CN113264857A - Epoxy vegetable oil-based polyol and preparation method thereof, epoxy vegetable oil-based hyperbranched polyurethane resin and application thereof - Google Patents
Epoxy vegetable oil-based polyol and preparation method thereof, epoxy vegetable oil-based hyperbranched polyurethane resin and application thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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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
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
- C08G18/387—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group in addition to a perfluoroalkyl group
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- 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
- C09D11/00—Inks
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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
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an epoxy vegetable oil-based polyol, a preparation method thereof, an epoxy vegetable oil-based hyperbranched polyurethane resin and application thereof. The invention utilizes the ring-opening reaction of the thioglycerol and the epoxidized vegetable oil under the action of the catalyst to prepare the epoxidized vegetable oil-based polyol, and the obtained epoxidized vegetable oil-based polyol has the advantage of high hydroxyl value and polyfunctionality. The invention also applies the obtained epoxy vegetable oil-based polyol to the preparation of epoxy vegetable oil-based hyperbranched polyurethane acrylate resin and epoxy vegetable oil-based hyperbranched polyurethane resin, and the obtained resin belongs to a high-content bio-based polymer, and the product is degradable and more accords with the concept of environmental protection. The invention can be widely applied to the fields of coatings, adhesives, printing ink, nail polish glue, adhesives and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an epoxy vegetable oil-based polyol, a preparation method thereof, an epoxy vegetable oil-based hyperbranched polyurethane resin and application thereof.
Background
The bio-based polyol can replace part of petroleum-based polyol to be used for preparing polyurethane. Vegetable oil-based polyols can be prepared from vegetable oils such as soybean oil, palm oil, cottonseed oil, sunflower oil and the like, and then used as raw materials for preparing polyurethane. The use of the vegetable oil-based polyol can reduce the dependence on petroleum resources, and meanwhile, the product is degradable and has little influence on the ecological environment.
In the technical field of high molecular materials, polyurethane resin is mainly a linear polymer. In some applications, the higher viscosity affects the practical application. Hyperbranched polymers differ significantly in their properties compared to linear polymers due to their structure, such as: (1) low viscosity. Hyperbranched polymers will have much lower viscosity under the same conditions than linear polymers of the same molecular weight. The reason is that the hyperbranched polymer has small molecular size, and molecular chains are not intertwined, so that the intermolecular interaction force is small, and the viscosity is low. (2) And (4) isomerization. The addition point of each monomer on the hyperbranched polymer is random, so that a large number of isomers can appear, and the number of the isomers can be increased along with the difference of the monomers and the increase of the molecular weight. The occurrence of isomers has a relevant influence on the structure and the performance of the polymer.
Due to the influence of the structure of the hyperbranched polyurethane resin, the hyperbranched polyurethane resin has the common advantages of hyperbranched polymers and polyurethane resin, such as: low viscosity, more active groups, easy performance regulation and control, and the like, thereby having important application in various fields.
The traditional hyperbranched polyurethane resin raw material is derived from petroleum-based products, and causes environmental pollution in the processes of mining, transportation and synthesis. Therefore, there is a need to develop green bio-based materials to replace traditional petroleum-based materials to overcome the problems inherent therein.
Disclosure of Invention
According to a first aspect of the present invention, there is provided an epoxidized vegetable oil-based polyol having the structural formula:
wherein R is1Is composed of
The epoxy vegetable oil-based polyol is prepared from the following raw materials in parts by weight: 50-70 parts of epoxy vegetable oil, 15-35 parts of thioglycerol, 0.5-3 parts of a catalyst and 15-35 parts of a solvent.
The structure of the epoxy vegetable oil is modified by selecting thioglycerol, and the reasons are as follows: the thioglycerol contains a sulfydryl group and can perform sulfydryl-epoxy reaction with the epoxy vegetable oil, so that the branched chain structure of the epoxy vegetable oil is increased, and the thioglycerol also contains two hydroxyl groups, so that the epoxy vegetable oil has more active groups for the next reaction, and the formation of the resin with the hyperbranched structure is facilitated.
In some embodiments, the epoxidized vegetable oil is one or a mixture of more than one of epoxidized soybean oil, epoxidized castor oil, epoxidized tung oil, epoxidized linseed oil, and epoxidized rapeseed oil; the epoxidized vegetable oil may be epoxidized palm oil, epoxidized cottonseed oil, epoxidized sunflower oil, or the like.
In some embodiments, the catalyst is at least one of lithium hydroxide (LiOH), sodium hydroxide (NaOH), and potassium hydroxide (KOH), and the amount of the catalyst is 1.0-3.6% of the total mass of the feedstock.
In some embodiments, the solvent is methanol, ethanol, Dimethylformamide (DMF), Tetrahydrofuran (THF), Dimethylsulfoxide (DMSO).
According to a second aspect of the present invention, there is provided a process for preparing the above epoxidized vegetable oil-based polyol, comprising the steps of:
mixing the epoxy vegetable oil and the thioglycerol, adding a catalyst and a solvent, and reacting for 4-12 hours at normal temperature to obtain the epoxy vegetable oil-thioglycerol.
In some embodiments, the product is also subjected to rotary evaporation after the reaction is complete, thereby removing the solvent.
According to a third aspect of the invention, an epoxy vegetable oil-based hyperbranched polyurethane acrylate resin is provided, which is prepared by the following method:
(1) reacting isocyanate with hydroxyl acrylate until the mass fraction of isocyanate groups in the charge amount reaches half of the theoretical value before the reaction starts to obtain an isocyanate semi-terminated intermediate;
(2) adding epoxy vegetable oil-based polyol into the isocyanate half-terminated intermediate, and reacting until the content of isocyanate groups is lower than 0.5% to obtain an epoxy vegetable oil-based hyperbranched polyurethane acrylate prepolymer;
(3) adding a photoinitiator into the epoxy vegetable oil-based hyperbranched polyurethane acrylate prepolymer to obtain the epoxy vegetable oil-based hyperbranched polyurethane acrylate resin.
The content of isocyanate groups in the epoxy vegetable oil-based hyperbranched polyurethane acrylate prepolymer is controlled to be lower than 0.5%, and the system basically has no isocyanate groups, so that on one hand, the toxicity of the resin is reduced, and on the other hand, the stability of the resin during storage is improved.
In some embodiments, the isocyanate is a compound containing two isocyanate groups (-NCO), including any one of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), p-phenylene diisocyanate (PPDI), cyclohexane dimethylene diisocyanate (HXDI); the hydroxyl acrylate is one or more of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA), and hydroxypropyl methacrylate (HPMA); the photoinitiator is a free radical photoinitiator and comprises 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1-hydroxycyclohexyl phenyl ketone (Irgacure-184) and a mixture of the components in a mass ratio of 1: 1 (Irgacure-1000), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (Irgacure-907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and 2,4, 6-trimethylbenzoyl phenylphosphonic acid ethyl ester (TPO-L).
When the isocyanate is isophorone diisocyanate and the hydroxyl acrylate is hydroxyethyl acrylate, the structural formula of the obtained epoxy vegetable oil-based hyperbranched polyurethane acrylate resin is as follows:
wherein R is
In some embodiments, the molar ratio of isocyanate to hydroxy acrylate is 1: (0.9-1.1).
According to a fourth aspect of the invention, an epoxy vegetable oil-based hyperbranched polyurethane resin is provided, wherein the epoxy vegetable oil-based hyperbranched polyurethane resin is obtained by uniformly mixing isocyanate, epoxy vegetable oil-based polyol and a catalyst, pouring the mixture into a silica gel mold, standing for a certain time, and completely curing.
In some embodiments, the catalyst is at least one of dibutyltin dilaurate, triethanolamine, bismuth naphthenate, cobalt octoate and triethylenediamine, and the amount of the catalyst is 0.05-0.2 wt% of the total mass of the reaction materials.
The invention leads the epoxy vegetable oil to have more active groups for reacting with isocyanate by introducing the thioglycerol, thereby forming a hyperbranched structure. The epoxy vegetable oil exists as a three-dimensional central 'nucleus' containing polyhydroxy functionality in the hyperbranched polyurethane resin in a triglyceride structure, and isocyanate reacts with hydroxyl by taking an isocyanate group as a reaction unit and is connected through chemical bonds to be gradually extended, so that the hyperbranched structure is formed.
According to a fifth aspect of the present invention, there is provided a use of the epoxy vegetable oil-based hyperbranched urethane acrylate resin described above in a coating, an adhesive, an ink, a nail polish glue or a binder.
According to a sixth aspect of the present invention, there is provided a use of the epoxy vegetable oil-based hyperbranched polyurethane resin described above in a coating, an adhesive, an ink, a nail polish glue or a binder.
The epoxy vegetable oil-based polyol is multifunctional polyol with high hydroxyl value, the functionality can reach twelve hydroxyl groups, the hydroxyl value can reach more than 400mgKOH/g, and rich active sites are provided for the next reaction. An increase in the hydroxyl number of the polyol increases the crosslinking density of the corresponding polyurethane, which in turn increases its tensile strength and decreases its elongation at break. The obtained polyalcohol can be used for preparing various polymers, all the obtained polymers are high-content bio-based polymers, petroleum-based raw materials are not used, the environmental pollution in the transportation and use processes is reduced, and the environment-friendly concept is better met.
The epoxy vegetable oil-based hyperbranched polyurethane acrylate resin prepared by the invention not only has the common advantages of hyperbranched polyurethane resin and acrylate resin, such as: the modified biomass modified polyester has the advantages of multiple active groups, low viscosity, easy performance regulation and control and the like, and the biomass content of the modified biomass modified polyester exceeds 50%, so that the modified biomass modified polyester belongs to a high-content bio-based polymer, is degradable, has little influence on the ecological environment, and better accords with the green environmental protection concept.
Drawings
FIG. 1 is a synthetic scheme of the preparation process of example 1 of the present invention.
FIG. 2 is a Fourier transform infrared spectrum of epoxidized soybean oil, thioglycerol, and epoxidized soybean oil-based polyol of example 1 of the present invention.
Fig. 3 is a fourier transform infrared spectrum of the epoxy soybean oil-based hyperbranched urethane acrylate prepolymer of example 8 of the present invention before and after reaction.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available.
Example 1
The preparation method of the epoxidized soybean oil-based polyol of the embodiment comprises the following steps:
adding 55g of epoxidized soybean oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of lithium hydroxide catalyst and 20g of ethanol, wherein the mass of the mixture is 3% of the total mass of the raw materials, reacting for 4 hours at normal temperature, and removing the ethanol from a crude product through rotary evaporation to obtain the epoxidized soybean oil-based polyol.
The synthetic scheme of the preparation method is shown in figure 1. As can be seen from fig. 1, three hydroxyl groups can be obtained by opening one ring of thioglycerol, and twelve hydroxyl groups can be obtained by opening four rings of epoxidized soybean oil by thioglycerol at a proper material ratio.
It is noted that under theoretical conditions the three chains of epoxidized soybean oil are identical in structure, with two epoxy groups per chain, for a total of six epoxy groups. However, the epoxidized soybean oil used in this example is a commercially available epoxidized soybean oil having two epoxy groups on one chain and only one epoxy group on each of the other two chains, for a total of only four epoxy groups. The Epoxidized Soybean Oil (ESO) structure shown in fig. 1 is that of a commercially available finished epoxidized soybean oil product.
Real-time NCO group synthesis process by Nicolet iS10 Fourier transform infrared spectrometer of Sammerfo corporationMonitoring and analyzing, wherein the scanning measurement range is 4000cm-1To 400cm-1The results are shown in FIG. 2.
As can be seen from figure 2, the product is an epoxidized soybean oil based polyol (noted as ESOP). Specifically, the method comprises the following steps:
it is clearly observed in the ESOP infrared image at 3381cm, compared to the epoxidized soybean oil (noted ESO) infrared image-1A sharper characteristic peak appears at the position, which is an-OH stretching vibration peak; 2924cm-1And 2860cm-1Are respectively-CH3and-CH2The stretching vibration peak of (1). 2555cm were observed in the infrared image of thioglycerol-1The characteristic absorption peak at S-H, which completely disappeared in the ESOP infrared image, confirms the completion of the reaction. Thus, the FT-IR results indicate that the product is an epoxidized soybean oil-based polyol.
Example 2
The preparation method of the epoxidized castor oil-based polyol of the embodiment includes the following steps:
adding 55g of epoxy castor oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of a catalyst lithium hydroxide with the total mass of 3% of the raw materials and 20g of ethanol, reacting for 4 hours at normal temperature, and removing the ethanol from a crude product through rotary evaporation to obtain the epoxy castor oil-based polyol.
NCO groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that of the example 1, and the product is determined to be the epoxy castor oil-based polyol by analysis. For economy of disclosure, further description is omitted here.
Example 3
The preparation method of the epoxy tung oil-based polyol comprises the following steps:
adding 55g of epoxy tung oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of a catalyst lithium hydroxide with the total mass of 3% of the raw materials and 20g of ethanol, reacting for 4 hours at normal temperature, and removing the ethanol from a crude product through rotary evaporation to obtain the epoxy tung oil-based polyol.
NCO groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that of the example 1, and the product is determined to be epoxy tung oil-based polyol by analysis. For economy of disclosure, further description is omitted here.
Example 4
The preparation method of the epoxidized soybean oil-based polyol of the embodiment comprises the following steps:
adding 55g of epoxidized soybean oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of sodium hydroxide catalyst and 20g of ethanol which are 3% of the total mass of the raw materials, reacting for 4 hours at normal temperature, and removing the ethanol from the crude product through rotary evaporation to obtain the epoxidized soybean oil-based polyol.
NCO groups in the synthesis process were monitored and analyzed in real time by the same analysis method as in example 1, and the product was determined to be epoxidized soybean oil-based polyol. For economy of disclosure, further description is omitted here.
Example 5
The preparation method of the epoxidized castor oil-based polyol of the embodiment includes the following steps:
adding 55g of epoxy castor oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of a catalyst sodium hydroxide and 20g of ethanol, wherein the mass of the catalyst sodium hydroxide is 3% of the total mass of the raw materials, reacting for 4 hours at normal temperature, and removing the ethanol from a crude product through rotary evaporation to obtain the epoxy castor oil-based polyol.
NCO groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that of the example 1, and the product is determined to be the epoxy castor oil-based polyol by analysis. For economy of disclosure, further description is omitted here.
Example 6
The preparation method of the epoxidized linseed oil based polyol of the present embodiment includes the following steps:
adding 55g of epoxy linseed oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of a catalyst lithium hydroxide with the total mass of 3% of the raw materials and 20g of ethanol, reacting for 4 hours at normal temperature, and removing the ethanol from a crude product through rotary evaporation to obtain the epoxy linseed oil-based polyol.
NCO groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that of the example 1, and the product is determined to be the epoxidized linseed oil based polyol through analysis. For economy of disclosure, further description is omitted here.
Example 7
The preparation method of the epoxy rapeseed oil-based polyol of the embodiment comprises the following steps:
adding 55g of epoxy rapeseed oil and 25g of thioglycerol into a 250mL three-neck flask, uniformly mixing, adding a mixture of a catalyst lithium hydroxide with the total mass of 3% of the raw materials and 20g of ethanol, reacting for 4 hours at normal temperature, and removing the ethanol from a crude product through rotary evaporation to obtain the epoxy rapeseed oil-based polyol.
NCO groups in the synthesis process were monitored and analyzed in real time by the same analysis method as in example 1, and the product was determined to be an epoxy rapeseed oil-based polyol. For economy of disclosure, further description is omitted here.
Example 8
The epoxy soybean oil-based hyperbranched polyurethane acrylate resin of the embodiment is prepared by the following specific steps:
(1) adding 33g of hydroxyethyl acrylate (HEA) and 33g of isophorone diisocyanate (IPDI) into a 250mL three-neck flask as raw materials, antioxidant hydroquinone accounting for 0.1% of the total mass of the raw materials and catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials, heating to 45 ℃ and reacting for 2 hours to obtain an isocyanate semi-terminated intermediate.
(2) And (2) adding 34g of epoxidized soybean oil-based polyol synthesized in the example 1 into the isocyanate half-terminated intermediate obtained in the step (1), heating to 75 ℃, and continuing to react for 3 hours until the content of isocyanate groups is lower than 0.5%, so as to obtain an epoxidized soybean oil-based hyperbranched polyurethane acrylate prepolymer.
(3) And (3) adding 95g of the epoxy soybean oil-based hyperbranched polyurethane acrylate prepolymer obtained in the step (2) and 5g of a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) into a 100mL single-neck flask, stirring for 20 minutes at 40 ℃ in the dark, defoaming and preparing a membrane after uniformly mixing, and initiating curing under the irradiation of UV light to obtain the UV light-cured epoxy soybean oil-based hyperbranched polyurethane acrylate resin.
By the Sammerfo companyThe Nicolet iS10 Fourier transform infrared spectrometer monitors and analyzes the characteristic groups in the synthesis process in real time, and the scanning measurement range iS 4000cm-1To 400cm-1The results are shown in FIG. 3.
As can be seen from the comparison of fig. 3, the product is epoxy soybean oil-based hyperbranched urethane acrylate (noted as espua). Specifically, the method comprises the following steps:
3433cm are clearly visible in the HEA-IPDI (before reaction) infrared image before reaction-1The characteristic peak appeared nearby is-OH stretching vibration peak, 2260cm-1The absorption peak is assigned to the characteristic peak of the-NCO group in IPDI. 3433cm after reaction of HEA and IPDI-1The hydroxyl peak disappeared. Continuing to add ESOP to participate in the reaction, 2260cm-1The disappearance of the-NCO absorption peak indicates the reaction of ESOP with HEA-IPDI. In the ESOPUA (post-reaction) spectrum, 3356cm-1And 1726cm-1The peaks are characteristic peaks of carbamate N-H and C ═ O respectively. Therefore, the FT-IR result shows that the product is epoxy soybean oil-based hyperbranched polyurethane acrylate.
Example 9
The epoxy castor oil based hyperbranched polyurethane acrylate resin of the embodiment is prepared by the following specific steps:
(1) 34g of hydroxyethyl methacrylate and 33g of Toluene Diisocyanate (TDI) are added into a 250mL three-neck flask as raw materials, a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials and an antioxidant 2, 6-di-tert-butyl-p-cresol (antioxidant 264) accounting for 0.1% of the total mass of the raw materials, and the temperature is raised to 45 ℃ to react for 2 hours, so that an isocyanate half-terminated intermediate is obtained.
(2) And (2) adding 33g of the epoxy castor oil-based polyol synthesized in the example 2 into the isocyanate half-terminated intermediate obtained in the step (1), heating to 75 ℃, and continuing to react for 3 hours until the content of isocyanate groups is lower than 0.5%, so as to obtain the epoxy castor oil-based hyperbranched polyurethane acrylate prepolymer.
(3) And (3) adding 95g of the epoxy castor oil based hyperbranched polyurethane acrylate prepolymer obtained in the step (2) and 5g of a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) into a 100mL single-neck flask, stirring for 20 minutes at 40 ℃ in the dark, defoaming and preparing a membrane after uniformly mixing, and initiating curing under the irradiation of UV light to obtain the UV light-cured epoxy castor oil based hyperbranched polyurethane acrylate resin.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that in the example 8, and the product is determined to be the epoxy castor oil based hyperbranched polyurethane acrylate resin after analysis. For economy of disclosure, further description is omitted here.
Example 10
The preparation method of the epoxy tung oil-based hyperbranched polyurethane resin of the embodiment comprises the following steps:
45g of Toluene Diisocyanate (TDI), 55g of the epoxy tung oil-based polyol synthesized in example 3 and a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials are added into a 250mL beaker, the mixture is uniformly stirred at normal temperature, the mixture is poured into a silica gel mold, and after the mixture is cured for 48 hours, the thermosetting epoxy tung oil-based hyperbranched polyurethane resin is obtained.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that of the example 8, and the product is determined to be epoxy tung oil based hyperbranched polyurethane resin after analysis. For economy of disclosure, further description is omitted here.
Example 11
The epoxy soybean oil-based hyperbranched polyurethane resin of the embodiment is prepared by the following specific method:
45g of Toluene Diisocyanate (TDI) and 55g of epoxidized soybean oil-based polyol synthesized in example 4 and a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials are added into a 250mL beaker, uniformly stirred at normal temperature, poured into a silica gel mold, and cured for 48 hours to obtain the thermosetting epoxidized soybean oil-based hyperbranched polyurethane resin.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that in the example 8, and the product is determined to be the epoxy soybean oil-based hyperbranched polyurethane resin after analysis. For economy of disclosure, further description is omitted here.
Example 12
The preparation method of the epoxy tung oil-based hyperbranched polyurethane acrylic resin of the embodiment comprises the following steps:
(1) 34g of hydroxypropyl acrylate and 33g of diphenylmethane diisocyanate (MDI) are added into a 250mL three-neck flask as raw materials, a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials and an antioxidant 2, 6-di-tert-butyl-p-cresol (antioxidant 264) accounting for 0.1% of the total mass of the raw materials, and the temperature is raised to 45 ℃ for reaction for 3 hours to obtain an isocyanate semi-terminated intermediate.
(2) And (2) adding 33g of epoxy tung oil-based polyol synthesized in the example 3 into the isocyanate half-terminated intermediate obtained in the step (1), heating to 75 ℃, and continuing to react for 3 hours until the content of isocyanate groups is lower than 0.5%, so as to obtain the epoxy tung oil-based hyperbranched polyurethane acrylate prepolymer.
(3) And (3) adding 95g of epoxy tung oil-based polyurethane acrylate prepolymer obtained in the step (2) and 5g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) into a 100mL single-neck flask, stirring for 20 minutes at 40 ℃ in the dark, defoaming and preparing a membrane after uniformly mixing, and initiating curing under the irradiation of UV light to obtain the UV light-cured epoxy tung oil-based hyperbranched polyurethane acrylic resin.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that of the example 8, and the product is determined to be the epoxy tung oil based hyperbranched polyurethane acrylate resin after analysis. For economy of disclosure, further description is omitted here.
Example 13
The epoxy soybean oil-based hyperbranched polyurethane acrylic resin of the embodiment is prepared by the following specific steps:
(1) 34g of hydroxypropyl methacrylate and 33g of isophorone diisocyanate (IPDI) are added into a 250mL three-neck flask as raw materials, a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials and an antioxidant 2, 6-di-tert-butyl-p-cresol (antioxidant 264) accounting for 0.1% of the total mass of the raw materials, and the temperature is increased to 45 ℃ to react for 3 hours, so that an isocyanate semi-terminated intermediate is obtained.
(2) And (2) adding 33g of epoxidized soybean oil-based polyol synthesized in the example 4 into the isocyanate half-terminated intermediate obtained in the step (1), heating to 75 ℃, and continuing to react for 3 hours until the content of isocyanate groups is lower than 0.5%, so as to obtain an epoxidized soybean oil-based hyperbranched polyurethane acrylate prepolymer.
(3) And (3) adding 95g of the epoxidized soybean oil-based polyurethane acrylate prepolymer obtained in the step (2) and 5g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) into a 100mL single-neck flask, stirring for 20 minutes at 40 ℃ in the dark, defoaming and preparing a membrane after uniformly mixing, and initiating curing under the irradiation of UV light to obtain the UV light-cured epoxidized soybean oil-based hyperbranched polyurethane acrylic resin.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that in the example 8, and the product is determined to be the epoxy soybean oil based hyperbranched polyurethane acrylate resin after analysis. For economy of disclosure, further description is omitted here.
Example 14
The epoxy castor oil based hyperbranched polyurethane acrylic resin of the embodiment is prepared by the following specific steps:
(1) 34g of hydroxyethyl acrylate and 33g of Hexamethylene Diisocyanate (HDI) are added into a 250mL three-neck flask as raw materials, a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials and an antioxidant 2, 6-di-tert-butyl-p-cresol (antioxidant 264) accounting for 0.1% of the total mass of the raw materials, and the temperature is increased to 45 ℃ to react for 3 hours, so that an isocyanate half-terminated intermediate is obtained.
(2) And (2) adding 33g of the epoxy castor oil-based polyol synthesized in the example 5 into the isocyanate half-terminated intermediate obtained in the step (1), heating to 75 ℃, and continuing to react for 3 hours until the content of isocyanate groups is lower than 0.5%, so as to obtain the epoxy castor oil-based hyperbranched polyurethane acrylate prepolymer.
(3) And (3) adding 95g of the epoxy castor oil-based polyurethane acrylate prepolymer obtained in the step (2) and 5g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) into a 100mL single-neck flask, stirring for 20 minutes in the dark at 40 ℃, defoaming and preparing a membrane after uniformly mixing, and initiating curing under the irradiation of UV light to obtain the UV light-cured epoxy castor oil-based hyperbranched polyurethane acrylic resin.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that in the example 8, and the product is determined to be the epoxy castor oil based hyperbranched polyurethane acrylate resin after analysis. For economy of disclosure, further description is omitted here.
Example 15
The epoxy soybean oil-based hyperbranched polyurethane acrylic resin of the embodiment is prepared by the following specific steps:
(1) 34g of hydroxyethyl acrylate and 33g of Toluene Diisocyanate (TDI) are added into a 250mL three-neck flask as raw materials, a catalyst dibutyltin dilaurate accounting for 0.1% of the total mass of the raw materials and antioxidant hydroquinone accounting for 0.1% of the total mass of the raw materials, and the temperature is increased to 45 ℃ to react for 3 hours, so that an isocyanate semi-terminated intermediate is obtained.
(2) And (2) adding 33g of epoxidized soybean oil-based polyol synthesized in the example 1 into the isocyanate half-terminated intermediate obtained in the step (1), heating to 75 ℃, and continuing to react for 3 hours until the content of isocyanate groups is lower than 0.5%, so as to obtain an epoxidized soybean oil-based hyperbranched polyurethane acrylate prepolymer.
(3) And (3) adding 95g of the epoxidized soybean oil-based polyurethane acrylate prepolymer obtained in the step (2) and 5g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) into a 100mL single-neck flask, stirring for 20 minutes at 40 ℃ in the dark, defoaming and preparing a membrane after uniformly mixing, and initiating curing under the irradiation of UV light to obtain the UV light-cured epoxidized soybean oil-based hyperbranched polyurethane acrylic resin.
The characteristic groups in the synthesis process are monitored and analyzed in real time by adopting the same analysis method as that in the example 8, and the product is determined to be the epoxy soybean oil based hyperbranched polyurethane acrylate resin after analysis. For economy of disclosure, further description is omitted here.
The properties of the epoxidized vegetable oil-based polyols obtained in examples 1 to 7 and the epoxidized vegetable oil-based hyperbranched polyurethane resins obtained in examples 8 to 11 were examined.
1. The epoxidized vegetable oil-based polyols prepared in examples 1 to 7 were subjected to hydroxyl content measurement according to the national standard HG/T2709-95 "determination of hydroxyl value in polyester polyol". The hydroxyl number content in the sample means the amount of the substance of the hydroxyl group contained in 100g of the resin. The hydroxyl value commonly used in industry is the number of milligrams of potassium hydroxide (KOH) corresponding to the hydroxyl group contained in 1g of the sample, and is usually expressed as mgKOH/g. The hydroxyl number of the present invention is the same as that commonly used in industry, and the test results are shown in table 1:
TABLE 1 results of hydroxyl number value test of examples 1 to 7
| Examples | mgKOH/g |
| Example 1 | 422.23 |
| Example 2 | 424.66 |
| Example 3 | 419.88 |
| Example 4 | 415.35 |
| Example 5 | 423.76 |
| Example 6 | 427.11 |
| Example 7 | 418.54 |
As can be seen from Table 1, the hydroxyl value of the epoxidized vegetable oil-based polyol can reach more than 400mgKOH/g, and the epoxidized vegetable oil-based polyol has rich active sites and is applied to the next reaction.
2. The epoxy vegetable oil-based hyperbranched polyurethane resins prepared in examples 8 to 11 were subjected to a bio-based content test and a mechanical property test.
(1) Testing the content of the bio-base: the mass fraction of the bio-based material in the sample, namely the mass fraction of the epoxy vegetable oil in the epoxy vegetable oil-based hyperbranched polyurethane resin, is defined as the national standard information public service platform approved program number 20171126-T-469.
(2) And (3) testing mechanical properties: the measurement is carried out by adopting a Shenzhen Sansi company UTM 5000 universal tester. The crosshead speed was 100mm/min and the sample specifications were 50mm long and 10mm wide, and the final tensile strength and elongation at break were obtained as an average of at least three parallel samples, and the test results are shown in table 2.
TABLE 2 results of resin Performance test of examples 8-11
| Examples | Biobased content (%) | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 8 | 52.78 | 39.5±0.61 | 32±2.3 |
| Example 9 | 53.11 | 35.2±0.42 | 40±3.3 |
| Example 10 | 55.61 | 35.3±0.37 | 44±4.3 |
| Example 11 | 55.13 | 33.8±0.26 | 47±6.2 |
According to general understanding in China at present, the biomass content is higher than 25% and belongs to biomass products, and as can be seen from table 2, the biomass content of the epoxy plant oil-based hyperbranched polyurethane resin prepared in examples 8-11 exceeds 50%, so that the epoxy plant oil-based hyperbranched polyurethane resin prepared by the invention belongs to high-content biomass polymers, and the product is degradable and better accords with the concept of green environmental protection.
As can be seen from Table 2, the epoxy vegetable oil-based hyperbranched polyurethane resins prepared in examples 8 to 11 all have tensile strengths of 33MPa or more, elongation at break of 30% or more, and good mechanical properties.
The epoxy vegetable oil-based hyperbranched polyurethane acrylic resin obtained in examples 12-15 is tested for bio-based content and mechanical properties, and the test results are similar to those of examples 8-9.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The epoxy vegetable oil-based polyol is characterized in that the structural formula is as follows:
wherein R is1Is composed of
2. The epoxidized vegetable oil-based polyol according to claim 1, which is prepared from the following raw materials in parts by weight: 50-70 parts of epoxy vegetable oil, 15-35 parts of thioglycerol, 0.5-3 parts of a catalyst and 15-35 parts of a solvent.
3. The epoxidized vegetable oil-based polyol of claim 2, wherein the epoxidized vegetable oil is one or a mixture of more than one of epoxidized soybean oil, epoxidized castor oil, epoxidized tung oil, epoxidized linseed oil and epoxidized rapeseed oil; the catalyst is at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide; the solvent is one or more of methanol, ethanol, dimethylformamide, tetrahydrofuran and dimethyl sulfoxide.
4. A process for the preparation of an epoxidized vegetable oil based polyol as claimed in any of claims 1 to 3 comprising the steps of:
mixing the epoxy vegetable oil and the thioglycerol, adding a catalyst and a solvent, and reacting for 4-12 hours at normal temperature to obtain the epoxy vegetable oil-thioglycerol.
5. The epoxy vegetable oil-based hyperbranched polyurethane acrylate resin is characterized by being prepared by the following method:
(1) reacting isocyanate with hydroxyl acrylate until the mass fraction of isocyanate groups in the charge amount reaches half of the theoretical value before the reaction starts to obtain an isocyanate semi-terminated intermediate;
(2) adding the epoxy vegetable oil-based polyol of any one of claims 1-3 into the isocyanate half-terminated intermediate, and reacting until the content of isocyanate groups is lower than 0.5% to obtain an epoxy vegetable oil-based hyperbranched polyurethane acrylate prepolymer;
(3) adding a photoinitiator into the epoxy vegetable oil-based hyperbranched polyurethane acrylate prepolymer to obtain the epoxy vegetable oil-based hyperbranched polyurethane acrylate resin.
6. The epoxy vegetable oil-based hyperbranched polyurethane acrylate resin according to claim 5, wherein the isocyanate is any one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, and cyclohexane dimethylene diisocyanate; the hydroxyl acrylate is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-hydroxycyclohexyl phenyl ketone, and the mass ratio is 1: 1, 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate or any mixture of a plurality of compounds.
7. The epoxy vegetable oil-based hyperbranched polyurethane resin is characterized in that the epoxy vegetable oil-based hyperbranched polyurethane resin is prepared by uniformly mixing isocyanate, the epoxy vegetable oil-based polyol as claimed in any one of claims 1 to 3 and a catalyst and completely curing the mixture.
8. The epoxy vegetable oil-based hyperbranched polyurethane resin as set forth in claim 7, wherein the catalyst is at least one of dibutyltin dilaurate, triethanolamine, bismuth naphthenate, cobalt octoate, and triethylenediamine.
9. Use of the epoxy vegetable oil-based hyperbranched urethane acrylate resin of claim 5 or 6 in coatings, adhesives, inks, nail polish glues or adhesives.
10. Use of the epoxy vegetable oil-based hyperbranched polyurethane resin of claim 7 or 8 in coatings, adhesives, inks, nail polish glues or adhesives.
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| CN117586464A (en) * | 2024-01-19 | 2024-02-23 | 上海富晨新材料有限公司 | Thickening ultrahigh-toughness vinyl ester resin composition, and preparation method and application thereof |
| CN117586464B (en) * | 2024-01-19 | 2024-04-12 | 上海富晨新材料有限公司 | Thickening ultrahigh-toughness vinyl ester resin composition, and preparation method and application thereof |
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