A waste PET derived carbon dioxide-based polyurea and a preparation method and application thereof

Abstract

The application provides a waste PET derived carbon dioxide based polyurea and a preparation method and application thereof, an ionic liquid is used as a catalyst, an amine compound is used as a reactant, degradation products are obtained by catalytic degradation of waste PET; the waste PET derived carbon dioxide based polyurea is prepared by performing a polymerization reaction with the degradation products and CO2 as raw materials. No toxic isocyanate is used, waste PET is used as raw material to realize recycling of waste PET, and CO2 is used as a green monomer to realize resource utilization of CO2; the preparation method is simple, efficient, green and environment-friendly, conforms to the sustainable development concept, and has the value of popularization and application; and the prepared waste PET derived CO2 based polyurea has good structure adjustability and can be used in the field of high-strength adhesive materials.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis and relates to a carbon dioxide-based polyurea, specifically a carbon dioxide-based polyurea derived from waste PET, its preparation method, and its application. Background Technology

[0002] Polyethylene terephthalate (PET) is a common polyester plastic in modern life, widely used in the production of plastic films, mineral water bottles, and textiles. PET is non-biodegradable in the natural environment, and large quantities of waste PET plastic cause serious pollution and damage to water bodies and soil. Currently, the main recycling methods for waste PET are thermomechanical and chemical methods. PET products recycled using thermomechanical methods suffer significant loss of mechanical properties. Chemical recycling strategies mainly include methanololysis, ammonolysis, and hydrolysis, which can convert PET into smaller molecule raw materials for PET regeneration or the synthesis of other polymers. However, chemical methods often require high temperature, high pressure, strong acids, and strong alkalis, and suffer from high energy consumption, cumbersome post-processing, and severe equipment corrosion. Therefore, developing more effective and economical measures to upgrade waste PET for its sustainable utilization remains a significant challenge.

[0003] CO2 is one of the most common greenhouse gases on Earth, but it is also an abundant, inexpensive, and renewable source of C1. CO2 can be copolymerized with hydroxyl or amino functionalized monomers to prepare polycarbonates, polyurethanes, and polyureas. Converting CO2 into high-performance polymer materials is one of the important ways to solidify and utilize CO2. Polyureas, due to the strong hydrogen bonding between polymer chains, exhibit excellent wear resistance, corrosion resistance, and thermal stability, and have wide applications in functional fibers, films, thermoplastics, thermoplastic elastomers, and adhesives. If waste PET and CO2 can be converted into higher-value polymer materials to achieve the co-treatment of waste PET and CO2 waste gas, it would be of practical significance and could become one of the important directions for sustainable development now and in the future. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a method for preparing carbon dioxide-based polyurea derived from waste PET.

[0005] To achieve the above-mentioned technical objectives, the present invention provides a method for preparing carbon dioxide-based polyurea derived from waste PET.

[0006] Using ionic liquids as catalysts and amine compounds as reactants, waste PET is catalytically degraded to obtain degradation products.

[0007] The degradation products and CO2 were used as raw materials to carry out a polymerization reaction to obtain carbon dioxide-based polyurea derived from waste PET.

[0008] Ideally, the polymerization reaction is also carried out under the catalysis of the ionic liquid.

[0009] Furthermore, the ionic liquid is a mixture of one or more components selected from triazabicyclo and diazabicyclo-based ionic liquids.

[0010] In one embodiment of the present invention, the cation of the ionic liquid is selected from one or two of the following structural formulas: The anion of the ionic liquid is selected from one or more of the following structural formulas: In the formula, R includes -H, -CH3, -OCH3, and -NO2.

[0011] Preferably, the amine compound is a mixture selected from one or more of diamines, polyamines, and polyetheramines.

[0012] Furthermore, the amine compound is a mixture of one or more of the following structural formulas:

[0013]

[0014] In the formula, n represents the number of -CH2- linkages, which is an integer from 0 to 8; the number-average molecular weight M of the polyetheramine is... n The range is 200 to 4000.

[0015] Optimally, the molar content of the amine compound is 200-400 mol.% of waste PET, and the molar content of the ionic liquid is 20-400 mol.% of waste PET.

[0016] Optimally, the catalytic degradation conditions are: reaction temperature 60–150°C, reaction time 2–10 h;

[0017] The polymerization reaction conditions are: reaction temperature 150-220℃, reaction time 12-24h, and CO2 is introduced until the pressure is 1-10MPa.

[0018] Another object of the present invention is to provide a waste PET-derived carbon dioxide-based polyurea, which is prepared by the above-described preparation method.

[0019] Another object of the present invention is to provide an application of waste PET-derived carbon dioxide-based polyurea as an adhesive or component of an adhesive.

[0020] This invention discloses a method for preparing CO2-based polyurea derived from waste PET. This method avoids the use of toxic isocyanates, utilizes waste PET as a raw material to achieve waste PET recycling, and employs CO2 as a green monomer to realize the resource utilization of CO2. The preparation method is simple, efficient, environmentally friendly, and aligns with the concept of sustainable development, making it valuable for widespread application. Furthermore, the obtained CO2-based polyurea derived from waste PET exhibits good structural tunability: by changing the molecular structure of the amine compound, the thermodynamic properties, mechanical properties, hydrophilicity / hydrophobicity, and adhesive properties of the CO2-based polyurea derived from waste PET can be controlled, and it can be used in the field of high-strength adhesive materials. Attached Figure Description

[0021] Figure 1 The synthetic route for CO2-based polyurea derived from waste PET prepared in Example 1 is described.

[0022] Figure 2 The hydrogen spectrum and infrared spectrum of the CO2-based polyurea derived from waste PET prepared in Example 1.

[0023] Figure 3 The adhesion properties of the CO2-based polyurea derived from waste PET prepared in Example 1 to different substrates are shown in the figure. The actual object in the figure is a demonstration of lifting a 25kg weight on glass bonded with polyurea at room temperature and -80°C.

[0024] Figure 4 The hydrogen spectrum and infrared spectrum of the CO2-based polyurea derived from waste PET prepared in Example 5 are shown. Detailed Implementation

[0025] The present invention relates to a method for preparing carbon dioxide-based polyurea derived from waste PET, as follows: Figure 1 As shown, ionic liquids are used as catalysts and amine compounds as reactants to catalytically degrade waste PET to obtain degradation products; the degradation products and CO2 are then used as raw materials to carry out a polymerization reaction to obtain waste PET-derived carbon dioxide-based polyurea. The polymerization reaction is preferably also carried out under the catalysis of the ionic liquid. The waste PET is preferably selected from one or a mixture of several of PET powder, waste water bottles, plastic films, and fibrous fabrics.

[0026] The ionic liquid is a mixture of one or more components selected from triazabicyclo and diazabicyclo ionic liquids. The cation of the ionic liquid is preferably selected from one or two of the following structural formulas: (DBU + )and (TBD + The anion of the ionic liquid is selected from one or more of the following structural formulas: In the formula, R includes -H, -CH3, -OCH3, and -NO2.

[0027] The amine compound is a mixture selected from one or more of diamines, polyamines, and polyetheramines. Preferably, it is a mixture selected from one or more of the following structural formulas:

[0028]

[0029] In the formula, n represents the number of -CH2- linkages, which is an integer from 0 to 8; the number-average molecular weight M of the polyetheramine is... n The range is 200 to 4000.

[0030] The molar content of the amine compound is 200-400 mol.% of waste PET, and the molar content of the ionic liquid is 20-400 mol.% of waste PET.

[0031] The conditions for the catalytic degradation are: reaction temperature 60-150℃, reaction time 2-10h; the conditions for the polymerization reaction are: reaction temperature 150-220℃, reaction time 12-24h, and CO2 is introduced to a pressure of 1-10MPa. Specifically, the process includes the following steps: (1) Selecting a suitable organic solvent and adding a certain amount of waste PET; (2) Adding 200-400 mol% amine compounds of PET to the mixture prepared in step (1); (3) Adding 20-400 mol% ionic liquid catalyst of PET to the mixture solution prepared in step (2); (4) Injecting the precursor solution prepared in step (3) into the reactor, raising the temperature to 60-150°C, and reacting for 2-10 hours; (5) Subsequently, introducing CO2 into the reactor of step (4) to remove air, raising the temperature to 150-220°C, and then introducing CO2 at 1-10 MPa, and reacting for 12-24 hours to obtain waste PET-derived CO2-based polyurea.

[0032] The aforementioned waste PET-derived CO2-based polyurea possesses a tunable molecular structure; this waste PET-derived CO2-based polyurea achieves the resource utilization of waste PET and CO2. It can be used as an adhesive or a component of adhesives.

[0033] The preferred embodiments of the present invention will now be described in detail.

[0034] Example 1

[0035] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application, specifically including the following steps:

[0036] (1) Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner;

[0037] (2) Then add 200% of the molar amount of PET N'N-bis(3-aminopropyl)methylamine (2.3g);

[0038] (3) Add 100% of the molar amount of PET [DBU][PhO] (1.9g), and sonicate to obtain a homogeneous precursor solution;

[0039] (4) Inject the above precursor solution into the reactor, raise the temperature to 120°C and stir for 3 hours;

[0040] (5) After removing oxygen by purging with CO2 for 5 min, the temperature was raised to 180℃, and finally CO2 at 4 MPa was introduced and the reaction was stirred for 12 h. The solid was washed with diethyl ether and deionized water three times, and the precipitate was dried to obtain PET-derived CO2-based polyurea. Its 1H NMR spectrum and infrared spectrum are shown below. Figure 2 As shown.

[0041] The aforementioned PET-derived CO2-based polyurea was used directly as an adhesive to investigate its adhesion performance on different substrates. Figure 3 The experiment demonstrated the ability of glass bonded with polyurea to lift a 25kg weight at both room temperature and -80℃. The results show that this waste PET-derived CO2-based polyurea exhibits good adhesion properties and excellent temperature adaptability, indicating its potential application prospects in the field of adhesive materials.

[0042] Example 2

[0043] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0044] Add 1.5g of PET plastic film and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of N'N-bis(3-aminopropyl)methylamine and 100% of [DBU][PhO] of PET molar amount;

[0045] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, the temperature was raised to 180°C, and finally, CO2 at 4 MPa was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water several times and drying it, PET-derived CO2-based polyurea was obtained.

[0046] Example 3

[0047] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0048] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 400% of N'N-bis(3-aminopropyl)methylamine and 100% of [DBU][PhO] of PET molar amount;

[0049] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 180°C. Finally, CO2 at 4 MPa was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water multiple times and drying it, PET-derived CO2-based polyurea was obtained.

[0050] Example 4

[0051] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0052] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of N'N-bis(3-aminopropyl)methylamine and 20% of [DBU][PhO] of PET molar amount;

[0053] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 180°C. Finally, CO2 at 4 MPa was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water multiple times and drying it, PET-derived CO2-based polyurea was obtained.

[0054] Example 5

[0055] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0056] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of 4,7,10-trioxadecane-1,13-diamine by molar amount of PET and 100% of [DBU][PhO] by molar amount of PET.

[0057] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 180°C. Finally, CO2 at 4 MPa was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water multiple times and drying it, PET-derived CO2-based polyurea was obtained.

[0058] Figure 4The 1H NMR and IR spectra of CO2-based polyurea derived from waste PET prepared from the above-mentioned 4,7,10-trioxatridecane-1,13-diamine.

[0059] Example 6

[0060] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0061] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of N'N-bis(3-aminopropyl)methylamine and 100% of [TBD][MePhO] of PET molar amount;

[0062] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 180°C. Finally, CO2 at 4 MPa was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water multiple times and drying it, PET-derived CO2-based polyurea was obtained.

[0063] Example 7

[0064] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0065] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of N'N-bis(3-aminopropyl)methylamine and 100% of [DBU][PhO] of PET molar amount;

[0066] The above precursor solution was injected into a reactor, the temperature was raised to 85°C, and the reaction was stirred for 12 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 180°C. Finally, CO2 at 4 MPa was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water several times and drying it, PET-derived CO2-based polyurea was obtained.

[0067] Example 8

[0068] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0069] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of N'N-bis(3-aminopropyl)methylamine and 100% of [DBU][PhO] of PET molar amount;

[0070] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 140°C. Finally, CO2 at 4 MPa was introduced and the reaction was stirred for 24 hours. After washing the solid precipitate with ether and deionized water multiple times and drying it, PET-derived CO2-based polyurea was obtained.

[0071] Example 9

[0072] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method, and its application. It is basically similar to that in Example 1, except that:

[0073] Add 1.5g of PET powder and 6mL of N-methylpyrrolidone to the polytetrafluoroethylene liner, then add 200% of N'N-bis(3-aminopropyl)methylamine and 100% of [DBU][PhO] of PET molar amount;

[0074] The above precursor solution was injected into a reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Then, the oxygen was removed by purging with CO2 for 5 minutes, and the temperature was raised to 180°C. Finally, 1 MPa of CO2 was introduced and the reaction was stirred for 12 hours. After washing the solid precipitate with ether and deionized water several times and drying it, PET-derived CO2-based polyurea was obtained.

[0075] Comparative Example 1

[0076] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method and application, which is basically similar to that in Example 1, except that step (2) is not performed, the PET is not degraded, and cannot undergo polymerization to generate polyurea.

[0077] Comparative Example 2

[0078] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method and application. It is basically similar to that in Example 1, except that step (3) is not performed, the PET is not completely degraded, the system contains a variety of amino compounds, the polyurea obtained by polymerization with CO2 has a complex composition and structure, and the product is difficult to purify.

[0079] Comparative Example 3

[0080] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method and application, which is basically similar to that in Example 1, except that in step (5), 0.5 MPa of CO2 is introduced and stirred for 12 hours. The lower CO2 pressure will inhibit the polymerization reaction, resulting in a lower molecular weight and yield of the polyurea.

[0081] Comparative Example 4

[0082] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method and application, which is basically similar to that in Example 1, except that in step (5), the reaction is still kept at 120°C; due to the low activity of CO2, the CO2 polymerization reaction is difficult to carry out and polyurea cannot be obtained.

[0083] Comparative Example 5

[0084] This embodiment provides a waste PET-derived carbon dioxide-based polyurea, its preparation method and application, which is basically similar to that in Example 1, except that in step (5), the reaction is still maintained at 250°C, and the PET degradation products and ionic liquid catalyst decompose.

[0085] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing carbon dioxide-based polyurea derived from waste PET, characterized in that: Using ionic liquids as catalysts and amine compounds as reactants, waste PET is catalytically degraded to obtain degradation products. Carbon dioxide-based polyurea derived from waste PET is prepared by polymerization using the degradation products and CO2 as raw materials; the ionic liquid is a mixture of one or more of triazabicyclo and diazabicyclo ionic liquids; the molar content of the amine compound is 200-400 mol% of the waste PET, and the molar content of the ionic liquid is 20-400 mol% of the waste PET. The polymerization reaction also takes place under the catalysis of the ionic liquid. The cation of the ionic liquid is selected from one or two of the following structural formulas: and The anion of the ionic liquid is selected from one or more of the following structural formulas: In the formula, R includes -H, -CH3, -OCH3, and -NO2. The amine compound is a mixture of one or more selected from diamines, polyamines, and polyetheramines. The conditions for the catalytic degradation are: reaction temperature 60~150 ℃, reaction time 2~10 h; The polymerization reaction conditions are: reaction temperature 150~220℃, reaction time 12~24 h, and CO2 is introduced until the pressure is 1~10MPa.

2. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 1, characterized in that, The amine compound is a mixture of one or more of the following structural formulas: , In the formula, n represents the number of -CH2- linkages, which is an integer from 0 to 8; the number-average molecular weight M of the polyetheramine is... n The range is 200 to 4000.

3. A carbon dioxide-based polyurea derived from waste PET, characterized in that: It is prepared by any of the preparation methods described in claims 1 to 2.

4. The application of the waste PET-derived carbon dioxide-based polyurea according to claim 3, characterized in that: Used as an adhesive or a component of an adhesive.

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