler, which comprises the following steps:

modifying the fullerene to enable the surface of the fullerene to be modified with dimercapto to obtain modified fullerene;

mixing the modified fullerene with poly glycidyl methacrylate and acetone, reacting at 40-60 ℃ for 6-12 h, separating out solid substances after the reaction is finished, and drying to obtain microspheres;

and calcining the microspheres at 600-800 ℃ for 4-6 h to obtain the PET modified filler.

Optionally, the step of modifying the fullerene to modify the fullerene surface with a dimercapto group to obtain a modified fullerene includes:

mixing fullerene and ethanol, and stirring and reacting at normal temperature for 10-20 min to obtain a first solution;

mixing 2, 3-dimercaptosuccinic acid with ethanol, and stirring at normal temperature to react for 8-12 min to obtain a second solution;

and mixing the first solution and the second solution, reacting at 70-90 ℃ for 10-16 h, separating solid substances generated by the reaction, and drying to obtain the modified fullerene.

Optionally, after mixing the fullerene with ethanol, stirring and reacting at normal temperature for 10-20 min to obtain a first solution, the method comprises the following steps: the mass ratio of the fullerene to the ethanol is (60-80): (200 to 240); and/or the presence of a gas in the gas,

mixing 2, 3-dimercaptosuccinic acid with ethanol, stirring at normal temperature, and reacting for 8-12 min to obtain a second solution, wherein the step of: the mass ratio of the 2, 3-dimercaptosuccinic acid to the ethanol is (40-60): (180-240); and/or the presence of a gas in the gas,

mixing the first solution and the second solution, reacting at 70-90 ℃ for 10-16 h, separating solid substances generated by the reaction, and drying to obtain modified fullerene: the mass ratio of the first solution to the second solution is (70-90): (10-20).

Optionally, the first solution and the second solution are mixed, the mixture is reacted at 70-90 ℃ for 10-16 h, solid matters generated by the reaction are separated out and dried, and the modified fullerene is obtained:

the drying mode for drying the solid matter is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 3-5 hours.

Optionally, the method further comprises the following steps of mixing the modified fullerene with poly glycidyl methacrylate and acetone, reacting at 40-60 ℃ for 6-12 hours, separating solid substances from the mixture after the reaction is finished, and drying to obtain the microspheres, wherein the method further comprises the following steps:

mixing sodium hexametaphosphate, ethanol, glycidyl methacrylate and an initiator, reacting for 8-12 h at 80-100 ℃, separating solid substances generated by the reaction, and drying to obtain the polyglycidyl methacrylate.

Optionally, mixing sodium hexametaphosphate, ethanol, glycidyl methacrylate and an initiator, reacting at 80-100 ℃ for 8-12 h, separating solid substances generated by the reaction, and drying to obtain the polyglycidyl methacrylate, wherein the solid substances are obtained by the following steps:

the mass ratio of the sodium hexametaphosphate to the ethanol to the glycidyl methacrylate to the initiator is (1-3): (180-200): (60-80): (0.2 to 0.4); and/or the presence of a gas in the gas,

the initiator is cumene hydroperoxide.

the drying mode for drying the solid matter is vacuum drying, the drying temperature is 70-90 ℃, and the drying time is 4-6 hours.

Optionally, mixing the modified fullerene with poly (glycidyl methacrylate) and acetone, reacting at 40-60 ℃ for 6-12 h, separating solid substances from the mixture after the reaction is finished, and drying to obtain the microspheres, wherein the step of:

the mass ratio of the modified fullerene to the poly (glycidyl methacrylate) to the acetone is (60-80): (40-50): (180-240).

the drying mode for drying the solid matter is vacuum drying, the drying temperature is 80-100 ℃, and the drying time is 1-3 hours.

Optionally, the step of calcining the microspheres at 600-800 ℃ for 4-6 hours to obtain the PET modified filler comprises:

calcining the microspheres at 600-800 ℃ for 4-6 h, and sieving with a 800-1000 mesh sieve to obtain the PET modified filler.

The invention further provides a PET composite material, which comprises PET, a PET modified filler and an antioxidant, wherein the PET modified filler is prepared by the preparation method of the PET modified filler.

Optionally, in the PET composite: the PET, the PET modified filler and the antioxidant are 80-100 parts, 8-12 parts and 0.1-0.5 part by weight respectively; and/or the presence of a gas in the gas,

the antioxidant comprises at least one of antioxidant 168, antioxidant 1010 and antioxidant 1330.

In addition, the invention also provides a preparation method of the PET composite material, which comprises the following steps:

and mixing and stirring the PET, the PET modified filler and the antioxidant, and then preparing the PET composite material by melt extrusion.

Optionally, the step of preparing the PET composite material by melt extrusion after mixing and stirring the PET, the PET modified filler and the antioxidant comprises:

mixing and stirring PET, a PET modified filler and an antioxidant, and then extruding and molding the mixture by a double-screw extruder to obtain the PET composite material, wherein the double-screw extruder is provided with a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone and a sixth temperature zone from a feed port to a discharge port, the temperature of the first temperature zone is set to be 240-260 ℃, the temperature of the second temperature zone is set to be 280-300 ℃, the temperature of the third temperature zone is set to be 280-300 ℃, the temperature of the fourth temperature zone is set to be 280-300 ℃, the temperature of the fifth temperature zone is set to be 280-300 ℃, the temperature of the sixth temperature zone is set to be 280-300 ℃, the die head temperature of the extruder is set to be 280-300 ℃, and the screw rotation speed is set to be 200-280 r.

According to the technical scheme provided by the invention, firstly, fullerene is modified to prepare modified fullerene with high-activity group dimercapto modification on the surface, then the modified fullerene is reacted with poly glycidyl methacrylate, in the reaction process, dimercapto on the surface of the modified fullerene and anionic charge epoxy carried on the surface of the poly glycidyl methacrylate are chemically bonded, so that the fullerene is uniformly coated on the surface of the poly glycidyl methacrylate to form microspheres, and then the microspheres are calcined to prepare the PET modified filler, wherein the filler has high porosity and specific surface area, and when the PET material is modified by using the filler, the VOC performance of the PET material can be well improved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic flow diagram of one embodiment of a process for preparing a PET modified filler provided by the present invention;

fig. 2 is a schematic flowchart of step S10 in fig. 1.

The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. 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.

Polyethylene terephthalate (PET) has the advantages of good fatigue resistance, good heat resistance, excellent dimensional stability and the like as a widely-used high-molecular polyester resin, but the VOC performance of PET generally limits the application of PET composite materials in some specific fields. In view of this, the invention provides a method for preparing a PET modified filler, which uses modified fullerene with high active groups and polyglycidyl methacrylate as raw materials to prepare a novel modified filler capable of significantly improving the VOC performance of a PET material, and fig. 1 shows an embodiment of the method for preparing a PET modified filler provided by the invention. Referring to fig. 1, in this embodiment, the method for preparing the PET modified filler includes the following steps:

step S10, modifying the fullerene to enable the surface of the fullerene to be modified with dimercapto to obtain modified fullerene;

in this embodiment, referring to fig. 2, the step of modifying fullerene includes:

step S11, mixing fullerene and ethanol, and stirring and reacting at normal temperature for 10-20 min to obtain a first solution;

step S12, mixing 2, 3-dimercaptosuccinic acid with ethanol, stirring at normal temperature, and reacting for 8-12 min to obtain a second solution;

and step S13, mixing the first solution and the second solution, reacting for 10-16 h at 70-90 ℃, separating solid substances generated by the reaction, and drying to obtain the modified fullerene.

Wherein the mass ratio of the fullerene to the ethanol in the step S11 is (60-80): (200 to 240); and/or in the step S12, the mass ratio of the 2, 3-dimercaptosuccinic acid to the ethanol is (40-60): (180-240); and/or, in step S13: the mass ratio of the first solution to the second solution is (70-90): (10-20).

Weighing fullerene and ethanol according to a ratio, adding the fullerene and the ethanol into a reactor, and stirring and reacting for 10-20 min at normal temperature to obtain a first solution; weighing 2, 3-dimercaptosuccinic acid and ethanol according to a ratio, adding the weighed materials into a reactor, and stirring and reacting for 8-12 min at normal temperature to obtain a second solution; and then, weighing the first solution and the second solution in proportion, adding the first solution and the second solution into a reactor, reacting for 10-16 h at 70-90 ℃ to obtain a product solution with solid substances, carrying out suction filtration on the product solution, separating out the solid substances, and then washing and drying to obtain the dimercapto-modified fullerene. It should be noted that the sequence of step S11 and step S12 is not limited, and step S11 may be before step S12 and after step S12, or step S12 may be before step S11 and after step S11 and step S12 are performed simultaneously, and it is only necessary to prepare the first solution and the second solution separately before step S13. Further, in step S13: the drying mode for drying the solid matter is vacuum drying, the drying temperature is 60-80 ℃, the drying time is 3-5 hours, the drying efficiency is high, and the influence on the self performance of the dried matter is small.

Step S20, mixing the modified fullerene with poly glycidyl methacrylate and acetone, reacting at 40-60 ℃ for 6-12 h, separating solid substances from the mixture after the reaction is finished, and drying to obtain microspheres;

the surface of the modified fullerene obtained through the modification in the step S10 has a high-activity group of dimercapto, which can be chemically bonded with polyglycidyl methacrylate with an anionic charge (epoxy group), so that the fullerene is uniformly coated on the surface of the polyglycidyl methacrylate. In this embodiment, the method for preparing the PET modified filler further includes a step of preparing polyglycidyl methacrylate, that is, before step S20, the method further includes:

and step S21, mixing sodium hexametaphosphate, ethanol, glycidyl methacrylate and an initiator, reacting for 8-12 h at 80-100 ℃, separating solid substances generated by the reaction, and drying to obtain the glycidyl polymethacrylate.

Wherein the mass ratio of the sodium hexametaphosphate to the ethanol to the glycidyl methacrylate to the initiator is (1-3): (180-200): (60-80): (0.2-0.4). The initiator is used to initiate the polymerization of the monomer, and may be selected from, for example, benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, etc., and in this embodiment, the initiator is preferably cumene hydroperoxide, which has a high activation energy at a high reaction temperature.

Weighing sodium hexametaphosphate, ethanol, glycidyl methacrylate and an initiator according to a ratio, adding the sodium hexametaphosphate, the ethanol, the glycidyl methacrylate and the initiator into a reactor, heating to 80-100 ℃, reacting for 8-12 h to obtain a product solution with solid substances, filtering the product solution, separating the solid substances out, washing and drying to obtain the glycidyl methacrylate. It should be noted that the sequence of step S10 and step S21 is not limited, and step S10 may be before step S21 and after step S21, or step S21 may be before step S10 and after step S10 and step S21 are performed simultaneously, and it is only necessary to prepare the modified fullerene and the polyglycidyl methacrylate respectively before step S20. Further, in step S21: the drying mode for drying the solid matter is vacuum drying, the drying temperature is 70-90 ℃, the drying time is 4-6 hours, the drying efficiency is high, and the influence on the self performance of the dried matter is small.

Further, in step S20: the mass ratio of the modified fullerene to the poly (glycidyl methacrylate) to the acetone is (60-80): (40-50): (180-240). Weighing modified fullerene, poly glycidyl methacrylate and acetone according to a proportion, adding the modified fullerene, the poly glycidyl methacrylate and the acetone into a reactor, heating to 40-60 ℃, reacting for 6-12 h, filtering a reaction system solution after the reaction is finished, separating solid substances out, washing, and drying to obtain the microsphere with the fullerene coated on the surface of the poly glycidyl methacrylate. Preferably, in step S20: the drying mode for drying the solid matter is vacuum drying, the drying temperature is 80-100 ℃, the drying time is 1-3 h, the drying efficiency is high, and the influence of the environmental conditions in the drying process on the performance of the dried matter can be reduced as much as possible.

And step S30, calcining the microspheres at 600-800 ℃ for 4-6 h to obtain the PET modified filler.

After preparing the microspheres with fullerene coated on the surfaces of the poly glycidyl methacrylate, calcining the microspheres in a muffle furnace at 600-800 ℃ for 4-6 h to make the structure of the microspheres more stable, thus obtaining the modified filler capable of obviously improving the VOC (volatile organic compound) performance of the PET material. In addition, when the PET modified filler is used as a modification additive of a PET material, the PET modified filler needs to be fully mixed with a PET substrate, when the particles of the PET modified filler are too large, the dispersibility of the PET modified filler in the PET substrate is not good, and when the particles of the PET modified filler are too small, the particles of the PET modified filler are easy to agglomerate and influence the dispersibility of the PET modified filler when being mixed with the PET substrate.

According to the technical scheme provided by the invention, firstly, fullerene is modified to prepare modified fullerene with high-activity group dimercapto modification on the surface, then the modified fullerene is reacted with poly glycidyl methacrylate, in the reaction process, dimercapto on the surface of the modified fullerene and anionic charge epoxy carried on the surface of the poly glycidyl methacrylate are chemically bonded, so that the fullerene is uniformly coated on the surface of the poly glycidyl methacrylate to form microspheres, and then the microspheres are calcined to prepare the PET modified filler, wherein the filler has high porosity and specific surface area, and when the PET is modified by using the PET modified filler, the VOC performance of a PET material can be well improved.

Based on the preparation method of the PET modified filler, the invention also provides a PET composite material, wherein the PET composite material comprises PET, the PET modified filler and an antioxidant, and the PET modified filler is prepared by the preparation method of the PET modified filler. The PET composite material added with the PET modified filler has the advantages that the VOC (volatile organic compounds) performance of the PET material is obviously improved, and the application field of the PET material is greatly widened.

Furthermore, the PET modified filler provided by the invention is microspherical, and the addition amount of the PET modified filler is proper, so that the problems that the mechanical property of a PET material is influenced due to excessive addition amount and the VOC property improvement effect is not obvious due to too little addition amount are solved; similarly, the antioxidant should be added properly to avoid the problems that the antioxidant property of PET does not meet the use requirement due to too small addition amount and unnecessary waste is caused due to too much addition amount. In an embodiment of the PET composite material provided by the invention, the mass parts of the PET, the PET modified filler and the antioxidant in the PET composite material are 80-100 parts, 8-12 parts and 0.1-0.5 part respectively. In addition, the antioxidant can be any antioxidant suitable for PET materials, such as antioxidant TNP, antioxidant TPP, antioxidant 1010 and the like, more preferably at least one of antioxidant 168, antioxidant 1010 and antioxidant 1330, and can be any one of the antioxidants or a mixture of two or three of the antioxidants.

Based on the PET composite material provided above, the invention also provides a preparation method of the PET composite material, the method for preparing the PET composite material by using the PET, the PET modified filler and the antioxidant as raw materials can be a melt mixing or melt extrusion method, and in one embodiment of the preparation method of the PET composite material provided by the invention, the melt extrusion molding processing method is taken as an example, and the preparation method of the PET composite material comprises the following steps: and mixing and stirring the PET, the PET modified filler and the antioxidant, and then preparing the PET composite material by melt extrusion.

The melt extrusion molding processing equipment can be a single-screw extruder or a double-screw extruder, and in the embodiment, the double-screw extruder is preferred, and the mixing effect is better. Specifically, in this embodiment, the preparation method of the PET composite material can be realized by the following steps: mixing and stirring PET, PET modified filler and antioxidant, wherein the mixing and stirring can be performed by adopting equipment such as a high-speed mixer, the materials are mixed more uniformly, then the mixed materials are put into a feed inlet of a double-screw extruder, and are subjected to extrusion molding by the double-screw extruder to prepare the PET composite material, wherein the double-screw extruder is provided with a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone and a sixth temperature zone from the feed inlet to a discharge outlet, the temperature of the first temperature zone is set to be 240-260 ℃, the temperature of the second temperature zone is set to be 280-300 ℃, the temperature of the third temperature zone is set to be 280-300 ℃, the temperature of the fifth temperature zone is set to be 280-300 ℃, the temperature of the sixth temperature zone is set to be 280-300 ℃, and the temperature of a die head of the double-screw extruder is set to be 280-300 ℃. (the temperature of, The rotating speed of the screw is set to be 200-280 r/min. The double-screw extruder with six temperature zones is selected, so that materials can be fully melted and mixed in the extruder, and the problem that secondary extrusion is needed due to poor material mixing effect is solved. In addition, according to the product requirements of the PET composite material, after the PET composite material is subjected to extrusion molding by a double-screw extruder and is cooled by a cooling device, a winding device is utilized to obtain wires, or a granulator is used for cutting to obtain granules.

The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.

Example 1

(1) Weighing 600g of fullerene and 2000g of ethanol, adding the fullerene and the ethanol into a reactor, and stirring and reacting for 10min at normal temperature to obtain a first solution;

(2) weighing 400g of 2, 3-dimercaptosuccinic acid and 1800g of ethanol, adding into a reactor, and stirring at normal temperature for reacting for 8min to obtain a second solution;

(3) weighing 700g of first solution and 100g of second solution, adding the first solution and the second solution into a reactor, reacting for 10 hours at 70 ℃, after the reaction is finished, carrying out suction filtration on the product solution, separating out solid substances in the product solution, washing the solid substances, and then placing the product solution in a vacuum drying oven at 60 ℃ for drying for 3 hours to obtain dimercapto-modified fullerene;

(4) weighing 10g of sodium hexametaphosphate, 1800g of ethanol, 600g of glycidyl methacrylate and 2g of cumene hydroperoxide, adding the sodium hexametaphosphate, the ethanol, the glycidyl methacrylate and the cumene hydroperoxide into a reactor, heating the reactor to 80 ℃ for reaction for 8 hours, filtering a product solution after the reaction is finished, separating out solid substances from the product solution, washing the solid substances, and then drying the product solution in a vacuum drying oven at 70 ℃ for 4 hours to obtain the polyglycidyl methacrylate;

(5) weighing 600g of modified fullerene, 400g of poly glycidyl methacrylate and 1800g of acetone, adding the materials into a reactor, heating the reactor to 40 ℃ for reaction for 6 hours, filtering the solution of the reaction system after the reaction is finished, separating out solid substances in the solution, washing the solid substances, and then placing the solution in a vacuum drying oven at 80 ℃ for drying for 1 hour to obtain microspheres with the surfaces of the poly glycidyl methacrylate coated with the fullerene;

(6) and (3) calcining the prepared microspheres in a muffle furnace at 600 ℃ for 6h, and then sieving the microspheres with a 800-mesh sieve to obtain the PET modified filler.

Example 2

(1) Weighing 800g of fullerene and 2400g of ethanol, adding into a reactor, and stirring and reacting for 20min at normal temperature to obtain a first solution;

(2) weighing 600g of 2, 3-dimercaptosuccinic acid and 2400g of ethanol, adding into a reactor, and stirring at normal temperature for reaction for 12min to obtain a second solution;

(3) weighing 900g of first solution and 200g of second solution, adding the first solution and the second solution into a reactor, reacting for 16 hours at 90 ℃, after the reaction is finished, carrying out suction filtration on the product solution, separating out solid substances in the product solution, washing the solid substances, and then placing the product solution in a vacuum drying oven at 80 ℃ for drying for 5 hours to obtain dimercapto-modified fullerene;

(4) weighing 30g of sodium hexametaphosphate, 2000g of ethanol, 800g of glycidyl methacrylate and 4g of cumene hydroperoxide, adding the materials into a reactor, heating the materials to 100 ℃ for reaction for 12 hours, filtering the product solution after the reaction is finished, separating out solid substances, washing the solid substances, and then placing the solid substances in a vacuum drying oven at 90 ℃ for drying for 6 hours to obtain the poly (glycidyl methacrylate);

(5) weighing 800g of modified fullerene, 500g of poly glycidyl methacrylate and 2400g of acetone, adding the materials into a reactor, heating the reactor to 60 ℃ for reaction for 12 hours, filtering the solution of the reaction system after the reaction is finished, separating out solid substances in the solution, washing the solid substances, and then placing the solution in a vacuum drying oven at 100 ℃ for drying for 3 hours to obtain microspheres with the surfaces of the poly glycidyl methacrylate coated with the fullerene;

(6) and (3) calcining the prepared microspheres in a muffle furnace at 800 ℃ for 4h, and then sieving the microspheres with a 1000-mesh sieve to obtain the PET modified filler.

Example 3

(1) Weighing 700g of fullerene and 2200g of ethanol, adding into a reactor, and stirring and reacting for 15min at normal temperature to obtain a first solution;

(2) weighing 500g of 2, 3-dimercaptosuccinic acid and 2100g of ethanol, adding into a reactor, and stirring at normal temperature for reaction for 10min to obtain a second solution;

(3) weighing 800g of the first solution and 150g of the second solution, adding the first solution and the second solution into a reactor, reacting for 13 hours at 80 ℃, after the reaction is finished, carrying out suction filtration on the product solution, separating out solid substances in the product solution, washing the solid substances, and then placing the product solution in a vacuum drying oven at 70 ℃ for drying for 4 hours to obtain the dimercapto-modified fullerene;

(4) weighing 20g of sodium hexametaphosphate, 1900g of ethanol, 700g of glycidyl methacrylate and 3g of cumene hydroperoxide, adding the sodium hexametaphosphate, the ethanol, the glycidyl methacrylate and the cumene hydroperoxide into a reactor, heating to 90 ℃ for reaction for 10 hours, filtering a product solution after the reaction is finished, separating out solid substances, washing, and then drying in a vacuum drying oven at 80 ℃ for 5 hours to obtain the polyglycidyl methacrylate;

(5) weighing 700g of modified fullerene, 450g of poly glycidyl methacrylate and 2100g of acetone, adding the materials into a reactor, heating the reactor to 50 ℃ for reaction for 9 hours, filtering the solution of the reaction system after the reaction is finished, separating out solid substances in the solution, washing the solid substances, and then placing the solution in a vacuum drying oven at 90 ℃ for drying for 2 hours to obtain microspheres with the surfaces of the poly glycidyl methacrylate coated with the fullerene;

(6) and (3) calcining the prepared microspheres in a muffle furnace at 700 ℃ for 5 hours, and then sieving the microspheres with a 900-mesh sieve to obtain the PET modified filler.

Example 4

(1) Weighing 780g of fullerene and 2100g of ethanol, adding the fullerene and the ethanol into a reactor, and stirring and reacting for 12min at normal temperature to obtain a first solution;

(2) weighing 450g of 2, 3-dimercaptosuccinic acid and 1900g of ethanol, adding into a reactor, and stirring at normal temperature for reaction for 11min to obtain a second solution;

(3) weighing 780g of the first solution and 160g of the second solution, adding the first solution and the second solution into a reactor, reacting for 11 hours at 75 ℃, after the reaction is finished, carrying out suction filtration on the product solution, separating out solid substances in the product solution, washing the solid substances, and then placing the product solution in a vacuum drying oven at 65 ℃ for drying for 3 hours to obtain dimercapto-modified fullerene;

(4) weighing 24g of sodium hexametaphosphate, 1850g of ethanol, 720g of glycidyl methacrylate and 2g of cumene hydroperoxide, adding the materials into a reactor, heating the reactor to 95 ℃ for reaction for 9 hours, filtering the product solution after the reaction is finished, separating out solid substances, washing the solid substances, and then drying the solid substances in a vacuum drying oven at 75 ℃ for 4 hours to obtain the poly (glycidyl methacrylate);

(5) weighing 750g of modified fullerene, 440g of poly glycidyl methacrylate and 2300g of acetone, adding the materials into a reactor, heating the reactor to 45 ℃ for reaction for 9 hours, filtering the solution of the reaction system after the reaction is finished, separating out solid substances in the solution, washing the solid substances, and then placing the solution in a vacuum drying oven at 85 ℃ for drying for 1 hour to obtain microspheres with the surfaces of the poly glycidyl methacrylate coated with the fullerene;

(6) and (3) calcining the prepared microspheres in a muffle furnace at 640 ℃ for 5 hours, and then sieving the microspheres with a 800-mesh sieve to obtain the PET modified filler.

Example 5

(1) Weighing 620g of fullerene and 2300g of ethanol, adding into a reactor, and stirring and reacting at normal temperature for 12min to obtain a first solution;

(2) weighing 470g of 2, 3-dimercaptosuccinic acid and 2200g of ethanol, adding into a reactor, and stirring at normal temperature for reaction for 9min to obtain a second solution;

(3) weighing 720g of first solution and 180g of second solution, adding the first solution and the second solution into a reactor, reacting for 11 hours at 75 ℃, after the reaction is finished, carrying out suction filtration on the product solution, separating out solid substances in the product solution, washing the solid substances, and then placing the product solution in a vacuum drying oven at 75 ℃ for drying for 3 hours to obtain dimercapto-modified fullerene;

(4) weighing 28g of sodium hexametaphosphate, 1950g of ethanol, 780g of glycidyl methacrylate and 4g of cumene hydroperoxide, adding the materials into a reactor, heating to 85 ℃ for reaction for 12 hours, filtering a product solution after the reaction is finished, separating out solid substances, washing, and then drying in a vacuum drying oven at 85 ℃ for 4 hours to obtain the poly (glycidyl methacrylate);

(5) weighing 680g of modified fullerene, 420g of poly glycidyl methacrylate and 1900g of acetone, adding the materials into a reactor, heating the reactor to 45 ℃ for reaction for 7 hours, filtering the solution of the reaction system after the reaction is finished, separating out solid substances in the solution, washing the solid substances, and then placing the solution in a vacuum drying oven at 95 ℃ for drying for 1 hour to obtain microspheres with the surfaces of the poly glycidyl methacrylate coated with the fullerene;

(6) and (3) calcining the prepared microspheres in a muffle furnace at 620 ℃ for 5h, and then sieving the microspheres with a 800-mesh sieve to obtain the PET modified filler.

Example 6

(1) Weighing 80 parts of PET, 8 parts of PET modified filler (prepared in example 1) and 0.1 part of antioxidant 1010(Irganox1010), and uniformly mixing and stirring to obtain a mixed material;

(2) putting the mixed material into a double-screw extruder for extrusion and granulation to obtain a PET composite material; wherein, the temperature of each temperature zone and the screw rotating speed of the double-screw extruder are set as follows: the first zone temperature is 240 ℃, the second zone temperature is 280 ℃, the third zone temperature is 280 ℃, the fourth zone temperature is 280 ℃, the fifth zone temperature is 280 ℃, the sixth zone temperature is 280 ℃, the die head temperature is 280 ℃ and the screw rotation speed is 200 r/min.

Example 7

(1) Weighing 100 parts of PET, 12 parts of PET modified filler (prepared in example 2), 0.1 part of antioxidant 1010(Irganox1010), 0.2 part of antioxidant 168(Irganox168) and 0.2 part of antioxidant 1330(Irganox 1330), and uniformly mixing and stirring to obtain a mixed material;

(2) putting the mixed material into a double-screw extruder for extrusion and granulation to obtain a PET composite material; wherein, the temperature of each temperature zone and the screw rotating speed of the double-screw extruder are set as follows: the first zone temperature is 260 ℃, the second zone temperature is 300 ℃, the third zone temperature is 300 ℃, the fourth zone temperature is 300 ℃, the fifth zone temperature is 300 ℃, the sixth zone temperature is 300 ℃, the die head temperature is 300 ℃ and the screw rotation speed is 280 r/min.

Example 8

(1) Weighing 90 parts of PET, 10 parts of PET modified filler (prepared in example 3), 0.1 part of antioxidant 168(Irganox168) and 0.2 part of antioxidant 1010(Irganox1010), and uniformly mixing and stirring to obtain a mixed material;

(2) putting the mixed material into a double-screw extruder for extrusion and granulation to obtain a PET composite material; wherein, the temperature of each temperature zone and the screw rotating speed of the double-screw extruder are set as follows: the first zone temperature is 250 ℃, the second zone temperature is 290 ℃, the third zone temperature is 290 ℃, the fourth zone temperature is 290 ℃, the fifth zone temperature is 290 ℃, the sixth zone temperature is 290 ℃, the die head temperature is 290 ℃, and the screw rotation speed is 240 r/min.

Example 9

(1) Weighing 85 parts of PET, 9 parts of PET modified filler (prepared in example 4), 0.1 part of antioxidant 1010(Irganox1010) and 0.2 part of antioxidant 1330(Irganox 1330), and uniformly mixing and stirring to obtain a mixed material;

(2) putting the mixed material into a double-screw extruder for extrusion and granulation to obtain a PET composite material; wherein, the temperature of each temperature zone and the screw rotating speed of the double-screw extruder are set as follows: the first zone temperature is 245 ℃, the second zone temperature is 285 ℃, the third zone temperature is 285 ℃, the fourth zone temperature is 285 ℃, the fifth zone temperature is 285 ℃, the sixth zone temperature is 285 ℃, the die head temperature is 285 ℃ and the screw rotation speed is 255 r/min.

Example 10

(1) Weighing 95 parts of PET, 11 parts of PET modified filler (prepared in example 5), 0.1 part of antioxidant 1010(Irganox1010) and 0.1 part of antioxidant 168(Irganox168), and uniformly mixing and stirring to obtain a mixed material;

(2) putting the mixed material into a double-screw extruder for extrusion and granulation to obtain a PET composite material; wherein, the temperature of each temperature zone and the screw rotating speed of the double-screw extruder are set as follows: the temperature of the first zone is 250 ℃, the temperature of the second zone is 295 ℃, the temperature of the third zone is 295 ℃, the temperature of the fourth zone is 295 ℃, the temperature of the fifth zone is 295 ℃, the temperature of the sixth zone is 295 ℃, the temperature of the die head is 295 ℃ and the rotating speed of the screw is 270 r/min.

Comparative example

(1) Weighing 100 parts of PET, 0.1 part of antioxidant 1010(Irganox1010) and 0.2 part of antioxidant 168(Irganox168), and uniformly mixing and stirring to obtain a mixed material;

The PET composite materials obtained in examples 6 to 10 and comparative example were molded into test specimens by an injection molding machine, and the VOC properties of the test specimens were measured according to the method of GB/T27630, and the results are shown in Table 1 below.

TABLE 1 VOC Performance test results of PET composites prepared in examples and comparative examples

Test items	Example 6	Example 7	Example 8	Example 9	Example 10	Comparative example
							Benzene (. mu.g/m)³)	55	50	48	47	52	123
Toluene (. mu.g/m)³)	74	72	76	71	78	216
							Ethylbenzene (. mu.g/m)³)	94	92	105	90	99	237
Xylene (. mu.g/m)³)	148	142	138	141	152	276
							Styrene (a), (b), (c), (dμg/m³)	50	51	52	58	59	175
Formaldehyde (. mu.g/m)³)	41	43	49	42	48	107
							Acetaldehyde (. mu.g/m)³)	12	13	19	11	16	31
Acrolein (μ g/m)³)	4	3	6	4	5	11

The test results in table 1 show that the VOC performance of the PET composite material prepared in the embodiment of the present invention is significantly better than that of the comparative example, which indicates that the VOC performance of the PET material can be significantly improved and the application field of the PET material can be greatly widened by adding the PET modified filler prepared in the embodiment of the present invention to the PET material.

The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims

1. A preparation method of a PET modified filler is characterized by comprising the following steps:

2. The method of claim 1, wherein the step of modifying the fullerene to modify the fullerene surface with a dimercapto group to obtain a modified fullerene comprises:

3. The method for preparing the PET modified filler according to claim 2, wherein the step of mixing the fullerene with the ethanol and then stirring and reacting at normal temperature for 10-20 min to obtain the first solution comprises: the mass ratio of the fullerene to the ethanol is (60-80): (200 to 240); and/or the presence of a gas in the gas,

4. The method for preparing the PET modified filler according to claim 1, wherein the modified fullerene, the poly glycidyl methacrylate and the acetone are mixed and reacted at 40-60 ℃ for 6-12 h, after the reaction is finished, solid substances in the mixture are separated and dried, and before the step of obtaining the microsphere, the method further comprises:

5. The preparation method of the PET modified filler according to claim 4, wherein the preparation method comprises the steps of mixing sodium hexametaphosphate, ethanol, glycidyl methacrylate and an initiator, reacting at 80-100 ℃ for 8-12 h, separating solid substances generated by the reaction, and drying to obtain the polyglycidyl methacrylate:

the initiator is cumene hydroperoxide.

6. The preparation method of the PET modified filler according to claim 1, wherein the modified fullerene, the poly glycidyl methacrylate and the acetone are mixed, the mixture is reacted at 40-60 ℃ for 6-12 h, after the reaction is finished, solid matters in the mixture are separated and dried, and the microsphere is obtained by the following steps:

7. A PET composite comprising PET, a PET modified filler prepared by the method of preparing the PET modified filler according to any one of claims 1 to 6, and an antioxidant.

8. The PET composite of claim 7, wherein in the PET composite: the PET, the PET modified filler and the antioxidant are 80-100 parts, 8-12 parts and 0.1-0.5 part by weight respectively; and/or the presence of a gas in the gas,

9. A process for the preparation of a PET composite material according to claim 7 or 8, characterized in that it comprises the following steps:

10. The method of preparing a PET composite according to claim 9, wherein the step of preparing the PET composite by melt extrusion after mixing and stirring the PET, the PET modified filler and the antioxidant comprises: