CN115558254B - High mechanical property material prepared based on waste PET plastic and preparation method thereof - Google Patents
High mechanical property material prepared based on waste PET plastic and preparation method thereof Download PDFInfo
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- CN115558254B CN115558254B CN202211389451.XA CN202211389451A CN115558254B CN 115558254 B CN115558254 B CN 115558254B CN 202211389451 A CN202211389451 A CN 202211389451A CN 115558254 B CN115558254 B CN 115558254B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The application relates to a high mechanical property material prepared based on waste PET plastic and a preparation method thereof, belonging to the technical field of waste PET plastic recovery and disposal. The interaction of new chemical bonds improves the compressive strength and stability of the material under extreme conditions. Compared with other chemical treatment methods, the method realizes the conversion of waste PET plastics into materials with excellent mechanical strength and high stability under extreme conditions at low temperature without a catalyst. The method has the advantages of simple operation steps, mild reaction conditions, good repeatability, low price of the toughening agent, environmental protection and suitability for industrial production. In addition, the product obtained can be used directly without further isolation and purification.
Description
Technical Field
The application belongs to the technical field of waste PET plastic recovery and disposal, and particularly relates to a high mechanical property material prepared based on waste PET plastic and a preparation method thereof.
Background
Polyethylene terephthalate (PET) accounts for approximately 1/3 of the global plastic consumption and is one of the most important thermoplastic polyester varieties, thereby producing large amounts of waste PET plastic waste. The garbage treatment method mainly comprises a physical method and a chemical method. The physical method is to crush waste PET plastics into fibers for manufacturing various related products. Compared with the physical recovery process, the chemical recovery method has relatively high product value. The chemical treatment method mainly comprises pyrolysis, hydrolysis, methanolysis and the like.
The aim is to obtain monomers, oligomers and other compounds by breaking the polymer chain. CO production by pyrolysis or microwave heating of waste PET plastics 2 Polyester monomers such as benzoic acid, etc., but the heating temperature must be 450 ℃ or higher. Under the conditions of 180-280 ℃ and 2-4 MPa, the waste PET plastic can be depolymerized into dimethyl terephthalate and glycol by methanol. However, this reaction requires the addition of a catalyst. The process is gradually eliminated due to the high cost and the complex hydrolysis process of terephthalic acid. Carboxyl groups can be obtained by hydrolyzing waste PET plastics. However, the hydrolysis temperature and pressure are required to be 200-250 ℃ and 1.2-2 MPa respectively, and a catalyst is required to be used. These catalysts or severe reaction conditions are very corrosive to equipment and have the disadvantage that the product must be further separated and purified. The catalyst is also required to be added to the waste PET plastics by ammonolysis, and the yield is still to be improved.
More importantly, in industrial production, there is an increasing demand for high molecular materials having excellent mechanical strength, and these materials are required to be able to adapt to extreme environments. For example, the material is subjected to extreme cold and hot shock, and is heated to above 1000 ℃ in air, and is not broken after being rapidly cooled and then rapidly heated. Or the material needs to be able to withstand corrosion by strong acids, strong bases or polar solvents, yet maintain structural stability in extreme environments.
However, no further treatment of waste PET material has been developed in the prior art to achieve the high performance.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide a high mechanical property material prepared based on waste PET plastic, a preparation method and application thereof, which can convert the waste PET plastic into a high polymer material with excellent mechanical strength and high stability under extreme conditions through simple process conditions at low temperature.
In one aspect, a method for preparing a high mechanical property material based on waste PET plastic comprises the steps of:
step one, mixing a solution of phenol and tetrachloroethane to obtain a solvent A;
step two, grinding the waste PET plastic into small particles, and adding the obtained waste PET plastic particles into the solvent A for dissolution to obtain a solution I;
step three, polymethyl methacrylate is dissolved in a chloroform solution, and the solution B is obtained after heating and dissolution;
step four, adding the solution B into the solution I under inert atmosphere to perform a first reaction, adding aluminum dihydrogen phosphate to perform a second reaction, and finally obtaining a viscous substance;
and fifthly, freezing and drying the viscous substance to obtain the material with high mechanical property.
Optionally, in step one, the phenol and tetrachloroethane are mixed in an equal volume ratio.
Optionally, in the second step, the mass of the waste PET plastic particles is 1% -15% of the mass of the solvent A, the dissolution temperature is 50-80 ℃, the dissolution time is 2-4 h, and continuous stirring is needed.
Optionally, in the third step, the mass-volume ratio of polymethyl methacrylate to chloroform is (1-3): 6 (g/ml), the dissolution temperature is 50-90 ℃ and the dissolution time is 1-3 h.
Optionally, in the fourth step, the dosage of the aluminum dihydrogen phosphate is 1-10% of the total mass of the solution I.
Optionally, in the fourth step, the temperature of the first reaction is 85-98 ℃ and the reaction time is 2-4 hours.
Optionally, in the fourth step, the temperature of the second reaction is the same as the temperature of the first reaction, and the reaction time is 2-4 h.
Optionally, in the fifth step, the drying comprises a freeze-drying step and a vacuum drying step, wherein the freeze-drying temperature is-43 ℃, and the drying time is 2-8 d; the vacuum drying temperature is 80-100 ℃ and the drying time is 2-8 d.
In another aspect, a high mechanical property material prepared based on waste PET plastic is prepared by any of the methods described above.
The application prepares the high-performance material which can adapt to extreme environments and has excellent mechanical strength based on waste PET plastics through simple process conditions, can not only recycle waste PET resources, but also change waste into valuable, and contributes to environmental protection industry; but also can prepare high-performance polymer materials and fill the application gap of the high-performance materials under extreme conditions.
Drawings
FIG. 1 is a process flow diagram of an exemplary embodiment of the present application for converting waste PET plastic into a solid material having excellent mechanical strength and extreme environmental stability;
fig. 2 is an effect diagram of an exemplary embodiment of the present application for converting waste PET plastic into a solid material having excellent mechanical strength and extreme environmental stability.
Fig. 3 is a mechanical strength test chart of an exemplary embodiment of the present application converting waste PET plastic into a solid material with excellent mechanical strength and extreme environmental stability.
Fig. 4 is a graph of mechanical strength testing after extreme cold and extreme heat treatment of an exemplary embodiment of the present application to convert waste PET plastic into a solid material with excellent mechanical strength and extreme environmental stability.
Fig. 5 is an SEM image of an exemplary embodiment of the present application for converting waste PET plastic into a solid material with excellent mechanical strength and extreme environmental stability.
Detailed Description
The method for preparing the high mechanical property material based on the waste PET plastic in the specific embodiment of the application comprises the following steps:
step one, mixing a solution of phenol and tetrachloroethane to obtain a solvent A;
step two, grinding the waste PET plastic into small particles, and adding the obtained waste PET plastic particles into the solvent A for dissolution to obtain a solution I;
step three, polymethyl methacrylate is dissolved in a chloroform solution, and the solution B is obtained after heating and dissolution;
step four, adding the solution B into the solution I under inert atmosphere to perform a first reaction, adding aluminum dihydrogen phosphate to perform a second reaction, and finally obtaining a viscous substance;
and fifthly, freezing and drying the viscous substance to obtain the material with high mechanical property.
In the method for preparing the material with high mechanical properties based on the waste PET plastic, in the first step, the phenol and the tetrachloroethane are mixed according to the equal volume ratio, and the mixing ratio can lead the waste PET plastic particles to reach the optimal dissolution state.
In the method for preparing the high mechanical property material based on the waste PET plastic in the specific embodiment of the application, in the second step, the mass of the waste PET plastic particles is 1% -15% of the mass of the solvent A, the dissolution temperature is 50-80 ℃, the dissolution time is 2-4 h, and continuous stirring is needed, and the condition that the consumption of the waste PET plastic is not more and better, is not less and better, but the consumption of the waste PET plastic and the consumption of the solvent A are in the consumption interval can meet the setting of the temperature condition and the dissolution time, so that the method is efficient and energy-saving.
In the method for preparing the material with high mechanical properties based on the waste PET plastic, in the third step, the molar volume ratio of polymethyl methacrylate to chloroform is (1-3): 6 (mol/ml), the dissolution temperature is 50-90 ℃ and the dissolution time is 1-3 h.
In the method for preparing the material with high mechanical properties based on the waste PET plastic, in the fourth step, the dosage of the aluminum dihydrogen phosphate is 1-10% of the total mass of the solution I.
In the method for preparing the material with high mechanical properties based on the waste PET plastic, in the fourth step, the temperature of the first reaction is 85-98 ℃ and the reaction time is 2-4 hours.
In the method for preparing the high mechanical property material based on the waste PET plastic, in the fourth step, the temperature of the second reaction is the same as that of the first reaction, and the reaction time is 2-4 hours.
The embodiment of the application provides a method capable of converting waste PET plastics into materials with excellent mechanical strength and high stability under the condition of low temperature (below 100 ℃), and the materials can be applied to production of smelting workshops or extreme conditions. Polymethyl methacrylate has the advantages of large branched chain, high viscosity, low melting point and the like, and is extremely easy to react with other substances to generate a polymer with high mechanical strength. The high temperature binder aluminum dihydrogen phosphate is often used to construct a high temperature resistant cross-linked structure in a material, thereby improving the high temperature stability of the material. Therefore, the specific embodiment of the application firstly utilizes a special solvent to dissolve waste PET plastics at normal pressure and low temperature, then introduces polymethyl methacrylate and aluminum dihydrogen phosphate to react, and forms new chemical bonds in the material through bond breaking and recombination. The interaction of new chemical bonds improves the compressive strength and stability of the material under extreme conditions. Compared with other chemical treatment methods, the method realizes the conversion of waste PET plastics into materials with excellent mechanical strength and high stability under extreme conditions at low temperature without a catalyst. In addition, the product obtained can be used directly without further isolation and purification.
The application is further described in connection with the following examples which are intended to illustrate the application and are not intended to be limiting.
Example 1
Mixing phenol and tetrachloroethane according to equal volume to obtain 100ml,133.55g solvent A;
step two, adding 5g of waste PET plastic particles into the solvent A, and then placing the mixture into a 70 ℃ constant temperature water bath kettle with a magnetic stirring function to dissolve for 1h to obtain 138.55g of solution I;
step three, dissolving 2.5g of polymethyl methacrylate in 15mL of chloroform solution in a nitrogen environment at the temperature of 70 ℃ to obtain a solution B;
step four, adding the solution B into the solution I, keeping the temperature at 70-90 ℃, reacting for 3 hours, adding 3g of aluminum dihydrogen phosphate, and continuously reacting for 6 hours after the temperature is increased to 98 ℃ to obtain a viscous substance;
and fifthly, pouring the viscous substance into a centrifuge tube, freezing for 24 hours, drying for 5d by adopting a freeze dryer with the temperature of-43 ℃, and then drying for 5d by adopting a vacuum drying oven with the temperature of 80 ℃ to obtain the three-dimensional solid material with excellent mechanical strength and extreme environmental stability.
Example 2
Mixing phenol and tetrachloroethane according to equal volume to obtain 100ml,133.55g solvent A;
step two, adding 8g of waste PET plastic particles into the solvent A, and then placing the mixture into a 70 ℃ constant-temperature water bath kettle with a magnetic stirring function to dissolve for 1h to obtain 141.55g of solution I;
step three, dissolving 3.5g of polymethyl methacrylate in 15mL of trichloromethane solution in a nitrogen environment at the temperature of 70 ℃ to obtain a solution B;
step four, adding the solution B into the solution I, keeping the temperature at 70-90 ℃, reacting for 3 hours, adding 3g of aluminum dihydrogen phosphate, and continuously reacting for 6 hours after the temperature is increased to 98 ℃ to obtain a viscous substance;
and fifthly, pouring the viscous substance into a centrifuge tube, freezing for 24 hours, drying for 5d by adopting a freeze dryer with the temperature of-43 ℃, and then drying for 5d by adopting a vacuum drying oven with the temperature of 80 ℃ to obtain the three-dimensional solid material with excellent mechanical strength and extreme environmental stability.
Example 3
Mixing phenol and tetrachloroethane according to equal volume to obtain 100ml,133.55g solvent A;
step two, adding 10g of waste PET plastic particles into the solvent A, and then placing the mixture into a 70 ℃ constant temperature water bath kettle with a magnetic stirring function to dissolve for 1h to obtain 143.55g of solution I;
step three, in a nitrogen environment, at the temperature of 70 ℃, dissolving 5g of polymethyl methacrylate into 15mL of chloroform solution to obtain solution B;
step four, adding the solution B into the solution I, keeping the temperature at 70-90 ℃, reacting for 3 hours, adding 5g of aluminum dihydrogen phosphate, and continuously reacting for 6 hours after the temperature is increased to 98 ℃ to obtain a viscous substance;
and fifthly, pouring the viscous substance into a centrifuge tube, freezing for 24 hours, drying for 5d by adopting a freeze dryer with the temperature of-43 ℃, and then drying for 5d by adopting a vacuum drying oven with the temperature of 80 ℃ to obtain the three-dimensional solid material with excellent mechanical strength and extreme environmental stability.
Example 4
Mixing phenol and tetrachloroethane according to equal volume to obtain 100ml,133.55g solvent A;
step two, adding 15g of waste PET plastic particles into the solvent A, and then placing the mixture into a 70 ℃ constant temperature water bath kettle with a magnetic stirring function to dissolve for 1h to obtain 148.55g of solution I;
step three, 7.5g of polymethyl methacrylate is dissolved in 15mL of chloroform solution in a nitrogen environment at the temperature of 70 ℃ to obtain a solution B;
step four, adding the solution B into the solution I, keeping the temperature at 70-90 ℃, reacting for 3 hours, adding 9g of aluminum dihydrogen phosphate, and continuously reacting for 6 hours after the temperature is increased to 98 ℃ to obtain a viscous substance;
and fifthly, pouring the viscous substance into a centrifuge tube, freezing for 24 hours, drying for 5d by adopting a freeze dryer with the temperature of-43 ℃, and then drying for 5d by adopting a vacuum drying oven with the temperature of 80 ℃ to obtain the three-dimensional solid material with excellent mechanical strength and extreme environmental stability.
Example 5
Mixing phenol and tetrachloroethane according to equal volume to obtain 100ml,133.55g solvent A;
step two, adding 18g of waste PET plastic particles into the solvent A, and then placing the mixture into a 70 ℃ constant temperature water bath kettle with a magnetic stirring function to dissolve for 1h to obtain 151.55g of solution I;
step three, dissolving 6.5g of polymethyl methacrylate in 15mL of chloroform solution in a nitrogen environment at the temperature of 70 ℃ to obtain a solution B;
step four, adding the solution B into the solution I, keeping the temperature at 70-90 ℃, reacting for 3 hours, adding 9g of aluminum dihydrogen phosphate, and continuously reacting for 6 hours after the temperature is increased to 98 ℃ to obtain a viscous substance;
and fifthly, pouring the viscous substance into a centrifuge tube, freezing for 24 hours, drying for 5d by adopting a freeze dryer with the temperature of-43 ℃, and then drying for 5d by adopting a vacuum drying oven with the temperature of 80 ℃ to obtain the three-dimensional solid material with excellent mechanical strength and extreme environmental stability.
Example 6
Mixing phenol and tetrachloroethane according to equal volume to obtain 100ml,133.55g solvent A;
step two, adding 20g of waste PET plastic particles into the solvent A, and then placing the mixture into a 70 ℃ constant-temperature water bath kettle with a magnetic stirring function to dissolve for 1h to obtain 153.55g of solution I;
step three, in a nitrogen environment, dissolving 5.5g of polymethyl methacrylate in 15mL of trichloromethane solution at the temperature of 70 ℃ to obtain a solution B;
step four, adding the solution B into the solution I, keeping the temperature at 70-90 ℃, reacting for 3 hours, adding 15g of aluminum dihydrogen phosphate, and continuously reacting for 6 hours after the temperature is increased to 98 ℃ to obtain a viscous substance;
and fifthly, pouring the viscous substance into a centrifuge tube, freezing for 24 hours, drying for 5d by adopting a freeze dryer with the temperature of-43 ℃, and then drying for 5d by adopting a vacuum drying oven with the temperature of 80 ℃ to obtain the three-dimensional solid material with excellent mechanical strength and extreme environmental stability.
As shown in fig. 2, a photograph of the three-dimensional solid material having excellent mechanical strength and extreme environmental stability was obtained as prepared in the above examples 1 and 6. The product obtained by the conversion method has a good three-dimensional block structure; fig. 3a and 3b are mechanical strength test charts of three-dimensional solid materials prepared using example 2 and example 5, showing that three-dimensional solid materials converted from waste PET plastics have excellent mechanical strength. FIGS. 4a and 4b show the three-dimensional solid materials prepared in example 3 and example 4 in strong acid (HCl), strong base, respectively(NaOH)、(CCl 4 ) And stability performance test after 36h of treatment in ammonia solution and high temperature treatment of frozen liquid nitrogen (-196 ℃) and-1300 ℃. The results show that the material does not dissolve and still has excellent compression resistance, indicating that the material has good stability in extreme environments. Fig. 5 (a-d) are SEM images of three-dimensional solid materials prepared using example 2. It can be seen that the internal structure of the material is compact, indicating the reason why the material has excellent mechanical strength and extreme environmental stability.
In summary, the method developed by the application for converting waste PET plastics into three-dimensional solid materials with excellent mechanical strength and extreme environmental stability has great feasibility. In the process of converting waste PET plastics into three-dimensional solid materials with excellent mechanical strength and extreme environmental stability, the application obviously improves the defect that the mechanical strength and the stability are drastically reduced when the waste PET plastics are recycled by adding different amounts of polymethyl methacrylate and aluminum dihydrogen phosphate as reaction reagents and crosslinking agents. Compared with the existing waste PET plastic treatment method, the method has the remarkable advantages of simple steps, mild reaction conditions, low cost and no need of any catalyst; the three-dimensional solid material obtained after conversion has the characteristics of high mechanical strength, good stability under extreme conditions and the like. Therefore, the method for converting waste PET plastic into the three-dimensional solid material with excellent mechanical strength and extreme environmental stability has outstanding advantages and has important potential for industrial production and practical popularization and application. Meanwhile, a new idea is provided for treating waste PET plastics at low temperature.
The foregoing is only a preferred embodiment of the application, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present application, and such modifications and adaptations are intended to be comprehended within the scope of the application.
Claims (7)
1. A method for preparing a material with high mechanical properties based on waste PET plastics, which is characterized by comprising the following steps:
step one, mixing phenol and tetrachloroethane to obtain a solvent A;
step two, adding waste PET plastic particles into the solvent A for dissolution to obtain a solution I;
step three, polymethyl methacrylate is dissolved in a chloroform solution, and the solution B is obtained after heating and dissolution;
step four, adding the solution B into the solution I under inert atmosphere to perform a first reaction, adding aluminum dihydrogen phosphate to perform a second reaction, and finally obtaining a viscous substance;
the temperature of the first reaction is 85-98 ℃ and the reaction time is 2-4 hours;
the temperature of the second reaction is the same as that of the first reaction, and the reaction time is 2-4 h;
and fifthly, freezing and drying the viscous substance to obtain the material with high mechanical property.
2. The method for producing a high mechanical property material based on waste PET plastic according to claim 1, wherein in the first step, the phenol and tetrachloroethane are mixed in an equal volume ratio.
3. The method for preparing a material with high mechanical properties based on waste PET plastic according to claim 1, wherein in the second step, the mass of the waste PET plastic particles is 1% -15% of the mass of the solvent A, the dissolution temperature is 50-80 ℃, the dissolution time is 2-4 h, and continuous stirring is required.
4. The method for preparing a material with high mechanical properties based on waste PET plastics according to claim 1, wherein in the third step, the mass-volume ratio of polymethyl methacrylate to chloroform is (1-3): 6 (g/ml), the dissolution temperature is 50-90 ℃ and the dissolution time is 1-3 h.
5. The method for producing a high mechanical properties material based on waste PET plastic according to claim 1, wherein in step four, the amount of aluminum dihydrogen phosphate is 1 to 10% of the total mass of the solution I.
6. The method for producing a high mechanical property material based on waste PET plastic according to claim 1, wherein in the fifth step, the drying comprises a freeze-drying step and a vacuum-drying step, the freeze-drying temperature is-43 ℃, and the drying time is 2-8 d; the vacuum drying temperature is 80-100 ℃ and the drying time is 2-8 d.
7. A high mechanical property material prepared based on waste PET plastics, characterized in that it is prepared by the method of any one of claims 1 to 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022054669A1 (en) * | 2020-09-11 | 2022-03-17 | 東洋紡株式会社 | Method for producing polyester resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022054669A1 (en) * | 2020-09-11 | 2022-03-17 | 東洋紡株式会社 | Method for producing polyester resin composition |
Non-Patent Citations (2)
| Title |
|---|
| A new strategy to chemically transform waste PET plastic into aerogel with high fire resistnace and mechanical strength;Bingying Gao, et al.;《Polymer》(254);125074 * |
| PMMA对PET性能的影响;涂定军等;《塑料》;第47卷(第1期);5-8,12 * |
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