Thermoplastic polyurethane prepared based on urea as well as preparation method and application thereof

Abstract

The invention belongs to the field of high polymer materials, and discloses thermoplastic polyurethane prepared based on urea as well as a preparation method and application thereof. The thermoplastic polyurethane is synthesized from urea, decamethylenediamine, decamethylene glycol and macromolecular dihydric alcohol through polycondensation, and the specific steps are as follows: heating and stirring the urea, the decamethylenediamine, the decamethylene glycol and the macromolecular dihydric alcohol in the absence of a solvent at 170-190 DEG C for 10-20 minutes to melt reactants; and heating and stirring to react for 6-24 hours at 220-260 DEG C in the absence of a catalyst or under the catalysis of the catalyst, thereby obtaining the thermoplastic polyurethane. The preparation method adopts a one-pot melting reaction, and has the advantages that the preparation process is simple, an isocyanate monomer and a solvent are not needed, a reaction product can be directly used without further purification, and the like.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and particularly relates to a thermoplastic polyurethane prepared based on urea, a preparation method thereof, and an application thereof. Background Art

[0002] Due to its excellent mechanical, chemical, and physical properties, polyurethane is widely used in fields such as plastics, elastomers, fibers, coatings, etc. Thermoplastic polyurethane is one of the most important polyurethane products and is widely used in many industries due to its excellent abrasion resistance, high elasticity, and good chemical resistance. Its abrasion resistance enables it to remain durable in a long-term friction environment, its high elasticity endows it with the ability to quickly return to its original state after repeated deformation, and its good chemical resistance enables it to maintain stable performance in different chemical environments. According to the classification of synthetic raw materials, polyurethane can be divided into two types: traditional polyurethane with isocyanate as the raw material and non-isocyanate polyurethane without using isocyanate. Since the preparation, storage, and transportation conditions of isocyanate are relatively harsh, its synthesis also requires the use of highly toxic phosgene, and the current types of isocyanates are limited, the synthetic route for preparing polyurethane by the non-isocyanate method has attracted much attention from researchers.

[0003] Currently, several synthetic methods for non-isocyanate polyurethane have been developed, such as the ammonolysis of cyclic carbonate, the transesterification of carbamate, and the rearrangement method. The polyhydroxyurethane prepared by the ammonolysis of cyclic carbonate contains side hydroxyl groups, which is not conducive to the microphase separation behavior of thermoplastic polyurethane. The transesterification of carbamate method is to prepare non-isocyanate thermoplastic polyurethane by the polycondensation reaction of dicarbamate and diamine, and its structure is the same as that of traditional polyurethane, while dicarbamate is synthesized by the alcoholysis reaction of urea. Therefore, directly using urea, alcohol, and amine as reaction raw materials to synthesize thermoplastic polyurethane has more advantages. The present invention synthesizes non-isocyanate thermoplastic polyurethane by the melt polycondensation one-pot method, avoiding the use of isocyanate monomers and solvents, and the product can be directly used without purification, having the advantages of simple process, easy operation, and environmental friendliness.

[0004] CN115322367A discloses a polyurethane prepared based on urea, a preparation method thereof, and an application thereof, which is to melt urea, diamine, and diol without solvent or dissolve them in a solvent, and heat and stir at 40 - 300 °C for 0.5 - 24 hours under the catalysis of no catalyst or a catalyst, and then react at a pressure of 0 - 2000 Pa for 1 - 48 hours, and obtain the polyurethane through post-treatment. The disadvantage of this scheme is that the post-polymerization in the second step needs to be carried out under reduced pressure, and this scheme is not aimed at the research direction of thermoplastic polyurethane, which limits the application range of the product. Summary of the Invention

[0005] In view of the deficiencies of the prior art, the present invention has developed a new method for preparing non-isocyanate thermoplastic polyurethane. The thermoplastic polyurethane is prepared by one-pot melt polymerization. The steps are simple and easy to operate. All reactants can be added at one time. The reaction process is green and environmentally friendly, without the use of reduced pressure conditions, without the use of any solvents, and the product does not need to be further purified. The raw materials except for the macromolecular diol are renewable bio-based resources, which conform to the principle of sustainable development. The method of the present invention is helpful for the synthesis of bio-based thermoplastic polyurethane.

[0006] The present invention is realized through the following technical solutions:

[0007] A preparation method of thermoplastic polyurethane prepared based on urea, which heats urea, decamethylene diamine, decamethylene diol and macromolecular diol in the absence of solvent to melt all reactants, and then raises the reaction temperature to carry out melt polycondensation under the condition of no catalyst or catalyst catalysis. The specific steps are as follows:

[0008] (1) Under an inert gas atmosphere, heat and stir urea, decamethylene diamine, decamethylene diol and macromolecular diol at 170 - 190 °C for 10 - 20 minutes in the absence of solvent to melt the reactants;

[0009] (2) Then heat and stir at 220 - 260 °C for 6 - 24 hours under the condition of no catalyst or catalyst catalysis to obtain thermoplastic polyurethane.

[0010] Further, in step (1), there is no restriction on the feeding order of urea, diamine and diol.

[0011] Further, the macromolecular diol in step (1) is selected from one or a mixture of polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentylene glycol, polyhexylene glycol, polytetrahydrofuran, polylactic acid, polycaprolactone, ethylene glycol poly(malonate), propylene glycol poly(malonate), butylene glycol poly(malonate), pentylene glycol poly(malonate), hexylene glycol poly(malonate), ethylene glycol poly(succinate), propylene glycol poly(succinate), butylene glycol poly(succinate), pentylene glycol poly(succinate), hexylene glycol poly(succinate), ethylene glycol poly(glutarate), propylene glycol poly(glutarate), butylene glycol poly(glutarate), pentylene glycol poly(glutarate), hexylene glycol poly(glutarate), ethylene glycol poly(adipate), propylene glycol poly(adipate), butylene glycol poly(adipate), pentylene glycol poly(adipate), hexylene glycol poly(adipate) or a dihydroxy-terminated polysiloxane with a molecular weight of 1000 - 2000 Da.

[0012] Further, the molar ratio of urea, decamethylene diamine, decamethylene diol and macromolecular diol in step (1) is (4 - 8):2:1:(0.8 - 1).

[0013] Further, step (2) can be carried out without a catalyst or with the catalysis of a catalyst. If a catalyst is used, the catalyst is one or a mixture of more than one of calcium methyl sulfonate, triphenylphosphine, trimethylphosphine, triethylphosphine, trihexylphosphine, tricyclohexylphosphine, lithium methyl sulfonate, lithium trifluoroacetate, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, lithium bisulfate, lithium sulfate, lithium phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium bisulfate, sodium sulfate, sodium phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, potassium bisulfate, potassium sulfate, potassium phosphate, rubidium dihydrogen phosphate, rubidium hydrogen phosphate, rubidium bisulfate, rubidium sulfate, rubidium phosphate, cesium dihydrogen phosphate, cesium hydrogen phosphate, cesium bisulfate, cesium sulfate, cesium phosphate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene sulfate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene phosphate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene methanesulfonate.

[0014] Among them, 1,5,7-triazabicyclo[4.4.0]dec-5-ene sulfate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene phosphate, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene methanesulfonate are respectively obtained by reacting 1,5,7-triazabicyclo[4.4.0]dec-5-ene with an equal amount of sulfuric acid, phosphoric acid, and methanesulfonic acid at room temperature with stirring for 1 - 2 hours.

[0015] Further, the dosage of the catalyst in step (2) is 0.01% - 10% of the dosage of decamethylenediamine.

[0016] Under the condition of using a catalyst, the reaction temperature of step (2) is 220 - 260 °C, and the reaction time is 12 - 24 hours.

[0017] Under the condition of not using a catalyst, the reaction temperature of step (2) is 220 - 260 °C, and the reaction time is 6 - 12 hours.

[0018] The thermoplastic polyurethane obtained by the above preparation method has the general formula shown in formula (I):

[0019]

[0020] Wherein R is polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(pentylene glycol), poly(hexylene glycol), polytetrahydrofuran, polylactic acid, polycaprolactone, ethylene glycol poly(malonic acid) ester, propylene glycol poly(malonic acid) ester, butylene glycol poly(malonic acid) ester, pentylene glycol poly(malonic acid) ester, hexylene glycol poly(malonic acid) ester, ethylene glycol poly(succinic acid) ester, propylene glycol poly(succinic acid) ester, butylene glycol poly(succinic acid) ester, pentylene glycol poly(succinic acid) ester, hexylene glycol poly(succinic acid) ester, ethylene glycol poly(glutaric acid) ester, propylene glycol poly(glutaric acid) ester, butylene glycol poly(glutaric acid) ester, pentylene glycol poly(glutaric acid) ester, hexylene glycol poly(glutaric acid) ester, ethylene glycol poly(adipic acid) ester, propylene glycol poly(adipic acid) ester, butylene glycol poly(adipic acid) ester, pentylene glycol poly(adipic acid) ester, hexylene glycol poly(adipic acid) ester or a dihydroxy-terminated polydimethylsiloxane chain segment with a molecular weight of 1000 - 2000 Da, and n is any integer between 2 and 20.

[0021] The application of the thermoplastic polyurethane prepared based on urea in the preparation of construction engineering pipes or material conveying pipes.

[0022] The thermoplastic polyurethane based on urea described in the present invention and its preparation method have the following advantages and beneficial effects:

[0023] (1) The present invention provides a new method for preparing non-isocyanate thermoplastic polyurethane, which does not require high-pressure conditions, reduced-pressure conditions, light avoidance or isolation of water and oxygen. The preparation process only needs to carry out the reaction under normal pressure conditions and in an inert gas atmosphere. The steps are simple, the operation is convenient, and the reaction conditions are mild.

[0024] (2) The reactants of the present invention can be added to the reactor simultaneously, and the product is prepared by one-pot melt polymerization. The reaction proceeds homogeneously through the melting of the reactants, avoiding the use of any solvents. The reaction product can be directly used without further purification, having the advantages of environmental friendliness. Description of the Drawings

[0025] Figure 1 13C solid nuclear magnetic resonance spectrum of the thermoplastic polyurethane prepared in Example 1 13 13C solid nuclear magnetic resonance spectrum of the thermoplastic polyurethane prepared in Example 1

[0026] Figure 2 Fourier transform infrared transmission spectrum of the thermoplastic polyurethane prepared in Example 1

[0027] Figure 3 13C solid nuclear magnetic resonance spectrum of the thermoplastic polyurethane prepared in Example 2 13 13C solid nuclear magnetic resonance spectrum of the thermoplastic polyurethane prepared in Example 2

[0028] Figure 4 1H NMR liquid nuclear magnetic resonance spectrum of the thermoplastic polyurethane prepared in Example 11 1 1H NMR liquid nuclear magnetic resonance spectrum of the thermoplastic polyurethane prepared in Example 11

[0029] Figure 5Fourier transform infrared transmission spectrum of the thermoplastic polyurethane prepared in Example 11. Detailed implementation mode

[0030] The present invention will be further described in detail below with reference to examples, but the implementation modes and protection scope of the present invention are not limited thereto.

[0031] The 1,5,7-triazabicyclo[4.4.0]dec-5-ene sulfate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene phosphate, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene methyl sulfonate used in the following examples were respectively obtained by reacting 1,5,7-triazabicyclo[4.4.0]dec-5-ene with an equal amount of sulfuric acid, phosphoric acid, and methanesulfonic acid at room temperature with stirring for 1-2 hours.

[0032] Example 1

[0033] Add 240 g (4.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylene diamine, and 400 g (0.4 mol) of polytetrahydrofuran (1000 Da) to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 220 °C and stir for 24 hours to obtain a thermoplastic polyurethane. The yield is 94%.

[0034] Figure 1 is the 13 C solid nuclear magnetic resonance spectrum of the thermoplastic polyurethane product obtained in this example, where the carbonyl carbon signal peak of the carbamate is at 160 ppm, the signal peak of the methylene carbon adjacent to O in the polytetrahydrofuran chain segment is at 71 ppm, the signal peak of the methylene carbon adjacent to NH is at 43 ppm, and the signal peak of the middle methylene carbon is at 28-34 ppm. Figure 2 is the Fourier transform infrared transmission spectrum of the thermoplastic polyurethane product obtained in this example, where the vibration peak of NH in the carbamate is at 3329 cm -1 and the carbonyl vibration peak of the carbamate is at 865 cm -1 .

[0035] Example 2

[0036] Add 240 g (4.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylene diamine, and 800 g (0.4 mol) of polytetrahydrofuran (2000 Da) to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 240 °C and stir for 24 hours to obtain a thermoplastic polyurethane. The yield is 92%.

[0037] Figure 3The 13 C solid nuclear magnetic resonance spectrum of the thermoplastic polyurethane product obtained in this example, where the carbonyl carbon signal peak of the carbamate is at 160 ppm, the signal peak of the methylene carbon adjacent to O in the polytetrahydrofuran segment is at 71 ppm, the signal peak of the methylene carbon adjacent to NH in the carbamate is at 43 ppm, and the signal peak of the middle methylene carbon is at 28 - 34 ppm.

[0038] Example 3

[0039] Add 180 g (3.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 400 g (0.4 mol) of polyethylene glycol (1000 Da), and 1.56 g of lithium methyl sulfonate to a three-necked flask equipped with an air condenser. Heat and stir at 180 °C for 15 minutes, then raise the temperature to 240 °C and heat and stir for 11 hours to obtain thermoplastic polyurethane. The yield is 96%.

[0040] Example 4

[0041] Add 120 g (2.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 800 g (0.4 mol) of polypropylene glycol (2000 Da), and 2.3 g of calcium methyl sulfonate to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 240 °C and heat and stir for 10 hours to obtain thermoplastic polyurethane. The yield is 98%.

[0042] Example 5

[0043] Add 120 g (2.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 400 g (0.4 mol) of polytetrahydrofuran (1000 Da), and 1.39 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 260 °C and heat and stir for 8 hours to obtain thermoplastic polyurethane. The yield is 94%.

[0044] Example 6

[0045] Add 120 g (2.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 500 g (0.5 mol) of polypropylene glycol (1000 Da), and 6.95 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 20 minutes, then raise the temperature to 220 °C and heat and stir for 9 hours to obtain thermoplastic polyurethane. The yield is 95%.

[0046] Example 7

[0047] Add 180 g (3.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 400 g (0.4 mol) of polytetrahydrofuran (1000 Da), and 2.35 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene phosphate to a three-necked flask equipped with an air condenser. Heat and stir at 190 °C for 10 minutes, then raise the temperature to 230 °C and heat and stir for 12 hours to obtain thermoplastic polyurethane. The yield is 91%.

[0048] Example 8

[0049] Add 240 g (4.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 450 g (0.45 mol) of polylactic acid (1000 Da), and 2.40 g of sodium dihydrogen phosphate to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 250 °C and heat and stir for 8 hours to obtain thermoplastic polyurethane. The yield is 95%.

[0050] Example 9

[0051] Add 240 g (4.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 450 g (0.45 mol) of polylactic acid (1000 Da), and 2.35 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene methanesulfonate to a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 240 °C and heat and stir for 9 hours to obtain thermoplastic polyurethane. The yield is 95%.

[0052] Example 10

[0053] Add 240 g (4.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 450 g (0.45 mol) of poly(butylene succinate) (1000 Da), and 1.36 g of potassium dihydrogen phosphate into a three-necked flask equipped with an air condenser. Heat and stir at 170 °C for 10 minutes, then raise the temperature to 230 °C and heat and stir for 12 hours to obtain thermoplastic polyurethane. The yield is 97%.

[0054] Example 11

[0055] Add 240 g (4.0 mol) of urea, 174 g (1.0 mol) of decamethylene glycol, 86 g (0.5 mol) of decamethylenediamine, 500 g (0.5 mol) of polyethylene glycol (1000 Da), and 1.36 g of potassium dihydrogen phosphate into a three-necked flask equipped with an air condenser. Heat and stir at 190 °C for 10 minutes, then raise the temperature to 250 °C and heat and stir for 6 hours to obtain thermoplastic polyurethane. The yield is 96%.

[0056] Figure 4 For the thermoplastic polyurethane product obtained in this example 1 1H NMR liquid nuclear magnetic resonance spectrum, where the signal peak of the NH proton in the urethane group is at 6.99 ppm, the signal peaks of the methylene carbon adjacent to NH in the urethane and the methylene carbon proton adjacent to O in the urethane are at 3.90 ppm and 2.93 ppm respectively, the signal peak of the methylene proton adjacent to the hydroxyl group and ether bond of polytetrahydrofuran is at 3.31 ppm, and the signal peaks of the terminal hydroxyl protons of decamethylene glycol and polytetrahydrofuran are at 4.34 ppm and 4.30 ppm respectively. Figure 5 Is the Fourier transform infrared transmission spectrum of the thermoplastic polyurethane product obtained in this example, where at 3329 cm -1 is the vibration peak of NH in the urethane, and at 865 cm -1 is the carbonyl vibration peak of the urethane.

[0057] The above examples are only the preferred embodiments of the present invention, which are only used to explain the present invention, rather than limiting the present invention. Any changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit and essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A preparation method of a thermoplastic polyurethane based on urea, characterized in that, The specific steps are as follows: (1) In an inert gas atmosphere, urea, decamethylenediamine, decamethylene glycol, and a macromolecular diol are heated and stirred at 170 - 190 °C for 10 - 20 minutes without solvent to melt the reactants; (2) Then, it is heated and stirred at 220 - 260 °C for 6 - 24 hours with or without a catalyst to obtain thermoplastic polyurethane.

2. The preparation method of the thermoplastic polyurethane prepared based on urea according to claim 1, characterized in that, The macromolecular diol described in step (1) is selected from one or more of polyethylene glycol, polypropylene glycol, polybutylene glycol, polyvalerylene glycol, polyhexylene glycol, polytetrahydrofuran, polylactic acid, polycaprolactone, ethylene glycol polypropanedioate, propylene glycol polypropanedioate, butylene glycol polypropanedioate, pentylene glycol polypropanedioate, hexylene glycol polypropanedioate, ethylene glycol polybutanedioate, propylene glycol polybutanedioate, butylene glycol polybutanedioate, pentylene glycol polybutanedioate, hexylene glycol polybutanedioate, ethylene glycol polyvaleratedioate, propylene glycol polyvaleratedioate, butylene glycol polyvaleratedioate, pentylene glycol polyvaleratedioate, hexylene glycol polyvaleratedioate, ethylene glycol polyadipate, propylene glycol polyadipate, butylene glycol polyadipate, pentylene glycol polyadipate, hexylene glycol polyadipate, or a hydroxyl-terminated polysiloxane with a molecular weight of 1000 - 2000.

3. The preparation method of the thermoplastic polyurethane based on urea according to claim 1, characterized in that, The molar ratio of urea, decamethylenediamine, decamethylene glycol, and macromolecular diol described in step (1) is (4 - 8):2:1:(0.8 - 1).

4. The preparation method of the thermoplastic polyurethane based on urea according to claim 1, characterized in that The dosage of the catalyst described in step (2) is 0.01% - 10% of the dosage of decamethylenediamine.

5. The preparation method of the thermoplastic polyurethane based on urea according to claim 1, characterized in that, The catalyst described in step (2) is one or more of calcium methylsulfonate, triphenylphosphine, trimethylphosphine, triethylphosphine, trihexylphosphine, tricyclohexylphosphine, lithium methylsulfonate, lithium trifluoroacetate, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, lithium bisulfate, lithium sulfate, lithium phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium bisulfate, sodium sulfate, sodium phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, potassium bisulfate, potassium sulfate, potassium phosphate, rubidium dihydrogen phosphate, rubidium hydrogen phosphate, rubidium bisulfate, rubidium sulfate, rubidium phosphate, cesium dihydrogen phosphate, cesium hydrogen phosphate, cesium bisulfate, cesium sulfate, cesium phosphate, 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene, 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene sulfate, 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene phosphate, 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene methanesulfonate.

6. The preparation method of the thermoplastic polyurethane based on urea according to claim 5, characterized in that, 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene sulfate, 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene phosphate, and 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene methanesulfonate are respectively obtained by stirring and reacting 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene with an equal amount of sulfuric acid, phosphoric acid, and methanesulfonic acid at room temperature for 1 - 2 hours.

7. The preparation method of the thermoplastic polyurethane prepared based on urea according to claim 1, characterized in that, Under the condition of using a catalyst, the reaction temperature of step (2) is 220 - 260 °C, and the reaction time is 12 - 24 hours; under the condition of not using a catalyst, the reaction temperature of step (2) is 220 - 260 °C, and the reaction time is 6 - 12 hours.

8. A thermoplastic polyurethane prepared based on urea by the preparation method according to any one of claims 1 - 7.

9. The thermoplastic polyurethane prepared based on urea according to claim 8, wherein, The general formula of the thermoplastic polyurethane is shown in formula (I): In the formula, R is polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene glycol, polyhexylene glycol, polytetrahydrofuran, polylactic acid, polycaprolactone, ethylene glycol polypropylmalonate, propylene glycol polypropylmalonate, butylene glycol polypropylmalonate, pentylene glycol polypropylmalonate, hexylene glycol polypropylmalonate, ethylene glycol polybutylmalonate, propylene glycol polybutylmalonate, butylene glycol polybutylmalonate, pentylene glycol polybutylmalonate, hexylene glycol polybutylmalonate, ethylene glycol polypentylmalonate, propylene glycol polypentylmalonate, butylene glycol polypentylmalonate, pentylene glycol polypentylmalonate, hexylene glycol polypentylmalonate, ethylene glycol polyhexylmalonate, propylene glycol polyhexylmalonate, butylene glycol polyhexylmalonate, pentylene glycol polyhexylmalonate, hexylene glycol polyhexylmalonate or a dihydroxy-terminated polysiloxane segment with a molecular weight of 1000 - 2000 Da, and n is any integer from 2 to 20.

10. Use of a thermoplastic polyurethane prepared based on urea according to claim 8 or 9 in the preparation of building engineering pipes or material transportation pipes.

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