CN112430308B - Preparation method of bio-based high-performance waterborne polyurethane resin and product thereof - Google Patents
Preparation method of bio-based high-performance waterborne polyurethane resin and product thereof Download PDFInfo
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses a preparation method of bio-based high-performance waterborne polyurethane resin and a product thereof, wherein the preparation method comprises the following steps: 1) putting bio-based polyol, an internal emulsifier and diisocyanate into a three-neck flask for mixing, adding a catalyst, and reacting at a set temperature and a stirring speed to obtain a polyurethane prepolymer; 2) adding a bio-based micromolecular chain extender into the polyurethane prepolymer in the step 1), carrying out chain extension reaction, adding a neutralizer after the reaction is finished, continuously stirring, and then dropwise adding deionized water into the reaction liquid for emulsification to obtain the bio-based high-performance waterborne polyurethane resin. According to the invention, a bio-based small molecular chain monomer (cyclic dipeptide) with a rigid structure is introduced into the vegetable oil-based waterborne polyurethane chain segment, so that the thermal stability and the mechanical property of the waterborne polyurethane are improved, and meanwhile, the solid content of the waterborne polyurethane bio-based can be further improved.
Description
Technical Field
The invention belongs to the technical field of waterborne polyurethane resin preparation, and particularly relates to a preparation method of a bio-based high-performance waterborne polyurethane resin and a product thereof.
Background
Waterborne Polyurethane (WPU) is a synthetic resin material developed based on traditional solvent type polyurethane, partially inherits the advantages of high physical and mechanical strength, good wear resistance and the like of the traditional polyurethane material, simultaneously reduces the release problem of Volatile Organic Compounds (VOC), has new characteristics of environmental protection, low toxicity, good compatibility and the like, and is widely applied to the fields of coatings, adhesives, fabric coatings and finishing agents, leather and synthetic leather finishing agents and the like.
In recent years, the production of petroleum product derivatives has been reduced year by year due to depletion of petroleum resources, affecting many fields including polyurethane manufacturing industry, and in order to cope with energy crisis, research for replacing petrochemical raw materials with renewable resources such as cellulose, lignin, vegetable oils and the like has become a promising new field from the viewpoint of sustainable development.
However, compared with solvent type polyurethane products, the solid content of single vegetable oil-based waterborne polyurethane is lower, and the mechanical property, the thermal stability, the water resistance and the like are insufficient. This is also a general deficiency of most of the presently disclosed vegetable oil-based waterborne polyurethane inventions:
chinese patent application CN 111087572A discloses a bio-based waterborne polyurethane resin with wear resistance, solvent resistance and water resistance and a preparation method thereof, the emulsion is mainly prepared from polyhydric alcohol containing active hydrogen, a long-chain compound with a main chain of dimer fatty acid, a hydrophilic chain extender, a small-molecule chain extender, a salt forming agent, deionized water, a post-chain extender and a solvent, wherein the small-molecule chain extender mainly adopts small-molecule dihydric alcohol such as 1, 4-butanediol, diethylene glycol, cyclohexanedimethanol and the like, the post-chain extender mainly adopts diamine such as ethylenediamine, hexamethylenediamine, isophoronediamine and the like, the breaking strength of the prepared waterborne polyurethane is only 14-24 MPa, and the solid content is 20-40%.
Chinese invention patent application CN 108467467A discloses a vegetable oil-based anionic waterborne polyurethane emulsion and a preparation method and application thereof. The waterborne polyurethane is prepared from plant-based polyol, diisocyanate, a chain extender, a neutralizer and a catalyst, wherein the chain extender is DMPA or DMBA. Due to the special pre-crosslinking structure of the polyol, the crosslinking density of the polyurethane is improved, the mechanical property and the water resistance of the material are improved, the preparation success rate is high, but the tensile strength is not high, the maximum is 17.5MPa, and the solid content is 10-15%. The two waterborne polyurethanes are low in strength and solid content and are often limited in specific application, so that the research and development of the high-performance waterborne polyurethane are further promising and are a great research direction.
Disclosure of Invention
The invention aims to provide a preparation method of a bio-based high-performance waterborne polyurethane resin with high strength and high solid content and a product thereof, and broadens the application field of waterborne polyurethane.
The preparation method of the bio-based high-performance waterborne polyurethane resin comprises the following steps:
1) preparation of prepolymer: putting bio-based polyol, an internal emulsifier and diisocyanate into a three-neck flask for mixing, adding a catalyst, and reacting at a set temperature and a stirring speed to obtain a polyurethane prepolymer;
2) preparation of bio-based high-performance aqueous polyurethane resin: adding a bio-based micromolecular chain extender into the polyurethane prepolymer in the step 1), carrying out chain extension reaction, adding a neutralizer after the reaction is finished, continuously stirring, and then dropwise adding deionized water into the reaction liquid for emulsification to obtain the bio-based high-performance waterborne polyurethane resin.
In the step 1), the bio-based polyol is castor oil, and the hydroxyl value of the bio-based polyol is 162-168mg KOH/g; the diisocyanate is any one of isophorone diisocyanate, toluene diisocyanate and dimethyl methane diisocyanate; the internal emulsifier is any one of dimethylolpropionic acid, dimethylolbutyric acid, 2, 5-dihydroxybenzoic acid and caffeic acid, and the catalyst is one of an organic tin catalyst and a tertiary amine catalyst; the set temperature is 78-85 ℃, the stirring is mechanical stirring, the reaction stirring speed is 180-250 r/min, and the reaction time is 3-4 h.
The mass ratio of the bio-based polyol, the internal emulsifier, the diisocyanate and the catalyst is (33-46): 8-10): 25-36): 1-2.
In the step 2), the mass ratio of the bio-based micromolecule chain extender to the bio-based polyol is (2-6) to (33-46); the bio-based micromolecular chain extender is one of isosorbide and cyclic dipeptide; the chain extension reaction time is 1.5-2.5 h; the neutralizer is one of triethylamine, triethanolamine, N-methyldiethanolamine, ammonia water, sodium bicarbonate and sodium carbonate; the mass ratio of the neutralizer to the deionized water to the bio-based polyol (6-8) is 150 to (33-46); the neutralization time is 20-40 min, the emulsifying and stirring speed is 1100-1300 r/min, and the emulsifying time is 20-40 min.
The preparation method of the cyclic dipeptide comprises the following steps: adding an upstream bio-based material into a solvent, discharging air, introducing nitrogen, reacting under magnetic stirring and a set temperature, filtering a reaction solution after the reaction is finished, washing filter residues, and recrystallizing in ethanol to obtain the cyclic dipeptide.
The upstream bio-based material is one of tyrosine, tryptophan, serine, threonine, cysteine, aspartic acid, glutamine, lysine, arginine and histidine; the solvent is one of ethylene glycol; the concentration of the upstream biobased material in the solvent is (0.5-1.5) 10 g/mL; setting the temperature to be 190-210 ℃, reacting for 18-22 h, then mixing and washing ethylene glycol and ethanol, performing suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol.
Preferably, the upstream biobased material is tyrosine, and the solvent is ethylene glycol; the concentration of the upstream biobased material in the solvent is 1:10 g/mL; the temperature was set at 200 ℃ and the reaction time was 20 h.
The bio-based high-performance waterborne polyurethane resin is prepared according to the preparation method.
The solid content of the bio-based high-performance waterborne polyurethane resin is more than 50%.
The bio-based high-performance waterborne polyurethane resin is applied to coatings, adhesives, fabric coatings and finishing agents and leather and synthetic leather finishing agents.
The invention has the beneficial effects that: 1) according to the invention, a bio-based small molecular chain monomer (cyclic dipeptide) with a rigid structure is introduced into the vegetable oil-based waterborne polyurethane chain segment, so that the thermal stability and the mechanical property of the waterborne polyurethane are improved, and meanwhile, the solid content of the waterborne polyurethane bio-based can be further improved. 2) The waterborne polyurethane prepared by the preparation method provided by the invention overcomes the defect that the traditional single vegetable oil-based waterborne polyurethane is low in solid content, and has the characteristics of environmental friendliness, high mechanical property, good thermal stability and the like. 3) The novel waterborne polyurethane material prepared by the invention has good mechanical property, high solid content and high water resistance, can fully meet various application occasions, and can be used in the fields of coatings, adhesives, fabric coatings and finishing agents, leather and synthetic leather finishing agents and the like.
Description of the drawings:
FIG. 1 is a schematic flow chart of a method according to an embodiment of the present invention;
FIG. 2 is a photograph showing the products prepared in examples 1 to 3.
Detailed description of the invention
Example 1
The bio-based small-molecule chain extender adopts L-tyrosine cyclic dipeptide, and the preparation process comprises the following steps:
preparing 1g/10ml solution of L-tyrosine and ethylene glycol into a single-neck flask, pumping out air in the flask, introducing nitrogen for protection, and reacting for 20 hours at 200 ℃ under magnetic stirring; after the reaction is finished, mixing and washing the obtained product with ethylene glycol and ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol to obtain a white powder solid, namely the cyclic dipeptide (L-tyrosine cyclic dipeptide).
Preparing high-performance bio-based waterborne polyurethane:
the high-performance bio-based waterborne polyurethane emulsion comprises the following raw materials in percentage by mass:
castor oil: 15.31g of hydroxyl value of 165mg KOH/g
Isophorone diisocyanate: 11.67g
Dimethylolpropionic acid: 2.98g
L-tyrosine cyclic dipeptide: 0.80g
Dibutyltin dilaurate: 0.57g
Triethylamine: 2.25g
Deionized water: 50.00g
The preparation process is shown as the following figure 1, and the specific steps are as follows:
a reaction vessel three-necked flask was provided as indicated by S1.
As shown at S2: adding castor oil and dimethylolpropionic acid into a three-neck flask, introducing nitrogen, drying at 95 ℃ for 1h, adding isophorone diisocyanate and dibutyltin dilaurate, and mechanically stirring at 80 ℃ and at the rotating speed of 200r/min for reacting for 4h to obtain the polyurethane prepolymer.
As shown at S3: adding L-tyrosine cyclic dipeptide into the polyurethane prepolymer, and carrying out chain extension reaction for 2 h.
As shown at S4: and adding triethylamine into the polyurethane prepolymer after chain extension is completed, stirring for 30min, then adjusting the mechanical stirring speed to 1200r/min, dropwise adding deionized water, and emulsifying for 30min to obtain the aqueous polyurethane emulsion, wherein the final product is shown in figure 2 a.
Comparative example 1
Castor oil: 15.31g of hydroxyl value of 165mg KOH/g
Isophorone diisocyanate: 11.67g
Dimethylolpropionic acid: 2.98g
Ethylene glycol: 0.15g
Dibutyltin dilaurate: 0.57g
Triethylamine: 2.25g
Deionized water: 50.00g
The preparation process is shown as the following figure 1, and the specific steps are as follows:
a reaction vessel three-necked flask was provided as indicated by S1.
As shown at S2: adding castor oil and dimethylolpropionic acid into a three-neck flask, introducing nitrogen, drying at 95 ℃ for 1h, adding isophorone diisocyanate and dibutyltin dilaurate, and mechanically stirring at 80 ℃ and at the rotating speed of 200r/min for reacting for 4h to obtain the polyurethane prepolymer.
As shown at S3: and adding ethylene glycol into the polyurethane prepolymer, and carrying out chain extension reaction for 2 hours.
As shown at S4: and adding triethylamine into the polyurethane prepolymer which is subjected to chain extension, stirring for 30min for neutralization, then adjusting the mechanical stirring rotation speed to 1200r/min, dropwise adding deionized water, and emulsifying for 30min to obtain a water-based polyurethane emulsion, wherein the final product is shown in figure 2 d.
Example 2
The bio-based small-molecule chain extender adopts L-tyrosine cyclic dipeptide, and the preparation process comprises the following steps:
preparing 1g/10ml solution of histidine and ethylene glycol, adding the solution into a single-neck flask, completely pumping air in the flask, introducing nitrogen for protection, and reacting for 22 hours at 180 ℃ under magnetic stirring; after the reaction is finished, mixing and washing the obtained product with ethylene glycol and ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol to obtain a white powder solid, namely the cyclic dipeptide (histidine cyclic dipeptide).
Preparing high-performance bio-based waterborne polyurethane:
the high-performance bio-based waterborne polyurethane emulsion comprises the following raw materials in percentage by mass:
castor oil: 13.87g of hydroxyl number 165mg KOH/g
Isophorone diisocyanate: 11.67g
Dimethylolpropionic acid: 2.98g
Histidine cyclic dipeptide: 1.36g
Dibutyltin dilaurate: 0.53g
Triethylamine: 2.25g
Deionized water: 50.00g
In this example, the specific preparation process is as follows:
a reaction vessel three-necked flask was provided as indicated by S1.
As shown at S2: adding castor oil and dimethylolpropionic acid into a three-neck flask, introducing nitrogen, drying at 95 ℃ for 1h, adding isophorone diisocyanate and dibutyltin dilaurate, and mechanically stirring at 80 ℃ and at the rotating speed of 200r/min for reacting for 4h to obtain the polyurethane prepolymer.
As shown at S3: adding histidine cyclic dipeptide into the polyurethane prepolymer, and carrying out chain extension reaction for 2 h.
As shown at S4: and adding triethylamine into the polyurethane prepolymer which is subjected to chain extension, stirring for 30min for neutralization, then adjusting the mechanical stirring rotation speed to 1200r/min, dropwise adding deionized water, and emulsifying for 30min to obtain the aqueous polyurethane emulsion, wherein the product is shown in figure 2 b.
Example 3
The bio-based small-molecule chain extender adopts L-tyrosine cyclic dipeptide, and the preparation process comprises the following steps:
preparing 1g/10ml solution of L-tyrosine and ethylene glycol into a single-neck flask, pumping out air in the flask, introducing nitrogen for protection, and reacting for 20 hours at 200 ℃ under magnetic stirring; after the reaction is finished, mixing and washing the obtained product with ethylene glycol and ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol to obtain a white powder solid, namely the cyclic dipeptide (L-tyrosine cyclic dipeptide).
Preparing high-performance bio-based waterborne polyurethane:
the high-performance bio-based waterborne polyurethane emulsion comprises the following raw materials in percentage by mass:
castor oil: 11.20g of hydroxyl number 162mg KOH/g
Isophorone diisocyanate: 11.67g
Dimethylolpropionic acid: 2.98g
L-tyrosine cyclic dipeptide: 1.75g
Dibutyltin dilaurate: 0.48g
Triethylamine: 2.25g
Deionized water: 50.00g
In this example, the specific preparation process is as follows:
a reaction vessel three-necked flask was provided as indicated by S1.
As shown at S2: adding castor oil and dimethylolpropionic acid into a three-neck flask, introducing nitrogen, drying at 95 ℃ for 1h, adding isophorone diisocyanate and dibutyltin dilaurate, and mechanically stirring at 80 ℃ and at the rotating speed of 200r/min for reacting for 4h to obtain the polyurethane prepolymer.
As shown at S3: adding L-tyrosine cyclic dipeptide into the polyurethane prepolymer, and carrying out chain extension reaction for 2 h.
As shown at S4: and adding triethylamine into the polyurethane prepolymer which is subjected to chain extension, stirring for 30min for neutralization, then adjusting the mechanical stirring rotation speed to 1200r/min, dropwise adding deionized water, and emulsifying for 30min to obtain the aqueous polyurethane emulsion, wherein the product is shown in figure 2 c.
Example 4
The aqueous polyurethane emulsion prepared in the above examples 1 to 3 and comparative example 1 was spread on a polytetrafluoroethylene mold plate, left at room temperature for 72 hours, and after water was evaporated to dryness, the resultant aqueous polyurethane film was dried in an oven at 70 ℃ for 24 hours to test mechanical properties, abrasion resistance and water absorption.
5ml of aqueous polyurethane emulsion is absorbed and dripped into the tin foil paper, and the mass m is weigheda(mass m of the tin foil paper), then the paper is put into an oven for 24 hours at 80 ℃ to remove the water, and the mass m is weighed againbThe solid content calculation formula is as follows:
the mechanical property of the waterborne polyurethane is tested by adopting a tensile testing machine according to the standard ISO1184-1983 (determination of tensile property of plastic film).
The wear resistance of the waterborne polyurethane is tested according to the standard ISO7784-2-1997 determination of wear resistance of paint and varnish by adopting a Taber wear tester to test the wear resistance of the waterborne polyurethane film, and the hardness of the film is tested by adopting a pencil scratch hardness tester according to the specific requirements of GB/T6739-.
Drying the waterborne polyurethane dry film at 60 ℃ for 48h, weighing m1 before water absorption, then putting the dried waterborne polyurethane dry film into deionized water for 24h, taking out the film, wiping off water on the surface of the film, weighing the mass m2 after water absorption, and calculating the formula of water absorption
Mechanical properties of the examples and comparative examples are shown in Table 1
TABLE 1 mechanical Properties and solid contents of waterborne polyurethane films
TABLE 2 Water absorption, abrasion resistance and hardness of waterborne polyurethane films
Example 5
The bio-based small-molecule chain extender adopts L-tyrosine cyclic dipeptide, and the preparation process comprises the following steps:
preparing 1.5g/10ml solution of lysine and ethylene glycol into a single-neck flask, pumping out air in the flask, introducing nitrogen for protection, and reacting at 190 ℃ for 22h under magnetic stirring; after the reaction is finished, mixing and washing the obtained product with ethylene glycol and ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol to obtain a white powder solid, namely the cyclic dipeptide (lysine cyclic dipeptide).
Preparing high-performance bio-based waterborne polyurethane:
the high-performance bio-based waterborne polyurethane emulsion comprises the following raw materials in percentage by mass:
castor oil: 11.20g of hydroxyl number 162mg KOH/g
Toluene diisocyanate: 10.44g
Dimethylolbutyric acid: 2.74g
Lysine cyclic dipeptide: 1.35g
Dibutyltin dilaurate: 0.39g
Triethanolamine: 3.45g
Deionized water: 50.00g
In this example, the specific preparation process is as follows:
a reaction vessel three-necked flask was provided as indicated by S1.
As shown at S2: adding castor oil and dimethylolbutyric acid into a three-neck flask, introducing nitrogen, drying at 95 ℃ for 1h, adding toluene diisocyanate and dibutyltin dilaurate, and reacting for 3.5h at 78 ℃ under mechanical stirring at the rotating speed of 250r/min to obtain the polyurethane prepolymer.
As shown at S3: and adding lysine cyclic dipeptide into the polyurethane prepolymer, and carrying out chain extension reaction for 2 hours.
As shown at S4: adding triethanolamine into the polyurethane prepolymer which is subjected to chain extension, stirring for 40min for neutralization, then adjusting the mechanical stirring speed to 1300r/min, and dropwise adding deionized water for emulsification for 20min to obtain the waterborne polyurethane emulsion.
Example 6
The bio-based small-molecule chain extender adopts L-tyrosine cyclic dipeptide, and the preparation process comprises the following steps:
preparing 0.5g/10ml solution of serine and ethylene glycol into a single-neck flask, adding the solution into the single-neck flask, completely pumping air in the flask, introducing nitrogen for protection, and reacting for 18 hours at 210 ℃ under magnetic stirring; after the reaction is finished, mixing and washing the obtained product with ethylene glycol and ethanol, carrying out suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol to obtain a white powder solid, namely the cyclic dipeptide (serine cyclic dipeptide).
Preparing high-performance bio-based waterborne polyurethane:
the high-performance bio-based waterborne polyurethane emulsion comprises the following raw materials in percentage by mass:
castor oil: 11.20g of hydroxyl number 162mg KOH/g
Dimethyl methane diisocyanate: 9.50g
2, 5-dihydroxybenzoic acid: 3.28g
Serine cyclic dipeptides: 1.85g
Dibutyltin dilaurate: 0.45g
N-methyldiethanolamine: 3.45g
Deionized water: 50.00g
In this example, the specific preparation process is as follows:
a reaction vessel three-necked flask was provided as indicated by S1.
As shown at S2: adding castor oil and 2, 5-dihydroxybenzoic acid into a three-neck flask, introducing nitrogen, drying at 95 ℃ for 1h, adding dimethyl methane diisocyanate and dibutyltin dilaurate, and mechanically stirring at 85 ℃ and 180r/min for reaction for 4h to obtain the polyurethane prepolymer.
As shown at S3: adding serine cyclic dipeptide into the polyurethane prepolymer, and carrying out chain extension reaction for 2.5 h.
As shown at S4: and adding the polyurethane prepolymer after chain extension into N-methyldiethanolamine, stirring for 20min for neutralization, then adjusting the mechanical stirring speed to 1100r/min, and dropwise adding deionized water for emulsification for 40min to obtain the aqueous polyurethane emulsion.
The above embodiments are merely illustrative of the technical idea of the present invention, and the technical idea proposed by the present invention is not limited to the scope of the present invention, and any non-inventive changes made on the basis of the technical solution of the present invention fall within the scope of the present invention, which is subject to the claims.
Claims (7)
1. A preparation method of bio-based high-performance waterborne polyurethane resin comprises the following steps:
1) preparation of polyurethane prepolymer: putting bio-based polyol, an internal emulsifier and diisocyanate into a three-neck flask for mixing, adding a catalyst, and reacting at a set temperature and a stirring speed to obtain a polyurethane prepolymer;
2) preparation of bio-based high-performance aqueous polyurethane resin: adding a bio-based micromolecular chain extender into the polyurethane prepolymer in the step 1), carrying out chain extension reaction, adding a neutralizer to continue stirring after the reaction is finished, and then dropwise adding deionized water into the reaction liquid for emulsification to obtain a bio-based high-performance waterborne polyurethane resin;
in the step 1), the bio-based polyol is castor oil, and the hydroxyl value of the bio-based polyol is 162-168mg KOH/g; the diisocyanate is any one of isophorone diisocyanate, toluene diisocyanate and dimethyl methane diisocyanate; the internal emulsifier is any one of dimethylolpropionic acid, dimethylolbutyric acid, 2, 5-dihydroxybenzoic acid and caffeic acid; the mass ratio of the bio-based polyol to the internal emulsifier to the diisocyanate to the catalyst is (33-46) to (8-10) to (25-36) to (1-2);
in the step 2): the bio-based micromolecular chain extender is cyclic dipeptide; the preparation method of the cyclic dipeptide comprises the following steps: adding an upstream bio-based material into a solvent, discharging air, introducing nitrogen, reacting under magnetic stirring and a set temperature, after the reaction is finished, carrying out suction filtration on a reaction solution, washing a product, and recrystallizing in ethanol to obtain the cyclic dipeptide.
2. The method for preparing the bio-based high-performance aqueous polyurethane resin according to claim 1, wherein in the step 1), the catalyst is one of an organotin catalyst and a tertiary amine catalyst; the set temperature is 78-85 ℃, the stirring is mechanical stirring, the reaction stirring speed is 180-250 r/min, and the reaction time is 3-4 h.
3. The preparation method of the bio-based high-performance aqueous polyurethane resin as claimed in claim 1, wherein in the step 2), the mass ratio of the bio-based small-molecule chain extender to the bio-based polyol is (2-6): (33-46); the chain extension reaction time is 1.5-2.5 h; the neutralizer is one of triethylamine, triethanolamine, N-methyldiethanolamine, ammonia water, sodium bicarbonate and sodium carbonate; the mass ratio of the neutralizer to the deionized water to the bio-based polyol (6-8) is 150 to (33-46); the neutralization time is 20-40 min, the emulsifying and stirring speed is 1100-1300 r/min, and the emulsifying time is 20-40 min.
4. The method for preparing bio-based high-performance aqueous polyurethane resin according to claim 1, wherein the upstream bio-based material is one of tyrosine, tryptophan, serine, threonine, cysteine, aspartic acid, glutamine, lysine, arginine and histidine; the solvent is ethylene glycol; the concentration of the upstream biobased material in the solvent is (0.5-1.5) 10 g/mL; setting the temperature to be 190-210 ℃, reacting for 18-22 h, then mixing and washing ethylene glycol and ethanol, performing suction filtration to obtain a light yellow solid, and then recrystallizing in ethanol.
5. The bio-based high-performance aqueous polyurethane resin prepared by the preparation method according to any one of claims 1 to 4.
6. The bio-based high-performance aqueous polyurethane resin according to claim 5, wherein the solid content of the bio-based high-performance aqueous polyurethane resin is 50% or more.
7. The use of the bio-based high-performance aqueous polyurethane resin according to claim 5 in coatings, adhesives, textile coatings and finishes, leather and synthetic leather finishes.
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| CN106349448A (en) * | 2016-08-30 | 2017-01-25 | 孝感市易生新材料有限公司 | Biologic water-based polyurethane and preparation method thereof |
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| CN105924616A (en) * | 2016-07-05 | 2016-09-07 | 陕西科技大学 | Biomass-resource-modified water-based polyurethane emulsion and preparation method thereof |
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