CN116903854B - Bio-based non-isocyanate polyurethane and preparation method thereof - Google Patents

Bio-based non-isocyanate polyurethane and preparation method thereof Download PDF

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CN116903854B
CN116903854B CN202311173957.1A CN202311173957A CN116903854B CN 116903854 B CN116903854 B CN 116903854B CN 202311173957 A CN202311173957 A CN 202311173957A CN 116903854 B CN116903854 B CN 116903854B
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isosorbide
polyurethane
polycondensation
reaction
molar ratio
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CN116903854A (en
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郑柳春
宋丹青
范世豪
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Tianjin Polytechnic University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The application provides bio-based non-isocyanate polyurethane and a preparation method thereof, and belongs to the fields of green chemical industry and bio-based polymers. The application synthesizes non-isocyanate polyurethane by taking dimethyl carbonate or diethyl carbonate, diamine and bio-based isosorbide as raw materials and small molecular dihydric alcohol. The prepared polyurethane has high molecular weight, excellent mechanical property and good heat resistance by introducing the bio-based isosorbide with excellent rigidity into the hard segment and/or the soft segment, thereby meeting the application requirements of the fields of packaging, plastics, films, fibers, engineering materials and the like.

Description

Bio-based non-isocyanate polyurethane and preparation method thereof
Technical Field
The application relates to the field of polymerization of biological high molecular materials and the field of green chemical industry, in particular to bio-based non-isocyanate polyurethane and a preparation method thereof.
Background
Polyurethane, also known as polyurethane, refers to polymers containing urethane groups in the main chain of the macromolecule. By changing the structure and the composition, polyurethane can have very wide mechanical properties (excellent elasticity, toughness, wear resistance and the like) and processing properties, and has become a sixth largest synthetic material, and is widely used for foamed plastics, fibers, elastomers, synthetic leather, coatings, adhesives, paving materials, medical materials and the like. However, the synthesis of conventional polyurethanes must use highly toxic di-or polyisocyanates, while the main raw material for the production of isocyanates is highly toxic phosgene, which is a great hazard to people and the environment. In addition, other raw materials for preparing isocyanate-based polyurethane belong to petroleum-based materials and are not renewable. Therefore, the development of a green and environment-friendly route for preparing the bio-based non-isocyanate polyurethane has great scientific significance and research value.
Currently, most bio-based non-isocyanate polyurethane adopts bio-based raw materials such as soybean oil, limonene, tannin and the like, binary or multi-ring carbonic ester is synthesized firstly, and then the binary or multi-ring carbonic ester reacts with amine compounds to prepare the non-isocyanate polyurethane. The polyurethane has the defects of low molecular weight, mechanical property and heat resistance far lower than those of the traditional polyurethane, and faces the serious situation that the traditional polyurethane cannot be replaced. In patent CN 114380994A, the non-isocyanate polyurethane is obtained by condensation reaction of the bio-based polyester bicyclic carbonate intermediate and the amine compound, and the tensile strength of the polyurethane prepared by the method is only 2.3-4.3 MPa. In the patent CN 111484613B, non-isocyanate polyurethane is prepared by reacting soybean oil carbonate with methoxy polyethylene glycol amine, and the polyurethane chain segment is structurally different from the traditional polyurethane, and has primary hydroxyl or secondary hydroxyl, so that the molecular weight is low, the mechanical property is poor, and the heat resistance is poor. Therefore, the bio-based polyurethane with high molecular weight, excellent mechanical property and heat resistance synthesized by using a non-isocyanate route has important value in practical production and application.
Isosorbide is the only rigid and nontoxic bio-based diol that has been produced industrially, and can be produced by the decomposition of starch into polysaccharides followed by hydrogenation and dehydration. The molecular structure of the polyurethane has two cis condensed rings, and the double ring structure can improve the rigidity and the glass transition temperature of polyurethane molecular chainsT g ) And mechanical properties, but most are polyurethane prepared by introducing isosorbide into the isocyanate route. According to the application, isocyanate is not used, and the rigid and nontoxic bio-based raw material isosorbide is introduced into the hard segment and/or the soft segment of polyurethane, so that the heat resistance and mechanical property of non-isocyanate polyurethane are improved, and the application range of polyurethane is enlarged.
Disclosure of Invention
The application provides a preparation method of bio-based non-isocyanate polyurethane, which aims at the defects in the prior art and comprises the following steps:
(1) Synthesis of dicarbamate intermediates
Diamine reacts with excessive dimethyl carbonate or diethyl carbonate under the catalysis of a catalyst, and a dicarbamate intermediate is obtained after the reaction is completed;
(2) Synthesis of polyurethane hard segment
The dicarbamate intermediate prepared in the step (1) and excessive small molecular dihydric alcohol and/or isosorbide are subjected to transesterification and polycondensation to generate hydroxyl-terminated polyurethane hard segment prepolymer;
(3) Synthesis of polyurethane soft segment
The soft segment of the polyurethane comprises polycarbonate diol, polyester diol and polyether diol;
preparing a polycarbonate diol soft segment by using dimethyl carbonate, small molecular diol and/or isosorbide through transesterification and polycondensation;
or preparing a polyester diol soft segment by using dibasic acid, micromolecular diol and/or isosorbide through esterification reaction and polycondensation reaction;
alternatively, polyether glycol is used as the polyurethane soft segment.
(4) Melt polycondensation for preparing polyurethane
And (3) preparing the non-isocyanate polyurethane by melt polycondensation of the hard polyurethane segments and the soft polyurethane segments prepared in the step (2) and the step (3).
Further, in the step (1), the molar ratio of diamine to dimethyl carbonate or diethyl carbonate is 1:2-6, preferably 1:2.5-4.5.
Further, the catalyst in the step (1) is 0.01 to 0.5 percent by mass of diamine, preferably 0.05 to 0.3 percent by mass.
Further, the reaction temperature in the step (1) is 50 to 200 ℃, preferably 70 to 160 ℃.
Further, the reaction time in the step (1) is 3 to 20 hours, preferably 5 to 10 hours.
Further, the diamine is one or more of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexamethylenediamine, 1, 8-octylenediamine, 1, 10-decylenediamine, 1, 12-dodecylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, isophoronediamine, 1, 6-cyclohexanediamine, menthanediamine, piperazine, azo diamine and conjugated unsaturated alkyl diamine, preferably 1, 6-hexamethylenediamine, 1, 8-octylenediamine, 1, 10-decylenediamine, p-phenylenediamine and isophoronediamine.
The catalyst is one or more of zinc organic acid salt, stannous or lead carboxylate, nitrate, metal chloride, metal oxysalt and metal oxide. Such as: zinc naphthenate, zinc acetate, zinc propionate, zinc octoate, zinc acetate, zinc oxalate, zinc stearate, zinc adipate, tin formate, tin trichloroacetate, stannous octoate, tin adipate, tin oxalate, lead acetate, lead nitrate, bismuth nitrate, sodium acetate, lithium methoxide, sodium tert-butoxide, lithium ethoxide, sodium ethoxide, copper subcarbonate, zinc subcarbonate, lead oxide, aluminum oxide, tin oxide, lead dioxide triflate, calcium chloride, zinc chloride, ferric chloride, zinc oxide, calcium oxide, lead oxide, tetrabutyl titanate. Preferably one or more of zinc acetate, zinc oxide, zinc stearate, lead acetate, bismuth nitrate, aluminum oxide, zinc acetate, sodium methoxide and basic zinc carbonate.
Further, the molar ratio of the dicarbamate to the small molecular dihydric alcohol and/or the isosorbide in the step (2) satisfies the molar ratio of the amino group to the hydroxyl group of 1:1.2-3, preferably 1:1.5-2.5.
Further, in the step (2), the molar ratio of the small molecular dihydric alcohol to the isosorbide is 10:0-1:9, preferably 8:2-2:8.
Further, the transesterification reaction in the step (2) is carried out in a nitrogen atmosphere, the temperature of the transesterification reaction is 100-190 ℃, and the reaction time is 1-24 hours; preferably, the reaction temperature is 140-180 ℃ and the reaction time is 1-10 h.
Further, the polycondensation reaction is carried out under a vacuum environment at a pressure of less than 100Pa, wherein the polycondensation reaction temperature is 150 to 250 ℃, the polycondensation reaction time is 1 to 15 hours, preferably, the polycondensation temperature is 170 to 230 ℃, and the polycondensation time is 1 to 10 hours.
It is to be noted that the "small molecular diol" as used herein refers to a small molecular diol other than isosorbide. The small molecular diol in the step (2) comprises one or more of ethylene glycol, diethylene glycol, glycerol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, cyclohexanedimethanol, cyclohexanediol, dodecanecycloalkanediol, hydrogenated bisphenol A, dimethylene phenyl glycol and the like, preferably 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, cyclohexanedimethanol and 1, 4-cyclohexanediol.
The polyurethane hard segment molecular weight prepared in the step (2)M n 500 to 10000, preferably 1000 to 5000.
The soft segments of the polyurethane include polycarbonate diol, polyester diol and polyether diol.
Further, in the step (3) of preparing the polycarbonate diol soft segment, the transesterification reaction is carried out under the protection of nitrogen, the reaction temperature is 100-190 ℃, and the transesterification reaction time is 1-20 h; preferably, the reaction temperature is 150-180 ℃ and the reaction time is 1-10 h. The polycondensation is carried out under the high vacuum condition that the system pressure is less than 100Pa, the polycondensation reaction temperature is 150-250 ℃, the reaction time is 1-15 h, preferably, the polycondensation temperature is 160-230 ℃, and the polycondensation time is 1-10 h. The molar ratio of the dimethyl carbonate to the small molecular dihydric alcohol in the step (3) is 1:1.2-3, and/or the molar ratio of the dimethyl carbonate to the isosorbide is 1:1.2-3, preferably 1:1.5-2.5. The molar ratio of the small molecular dihydric alcohol to the isosorbide in the step (3) is 10:0-1:9, preferably 8:2-2:8.
The small molecular diol in the step (3) comprises one or more of ethylene glycol, diethylene glycol, glycerol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, cyclohexanedimethanol, cyclohexanediol, dodecanecycloalkanediol, hydrogenated bisphenol A, dimethylene phenyl glycol and the like, preferably 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, cyclohexanedimethanol and 1, 4-cyclohexanediol. Molecular weight of the polycarbonate diol soft segment preparedM n 500 to 10000, preferably 1000 to 5000.
Further, in the step (3) of preparing the polyester diol soft segment, the temperature of the esterification reaction is 140-190 ℃ and the reaction time is 1-15 h; preferably, the esterification temperature is 150-180 ℃ and the reaction time is 1-10 h. The polycondensation temperature is 150-250 ℃, the reaction time is 1-15 h, preferably, the polycondensation temperature is 170-230 ℃, and the reaction time is 1-10 h.
Wherein the mol ratio of the dibasic acid and the micromolecular dihydric alcohol is 1:1.1-3, and/or the mol ratio of the dibasic acid and the isosorbide is 1:1.1-3, preferably 1:1.2-2.5;
wherein the molar mass ratio of the small molecular dihydric alcohol to the isosorbide is 10:0-1:9, and is preferably 8:2-2:8.
Wherein the small molecular dihydric alcohol comprises one or more of ethylene glycol, diethylene glycol, glycerol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, cyclohexanedimethanol, cyclohexanediol, dodecanecycloalkanediol, hydrogenated bisphenol A, and dimethylene phenyl glycol. The dibasic acid includes one or more of succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, furandicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and is preferably adipic acid, suberic acid, sebacic acid, and terephthalic acid. Wherein the molecular weight of the polyester diol soft segment preparedM n 500 to 10000, preferably 1000 to 5000.
Further, in the step (3) of selecting polyether glycol as the polyurethane soft segment, the polyether glycol is one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol. Molecular weight of selected polyether glycol soft segmentM n 500 to 10000, preferably 1000 to 5000.
Further, the non-isocyanate polyurethane in the step (4) is a polyurethane with soft segments containing isosorbide or hard segments containing isosorbide or both soft and hard segments containing isosorbide.
Further, in the step (4), the polycondensation temperature is 150 to 250 ℃, the polycondensation time is 1 to 15 hours, preferably the polycondensation temperature is 170 to 230 ℃, and the polycondensation time is 1 to 10 hours. Polyurethane with different structures and performances can be prepared by selecting different types of soft and hard segments and adjusting different soft and hard segment proportions.
The second aspect of the application discloses a bio-based non-isocyanate polyurethane obtained by the preparation method.
The application has the beneficial effects that:
the preparation method does not use toxic isocyanate as a raw material, and introduces the bio-based isosorbide to synthesize polyurethane, so that the polyurethane has excellent mechanical property and heat resistance, the tensile strength is up to 96MPa, the initial decomposition temperature is over 300 ℃, the thermal deformation temperature is up to 100 ℃, and the polyurethane is superior to the polyurethane prepared by the traditional isocyanate method. Meanwhile, the whole synthesis process is green and pollution-free, accords with the concept of the modern green chemical industry, and has wide application prospect. In addition, polyurethane with different structures and performances can be prepared by adjusting the components of the soft segment and the hard segment and the proportion of the soft segment, so that the application requirements of the fields of packaging, plastics, films, fibers, engineering materials and the like are met.
Detailed Description
The technical solutions provided by the present application are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The chemical structure of the application is characterized by nuclear magnetic hydrogen spectrum, and is tested by adopting Bruker DMX-400 nuclear magnetic resonance at room temperature and using deuterated dimethyl sulfoxide or deuterated chloroform as a solvent, wherein the concentration of the sample is about 10 mg/mL. The molecular weight and molecular weight distribution of the polymer were measured on a Waters2414 type gel permeation chromatograph (Waters 2414). The measurement temperature was 45℃and the flow rate of the mobile phase was 1.0. 1.0 mL/min with chromatographically pure N, N' -dimethylformamide as the mobile phase, and monodisperse polystyrene as the standard.
The mechanical properties of the polymers in the application are tested by using an Instron 1122 tensile tester according to the standard ISO 527, the moving speed of the clamp beam during stretching is 50 mm/min, and the stretching data are the average value of five times of measurement data. The injection molded sample was a dumbbell sample with dimensions 10.0x4.0x2.0 cm.
The heat deformation temperature of the application is tested according to GB/T8802-88, and the test requirements are as follows: the temperature rising speed is 5+/-0.5 ℃/6min, the heating medium adopts methyl silicone oil, and the cooling mode adopts water cooling.
Basic thermal Property (DSC) determination of glass transition temperature Using NETZSCH DSC204F1, germany differential scanning calorimeterT g ) And crystallization/melting behavior. Weighing about 5-7 mg of sample, placing into aluminum crucible, adding high-purity N 2 Scanning from room temperature to 200deg.C at a heating rate of 10deg.C/min in atmosphere, keeping constant temperature for 5min, and eliminating heat historyThen 100 ℃/min is reduced to-70 ℃, then 10 ℃/min is increased to 200 ℃, and a temperature increase curve is recorded. Finally, after 5min of constant temperature, the temperature is reduced to-70 ℃ at 10 ℃/min, and the cooling curve of the polymer is preserved.
Thermal stability was determined by thermogravimetric analysis (Perkin-Elmer pyres 1 TGA) under nitrogen atmosphere. 2-3 mg of the sample is weighed and placed in a platinum crucible, the temperature is raised from room temperature to 600 ℃ at a heating rate of 20 ℃/min, and the thermal degradation curve of the polymer is recorded.
Example 1
Example 1 a total of 10 experiments were performed.
Example 1.1
(1) Adding 1, 10-decanediamine and dimethyl carbonate into a flask, wherein the molar ratio of the 1, 10-decanediamine to the dimethyl carbonate is 1:3, adding a catalyst zinc acetate, wherein the zinc acetate accounts for 0.08 percent of the mass of the 1, 10-octanediamine, heating to 85 ℃ for reaction, and reacting for 8 hours to obtain the 1, 10-decamethylenedicarbamate.
(2) Reacting 1, 10-decamethylene dicarbamate with 1, 4-butanediol to generate a hydroxyl-terminated polyurethane hard segment prepolymer, wherein the molar ratio of the dicarbamate to the dihydric alcohol is 1:1.2, carrying out transesterification under the protection of nitrogen, wherein the transesterification temperature is 100 ℃, the transesterification time is 20h, and carrying out polycondensation under the pressure of 40Pa after the transesterification stage is finished, wherein the polycondensation temperature is 150 ℃ and the reaction time is 8h. Molecular weight of the hard polyurethane segments producedM n 2000.
(3) Dimethyl carbonate and 1, 10-decanediol are put into a four-necked flask, and a polycarbonate diol soft segment is prepared through transesterification and polycondensation. The molar ratio of dimethyl carbonate to 1, 10-decanediol was 1:1.2. Under the protection of nitrogen, the temperature of the transesterification reaction is 160 ℃, and the transesterification reaction time is 10 hours; after the transesterification stage is finished, the polycondensation is carried out under the system pressure of 50Pa, the polycondensation temperature is 170 ℃, and the reaction time is 6 hours. Molecular weight of the soft segment of the polycarbonate diol preparedM n 2600.
(4) Putting the prepared soft and hard segments into a reaction kettle, wherein the content of the hard segments is 80%, the content of the soft segments is 20%, and the pressure of a reaction system is below 40Pa, and the pressure is increasedMelt polycondensation is carried out at the temperature of 150 ℃ for 6 hours, and the obtained polyurethane is denoted as S 1 IS 0 PCU (i.e., no isosorbide was used in example 1.1).
Example 1.2 differs from example 1.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 8:2, the polyurethane obtained being designated S 1 IS 1 PCU。
Example 1.3 differs from example 1.1 in that isosorbide is added in the second step, the molar ratio of glycol to isosorbide being 6:4, the polyurethane obtained is designated S 1 IS 2 PCU。
Example 1.4 differs from example 1.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 4:6, the polyurethane obtained being designated S 1 IS 3 PCU。
Example 1.5 differs from example 1.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 2:8, the polyurethane obtained being designated S 1 IS 4 PCU。
Example 1.6 differs from example 1.1 in that isosorbide is added in the third step, the molar ratio of diol to isosorbide being 5:5, the polyurethane obtained being designated S 1 IS 5 PCU。
Example 1.7 differs from example 1.1 in that isosorbide is added in the third step, wherein the molar ratio of diol to isosorbide is 2:8, and the resulting polyurethane is designated S 1 IS 6 PCU。
Example 1.8 differs from example 1.1 in that isosorbide is added in the second step in a molar ratio of glycol to isosorbide of 5:5, isosorbide is also added in the third step, the molar ratio of glycol to isosorbide added in the third step is 5:5, and the resulting polyurethane is designated as S 1 IS 7 PCU。
Example 1.9 differs from example 1.1 in that isosorbide is added in the second step in a molar ratio of glycol to isosorbide of 7:3, isosorbide is also added in the third step, the molar ratio of glycol to isosorbide added in the third step is 3:7, and the resulting polyurethane is designated as S 1 IS 8 PCU。
Examples1.10 differs from example 1.1 in that isosorbide is added in the second step in a molar ratio of glycol to isosorbide of 3:7, isosorbide is also added in the third step, the molar ratio of glycol to isosorbide added in the third step is 3:7, and the resulting polyurethane is designated S 1 IS 9 PCU. Experimental data for the polyurethanes in example 1 are shown in table 1.
Table 1 experimental data for polyurethanes
Example 2
Example 2 a total of 5 experiments were performed.
Example 2.1
(1) Adding p-phenylenediamine and diethyl carbonate into a flask, wherein the molar ratio of the p-phenylenediamine to the dimethyl carbonate is 1:3.5, adding anhydrous sodium acetate serving as a catalyst, wherein the anhydrous sodium acetate is 0.1% of the mass of the p-phenylenediamine, heating to 140 ℃ for reaction, and reacting for 7 hours to obtain the p-phenylene dicarbamate.
(2) And (3) reacting terephthalyl carbamate with 1, 8-octanediol to generate hydroxyl-terminated polyurethane hard-segment prepolymer, wherein the molar ratio of the dicarbamate to the dihydric alcohol is 1:2, carrying out transesterification under the protection of nitrogen, wherein the transesterification temperature is 120 ℃, the transesterification time is 15h, vacuumizing the reaction system until the vacuum degree is reduced to below 40Pa after the transesterification stage is finished, and carrying out polycondensation, wherein the polycondensation temperature is 175 ℃, and the reaction time is 10h. Molecular weight of the hard polyurethane segments producedM n 4200.
(3) Dimethyl carbonate and cyclohexanedimethanol are put into a four-neck flask, and a polycarbonate diol soft segment is prepared through transesterification and polycondensation. The molar ratio of dimethyl carbonate to cyclohexanedimethanol was 1:1.9. Under the protection of nitrogen, the temperature of the transesterification reaction is 150 ℃, and the transesterification reaction time is 10 hours; after the transesterification stage is finished, the reaction system is vacuumized until the vacuum degree is reduced to below 40Pa, polycondensation is carried out, the polycondensation temperature is 200 ℃, and the reaction time is 8 hours. Molecular weight of the soft segment of the polycarbonate diol preparedM n 6560.
(4) Putting the prepared soft and hard segments into a reaction kettle, wherein the content of the hard segments is 60%, the content of the soft segments is 40%, heating to 210 ℃ under the system pressure of below 20Pa, performing melt polycondensation, and performing polycondensation for 5h to obtain polyurethane, namely S 2 IS 0 PCU (i.e., no isosorbide was used in example 2.1).
Example 2.2 differs from example 2.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 7:3, the polyurethane obtained being designated S 2 IS 2 PCU。
Example 2.3 differs from example 2.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 5:5, the polyurethane obtained being designated S 2 IS 3 PCU。
Example 2.4 differs from example 2.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 3:7, the polyurethane obtained being designated S 2 IS 4 PCU。
Example 2.5 differs from example 2.1 in that isosorbide is added in the second step in a molar ratio of glycol to isosorbide of 3:7, isosorbide is also added in the third step, the molar ratio of glycol to isosorbide added in the third step is 5:5, and the resulting polyurethane is designated as S 2 IS 4 PCU. Experimental data for the polyurethanes in example 2 are shown in table 2.
Table 2 experimental data for polyurethanes
Example 3
Example 3 a total of 5 experiments were performed.
Example 3.1
(1) Adding 1, 12-dodecanediamine and dimethyl carbonate into a flask, wherein the molar ratio of the 1, 12-dodecanediamine to the dimethyl carbonate is 1:4, adding a catalyst sodium methoxide, wherein the mass of the sodium methoxide is 0.14% of that of the 1, 12-dodecanediamine, heating to 90 ℃ for reaction, and reacting for 8 hours to obtain the 1, 12-dodecanedicarbamate.
(2) Reacting 1, 12-dodecyl methyl dicarbamate with 1, 10-decanediol to generate hydroxyl terminated polyurethane hard segment prepolymer, wherein the mol ratio of the 1, 12-dodecyl methyl dicarbamate to the dihydric alcohol is 1:3, carrying out transesterification under the protection of nitrogen, wherein the transesterification temperature is 150 ℃, the transesterification time is 9h, vacuumizing the reaction system until the air pressure is reduced to below 40Pa after the transesterification is finished, and carrying out polycondensation, wherein the polycondensation temperature is 190 ℃, and the reaction time is 5h. Molecular weight of the hard polyurethane segments producedM n 3500.
(3) Dimethyl carbonate and 1, 4-cyclohexanediol are put into a four-neck flask, and a polycarbonate diol soft segment is prepared through transesterification and polycondensation. The molar ratio of dimethyl carbonate to cyclohexanediol was 1:2.5.
Under the protection of nitrogen, the temperature of the transesterification reaction is 180 ℃, and the transesterification reaction time is 9h; and after the transesterification stage is finished, vacuumizing the reaction system until the pressure is reduced to below 40Pa, and performing polycondensation, wherein the polycondensation temperature is 190 ℃, and the reaction time is 6 hours. Molecular weight of the soft segment of the polycarbonate diol preparedM n 4500.
(4) Putting the prepared soft and hard segments into a reaction kettle, wherein the content of the hard segments is 70 percent, the content of the soft segments is 30 percent, reducing the pressure of a reaction system to below 30Pa, heating to 160 ℃ for melt polycondensation, and carrying out polycondensation for 5 hours to obtain polyurethane which is marked as S 3 IS 0 PCU (i.e., no isosorbide was used in example 3.1).
Example 3.2 differs from example 3.1 in that isosorbide is added in a third step, the molar ratio of 1, 4-cyclohexanediol to isosorbide being 9:1, the polyurethane obtained being designated S 3 IS 2 PCU。
Example 3.3 differs from example 3.1 in that isosorbide is added in a third step, the molar ratio of 1, 4-cyclohexanediol to isosorbide being 6:4, the polyurethane obtained being designated S 3 IS 3 PCU。
Example 3.4 differs from example 3.1 in that isosorbide is added in the third step, the molar ratio of 1, 4-cyclohexanediol to isosorbide being 4:6, the polyurethane obtained being designated S 3 IS 4 PCU。
Example 3.5 differs from example 3.1 in that isosorbide is added in the third step, the molar ratio of cyclohexanediol to isosorbide being 1:9, the polyurethane obtained being designated S 3 IS 4 PCU. Experimental data for the polyurethanes in example 3 are shown in table 3.
TABLE 3 Experimental data for polyurethanes
Example 4
Example 4 a total of 7 experiments were performed.
Example 4.1
(1) Adding 1, 6-cyclohexanediamine and diethyl carbonate into a flask, wherein the molar ratio of the 1, 6-cyclohexanediamine to the dimethyl carbonate is 1:5, adding a catalyst alumina which is 0.14% of the mass of the 1, 6-cyclohexanediamine, heating to 100 ℃ for reaction, and reacting for 10 hours to obtain the 1, 6-cyclohexanedicarbamate.
(2) Reacting 1, 6-cyclohexanedicarboxylate with 1, 12-dodecanediol to generate a hydroxyl terminated polyurethane hard segment prepolymer, carrying out transesterification reaction under the protection of nitrogen at a transesterification temperature of 160 ℃ and a transesterification time of 8 hours, reducing the pressure of a reaction system to below 50Pa after the transesterification stage is finished, and carrying out polycondensation at a polycondensation temperature of 200 ℃ and a reaction time of 5 hours, wherein the molar ratio of the 1, 6-cyclohexanedicarboxylate to the dihydric alcohol is 1:2.5. Molecular weight of the hard polyurethane segments producedM n 3500.
(3) Adipic acid and 1, 6-hexanediol are put into a four-neck flask, and polyester diol soft segments are prepared through esterification reaction and polycondensation reaction. The molar ratio of adipic acid to 1, 6-hexanediol was 1:1.5. Under the protection of nitrogen, the temperature of the esterification reaction is 175 ℃, and the transesterification reaction time is 6 hours; and after the esterification stage is finished, the pressure of the reaction system is reduced to below 50Pa for polycondensation, the polycondensation temperature is 180 ℃, and the reaction time is 8 hours. Molecular weight of the soft segment of the polycarbonate diol preparedM n 2900.
(4) The prepared soft and hard segments are put into a reaction kettle, the content of the hard segments is 50 percent, the content of the soft segments is 50 percent,heating to 190 ℃ under the pressure of 50Pa or lower, and performing melt polycondensation for 8 hours to obtain polyurethane, namely S 4 IS 0 PETU (i.e., no isosorbide is used in example 4.1).
Example 4.2 differs from example 4.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 8:2, the polyurethane obtained being designated S 4 IS 1 PETU。
Example 4.3 differs from example 4.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 6:4, the polyurethane obtained being designated S 4 IS 2 PETU。
Example 4.4 differs from example 4.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 4:6, the polyurethane obtained being designated S 4 IS 3 PETU。
Example 4.5 differs from example 4.1 in that isosorbide is added in the second stage in a molar ratio of glycol to isosorbide of 2:8, the polyurethane obtained being designated S 4 IS 4 PETU。
Example 4.6 differs from example 4.1 in that isosorbide is added in the third step, the molar ratio of diol to isosorbide being 5:5, the polyurethane obtained being designated S 4 IS 5 PETU。
Example 4.7 differs from example 4.1 in that isosorbide is added in the second step in a molar ratio of glycol to isosorbide of 5:5, and isosorbide is also added in the third step in a molar ratio of glycol to isosorbide of 5:5, the resulting polyurethane is designated S 4 IS 6 PETU. The experimental data for the polyurethanes in example 4 are shown in table 4.
Table 4 experimental data for polyurethanes
Example 5
Example 5 a total of 5 experiments were performed.
Example 5.1
(1) Adding 1, 6-cyclohexanediamine and dimethyl carbonate into a flask, wherein the molar ratio of the 1, 6-cyclohexanediamine to the dimethyl carbonate is 1:5, adding a catalyst alumina which is 0.14% of the mass of the 1, 6-cyclohexanediamine, heating to 100 ℃ for reaction, and reacting for 10 hours to obtain the 1, 6-cyclohexanedicarbamate.
(2) Reacting 1, 6-cyclohexanedicarboxylate with 1, 12-dodecanediol to generate a hydroxyl terminated polyurethane hard segment prepolymer, carrying out transesterification reaction under the protection of nitrogen at a transesterification temperature of 160 ℃ and a transesterification time of 8 hours, reducing the pressure of a reaction system to below 50Pa after the transesterification stage is finished, and carrying out polycondensation at a polycondensation temperature of 200 ℃ and a reaction time of 5 hours, wherein the molar ratio of the 1, 6-cyclohexanedicarboxylate to the dihydric alcohol is 1:2.2. Molecular weight of the hard polyurethane segments producedM n 3800.
(3) Putting the hard segment prepared in the step (2) and soft segment PTMG with molecular weight of 1000 into a reaction kettle, wherein the content of the hard segment is 30% and the content of the soft segment is 70%, heating to 190 ℃ under the system pressure of 50Pa or lower, carrying out melt polycondensation, and carrying out polycondensation for 8 hours to obtain polyurethane, which is marked as S 5 IS 0 PEU 1000 (i.e., no isosorbide is used in example 5.1).
Example 5.2 differs from example 5.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 5:5 and PTMG molecular weight of 1000, the polyurethane obtained being designated S 5 IS 1 PEU 1000 。
Example 5.3 differs from example 5.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 3:7, the polyurethane obtained with a PTMG molecular weight of 1000 being denoted S 5 IS 2 PEU 1000 。
Example 5.4 differs from example 5.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 5:5 and PTMG molecular weight of 2000, the polyurethane obtained being designated S 5 IS 3 PEU 2000 。
Example 5.5 differs from example 5.1 in that isosorbide is added in the second stage in a molar ratio of diol to isosorbide of 3:7, the polyurethane obtained with PTMG molecular weight 2000 being denoted S 5 IS 4 PEU 2000 . Experimental data for the polyurethanes in example 5 are shown in table 5.
TABLE 5 Experimental data for polyurethanes
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (6)

1. The preparation method of the bio-based non-isocyanate polyurethane is characterized by comprising the following steps of:
(1) Synthesis of dicarbamate intermediates
Diamine reacts with excessive dimethyl carbonate or diethyl carbonate under the catalysis of a catalyst, and a dicarbamate intermediate is obtained after the reaction is completed;
the mol ratio of diamine to dimethyl carbonate or diethyl carbonate is 1:2-6, and the mass of the catalyst is 0.01-0.5% of that of diamine;
(2) Synthesis of polyurethane hard segment
The dicarbamate intermediate prepared in the step (1) and excessive small molecular dihydric alcohol and isosorbide are subjected to transesterification and polycondensation to generate hydroxyl-terminated polyurethane hard segment prepolymer;
the molar ratio of the dicarbamate to the small molecular dihydric alcohol to the isosorbide is 1:1.2-3, and the molar ratio of the small molecular dihydric alcohol to the isosorbide is 8:2-2:8;
(3) Synthesis of polyurethane soft segment
Preparing a polycarbonate diol soft segment from dimethyl carbonate, small molecular diol and isosorbide through transesterification and polycondensation;
the molar ratio of the dimethyl carbonate to the small molecular dihydric alcohol is 1:1.2-3, and/or the molar ratio of the dimethyl carbonate to the isosorbide is 1:1.2-3; the mole ratio of the small molecular dihydric alcohol to the isosorbide is 8:2-2:8;
or preparing a polyester diol soft segment by using dibasic acid, micromolecular diol and isosorbide through esterification reaction and polycondensation reaction;
the mol ratio of the dibasic acid to the micromolecular dihydric alcohol is 1:1.1-3; and/or the molar ratio of the dibasic acid to the isosorbide is 1:1.1-3; the molar ratio of the small molecular dihydric alcohol to the isosorbide is 8:2-2:8;
(4) Melt polycondensation for preparing polyurethane
And (3) preparing the non-isocyanate polyurethane by melt polycondensation of the hard polyurethane segments and the soft polyurethane segments prepared in the step (2) and the step (3).
2. The method for producing a biobased non-isocyanate polyurethane according to claim 1, wherein the reaction temperature in the step (1) is 50 to 200 ℃ and the reaction time is 3 to 20 hours.
3. The method for preparing bio-based non-isocyanate polyurethane according to claim 1, wherein the step (2) is performed with a transesterification reaction in a nitrogen atmosphere at a temperature of 100-190 ℃ for a reaction time of 1-24 hours; and (3) performing polycondensation reaction in a vacuum environment with the pressure less than 100Pa, wherein the polycondensation reaction temperature is 150-250 ℃ and the polycondensation reaction time is 1-15 h.
4. The method for preparing bio-based non-isocyanate polyurethane according to claim 1, wherein the step (3) is characterized in that the polycarbonate diol soft segment is subjected to transesterification under the protection of nitrogen, the temperature of the transesterification is 100-190 ℃, and the reaction time is 1-20 h; performing polycondensation in a vacuum environment with a pressure of less than 100 Pa; wherein the polycondensation reaction temperature is 150-250 ℃ and the reaction time is 1-10 h.
5. The method for preparing bio-based non-isocyanate polyurethane according to claim 1, wherein the esterification reaction temperature of the polyester diol soft segment prepared in the step (3) is 140-190 ℃ and the reaction time is 1-15 h; the polycondensation temperature is 150-250 ℃, and the reaction time is 1-15 h.
6. A biobased non-isocyanate polyurethane obtainable by the process according to any one of claims 1 to 5.
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