CN102936323A - Preparation method of lignin-phenol-formaldehyde resin and preparation method of lignin-phenol-formaldehyde resin foam - Google Patents
Preparation method of lignin-phenol-formaldehyde resin and preparation method of lignin-phenol-formaldehyde resin foam Download PDFInfo
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Abstract
The invention provides a preparation method of lignin-phenol-formaldehyde resin and a preparation method of lignin-phenol-formaldehyde resin foam. The preparation method of the lignin-phenol-formaldehyde resin comprises the following steps: mixing and reacting lignin and a phenolic compound with a nucleophilic reagent to obtain a lignin phenol compound; adjusting the pH (Potential of Hydrogen) of the lignin phenol compound to reach alkalinity; then mixing and reacting the lignin phenol compound with formaldehyde, so as to obtain the lignin-phenol-formaldehyde resin. The preparation method of the lignin-phenol-formaldehyde resin foam comprises the following steps: mixing the obtained lignin-phenol-formaldehyde resin with a foaming agent, a curing agent and a surface active agent; and foaming and curing to obtain the lignin-phenol-formaldehyde resin foam. According to the preparation methods, the phenol compound serves as a solvent, and the ether bonds in the Alpha-aryl ether, Alpha-alkyl ether, phenol type Beta-aryl ether, non-phenol type Beta-aryl ether containing Alpha-alcoholic hydroxyl, and methyl aryl ether in the lignin are broken, so that lignin macromolecule can be degraded well, and as a result, the activity of the lignin and the strength of the lignin-phenol-formaldehyde resin foam are improved. By adopting the preparation methods, the existing forestry and agricultural residues which have no economic value and bring pollution to the environment are used as the environment-friendly new bio-based polymer materials, and remarkable economic benefits, social benefits and eco-environment benefits are brought thereby.
Description
Technical field
The present invention relates to the bio-based technical field of macromolecules, relate in particular to a kind of preparation method of lignin phenol formaldehyde resin and the preparation method of lignin phenol formaldehyde resin foam.
Background technology
Xylogen claims again lignin, be a ubiquitous class aromaticity superpolymer in the plant materials, be bonded together the primary structure that consists of plant with Mierocrystalline cellulose, hemicellulose, have the effect of strengthening wood fibre, it is next in number only to Mierocrystalline cellulose, is the abundant organic polymer of vegitabilia second.The content of xylogen in timber is generally 20%～40%, and content of lignin is generally low than timber in the grass, is 15%～25%.The xylogen source is abundant, is renewable resources, and according to estimates, the annual output in its whole world is about 6 * 10
5Hundred million tons be the non-oil resource that nature can provide renewable compound aromatic base, and its productive rate is higher, is regarded as good environmental type industrial chemicals.
Xylogen is by the high molecular polymer that has the phenyl-propane cell formation of hydroxyphenyl, lignum-vitae base and Syringa oblata Lindl. base, contain phenolic hydroxyl group and aldehyde radical in its molecule, has certain reactive behavior, can react with phenol, formaldehyde etc. under certain condition and form lignin-base resol, can save the petroleum resources such as phenol simultaneously.But the molecular weight of natural lignin is higher, and the substituting group steric hindrance on the phenyl ring of xylogen own is larger, therefore can not be effectively and resol react.For example expandable phenolic resin is a kind of resole, mix with whipping agent, solidifying agent, tensio-active agent etc. and can get phenolic foams, phenol formaldehyde foam has good flame retardant resistance and heat insulating ability, be widely used in the industries such as building, petrochemical complex, electric, instrument as heat-insulating heat-preserving material, expandable phenolic resin requires the activity of resin higher, and natural lignin's molecular weight is large, active low, xylogen directly adds the activity that can reduce resol in the expandable phenolic resin, improve its foaming difficulty, and the phenolic foams intensity of producing is low.This solves the active low problem of xylogen with regard to needs.
Patent CN101260283 discloses take phenol as liquefied reagent, add xylogen, take acid as liquefied catalytic reagent, be warming up to 90～150 ℃, the insulation liquefaction reaction, then in liquefier, add basic catalyst and formaldehyde, normal pressure is warming up to 70～97 ℃ of reactions 1～3 hour, prepare the technology of the phenolic resin adhesive of liquefying lignin, but in this technology, the xylogen catalytic liquefaction is only take acid as catalytic reagent, the catalyzed degradation weak effect of xylogen, and what prepare is the phenolic aldehyde sizing agent, and active low than expandable phenolic resin of phenolic aldehyde sizing agent.Patent CN200810243419.4 discloses xylogen under alkaline condition, take phenol as solvent liquefied wood quality, then the technology for preparing resole with phenol, formaldehyde condensation polymer, its performance index reach the petroleum chemicals level, but the Liquefaction Products in Phenol xylogen can only substitute 10%～20% phenol and prepare resole, and still cost is higher.Patent CN101269930A discloses enzymolysis xylogen or derivatives thereof and phenol and formaldehyde addition condensation under alkaline condition and has prepared expandable resin, then with the technology of solidifying agent, whipping agent and tensio-active agent mixed foaming, but the enzymolysis xylogen that adopts needs to be further purified processing in the laboratory, has increased production cost.Patent CN102504477 discloses xylogen and added the oxidising agent degraded under alkaline condition, replace phenol to prepare the lignin modification resole, then with solidifying agent, whipping agent and tensio-active agent blend, obtain the technology of modified phenolic foam plastic after solidifying, but during its lignin degradation only take alkali as catalyzer, catalytic effect is relatively poor, and the hydrogen peroxide of using in the reaction, the xylogen benzene ring structure can be destroyed, is degraded to the low-molecular-weight fat compounds of group, thereby reduce the reactive behavior of xylogen.Patent CN101985492 discloses a kind of foaming lignin modification resole and preparation method thereof, the method directly joins in the resol undressed xylogen in batches, used xylogen is the thick enzymolysis xylogen of by product of maize straw fermenting and preparing biological butyl alcohol, saccharan product, and wherein the enzymolysis xylogen mass content only is 70%.It is too low that xylogen is applied directly in the resole activity without pre-treatment, and can cause resol viscosity significantly to increase, and improves the foaming difficulty, reduces phenol formaldehyde foam intensity.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of lignin phenol formaldehyde resin and the preparation method of lignin phenol formaldehyde resin foam, and method provided by the invention is simple, and the xylogen activity is good, and the phenolic resin foam intensity that obtains is high.
The invention provides a kind of preparation method of lignin phenol formaldehyde resin, may further comprise the steps:
A) xylogen, phenolic compound and nucleophilic reagent mixing, reaction are obtained lignin phenol's compound;
Then the pH value of the lignin phenol's compound that B) regulating step A) obtains is mixed with aldehyde, is reacted and obtain lignin phenol formaldehyde resin to alkalescence.
Preferably, described nucleophilic reagent is selected from oxyhydroxide, sulfide, sulfohydrate, sulphite, hydrosulphite, vitriol, hydrosulfate, H
2S, H
2SO
3And H
2SO
4In any one or a few.
Preferably, described phenolic compound is selected from any one or a few in phenol, cresols, Resorcinol, nonylphenol and the cardanol.
Preferably, described aldehyde is selected from any one or a few in formaldehyde, acetaldehyde, furfural and the Paraformaldehyde 96.
Preferably, the mass ratio of described xylogen and phenolic compound is 1 ~ 10:5.
Preferably, the mass ratio of described nucleophilic reagent and xylogen is 0.1 ~ 10:100.
Preferably, the mol ratio of described aldehyde and phenolic compound is 1 ~ 3:1.
Preferably, described steps A) in, the temperature of described reaction is 100 ℃ ~ 200 ℃, the time of described reaction is 1h ~ 10h.
Preferably, described step B) in, the temperature of described reaction is 60 ℃ ~ 100 ℃, the time of described reaction is 1h ~ 6h.
The present invention also provides a kind of preparation method of lignin phenol formaldehyde resin foam, may further comprise the steps:
A) xylogen, phenolic compound and nucleophilic reagent mixing, reaction are obtained lignin phenol's compound;
Then the pH value of the lignin phenol's compound that B) regulating step A) obtains is mixed with aldehyde, is reacted and obtain lignin phenol formaldehyde resin to alkalescence;
C) with step B) lignin phenol formaldehyde resin that obtains mixes with whipping agent, solidifying agent and tensio-active agent, and foamed solidification obtains the lignin phenol formaldehyde resin foam.
The present invention at first mixes xylogen, phenolic compound and nucleophilic reagent, reaction obtains lignin phenol's compound; Then regulate its pH value to alkalescence, and mix with aldehyde, react and obtain lignin phenol formaldehyde resin.Compared with prior art, the present invention adopts phenolic compound as solvent, then add nucleophilic reagent, with the alpha-aromatic ether in the xylogen, alpha-alkyl ether, phenol type beta-aromatic ether, the non-phenol type beta-aromatic ether that contains α-alcoholic extract hydroxyl group and the ether bond rupture in the methyl aryl ether, the xylogen macromole can be degraded preferably, acquisition has the liquefying lignin product of high reaction activity, then prepares to have the alternative amount of high phenol and highly active expandability lignin phenol formaldehyde resin; After preparing lignin phenol formaldehyde resin by present method, it is mixed with whipping agent, solidifying agent and tensio-active agent, foamed solidification can obtain the lignin phenol formaldehyde resin foam.Lignin phenol formaldehyde resin foam to preparation carries out performance test, and the result shows, the lignin phenol formaldehyde resin foam of the present invention's preparation has higher intensity, lower water-intake rate and lower thermal conductivity.Simultaneously, the xylogen raw material sources are abundant, the present invention will not have at present economic worth and cause the agriculture and forestry organic waste material of environmental pollution, be developed as eco-friendly bio-based polymer novel material, thereby improve the processing and utilization level of agricultural resource, increase value-added content of product, extend the forestry industry chain, have significant economy, society and ecological environment benefit.
Embodiment
The invention provides a kind of preparation method of lignin phenol formaldehyde resin, may further comprise the steps:
A) xylogen, phenolic compound and nucleophilic reagent mixing, reaction are obtained lignin phenol's compound;
Then the pH value of the lignin phenol's compound that B) regulating step A) obtains is mixed with aldehyde, is reacted and obtain lignin phenol formaldehyde resin to alkalescence.
After preparing lignin phenol formaldehyde resin, it is mixed with whipping agent, solidifying agent and tensio-active agent, foamed solidification can obtain the lignin phenol formaldehyde resin foam.
Compared with prior art, the present invention adopts phenolic compound as solvent, then add nucleophilic reagent, with the alpha-aromatic ether in the xylogen, alpha-alkyl ether, phenol type beta-aromatic ether, the non-phenol type beta-aromatic ether that contains α-alcoholic extract hydroxyl group and the ether bond rupture in the methyl aryl ether, the xylogen macromole can be degraded preferably, acquisition has the liquefying lignin product of high reaction activity, then prepares to have the alternative amount of high phenol and highly active expandability lignin phenol formaldehyde resin; After preparing lignin phenol formaldehyde resin by present method, it is mixed with whipping agent, solidifying agent and tensio-active agent, foamed solidification can obtain the lignin phenol formaldehyde resin foam.
The present invention at first mixes xylogen, phenolic compound and nucleophilic reagent, reaction obtains lignin phenol's compound.
The present invention there is no particular requirement to the source of employed xylogen, can be xylogen well known to those skilled in the art, the present invention preferably extracts from straw such as maize straw, rice straw, reed stalk etc. or corn cob and obtains, the present invention there is no particular requirement to its extracting method, can be the method for extraction xylogen well known to those skilled in the art, the present invention preferably extracts in accordance with the following methods and obtains xylogen:
At first straw such as maize straw, rice straw, reed stalk etc. or corn cob are joined in alkaline solution or the sulfate liquor after crushed, carry out boiling, obtain being dissolved with the solution of xylogen, hemicellulose, the solution filter that obtains is removed the Mierocrystalline cellulose insolubles, obtain the xylogen black liquor; Add acid in the xylogen black liquor, regulate pH value to 3～6,60 ℃～90 ℃ insulations, the xylogen black liquor is flocculation and delamination, by press filtration, and hot wash, namely get xylogen.Preferably, obtain xylogen after, it is carried out cryodrying, obtain dried xylogen.The present invention does not have particular requirement to the method for described cryodrying, can be the method for cryodrying well known to those skilled in the art.The present invention there is no particular requirement to described alkaline solution, can be alkaline solution well known to those skilled in the art, and the present invention is preferably aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or baryta water; The present invention there is no particular restriction to described sulfate liquor, can be sulfate liquor well known to those skilled in the art, and the present invention is preferably aqueous sodium persulfate solution or potassium sulfate solution; The present invention there is no particular requirement to described acid, can be acid well known to those skilled in the art, and the present invention is preferably any one or a few in hydrochloric acid, nitric acid and the sulfuric acid.
Preferably, can also extract in accordance with the following methods xylogen: straw (maize straw, rice straw, reed stalk etc.) or corn cob are pulverized, the adding mass content is 45% ~ 80% acid solution stirring, the temperature of described stirring is preferably 5 ℃～30 ℃, and the time of described stirring is preferably 1h ~ 3h; Add entry, described water is preferably 1 ~ 3:1 with the volume ratio of acid again, and behind placement 5h ~ 24h, adding entry is 1% ~ 5% with solution dilution to sour mass content, and backflow 2h ~ 5h filters, and water washs rear drying to filter residue, obtains xylogen.The present invention does not have particular restriction to described acid solution, can be acid solution well known to those skilled in the art, and the present invention is preferably aqueous sulfuric acid, aqueous hydrochloric acid or aqueous nitric acid.
Among the present invention, described phenolic compound is preferably any one or a few in phenol, cresols, Resorcinol, nonylphenol and the cardanol, more preferably phenol.Described nucleophilic reagent is preferably oxyhydroxide, sulfide, sulfohydrate, sulphite, hydrosulphite, vitriol, hydrosulfate, H
2S, H
2SO
3And H
2SO
4In any one or a few, more preferably sodium hydroxide, potassium hydroxide, sodium sulphite, potassium sulphide, Sodium sulfhydrate, S-WAT, potassium sulfite, sodium bisulfite, Potassium hydrogen sulfite, sodium sulfate, vitriolate of tartar, sodium pyrosulfate, sal enixum, H
2S, H
2SO
3And H
2SO
4In any one or a few, most preferably be sodium hydroxide, S-WAT, sodium sulphite and H
2SO
4In any one or a few.The present invention there is no particular requirement to the source of described phenolic compound and nucleophilic reagent, can be for generally commercially available.
At first, xylogen, phenolic compound and nucleophilic reagent are mixed, react.Among the present invention, described phenolic compound is preferably molten state or liquid state.The present invention there is no particular requirement to the order of described mixing, and is preferred, first xylogen and phenolic compound mixed, and under the agitation condition, adds nucleophilic reagent.Described nucleophilic reagent can directly add, also can be with adding after the water dissolution, and the present invention there is no particular requirement to this.The mass ratio of described xylogen and phenolic compound is preferably 1 ~ 10:5, more preferably 1 ~ 6:5; The mass ratio of described nucleophilic reagent and xylogen is preferably 0.1 ~ 10:100, more preferably 0.1 ~ 5:100.The temperature of described reaction is preferably 100 ℃ ~ 200 ℃, more preferably 140 ℃ ~ 180 ℃; The time of described reaction is preferably 1h ~ 10h, more preferably 1h ~ 6h.
The present invention adopts phenolic compound as solvent, then add nucleophilic reagent, with the alpha-aromatic ether in the xylogen, alpha-alkyl ether, phenol type beta-aromatic ether, the non-phenol type beta-aromatic ether that contains α-alcoholic extract hydroxyl group and the ether bond rupture in the methyl aryl ether, the xylogen macromole can be degraded preferably, acquisition has the liquefying lignin product of high reaction activity, thereby improves the activity of resol.
After obtaining lignin phenol's compound, its pH value is transferred to alkalescence, then mix with aldehyde, react and obtain lignin phenol formaldehyde resin.
Described aldehyde is preferably any one or a few in formaldehyde, acetaldehyde, furfural and the Paraformaldehyde 96, more preferably formaldehyde and Paraformaldehyde 96.Use the mixture of formaldehyde and Paraformaldehyde 96, can make in the production of resins process generation without waste water, relatively environmental protection.
Concrete, at first lignin phenol's compound is warming up to 50 ℃ ~ 70 ℃, then regulate its pH value to alkalescence with acid or alkali, preferably regulate its pH value to 7.50 ~ 10.00.The present invention does not have particular restriction to described acid, can be acid well known to those skilled in the art, is preferably hydrochloric acid, sulfuric acid, nitric acid; The present invention does not have particular restriction to described alkali, can be alkali well known to those skilled in the art, is preferably sodium hydroxide, potassium hydroxide.Regulate the pH value to alkalescence, add aldehyde, react, obtain lignin phenol formaldehyde resin.The present invention there is no particular restriction to the adding mode of described aldehyde, is preferably in batches to add, and adds in preferred 1h ~ 3h.The mol ratio of described aldehyde and phenolic compound is preferably 1 ~ 3:1, more preferably 1.4 ~ 2.2:1; The temperature of described reaction is preferably 60 ℃ ~ 100 ℃, more preferably 70 ℃ ~ 95 ℃; The time of described reaction is preferably 1h ~ 6h, more preferably 1h ~ 4h.
The lignin phenol formaldehyde resin for preparing is carried out performance test, and the result shows that lignin phenol formaldehyde resin water ratio provided by the invention is 8% ~ 16%, solid content is that 74% ~ 85%, 25 ℃ of viscosity is that 3000mPa.S ~ 20000mPa.S, pH value are 6.0～8.0, free formaldehyde≤1.0%.
After utilizing aforesaid method to obtain lignin phenol formaldehyde resin, it is mixed with whipping agent, solidifying agent and tensio-active agent, foamed solidification can obtain the lignin phenol formaldehyde resin foam.
Among the present invention, described whipping agent is preferably any one or a few in normal butane, Skellysolve A, Trimethylmethane, iso-pentane, normal hexane, pentamethylene, sherwood oil and dichloro one fluoroethane, more preferably Skellysolve A; Described solidifying agent is preferably any one or a few in Phenylsulfonic acid, tosic acid, xylene monosulfonic acid, sulfocarbolic acid, sulfuric acid, phosphoric acid and the hydrochloric acid, more preferably hydrochloric acid; Described tensio-active agent is preferably any one or a few in polyoxyethylene, polyethenoxy ether, polysorbate and the tween-80, more preferably tween-80.The present invention there is no particular requirement to the source of described whipping agent, solidifying agent and tensio-active agent, can be for generally commercially available.The mass ratio of described whipping agent, solidifying agent and tensio-active agent and resol is preferably 1 ~ 25:5 ~ 25:1 ~ 6:100, more preferably 5 ~ 20:10 ~ 20:1 ~ 4:100.
Concrete, with described lignin phenol formaldehyde resin mix with whipping agent, solidifying agent and tensio-active agent, stirring obtains mixture, the mixture that obtains is warming up to 50 ℃ ~ 80 ℃ foams, and curing 10min ~ 1h, obtains the lignin phenol formaldehyde resin foam.
The lignin phenol formaldehyde resin foam that obtains is carried out performance test, and the result shows, lignin phenol formaldehyde resin foam provided by the invention has higher intensity, lower water-intake rate and lower thermal conductivity.
The present invention at first mixes xylogen, phenolic compound and nucleophilic reagent, reaction obtains lignin phenol's compound; Then regulate its pH value to alkalescence, and mix with aldehyde, react and obtain lignin phenol formaldehyde resin.Compared with prior art, the present invention adopts phenolic compound as solvent, then add nucleophilic reagent, with the alpha-aromatic ether in the xylogen, alpha-alkyl ether, phenol type beta-aromatic ether, the non-phenol type beta-aromatic ether that contains α-alcoholic extract hydroxyl group and the ether bond rupture in the methyl aryl ether, the xylogen macromole can be degraded preferably, acquisition has the liquefying lignin product of high reaction activity, then prepares to have the alternative amount of high phenol and highly active expandability lignin phenol formaldehyde resin; After preparing lignin phenol formaldehyde resin by present method, it is mixed with whipping agent, solidifying agent and tensio-active agent, foamed solidification can obtain the lignin phenol formaldehyde resin foam.Lignin phenol formaldehyde resin foam to preparation carries out performance test, and the result shows, the lignin phenol formaldehyde resin foam of the present invention's preparation has higher intensity, lower water-intake rate and lower thermal conductivity.Simultaneously, the xylogen raw material sources are abundant, the present invention will not have at present economic worth and cause the agriculture and forestry organic waste material of environmental pollution, be developed as eco-friendly bio-based polymer novel material, thereby improve the processing and utilization level of agricultural resource, increase value-added content of product, extend the forestry industry chain, have significant economy, society and ecological environment benefit.
In order to further specify the present invention, below in conjunction with embodiment the preparation method of lignin phenol formaldehyde resin provided by the invention and the preparation method of lignin phenol formaldehyde resin foam are described in detail.
Embodiment 1
Maize straw is joined in the aqueous sodium hydroxide solution after crushed, carry out boiling, obtain being dissolved with the solution of xylogen, hemicellulose, the solution filter that obtains is removed the Mierocrystalline cellulose insolubles, obtain the xylogen black liquor; In the xylogen black liquor, add hydrochloric acid, regulate pH value to 4,80 ℃ of insulations, the xylogen black liquor is flocculation and delamination, by press filtration, and hot wash, obtain xylogen after the cryodrying.After testing, its solid content is 97.5%.
Embodiment 2
The xylogen 1g of embodiment 1 preparation is mixed with melting phenol 5g, add nucleophilic reagent NaOH 0.001g under the agitation condition, reaction system is heated to 140 ℃, isothermal reaction 6h, cooling obtains lignin phenol's compound; Lignin phenol's compound is warming up to 70 ℃, regulates its pH value to 7.50 with hydrochloric acid, 2.2g formaldehyde is joined in lignin phenol's compound in 1h in batches, and reaction 6h, lignin phenol formaldehyde resin obtained.
The lignin phenol formaldehyde resin that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Comparative example 2
5g phenol is heated to 70 ℃, regulates its pH value to 7.50 with the NaOH aqueous solution, then 2.2g formaldehyde is joined in the phenol in 1h in batches, and reaction 6h, resol obtained.
The resol that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Embodiment 3
The xylogen 5g of embodiment 1 preparation is mixed with melting phenol 5g, add nucleophilic reagent Na under the agitation condition
2SO
30.15g, reaction system is heated to 160 ℃, isothermal reaction 4h, cooling obtains lignin phenol's compound; Lignin phenol's compound is warming up to 50 ℃, regulates its pH value to 10.00 with hydrochloric acid, 2.4g formaldehyde is joined in 3h in lignin phenol's compound in batches, reaction system is warming up to 90 ℃ and react 1h, obtain lignin phenol formaldehyde resin.
The lignin phenol formaldehyde resin that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Comparative example 3
5g phenol is heated to 50 ℃, regulates its pH value to 10.00 with the NaOH aqueous solution, 2.4g formaldehyde is joined in the phenol in 3h in batches, and in 90 ℃ of reaction 1h, obtain resol.
The resol that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Embodiment 4
The xylogen 6g of embodiment 1 preparation is mixed with melting phenol 5g, add nucleophilic reagent H under the agitation condition
2SO
40.15g and Na
2SO
30.15g, reaction system is heated to 180 ℃, isothermal reaction 1h, cooling obtains lignin phenol's compound; Lignin phenol's compound is warming up to 60 ℃, regulates its pH value to 9.00 with NaOH, 3.2g formaldehyde is joined in 2h in lignin phenol's compound in batches, reaction system is warming up to 90 ℃ and react 2h, obtain lignin phenol formaldehyde resin.
The lignin phenol formaldehyde resin that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Comparative example 4
5g phenol is heated to 60 ℃, regulates its pH value to 9.00 with the NaOH aqueous solution, 3.2g formaldehyde is joined in the phenol in 2h in batches, and in 90 ℃ of reaction 2h, obtain resol.
The resol that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Embodiment 5
The xylogen 5g of embodiment 1 preparation is mixed with melting phenol 5g, add nucleophilic reagent NaOH 0.11g and Na under the agitation condition
2S 0.04g is heated to 180 ℃ with reaction system, isothermal reaction 1h, and cooling obtains lignin phenol's compound; Lignin phenol's compound is warming up to 70 ℃, regulates its pH value to 10.00 with HCl, 3.5g formaldehyde is joined in 3h in lignin phenol's compound in batches, reaction system is warming up to 95 ℃ and react 1h, obtain lignin phenol formaldehyde resin.
The lignin phenol formaldehyde resin that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Comparative example 5
5g phenol is heated to 70 ℃, regulates its pH value to 10.00 with the NaOH aqueous solution, 3.5g formaldehyde is joined in the phenol in 3h in batches, and in 95 ℃ of reaction 1h, obtain resol.
The resol that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Embodiment 6
The xylogen 2g of embodiment 1 preparation is mixed with melting phenol 5g, add nucleophilic reagent NaOH 0.0029g and Na under the agitation condition
2S 0.0011g is heated to 180 ℃ with reaction system, isothermal reaction 2h, and cooling obtains lignin phenol's compound; Lignin phenol's compound is warming up to 70 ℃, regulates its pH value to 10.00 with HCl, 3.2g formaldehyde is joined in 2h in lignin phenol's compound in batches, reaction system is warming up to 95 ℃ and react 1.5h, obtain lignin phenol formaldehyde resin.
The lignin phenol formaldehyde resin that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
Comparative example 6
5g phenol is heated to 70 ℃, regulates its pH value to 10.00 with the NaOH aqueous solution, 3.2g formaldehyde is joined in the phenol in 2h in batches, and in 95 ℃ of reaction 1.5h, obtain resol.
The resol that obtains is carried out performance test, the results are shown in Table 1, table 1 is the performance perameter of the resol of the embodiment of the invention and comparative example preparation.
The performance perameter of the resol of table 1 embodiment of the invention and comparative example preparation
Embodiment 7 ~ 11
The lignin phenol formaldehyde resin 100g that the embodiment of the invention 2 ~ 6 is obtained mixes with Skellysolve A 15g, concentrated hydrochloric acid 15mL, tween-80 3g, stir and obtain mixture, mixture is warming up to 70 ℃ of foaming, and at 70 ℃ of lower 30min that solidify, obtains the lignin phenol formaldehyde resin foam.The lignin phenol formaldehyde resin foam that obtains is carried out performance test, the results are shown in Table 2, table 2 is performance perameters of the phenolic resin foam of the embodiment of the invention and comparative example preparation.
Comparative example 7 ~ 11
The resol 100g that comparative example 2 ~ 6 of the present invention is obtained mixes with Skellysolve A 15g, concentrated hydrochloric acid 15mL, tween-80 3g, and stirring obtains mixture, and mixture is warming up to 70 ℃ of foaming, and at 70 ℃ of lower 30min that solidify, obtains phenolic resin foam.The phenolic resin foam that obtains is carried out performance test, the results are shown in Table 2, table 2 is performance perameters of the phenolic resin foam of the embodiment of the invention and comparative example preparation.
The performance perameter of the phenolic resin foam of table 2 embodiment of the invention and comparative example preparation
By above-described embodiment and comparative example as can be known, the present invention as solvent, then adds nucleophilic reagent with phenolic compound when preparation lignin phenol formaldehyde resin and lignin phenol formaldehyde resin foam, so that xylogen is better active, the phenolic resin foam intensity that obtains is high.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a lignin phenol formaldehyde resin is characterized in that, may further comprise the steps:
A) xylogen, phenolic compound and nucleophilic reagent mixing, reaction are obtained lignin phenol's compound;
Then the pH value of the lignin phenol's compound that B) regulating step A) obtains is mixed with aldehyde, is reacted and obtain lignin phenol formaldehyde resin to alkalescence.
2. method according to claim 1 is characterized in that, described nucleophilic reagent is selected from oxyhydroxide, sulfide, sulfohydrate, sulphite, hydrosulphite, vitriol, hydrosulfate, H
2S, H
2SO
3And H
2SO
4In any one or a few.
3. method according to claim 1 is characterized in that, described phenolic compound is selected from any one or a few in phenol, cresols, Resorcinol, nonylphenol and the cardanol.
4. method according to claim 1 is characterized in that, described aldehyde is selected from any one or a few in formaldehyde, acetaldehyde, furfural and the Paraformaldehyde 96.
5. method according to claim 1 is characterized in that, the mass ratio of described xylogen and phenolic compound is 1 ~ 10:5.
6. method according to claim 1 is characterized in that, the mass ratio of described nucleophilic reagent and xylogen is 0.1 ~ 10:100.
7. method according to claim 1 is characterized in that, the mol ratio of described aldehyde and phenolic compound is 1 ~ 3:1.
8. method according to claim 1 is characterized in that, described steps A) in, the temperature of described reaction is 100 ℃ ~ 200 ℃, the time of described reaction is 1h ~ 10h.
9. method according to claim 1 is characterized in that, described step B) in, the temperature of described reaction is 60 ℃ ~ 100 ℃, the time of described reaction is 1h ~ 6h.
10. the preparation method of a lignin phenol formaldehyde resin foam is characterized in that, may further comprise the steps:
A) xylogen, phenolic compound and nucleophilic reagent mixing, reaction are obtained lignin phenol's compound;
Then the pH value of the lignin phenol's compound that B) regulating step A) obtains is mixed with aldehyde, is reacted and obtain lignin phenol formaldehyde resin to alkalescence;
C) with step B) lignin phenol formaldehyde resin that obtains mixes with whipping agent, solidifying agent and tensio-active agent, and foamed solidification obtains the lignin phenol formaldehyde resin foam.
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| CN103613728A (en) * | 2013-12-13 | 2014-03-05 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin phenolic foams |
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| CN104250361A (en) * | 2013-06-26 | 2014-12-31 | 中国科学院化学研究所 | Lignin modified phenolic resin, foam thereof, preparation method of resin, and preparation method of foam |
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| CN107099010B (en) * | 2017-05-26 | 2019-07-02 | 南京工业大学 | Preparation method of lignin-based resorcinol-phenol-formaldehyde resin adhesive |
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| CN110964224A (en) * | 2019-12-10 | 2020-04-07 | 大连工业大学 | Preparation method of copolymerization type phenolic alkali lignin-based phenolic foam material |
| CN110964224B (en) * | 2019-12-10 | 2023-01-10 | 大连工业大学 | Preparation method of copolymerization type phenolic alkali lignin-based phenolic foam material |
| CN112029058A (en) * | 2020-09-10 | 2020-12-04 | 江南大学 | Method for improving toughness of alkali lignin phenolic resin |
| CN112661920A (en) * | 2020-12-28 | 2021-04-16 | 齐鲁工业大学 | Preparation method and application of phenolated lignin-phenolic resin nanospheres |
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