CN109467716A - A kind of method of modifying of lignin and the preparation method of Lignin-based epoxy resin - Google Patents
A kind of method of modifying of lignin and the preparation method of Lignin-based epoxy resin Download PDFInfo
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- CN109467716A CN109467716A CN201811314354.8A CN201811314354A CN109467716A CN 109467716 A CN109467716 A CN 109467716A CN 201811314354 A CN201811314354 A CN 201811314354A CN 109467716 A CN109467716 A CN 109467716A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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Abstract
The invention discloses a kind of method of modifying of lignin, comprising the following steps: lignin and metal oxide are added in eutectic and are modified reaction, after reaction, by separation, obtains modified lignin resin.Method of modifying based on the lignin, the present invention also provides a kind of preparation methods of Lignin-based epoxy resin.The method of modifying of lignin of the present invention is using eutectic as solvent, cooperate with metal oxide modified lignin, hydrogen bond is formed to C-C in lignin structure using urea in eutectic and choline chloride, C-O key and surface functional group carry out controllable fracture, achieve the effect that sufficiently to dissolve lignin, the Lattice Oxygen formed in metal oxide M=O key is recycled to be selectively oxidized lignin, and then the methoxyl group on efficiently catalytic eliminating lignin surface, the C-O key being broken in lignin, realize the purpose for reducing lignin space structure steric hindrance and increasing the adsorbed hydroxyl content, it can be improved the reactivity of lignin and epoxychloropropane.
Description
Technical field
The present invention relates to the method for modifying of compound, relate in particular to the method for modifying and lignin-base of a kind of lignin
The preparation method of epoxy resin.
Background technique
Lignin is the non-oil resource that uniquely can provide aryl compound in nature.According to statistics, black from slurrying every year
The lignin produced in liquid and bio-ethanol fermentation is more than 50,000,000 tons, is a kind of renewable resource of great potential.Lignin
It is to pass through the three-dimensional netted macromolecular structure that the connections such as C-C key and C-O key are formed by phenylpropane monomer, it is most of wooden
Element is not soluble in water, various active functional group is contained in molecular structure, and nontoxic, inexpensive, there is higher utility value.However,
Since structure is complicated, the inhomogeneity of physicochemical properties, separation and Extraction are difficult for lignin, so that it is not extensive so far
Ground utilizes.Currently, lignin by the way of be divided into two kinds: first is that by chemistry or biological method by lignin degradation be platform
Molecule has the chemicals of added value for Chemical Manufacture etc.;Second is that lignin modification is retained it greatly by physico-chemical process
Molecular structure increases its reactivity for synthetic adhesive, epoxy resin etc..
Epoxy resin has excellent physical chemistry resistance, gumminess and electric property, is widely used as coating, bonding
Agent and semiconductor etc..Epoxy resin can react preparation with bisphenol-A or polymerization by epoxychloropropane.Wherein, although
Epoxychloropropane is converted by reproducible biomass-based glycerol and one of obtains, but prepare the raw material of epoxychloropropane bisphenol-A
It is obtained still through petroleum.With the appearance of the energy and environmental crisis, more researchers can in utilization by target diversion
Regenerated Material synthesis epoxy resin.Currently, more and more focusing on using reproducible lignin is raw material system
Standby Lignin-based epoxy resin.But due to the perfection of lignin structure and loading, Yao Liyong lignin synthesis asphalt mixtures modified by epoxy resin
The crucial problem of rouge is to carry out rationally, being adequately modified to wooden structures, to improve its adsorbed hydroxyl content, smaller steric hindrance
To improve its reactivity with epoxychloropropane.
During lignin modification, the selection of type of solvent has highly important influence to modified effect.Currently, ion
Liquid is widely used in lignin processing as a kind of novel solvent.But the synthesis complexity of ionic liquid, biology can not drop
Solution property and certain toxicity, be widely used in it can not in industrial production.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind can reduce lignin space structure steric hindrance, increases wooden
The method of modifying of the lignin of plain the adsorbed hydroxyl content, and a kind of preparation side of Lignin-based epoxy resin is provided based on this method
Method.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme: a kind of method of modifying of lignin, including
Following steps: lignin and metal oxide being added in eutectic and are modified reaction, after reaction, through excessive
From obtaining modified lignin resin.
Eutectic is the mixture being made of two or more component, and fusing point is lower than the composition mixture
Any component fusing point.Eutectic can be very good substitutional ion liquid, this is because on the one hand, eutectic have with
The similar some solvent properties of ionic liquid, such as: having to inorganic salts, aromatic acid, amino acid and metal oxide preferable molten
Xie Xing;On the other hand, compared with ionic liquid, eutectic shows some unique excellent not available for ionic liquid again
Property, such as: it is easily prepared, do not have an effect with water, biodegradable and toxicology it is easily studied.From these features
Can clearly it find out, eutectic replaces ionic liquid processing, modified lignin resin to have more advantage, is a kind of more green and cheap
Solvent.
Further, the mass ratio of the lignin and the eutectic, the metal oxide is 1:20~40:
0.1~0.5.In implementing the present invention, it may, inventors have found that eutectic can be formed, be mentioned in this ratio range
Realize the maximum dissolution to lignin for enough hydrogen bonds, metal oxide as catalyst, content it is excessive (>
0.5) advantage of catalyst can not be embodied, and very few (< 0.1) can not provide sufficient active site and realize catalysis reaction.
Further, the eutectic is the mixture of the choline chloride and urea that are 2.1~4 by molar ratio, 70
The homogeneous solution of formation is stirred under the conditions of~100 DEG C.In implementing the present invention, it may, inventors have found that using this raw material
The eutectic of proportion has fabulous dissolubility to lignin raw material and metal oxide, can make lignin structure and metal
It is come into full contact between oxide active particle.
Further, the metal oxide is nickel oxide, cobalt oxide, iron oxide, copper oxide, titanium oxide, zinc oxide, oxygen
Any one or any two or more mixtures mixed in any proportion in change chromium, manganese oxide.Implementing mistake of the invention
Cheng Zhong can effective catalytic metal surface inventors have found that contain Lattice Oxygen in the M=O key of these metal oxide surfaces
Oxidation reaction realizes the effect of fracture lignin structure.
Further, the lignin is alkali lignin, lignosulfonates, rice husk lignin, appointing in bamboo lignin
It anticipates one kind.
Further, modified-reaction carries out under the conditions of 1~2Mpa nitrogen pressure, 80~110 DEG C, and the time is 2~5h.In reality
It, can modified lignin resin structure, again to the greatest extent inventors have found that using above-mentioned reaction condition during applying the present invention
Not will lead to lignin structure is broken to small molecule structure comprehensively.
The present invention also provides modified lignin resins made from the method for modifying according to above-mentioned lignin in preparing epoxy resin
Application.
A kind of preparation method of Lignin-based epoxy resin of the present invention, comprising the following steps:
(1) by according to modified lignin resin made from the method for modifying of above-mentioned lignin and solid sodium hydroxide according to mass ratio
The ratio of 2:1 mixes, and stirs evenly, obtains mixture I;
(2) mixture I is added in NaOH solution, adds epoxychloropropane, epoxychloropropane and the innovation wood
The mass ratio of quality is 1~20:1, and after being sufficiently mixed, dislocation is reacted in reaction kettle;
(3) after reaction, curing agent is added and obtains the Lignin-based epoxy resin after curing process.
Further, the concentration of NaOH solution is 2.1~4.9mol/L.In implementing the present invention, it may, invention human hair
It is existing, it can fully make modified lignin resin and epoxychloropropane that epoxidation reaction occur under this concentration.
Further, reaction 2~5Mpa, 70~100 DEG C, be stirred continuously under the conditions of carry out, the time be 5~10h.In reality
During applying the present invention, inventors have found that using above-mentioned reaction condition, reaction can be made more comprehensively, sufficiently, make to be formed
Epoxy resin presoma performance is more excellent.
Further, curing process carries out under the conditions of 200~400 DEG C, 5~10Mpa, the time be 12~for 24 hours.
The beneficial effects of the present invention are embodied in:
1. the method for modifying of lignin of the present invention using eutectic as solvent, cooperates with metal oxide modified lignin, benefit
Hydrogen bond is formed with urea in eutectic and choline chloride to carry out controllably C-C, C-O key in lignin structure and surface functional group
Fracture, achieve the effect that sufficiently to dissolve lignin, recycle in metal oxide M=O key the Lattice Oxygen that is formed to wooden
Element is selectively oxidized, and then the efficiently methoxyl group on catalytic eliminating lignin surface, the C-O key being broken in lignin, real
It now reduces lignin space structure steric hindrance and increases the purpose of the adsorbed hydroxyl content, the modified lignin resin obtained in this way is preparing ring
When oxygen resin, the reactivity of lignin and epoxychloropropane can be improved, realization efficiently synthesizes Lignin-based epoxy resin.
2. the preparation method of Lignin-based epoxy resin of the present invention replaces bisphenol-A using the modified lignin resin that the present invention obtains
Lignin-based epoxy resin is synthesized with epichlorohydrin reaction, sodium hydroxide can make the further open loop of the structure of modified lignin resin,
Preparation method lignin utilization efficiency is high, can reach 87~95%, the tensile strength of Lignin-based epoxy resin obtained can
Reach 30~50MPa, realize it is renewable prepare epoxy resin, can reduce oil product bisphenol-A dosage, alleviate the energy danger
Machine.
3. the method for modifying simple process of lignin of the present invention, low energy consumption, be easy implement and it is renewable, have it is very good
Application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrum comparison diagram of unmodified lignin and modified lignin resin 1,2,9.
Specific embodiment
The present invention will be further described below with reference to examples:
This part carries out general description to the material and experimental method that arrive used in present invention experiment.Although being
It realizes many materials used in the object of the invention and operating method is it is known in the art that still the present invention makees as far as possible herein
Detailed description.It will be apparent to those skilled in the art that hereinafter, if not specified, material therefor, equipment and operation of the present invention
Method is well known in the art.
Embodiment 1
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 70 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 2.1 is made;Weigh 1.0g lignin and 0.1g nickel oxide to be placed in high pressure anti-
Answer in kettle, by eutectic I obtained be added autoclave in (mass ratio of lignin, eutectic and metal oxide be 1:
20:0.1), under 1Mpa nitrogen atmosphere, it is stirred continuously lower reaction 2h in 80 DEG C, 100r/min, then product is carried out plus washed
It washs, be centrifugated, filter, be dried in vacuo, can be obtained modified lignin resin 1.
Embodiment 2
The modification of lignin
It weighs choline chloride and urea is placed in 250mL beaker, stirring is uniformly molten to being formed under 100 DEG C of water bath conditions
The eutectic I that choline chloride and urea mol ratio are 2.5 is made in liquid;It weighs 1.0g lignin and 0.1g cobalt oxide is placed in height
It presses in reaction kettle, (the mass ratio of lignin, eutectic and metal oxide in autoclave is added in eutectic I obtained
It is stirred continuously lower reaction 5h in 110 DEG C, 100r/min under 1Mpa nitrogen atmosphere for 1:40:0.1), then product is carried out
Add water washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 2.
Embodiment 3
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 90 DEG C of water bath conditions,
Obtain the eutectic I that choline chloride and urea mol ratio are 4;Weigh 1.0g lignin and 0.5g chromium oxide to be placed in high pressure anti-
Answer in kettle, by eutectic I obtained be added autoclave in (mass ratio of lignin, eutectic and metal oxide be 1:
30:0.5), under 1Mpa nitrogen atmosphere, it is stirred continuously lower reaction 4h in 100 DEG C, 200r/min, then product is carried out to add water
Washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 3.
Embodiment 4
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 80 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 3 is made;It weighs 1.0g lignin and 0.2g copper oxide is placed in reaction under high pressure
In kettle, by eutectic I obtained be added autoclave in (mass ratio of lignin, eutectic and metal oxide be 1:25:
0.2), under 2Mpa nitrogen atmosphere, be stirred continuously lower reaction 3h in 90 DEG C, 150r/min, then to product carry out plus water washing,
Centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 4.
Embodiment 5
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 90 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 3.5 is made;Weigh 1.0g lignin and 0.3g titanium oxide to be placed in high pressure anti-
Answer in kettle, by eutectic I obtained be added autoclave in (mass ratio of lignin, eutectic and metal oxide be 1:
25:0.3), under 1.5Mpa nitrogen atmosphere, it is stirred continuously lower reaction 4h in 90 DEG C, 150r/min, then product is carried out to add water
Washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 5.
Embodiment 6
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 70 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 4 is made;It weighs 1.0g lignin and 0.5g chromium oxide is placed in reaction under high pressure
In kettle, by eutectic I obtained be added autoclave in (mass ratio of lignin, eutectic and metal oxide be 1:30:
0.5), under 1Mpa nitrogen atmosphere, it is stirred continuously lower reaction 4h in 100 DEG C, 200r/min, then product is carried out plus washed
It washs, be centrifugated, filter, be dried in vacuo, can be obtained modified lignin resin 3.
Embodiment 6
The modification of lignin
It weighs choline chloride and urea is placed in 250mL beaker, stirring is uniformly molten to being formed under 100 DEG C of water bath conditions
The eutectic I that choline chloride and urea mol ratio are 2.8 is made in liquid;It weighs 1.0g lignin and 0.4g zinc oxide is placed in height
It presses in reaction kettle, (the mass ratio of lignin, eutectic and metal oxide in autoclave is added in eutectic I obtained
Be stirred continuously lower reaction 3h in 100 DEG C, 200r/min under 1.5Mpa nitrogen atmosphere for 1:25:0.4), then to product into
Row plus water washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 6.
Embodiment 7
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 70 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 2.3 is made;Weigh 1.0g lignin and 0.1g iron oxide to be placed in high pressure anti-
Answer in kettle, by eutectic I obtained be added autoclave in (mass ratio of lignin, eutectic and metal oxide be 1:
20:0.1), under 1Mpa nitrogen atmosphere, after 80 DEG C, 100r/min are stirred continuously lower reaction 2h, product is carried out plus is washed
It washs, be centrifugated, filter, be dried in vacuo, can be obtained modified lignin resin 7.
Embodiment 8
The modification of lignin
It weighs choline chloride and urea is placed in 250mL beaker, stirring is uniformly molten to being formed under 100 DEG C of water bath conditions
The eutectic I that choline chloride and urea mol ratio are 3.8 is made in liquid;It weighs 1.0g lignin and 0.2g manganese oxide is placed in height
It presses in reaction kettle, (the mass ratio of lignin, eutectic and metal oxide in autoclave is added in eutectic I obtained
It is stirred continuously lower reaction 5h in 110 DEG C, 100r/min under 1Mpa nitrogen atmosphere for 1:40:0.2), then product is carried out
Add water washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 8.
Embodiment 9
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 90 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 3.6 is made;Weigh 1.0g lignin, 0.1g nickel oxide, 0.1g iron oxide
Be placed in autoclave with 0.1g titanium oxide, by eutectic I obtained be added autoclave in (lignin, eutectic and
The mass ratio of metal oxide is 1:25:0.3), under 1.5Mpa nitrogen atmosphere, it is stirred continuously in 90 DEG C, 150r/min lower anti-
4h is answered, then product is carried out to add water washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 9.
Embodiment 10
The modification of lignin
It weighing choline chloride and urea is placed in 250mL beaker, stirring extremely forms homogeneous solution under 90 DEG C of water bath conditions,
The eutectic I that choline chloride and urea mol ratio are 3 is made;Weigh 1.0g lignin, 0.1g copper oxide, 0.1g zinc oxide and
0.1g manganese oxide is placed in autoclave, and (lignin, eutectic and gold in autoclave is added in eutectic I obtained
The mass ratio for belonging to oxide is 1:25:0.3), under 1.5Mpa nitrogen atmosphere, lower reaction is stirred continuously in 90 DEG C, 150r/min
Then 4h carries out product adding water washing, centrifuge separation, filtering, vacuum drying, can be obtained modified lignin resin 10.
Embodiment 11
The preparation of Lignin-based epoxy resin
1g modified lignin resin is weighed, is mixed with 0.5g solid sodium hydroxide, stirs evenly to form mixture I, then adds I
In the NaOH solution for entering the 3.5mol/L of 75mL, the epoxychloropropane of 10g is added, after being sufficiently mixed, dislocation is in reaction under high pressure
In kettle, it is stirred continuously lower reaction 7.5h in 3.5Mpa, 85 DEG C, after reaction, it is solid that 0.15g triethylene tetramine is added into system
Agent solidifies 18h in 300 DEG C, 7.5Mpa, obtains Lignin-based epoxy resin solidfied material.
Embodiment 12
The preparation of Lignin-based epoxy resin
1g modified lignin resin is weighed, is mixed with 0.5g solid sodium hydroxide, stirs evenly to form mixture I, then adds I
In the NaOH solution for entering the 2.1mol/L of 50mL, the epoxychloropropane of 1g is added, after being sufficiently mixed, dislocation is in autoclave
In, it is stirred continuously lower reaction 10h in 2Mpa, 70 DEG C, after reaction, 0.1g triethylene tetramine curing agent is added into system,
Solidify for 24 hours in 200 DEG C, 5Mpa, obtains Lignin-based epoxy resin solidfied material.
Embodiment 13
The preparation of Lignin-based epoxy resin
1g modified lignin resin is weighed, is mixed with 0.5g solid sodium hydroxide, stirs evenly to form mixture I, then adds I
In the NaOH solution for entering the 4.9mol/L of 100mL, the epoxychloropropane of 20g is added, after being sufficiently mixed, dislocation is in reaction under high pressure
In kettle, it is stirred continuously lower reaction 5h in 5Mpa, 100 DEG C, after reaction, the solidification of 0.2g triethylene tetramine is added into system
Agent solidifies 12h in 400 DEG C, 10Mpa, obtains Lignin-based epoxy resin solidfied material.
Embodiment 14
Examination of infrared spectrum is carried out respectively to unmodified lignin and modified lignin resin 1,2,9
As a result referring to Fig. 1, lignin phenol hydroxyl absorption peak 1218cm-1With the absorption peak 3400cm of surface-OH-1Neighbouring
Intensity is remarkably reinforced, and after eutectic and metal oxide modified synergic lignin in 2900cm-1Place belongs to C-O key
Stretching vibration and in 1050cm-1Place belongs to CH in wooden structures2The c h bond stretching vibration intensity of group enhances.Explanation
Obviously increased by the hydroxy radical content on its surface of modified lignin resin produced by the present invention, three-D space structure become it is more fluffy,
It more conducively reacts with epoxychloropropane and synthesizes Lignin-based epoxy resin.
Embodiment 15
Atomic force microscope test analysis, each sample are carried out respectively to unmodified lignin and modified lignin resin 1,2,9
Average surface roughness (Ra), rms surface roughness (Rq) and maximum normal distance (Rmax) as shown in table 1.It is compared to
Log quality, the surface roughness of modified lignin increases, maximum normal distance reduces, this illustrates the steric hindrance of lignin
It is modified through the invention to be substantially reduced.
Table 1
Embodiment 16
The performance and its preparation process lignin utilization rate of Lignin-based epoxy resin see the table below 2.
Table 2
The Lignin-based epoxy resin of number 1# to 10# is i.e. respectively using modified lignin resin 1 to 10 according to embodiment 11
Lignin-based epoxy resin obtained by method.
As can be seen that when using modified lignin resin produced by the present invention synthesis Lignin-based epoxy resin, lignin benefit
Reach 87~95% with rate, the tensile strength of Lignin-based epoxy resin obtained can reach 30~50MPa.
It should be understood that example as described herein and embodiment are not intended to restrict the invention, this field only for explanation
Technical staff can make various modifications or variation according to it, all within the spirits and principles of the present invention, made any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of modifying of lignin, which comprises the following steps: lignin and metal oxide to be added to
It is modified reaction in eutectic, after reaction, by separation, obtains modified lignin resin.
2. the method for modifying of lignin as described in claim 1, which is characterized in that the lignin and the eutectic,
The mass ratio of the metal oxide is 1:20~40:0.1~0.5.
3. the method for modifying of lignin as claimed in claim 1 or 2, which is characterized in that the eutectic is by molar ratio
For 2.1~4 choline chloride and the mixture of urea, the homogeneous solution of formation is stirred under the conditions of 70~100 DEG C.
4. the method for modifying of lignin as claimed in claim 1 or 2, which is characterized in that the metal oxide be nickel oxide,
Cobalt oxide, iron oxide, copper oxide, titanium oxide, zinc oxide, chromium oxide, any one or any two or more in manganese oxide are pressed
The mixture of arbitrary proportion mixing.
5. the method for modifying of lignin as claimed in claim 1 or 2, which is characterized in that the lignin is alkali lignin, wood
Mahogany sulfonate, rice husk lignin, any one in bamboo lignin.
6. the method for modifying of lignin as claimed in claim 1 or 2, which is characterized in that modified-reaction is in 1~2Mpa nitrogen
It presses, carried out under the conditions of 80~110 DEG C, the time is 2~5h.
7. being prepared according to modified lignin resin made from the method for modifying such as lignin described in any one of claims 1 to 6
Application in epoxy resin.
8. a kind of preparation method of Lignin-based epoxy resin, which comprises the following steps:
It (1) will be according to modified lignin resin made from the method for modifying such as lignin described in any one of claims 1 to 6 and admittedly
Body sodium hydroxide is mixed according to the ratio of mass ratio 2:1, is stirred evenly, is obtained mixture I;
(2) mixture I is added in NaOH solution, adds epoxychloropropane, epoxychloropropane and the modified lignin resin
Mass ratio be 1~20:1, after being sufficiently mixed, dislocation is reacted in reaction kettle;
(3) after reaction, curing agent is added and obtains the Lignin-based epoxy resin after curing process.
9. the preparation method of Lignin-based epoxy resin as claimed in claim 8, which is characterized in that the concentration of NaOH solution is
2.1~4.9mol/L.
10. the preparation method of Lignin-based epoxy resin as claimed in claim 8 or 9, which is characterized in that reaction 2~
5Mpa, 70~100 DEG C, be stirred continuously under the conditions of carry out, the time be 5~10h.
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CN111187190A (en) * | 2020-01-10 | 2020-05-22 | 华南理工大学 | Epoxy resin based on vanillin and amino acid and preparation method and application thereof |
CN112094611A (en) * | 2020-09-25 | 2020-12-18 | 大连工业大学 | Low-temperature-resistant lignin-based epoxy resin adhesive and preparation method thereof |
CN112126391A (en) * | 2020-09-25 | 2020-12-25 | 大连工业大学 | Waterproof lignin-based epoxy resin adhesive and preparation method thereof |
CN112979988A (en) * | 2021-03-30 | 2021-06-18 | 北京林业大学 | Preparation of epoxidized lignin and application method thereof in preparation of carbonic ester |
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CN110947421A (en) * | 2019-11-19 | 2020-04-03 | 华侨大学 | Preparation method of functionalized lignin-loaded eutectic solvent heterogeneous catalyst and application of functionalized lignin-loaded eutectic solvent heterogeneous catalyst in chemical conversion of carbon dioxide |
CN110947421B (en) * | 2019-11-19 | 2022-06-07 | 华侨大学 | Preparation method of functionalized lignin supported eutectic solvent heterogeneous catalyst and application of functionalized lignin supported eutectic solvent heterogeneous catalyst in chemical conversion of carbon dioxide |
CN111187190A (en) * | 2020-01-10 | 2020-05-22 | 华南理工大学 | Epoxy resin based on vanillin and amino acid and preparation method and application thereof |
CN112094611A (en) * | 2020-09-25 | 2020-12-18 | 大连工业大学 | Low-temperature-resistant lignin-based epoxy resin adhesive and preparation method thereof |
CN112126391A (en) * | 2020-09-25 | 2020-12-25 | 大连工业大学 | Waterproof lignin-based epoxy resin adhesive and preparation method thereof |
CN112979988A (en) * | 2021-03-30 | 2021-06-18 | 北京林业大学 | Preparation of epoxidized lignin and application method thereof in preparation of carbonic ester |
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