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CN109293941A - A kind of depolymerized lignin and its preparation method and application - Google Patents

A kind of depolymerized lignin and its preparation method and application Download PDF

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Publication number
CN109293941A
CN109293941A CN201810897150.5A CN201810897150A CN109293941A CN 109293941 A CN109293941 A CN 109293941A CN 201810897150 A CN201810897150 A CN 201810897150A CN 109293941 A CN109293941 A CN 109293941A
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lignin
mass
phenol
added
mass parts
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杨晓慧
景菲
周永红
贾普友
博采颖
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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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
    • 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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/12—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

A kind of depolymerization lignin and its preparation method and application, in proportion, 100 g lignin is suspended in 0.5-2 L fused salt hydrate, and the inorganic acid that 5~20 mL are added is stirred to react 0.5~5 h at 90~150 DEG C；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin.When the substitution amount 30% of lignin of the present invention, Lignin phenolic foam overall performance is preferable, and compressive strength is 235 kPa, critical oxygen index 38.1%, 0.028 W/mk of thermal coefficient, category nonflammable efficient thermal insulation material.

Description

A kind of depolymerization lignin and its preparation method and application
Technical field
The invention belongs to lignin processing technique and application fields, and in particular to a kind of lignin depolymerization and preparation method thereof With the application in modified phenolic foam.
Background technique
In recent years, phenol formaldehyde foam is as novel foam plastic, and thermal coefficient is low, good heat-insulation effect, referred to as " keeps the temperature it King " [Xie Jianjun is clean and air-conditioning technical, 2004,4:39-43], the organic heat-insulating foam with existing market, as polystyrene, Polyurethane, polyethylene etc. compare, and phenolic resin has the advantages such as high temperature resistant, fire retardant, self-extinguishment, flame resistant, and [is novel at the beginning of Yin Yi builds Build material, 2004 (10): 46-48].It is with light-weight, rigidity is big, good stability of the dimension, insulation, water absorption rate is low, meets simultaneously The advantages that fire is without object is trickled down, is the ideal insulated heat thermal insulation material of the industries such as building, electric appliance, instrument and petrochemical industry [crown China, Chen Hong chapter bioengineering journal, 2014,30 (6): 901-910].It has been widely used in aerospace, national defence The fields such as military project, building trade, communal facility [Liu Cuiyun, Jia Hongyu, Xia Yue, crown China, department, which passes, leads the papermaking of the Tianjin, and 2016, 38(4):3-6].However, due to the shortage of petroleum resources, the synthesis material of phenolic foam such as the price of phenol it is continuous on Rise, so that the cost for preparing phenol formaldehyde foam increasingly increases；And phenol and formaldehyde are all from the non-renewable money such as petroleum, coal Source, biodegradability is poor, these all limit traditional phenolic foam and are further widely used and Green Development [Lee Red mark, Zhang Zeguang, Shen Guopeng, Hao Xinying, Qiao come clever plastics industry, 2014,42 (9): 122-125].
Lignin is a kind of complicated, noncrystalline, three-dimensional netted phenols high molecular polymer, it is widely present in height It is one of the basic chemical composition of coniferals, broad leaf tree class and straw or like vegetable in equal plant cells.The lignin in plant Supramolecular system, adhesive of the lignin as cellulose, to enhance plant are constituted together with cellulose, hemicellulose etc. Mechanical strength.Lignin is the second largest renewable resource that cellulose is only second in nature, and according to estimation, the whole world can produce every year About 6 × 1014Ton.But due to the molecular structure of lignin complexity, active site such as hydroxy radical content is lower, causes reactivity low, It is difficult to be utilized [summer Cheng Long, Xu Yuzhi, Liu Xiaohuan, Wang Chun roc chemistry of forest product and industry, 2016,36 (2), 57-63].Currently, Lignin is largely used as fuel burn-up, be only used on a small quantity phenolic resin, polyurethane and rubber [Kosikova B, Gregorova A.Journal of Applied Polymer Science, 2005,97 (3), 924-929] etc. resins and material In the preparation of material.Therefore, reproducible lignin is used to substitute non-renewable phenol resource, not only promotes wooden element money Sourceization utilizes, and reduces environmental pollution, and can reduce phenolic aldehyde foam thermal insulation material production cost, while improving the utilization of resources Sustainability.
But due to lignin structure complexity, physicochemical properties are inhomogenous, and reactive functional content is few, cause wooden The disadvantages of substitution rate of element is low, poor reproducibility, to limit the popularization and application of lignin.In the recent period, we report fused salt water The research for closing object depolymerization lignin, can effectively be broken β-O-4 and the α-O-4 structure of lignin, significantly reduce its molecular weight, And distribution is more uniform, and reactivity also greatly improves [Yang X.；Li N.；Lin X.；Pan X.；Zhou Y.J.Agric.Food Chem.2016,64,8379-8387].Therefore, we to acid fused salt hydrate depolymerization lignin and Its modified phenolic foam is studied.
Summary of the invention
The technical issues of solution: the present invention provides a kind of depolymerization lignin and its preparation method and application, and this method makes wood Quality is effectively degraded, its reactivity is improved, and therefore, in modified phenolic foam, the substitution amount of lignin is up to 30%, And foam overall performance is preferable, can effectively reduce the cost of phenol formaldehyde foam, also provides reason for the high value added utilization of lignin By foundation.
Technical solution: a kind of preparation method of depolymerization lignin, step are as follows: in proportion, 100g lignin is suspended in In 0.5-2L fused salt hydrate, the inorganic acid that 5~20mL is added is stirred to react 0.5~5h at 90~150 DEG C；React liquid cooling But it after, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin.
Preferably, above-mentioned lignin is at least one in Kraft lignin, organic solvent type lignin or enzymolysis xylogen Kind.
Preferably, above-mentioned fused salt hydrate is ZnCl2、ZnBr2、CuBr2、CaBr2, LiCl or LiBr.
Preferably, above-mentioned inorganic acid is HCl, HBr, HNO3Or H2SO4。
Depolymerization lignin made from the above method.
Above-mentioned depolymerization lignin is preparing the application in phenol formaldehyde foam.
The step of above-mentioned application are as follows: in proportion, the mixture of 300 mass parts phenol and depolymerization lignin is put into four mouthfuls of burnings In bottle, add 10.5 mass parts NaOH and 10 mass parts deionized waters, agitating and heating in 60 DEG C of water-bath is added total in three times The paraformaldehyde for measuring 162.6 mass parts then heats to 70 DEG C of reaction 1h, then is warming up to 80 DEG C, until viscosity up to 4000~ 5000mPa·s；It continuously adds 18 mass parts urea and terminates reaction, phenolic resin is made；By 100 mass parts phenolic resin, 10 matter Amount part foaming agent n-pentane, 3 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mould It in tool, is stirred, and is transferred to heat aging 30~120min in 75 DEG C of insulating box, curing molding obtains phenol formaldehyde foam.
Above-mentioned depolymerization lignin dosage be phenol quality 10wt.%, 20wt.%, 30wt.%, 40wt.% or 50wt.%.
The amount of above-mentioned paraformaldehyde is by phenol and formaldehyde mole ratio 1:(1.5~1.7) it is added.
Above-mentioned curing agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid.
The utility model has the advantages that acid fused salt hydrate medium is 1. utilized to be used for the depolymerization of lignin, lignin is made effectively to be degraded, And it is more uniform；2. reaction condition mild (low acid, low temperature), efficient, environmental-friendly；3. lignin substitution phenol prepares phenolic aldehyde bubble Foam can not only be effectively improved the mechanical performance of lignin, but also can substantially reduce its industrial cost.Research is found: lignin When substitution amount 30%, Lignin phenolic foam overall performance is preferable, compressive strength 235kPa, and critical oxygen index is 38.1%, thermal coefficient 0.028W/mk belong to nonflammable efficient thermal insulation material.
Detailed description of the invention
Fig. 1 is the infrared spectrum before and after lignin depolymerization；
3380cm as seen from the figure-1For alcoholic extract hydroxyl group and phenolic hydroxyl group O-H stretching vibration absworption peak；2932,2856cm-1For methyl With the C-H stretching vibration absworption peak of methylene；1702cm-1For non-conjugated carbonyl C=O stretching vibration absworption peak；1690cm-1For It is conjugated carbonyl C=O stretching vibration absworption peak；1595,1510,1450cm-1For phenyl ring skeletal vibration absorption peak；1266,1205cm-1The respectively C-O stretching vibration absworption peak of guaiacyl and phenolic hydroxyl group；1030cm-1For the C-O stretching vibration of primary alconol and ehter bond C-O-C stretching vibration absworption peak.As can be seen from Fig., after lignin depolymerization, 1030cm-1Absorption peak obviously weakens, therefore, wood β-the O-4 or α-O-4 of quality are effectively degraded；In addition, phenyl ring skeleton, C-O stretching vibration and O-H stretch after lignin depolymerization Contracting vibration all obviously increases, and can also prove that lignin can effectively be degraded；In addition, to acid lithium bromide fused salt water before us In the mechanism study for closing object depolymerization lignin, it was recently reported that non-conjugated carbonyl structure can be generated after lignin depolymerization, as shown in the figure 1702cm-1It is remarkably reinforced, lignin can also be confirmed by effective depolymerization.
Fig. 2 is influence diagram of the lignin additional amount to phenol formaldehyde foam compressive strength；
As seen from the figure, the compressive strength of foam first increases with the increase of lignin additional amount and reduces afterwards, when lignin substitutes When amount is 30%, the compressive strength of foam is maximum.The reason is that lignin can be very good when lignin degrading substitution amount is lower It is dispersed in resin, small molecule phenols therein and aldehydes can sufficiently be reacted with phenol and formaldehyde, due to lignin phenyl ring side Chain contains alkyl carbon chain, reduces the rigid structure phenyl ring content of resin, therefore the toughness of foam is improved, and can be very good External strength is dispersed, so compressive strength increases, but when substitution amount reaches 40%, the content of lignin in system significantly increases Add, but the reactivity of lignin is far below phenol, unreacted lignin can reduce the compressive strength of foam instead.But from figure It can also be seen that the foamy body that lignin substitution amount is 40% is still higher than pure phenol formaldehyde foam, therefore, the lignin after depolymerization is most Big substitution rate is up to 40%.
Fig. 3 is thermogravimetic analysis (TGA) figure；
As seen from the figure, Lignin phenolic foam and the thermal weight loss process general trend of phenol formaldehyde foam are essentially identical, and thermogravimetric is bent Line can be divided into three phases: (1) some small-molecule substances evolution within 200 DEG C mainly in foam, such as free phenol, Formaldehyde and water.In addition, the gas in this stage foam expands in heated situation, steep that wall evolution is broken through, foam weight-loss ratio exists Within 15%；(2) 200-600 DEG C of stage is mainly the ether bond rupture that is formed in resin curing process into more stable methylene bridged bond Water outlet is discharged simultaneously, in this stage and lignin skeleton starts degradation period (400 DEG C or so), but the figure knot of foam Structure does not change, and illustrates that the thermostabilization of phenol formaldehyde foam is fine, and 600 DEG C of foam residual quantities are 55% or more；(3)600-900℃ Stage is mainly that foam structure is destroyed at high temperature, and methylene bridge structure is broken, and generates more stable substance, arrives 800 DEG C of weightlessness are basicly stable, and the residual quantity of foam illustrates that Lignin phenolic foam has good thermostabilization 47% or more Property.
Specific embodiment
The specific steps of novel depolymerization lignin and its modified phenolic foam are as follows:
In proportion, 100g lignin is suspended in 0.5-2L fused salt hydrate, the inorganic acid of 5~20mL is added, 90 At~150 DEG C, it is stirred to react 0.5~5h；It after reaction solution is cooling, filters, washes 3~4 times, it is wooden that vacuum drying can obtain depolymerization Element；300g phenol, depolymerization lignin (substituting part phenol by a certain percentage) and formaldehyde are put into four-hole boiling flask, 10.5g is added NaOH and 10g deionized water.Agitating and heating in 60 DEG C of water-bath is added 162.6g paraformaldehyde and in three times then heats up To 70 DEG C of reaction 1h, then 80 DEG C are warming up to, until viscosity is (4000~5000mPas) up to standard.It is whole that urea 18g is added after reaction Only react；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n-pentane, 3.0 mass parts Tween 80, 10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, are stirred, and are transferred in 75 DEG C of insulating box Heat aging 30~120min, curing molding obtain phenol formaldehyde foam.
The lignin is any one of Kraft lignin, organic solvent type lignin or enzymolysis xylogen or more Kind；The fused salt hydrate is ZnCl2、ZnBr2、CuBr2、CaBr2, LiCl, LiBr etc.；The catalyst agent be HCl, HBr、HNO3Or H2SO4Any one of；The substitution amount of depolymerization lignin be phenol quality 10wt.%, 20wt.%, 30wt.%, 40wt.% or 50wt.%；The amount of paraformaldehyde is added by phenol and formaldehyde mole ratio 1:1.5~1.7；Curing agent For oxalic acid, p-methyl benzenesulfonic acid and phosphoric acid (mass ratio 1:2:2).
Embodiment 1
100g Kraft lignin is suspended in 0.5L ZnCl2In fused salt hydrate, the HCl of 5mL is added, at 90 DEG C, It is stirred to react 0.5h；It after reaction solution is cooled to room temperature, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g Phenol is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, and the depolymerization that phenol substitution amount 10wt.% is added is wooden Element.162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.7) is added in agitating and heating in 60 DEG C of water-bath, and respectively three Secondary addition then heats to 70 DEG C of reaction 1h, then is warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Reaction Urea 18g termination is added afterwards and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 30min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 195kPa.
Embodiment 2
100g organic solvent type lignin is suspended in 1.0L ZnCl2In fused salt hydrate, the HBr of 10mL is added, At 100 DEG C, it is stirred to react 1h；It after reaction solution is cooled to room temperature, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin； 300g phenol is put into four-hole boiling flask, 10.5g NaOH and 10g deionized water is added, the solution of phenol substitution amount 20wt.% is added Poly- lignin.162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6) is added in agitating and heating in 60 DEG C of water-bath, It is added in three times, 70 DEG C of reaction 1h is then heated to, then be warming up to 80 DEG C, until viscosity (4000~5000mPa up to standard s).Urea 18g termination is added after reaction and reacts to obtain phenolic resin；Finally 100 mass parts phenolic resin, 10.0 mass parts are foamed Agent n-pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, Curing agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C insulating box in heat aging 40min, curing molding obtains phenol formaldehyde foam, compressive strength 220kPa.
Embodiment 3
100g enzymolysis xylogen is suspended in 1.5L CaBr2In fused salt hydrate, the inorganic acid of 15mL is added, at 110 DEG C Under, it is stirred to react 1.5h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g benzene Phenol is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, and the depolymerization lignin of phenol substitution amount 30wt.% is added. Agitating and heating in 60 DEG C of water-bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6), adds in three times Enter, then heat to 70 DEG C of reaction 1h, then be warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Add after reaction Enter urea 18g termination and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, stirring Mixing, curing agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, and is transferred to 75 DEG C Heat aging 50min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 231kPa.
Embodiment 4
100g organic solvent type lignin is suspended in 2.0L CuBr2In fused salt hydrate, the HNO of 20mL is added3, At 120 DEG C, it is stirred to react 2h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g Phenol is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, and the depolymerization that phenol substitution amount 40wt.% is added is wooden Element.162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.5) is added in agitating and heating in 60 DEG C of water-bath, and respectively three Secondary addition then heats to 70 DEG C of reaction 1h, then is warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Reaction Urea 18g termination is added afterwards and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 60min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 202kPa.
Embodiment 5
100g enzymolysis xylogen is suspended in 2.0L LiBr fused salt hydrate, the HCl of 10mL is added, at 130 DEG C, It is stirred to react 3h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；300g phenol is put into In four-hole boiling flask, add 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 30wt.% is added.60 DEG C Agitating and heating in water-bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6), is added in three times, so After be warming up to 70 DEG C of reaction 1h, then 80 DEG C are warming up to, until viscosity is (4000~5000mPas) up to standard.Urea is added after reaction Phenolic resin is reacted to obtain in 18g termination；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n-pentane, 3.0 matter Amount part Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, and curing agent is that mass ratio is 1: 2:2 composition oxalic acid, p-methyl benzenesulfonic acid and phosphoric acid mixed acid, be stirred, and be transferred in 75 DEG C of insulating box heat it is ripe Change 90min, curing molding obtains phenol formaldehyde foam.
As it can be seen from table 1 the weight average molecular weight of lignin is reduced to 1600g/mol from 3900g/mol after depolymerization, and The coefficient of dispersion is significantly reduced, and is reduced to 1.78 from 4.10.
Molecular weight test before and after 1 lignin depolymerization of table
Foam combination property analysis
As shown in Table 2, the phenol formaldehyde foam compressive strength that lignin substitution amount is 30% is higher than pure phenol formaldehyde foam, illustrates wooden Plain phenol formaldehyde foam mechanical property is preferable, and critical oxygen index, thermal coefficient and phenol formaldehyde foam are close, belongs to nonflammable thermal insulation material；It inhales Water rate and dimensional stability are slightly below phenol formaldehyde foam.In short, its comprehensive performance is good, just there is good application prospect.
The combination property analysis of 2 phenol formaldehyde foam of table and Lignin phenolic bubble
Embodiment 6
100g Kraft lignin is suspended in 1.0L ZnCl2In fused salt hydrate, the H of 15mL is added2SO4, at 140 DEG C Under, it is stirred to react 4h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g phenol It is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 20wt.% is added.60 DEG C water-bath in agitating and heating, 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6) is added, in three times plus Enter, then heat to 70 DEG C of reaction 1h, then be warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Add after reaction Enter urea 18g termination and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 120min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 222kPa.
Embodiment 7
100g organic solvent type lignin is suspended in 1.5L CuBr2In fused salt hydrate, the HBr of 10mL is added, At 150 DEG C, it is stirred to react 5h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g Phenol is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, and the depolymerization that phenol substitution amount 10wt.% is added is wooden Element.162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.7) is added in agitating and heating in 60 DEG C of water-bath, and respectively three Secondary addition then heats to 70 DEG C of reaction 1h, then is warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Reaction Urea 18g termination is added afterwards and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 100min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 193kPa.
Embodiment 8
100g Kraft lignin is suspended in 0.5L CaBr2In fused salt hydrate, the HNO of 20mL is added3, at 90 DEG C Under, it is stirred to react 1h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g phenol It is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 20wt.% is added.60 DEG C water-bath in agitating and heating, 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6) is added, in three times plus Enter, then heat to 70 DEG C of reaction 1h, then be warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Add after reaction Enter urea 18g termination and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 80min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 222kPa.
Embodiment 9
100g Kraft lignin is suspended in 1.0L ZnBr2In fused salt hydrate, the HNO of 10mL is added3, at 100 DEG C Under, it is stirred to react 1.5h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g benzene Phenol is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, and the depolymerization lignin of phenol substitution amount 20wt.% is added. Agitating and heating in 60 DEG C of water-bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.7), adds in three times Enter, then heat to 70 DEG C of reaction 1h, then be warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Add after reaction Enter urea 18g termination and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 60min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 224kPa.
Embodiment 10
100g enzymolysis xylogen is suspended in 1.0L ZnCl2In fused salt hydrate, the H of 15mL is added2SO4, at 120 DEG C Under, it is stirred to react 3h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g phenol It is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 30wt.% is added.60 DEG C water-bath in agitating and heating, 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.7) is added, in three times plus Enter, then heat to 70 DEG C of reaction 1h, then be warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Add after reaction Enter urea 18g termination and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 40min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 231kPa.
Embodiment 11
100g organic solvent type lignin is floated in 2.0L LiCl fused salt hydrate, the HCl of 20mL is added, at 140 DEG C Under, it is stirred to react 2h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；By 300g phenol It is put into four-hole boiling flask, adds 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 30wt.% is added.60 DEG C water-bath in agitating and heating, 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6) is added, in three times plus Enter, then heat to 70 DEG C of reaction 1h, then be warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Add after reaction Enter urea 18g termination and reacts to obtain phenolic resin；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n- Pentane, 3.0 mass parts Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, solidification Agent is the mixed acid that mass ratio is the oxalic acid of 1:2:2 composition, p-methyl benzenesulfonic acid and phosphoric acid, is stirred, and be transferred to 75 DEG C Heat aging 30min in insulating box, curing molding obtain phenol formaldehyde foam, compressive strength 232kPa.
Embodiment 12
100g Kraft lignin is floated in 2.0L LiBr fused salt hydrate, the HBr of 10mL is added, at 110 DEG C, It is stirred to react 4h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；300g phenol is put into In four-hole boiling flask, add 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 30wt.% is added.60 DEG C Agitating and heating in water-bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.6), is added in three times, so After be warming up to 70 DEG C of reaction 1h, then 80 DEG C are warming up to, until viscosity is (4000~5000mPas) up to standard.Urea is added after reaction Phenolic resin is reacted to obtain in 18g termination；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n-pentane, 3.0 matter Amount part Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, and curing agent is that mass ratio is 1: 2:2 composition oxalic acid, p-methyl benzenesulfonic acid and phosphoric acid mixed acid, be stirred, and be transferred in 75 DEG C of insulating box heat it is ripe Change 60min, curing molding obtains phenol formaldehyde foam, compressive strength 234kPa.
Embodiment 13
100g enzymolysis xylogen is floated in 2.0L LiBr fused salt hydrate, the HCl of 15mL is added, at 120 DEG C, stirs Mix reaction 3h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；300g phenol is put into four In mouth flask, add 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 50wt.% is added.60 DEG C of water Agitating and heating in bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.5), is added in three times, then 70 DEG C of reaction 1h are warming up to, then are warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Urea is added after reaction Phenolic resin is reacted to obtain in 18g termination；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n-pentane, 3.0 matter Amount part Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, and curing agent is that mass ratio is 1: 2:2 composition oxalic acid, p-methyl benzenesulfonic acid and phosphoric acid mixed acid, be stirred, and be transferred in 75 DEG C of insulating box heat it is ripe Change 90min, curing molding obtains phenol formaldehyde foam, compressive strength 159kPa.
Embodiment 14
100g organic solvent type is floated in 1.5L LiCl fused salt hydrate, the HBr of 10mL is added, at 110 DEG C, stirs Mix reaction 2h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；300g phenol is put into four In mouth flask, add 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 50wt.% is added.60 DEG C of water Agitating and heating in bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.5), is added in three times, then 70 DEG C of reaction 1h are warming up to, then are warming up to 80 DEG C, until viscosity is (4000~5000mPas) up to standard.Urea is added after reaction Phenolic resin is reacted to obtain in 18g termination；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n-pentane, 3.0 matter Amount part Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, and curing agent is that mass ratio is 1: 2:2 composition oxalic acid, p-methyl benzenesulfonic acid and phosphoric acid mixed acid, be stirred, and be transferred in 75 DEG C of insulating box heat it is ripe Change 120min, curing molding obtains phenol formaldehyde foam, compressive strength 162kPa.
Embodiment 15
100g Kraft lignin is floated in 2.0L LiBr fused salt hydrate, the H of 10mL is added2SO4, at 110 DEG C, It is stirred to react 2h；It after reaction solution is cooling, filters, washes 3~4 times, vacuum drying can obtain depolymerization lignin；300g phenol is put into In four-hole boiling flask, add 10.5g NaOH and 10g deionized water, the depolymerization lignin of phenol substitution amount 50wt.% is added.60 DEG C Agitating and heating in water-bath is added 162.6g paraformaldehyde (by phenol and formaldehyde mole ratio 1:1.5), is added in three times, so After be warming up to 70 DEG C of reaction 1h, then 80 DEG C are warming up to, until viscosity is (4000~5000mPas) up to standard.Urea is added after reaction Phenolic resin is reacted to obtain in 18g termination；Finally by 100 mass parts phenolic resin, 10.0 mass parts foaming agent n-pentane, 3.0 matter Amount part Tween 80,10.0 mass parts curing agent and 3.0 mass parts OFX-0193 are placed in mold, and curing agent is that mass ratio is 1: 2:2 composition oxalic acid, p-methyl benzenesulfonic acid and phosphoric acid mixed acid, be stirred, and be transferred in 75 DEG C of insulating box heat it is ripe Change 100min, curing molding obtains phenol formaldehyde foam, compressive strength 164kPa.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.

Claims (10)

1.一种解聚木质素的制备方法，其特征在于步骤为：按比例，把100 g木质素悬浮于0.5-2 L熔盐水合物中，加入5～20 mL的无机酸，在90～150℃下，搅拌反应0.5～5 h；反应液冷却后，抽滤，水洗3～4次，真空干燥可得解聚木质素。1. a preparation method of depolymerized lignin is characterized in that the step is: in proportion, 100 g of lignin are suspended in 0.5-2 L molten salt hydrate, add the mineral acid of 5～20 mL, at 90～ At 150 °C, the reaction is stirred for 0.5 to 5 h; after the reaction solution is cooled, it is filtered with suction, washed with water for 3 to 4 times, and dried in vacuum to obtain depolymerized lignin. 2.根据权利要求1所述解聚木质素的制备方法，其特征在于所述木质素为Kraft木质素、有机溶剂型木质素或酶解木质素中的至少一种。2 . The method for preparing depolymerized lignin according to claim 1 , wherein the lignin is at least one of Kraft lignin, organic solvent-based lignin or enzymatic hydrolyzed lignin. 3 . 3.根据权利要求1所述解聚木质素的制备方法，其特征在于所述熔盐水合物为ZnCl2、ZnBr2、CuBr2、CaBr2、LiCl或LiBr。3 . The method for preparing depolymerized lignin according to claim 1 , wherein the molten salt hydrate is ZnCl 2 , ZnBr 2 , CuBr 2 , CaBr 2 , LiCl or LiBr. 4 . 4.根据权利要求1所述解聚木质素的制备方法，其特征在于所述无机酸为HCl、HBr、HNO3或H2SO4。4 . The method for preparing depolymerized lignin according to claim 1 , wherein the inorganic acid is HCl, HBr, HNO 3 or H 2 SO 4 . 5 . 5.权利要求1~4任一所述方法制得的解聚木质素。5. The depolymerized lignin obtained by the method of any one of claims 1 to 4. 6.权利要求5所述解聚木质素在制备酚醛泡沫中的应用。6. The application of the depolymerized lignin of claim 5 in the preparation of phenolic foam. 7.根据权利要求6所述的应用，其特征在于步骤为：按比例，将300 质量份苯酚和解聚木质素的混合物放入四口烧瓶中，加10.5质量份NaOH和10质量份去离子水，60℃的水浴锅里搅拌加热，均分三次加入总量162.6 质量份的多聚甲醛，然后升温至70℃反应1 h，再升温至80℃，直到粘度达4000～5000 mPa·s；继续加入18 质量份尿素终止反应，制得酚醛树脂；将100质量份酚醛树脂、10质量份发泡剂n-pentane、3质量份Tween 80、10.0质量份固化剂及3.0质量份OFX-0193置于模具中，搅拌混合，并转移至75℃ 的恒温箱中加热熟化30～120 min，固化成型得到酚醛泡沫。7. application according to claim 6 is characterized in that the step is: in proportion, the mixture of 300 mass parts of phenol and depolymerized lignin is put into a four-necked flask, and 10.5 mass parts of NaOH and 10 mass parts of deionized water are added. , stir and heat in a water bath at 60°C, add a total of 162.6 parts by mass of paraformaldehyde in three equal portions, then heat up to 70°C for 1 h, and then heat up to 80°C until the viscosity reaches 4000-5000 mPa·s; continue 18 parts by mass of urea was added to terminate the reaction to obtain a phenolic resin; 100 parts by mass of phenolic resin, 10 parts by mass of foaming agent n-pentane, 3 parts by mass of Tween 80, 10.0 parts by mass of curing agent and 3.0 parts by mass of OFX-0193 were placed in In the mold, stir and mix, and transfer to a constant temperature oven at 75°C for heating and aging for 30-120 min, and then solidify and form to obtain phenolic foam. 8.根据权利要求7所述的应用，其特征在于所述解聚木质素用量为苯酚质量的10wt.%、20 wt.%、30 wt.%、40 wt.%或50 wt.%。8. The application according to claim 7, wherein the amount of depolymerized lignin is 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.% or 50 wt.% of phenol mass. 9.根据权利要求7所述的应用，其特征在于所述多聚甲醛的量按苯酚和甲醛摩尔比1:（1.5～1.7）加入。9 . The application according to claim 7 , wherein the amount of the paraformaldehyde is added in a molar ratio of phenol and formaldehyde of 1: (1.5 to 1.7). 10 . 10.根据权利要求7所述的应用，其特征在于所述固化剂为质量比1:2:2组成的草酸、对甲苯磺酸和磷酸。10. application according to claim 7, is characterized in that described solidifying agent is oxalic acid, p-toluenesulfonic acid and phosphoric acid that mass ratio 1:2:2 forms.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861244A (en) * 2021-09-14 2021-12-31 中国林业科学研究院林产化学工业研究所 Lignin bacteriostatic agent and preparation method and application thereof
CN115521345A (en) * 2022-09-23 2022-12-27 大连工业大学 Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106052A1 (en) * 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
CN102504477A (en) * 2011-10-18 2012-06-20 中国林业科学研究院林产化学工业研究所 Lignin-modified phenolic foam and preparation method thereof
CN102558596A (en) * 2011-12-31 2012-07-11 中国林业科学研究院林产化学工业研究所 Lignin-based phenolic foam material and preparation method thereof
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
CN103898244A (en) * 2014-04-15 2014-07-02 中国科学技术大学 Method for degrading plant biomass
CN104211885A (en) * 2013-05-31 2014-12-17 常州市乾翔新材料科技有限公司 Low-temperature expandable phenolic resin and method of employing same to prepare phenolic foam
CN104211889A (en) * 2013-05-31 2014-12-17 常州市乾翔新材料科技有限公司 Foaming lignin-modified phenolic resin and preparation method thereof
CN106750179A (en) * 2017-03-21 2017-05-31 南京林业大学 A kind of preparation method of enzymolysis xylogen base epoxy
CN107652331A (en) * 2017-09-27 2018-02-02 中国林业科学研究院林产化学工业研究所 A kind of lignin depolymerization method
CN107722295A (en) * 2017-09-27 2018-02-23 中国林业科学研究院林产化学工业研究所 The method of lignin demethoxylation

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106052A1 (en) * 2009-03-17 2010-09-23 Bioecon International Holding N.V. Process for converting polysaccharides in an inorganic molten salt hydrate
CN102504477A (en) * 2011-10-18 2012-06-20 中国林业科学研究院林产化学工业研究所 Lignin-modified phenolic foam and preparation method thereof
CN102558596A (en) * 2011-12-31 2012-07-11 中国林业科学研究院林产化学工业研究所 Lignin-based phenolic foam material and preparation method thereof
CN104211885A (en) * 2013-05-31 2014-12-17 常州市乾翔新材料科技有限公司 Low-temperature expandable phenolic resin and method of employing same to prepare phenolic foam
CN104211889A (en) * 2013-05-31 2014-12-17 常州市乾翔新材料科技有限公司 Foaming lignin-modified phenolic resin and preparation method thereof
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
CN103898244A (en) * 2014-04-15 2014-07-02 中国科学技术大学 Method for degrading plant biomass
CN106750179A (en) * 2017-03-21 2017-05-31 南京林业大学 A kind of preparation method of enzymolysis xylogen base epoxy
CN107652331A (en) * 2017-09-27 2018-02-02 中国林业科学研究院林产化学工业研究所 A kind of lignin depolymerization method
CN107722295A (en) * 2017-09-27 2018-02-23 中国林业科学研究院林产化学工业研究所 The method of lignin demethoxylation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FU-CHENG WANG等: "Synthesis and characterization of silicon carbide nanowires from lignin-phenolic resin and silicon powder with an in-situ formed molten salt as catalyst", 《NEW CARBON MATERIALS》 *
XIAOHUI YANG等: "Selective Cleavage of the Aryl Ether Bonds in Lignin for Depolymerization by Acidic Lithium Bromide Molten Salt Hydrate under Mild Conditions", 《J. AGRIC. FOOD CHEM.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861244A (en) * 2021-09-14 2021-12-31 中国林业科学研究院林产化学工业研究所 Lignin bacteriostatic agent and preparation method and application thereof
WO2023040251A1 (en) * 2021-09-14 2023-03-23 中国林业科学研究院林产化学工业研究所 Lignin bacteriostatic agent and preparation method therefor and application thereof
CN115521345A (en) * 2022-09-23 2022-12-27 大连工业大学 Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system
CN115521345B (en) * 2022-09-23 2024-03-01 大连工业大学 Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system

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