CN104910335A - Lignin-based epoxy acrylate resin and preparation method thereof - Google Patents
Lignin-based epoxy acrylate resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lignin-based epoxy acrylate resin and a preparation method thereof, and belongs to the field of the synthesis of a high polymer material and an application thereof. The method comprises the steps of adding a lignin and an epoxy resin into a solvent to generate the lignin-based epoxy acrylate resin, and then adding an acrylic monitor to react to generate the lignin-based epoxy acrylate resin, and finally adding diluents to cure and form the lignin-based epoxy acrylate resin through catalysis or photo-initiation. The invention further provides the lignin-based epoxy acrylate resin. According to the lignin-based epoxy acrylate resin provided by the invention, natural high polymer lignin can be introduced into the epoxy acrylate resin through chemical reaction; furthermore, the lignin has three-dimensional network natural polymers with excellent mechanical property, heat stability and certain biodegradability, therefore the mechanical property and the flame resistance of the prepared environmental-protection lignin-based epoxy acrylate resin can be improved well.
Description
Technical field
The invention belongs to synthesis of polymer material and Application Areas thereof, be specifically related to a kind of lignin-base Epocryl and preparation method thereof.
Background technology
Xylogen (Lignin) is the renewable resources that on the earth, a kind of reserves are very abundant, and output is large, and reproduction speed is fast, biodegradable, is that content is only second to cellulosic abundant natural macromolecular organism.It is the three-dimensional netted polymer substance be formed by connecting by carbon one carbon bond (C-C) and ehter bond (-O-) by phenylpropyl alcohol alkyl structure unit, is complicated aromatic polymer.Due to its aromatic nature, side switch ALIPHATIC feature and various function base, xylogen can become energy substance as oil and important industrial chemicals.Xylogen is the byproduct of pulp and paper industry, effectively utilizes xylogen, alleviates environmental pollution on the one hand, is conducive to further improvement, develops renewable resources on the other hand, solves the waste problem of resource.
Epoxy acrylate (EA) is current most widely used general, Photocurable oligomers that consumption is maximum, be by epoxy resin and acrylic or methacrylic Esterification and obtained.The essentially consist of Epocryl comprises epoxy resin (bisphenol A-type, bisphenol-f type, phenol aldehyde type etc.), unsaturated monoprotic acid (as: vinylformic acid, methacrylic acid etc.), linking agent, properties-correcting agent etc.Epocryl has the good characteristic of epoxy resin, but solidified nature and formability aspect more outstanding, loaded down with trivial details unlike epoxy resin, be a kind of heat-curing resin.The synthesis of EA just has patent report as far back as the 1950's, the advantages such as curing speed is fast, bonding strength is large, hardness is high, glossiness is high, chemical proofing, water tolerance that it has, but also there is the shortcomings such as flame retardant properties is poor.
EA just can be cured by organic peroxide curing method (hypo-hyperthermia) or photocuring processes, be widely used in: corrosion resistant fiber strengthens composite plastic (FRP) goods, as glass fibre reinforced plastic groove tank, pipeline, tower and corrosion-resistant grid etc.; Anticorrosion engineering, as cement based or iron based glasses Leak-tight liner, highly corrosion resistant terrace; High-strength FRP, such as: pulling and extruding glass fiber section bar, sports goods, FRP ships and light boats etc.; Heavy antisepsis glass-flake coating; Other are as UV ink, heavy antisepsis industry ground slab etc.See Sun Xingping, Wang Dehai. the progress of epoxy acrylic Lipase absobed and application. coatings industry, 2007,11 (37): 53-60.Xylogen is not introduced the report of epoxy acrylic resin aspect in prior art.
Summary of the invention
The object of this invention is to provide a kind of lignin-base Epocryl and preparation method thereof, this lignin-base Epocryl has excellent mechanical property and flame retardant properties.
The invention provides a kind of preparation method of lignin-base Epocryl, comprising:
Step one: xylogen, epoxy resin and DMF are reacted, obtains Lignin-based epoxy resin;
Step 2: Lignin-based epoxy resin step one obtained, stopper, catalyzer and acrylic monomer react, and obtain lignin-base epoxy acrylate;
Step 3: lignin-base epoxy acrylate step 2 obtained and mixing diluents, obtains lignin-base epoxy acrylate mixed system;
Step 4: lignin-base epoxy acrylate mixed system curing molding step 3 obtained, obtains lignin-base Epocryl.
Preferably, described xylogen is organic solvent xylogen or sulfonate xylogen.
Preferably, described acrylic monomer is acrylic or methacrylic acid.
Preferably, in described step one, the mass ratio of xylogen and epoxy resin is (6-24): (96-114).
Preferably, the temperature of reaction of described step one is 80-120 DEG C, and the reaction times is 1-8h.
Preferably, in described step 2, Lignin-based epoxy resin and vinylformic acid mol ratio are 1:(1-2).
Preferably, described step 2 temperature of reaction is 80-100 DEG C, and the reaction times is 1-4h.
Preferably, thinner in described step 3 is selected from vinylbenzene, Hydroxyethyl acrylate, lauric acid acrylate, poly(oxyethylene glycol) 400 diacrylate, Viscoat 295, 1, 6 hexanediyl esters, isobornyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, octadecyl acrylate, three ring propoxylated glycerol triacrylates, methyl propenoic acid glycidyl ether, tricarboxylic trimethylolpropane tetra-acrylate, Dipentaerythritol Pentaacrylate, 4-hydroxy butyl vinyl ether, methoxy poly (ethylene glycol) monomethacrylates, one or more in aliphatic monoacrylate or acrylated phosphate.
Preferably, described step 4 be cured as thermofixation or photocuring.
The lignin-base Epocryl that the present invention also provides above-mentioned preparation method to obtain.
Beneficial effect of the present invention
The invention provides a kind of preparation method of lignin-base Epocryl, xylogen and epoxy resin are first joined reaction in a small amount of DMF solvent and generate Lignin-based epoxy resin by the method, then add acrylic monomer to carry out reaction and generate lignin-base Epocryl, finally add thinner through catalysis or light-initiated after fixing shaping.Compare with prior art, xylogen and epoxy resin directly react by the present invention, the lignin-base Epocryl react with acrylic monomer further, not through purifying or modification, this preparation method is simple, cost is low, preparing has good over-all properties.
The present invention also provides a kind of lignin-base Epocryl, this lignin-base Epocryl is incorporated in Epocryl by natural polymer xylogen by chemical reaction, because xylogen is the three-dimensional netted natural polymer with excellent mechanical property, thermostability and certain biodegradability, mechanical property and the flame retardant properties of the environmental protection lignin-base Epocryl obtained obtain good improvement.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the Lignin-based epoxy resin that obtains of comparative example 1 and embodiment 1-3 and lignin-base epoxy acrylate;
Fig. 2 is the graphic representation that the oxirane value of the Lignin-based epoxy resin that embodiment 1 and embodiment 3 obtain changed with xylogen and epoxy resin reaction times.
Embodiment
The invention provides a kind of preparation method of lignin-base Epocryl, comprising:
Step one: xylogen, epoxy resin and DMF (DMF) are reacted, obtains Lignin-based epoxy resin;
Step 2: Lignin-based epoxy resin step one obtained, stopper, catalyzer and acrylic monomer react, and obtain lignin-base epoxy acrylate;
Step 3: lignin-base epoxy acrylate step 2 obtained and thinner (reactive monomer) mixing, obtain lignin-base epoxy acrylate mixed system;
Step 4: lignin-base epoxy acrylate mixed system curing molding step 3 obtained, obtains lignin-base Epocryl.
According to the present invention, first by xylogen and epoxy resin mixing, then add solvent DMF (DMF) mixing, obtain mixture and preferably at 80-120 DEG C, react 1-8h, obtain Lignin-based epoxy resin; Described xylogen is preferably organic solvent xylogen or sulfonate xylogen; Described temperature of reaction is relevant with the content of xylogen according to the kind of xylogen with the time, and when xylogen is organic solvent xylogen, when content of lignin is 20%, temperature of reaction is 80-90 DEG C, and the reaction times is 1-2h; When content of lignin is 10-15%, at 80-90 DEG C of reaction 1-2h, then temperature is risen to 100-110 DEG C, reaction 1-2h; When content of lignin is less than 10%, at 80-90 DEG C of reaction 1-2h, then temperature is risen to 100-110 DEG C, reaction 1-2h, continues temperature to rise to 110-120 DEG C, reaction 2-4h; When xylogen is sulfonate xylogen, content of lignin can reach 20%, and xylogen and epoxy resin react 1-2h at 80-90 DEG C, then temperature is risen to 100-110 DEG C, and reaction 1-2h, continues temperature to rise to 110-120 DEG C, reaction 2-4h; Described epoxy resin kind is not particularly limited, namely commercially available epoxy resin, and the viscosity of preferred epoxy is at below 10.0Pas, and viscosity is too high, cannot stirring reaction even, easily occur crosslinked.Described xylogen and the mass ratio of epoxy resin are preferably (6-24): (96-114); Described is not particularly limited the amount of solvent, can dissolved lignin and epoxy resin.
According to the present invention, the Lignin-based epoxy resin obtained, stopper, catalyzer and acrylic monomer are preferably reacted 1-4h at 80-100 DEG C, obtain lignin-base epoxy acrylate; Described acrylic monomer is preferably acrylic or methacrylic acid, and Lignin-based epoxy resin and acrylic monomer mol ratio are preferably 1:(1-2); Described stopper is preferably Resorcinol, para hydroxybenzene methane, 2,5-dimethyl Resorcinol or 2,6-di-t-butyl to phenyl methylcarbamate, and the add-on of stopper is preferably the 0.01-1% of total system; Catalyzer is preferably Tetrabutylammonium bromide, pyridine, xylidene(s), triethylamine, diethylamine, N, N-dimethyl benzylamine, trimethyl benzyl ammonia chloride, triphenyl phosphorus, antimony triphenyl, chromium acetylacetonate or tetraethylammonium bromide, the add-on of catalyzer is preferably the 0.1-3% of total system.
According to the present invention, temperature of reaction system step 2 obtained is down to 50-70 DEG C, then adds thinner and is uniformly mixed, and obtains lignin-base epoxy acrylate mixed system, described thinner is preferably from vinylbenzene, Hydroxyethyl acrylate, lauric acid acrylate (LA), poly(oxyethylene glycol) 400 diacrylate (PEG400DA), Viscoat 295 (TMPTA), 1, 6 hexanediyl esters (HDDA), isobornyl methacrylate (IBOA), pentaerythritol triacrylate (PETA), ethoxylated trimethylolpropane triacrylate (E30-TMPTA), octadecyl acrylate, three ring propoxylated glycerol triacrylates, methyl propenoic acid glycidyl ether, tricarboxylic trimethylolpropane tetra-acrylate, Dipentaerythritol Pentaacrylate, 4-hydroxy butyl vinyl ether, methoxy poly (ethylene glycol) monomethacrylates, one or more in aliphatic monoacrylate or acrylated phosphate, add-on is preferably the 15-50% of total system.
According to the present invention, by the lignin-base epoxy acrylate mixed system curing molding obtained, obtain lignin-base Epocryl, described solidification is preferably thermofixation or photocuring.Described photocuring is preferably ultraviolet light polymerization.
According to the present invention, the detailed process of described thermofixation is preferably: mixed with initiator, promotor by lignin-base epoxy acrylate mixed system, preferably at 50 DEG C, solidify 5-10h, and then 2-4h is solidified at 80 DEG C, finally at 100 DEG C, solidify 1-3h, obtain lignin-base Epocryl, described initiator is preferably methylethyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, diacetone peroxide, isopropyl benzene hydroperoxide, ketone peroxide, and consumption is the 0.5-5% of total system; Promotor is preferably isocyanic acid cobalt, cobalt naphthenate, cobalt iso-octoate, manganese naphthenate, different zincic acid manganese, different potassium zincate, different calcium zincates, phosphoric acid alum, dimethyl-p-toluidine, xylidine, Diethyl Aniline, lauryl mercaptan, cobalt-potassium-calcium-transition metal compound accelerant, and consumption is the 0.5-3% of total system.
According to the present invention, the detailed process of described ultra-violet curing is preferably: lignin-base epoxy acrylate mixed system, light trigger, additive and auxiliary agent are mixed, preferably be paved into the film of 10-200 micron thickness, film is solidified 5S-90S under 250-405nm ultraviolet lighting in ultra-violet curing case, obtains lignin-base Epocryl.Described light trigger is preferably one or more the mixed light initiators in light trigger TPO, light trigger 819, light trigger 907, light trigger 2022, light trigger ITAX, light trigger 1173, light trigger 369, light trigger 651, light trigger 184, light trigger 1000, light trigger 1800, light trigger 2959, light trigger 784, light trigger 1300, light trigger 1700, light trigger 4625, light trigger 1850, and addition is preferably the 1-10% of total system; Described additive is preferably nanometer or micron silica, and consumption is the 2-10% of total system; Auxiliary agent is preferably commercially available defoamer or flow agent, and be not particularly limited for the type of defoamer or flow agent or the trade mark, consumption is the 2-10% of total system.
The lignin-base Epocryl that the present invention also provides above-mentioned preparation method to obtain.
Below in conjunction with specific embodiments preparation method of the present invention is described in further detail.Object is to make those skilled in the art have understanding and cognition clearly to the application.Following specific embodiment should not be understood or be interpreted as the restriction to the application's claims request protection domain in any degree.
Comparative example 1
Bisphenol A epoxide resin Epon827 and 45.4ml vinylformic acid are reacted according to mol ratio 1:1.05, then add 0.338g Resorcinol, 0.341ml pyridine, stir at 80 DEG C, dropwise add 45.4ml vinylformic acid, 15min adds, and continues to react 6h at 80 DEG C, to take a morsel sample every appropriate time, survey acidity, reaction terminates, and obtains epoxy acrylate, is labeled as EA;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain EA/TPGDA epoxy acrylate mixed system.
0.175g light trigger 819,0.525g light trigger TPO, 0.588ml defoamer BYK A555,0.594ml flow agent is added in 10gEA/TPGDA epoxy acrylate mixed system, auxiliary agent 1g nano silicon, mix, the film of 30 micron thickness is paved into coating device, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain organic solvent lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that comparative example 1 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
The infrared spectrum of the epoxy acrylate EA that comparative example 1 obtains is as shown in the c curve in Fig. 1, show that wave number is the charateristic avsorption band completely dissolve of 913cm-1 place epoxy group(ing), illustrate and the esterification that whole epoxide groups and vinylformic acid occur generate epoxy acrylate.
Embodiment 1
Organic solvent content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 5%
After 6g organic solvent xylogen, 114g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, temperature is raised to 100 DEG C, reaction 2h, to take a morsel sample every appropriate time in reaction process, surveys oxirane value, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 5%, be labeled as LBE-5; Oxirane value test wrapper oxygen value is 0.44; The oxirane value time history plot of the Lignin-based epoxy resin obtained as shown in Figure 2;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 39.0ml, add the Resorcinol of 0.354g again, 0.357ml pyridine, stir at 80 DEG C, then 39.0ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 2h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 5%, be labeled as LBEA-5;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-5/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gLBEA-5/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.The tensile strength of the resin that embodiment 1 obtains, shock strength, oxygen index and gel content are as shown in table 1.TGA result shows that the thermal degradation temperature of 10% of the resin that embodiment 1 obtains is 204 DEG C.
The infrared spectrum of the Lignin-based epoxy resin that embodiment 1 obtains and lignin-base epoxy acrylate is as shown in the d curve in Fig. 1 and g curve, wherein a curve is the infrared spectrum of organic solvent xylogen, b curve is the infrared spectrum of epoxy resin, and d curve shows that wave number is 913cm
-1place is that the charateristic avsorption band of epoxy group(ing) occurs on the infrared absorption curve of Lignin-based epoxy resin, this is due to the PART EPOXY base on epoxy resin and the hydroxyl generation ring opening etherification reaction on xylogen, remaining epoxide group has been linked on xylogen, defines Lignin-based epoxy resin.G curve shows that wave number is 913cm
-1place is that the charateristic avsorption band of epoxy group(ing) disappears on the infrared absorption curve of lignin-base epoxy acrylate, illustrates that the whole epoxide group of residue and vinylformic acid there occurs esterification.
Embodiment 2
Organic solvent content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 10%
After 12g organic solvent xylogen, 108g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, fell prolong, add distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, reaction 1.5h, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 10%, be labeled as LBE-10; Oxirane value test wrapper oxygen value is 0.4;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 35.5ml, add the Resorcinol of 0.323g again, 0.326ml pyridine, stir at 80 DEG C, then 35.5mml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 1.5h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 10%, be labeled as LBEA-10;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-10/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gLBEA-10/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.TGA result shows that the thermal degradation temperature of 10% of the resin that embodiment 2 obtains is 227 DEG C.
The infrared spectrum of the Lignin-based epoxy resin that embodiment 2 obtains and lignin-base epoxy acrylate is as shown in the e curve in Fig. 1 and h curve, and e curve shows that wave number is 913cm
-1place is that the charateristic avsorption band of epoxy group(ing) occurs on the infrared absorption curve of Lignin-based epoxy resin, this is due to the PART EPOXY base on epoxy resin and the hydroxyl generation ring opening etherification reaction on xylogen, remaining epoxide group has been linked on xylogen, defines Lignin-based epoxy resin.H curve shows that wave number is 913cm
-1place is that the charateristic avsorption band of epoxy group(ing) disappears on the infrared absorption curve of lignin-base epoxy acrylate, illustrates that the whole epoxide group of residue and vinylformic acid there occurs esterification.The tensile strength of the resin that embodiment 2 obtains, shock strength, oxygen index and gel content are as shown in table 1.
Embodiment 3
Organic solvent content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 15%
After 18g organic solvent xylogen, 102g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, temperature is raised to 100 DEG C, reaction 1h, to take a morsel sample every appropriate time in reaction process, surveys oxirane value, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 15%, be labeled as LBE-15; Oxirane value test wrapper oxygen value is 0.37; The oxirane value time history plot of the Lignin-based epoxy resin obtained as shown in Figure 2;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 33.0ml, add the Resorcinol of 0.345g in product, 0.349ml pyridine, stir at 80 DEG C, then 33.0ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 50min terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 15%, be labeled as LBEA-15;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-15/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gLBEA-15/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.TGA result shows that the thermal degradation temperature of 10% of the resin that embodiment 3 obtains is 230 DEG C.
The infrared spectrum of the Lignin-based epoxy resin that embodiment 3 obtains and lignin-base epoxy acrylate is as shown in the f curve in Fig. 1 and i curve, and f curve shows that wave number is 913cm
-1place is that the charateristic avsorption band of epoxy group(ing) occurs on the infrared absorption curve of Lignin-based epoxy resin, this is due to the PART EPOXY base on epoxy resin and the hydroxyl generation ring opening etherification reaction on xylogen, remaining epoxide group has been linked on xylogen, defines Lignin-based epoxy resin.I curve shows that wave number is 913cm
-1place is that the charateristic avsorption band of epoxy group(ing) disappears on the infrared absorption curve of lignin-base epoxy acrylate, illustrates that the whole epoxide group of residue and vinylformic acid there occurs esterification.The tensile strength of the resin that embodiment 3 obtains, shock strength, oxygen index and gel content are as shown in table 1.
Embodiment 4
Organic solvent content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 20%
After 24g organic solvent xylogen, 96g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 20%, be labeled as LBE-20, oxirane value test wrapper oxygen value is 0.32;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 28.4ml, add the Resorcinol of 0.315g in product, 0.318ml pyridine, stir at 80 DEG C, then 28.4ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 30min terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 20%, be labeled as LBEA-20;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-20/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gLBEA-20/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.The tensile strength of the resin that embodiment 4 obtains, shock strength, oxygen index and gel content are as shown in table 1.TGA result shows that the thermal degradation temperature of 10% of the resin that embodiment 4 obtains is 246 DEG C.
Embodiment 5
Sulfonate content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 5%
After the DMF mixed at room temperature of 6g sulfonate xylogen, 114g epoxy resin and 24ml, 80 DEG C of reaction 2h.Fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, and temperature is raised to 100 DEG C, reaction 2h, continues intensification 120 DEG C, reaction 4h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 5%, be labeled as SLBE-5, oxirane value test wrapper oxygen value is 0.35;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 30.71ml, add the Resorcinol of 0.245g in product, 0.247ml pyridine, stir at 80 DEG C, then 30.71ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 3h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 5%, be labeled as SLBEA-5;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain SLBEA-5/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gSLBEA-5/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The tensile strength of the resin that embodiment 5 obtains, shock strength, oxygen index and gel content are as shown in table 1.
Embodiment 6
Sulfonate content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 10%
After the DMF mixed at room temperature of 12g sulfonate xylogen, 108g epoxy resin and 24ml, 80 DEG C of reaction 2h.Fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, and temperature is raised to 100 DEG C, reaction 2h, continues to be warmed up to 120 DEG C, reaction 3h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 10%, be labeled as SLBE-10, oxirane value test wrapper oxygen value is 0.30;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 25.36ml, add the Resorcinol of 0.235g in product, 0.237ml pyridine, stir at 80 DEG C, then 25.36ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 2h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 10%, be labeled as SLBEA-10;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-10/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gLBEA-10/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The tensile strength of the resin that embodiment 6 obtains, shock strength, oxygen index and gel content are as shown in table 1.
Embodiment 7
Sulfonate content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 15%:
After the DMF mixed at room temperature of 18g sulfonate xylogen, 102g epoxy resin and 24ml, 80 DEG C of reaction 2h, fell prolong, adds distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, and reaction 2h, continues intensification 120 DEG C, reaction 2h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 15%, be labeled as SLBE-15, oxirane value test wrapper oxygen value is 0.28;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 25.0ml, add the Resorcinol of 0.233g in product, 0.235ml pyridine, stir at 80 DEG C, then 25.0ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 2h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 15%, be labeled as SLBEA-15;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain SLBEA-15/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gSLBEA-15/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The tensile strength of the resin that embodiment 7 obtains, shock strength, oxygen index and gel content are as shown in table 1.
Embodiment 8
Sulfonate content of lignin is initially the thermofixation preparation of the lignin-base Epocryl of 20%:
After the DMF mixed at room temperature of 24g sulfonate xylogen, 96g epoxy resin and 24ml, 80 DEG C of reaction 2h.Fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, and temperature is raised to 100 DEG C, reaction 2h, continues intensification 120 DEG C, reaction 1h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 20%, be labeled as SLBE-20, oxirane value test wrapper oxygen value is 0.24;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 22.31ml, add the Resorcinol of 0.213g in product, 0.215ml pyridine, stir at 80 DEG C, then 22.31ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 1.5h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 20%, be labeled as SLBEA-20;
Add the vinylbenzene that the system total mass of accounting for is 35% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain SLBEA-20/ vinylbenzene epoxy acrylate mixed system;
The methylethyl ketone peroxide of the promotor isocyanic acid cobalt and 0.292ml that add 0.112ml in 10gSLBEA-20/ vinylbenzene epoxy acrylate mixed system is stirred, through 8h curing molding at 50 DEG C, 2h is solidified again at 80 DEG C, finally after fixing 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The tensile strength of the resin that embodiment 8 obtains, shock strength, oxygen index and gel content are as shown in table 1.
Embodiment 9
Organic solvent content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 5%
After 6g organic solvent xylogen, 114g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, fell prolong, add distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, reaction 2h, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 5%, be labeled as LBE-5; Oxirane value test wrapper oxygen value is 0.44.
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 39.0ml, add the Resorcinol of 0.354g again, 0.357ml pyridine, stir at 80 DEG C, then 39.0ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 2h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 5%, be labeled as LBEA-5;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-5/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g light trigger TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gLBEA-5/TPGDA epoxy acrylate mixed system, auxiliary agent 1g nano silicon, mix, the film of 30 micron thickness is paved into coating device, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain organic solvent lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 9 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 10
Organic solvent content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 10%
After 12g organic solvent xylogen, 108g epoxy resin and 24mlDMF mixed at room temperature, 80 DEG C of reaction 2h, fell prolong, add distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, reaction 1.5h, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 10%, be labeled as LBE-10; Oxirane value test wrapper oxygen value is 0.4;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 35.5ml, add the Resorcinol of 0.323g again, 0.326ml pyridine, stir at 80 DEG C, then 35.5mml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 1.5h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 10%, be labeled as LBEA-10;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-10/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g light trigger TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gLBEA-10/TPGDA epoxy acrylate mixed system, auxiliary agent 1g nano silicon, mix, the film of 30 micron thickness is paved into coating device, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain organic solvent lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 10 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 11
Organic solvent content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 15%
After 18g organic solvent xylogen, 102g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, fell prolong, add distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, reaction 1h, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 15%, be labeled as LBE-15; Oxirane value test wrapper oxygen value is 0.37;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 33.0ml, add the Resorcinol of 0.345g in product, 0.349ml pyridine, stir at 80 DEG C, then 33.0ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 50min terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 15%, be labeled as LBEA-15;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-15/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g light trigger TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gLBEA-15/TPGDA epoxy acrylate mixed system, auxiliary agent 1g nano silicon, mix, useful coating device is paved into the film of 30 micron thickness, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain organic solvent lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 11 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 12
Organic solvent content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 20%
After 24g organic solvent xylogen, 96g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h, obtain the Lignin-based epoxy resin that organic solvent content of lignin is 20%, be labeled as LBE-20, oxirane value test wrapper oxygen value is 0.32;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 28.4ml, add the Resorcinol of 0.315g in product, 0.318ml pyridine, stir at 80 DEG C, then 28.4ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 30min terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 20%, be labeled as LBEA-20;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain LBEA-20/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g light trigger TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gLBEA-20/TPGDA epoxy acrylate mixed system, auxiliary agent 1g nano silicon, mix, coating device is had to be paved into the film of 30 micron thickness, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain organic solvent lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 12 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 13
Sulfonate content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 5%
After the DMF mixed at room temperature of 6g sulfonate xylogen, 114g epoxy resin and 24ml, 80 DEG C of reaction 2h.Fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, and temperature is raised to 100 DEG C, reaction 2h, continues intensification 120 DEG C, reaction 4h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 5%, be labeled as SLBE-5, oxirane value test wrapper oxygen value is 0.35;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 30.71ml, add the Resorcinol of 0.245g in product, 0.247ml pyridine, stir at 80 DEG C, then 30.71ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 3h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 5%, be labeled as SLBEA-5;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain SLBEA-5/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g initiator TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gSLBEA-5/TPGDA epoxy acrylate mixed system, auxiliary agent nano silicon 1g, mix, coating device is had to be paved into the film of 30 micron thickness, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain sulfonate lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 13 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 14
Sulfonate content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 10%
After the DMF mixed at room temperature of 12g sulfonate xylogen, 108g epoxy resin and 24ml, 80 DEG C of reaction 2h.Fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, and temperature is raised to 100 DEG C, reaction 2h, continues to be warmed up to 120 DEG C, reaction 3h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 10%, be labeled as SLBE-10, oxirane value test wrapper oxygen value is 0.30;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 25.36ml, add the Resorcinol of 0.235g in product, 0.237ml pyridine, stir at 80 DEG C, then 25.36ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 2h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 10%, be labeled as SLBEA-10;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5min, obtain SLBEA-10/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g initiator TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gSLBEA-10/TPGDA epoxy acrylate mixed system, auxiliary agent nano silicon 1g, mix, coating device is had to be paved into the film of 30 micron thickness, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain sulfonate lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 14 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 15
Sulfonate content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 15%:
After the DMF mixed at room temperature of 18g sulfonate xylogen, 102g epoxy resin and 24ml, 80 DEG C of reaction 2h, fell prolong, adds distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, and reaction 2h, continues intensification 120 DEG C, reaction 2h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 15%, be labeled as SLBE-15, oxirane value test wrapper oxygen value is 0.28;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 25.0ml, add the Resorcinol of 0.233g in product, 0.235ml pyridine, stir at 80 DEG C, then 25.0ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 2h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 15%, be labeled as SLBEA-15;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5in, obtain SLBEA-15/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g initiator TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gSLBEA-15/TPGDA epoxy acrylate mixed system, auxiliary agent nano silicon 1g, mix, coating device is had to be paved into the film of 30 micron thickness, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain sulfonate lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 15 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Embodiment 16
Sulfonate content of lignin is initially the photocuring preparation of the lignin-base Epocryl of 20%:
After the DMF mixed at room temperature of 24g sulfonate xylogen, 96g epoxy resin and 24ml, 80 DEG C of reaction 2h.Fell prolong, adds distillation receiving bottle, mainly receives the DMF evaporated, and temperature is raised to 100 DEG C, reaction 2h, continues intensification 120 DEG C, reaction 1h, obtain the Lignin-based epoxy resin that sulfonate content of lignin is 20%, be labeled as SLBE-20, oxirane value test wrapper oxygen value is 0.24;
The Lignin-based epoxy resin prepared and vinylformic acid are reacted according to mol ratio 1:1.05, calculate required vinylformic acid 22.31ml, add the Resorcinol of 0.213g in product, 0.215ml pyridine, stir at 80 DEG C, then 22.31ml vinylformic acid is dropwise added, 15min adds, and reacts at continuing at 80 DEG C, and reaction 1.5h terminates, obtain the lignin-base epoxy acrylate that content of lignin is initially 20%, be labeled as SLBEA-20;
Add the TPGDA that the system total mass of accounting for is 25% when the temperature of reaction system is dropped to 60 DEG C, stir 5in, obtain SLBEA-20/TPGDA epoxy acrylate mixed system;
0.175g light trigger 819,0.525g initiator TPO, 0.588ml defoamer BYKA555,0.594ml flow agent is added in 10gSLBEA-20/TPGDA epoxy acrylate mixed system, auxiliary agent nano silicon 1g, mix, coating device is had to be paved into the film of 30 micron thickness, solidify 1 minute under 365-405nm illumination in ultraviolet case, obtain sulfonate lignin-base epoxy acrylate/TPGDA resin molding material.The hardness of the resin that embodiment 16 obtains, flexural strength, sticking power, oxygen index and gel content are as shown in table 2.
Table 1
As can be seen from tensile strength and the shock strength of table 1, lignin-base Epocryl of the present invention has excellent mechanical property, when organic solvent xylogen initial content is 5-10%, mechanical property is fine, but when content of lignin continues to increase, mechanical property increases with content of lignin and reduces.Due to the complicacy of the three-dimensional hyperstructure of xylogen, and the diversity of its structural chemical group, when content of lignin is too high, cause being easy in its reaction process side reaction occurs, cause crosslinking degree to decline, and have influence on mechanical property.As can be seen from the oxygen index of table 1, lignin-base Epocryl of the present invention has good flame retardant properties, and the oxygen index of resin increases along with content of lignin and improves.
Table 2
As can be seen from hardness and the flexural strength of table 2, the organic solvent lignin-base Epocryl mould material that ultraviolet light polymerization mode of the present invention obtains has excellent mechanical property, and hardness and the pure Epocryl of bending strength ratio are significantly improved.The sticking power of the mould material obtained also is greatly improved.The gel content of resin, all higher than 90%, illustrates that crosslinking degree is very high.As can be seen from the oxygen index of table 2, lignin-base Epocryl of the present invention has good flame retardant properties, and the oxygen index of resin increases with content of lignin and improves.The performance of the sulfonate lignin-base Epocryl mould material that ultraviolet light polymerization mode of the present invention obtains also makes moderate progress.Can illustrate that the lignin-base Epocryl that ultraviolet light polymerization mode provided by the invention obtains has good practicality and application prospect by table 2.
Claims (10)
1. a preparation method for lignin-base Epocryl, is characterized in that, comprising:
Step one: xylogen, epoxy resin and DMF are reacted, obtains Lignin-based epoxy resin;
Step 2: Lignin-based epoxy resin step one obtained, stopper, catalyzer and acrylic monomer react, and obtain lignin-base epoxy acrylate;
Step 3: lignin-base epoxy acrylate step 2 obtained and mixing diluents, obtains lignin-base epoxy acrylate mixed system;
Step 4: lignin-base epoxy acrylate mixed system curing molding step 3 obtained, obtains lignin-base Epocryl.
2. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, described xylogen is organic solvent xylogen or sulfonate xylogen.
3. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, described acrylic monomer is acrylic or methacrylic acid.
4. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, in described step one, the mass ratio of xylogen and epoxy resin is (6-24): (96-114).
5. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, the temperature of reaction of described step one is 80-120 DEG C, and the reaction times is 1-8h.
6. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, in described step 2, the mol ratio of Lignin-based epoxy resin and acrylic monomer is 1:(1-2).
7. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, described step 2 temperature of reaction is 80-100 DEG C, and the reaction times is 1-4h.
8. the preparation method of a kind of lignin-base Epocryl according to claim 1, it is characterized in that, thinner in described step 3 is selected from vinylbenzene, Hydroxyethyl acrylate, lauric acid acrylate, poly(oxyethylene glycol) 400 diacrylate, Viscoat 295, 1, 6 hexanediyl esters, isobornyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, octadecyl acrylate, three ring propoxylated glycerol triacrylates, methyl propenoic acid glycidyl ether, tricarboxylic trimethylolpropane tetra-acrylate, Dipentaerythritol Pentaacrylate, 4-hydroxy butyl vinyl ether, methoxy poly (ethylene glycol) monomethacrylates, one or more in aliphatic monoacrylate or acrylated phosphate.
9. the preparation method of a kind of lignin-base Epocryl according to claim 1, is characterized in that, described step 4 be cured as thermofixation or photocuring.
10. the lignin-base Epocryl that obtains of the preparation method of claim 1-9 described in any one.
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