CN106750068A - A kind of preparation method of lignin modification phenolic resin - Google Patents
A kind of preparation method of lignin modification phenolic resin Download PDFInfo
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- CN106750068A CN106750068A CN201611168488.4A CN201611168488A CN106750068A CN 106750068 A CN106750068 A CN 106750068A CN 201611168488 A CN201611168488 A CN 201611168488A CN 106750068 A CN106750068 A CN 106750068A
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to Polymer Synthesizing and technical field of modification, specifically a kind of preparation method of lignin modification phenolic resin comprises the following steps:1) lignin and formaldehyde are reacted into the methylolated lignin of generation in the basic conditions, is component A;2) phenol is reacted in acid condition with formaldehyde, B component is obtained after dehydration;3) component A and acidic catalyst are added into B component, dehydration obtains lignin modification phenolic resin after reaction.The beneficial effects of the present invention are:The preparation method of lignin modification phenolic resin of the present invention, polycondensation reaction is carried out by the phenolic aldehyde performed polymer of hydroxymethylated lignin and low-molecular-weight in acid condition, and dehydration obtains lignin modification phenolic resin.The ratio that lignin participates in chemical reaction is the method increase, content of lignin is high in the phenolic resin strand for preparing, low production cost, resin high comprehensive performance.
Description
Technical field
The present invention relates to Polymer Synthesizing and technical field of modification, specifically a kind of system of lignin modification phenolic resin
Preparation Method.
Background technology
Phenolic resin is the macromolecular compound of first man work synthesis, mechanical property and the premium properties such as heat-resist,
The application field of macromolecular material occupies very big ratio, is used widely in fields such as national defence, industrial or agricultural, building, traffic.
But phenolic resin exist poor toughness, cost of material it is high and non-renewable the shortcomings of, increasingly reduced in petrochemical, therefore
Have to look for substituting the renewable resource of phenol.
Lignin is renewable, nonoil compound aromatic base, and the reserves in nature are only second to cellulose, the whole world
Pulp and paper industry will isolate about 1.4 hundred million tons of celluloses from plant every year, while 50,000,000 tons or so of generation is wooden
Plain byproduct, wherein 95% lignin is burnt after rivers or concentration are still directly discharged into the way of " black liquor ", is seldom had
Effect is utilized.Due to containing more aldehyde radical and hydroxyl on lignin molecule, hydroxyl exists in two kinds of forms of alcoholic extract hydroxyl group and phenolic hydroxyl group,
Phenol can be partly substituted under certain condition or formaldehyde participates in the condensation reaction of phenolic resin, and lignin is reproducible
Natural organic high-molecular material, the effective road that sustainable development is not only conformed with using lignin, moreover it is possible to solve environmental pollution
Problem.Lignin is substituted into part formaldehyde or phenol may also operate as improving phenolic resin modified effect the property of resin
Energy.
At present, lignin modification phenolic resin mainly has following several method:1st, lignin first reacts with phenol, adds again afterwards
Enter aldehyde to be reacted, finally dehydration obtains lignin modification phenolic resin.As number of patent application be 201210557028.6 it is special
Profit discloses a kind of preparation method of lignin phenol formaldehyde resin:By lignin compound, phenolic compound and acidic catalyst
Mixing, is heated to 180~350 DEG C and is reacted, and obtains mixed reaction solution;The mixed reaction solution is mixed with formaldehyde, polycondensation
Lignin phenol formaldehyde resin performed polymer is obtained after reaction.Number of patent application is that 201310745400.0 patent discloses a kind of modified
The preparation method of phenolic resin:Phenolic compound heats generation first and reacts in acid condition with lignin, obtains first anti-
Answer mixture;First reactant mixture, phenolic compound and aldehyde compound are carried out into the second reaction, the second reaction mixing is obtained
Thing;After above-mentioned second reactant mixture is mixed with modifying agent, phenol-formaldehyde resin modified is obtained.Number of patent application is
Lignin modification phenolic resin is also based on above procedure disclosed in 201210393232.9 and 201310259451.2 patent.
2nd, phenol and formaldehyde are reacted, and lignin is reacted afterwards, and finally dehydration obtains lignin modification phenolic resin such as Application No.
201010252819.9 patent.3rd, phenol, formaldehyde, lignin add reactor to be reacted together, such as application number:
201010269425.4 patent discloses a kind of preparation method of lignin phenol formaldehyde resin, is directly to use the same benzene of liquid lignin
The lignin phenol formaldehyde resin that phenol, formaldehyde are obtained under liquid caustic soda effect in 70~100 DEG C of stirring reactions.Application No.
A kind of preparation method of phenolic resin for wet curtain paper is also based on above course of reaction disclosed in 201110074525.6 patent.
Additionally, also disclosing a kind of original of industrial alkali lignin modified phenolic resin just like the patent of Application No. 201310477129.7
Position ultrasound polymerization preparation method, the patent of Application No. 201210265304.1 discloses a kind of two-step method akaline liquid lignin
The preparation method of phenolic resin.But because lignin molecule amount is big, reactivity is relatively low, directly participates in the lignin of chemical reaction
Content is small, and modified effect is not enough, does not give full play to improvement effect of the lignin to phenolic resin properties, most of lignin
Simply act as the effect of physical modification.
The content of the invention
The technical problems to be solved by the invention are:It is an object of the invention to provide content of lignin is high, it is low cost, comprehensive
Close the preparation method of the lignin modification phenolic resin of function admirable.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is:A kind of lignin modification phenolic aldehyde tree is provided
The preparation method of fat, comprises the following steps:
1) lignin and formaldehyde are reacted into the methylolated lignin of generation in the basic conditions, is component A;
2) phenol is reacted in acid condition with formaldehyde, B component is obtained after dehydration;
3) component A and acidic catalyst are added into B component, dehydration obtains lignin modification phenolic resin after reaction.
Preferably, the preparation method of above-mentioned lignin modification phenolic resin, specifically includes following steps:
1) by lignin and formaldehyde addition reactor, stir, the pH that reaction solution is adjusted with alkali is 8-12, is warming up to
80-100 DEG C, 1-6h is reacted, obtain component A;
2) by phenol and another reactor of formaldehyde addition, stir, be 1-4 with acid for adjusting pH, be 70- in temperature
1-5h is reacted at 100 DEG C, B component is obtained after dehydration;
3) component A and acid are added into B component, back flow reaction 1-5h, dehydration obtains lignin modification phenolic resin.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, the lignin be lignosulfonates,
One kind in alkali lignin, enzymolysis xylogen, acidolysis lignin, high-boiling alcohol lignin.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, the addition of the lignin is phenol
The 1%-20% of quality.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, the formaldehyde is the formalin of 35-50%
Solution.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, total consumption of the phenol and formaldehyde
Mol ratio is 1:0.7-1.0, the step 2) in phenol and formaldehyde mol ratio be 1:0.6-0.8.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, the alkali is selected from NaOH, hydroxide
Potassium, barium hydroxide, calcium oxide, zinc oxide, aluminum oxide, magnesia, phosphate, carbonate, borate, silicate, organic metal
Compound, amine R3N and amine oxide R3One or more in NO, the organo-metallic compound is selected from RLi, R2Zn and R2Mg
In one or more, wherein R represents one or more organic substituents that are identical or differing.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, it is described acid selected from oxalic acid, acetic acid, hydrochloric acid,
One or more in sulfuric acid, phosphoric acid, phosphonic acids, benzene sulfonic acid and p-methyl benzenesulfonic acid.
Preferably, in the preparation method of above-mentioned lignin modification phenolic resin, the step 3) in sour consumption be
The 0.1-10% of phenol quality.
The beneficial effects of the present invention are:The preparation method of lignin modification phenolic resin of the present invention, by methylolation wood
Quality carries out polycondensation reaction in acid condition with the phenolic aldehyde performed polymer of low-molecular-weight, and dehydration obtains lignin modification phenolic aldehyde tree
Fat.The method increase the ratio that lignin participates in chemical reaction, content of lignin in the phenolic resin strand for preparing
Height, low production cost, resin high comprehensive performance.
Specific embodiment
To describe technology contents of the invention, the objects and the effects in detail, it is explained below in conjunction with implementation method.
The design of most critical of the present invention is:Methylolation is carried out to lignin using formaldehyde in the basic conditions, is formed
Methylolation short chain polymer, to improve the reactivity of lignin;Again by methylolated lignin short chain polymer with it is low
The phenolic aldehyde performed polymer of molecular weight carries out further polycondensation reaction, so as to realize introducing lignin in phenolic resin strand
Purpose, and content of lignin is high.
Specifically, the preparation method of the lignin modification phenolic resin of embodiment of the present invention, comprises the following steps:1) will
Lignin reacts the methylolated lignin of generation in the basic conditions with formaldehyde, is component A;2) by phenol and formaldehyde in acidity
Under the conditions of react, B component is obtained after dehydration;3) component A and acidic catalyst are added into B component, dehydration obtains wooden after reaction
Plain phenol-formaldehyde resin modified.
Knowable to foregoing description, the beneficial effects of the present invention are:By hydroxymethylated lignin and the phenolic aldehyde of low-molecular-weight
Performed polymer carries out polycondensation reaction in acid condition, and dehydration obtains lignin modification phenolic resin.The method increase lignin
The ratio of chemical reaction is participated in, content of lignin is high in the phenolic resin strand for preparing, low production cost, resin synthesis
Function admirable.
Further, the preparation method of lignin modification phenolic resin of the invention, comprises the following steps:
1) by lignin and formaldehyde addition reactor, stir, the pH that reaction solution is adjusted with alkali is 8-12, is warming up to
80-100 DEG C, 1-6h is reacted, obtain component A;
2) by phenol and another reactor of formaldehyde addition, stir, be 1-4 with acid for adjusting pH, be 70- in temperature
1-5h is reacted at 100 DEG C, B component is obtained after dehydration;
3) component A and acid are added into B component, back flow reaction 1-5h, dehydration obtains lignin modification phenolic resin.
In above-mentioned course of reaction, lignin and formaldehyde are carried out into methylolation in the basic conditions first.Wherein described alkali
Property condition be preferably pH under conditions of 8-12, reaction temperature is preferably 80-100 DEG C, and the reaction time is preferably 1-6h.
Wherein, the lignin is lignosulfonates, alkali lignin, enzymolysis xylogen, acidolysis lignin, high boiling alcohol wood
One kind in quality.Lignin has certain molecular weight, though containing some active groups, the content of active group is less,
And influenceed by steric hindrance, its reactivity is not high, and it is bad to be directly used in phenol-formaldehyde resin modified effect, participationization
The content of lignin for learning reaction is few, and most of lignin is to be distributed in resin in the way of physical mixed.The present invention is in alkali
Property under the conditions of methylolation carried out to lignin with formaldehyde be modified, improve lignin reaction's activity, modified lignin
Active group is methylol, and reactivity of the methylol further with phenol or phenolic aldehyde performed polymer is greatly improved.Wherein described formaldehyde
It is the formalin of 35-50%, preferably 37% formalin.The consumption of the lignin is the 1%- of phenol quality
20%.
In order to reach the alkalescence condition, alkali can be added, to adjust pH value in reaction.Wherein described alkali can be hydroxide
Sodium, potassium hydroxide, barium hydroxide, calcium oxide, zinc oxide, aluminum oxide, magnesia, phosphate, carbonate, borate, silicate,
Organo-metallic compound, amine R3N and amine oxide R3One or more in NO, the organo-metallic compound be selected from RLi,
R2Zn and R2One or more in Mg, wherein R represents one or more organic substituents that are identical or differing.
In another reactor, phenol and formaldehyde are reacted in acid condition, and dehydration obtains the phenol of low-molecular-weight
Aldehyde performed polymer.Wherein, the acid condition refers to that pH is 1-4, and reaction temperature is preferably 70-100 DEG C, and the reaction time is preferably 1-
5h, obtains phenolic aldehyde performed polymer after dehydration.Resulting phenolic aldehyde performed polymer also contains necessarily in still having reactivity, and performed polymer
The free-phenol and formaldehyde of amount, can further participate in reaction.The mol ratio of phenol and formaldehyde is 1 wherein described in this step:
0.6-0.8, preferably 1:0.6-0.7.Phenol can control the molecular weight of performed polymer with the mol ratio of aldehyde, and performed polymer molecular weight is unsuitable
It is too high, to retain its reactivity.
In order to reach described acid condition, acid can be added, to adjust pH value in reaction.Wherein described acid can be grass
One or more in acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acids, benzene sulfonic acid and p-methyl benzenesulfonic acid, more preferably oxalic acid
Or hydrochloric acid.
Finally, methylolated lignin is carried out into polycondensation reaction again with acid and phenolic aldehyde performed polymer, by lignin molecule
Chain is connected in phenolic aldehyde strand.Wherein described acid can for oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acids, benzene sulfonic acid and
One or more in p-methyl benzenesulfonic acid, more preferably oxalic acid or hydrochloric acid.Described sour consumption is phenol quality
0.1-10%.Reaction time is preferably 1-5h.
In whole course of reaction, the mol ratio of phenol and formaldehyde is preferably 1:0.7-1.0.Mol ratio is too high, and strand is big,
Poor processability.Mol ratio is too low, and molecular resin amount is small, and softening point is low, intensity difference.Suitable control phenolic aldehyde mol ratio is to realize wood
One important step of quality phenol-formaldehyde resin modified Good All-around Property.
Embodiment 1
1) by lignin 1.5g and 37% formalin 13g addition reactors, stir, adjusted with NaOH
The pH of reaction solution is 9, is warming up to 100 DEG C, reacts 3h, obtains component A;
2) by phenol 100g and 37% formalin 56g another reactors of addition, stir, use salt acid for adjusting pH
It is 1.5,2h is reacted at being 95 DEG C in temperature, B component is obtained after dehydration;
3) component A and oxalic acid 0.3g are added into B component, back flow reaction 4h, dehydration obtains lignin modification phenolic resin.
Embodiment 2
1) by lignin 1.5g and 37% formalin 17g addition reactors, stir, adjusted with NaOH
The pH of reaction solution is 8, is warming up to 100 DEG C, reacts 3h, obtains component A;
2) by phenol 100g and 37% formalin 53g another reactors of addition, stir, use careless acid for adjusting pH
It is 2,2h is reacted at being 95 DEG C in temperature, B component is obtained after dehydration;
3) component A and oxalic acid 0.2g are added into B component, back flow reaction 4h, dehydration obtains lignin modification phenolic resin.
Embodiment 3
1) by lignin 1.0g and 37% formalin 9g addition reactors, stir, adjusted with potassium hydroxide
The pH of reaction solution is 9, is warming up to 100 DEG C, reacts 3h, obtains component A;
2) by phenol 100g and 37% formalin 60g another reactors of addition, stir, use salt acid for adjusting pH
It is 2,2h is reacted at being 100 DEG C in temperature, B component is obtained after dehydration;
3) component A and hydrochloric acid 0.2g are added into B component, back flow reaction 4h, dehydration obtains lignin modification phenolic resin.
The lignin modification phenolic resin that above-described embodiment 1-3 is prepared is carried out with unmodified phenolic resin
Contrast, control methods is as follows:
The phenolic resin of the lignin modification that above-described embodiment 1-3 is prepared prepares phenol according to the formula shown in table 1
Aldehyde moulding compound (consumption unit is weight portion), phenolic aldehyde mould is prepared by unmodified phenolic resin according to the formula shown in table 2
Plastics (consumption unit is weight portion).The method that the phenolic resin and phenolic resin of lignin modification prepare phenolaldehyde moulding compound
It is as follows:
1) each raw material is weighed according to formula shown in form, is well mixed during each raw material is added into mixer;
2) in the material feeding mill that will be mixed or extruder, phenol is obtained after over-mastication, compressing tablet, cooling, crushing
Aldehyde moulding compound.
The formula of the phenolaldehyde moulding compound of table 1
The formula of the phenolaldehyde moulding compound of table 2
The performance test data of each embodiment and comparative example is as shown in table 3 below.
The gained phenolaldehyde moulding compound performance data of table 3 is contrasted
Knowable to shown in above-mentioned table 3, under same raw material, proportion and technology condition, changed using lignin of the invention
Property phenolic resin obtained by phenolaldehyde moulding compound, compared to using the phenolic molding compound obtained by unmodified phenolic resin
Material, with more excellent mechanical performance, also preferably, combination property is preferable for dimensional stability.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, it is every to utilize this hair
The equivalents that bright description is made, or the technical field of correlation is directly or indirectly used in, similarly it is included in this hair
In bright scope of patent protection.
Claims (9)
1. a kind of preparation method of lignin modification phenolic resin, it is characterised in that:Comprise the following steps:
1) lignin and formaldehyde are reacted into the methylolated lignin of generation in the basic conditions, is component A;
2) phenol is reacted in acid condition with formaldehyde, B component is obtained after dehydration;
3) component A and acidic catalyst are added into B component, dehydration obtains lignin modification phenolic resin after reaction.
2. the preparation method of a kind of lignin modification phenolic resin according to claim 1, it is characterised in that specifically include
Following steps:
1) by lignin and formaldehyde addition reactor, stir, the pH that reaction solution is adjusted with alkali is 8-12, is warming up to 80-
100 DEG C, 1-6h is reacted, obtain component A;
2) by phenol and another reactor of formaldehyde addition, stir, be 1-4 with acid for adjusting pH, be 70-100 DEG C in temperature
Lower reaction 1-5h, obtains B component after dehydration;
3) component A and acid are added into B component, back flow reaction 1-5h, dehydration obtains lignin modification phenolic resin.
3. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:It is described wooden
Element is the one kind in lignosulfonates, alkali lignin, enzymolysis xylogen, acidolysis lignin, high-boiling alcohol lignin.
4. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:It is described wooden
The addition of element is the 1%-20% of phenol quality.
5. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:The formaldehyde
It is the formalin of 35-50%.
6. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:The phenol
It is 1 with total consumption mol ratio of formaldehyde:0.7-1.0, the step 2) in phenol and formaldehyde mol ratio be 1:0.6-
0.8。
7. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:The alkali choosing
From NaOH, potassium hydroxide, barium hydroxide, calcium oxide, zinc oxide, aluminum oxide, magnesia, phosphate, carbonate, boric acid
Salt, silicate, organo-metallic compound, amine R3N and amine oxide R3One or more in NO, the organo-metallic compound
Selected from RLi, R2Zn and R2One or more in Mg, wherein R represents one or more organic substituents that are identical or differing.
8. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:The acid choosing
One or more from oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acids, benzene sulfonic acid and p-methyl benzenesulfonic acid.
9. the preparation method of a kind of lignin modification phenolic resin according to claim 2, it is characterised in that:The step
3) the sour consumption in is the 0.1-10% of phenol quality.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112940209A (en) * | 2021-01-22 | 2021-06-11 | 福建船政交通职业学院 | Hydroxymethylation modified lignin phenolic resin adsorption microspheres and preparation method thereof |
CN113816373A (en) * | 2021-09-16 | 2021-12-21 | 常州大学 | Preparation method of biomass modified phenolic resin carbon spheres with controllable particle size |
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CN102558473A (en) * | 2011-12-28 | 2012-07-11 | 北京彤程创展科技有限公司 | Cashew nut oil-modified phenolic resin and preparation method thereof |
CN102775568A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of modified phenolic resin |
CN102775569A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of lignin modified phenolic resin |
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Patent Citations (3)
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CN102558473A (en) * | 2011-12-28 | 2012-07-11 | 北京彤程创展科技有限公司 | Cashew nut oil-modified phenolic resin and preparation method thereof |
CN102775568A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of modified phenolic resin |
CN102775569A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of lignin modified phenolic resin |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112940209A (en) * | 2021-01-22 | 2021-06-11 | 福建船政交通职业学院 | Hydroxymethylation modified lignin phenolic resin adsorption microspheres and preparation method thereof |
CN113816373A (en) * | 2021-09-16 | 2021-12-21 | 常州大学 | Preparation method of biomass modified phenolic resin carbon spheres with controllable particle size |
CN113816373B (en) * | 2021-09-16 | 2023-10-27 | 常州大学 | Preparation method of particle size-controllable biomass modified phenolic resin carbon spheres |
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