CN116102702A - Method for preparing castor oil-based polyurethane without solvent and catalyst and application thereof - Google Patents
Method for preparing castor oil-based polyurethane without solvent and catalyst and application thereof Download PDFInfo
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- CN116102702A CN116102702A CN202310119648.XA CN202310119648A CN116102702A CN 116102702 A CN116102702 A CN 116102702A CN 202310119648 A CN202310119648 A CN 202310119648A CN 116102702 A CN116102702 A CN 116102702A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a solvent-free and catalyst-free method for preparing castor oil-based polyurethane and application thereof. The method comprises the following steps: carrying out a sulfhydryl olefin click reaction on a mixed reaction system containing castor oil, monothioglycolate and 2-hydroxy-2, 2-dimethyl acetophenone to prepare monothioglycolate modified castor oil-based polyol; and curing the glyceryl monothioglycolate modified castor oil-based polyol with isocyanate to obtain the castor oil-based polyurethane. The castor oil-based polyurethane prepared by the invention has tensile modulus of 827-1476MPa, tensile strength of 51-83MPa, elongation at break of 5-19%, and good gel content, pencil hardness, transverse cutting adhesion and optical performance.
Description
Technical Field
The invention belongs to the technical field of bio-based polymer materials, and particularly relates to a solvent-free and catalyst-free method for preparing castor oil-based polyurethane and application thereof.
Background
Concerns over shortage of fossil resources and rising prices have led to the search for renewable alternatives, and the importance of many widely available sustainable biomass resources, such as lignin, cellulose, hemicellulose, vegetable oils, starches and proteins, has increased. Vegetable oils are one of the most important biomass resources, and have received much attention due to their availability, sustainability, low toxicity, competitive costs, and potential for chemical modification.
Polyurethane is one of the most common polymers and is widely used in the fields of wear, construction, automobiles, aerospace and the like. Polyols are an indispensable raw material in the industrial production of polyurethanes, mainly from non-renewable fossil raw materials. The inedibility of castor oil makes it suitable as a biomass feedstock for large-scale industrial production, and its unique hydroxyl structure makes it possible to synthesize sustainable polyurethanes as biobased polyols without additional modification.
At present, the utilization of castor oil has some problems, namely, firstly, the content of hydroxyl groups is smaller, and finally, the obtained polyurethane has weaker performance and is difficult to utilize; secondly, in the process of introducing more hydroxyl groups by modification, the reaction process is complex and low-efficiency and is accompanied by the generation of byproducts.
Disclosure of Invention
The invention mainly aims to provide a solvent-free and catalyst-free method for preparing castor oil-based polyurethane and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a solvent-free and catalyst-free method for preparing castor oil-based polyurethane, which comprises the following steps:
carrying out a sulfhydryl olefin click reaction on a mixed reaction system containing castor oil, monothioglycolate and 2-hydroxy-2, 2-dimethyl acetophenone to prepare monothioglycolate modified castor oil-based polyol;
and curing the glyceryl monothioglycolate modified castor oil-based polyol with isocyanate to obtain the castor oil-based polyurethane.
The embodiment of the invention also provides the castor oil-based polyurethane prepared by the method, wherein the tensile modulus of the castor oil-based polyurethane is 827-1476MPa, the tensile strength of the castor oil-based polyurethane is 51-83MPa, and the elongation at break is 5-19%.
The embodiment of the invention also provides application of the castor oil-based polyurethane in preparing paint or adhesive.
The embodiment of the invention also provides a polyurethane coating which at least comprises the castor oil-based polyurethane.
Compared with the prior art, the invention has the beneficial effects that:
(1) The thioglycollic acid glyceride modified castor oil-based polyol provided by the invention is prepared by a thioolefine click reaction at low temperature under the condition of no solvent, has very high double bond conversion rate and conversion efficiency, and can obtain the thioglycollic acid glyceride modified castor oil-based polyol with the hydroxyl value of up to 463mg KOH/g;
(2) The castor oil-based polyurethane is obtained by reaction under the condition of no solvent and no catalyst, and the reaction is more green;
(3) The castor oil-based polyurethane has uniform appearance, good coating performance, high optical performance, good crosslinking density and tensile strength, and is suitable for the fields of preparing paint, adhesive and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic representation of the synthesis of a glycerol monothioglycolate modified castor oil-based polyol in an exemplary embodiment of the present invention;
FIG. 2 is a graph of tensile properties of castor oil-based polyurethanes prepared in examples 2-4 and comparative examples 1, 2 of the present invention.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the method for preparing castor oil-based polyurethane without solvent and catalyst comprises the following steps:
carrying out a sulfhydryl olefin click reaction on a mixed reaction system containing castor oil, monothioglycolate and 2-hydroxy-2, 2-dimethyl acetophenone to prepare monothioglycolate modified castor oil-based polyol;
and curing the glyceryl monothioglycolate modified castor oil-based polyol with isocyanate to obtain the castor oil-based polyurethane.
The synthetic schematic of the glycerol monothioglycolate modified castor oil-based polyol in the invention is shown in figure 1.
In some preferred embodiments, the method specifically comprises: castor oil, monothioglycolate and 2-hydroxy-2, 2-dimethyl acetophenone are mixed to form the mixed reaction system, and a sulfhydryl olefin clicking reaction is carried out at the temperature of-5 to 10 ℃ to prepare the castor oil-based polyol.
Further, the molar ratio of the castor oil to the gycerine monothioglycolate is 1:2-1:3.
Further, the molar ratio of the monothioglycollic glyceride to the 2-hydroxy-2, 2-dimethyl acetophenone is 2:0.05-3:0.05.
In some preferred embodiments, the method specifically comprises: mixing the monothioglycolate modified castor oil-based polyol with isocyanate, stirring at 50-70 ℃ for pre-reaction, and then heating to 80-100 ℃ for reaction for 1-2h to obtain the castor oil-based polyurethane; wherein the pre-reaction at least renders the obtained product in a transparent state.
Further, the isocyanate includes any one or a combination of two or more of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, toluene diisocyanate, and dicyclohexyl diisocyanate, and is not limited thereto.
Further, the molar ratio of hydroxyl in the isocyanate to hydroxyl in the monothioglycolate modified castor oil-based polyol is 1:0.6-1:1.
In some preferred embodiments, the method further comprises: and after the mercapto olefin clicking reaction is finished, diluting, washing, extracting, drying and evaporating the obtained product to obtain the monothiol glyceryl acetate modified castor oil-based polyol.
In some more specific embodiments, the solvent-free, catalyst-free process for preparing castor oil-based polyurethane comprises:
(1) 1mol castor oil, 2-3mol gycerine monothioglycolate, 0.05mol 2-hydroxy-2, 2-dimethyl acetophenone were mixed in a 250ml conical flask; magnetic stirring at a rotation speed of 300r/min, and irradiating with 365nm ultraviolet lamp of 50W at-5deg.C to 10deg.C for 1-2 hr;
(2) Diluting the reaction product obtained in the step (1) with ethyl acetate, washing 3 times with saturated NaCl solution, washing 2 times with deionized water, extracting the obtained organic layer with anhydrous Na 2 SO 4 Drying, filtering, and removing residual ethyl acetate by rotary evaporation at 70 ℃ to obtain the gycerine monothioglycolate modified castor oil-based polyol;
(3) Mixing the monothioglycolate modified castor oil-based polyol and isocyanate according to the dosage ratio of 1mol to (0.6-1) mol of hydroxyl and isocyanate under the condition of no solvent, stirring and pre-reacting at 70 ℃ to a transparent state, taking out a transparent sample, and curing at 100 ℃ for 1-2 hours to obtain the thermocuring castor oil-based polyurethane.
According to the invention, through solvent-free mercapto-olefin click reaction, 2-hydroxy-2, 2-dimethyl acetophenone is used as a photoinitiator, and the monothioglycolate modified castor oil polyol is easily synthesized at a low temperature, and the hydroxyl value of the monothioglycolate polyol is up to 463mg KOH/g. The crosslinked polyurethane is constructed by the reaction of a gycerine monothioglycolate modified castor oil polyol and an isocyanate.
In order to produce high-performance castor oil-based polyurethane, the castor oil-based polyol modified by monothioglycolate is synthesized at low temperature by taking 2-hydroxy-2, 2-dimethyl acetophenone as a photoinitiator through solvent-free mercapto-olefin click reaction, the hydroxyl value of the castor oil-based polyol is up to 463mg KOH/g, and no by-product is generated in the synthesis process, so that the castor oil-based polyurethane is more environment-friendly. The crosslinked polyurethane is constructed by the reaction of a gycerine monothioglycolate modified castor oil polyol and an isocyanate. The polyurethane is extremely excellent, and has better mechanical property, coating property and optical property, thus greatly expanding the application and prospect of castor oil-based polyurethane.
In another aspect of the embodiment of the invention, the castor oil-based polyurethane prepared by the method has a tensile modulus of 827-1476MPa, a tensile strength of 51-83MPa and an elongation at break of 5-19%.
Further, the castor oil-based polyurethane has a gel content of 90-97wt%, a pencil hardness of 4H-5H, a transverse adhesive force of 3B-4B, a haze value of 1.06-2.61, a light transmittance of 90.06-91.38, and a yellowness value of 1.84-2.01.
Another aspect of embodiments of the present invention also provides the use of the castor oil-based polyurethane described above in the preparation of a coating or adhesive.
Another aspect of embodiments of the present invention also provides a polyurethane coating comprising at least the castor oil-based polyurethane described above.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
The preparation process of the monothioglycolate modified castor oil-based polyol of the embodiment is as follows:
100g of castor oil (denoted as CO), 159g of gyceryl monothioglycolate, 2g of 2-hydroxy-2, 2-dimethyl acetophenone were mixed in 500ml conical flasks; the magnetic stirring speed was 300r/min, and then the transparent homogeneous mixture was irradiated with ultraviolet light of 365nm at 50W at-5℃for 1.5 hours to yellowish. The reaction product was diluted with ethyl acetate, washed 3 times with saturated NaCl solution, washed 2 times with deionized water, and the extracted organic layer was dried with anhydrous NaSO4 and filtered. Finally, removing residual ethyl acetate by a rotary evaporation method at 70 ℃ to obtain the gycerine monothioglycolate modified castor oil-based polyol. The hydroxyl number of the glycerol monothioglycolate modified castor oil-based polyol (recorded as TCO) prepared in this example was 463mg KOH/g.
Example 2
TCO was prepared as in example 1, using isophorone diisocyanate (designated as IPDI) as a curing agent, mixing the above castor oil-based polyol with isocyanate in a ratio of 1 mol:0.6 mol of hydroxyl and isocyanate in the absence of solvent, stirring at 70℃until a transparent state was exhibited, taking out a sample in the transparent state, and curing at 100℃for 1-2 hours to obtain a heat-cured castor oil-based polyurethane (designated as TCO-IPDI-0.6).
TCO-IPDI-0.6 was cut into dumbbell tensile bars using International Standard ISO 527-1:2012, it was found by testing with a universal style stretcher that TCO-IPDI-0.6 had a modulus of 1104MPa, a tensile strength of 56MPa, and an elongation at break of 9%.
The TCO-IPDI-0.6 is used as a coating film, and the optical properties of the film are tested by an ultraviolet visible near infrared spectrophotometer and an UltraScan VIS spectrophotometer to obtain the film with a haze value of 2.61, a transmittance of 90.89 and a yellowness value of 2.01.
Example 3
The preparation method is as in example 2, wherein the ratio of the gyceryl monothioglycolate modified castor oil based polyol to the isophorone diisocyanate is replaced by 1mol to 0.8mol according to the ratio of hydroxyl groups to isocyanate groups, and each property of the gyceryl monothioglycolate modified castor oil based polyol is tested by the same method, and the TCO-IPDI-0.8 has a modulus of 1217MPa, a tensile strength of 72MPa and an elongation at break of 10%. The haze value was 1.72, transmittance was 91.36%, and yellowness value was 1.93.
Example 4
The preparation method is carried out according to the preparation method of the example 2, wherein the single-thioglycollic acid glyceride modified castor oil-based polyol and the isophorone diisocyanate are replaced by 1mol to 1mol according to the proportion of hydroxyl groups and isocyanato groups, and each property of the single-thioglycollic acid glyceride modified castor oil-based polyol is tested by the same method, and the TCO-IPDI-1.0 has the modulus of 1459MPa, the tensile strength of 83MPa and the elongation at break of 12 percent. The haze value was 1.06, the transmittance was 91.68%, and the yellowness value was 1.72.
The reason for the improved properties after processing of this ratio is that the crosslink density is increased and the properties are improved accordingly.
Example 5
The preparation was carried out according to example 2, wherein the gyceryl monothioglycolate modified castor oil based polyol and Hexamethylene Diisocyanate (HDI) were tested in the same manner as above in a ratio of 1 mol:1 mol of hydroxyl groups to isocyanate groups, and the TCO-HDI-1.0 was found to have a modulus of 827MPa, a tensile strength of 51MPa and an elongation at break of 19%. The haze value was 2.37, transmittance was 90.06%, and yellowness value was 1.94.
Example 6
The preparation was carried out according to example 2, wherein the gyceryl monothioglycolate modified castor oil based polyol and Toluene Diisocyanate (TDI) were tested in the same manner as above in a ratio of hydroxyl groups to isocyanate groups of 1 mol:1 mol, and the TCO-TDI-1.0 was found to have a modulus of 1124MPa, a tensile strength of 66MPa and an elongation at break of 5%. The haze value was 1.92, the transmittance was 90.65%, and the yellowness value was 1.88.
Example 7
The preparation was carried out according to example 2, wherein the gyceryl monothioglycolate modified castor oil based polyol and dicyclohexylmethane diisocyanate (HMDI) were tested in the same manner as above in a ratio of hydroxyl groups to isocyanate groups of 1 mol:1 mol, and the TCO-HMDI-1.0 was found to have a modulus of 1476MPa, a tensile strength of 79MPa and an elongation at break of 10%. The haze value was 1.09, the transmittance was 90.93%, and the yellowness value was 1.86.
Example 8
The preparation was carried out according to example 2, wherein the gyceryl monothioglycolate modified castor oil based polyol and diphenylmethane diisocyanate (MDI) were replaced by 1 mol:1 mol in terms of the ratio of hydroxyl groups to isocyanate groups, and the properties thereof were tested in the same manner as above, and it was found that TCO-MDI-1.0 had a modulus of 1224MPa, a tensile strength of 72MPa and an elongation at break of 6%. The haze value was 1.22, transmittance was 91.02%, and yellowness value was 1.85.
Comparative example 1
According to the preparation method of example 4, raw castor oil and isocyanate are mixed according to the ratio of 1mol to 1mol of hydroxyl and isocyanate under the condition of no solvent, stirred at 70 ℃ until the castor oil and isocyanate are in a transparent state, a sample in the transparent state is taken out, and the castor oil-based polyurethane (recorded as CO-IPDI) is obtained after curing for 1 to 2 hours at 100 ℃.
Comparative example 2
The epoxidized soybean oil is taken as a raw material, PEG-600 ring-opened epoxy groups are used for obtaining soybean oil-based polyol PSO, the soybean oil-based polyol and isocyanate are mixed according to the proportion of 1mol to 1mol of hydroxyl and isocyanate under the condition of no solvent, the mixture is stirred at 70 ℃ until the mixture is in a transparent state, a sample in the transparent state is taken out, and the sample is cured at 100 ℃ for 1 to 2 hours, so that the epoxidized soybean oil-based polyurethane (marked as PSO-IPDI) is obtained.
1. Test method
The mechanical property testing method comprises the following steps: the samples were tested using British Instron Universal Testing Machine (No. 5567) and the sample size was 20.0mm (length) by 5.0mm (width) by 0.4mm (thickness) with a crosshead speed of 100.00mm/min. For accuracy, 5 measurements were made for each sample and averaged.
The pencil hardness testing method comprises the following steps: the pencil hardness of the sample was measured by the national standard GB/T6739-2006 method (hardness scale range 7B-HB-7H, where 7H is the hardest and 7B is the softest). The specific operation is as follows: the pencil hardness tester is used for testing, the included angle between the pencil and the surface of the sample is 45 degrees, the tester is used for sliding on the surface of the sample with a force with the pressure of 1+/-0.05 kg, the damage condition of the sample is observed, when the pencil is damaged for not more than 2 times in 5 times of tests, the pencil with the hardness of a large level is replaced for testing, when the damage of the sample exceeds 2 times, the pencil level at the moment can be read, and the next level of the pencil level can be recorded. For accuracy, three measurements were made for each sample and averaged.
Transverse cut adhesion test method: the adhesion of the samples was determined using national standard GB/T9286-98. The specific operation is as follows: the above procedure was repeated on the cut cuts by rotating the blade by 90 ° using a QFH-a paint film scriber at a uniform pressure on the coating layer so that the cutter blade cut at a speed of 20-50mm/s on the surface of the coating layer, and the paint film was peeled off vertically using a standard 3M tape, and the percentage of the number of small cells stuck by the tape to the total number of cells was calculated (the test result was 5B-0B in terms of percentage). For accuracy, three measurement runs were made at three different positions for each paint film.
Gel content testing method: weighing a proper amount of sample at 70 ℃ and placing the sample in a Soxhlet extractor for refluxing for 24 hours, taking out the sample, placing the sample in a vacuum drying oven at 70 ℃ for drying to constant weight, and recording the mass m of the sample before soaking 0 And mass m after drying 1 . The gel fraction was calculated according to the following formula:
for the sake of accuracy, three samples were run for each sampleSecondary measurements and averages were taken.
The optical performance testing method comprises the following steps: haze and yellowness were measured at an observation angle of 10 ° using an UltraScan VIS spectrophotometer, using a standard D65 light source according to CIE (international society of illumination) requirements; the transmittance was measured in transmission mode using a Lambda 950 spectrometer for castor oil-based polyurethane films having a thickness of about 150 μm in the range of 300-800 nm.
2. Test results
The results of the comprehensive performance tests of the polyurethanes prepared in examples 2 to 8 and comparative examples 1 and 2 are shown in Table 1, and FIG. 2 is a graph showing the tensile properties of the castor oil-based polyurethanes prepared in examples 2 to 4 and comparative examples 1 and 2;
TABLE 1 results of the test for the comprehensive properties of the polyurethanes prepared in examples 2 to 8, comparative example 1, comparative example 2
As can be seen from Table 1, the castor oil-based polyurethane prepared by the invention has tensile strength of up to 83MPa and Young's modulus of 1476MPa, and has better mechanical properties compared with the original castor oil; the hardness grade of the pencil is 4H-5H, and the hardness is high; the gel content is 90-97%, the gel rate is good, and the crosslinking density is high; the adhesive force is 3B-4B, and the adhesive force is better; meanwhile, the glass has better optical performance, the haze value is 1.06-2.61, the transmittance is 90.06-91.68, and the yellowness value is 1.84-2.01.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. A solvent-free, catalyst-free process for preparing castor oil-based polyurethane comprising:
carrying out a sulfhydryl olefin click reaction on a mixed reaction system containing castor oil, monothioglycolate and 2-hydroxy-2, 2-dimethyl acetophenone to prepare monothioglycolate modified castor oil-based polyol;
and curing the glyceryl monothioglycolate modified castor oil-based polyol with isocyanate to obtain the castor oil-based polyurethane.
2. The method according to claim 1, characterized in that it comprises in particular: castor oil, monothioglycolate and 2-hydroxy-2, 2-dimethyl acetophenone are mixed to form the mixed reaction system, and a sulfhydryl olefin clicking reaction is carried out at the temperature of-5 to 10 ℃ to prepare the castor oil-based polyol.
3. The method according to claim 2, characterized in that: the mol ratio of the castor oil to the monothioglycolate is 1:2-1:3;
and/or the molar ratio of the gycerine monothioglycolate to the 2-hydroxy-2, 2-dimethyl acetophenone is 2:0.05-3:0.05.
4. The method according to claim 1, characterized in that it comprises in particular: mixing the monothioglycolate modified castor oil-based polyol with isocyanate, stirring at 50-70 ℃ for pre-reaction, and then heating to 80-100 ℃ for reaction for 1-2h to obtain the castor oil-based polyurethane; wherein the pre-reaction at least renders the obtained product in a transparent state.
5. The method according to claim 4, wherein: the isocyanate comprises any one or more than two of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, toluene diisocyanate and dicyclohexyl diisocyanate.
6. The method according to claim 4, wherein: the molar ratio of the hydroxyl in the isocyanate to the hydroxyl in the glyceryl monothioglycolate modified castor oil-based polyol is 1:0.6-1:1.
7. The method as recited in claim 1, further comprising: and after the mercapto olefin clicking reaction is finished, diluting, washing, extracting, drying and evaporating the obtained product to obtain the monothiol glyceryl acetate modified castor oil-based polyol.
8. A castor oil-based polyurethane prepared by the process of any one of claims 1-7, having a tensile modulus of 827-1476MPa, a tensile strength of 51-83MPa, and an elongation at break of 5-19%;
preferably, the castor oil-based polyurethane has a gel content of 90-97wt%, a pencil hardness of 4H-5H, a transverse adhesion of 3B-4B, a haze value of 1.06-2.61, a light transmittance of 90.06-91.38, and a yellowness value of 1.84-2.01.
9. Use of the castor oil-based polyurethane of claim 8 for the preparation of a coating or binder.
10. A polyurethane coating comprising at least the castor oil-based polyurethane of claim 8.
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| CN116875163A (en) * | 2023-07-25 | 2023-10-13 | 上海灿达建材科技有限公司 | Weather-resistant high-hardness high-film-thickness solvent-free polyurethane coating and preparation method thereof |
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| CN116875163A (en) * | 2023-07-25 | 2023-10-13 | 上海灿达建材科技有限公司 | Weather-resistant high-hardness high-film-thickness solvent-free polyurethane coating and preparation method thereof |
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