CN115322367A - Polyurethane prepared based on urea and preparation method and application thereof - Google Patents

Polyurethane prepared based on urea and preparation method and application thereof Download PDF

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CN115322367A
CN115322367A CN202211016148.5A CN202211016148A CN115322367A CN 115322367 A CN115322367 A CN 115322367A CN 202211016148 A CN202211016148 A CN 202211016148A CN 115322367 A CN115322367 A CN 115322367A
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urea
diamine
polyurethane
hydroxide
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CN115322367B (en
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汤栋霖
潘伯超
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract

The invention belongs to the field of high polymer materials, and discloses polyurethane prepared based on urea, and a preparation method and application thereof. The polyurethane contains a polymer with a urethane bond, and is obtained by condensation polymerization of urea, diamine and dihydric alcohol. The method comprises the following specific steps: (1) Melting urea, diamine and dihydric alcohol in the absence of a solvent or dissolving the urea, the diamine and the dihydric alcohol in the solvent, and heating and stirring the mixture for 0.5 to 24 hours at the temperature of between 40 and 300 ℃ in the absence of a catalyst or the catalysis of the catalyst; (2) Then reacting for 1-48 hours under the pressure of 0-2000Pa, and obtaining the polyurethane after post-treatment. The invention adopts a one-pot one-step method to obtain a polymerization product without preparing or extracting an intermediate product, and the used solvent can dissolve reactants to form a homogeneous system on one hand, so that the reaction can be carried out at a lower temperature; on the other hand, some solvents can be used as catalysts for the reaction, and the reaction can be efficiently carried out without adding catalysts.

Description

Polyurethane prepared based on urea and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to polyurethane prepared based on urea, and a preparation method and application thereof.
Background
The polyurethane has excellent mechanical property, is widely applied to industries such as furniture, construction, shoemaking, sports, household appliances, transportation and the like, and is prepared by reacting common isocyanate with alcohols. The isocyanate is limited in variety, the preparation process of the isocyanate involves phosgene with high toxicity, in addition, the isocyanate has high activity and high requirements on storage and transportation, and meanwhile, the preparation technology of the isocyanate is monopolized by foreign technologies for a long time and is changed in some cases in recent years.
In recent years, the preparation of polyurethane by non-isocyanate method is emphasized, the method can bypass the technical barrier of isocyanate and prepare polyurethane in a relatively low-toxicity mode, and most importantly, the selectable molecular structure of the non-isocyanate method is more diversified, which is very important for the diversification of the performance and application range of the finished polyurethane. The non-isocyanate method for preparing polyurethane means that polyurethane is not directly prepared by using the reaction of isocyanate with alcohol or amine.
Polyurethanes can now be synthesized mainly by several non-isocyanate processes as follows. First, polycondensations of polycarbamoyl chlorides with polyols or polychloroformates with diamines, etc., are used, and although isocyanates are not used, the synthesis of many of the starting materials requires the use of phosgene. Second, acyl azide rearrangement or carboxamide rearrangement (Hofmann rearrangement) and the like, which utilize toxic and harmful substances such as acyl azide, carboxamide and hydroxamic azide. Third, aziridine or cyclic carbamate ring opening polymerization, which still involves phosgene, is toxic. Fourth, the polycarbonate is prepared by reacting a polycarbonate with an aliphatic diamine or a cycloaliphatic diamine, which is a currently preferred embodiment, but the synthesis of the carbonate generally involves high temperatures and pressures, and requires high equipment. CN112646176A, a polyurethane prepared by alcoholysis of urea, a preparation method and application thereof, prepares the polyurethane by reacting diurea and diamine, firstly, heating and stirring diurea and dihydric alcohol at 60-300 ℃ for 0.5-12 hours without catalyst or catalyst, then reacting for 1-24 hours under the pressure of 0-1000Pa, and obtaining the polyurethane by post-treatment. The scheme has certain limitation, and diurea needs to be prepared in advance and then reacts with diol to obtain polyurethane; in addition, the melting point of diurea is usually high (> 180 ℃ C.), which is close to its decomposition temperature, diurea is easily decomposed at high temperature so that the reaction does not proceed normally, and diurea has low solubility in common solvents, so that it is difficult to prepare polyurethane having a large molecular weight by solution polymerization, which greatly limits the industrial application of this method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyurethane prepared based on urea and a preparation method and application thereof.
The polyurethane contains a polymer of a urethane bond, the polyurethane is obtained by condensation polymerization of urea, diamine and dihydric alcohol, reactants can be added at one time, an intermediate product (such as insoluble and infusible diurea) is not required to be prepared or extracted, a needed polyurethane product can be obtained by a one-pot one-step method, and the method has simple steps and is easy to operate. Because the urea, the diamine and the dihydric alcohol have excellent solubility in common solvents, the used solvents can dissolve reactants to form a homogeneous system on one hand, so that the reaction can be carried out at a lower temperature, on the other hand, some solvents can be used as catalysts for the reaction, the reaction can be carried out efficiently without adding catalysts, the reaction condition is mild, a high-pressure environment is not needed, the influence of water on the reaction is not feared, and high-toxicity substances are not involved. More importantly, the raw materials can be derived from renewable biomass resources, and the method has important significance on sustainable development of the resources.
The invention is realized by the following technologies:
a preparation method of polyurethane based on urea preparation is characterized in that urea, diamine and dihydric alcohol are melted or dissolved in a solvent without a solvent, and are subjected to polycondensation without a catalyst or under the catalysis of the catalyst, and the preparation method comprises the following specific steps:
(1) Melting urea, diamine and dihydric alcohol in the atmosphere of normal pressure air or dissolving in solvent, heating and stirring at 40-300 deg.C for 0.5-24 hr under the catalysis of no catalyst or catalyst;
(2) And reacting for 1-48 hours at 40-300 ℃ under the pressure of 0-2000Pa to obtain a polyurethane product.
Further, the diamine (a mixture of one, two or more diamines) in the step (1) has a general structural formula shown in formula (II):
Figure BDA0003812231450000021
in the formula R 1 Is C 2 -C 20 An alkylene group of (a).
Further, the diol (a mixture of one, two or more diols) in the step (1) has a structural general formula shown in formula (III):
Figure BDA0003812231450000022
in the formula R 2 Is C 2 -C 20 Alkylene group of (2) or C having an aromatic substituent on the main chain 1 -C 20 Is either a polyether segment, a polyester segment, a polysiloxane segment or a polyolefin segment having a molecular weight of 200-40000 Da.
Furthermore, the mol ratio of the urea, the diamine and the dihydric alcohol in the step (1) is (1-5) to 1 to (1-5).
Further, the feeding sequence of the urea, the diamine and the dihydric alcohol in the step (1) is as follows: urea, diamine, dihydric alcohol; or urea, glycols, diamines; or diols, ureas, diamines; or diols, diamines, ureas; or diamine, urea, diol; or diamine, diol, urea; or adding urea, diamine and dihydric alcohol simultaneously.
Further, the stirring time of 0.5-24 hours in the step (1) is the time when all materials are completely added.
Further, the reaction process of step (1) can be carried out without a catalyst or with a catalyst. If a catalyst is used, the catalyst is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, cesium carbonate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin didodecylthio, tetrabutyl titanate, 1, 8-diazabicycloundecene-7-ene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine.
Further, the dosage of the catalyst in the step (1) is 0.1-100 per mill of the total mass of the reaction monomers.
Further, the solvent in the step (1) is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, simethicone, diphenyl silicone oil, cyclohexanone, zinc chloride, lithium bromide and lithium chloride.
Further, the dosage of the solvent in the step (1) is 10-1000% of the total mass of the reaction monomers.
The polyurethane prepared based on urea obtained by the preparation method has the general formula shown in the formula (I):
Figure BDA0003812231450000031
in the formula R 1 Is C 2 -C 20 Alkylene of (A), R 2 Is C 2 -C 20 Alkylene group of (A) or C having an aromatic substituent on the main chain 1 -C 20 Is either a polyether segment, a polyester segment, a polysiloxane segment or a polyolefin segment having a molecular weight of 200-40000Da, and n is in the range of 3-600.
The polyurethane prepared based on urea is applied to preparing high-strength and high-toughness fibers and plates.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method is a novel method for preparing polyurethane by a non-isocyanate method, high-pressure equipment is not involved in the polyurethane preparation process, light shielding and water insulation are not needed, the preparation steps are simple, the reaction conditions are mild, a high-pressure environment is not needed, the influence of water on the reaction is not feared, and high-toxicity substances are not involved.
(2) The invention adopts a one-pot one-step method to obtain a polymerization product without preparing or extracting an intermediate product, and the used solvent can dissolve reactants to form a homogeneous system on one hand, so that the reaction can be carried out at a lower temperature; on the other hand, some solvents (such as lithium chloride, lithium bromide, zinc chloride and dimethyl sulfoxide) can be used as a catalyst for the reaction, and the reaction can be efficiently carried out without adding a catalyst.
(3) The reaction process does not need the participation of isocyanate and can be realized only by aminolysis and alcoholysis of urea. The final structure of the polyurethane can be regulated and controlled by designing the structures of diamine and dihydric alcohol, so that the thermal and mechanical properties of the polyurethane can be regulated and controlled.
(4) The polyurethane prepared by the invention has good flexibility, and can be used for preparing high-strength and high-toughness fibers and plates, such as high-elasticity spandex fibers.
Drawings
FIG. 1 is C of the polyurethane prepared in example 10 13 Solid nuclear magnetic resonance spectrogram;
FIG. 2 is C of the polyurethane prepared in example 11 13 Solid nuclear magnetic resonance spectrogram;
FIG. 3 is C of the polyurethane prepared in example 19 13 Solid nuclear magnetic resonance spectrum.
Detailed Description
The present invention is described in further detail below with reference to examples, but the embodiments and the scope of the present invention are not limited thereto.
Example 1
120g (2.0 mol) of urea, 116g (1.0 mol) of hexamethylenediamine, 90g (1.0 mol) of 1, 4-butanediol and 0.11g of potassium hydroxide were added in this order to a three-necked flask equipped with an air condenser, heated and stirred at 140 ℃ for 2 hours, and then reacted at the original temperature under reduced pressure of 400Pa for 6 hours to obtain polyurethane. The yield was 87%.
Example 2
120g (2.0 mol) of urea, 144g (1.0 mol) of octamethylenediamine, 118g (1.0 mol) of 1, 6-hexanediol, 500g of N, N-dimethylformamide and 0.28g of potassium carbonate were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 140 ℃ for 2 hours, and then reacted at the original temperature under reduced pressure of 200Pa for 4 hours to obtain polyurethane. The yield was 91%.
Example 3
88g (1.0 mol) of tetramethylenediamine, 120g (2.0 mol) of urea, 400g (1.0 mol) of polyethylene glycol 400, 600g of N, N-dimethylacetamide and 6.32g of dibutyltin dilaurate were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 140 ℃ for 1 hour, and then reacted at 160 ℃ under reduced pressure to 100Pa for 3 hours to obtain polyurethane. The yield was 85%.
Example 4
60g (1.0 mol) of dimethylenediamine, 60g (1.0 mol) of urea, 800g (1.0 mol) of polypropylene glycol 800, 1000g of dimethyl sulfoxide and 0.01g of tetrabutyl titanate were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 190 ℃ for 0.5 hour, and then reacted at 200 ℃ under reduced pressure to 100Pa for 8 hours to obtain polyurethane. The yield was 86%.
Example 5
146g (1.0 mol) of 1, 8-octanediol, 180g (3.0 mol) of urea, 172g (1.0 mol) of decamethylenediamine, 500g of N, N-dimethylacetamide, 10g of zinc chloride and 40.4g of stannous octoate were sequentially added to a three-necked flask equipped with an air condenser, heated and stirred at 150 ℃ for 3 hours, and then decompressed to 80Pa at 190 ℃ for reaction for 7 hours, thereby obtaining polyurethane. The yield was 83%.
Example 6
180g (3.0 mol) of urea, 4000g (1.0 mol) of polyethylene glycol 4000, 200g (1.0 mol) of dodecamethylenediamine, 5000g of N, N-dimethylformamide, 100g of lithium chloride and 1.71g of barium hydroxide were sequentially added to a three-necked flask equipped with an air condenser, heated and stirred at 170 ℃ for 0.5 hour, and then decompressed to 100Pa at 190 ℃ for reaction for 6 hours, thereby obtaining polyurethane. The yield was 85%.
Example 7
120g (2.0 mol) of urea, 104g (1.0 mol) of neopentyl glycol, 88g (1.0 mol) of tetramethylene diamine and 1000g of dimethyl silicone oil were added in this order to a three-necked flask equipped with an air condenser, heated and stirred at 110 ℃ for 0.5 hour, and then reacted at 150 ℃ under reduced pressure to 100Pa for 12 hours to obtain polyurethane. The yield was 80%.
Example 8
120g (2.0 mol) of urea, 400g (1.0 mol) of polyethylene glycol 400, 102g (1.0 mol) of pentamethylene diamine, 2000g of diphenyl silicone oil and 0.56g of potassium carbonate are sequentially added into a three-neck flask provided with an air condensation tube, heated and stirred at 130 ℃ for 2 hours, and then decompressed to 100Pa at 160 ℃ for reaction for 9 hours, thus obtaining the polyurethane. The yield was 90%.
Example 9
120g (2.0 mol) of urea, 144g (1.0 mol) of octamethylenediamine, 5600g (2.0 mol) of 1, 6-hexanediol polycarbonic acid (1, 6-hexanediol) diol (2800 Da), 10000g of cyclohexanone and 6.21g of 1, 5-diazabicyclo [4.3.0] non-5-ene were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 140 ℃ for 2 hours, and then reacted at 170 ℃ under reduced pressure of 100Pa for 12 hours to obtain polyurethane. The yield was 81%.
Example 10
118g (1.0 mol) of hexamethylene glycol, 300g (5.0 mol) of urea, 116g (1.0 mol) of hexamethylenediamine, 100g of lithium bromide and 500g of zinc chloride were added in this order to a three-necked flask equipped with an air condenser, heated and stirred at 150 ℃ for 6 hours, and then decompressed to 100Pa at 170 ℃ for reaction for 18 hours to obtain polyurethane. The yield was 82%. FIG. 1 shows C of the product obtained in this example 13 A solid nmr spectrum wherein 160ppm is the signal peak for the carbonyl carbon, 63ppm is the signal peak for the methylene carbon adjacent to COO, 41ppm is the signal peak for the methylene carbon adjacent to NH, and 28-30ppm is the signal peak for the intermediate methylene carbon.
Example 11
300g (5.0 mol) of urea, 172g (1.0 mol) of decamethylenediamine, 174g (1.0 mol) of decamethylenediol, 10000g of zinc chloride and 1000g of dimethyl sulfoxide were simultaneously added to a three-necked flask equipped with an air condenser, heated and stirred at 160 ℃ for 8 hours, and then decompressed to 300Pa at 180 ℃ for reaction for 8 hours, thereby obtaining polyurethane. The yield was 88%. FIG. 2 shows C of the product obtained in this example 13 Solid NMR spectrum, wherein 160ppm is the signal peak of carbonyl carbon, 158ppm is the signal peak of carbonyl carbon of carbamido group generated in the reaction process, 65ppm and 62ppm areThe signal peak at the methylene carbon adjacent to COO was found at 41ppm to be the signal peak at the methylene carbon adjacent to NH and at 28-30ppm to be the signal peak at the intermediate methylene carbon.
Example 12
60g (1.0 mol) of urea, 144g (1.0 mol) of octamethylenediamine, 520g (5.0 mol) of neopentyl glycol, 10000g of N, N-dimethylformamide and 6.21g of barium hydroxide were simultaneously added to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 170 ℃ for 1 hour, and then, the pressure was reduced to 200Pa at 190 ℃ for reaction for 7 hours, thereby obtaining polyurethane. The yield was 87%.
Example 13
180g (3.0 mol) of urea, 102g (1.0 mol) of pentamethylenediamine, 1600g (2.0 mol) of polypropylene glycol 800 and 6.21g of calcium hydroxide were added in this order to a three-necked flask equipped with an air condenser, heated and stirred at 100 ℃ for 6 hours, and then reacted at 150 ℃ under reduced pressure to 20Pa for 15 hours to obtain polyurethane. The yield was 92%.
Example 14
120g (2.0 mol) of urea, 118g (1.0 mol) of 1, 6-hexanediol, and 144g (1.0 mol) of octamethylenediamine were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated at 160 ℃ and stirred for 1 hour, and then reacted at the original temperature under reduced pressure of 40Pa for 6 hours to obtain polyurethane. The yield was 88%.
Example 15
300g (5.0 mol) of urea, 172g (1.0 mol) of decamethylenediamine, 2000g (1.0 mol) of 1, 6-hexanediol polycarbonic acid (1, 6-hexanediol) diol (2000 Da), 10000g of zinc chloride and 6.21g of 1, 5-diazabicyclo [4.3.0] non-5-ene were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 110 ℃ for 3 hours, and then reacted at 130 ℃ under reduced pressure to 1000Pa for 18 hours to obtain polyurethane. The yield was 80%.
Example 16
Into a three-necked flask equipped with an air condenser were simultaneously added 180g (3.0 mol) of urea, 130g (1.0 mol) of heptamethylenediamine, 400g (1.0 mol) of polypropylene glycol 400 and 6.32g of dibutyltin dilaurate, and the mixture was heated and stirred at 40 ℃ for 16 hours, and then reacted at 60 ℃ under reduced pressure to 80Pa for 30 hours to obtain polyurethane. The yield was 84%.
Example 17
120g (2.0 mol) of urea, 102g (1.0 mol) of pentamethylenediamine, 2000g (2.0 mol) of polypropylene glycol 1000 and 6.21g of cesium hydroxide were added in this order to a three-necked flask equipped with an air condenser, heated and stirred at 90 ℃ for 5 hours, and then reacted at 130 ℃ under reduced pressure to 200Pa for 24 hours to obtain polyurethane. The yield was 89%.
Example 18
180g (3.0 mol) of urea, 1600g (2.0 mol) of polyethylene glycol 800, 102g (1.0 mol) of pentamethylene diamine and 4.52g of potassium carbonate are simultaneously added into a three-neck flask provided with an air condensation tube, heated and stirred at 120 ℃ for 3 hours, and then decompressed to 30Pa at 160 ℃ for reaction for 12 hours, thus obtaining polyurethane. The yield was 90%.
Example 19
180g (3.0 mol) of urea, 172g (1.0 mol) of decamethylenediamine, 118g (1.0 mol) of hexamethylenediol, 1000g of lithium chloride and 7.98g of sodium carbonate were added in this order to a three-necked flask equipped with an air condenser, heated and stirred at 150 ℃ for 4 hours, and then reacted at 190 ℃ under reduced pressure to 80Pa for 8 hours to obtain polyurethane. The yield was 93%. FIG. 3 shows C of the product obtained in this example 13 Solid NMR spectrum of 160ppm as the signal peak of carbonyl carbon, 65ppm and 62ppm as the signal peaks of methylene carbon adjacent to COO, 41ppm as the signal peak of methylene carbon adjacent to NH, and 28-30ppm as the signal peak of intermediate methylene carbon.
Example 20
Into a three-necked flask equipped with an air condenser were added 90g (1.0 mol) of 1, 4-butanediol, 60g (1.0 mol) of urea, 102g (1.0 mol) of pentamethylenediamine and 5.71g of cesium carbonate in this order, and the mixture was heated and stirred at 80 ℃ for 12 hours, and then reacted at 120 ℃ under reduced pressure to 400Pa for 24 hours to obtain polyurethane. The yield was 88%.
Example 21
120g (2.0 mol) of urea, 200g (1.0 mol) of dodecamethylenediamine, 146g (1.0 mol) of 1, 8-octanediol and 600g of dimethylsulfoxide were simultaneously added to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 160 ℃ for 8 hours, and then reacted at 190 ℃ under reduced pressure to 60Pa for 16 hours to obtain polyurethane. The yield was 86%.
Example 22
180g (3.0 mol) of urea, 102g (1.0 mol) of pentamethylenediamine, 2400g (3.0 mol) of polypropylene glycol 800 and 8.67g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene were added in this order to a three-necked flask equipped with an air condenser, and the mixture was heated and stirred at 120 ℃ for 10 hours, and then, the mixture was reacted at 160 ℃ under reduced pressure to 10Pa for 18 hours to obtain polyurethane. The yield was 81%.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of polyurethane based on urea preparation is characterized by comprising the following specific steps:
(1) Melting urea, diamine and dihydric alcohol in the absence of solvent or dissolving in solvent in the atmosphere of normal pressure air or nitrogen, and heating and stirring at 40-300 deg.C for 0.5-24 hr in the absence of catalyst or catalysis of catalyst;
(2) And then reacting for 1-48 hours at 40-300 ℃ under the pressure of 0-2000Pa to obtain a polyurethane product.
2. The method according to claim 1, wherein the diamine of step (1) has a general structural formula shown in formula (II):
Figure FDA0003812231440000011
in the formula R 1 Is C 2 -C 20 An alkylene group of (a).
3. The method according to claim 1, wherein the diol obtained in step (1) has a general structural formula shown in formula (III):
Figure FDA0003812231440000012
in the formula R 2 Is C 2 -C 20 Alkylene group of (2) or C having an aromatic substituent on the main chain 1 -C 20 The alkylene group of (a) is either a polyether segment, a polyester segment, a polysiloxane segment or a polyolefin segment having a molecular weight of 200-40000 Da.
4. The method for preparing polyurethane based on urea according to claim 1, wherein the molar ratio of urea, diamine and diol in step (1) is (1-5) to 1 to (1-5).
5. The method of claim 1, wherein the urea, the diamine and the diol are added in the following order in step (1): urea, diamine, and diol; or urea, glycols, diamines; or diols, ureas, diamines; or diols, diamines, urea; or diamine, urea, diol; or diamine, diol, urea; or simultaneously adding urea, diamine and dihydric alcohol; and (2) the stirring in the step (1) for 0.5-24 hours is to start timing when all the materials are completely added.
6. The method of claim 1, wherein the catalyst in step (1) is one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, cesium carbonate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin bis (dodecylthio), tetrabutyl titanate, 1, 8-diazabicycloundecen-7-ene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, and 4-dimethylaminopyridine.
7. The method of claim 1, wherein the solvent in step (1) is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, simethicone, diphenylsilicone oil, cyclohexanone, zinc chloride, lithium bromide, and lithium chloride.
8. The method for preparing polyurethane based on urea preparation as claimed in claim 1, wherein the amount of the catalyst used in step (1) is 0.1 to 100% o of the total mass of the reaction monomers; the dosage of the solvent in the step (1) is 10-1000% of the total mass of the reaction monomers.
9. A polyurethane prepared on the basis of urea, obtained by the preparation process according to any one of claims 1 to 8, characterized in that it has the general formula of formula (I):
Figure FDA0003812231440000021
in the formula R 1 Is C 2 -C 20 Alkylene of (A), R 2 Is C 2 -C 20 Alkylene group of (A) or C having an aromatic substituent on the main chain 1 -C 20 Is either a polyether segment, a polyester segment, a polysiloxane segment or a polyolefin segment having a molecular weight of 200-40000Da, said n being in the range of 3-600.
10. Use of a urea-based polyurethane according to claim 9 for the production of high-strength and high-toughness fibers and sheets.
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CN104946159A (en) * 2015-07-16 2015-09-30 柳州市泓正生物科技有限公司 Powerful formaldehyde removal preparation
CN109369462A (en) * 2018-11-22 2019-02-22 四川大学 A kind of non-isocyanate polyurethane monomer and preparation method thereof
CN112209772A (en) * 2020-11-09 2021-01-12 吉林大学 Preparation method of oil-based polyurethane slow-release nitrogen fertilizer
CN112646176A (en) * 2020-12-17 2021-04-13 华南理工大学 Polyurethane prepared based on urea alcoholysis and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104946159A (en) * 2015-07-16 2015-09-30 柳州市泓正生物科技有限公司 Powerful formaldehyde removal preparation
CN109369462A (en) * 2018-11-22 2019-02-22 四川大学 A kind of non-isocyanate polyurethane monomer and preparation method thereof
CN112209772A (en) * 2020-11-09 2021-01-12 吉林大学 Preparation method of oil-based polyurethane slow-release nitrogen fertilizer
CN112646176A (en) * 2020-12-17 2021-04-13 华南理工大学 Polyurethane prepared based on urea alcoholysis and preparation method and application thereof

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