CN104910335B - Lignin-base Epocryl and preparation method thereof - Google Patents
Lignin-base Epocryl and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of lignin-base Epocryl and preparation method thereof, belongs to synthesis of polymer material and its application field.Lignin and epoxy resin are first added to reaction generation Lignin-based epoxy resin in solvent by this method, are then added acrylic monomer and are carried out reaction generation lignin-base Epocryl, are eventually adding diluent and are molded through catalysis or light-initiated solidify afterwards.The present invention also provides a kind of lignin-base Epocryl.The lignin-base Epocryl of the present invention is to be incorporated into natural polymer lignin in Epocryl by chemical reaction, because lignin is the three-dimensional netted natural polymer with excellent mechanical property, heat endurance and certain biodegradability, the mechanical property and fire resistance of the environmentally friendly lignin-base Epocryl of preparation have obtained good improvement.
Description
Technical field
The invention belongs to synthesis of polymer material and its application field, and in particular to a kind of lignin-base epoxy acrylate
Resin and preparation method thereof.
Background technology
Lignin (Lignin) is a kind of renewable resource of reserves very abundant on the earth, and yield is big, and reproduction speed is fast,
It is biodegradable, it is the abundant natural macromolecular organic matter that content is only second to cellulose.It is led to by phenylpropyl alcohol alkyl structure unit
The three-dimensional netted polymer substance that the carbon key (C-C) of carbon one and ehter bond (- O-) are formed by connecting is crossed, is complicated aromatic polymer.
Due to its aromatic nature, side switch ALIPHATIC feature and various functions base, lignin can turn into the energy as oil
Material and important industrial chemicals.Lignin is the byproduct of pulp and paper industry, effectively using lignin, is on the one hand alleviated
Environmental pollution, is conducive to further improvement, on the other hand develops renewable resource, solve the problems, such as the waste of resource.
Epoxy acrylate (EA) is the maximum Photocurable oligomers of current most widely used, consumption, is by epoxy resin
It is Esterification and obtained with acrylic or methacrylic.The basic composition of Epocryl includes epoxy resin (bisphenol-A
Type, bisphenol-f type, phenol aldehyde type etc.), unsaturated monoacid (such as：Acrylic acid, methacrylic acid etc.), crosslinking agent, modifying agent etc..Ring
Oxypropylene acid ester resin has the good characteristic of epoxy resin, but more outstanding in terms of curability and mouldability, unlike epoxy
Resin is cumbersome like that, is a kind of heat-curing resin.EA synthesis just has patent report early in 1950s, and it has solid
Change that speed is fast, adhesive strength is big, hardness is high, glossiness is high, chemical proofing, water resistance the advantages of, but there is also anti-flammability
Can be poor the shortcomings of.
EA just can be solidified by organic peroxide curing method (hypo-hyperthermia) or photocuring processes, be widely used in：
Corrosion resistant fiber strengthens composite plastic (FRP) product, such as fiberglass groove tank, pipeline, tower and corrosion-resistant grid；Anticorrosion
Engineering, such as cement base or iron based glasses Leak-tight liner, highly corrosion resistant terrace；High-strength FRP, for example：Pulling and extruding glass fiber section bar, physical culture
Articles for use, FRP ships and light boats etc.；Heavy antisepsis glass-flake coating；Other such as UV ink, heavy antisepsis industry ground slab.Referring to Sun Xingping, king
Moral sea epoxy acrylics Lipase absobed and the progress coatings industries of application, 2007,11 (37)：53-60.Do not have in the prior art
There is the report in terms of lignin is introduced into epoxy acrylic resin.
The content of the invention
It is an object of the invention to provide a kind of lignin-base Epocryl and preparation method thereof, the lignin-base
Epocryl has excellent mechanical property and fire resistance.
The present invention provides a kind of preparation method of lignin-base Epocryl, including：
Step one：By the reaction of lignin, epoxy resin and DMF, Lignin-based epoxy resin is obtained；
Step 2：Lignin-based epoxy resin, polymerization inhibitor, catalyst and the acrylic monomer that step one is obtained are anti-
Should, obtain lignin-base epoxy acrylate；
Step 3：Lignin-base epoxy acrylate and the diluent mixing that step 2 is obtained, obtain lignin basic ring
Oxypropylene acid esters mixed system；
Step 4：The lignin-base epoxy acrylate mixed system curing molding that step 3 is obtained, obtains lignin
Based epoxy acrylate resin.
Preferably, described lignin is organic solvent lignin or sulfonate lignin.
Preferably, described acrylic monomer is acrylic or methacrylic acid.
Preferably, the mass ratio of lignin and epoxy resin is (6-24) in described step one：(96-114).
Preferably, the reaction temperature of described step one is 80-120 DEG C, and the reaction time is 1-8h.
Preferably, Lignin-based epoxy resin and acrylic acid mol ratio are 1 in described step two:(1-2).
Preferably, described step two reaction temperature is 80-100 DEG C, and the reaction time is 1-4h.
Preferably, the diluent in described step three is selected from styrene, hydroxy-ethyl acrylate, bay acid acrylic acid
Ester, polyethylene glycol 400 diacrylate, trimethylolpropane trimethacrylate, 1,6 hexanediyl esters, metering system
Sour isobornyl thiocyanoacetate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, octadecyl base
Ester, three ring propoxylated glycerol triacrylates, methyl propenoic acid glycidyl ether, tricarboxylic trimethylolpropane tetra acid
Ester, Dipentaerythritol Pentaacrylate, 4- hydroxy butyl vinyl ethers, methoxy poly (ethylene glycol) monomethacrylates, aliphatic
One or more in mono acrylic ester or acrylated phosphate.
Preferably, described step four is cured as heat cure or photocuring.
The present invention also provides the lignin-base Epocryl that above-mentioned preparation method is obtained.
Beneficial effects of the present invention
The present invention provides a kind of preparation method of lignin-base Epocryl, and this method is first by lignin and ring
Oxygen tree fat is added to reaction generation Lignin-based epoxy resin in a small amount of DMF solvent, then adds acrylic monomer and carries out instead
Lignin-base Epocryl should be generated, diluent is eventually adding and is molded through catalysis or light-initiated solidify afterwards.With it is existing
Technology compares, and the present invention is directly to react lignin and epoxy resin, further reacts, does not have with acrylic monomer
By purifying or modified, the preparation method is simple, cost is low, the lignin-base Epocryl for preparing have it is good
Good combination property.
The present invention also provides a kind of lignin-base Epocryl, and the lignin-base Epocryl is
Natural polymer lignin is incorporated into Epocryl by chemical reaction, because lignin is with excellent
The three-dimensional netted natural polymer of mechanical property, heat endurance and certain biodegradability, obtained environmentally friendly lignin
The mechanical property and fire resistance of based epoxy acrylate resin have obtained good improvement.
Brief description of the drawings
Fig. 1 is the Lignin-based epoxy resin that comparative example 1 and embodiment 1-3 are obtained and lignin-base epoxy acrylate
Infrared spectrogram；
Fig. 2 is the epoxide number for the Lignin-based epoxy resin that embodiment 1 and embodiment 3 are obtained with lignin and epoxy resin
The curve map of reaction time change.
Embodiment
The present invention provides a kind of preparation method of lignin-base Epocryl, including：
Step one：By the reaction of lignin, epoxy resin and DMF (DMF), lignin-base epoxy is obtained
Resin；
Step 2：Lignin-based epoxy resin, polymerization inhibitor, catalyst and the acrylic monomer that step one is obtained are anti-
Should, obtain lignin-base epoxy acrylate；
Step 3：Lignin-base epoxy acrylate and diluent (activated monomer) mixing that step 2 is obtained, are obtained
Lignin-base epoxy acrylate mixed system；
Step 4：The lignin-base epoxy acrylate mixed system curing molding that step 3 is obtained, obtains lignin
Based epoxy acrylate resin.
According to the present invention, first lignin and epoxy resin are mixed, solvent DMF (DMF) is added and mixes
Close, obtain mixture and preferably react 1-8h at 80-120 DEG C, obtain Lignin-based epoxy resin；Described lignin is preferably
Organic solvent lignin or sulfonate lignin；Described reaction temperature and time are according to the species of lignin and containing for lignin
Amount is relevant, when lignin is organic solvent lignin, and content of lignin is 20%, and reaction temperature is 80-90 DEG C, reaction time
For 1-2h；When content of lignin is 10-15%, 1-2h is reacted at 80-90 DEG C, then temperature is risen to 100-110 DEG C, 1- is reacted
2h；When content of lignin is less than 10%, 1-2h is reacted at 80-90 DEG C, then temperature is risen to 100-110 DEG C, 1-2h is reacted,
Continue temperature rising to 110-120 DEG C, react 2-4h；When lignin is sulfonate lignin, content of lignin can reach
20%, lignin reacts 1-2h at 80-90 DEG C with epoxy resin, then temperature is risen into 100-110 DEG C, reacts 1-2h, and continuing will
Temperature rises to 110-120 DEG C, reacts 2-4h；Described epoxy resin species is not particularly limited, i.e., commercially available epoxy resin is
Can, the viscosity of preferred epoxy is in below 10.0Pas, and viscosity is too high, it is impossible to which stirring reaction is uniform, easily crosslinks.Institute
The lignin and the mass ratio of epoxy resin stated are preferably (6-24)：(96-114)；The described amount to solvent does not have special limit
System, can dissolved lignin and epoxy resin.
According to the present invention, obtained Lignin-based epoxy resin, polymerization inhibitor, catalyst and acrylic monomer are preferably existed
1-4h is reacted at 80-100 DEG C, lignin-base epoxy acrylate is obtained；Described acrylic monomer be preferably acrylic acid or
Methacrylic acid, Lignin-based epoxy resin and acrylic monomer mol ratio are preferably 1:(1-2)；Described polymerization inhibitor is preferred
It is hydroquinones, para hydroxybenzene methane, 2,5- dimethyl hydroquinones or 2,6- di-t-butyl to phenyl methylcarbamate, the addition of polymerization inhibitor
Amount is preferably the 0.01-1% of total system；Catalyst is preferably Tetrabutylammonium bromide, pyridine, dimethylaniline, triethylamine, diethyl
Amine, N, N- dimethyl benzylamines, trimethyl benzyl ammonia chloride, triphenyl phosphorus, antimony triphenyl, chromium acetylacetonate or tetraethyl bromination
Ammonium, the addition of catalyst is preferably the 0.1-3% of total system.
According to the present invention, the temperature of reaction system that step 2 is obtained is down to 50-70 DEG C, diluent stirring is then added mixed
Close uniform, obtain lignin-base epoxy acrylate mixed system；Described diluent preferably is selected from styrene, acrylic acid hydroxyl second
Ester, laurate acrylate (LA), polyethylene glycol 400 diacrylate (PEG400DA), trimethylolpropane trimethacrylate
(TMPTA), 1,6 hexanediyl esters (HDDA), isobornyl methacrylate (IBOA), pentaerythritol triacrylate
(PETA), ethoxylated trimethylolpropane triacrylate (E30-TMPTA), octadecyl acrylate, three ring propoxyl group
Change glycerol tri-acrylate, methyl propenoic acid glycidyl ether, tricarboxylic trimethylolpropane tetra-acrylate, dipentaerythritol five
Acrylate, 4- hydroxy butyl vinyl ethers, methoxy poly (ethylene glycol) monomethacrylates, aliphatic monoacrylate or propylene
One or more in acid phosphoric acid ester, addition is preferably the 15-50% of total system.
According to the present invention, by obtained lignin-base epoxy acrylate mixed system curing molding, lignin-base is obtained
Epocryl, described solidification is preferably heat cure or photocuring.Described photocuring is preferably ultraviolet light solidification.
According to the present invention, the detailed process of described heat cure is preferably：By lignin-base epoxy acrylate mixture
System mixes with initiator, accelerator, preferably solidifies 5-10h at 50 DEG C, then solidifies 2-4h at 80 DEG C, most after 100
Solidify 1-3h at DEG C, obtain lignin-base Epocryl, described initiator is preferably methyl ethyl ketone peroxide, peroxide
Change cyclohexanone, dibenzoyl peroxide, diacetone peroxide, isopropyl benzene hydroperoxide, ketone peroxide, consumption is total system
0.5-5%；Accelerator be 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, dimethylaniline, diethylaniline, lauryl mercaptan, cobalt-potassium-calcium-mistake
Metal composite accelerator is crossed, 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 is mixed
System, light trigger, additive and auxiliary agent are well mixed, the film of 10-200 micron thickness are preferably paved into, by film ultraviolet
Solidify 5S-90S under 250-405nm ultraviolet lightings in solidification case, obtain lignin-base Epocryl.Described light draws
Hair agent is preferably that light trigger TPO, light trigger 819, light trigger 907, light trigger 2022, light trigger ITAX, light draw
Send out agent 1173, it is light trigger 369, light trigger 651, light trigger 184, light trigger 1000, light trigger 1800, light-initiated
One in agent 2959, light trigger 784, light trigger 1300, light trigger 1700, light trigger 4625, light trigger 1850
Plant or several mixing light triggers, addition is preferably the 1-10% of total system；Described additive is preferably nanometer or micron
Silica, consumption is the 2-10% of total system；Auxiliary agent is preferably commercially available defoamer or levelling agent, for defoamer or levelling
The type or the trade mark of agent are not particularly limited, and consumption is the 2-10% of total system.
The present invention also provides the lignin-base Epocryl that above-mentioned preparation method is obtained.
The preparation method to the present invention is described in further detail below in conjunction with specific embodiments.Purpose is to make
Those skilled in the art are more clearly understood from and recognized to the application.Following specific embodiment should not be in any degree
It is understood or is construed to the application claims are claimed the limitation of scope.
Comparative example 1
By bisphenol A epoxide resin Epon827 and 45.4ml acrylic acid according to mol ratio 1:1.05 reactions, are then added
0.338g hydroquinones, 0.341ml pyridines stir at 80 DEG C, 45.4ml acrylic acid are added dropwise, 15min is added, and continue 80
6h is reacted at DEG C, a small amount of sample is taken every appropriate time, acidity is surveyed, reaction terminates, and epoxy acrylate is obtained, labeled as EA；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
EA/TPGDA epoxy acrylate mixed systems.
0.175g light triggers 819,0.525g are added in 10gEA/TPGDA epoxy acrylate mixed systems light-initiated
Agent TPO, 0.588ml defoamer BYK A555,0.594ml levelling agents, auxiliary agent 1g nano silicons are well mixed, use film
Device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains organic solvent lignin-base
Epoxy acrylate/TPGDA resin membrane materials.The hardness of the resin that comparative example 1 is obtained, bending strength, adhesive force, oxygen index (OI) and
Gel content is as shown in table 2.
The infrared spectrum for the epoxy acrylate EA that comparative example 1 is obtained shows that wave number is as shown in the c curves in Fig. 1
The characteristic absorption peak of epoxy radicals is wholly absent at 913cm-1, illustrates the esterification that the epoxide group of whole occurs with acrylic acid,
Generate epoxy acrylate.
Embodiment 1
It is prepared by the heat cure that organic solvent content of lignin is initially 5% lignin-base Epocryl
After 6g organic solvents lignin, 114g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, react in 2h, course of reaction every suitable
A small amount of sample is taken when the time, epoxide number is surveyed, the Lignin-based epoxy resin that organic solvent content of lignin is 5%, mark is obtained
For LBE-5；Epoxide number test epoxide number is 0.44；The curve that the epoxide number of obtained Lignin-based epoxy resin is changed over time
Figure is as shown in Figure 2；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 39.0ml, add 0.354g hydroquinones, 0.357ml pyridines are stirred at 80 DEG C, are then added dropwise
39.0ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 2h terminates, and obtains content of lignin and is initially 5%
Lignin-base epoxy acrylate, labeled as LBEA-5；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To LBEA-5/ styrene epoxy acrylate mixed systems；
By in 10gLBEA-5/ styrene epoxy acrylate mixed systems add 0.112ml accelerator isocyanic acid cobalt and
0.292ml methyl ethyl ketone peroxide stirs, and through 8h curing moldings at 50 DEG C, solidifies 2h at 80 DEG C, finally 100
Solidify afterwards 2h at DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.The resin that embodiment 1 is obtained
Tensile strength, impact strength, oxygen index (OI) and gel content are as shown in table 1.TGA results show the resin that embodiment 1 is obtained
10% thermal degradation temperature is 204 DEG C.
In Lignin-based epoxy resin and the infrared spectrum such as Fig. 1 of lignin-base epoxy acrylate that embodiment 1 is obtained
D curves and g curves shown in, wherein a curves are the infrared spectrum of organic solvent lignin, and b curves are infrared for epoxy resin
Spectrogram, d curves show that wave number is 913cm-1Place is infrared absorption of the characteristic absorption peak in Lignin-based epoxy resin of epoxy radicals
Occur on curve, this is due to the hydroxyl generation ring opening etherification reaction on PART EPOXY base and lignin on epoxy resin, remaining
Under epoxide group be linked on lignin, form Lignin-based epoxy resin.G curves show that wave number is 913cm-1Place
It is that the characteristic absorption peak of epoxy radicals disappears on the infrared absorption curve of lignin-base epoxy acrylate, illustrates remaining whole
Epoxide group there occurs esterification with acrylic acid.
Embodiment 2
It is prepared by the heat cure that organic solvent content of lignin is initially 10% lignin-base Epocryl
After 12g organic solvents lignin, 108g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell
Condenser pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 1.5h, obtains organic molten
Agent content of lignin is 10% Lignin-based epoxy resin, labeled as LBE-10；Epoxide number test epoxide number is 0.4；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 35.5ml, add 0.323g hydroquinones, 0.326ml pyridines are stirred at 80 DEG C, are then added dropwise
35.5mml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 1.5h terminates, and obtains content of lignin and is initially
10% lignin-base epoxy acrylate, labeled as LBEA-10；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To LBEA-10/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gLBEA-10/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.TGA results show embodiment
10% thermal degradation temperature of 2 obtained resins is 227 DEG C.
In Lignin-based epoxy resin and the infrared spectrum such as Fig. 1 of lignin-base epoxy acrylate that embodiment 2 is obtained
E curves and h curves shown in, e curves show wave number be 913cm-1Place is the characteristic absorption peak of epoxy radicals in lignin-base epoxy
Occur on the infrared absorption curve of resin, this is due to that PART EPOXY base on epoxy resin is opened with the hydroxyl on lignin
Ring etherification reaction, remaining epoxide group has been linked on lignin, forms Lignin-based epoxy resin.H curves show
Wave number is 913cm-1Place is that the characteristic absorption peak of epoxy radicals disappears on the infrared absorption curve of lignin-base epoxy acrylate,
Illustrate that the epoxide group of remaining whole there occurs esterification with acrylic acid.The tensile strength for the resin that embodiment 2 is obtained, impact
Intensity, oxygen index (OI) and gel content are as shown in table 1.
Embodiment 3
It is prepared by the heat cure that organic solvent content of lignin is initially 15% lignin-base Epocryl
After 18g organic solvents lignin, 102g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell
Condenser pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, temperature is raised to 100 DEG C, react in 1h, course of reaction every
Appropriate time takes a small amount of sample, surveys epoxide number, obtains the Lignin-based epoxy resin that organic solvent content of lignin is 15%, mark
It is designated as LBE-15；Epoxide number test epoxide number is 0.37；What the epoxide number of obtained Lignin-based epoxy resin was changed over time
Curve map is as shown in Figure 2；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 33.0ml, in product plus 0.345g hydroquinones, 0.349ml pyridines stir at 80 DEG C, are then added dropwise
33.0ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 50min terminates, and obtains content of lignin and is initially
15% lignin-base epoxy acrylate, labeled as LBEA-15；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To LBEA-15/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gLBEA-15/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.TGA results show embodiment
10% thermal degradation temperature of 3 obtained resins is 230 DEG C.
In Lignin-based epoxy resin and the infrared spectrum such as Fig. 1 of lignin-base epoxy acrylate that embodiment 3 is obtained
F curves and i curves shown in, f curves show wave number be 913cm-1Place is the characteristic absorption peak of epoxy radicals in lignin-base epoxy
Occur on the infrared absorption curve of resin, this is due to that PART EPOXY base on epoxy resin is opened with the hydroxyl on lignin
Ring etherification reaction, remaining epoxide group has been linked on lignin, forms Lignin-based epoxy resin.I curves show
Wave number is 913cm-1Place is that the characteristic absorption peak of epoxy radicals disappears on the infrared absorption curve of lignin-base epoxy acrylate,
Illustrate that the epoxide group of remaining whole there occurs esterification with acrylic acid.The tensile strength for the resin that embodiment 3 is obtained, impact
Intensity, oxygen index (OI) and gel content are as shown in table 1.
Embodiment 4
It is prepared by the heat cure that organic solvent content of lignin is initially 20% lignin-base Epocryl
After 24g organic solvents lignin, 96g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h are had
Machine solvent content of lignin is 20% Lignin-based epoxy resin, labeled as LBE-20, and epoxide number test epoxide number is 0.32；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 28.4ml, in product plus 0.315g hydroquinones, 0.318ml pyridines stir at 80 DEG C, are then added dropwise
28.4ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 30min terminates, and obtains content of lignin and is initially
20% lignin-base epoxy acrylate, labeled as LBEA-20；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To LBEA-20/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gLBEA-20/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains organic solvent lignin-base epoxy acrylate/styrene resin.The resin that embodiment 4 is obtained
Tensile strength, impact strength, oxygen index (OI) and gel content it is as shown in table 1.TGA results show the resin that embodiment 4 is obtained
10% thermal degradation temperature is 246 DEG C.
Embodiment 5
It is prepared by the heat cure that sulfonate content of lignin is initially 5% lignin-base Epocryl
After 6g sulfonate lignin, 114g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h.Fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continue to heat up 120 DEG C,
4h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 5% is obtained, labeled as SLBE-5, epoxide number test wrapper
Oxygen value is 0.35；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 30.71ml, in product plus 0.245g hydroquinones, 0.247ml pyridines stir at 80 DEG C, are then added dropwise
30.71ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 3h terminates, and obtains content of lignin and is initially 5%
Lignin-base epoxy acrylate, labeled as SLBEA-5；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To SLBEA-5/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gSLBEA-5/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The resin that embodiment 5 is obtained
Tensile strength, impact strength, oxygen index (OI) and gel content are as shown in table 1.
Embodiment 6
It is prepared by the heat cure that sulfonate content of lignin is initially 10% lignin-base Epocryl
After 12g sulfonate lignin, 108g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h.Fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continues to be warming up to 120
DEG C, 3h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 10% is obtained, labeled as SLBE-10, epoxide number is surveyed
Test ring oxygen value is 0.30；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 25.36ml, in product plus 0.235g hydroquinones, 0.237ml pyridines stir at 80 DEG C, are then added dropwise
25.36ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 2h terminates, and obtains content of lignin and is initially 10%
Lignin-base epoxy acrylate, labeled as SLBEA-10；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To LBEA-10/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gLBEA-10/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The resin that embodiment 6 is obtained
Tensile strength, impact strength, oxygen index (OI) and gel content are as shown in table 1.
Embodiment 7
It is prepared by the heat cure that sulfonate content of lignin is initially 15% lignin-base Epocryl:
After 18g sulfonate lignin, 102g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continue to heat up 120 DEG C,
2h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 15% is obtained, labeled as SLBE-15, epoxide number test
Epoxide number is 0.28；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 25.0ml, in product plus 0.233g hydroquinones, 0.235ml pyridines stir at 80 DEG C, are then added dropwise
25.0ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 2h terminates, and obtains content of lignin and is initially 15%
Lignin-base epoxy acrylate, labeled as SLBEA-15；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To SLBEA-15/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gSLBEA-15/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The resin that embodiment 7 is obtained
Tensile strength, impact strength, oxygen index (OI) and gel content are as shown in table 1.
Embodiment 8
It is prepared by the heat cure that sulfonate content of lignin is initially 20% lignin-base Epocryl:
After 24g sulfonate lignin, 96g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h.Fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continue to heat up 120 DEG C,
1h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 20% is obtained, labeled as SLBE-20, epoxide number test
Epoxide number is 0.24；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 22.31ml, in product plus 0.213g hydroquinones, 0.215ml pyridines stir at 80 DEG C, are then added dropwise
22.31ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 1.5h terminates, and obtains content of lignin and is initially
20% lignin-base epoxy acrylate, labeled as SLBEA-20；
The styrene for accounting for that system gross mass is 35% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
To SLBEA-20/ styrene epoxy acrylate mixed systems；
0.112ml accelerator isocyanic acid cobalt will be added in 10gSLBEA-20/ styrene epoxy acrylate mixed systems
Stirred with 0.292ml methyl ethyl ketone peroxide, through 8h curing moldings at 50 DEG C, solidify 2h at 80 DEG C, finally exist
Solidify afterwards 2h at 100 DEG C, obtains sulfonate lignin-base epoxy acrylate/styrene resin.The resin that embodiment 8 is obtained
Tensile strength, impact strength, oxygen index (OI) and gel content are as shown in table 1.
Embodiment 9
It is prepared by the photocuring that organic solvent content of lignin is initially 5% lignin-base Epocryl
After 6g organic solvents lignin, 114g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, obtain organic solvent wood
Lignin content is 5% Lignin-based epoxy resin, labeled as LBE-5；Epoxide number test epoxide number is 0.44.
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 39.0ml, add 0.354g hydroquinones, 0.357ml pyridines are stirred at 80 DEG C, are then added dropwise
39.0ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 2h terminates, and obtains content of lignin and is initially 5%
Lignin-base epoxy acrylate, labeled as LBEA-5；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
LBEA-5/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g light are added in 10gLBEA-5/TPGDA epoxy acrylate mixed systems
Initiator TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent 1g nano silicons are well mixed, with painting
Membrane device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains organic solvent lignin
Based epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 9 is obtained, bending strength, adhesive force, oxygen index (OI)
It is as shown in table 2 with gel content.
Embodiment 10
It is prepared by the photocuring that organic solvent content of lignin is initially 10% lignin-base Epocryl
After 12g organic solvents lignin, 108g epoxy resin and 24mlDMF mixed at room temperature, 80 DEG C of reaction 2h fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 1.5h, obtains organic solvent
Content of lignin is 10% Lignin-based epoxy resin, labeled as LBE-10；Epoxide number test epoxide number is 0.4；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 35.5ml, add 0.323g hydroquinones, 0.326ml pyridines are stirred at 80 DEG C, are then added dropwise
35.5mml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 1.5h terminates, and obtains content of lignin and is initially
10% lignin-base epoxy acrylate, labeled as LBEA-10；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
LBEA-10/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gLBEA-10/TPGDA epoxy acrylate mixed systems
Light trigger TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent 1g nano silicons are well mixed, and are used
Coating device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains organic solvent wooden
Plain based epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 10 is obtained, bending strength, adhesive force, oxygen
Index and gel content are as shown in table 2.
Embodiment 11
It is prepared by the photocuring that organic solvent content of lignin is initially 15% lignin-base Epocryl
After 18g organic solvents lignin, 102g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell
Condenser pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 1h, obtains organic solvent
Content of lignin is 15% Lignin-based epoxy resin, labeled as LBE-15；Epoxide number test epoxide number is 0.37；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 33.0ml, in product plus 0.345g hydroquinones, 0.349ml pyridines stir at 80 DEG C, are then added dropwise
33.0ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 50min terminates, and obtains content of lignin and is initially
15% lignin-base epoxy acrylate, labeled as LBEA-15；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
LBEA-15/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gLBEA-15/TPGDA epoxy acrylate mixed systems
Light trigger TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent 1g nano silicons are well mixed, had
30 microns of thick films are paved into coating device, are solidified 1 minute under 365-405nm illumination in ultraviolet case, organic solvent wood is obtained
Quality based epoxy acrylate/TPGDA resin membrane materials.The hardness of the resin that embodiment 11 is obtained, bending strength, adhesive force,
Oxygen index (OI) and gel content are as shown in table 2.
Embodiment 12
It is prepared by the photocuring that organic solvent content of lignin is initially 20% lignin-base Epocryl
After 24g organic solvents lignin, 96g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h are had
Machine solvent content of lignin is 20% Lignin-based epoxy resin, labeled as LBE-20, and epoxide number test epoxide number is 0.32；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 28.4ml, in product plus 0.315g hydroquinones, 0.318ml pyridines stir at 80 DEG C, are then added dropwise
28.4ml acrylic acid, 15min is added, continue at 80 DEG C and react, reaction 30min terminates, and obtains content of lignin and is initially
20% lignin-base epoxy acrylate, labeled as LBEA-20；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
LBEA-20/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gLBEA-20/TPGDA epoxy acrylate mixed systems
Light trigger TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent 1g nano silicons are well mixed, had
Coating device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains organic solvent wooden
Plain based epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 12 is obtained, bending strength, adhesive force, oxygen
Index and gel content are as shown in table 2.
Embodiment 13
It is prepared by the photocuring that sulfonate content of lignin is initially 5% lignin-base Epocryl
After 6g sulfonate lignin, 114g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h.Fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continue to heat up 120 DEG C,
4h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 5% is obtained, labeled as SLBE-5, epoxide number test wrapper
Oxygen value is 0.35；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 30.71ml, in product plus 0.245g hydroquinones, 0.247ml pyridines stir at 80 DEG C, are then added dropwise
30.71ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 3h terminates, and obtains content of lignin and is initially 5%
Lignin-base epoxy acrylate, labeled as SLBEA-5；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
SLBEA-5/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gSLBEA-5/TPGDA epoxy acrylate mixed systems
Initiator TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent nano silicon 1g is well mixed, there is painting
Membrane device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains sulfonate lignin-base
Epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 13 is obtained, bending strength, adhesive force, oxygen index (OI)
It is as shown in table 2 with gel content.
Embodiment 14
It is prepared by the photocuring that sulfonate content of lignin is initially 10% lignin-base Epocryl
After 12g sulfonate lignin, 108g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h.Fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continues to be warming up to 120
DEG C, 3h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 10% is obtained, labeled as SLBE-10, epoxide number is surveyed
Test ring oxygen value is 0.30；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 25.36ml, in product plus 0.235g hydroquinones, 0.237ml pyridines stir at 80 DEG C, are then added dropwise
25.36ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 2h terminates, and obtains content of lignin and is initially 10%
Lignin-base epoxy acrylate, labeled as SLBEA-10；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5min is stirred, obtains
SLBEA-10/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gSLBEA-10/TPGDA epoxy acrylate mixed systems
Initiator TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent nano silicon 1g is well mixed, there is painting
Membrane device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains sulfonate lignin-base
Epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 14 is obtained, bending strength, adhesive force, oxygen index (OI)
It is as shown in table 2 with gel content.
Embodiment 15
It is prepared by the photocuring that sulfonate content of lignin is initially 15% lignin-base Epocryl:
After 18g sulfonate lignin, 102g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continue to heat up 120 DEG C,
2h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 15% is obtained, labeled as SLBE-15, epoxide number test
Epoxide number is 0.28；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 25.0ml, in product plus 0.233g hydroquinones, 0.235ml pyridines stir at 80 DEG C, are then added dropwise
25.0ml acrylic acid, 15min is added, and is continued at 80 DEG C and is reacted, and reaction 2h terminates, and obtains content of lignin and is initially 15%
Lignin-base epoxy acrylate, labeled as SLBEA-15；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5in is stirred, obtains
SLBEA-15/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gSLBEA-15/TPGDA epoxy acrylate mixed systems
Initiator TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent nano silicon 1g is well mixed, there is painting
Membrane device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains sulfonate lignin-base
Epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 15 is obtained, bending strength, adhesive force, oxygen index (OI)
It is as shown in table 2 with gel content.
Embodiment 16
It is prepared by the photocuring that sulfonate content of lignin is initially 20% lignin-base Epocryl:
After 24g sulfonate lignin, 96g epoxy resin and 24ml DMF mixed at room temperature, 80 DEG C of reaction 2h.Fell cold
Solidifying pipe, plus distillation receiving bottle, mainly receive the DMF evaporated, and temperature is raised to 100 DEG C, reacts 2h, continue to heat up 120 DEG C,
1h is reacted, the Lignin-based epoxy resin that sulfonate content of lignin is 20% is obtained, labeled as SLBE-20, epoxide number test
Epoxide number is 0.24；
By the Lignin-based epoxy resin prepared and acrylic acid according to mol ratio 1:1.05 reactions, required for calculating
Acrylic acid 22.31ml, in product plus 0.213g hydroquinones, 0.215ml pyridines stir at 80 DEG C, are then added dropwise
22.31ml acrylic acid, 15min is added, continue at 80 DEG C and react, reaction 1.5h terminates, and obtains content of lignin and is initially
20% lignin-base epoxy acrylate, labeled as SLBEA-20；
The TPGDA for accounting for that system gross mass is 25% is added when the temperature of reaction system is dropped into 60 DEG C, 5in is stirred, obtains
SLBEA-20/TPGDA epoxy acrylate mixed systems；
0.175g light triggers 819,0.525g are added in 10gSLBEA-20/TPGDA epoxy acrylate mixed systems
Initiator TPO, 0.588ml defoamer BYKA555,0.594ml levelling agent, auxiliary agent nano silicon 1g is well mixed, there is painting
Membrane device is paved into 30 microns of thick films, solidifies 1 minute under 365-405nm illumination in ultraviolet case, obtains sulfonate lignin-base
Epoxy acrylate/TPGDA resin membrane materials.The hardness for the resin that embodiment 16 is obtained, bending strength, adhesive force, oxygen index (OI)
It is as shown in table 2 with gel content.
Table 1
The lignin-base Epocryl tool of the present invention is can be seen that from the tensile strength and impact strength of table 1
There is excellent mechanical property, when organic solvent lignin initial content is 5-10%, mechanical property is fine, but when lignin contains
When amount continues to increase, mechanical property increases and reduced with content of lignin.Due to the complexity of the three-dimensional hyperstructure of lignin
Property, and the chemical group in its structure diversity, when content of lignin is too high, cause to be prone to pair in its course of reaction
Reaction, causes crosslinking degree to decline, and has influence on mechanical property.The lignin-base of the present invention is can be seen that from the oxygen index (OI) of table 1
Epocryl has preferable fire resistance, and the oxygen index (OI) of resin is improved as content of lignin increases.
Table 2
The organic solvent wood that the ultraviolet light curing mode that can be seen that the present invention from the hardness and bending strength of table 2 is obtained
Quality based epoxy acrylate resin membrane material has excellent mechanical property, hardness and the pure epoxy acrylic of bending strength ratio
Ester resin is significantly improved.The adhesive force of obtained membrane material is also greatly improved.The gel content of resin is all higher than 90%, says
Bright crosslinking degree is very high.The lignin-base Epocryl that can be seen that the present invention from the oxygen index (OI) of table 2 has preferable
Fire resistance, the oxygen index (OI) of resin increases and improves with content of lignin.The sulphur that the ultraviolet light curing mode of the present invention is obtained
The performance of hydrochlorate lignin-base Epocryl membrane material also makes moderate progress.It can illustrate that the present invention provides by table 2
The lignin-base Epocryl that ultraviolet light curing mode is obtained has good practicality and application prospect.
Claims (8)
1. a kind of preparation method of lignin-base Epocryl, it is characterised in that including：
Step one：By the reaction of lignin, epoxy resin and DMF, Lignin-based epoxy resin is obtained；
Step 2：Lignin-based epoxy resin, polymerization inhibitor, catalyst and the acrylic monomer reaction that step one is obtained, are obtained
To lignin-base epoxy acrylate；
Step 3：Lignin-base epoxy acrylate and the diluent mixing that step 2 is obtained, obtain lignin-base epoxy third
Olefin(e) acid ester mixed system；
Step 4：The lignin-base epoxy acrylate mixed system curing molding that step 3 is obtained, obtains lignin basic ring
Oxypropylene acid ester resin；
The mass ratio of lignin and epoxy resin is (6-24) in described step one：(96-114)；
The reaction temperature of described step one is 80-120 DEG C, and the reaction time is 1-8h.
2. a kind of preparation method of lignin-base Epocryl according to claim 1, it is characterised in that institute
The lignin stated is organic solvent lignin or sulfonate lignin.
3. a kind of preparation method of lignin-base Epocryl according to claim 1, it is characterised in that institute
It is acrylic or methacrylic acid to state acrylic monomer.
4. a kind of preparation method of lignin-base Epocryl according to claim 1, it is characterised in that institute
The mol ratio of Lignin-based epoxy resin and acrylic monomer is 1 in the step of stating two:(1-2).
5. a kind of preparation method of lignin-base Epocryl according to claim 1, it is characterised in that institute
The reaction temperature of the step of stating two is 80-100 DEG C, and the reaction time is 1-4h.
6. a kind of preparation method of lignin-base Epocryl according to claim 1, it is characterised in that institute
Diluent in the step of stating three is selected from styrene, hydroxy-ethyl acrylate, laurate acrylate, the propylene of polyethylene glycol 400 two
Acid esters, trimethylolpropane trimethacrylate, 1,6 hexanediyl esters, isobornyl methacrylate, pentaerythrite three
Acrylate, ethoxylated trimethylolpropane triacrylate, octadecyl acrylate, three ring propoxylated glycerols 3 third
Olefin(e) acid ester, methyl propenoic acid glycidyl ether, tricarboxylic trimethylolpropane tetra-acrylate, Dipentaerythritol Pentaacrylate,
4- hydroxy butyl vinyl ethers, methoxy poly (ethylene glycol) monomethacrylates, aliphatic monoacrylate or acrylated phosphate
In one or more.
7. a kind of preparation method of lignin-base Epocryl according to claim 1, it is characterised in that institute
The step of stating four is cured as heat cure or photocuring.
8. the lignin-base Epocryl that the preparation method described in claim 1-7 any one is obtained.
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