Waste PET (polyethylene terephthalate) derived carbon dioxide-based polyurea as well as preparation method and application thereof

Abstract

The invention provides waste PET-derived carbon dioxide-based polyurea and a preparation method and application thereof.The preparation method comprises the steps that ionic liquid serves as a catalyst, an amine compound serves as a reactant, and waste PET is catalytically degraded to obtain a degradation product; and carrying out polymerization reaction by taking the degradation product and CO2 as raw materials to prepare the waste PET derived carbon dioxide-based polyurea. According to the present invention, the waste PET is adopted as the raw material so as to achieve the recycling of the waste PET, and the CO2 is adopted as the green monomer so as to achieve the resource utilization of the CO2; the preparation method is simple, efficient, green and environmentally friendly, conforms to the sustainable development concept and has application and popularization value. And the prepared waste PET derived CO2-based polyurea has good structural adjustability, and can be used in the field of high-strength adhesive materials.

Description

Technical Field

[0001] The invention belongs to the field of polymer macromolecular synthesis and relates to a carbon dioxide-based polyurea, in particular to a carbon dioxide-based polyurea derived from waste PET and a preparation method and application thereof. Background Art

[0002] Polyethylene terephthalate (PET) is a common polyester plastic in modern life, which is widely used to make plastic films, mineral water bottles and fiber fabrics. PET is non-degradable in the natural environment, and a large amount of waste PET plastics cause serious pollution and damage to water bodies, soil, etc. At present, the main recycling methods for waste PET are thermomechanical and chemical methods; the mechanical properties of PET products regenerated by thermomechanical methods are seriously lost; chemical recycling strategies mainly include methanolysis, aminolysis and hydrolysis, which can convert PET into small molecule raw materials for PET regeneration or synthesis of other polymers. However, chemical methods often require high temperature, high pressure, strong acid and strong alkali conditions, and have problems such as high energy consumption, cumbersome post-processing and severe equipment corrosion. Therefore, the development of more effective and economical measures to upgrade waste PET to achieve its sustainable utilization still faces great challenges.

[0003] CO2 is one of the most common greenhouse gases on Earth, but it is also an abundant, cheap and renewable C1 raw material. CO2 can be copolymerized with hydroxyl or amino functional monomers to prepare polycarbonate, polyurethane and polyurea. Converting CO2 into high-performance polymer materials is one of the important ways to solidify and utilize CO2. Polyurea exhibits excellent wear resistance, corrosion resistance and thermal stability due to the strong hydrogen bonding between polymer chains. It has a wide range of uses in functional fibers, films, thermoplastics, thermoplastic elastomers and adhesives. If waste PET and CO2 can be converted into higher-value polymer materials to achieve co-treatment of waste PET and CO2 waste gas, it will have practical significance and may become one of the important directions for sustainable development today and in the future. Summary of the invention

[0004] In order to solve the above technical problems, the object of the present invention is to provide a method for preparing carbon dioxide-based polyurea derived from waste PET.

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

[0006] Using ionic liquid as catalyst and amine compound as reactant to catalytically degrade waste PET to obtain degradation products;

[0007] The degradation product and CO2 are used as raw materials to carry out polymerization reaction to prepare waste PET derived carbon dioxide based polyurea.

[0008] Optimally, 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 selected from triazabicyclic and diazabicyclic ionic liquids.

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

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

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

[0013]

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

[0015] Optimally, 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.

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

[0017] The conditions of the polymerization reaction are: reaction temperature 150-220° C., reaction time 12-24 h, and introduction of CO 2 until the pressure is 1-10 MPa.

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

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

[0020] The preparation method of waste PET derived carbon dioxide-based polyurea of ​​the present invention does not use toxic isocyanate, adopts waste PET as a raw material to realize the recycling of waste PET, and adopts CO2 as a green monomer to realize the resource utilization of CO2; the preparation method is simple and efficient, green and environmentally friendly, in line with the concept of sustainable development, and has the value of popularization and application; and the obtained waste PET derived CO2-based polyurea has good structural adjustability: when the molecular structure of the amine compound is changed, the thermodynamic properties, mechanical properties, hydrophilicity and hydrophobicity and adhesion properties of the waste PET derived CO2-based polyurea can be regulated, and can be used in the field of high-strength adhesive materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the synthesis route of the waste PET-derived CO2-based polyurea prepared in Example 1.

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

[0023] Figure 3 The adhesion performance of the waste PET-derived CO2-based polyurea prepared in Example 1 to different substrates. The actual picture in the figure shows that the glass adhered with polyurea can lift a 25 kg weight at room temperature and -80°C.

[0024] Figure 4 These are the hydrogen spectrum and infrared spectrum of the waste PET-derived CO2-based polyurea prepared in Example 5. DETAILED DESCRIPTION

[0025] The method for preparing carbon dioxide-based polyurea derived from waste PET of the present invention is as follows: Figure 1 As shown, ionic liquid is used as a catalyst and amine compounds are used as reactants to catalytically degrade waste PET to obtain degradation products; the degradation products and CO2 are used as raw materials to carry out 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 PET powder, waste water bottles, plastic films and fiber fabrics.

[0026] The ionic liquid is a mixture of one or more selected from triazabicyclic and diazabicyclic 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 one or more selected from the following structural formulas: Wherein, R includes -H, -CH3, -OCH3 and -NO2.

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

[0028]

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

[0030] 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.

[0031] The conditions for the catalytic degradation are: reaction temperature 60-150°C, reaction time 2-10h; the conditions for the polymerization reaction are: reaction temperature 150-220°C, reaction time 12-24h, and CO2 is introduced to a pressure of 1-10MPa. Specifically, the method comprises the following steps: (1) selecting a suitable organic solvent and adding a certain amount of waste PET; (2) adding an amine compound having a molar weight of PET of 200 to 400 mol% to the mixture prepared in the reaction step (1); (3) adding an ionic liquid catalyst having a molar weight of PET of 20 to 400 mol% to the mixture solution prepared in the reaction step (2); (4) injecting the precursor solution prepared in the reaction step (3) into a reactor, heating the temperature to 60 to 150° C., and reacting for 2 to 10 hours; (5) subsequently introducing CO2 into the reactor of the reaction step (4) to exclude air, heating the temperature to 150 to 220° C., and then introducing 1 to 10 MPa of CO2, and reacting for 12 to 24 hours, thereby obtaining CO2-based polyurea derived from waste PET.

[0032] The waste PET-derived carbon dioxide-based polyurea obtained above has an adjustable molecular structure; the CO2-based polyurea derived from waste PET realizes the resource utilization of waste PET and CO2, and can be used as an adhesive or a component of an adhesive.

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

[0034] Example 1

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

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

[0037] (2) Then, N'N-bis(3-aminopropyl)methylamine (2.3 g) with a molar weight of 200% of PET was added;

[0038] (3) adding [DBU][PhO] (1.9 g) with a molar weight of 100% of PET and performing ultrasonic treatment to obtain a uniformly mixed precursor solution;

[0039] (4) injecting the above precursor solution into the reaction kettle, raising the temperature to 120°C, and stirring the reaction for 3 hours;

[0040] (5) CO2 was then purged for 5 min to remove oxygen, and the temperature was raised to 180°C. Finally, 4 MPa of CO2 was introduced and stirred for 12 h. The solid was washed with ether and deionized water for multiple times (3 times), and the precipitate was dried to obtain PET-derived CO2-based polyurea. Its H NMR spectrum and IR spectrum are shown in Figure 2. Figure 2 shown.

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

[0042] Example 2

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

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

[0045] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours; then, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0046] Example 3

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

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

[0049] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0050] Example 4

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

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

[0053] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0054] Example 5

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

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

[0057] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0058] Figure 4These are the H-NMR and IR spectra of the 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 and its preparation method and application, which is basically similar to that in embodiment 1, except that:

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

[0062] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0063] Example 7

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

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

[0066] The above precursor solution was injected into the reactor, the temperature was raised to 85°C, and the reaction was stirred for 12 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0067] Example 8

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

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

[0070] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 140°C. Finally, 4MPa of CO2 was introduced and the reaction was stirred for 24 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0071] Example 9

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

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

[0074] The above precursor solution was injected into the reactor, the temperature was raised to 120°C, and the reaction was stirred for 3 hours. Subsequently, CO2 was purged for 5 minutes to remove oxygen and the temperature was raised to 180°C. Finally, 1MPa CO2 was introduced and stirred for 12 hours. The solid precipitate was washed with ether and deionized water several times and dried to obtain PET-derived CO2-based polyurea.

[0075] Comparative Example 1

[0076] This embodiment provides a waste PET-derived carbon dioxide-based polyurea and a preparation method and application thereof, which is basically similar to that of Example 1, except that step (2) is not performed, PET is not degraded, and polymerization reaction to form polyurea cannot be performed.

[0077] Comparative Example 2

[0078] This embodiment provides a waste PET-derived carbon dioxide-based polyurea and a preparation method and application thereof, which is basically similar to that in Example 1, except that step (3) is not performed, PET degradation is incomplete, a variety of amino compounds exist in the system, the polyurea obtained by polymerization with CO2 has complex components 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 and a preparation method and application thereof, 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, and the molecular weight and yield of the obtained polyurea are lower.

[0081] Comparative Example 4

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

[0083] Comparative Example 5

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

[0085] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing carbon dioxide-based polyurea derived from waste PET, characterized in that: Using ionic liquid as catalyst and amine compound as reactant to catalytically degrade waste PET to obtain degradation products; The degradation product and CO2 are used as raw materials to carry out polymerization reaction to prepare waste PET derived carbon dioxide based polyurea.

2. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 1, characterized in that: The polymerization reaction is also carried out under the catalysis of the ionic liquid.

3. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 1 or 2, characterized in that: The ionic liquid is a mixture of one or more selected from triazabicyclic and diazabicyclic ionic liquids.

4. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 3, characterized in that: The cation of the ionic liquid is one or two selected from the following structural formulas: The anion of the ionic liquid is one or more selected from the following structural formulas: Wherein, R includes -H, -CH3, -OCH3 and -NO2.

5. 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 selected from diamines, polyamines and polyetheramines.

6. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 5, characterized in that: The amine compound is a mixture of one or more selected from the following structural formulas: In the formula, n represents the number of connected -CH2-, which is an integer of 0 to 8; the number average molecular weight M of the polyetheramine is n It ranges from 200 to 4000.

7. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 1, characterized in that: 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.

8. The method for preparing carbon dioxide-based polyurea derived from waste PET according to claim 1, characterized in that: The conditions of the catalytic degradation are: reaction temperature 60-150° C., reaction time 2-10 h; The conditions of the polymerization reaction are: reaction temperature 150-220° C., reaction time 12-24 h, and introduction of CO 2 until the pressure is 1-10 MPa.

9. A waste PET derived carbon dioxide based polyurea, characterized in that: It is prepared by the preparation method described in any one of claims 1 to 8.

10. The use of carbon dioxide-based polyurea derived from waste PET according to claim 9, characterized in that: Used as adhesive or component of adhesive.

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