CN105504191B - A kind of preparation method of eutectic ionic liquid Lignin-based phenolic - Google Patents
A kind of preparation method of eutectic ionic liquid Lignin-based phenolic Download PDFInfo
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- CN105504191B CN105504191B CN201610051105.9A CN201610051105A CN105504191B CN 105504191 B CN105504191 B CN 105504191B CN 201610051105 A CN201610051105 A CN 201610051105A CN 105504191 B CN105504191 B CN 105504191B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The present invention relates to a kind of preparation method of eutectic ionic liquid Lignin-based phenolic, its step is to stir phenol and ChCl to reaction solution is transparent under conditions of 55 DEG C~70 DEG C to obtain eutectic ionic liquid (DES).Modified lignin resin and DES mixtures are obtained after handling the 2h of lignin 1 under the conditions of 80 DEG C~100 DEG C with it.The mixture and formalin and alkali are sequentially added in reactor, by casings in twice, twice heats up, the addition condensation process such as are incubated and prepare lignin phenol formaldehyde resin.It is characterized in the quaternary ammonium moiety by the use of cheap and nontoxic Choline Chloride as eutectic ionic liquid, DES is quickly prepared in a mild condition with phenol, by the multiple synergy activation lignin such as its solvent, catalyst, and be not required to separate, directly substitute part phenol and prepare the lignin phenol formaldehyde resin adhesive that performance is excellent, phenol replacement amount is high.The present invention reduces need repeatedly to be washed, separate, the cumbersome link such as dry after conventional wooden element activation.
Description
Technical field
The invention belongs to based Wood Adhesives field, and in particular to a kind of industrial lignin prepares lignin modification phenolic resin
The method of adhesive.
Background technology
Industrial lignin comes from pulp and paper industry waste liquid, is the renewable resource of great potential, and day is replaced using it
Beneficial exhausted oil product is development trend as the raw material of synthetic adhesive.Lignin has aldehyde radical and phenol structure list in itself
Member, there is the primary condition for preparing phenolic resin, therefore people have been carried out greatly to lignin modification phenolic resin (LPF) adhesive
Quantifier elimination.But because lignin variability is larger, molecular weight distribution is uneven, and complicated, reactivity is low, is made of it gluing
Be present the problems such as bonding strength is low, and stability is poor, poor water resistance and energy consumption are big in agent, be really successfully applied at present in production
Example and few.
The key for preparing lignin modification phenolic resin is to carry out activation process to lignin.Traditional activation lignin
Method be mainly chemical method, the methylolation method using the gentle V á zquez of Ou Yangxin as representative, An Xinnan and Jolly's etc. is de-
Phenolate modification method under the alkalescence condition that methylation method and Alonso, Sudan are used etc. is three kinds of generally acknowledged effective ways, but
Because energy consumption is big and the reason such as the corrosivity of strong acid does not also industrialize further；With the development of science and technology, scientific research personnel gets over
Lignin is handled using more environmentally-friendly technological means come more, it is expected during lignin recovery utilizes, to avoid
Secondary pollution is caused to environment.This thought is implemented so that the overall applicability of lignin turns into the weight of Green Chemistry at this stage
Want one of research direction.
Ionic liquid (ILs) refers to the ionic system being in a liquid state under room temperature (or temperature of a little higher than room temperature), is by having
The salt for the salt that machine cation and inorganic anion are formed and be in a liquid state at a temperature of room temperature or near room temperature.Ionic liquid has
Stable performance, pollution-free, easily recovery, clear superiority is presented improving reaction rate, selectivity and catalytic action etc..
In wood fibre chemistry, the research of ionic liquid is mainly in the dissolving of cellulose and the conversion aspect of hemicellulose.Although from
There is the advantages of these are potential in sub- liquid, but with the continuous expansion of ionic liquid application field, during producing ionic liquid
Greenization and production cost problem also become increasingly conspicuous, and region of chemistry still suffers from certain dispute to its green, and synthesis technique is answered
It is miscellaneous, purification difficult.It will be apparent that on the basis of ionic liquid necessity characteristic is ensured, the industry of alternative costs relative moderate as far as possible
Raw material, the ionic liquid for preparing low cost is one of key issue of ionic liquid commercial application.Eutectic ionic liquid
The eutectic mixture being made up of two or more compositions, its synthesis material are very common compound, abundance and
Cheap, easily biological-degradable, without environment side effect, it has also become the new study hotspot in green chemistry chemical technology field.Before seminar
Phase research finds that urea/zinc chloride eutectic ionic liquid processing alkali lignin has demethylation, and lignin is degraded, portion
Methoxyl group is divided to be reduced, hydroxy radical content increase, lignin activity improves, but adds the separation process of ionic liquid and lignin,
Complex process.And use Choline Chloride (Choline chloride, ChCl) and phenol (Phenol, P) synthesis eutectic ion
Liquid (ChCl/P DES), and lignin is handled with it, without isolation, part phenol modified phenolic resin (PF) is directly substituted,
It is simpler, the effective method for realizing lignin modification phenolic resin, the breach to finding lignin comprehensive utilization, realizes
The purpose to turn waste into wealth is significant.
The content of the invention
The purpose of the present invention：Aim to provide that a kind of mild condition, manufacturing process be simple, the lignin modification phenol of function admirable
The preparation method of urea formaldehyde adhesive.Eutectic ion is prepared under conditions of as mild as a dove as raw material using Choline Chloride and phenol
Liquid (ChCl/P DES), it is wooden by the multiple synergy activation such as its solvent, catalyst as media processes lignin
Element, and be not required to separate, directly substitute part phenol and be used for phenol-formaldehyde resin modified (PF) adhesive, to solve conventional wooden element activation
When need to after activation lignin carry out repeatedly wash, precipitate, filtering, separation and dry etc. cumbersome technical process, more simply have
Prepare the lignin modification phenolic resin that performance is excellent, phenol replacement amount is high to effect.Phenol is substituted using industrial lignin to prepare
Phenolic resin is all significant at economical and environmentally friendly two aspects.
Technical solution of the present invention：Eutectic ion is prepared under conditions of as mild as a dove as raw material using Choline Chloride and phenol
Liquid, as media processes lignin, lignin is degraded by multiple actions such as its solvent, catalyst, show as
Ether bond rupture, methoxyl group removing are connected, the active group phenolic hydroxyl group of macromolecule internal shows reactivity, and formation includes room
Phenolic structure, while trigger itself and formaldehyde addition, prepare the lignin modification phenolic aldehyde that performance is excellent, phenol replacement amount is high
Resin.
A kind of preparation method of eutectic ionic liquid modified lignin resin-phenolic resin, is mainly included the following steps that：
(1) preparation of eutectic ionic liquid：Two kinds of raw materials are added in the container of sealing by certain mol ratio, at 55 DEG C
Stirred under conditions of~70 DEG C, it is transparent to reaction solution, that is, obtain eutectic ionic liquid (DES)；
(2) eutectic ionic liquid modified lignin resin：The product of step (1) is transferred to the conjunction equipped with stirring and condensing unit
Into in reactor, the raw material wood element of phenol quality 10%~50% in step (1) is added, is warming up under the conditions of 80 DEG C -100 DEG C
Modified lignin resin and DES mixtures are obtained after insulation 1-2h；
(3) product 50-70 mass parts, the formalin 15-25 mass parts that mass concentration is 37% obtained step (2)
Sodium hydroxide solution 15-25 mass parts with first mass concentration is 20%, that is, account for the 40% of sodium hydroxide gross mass, adds
In synthesis reactor equipped with stirring and condensing unit, 85-95 DEG C is warming up in 30-60min, react automatic after 15-30min
It is cooled to 75-85 DEG C；
(4) formalin that the mass concentration of 30-40 mass parts is 37% is added in the product reacted to step (3), is risen
Temperature reacts 15-20min to 85-95 DEG C；
(5) product that step (4) is reacted is cooled to 75-85 DEG C automatically, insulation at such a temperature carries out polycondensation reaction 1-
3h, after test viscosity reaches required viscosity, add second batch and account for sodium hydroxide gross massAfter 60% sodium hydroxide, go out
Material, lignin modification phenolic resin LPF is made；
(6) prepared by glued board：Using the flour of the LPF additions 8%~10% of preparation as filler, it is by two-sided resin added
280-320g/m2Veneer surface is applied to, glued board is hot pressed into after 30~40min is displayed after gluing.
Two kinds of raw materials described in the step (1) are Choline Chloride and phenol, and the mol ratio of Choline Chloride and phenol is 1
: 9~1: 3；
Raw material wood element in step (2) is lignosulphonates, alkali lignin, one kind in dealkalize lignin.
Hot compression parameterses in step (6) are：130~140 DEG C of temperature, 1.0~1.5MPa of hot pressing pressure, hot pressing time 1~
1.5min/mm thickness of slab.
The present invention has advantages below compared with prior art：
(1) the eutectic ionic liquid synthesized by the present invention is using cheap and nontoxic Choline Chloride and phenol as original
Material, its building-up process is easy, and synthesis temperature is low, and the reaction time is short；
(2) present invention is by the multiple synergy such as the solvent of ChCl/P eutectic ionic liquids, catalysis, activation, processing wood
Part phenol and formaldehyde addition are directly replaced after quality without isolation, reduces separation and the regeneration step of lignin, prepares work
Skill is simple, and reaction is easily controllable, and prepared resin has good performance.The performance test results show when lignin substitutes benzene
When phenol amount is 10~50%, with the bonding strength of its I class glued board suppressed in 0.75~1.43MPa.
Embodiment
Embodiment 1
Weigh Choline Chloride 14.1g, phenol 66.7g, add in the container of sealing, under conditions of 55 DEG C stir 5~
6min, it is transparent to reaction solution, that is, obtain ChCl/P DES.It will be transferred in the ChCl/P DES equipped with agitator and condensing unit
In synthesis reactor, dealkalize lignin 13.3g is added, modified lignin resin and DES mixing are obtained after 1h is reacted under the conditions of 90 DEG C
Thing.The sodium hydroxide solution 27.3g that formalin 25.7g, mass concentration that mass concentration is 37% are 20% is slowly added to, is risen
Temperature is cooled to 80 DEG C automatically to 90 DEG C after reacting 30min.The formalin that 108.1g mass concentrations are 37% is slowly added to, then
It is secondary to be warming up to 90 DEG C, 80 DEG C, when test reaction terminal reaches required viscosity are cooled to automatically after reacting 20min, add second
Sodium hydroxide 42.1g is criticized, discharging, lignin modification phenolic resin LPF is thus made.The LPF of preparation is added to 8% flour,
By 300g/m2The resin added of (two-sided), veneer surface is applied to, glued board, hot pressing temperature are hot pressed into after 30min is displayed after gluing
130 DEG C, hot pressing pressure 1.0MPa, hot pressing time 1.2min/mm thicknesss of slab.After tested, the glued board bonding strength being prepared is
1.29MPa。
Embodiment 2
Weigh Choline Chloride 12.1g, phenol 57.1g, add in the container of sealing, under conditions of 55 DEG C stir 5~
6min, it is transparent to reaction solution, that is, obtain ChCl/P DES.It will be transferred in the ChCl/P DES equipped with agitator and condensing unit
In synthesis reactor, lignin 22.9g is added, modified lignin resin and DES mixtures are obtained after reacting 1h under the conditions of 90 DEG C.It is slow
It is slow to add the sodium hydroxide solution 27.3g that formalin 25.7g, mass concentration that mass concentration is 37% are 20%, it is warming up to
90 DEG C, 80 DEG C are cooled to automatically after reacting 30min.The formalin that 108.1g mass concentrations are 37% is slowly added to, is risen again
Temperature is cooled to 80 DEG C, when test reaction terminal reaches required viscosity after reacting 20min, adds second batch hydrogen automatically to 90 DEG C
Sodium oxide molybdena 42.1g, discharging, lignin modification phenolic resin LPF is thus made.The LPF of preparation is added to 8% flour, pressed
300g/m2The resin added of (two-sided), veneer surface is applied to, glued board, hot pressing temperature 130 are hot pressed into after 30min is displayed after gluing
DEG C, hot pressing pressure 1.0MPa, hot pressing time 1.2min/mm thicknesss of slab.After tested, the glued board bonding strength being prepared is
0.98MPa。
Embodiment 3
Weigh Choline Chloride 12.1g, phenol 57.1g, add in the container of sealing, under conditions of 55 DEG C stir 5~
6min, it is transparent to reaction solution, that is, obtain ChCl/P DES.It will be transferred in the ChCl/P DES equipped with agitator and condensing unit
In synthesis reactor, sodium lignin sulfonate 22.9g is added, modified lignin resin is obtained after reacting 1h under the conditions of 90 DEG C and DES is mixed
Compound.The sodium hydroxide solution 27.3g that formalin 25.7g, mass concentration that mass concentration is 37% are 20% is slowly added to,
90 DEG C are warming up to, 80 DEG C are cooled to automatically after reacting 30min.The formalin that 108.1g mass concentrations are 37% is slowly added to,
It is warming up to 90 DEG C again, 80 DEG C, when test reaction terminal reaches required viscosity is cooled to automatically after reacting 20min, adds the
Two crowdes of sodium hydroxide 42.1g, discharging, lignin modification phenolic resin LPF is thus made.The LPF of preparation is added to 8% face
Powder, by 300g/m2The resin added of (two-sided), veneer surface is applied to, glued board, hot pressing temperature are hot pressed into after 30min is displayed after gluing
130 DEG C of degree, hot pressing pressure 1.0MPa, hot pressing time 1.2min/mm thicknesss of slab.After tested, the glued board bonding strength being prepared
For 0.89MPa.
Embodiment 4
Weigh Choline Chloride 12.1g, phenol 57.1g, add in the container of sealing, under conditions of 55 DEG C stir 5~
6min, it is transparent to reaction solution, that is, obtain ChCl/P DES.It will be transferred in the ChCl/P DES equipped with agitator and condensing unit
In synthesis reactor, Wheat Straw Lignin from Alkali Pulping 22.9g is added, modified lignin resin is obtained after reacting 1h under the conditions of 90 DEG C and DES is mixed
Compound.The sodium hydroxide solution 27.3g that formalin 25.7g, mass concentration that mass concentration is 37% are 20% is slowly added to,
90 DEG C are warming up under stirring, 80 DEG C are cooled to automatically after reacting 30min.It is 37% to be slowly added to 108.1g mass concentrations
Formalin, 90 DEG C are warming up to again, be cooled to 80 DEG C automatically after reacting 20min, test reaction terminal reaches required viscosity
When, second batch sodium hydroxide 42.1g is added, discharging, lignin modification phenolic resin LPF is thus made.The LPF of preparation is added
8% flour, by 300g/m2The resin added of (two-sided), veneer surface is applied to, glued board is hot pressed into after 30min is displayed after gluing,
130 DEG C of hot pressing temperature, hot pressing pressure 1.0MPa, hot pressing time 1.2min/mm thicknesss of slab.After tested, the plywood glue being prepared
Conjunction intensity is 0.96MPa.
Comparison example 1
Choline Chloride 141g is weighed, phenol 667g, is added in the container of sealing, 5-6min is stirred under conditions of 55 DEG C,
It is transparent to reaction solution, that is, obtain ChCl/P DES.The synthesis equipped with agitator and condensing unit will be transferred in the ChCl/P DES
In reactor, dealkalize lignin 133g is added, modified lignin resin and DES mixtures are obtained after reacting 1h under the conditions of 90 DEG C.To
Ethanol washing is added in mixture, centrifuges and retains sediment fraction, collects supernatant.Supernatant electrical conductivity is treated after repeatedly washing
When close with ethanol electrical conductivity, resulting sediment through 70 DEG C of dryings, recycled wood quality is obtained, supernatant is through being distilled to recover
Ionic liquid and ethanol.
13.3g recycled woods quality is added in the phenol after 66.7g melts, is slowly added to the formaldehyde that mass concentration is 37%
Solution 25.7g, the sodium hydroxide solution 27.3g that mass concentration is 20%, are warming up to 90 DEG C, are cooled to automatically after reacting 30min
80℃.The formalin that 108.1g mass concentrations are 37% is slowly added to, is warming up to 90 DEG C again, is dropped automatically after reacting 20min
Temperature is to 80 DEG C, when test reaction terminal reaches required viscosity, adds second batch sodium hydroxide 42.1g, discharging, wood is thus made
Quality phenol-formaldehyde resin modified LPF.The LPF of preparation is added to 8% flour, by 300g/m2The resin added of (two-sided), is applied to veneer
Surface, glued board, 130 DEG C of hot pressing temperature, hot pressing pressure 1.0MPa, hot pressing time are hot pressed into after displaying 30min after gluing
1.2min/mm thickness of slab.After tested, the glued board bonding strength being prepared is 1.47MPa.
The resin that lignin-phenolic resin prepared by dealkalize lignin of the table 1 through separating treatment is prepared with the present invention is compared
Compared with
The detection of above-mentioned resin：Method according to GB/T 9847-2004 and GB/T 17657-2013 is detected.
From the testing result of table 1, after Choline Chloride/phenol eutectic ionic liquid processing lignin, whether separate
It is little to the performance impact difference for preparing modified lignin resin-synvaren, but in real process, many points can be reduced
From the link of regeneration, cost is advantageously reduced, improves efficiency.
Claims (4)
1. a kind of preparation method of eutectic ionic liquid modified lignin resin-phenolic resin, its feature comprise the following steps that：
(1) preparation of eutectic ionic liquid：Two kinds of raw materials are added in the container of sealing by certain mol ratio, 55 DEG C~70
Stirred under conditions of DEG C, it is transparent to reaction solution, that is, eutectic ionic liquid (DES) is obtained, wherein two kinds of described raw materials are chlorinations
Choline and phenol, certain mol ratio are the mol ratios of Choline Chloride and phenol, and its value is 1: 9~1: 3；
(2) eutectic ionic liquid modified lignin resin：It is anti-that the product of step (1) is transferred to the synthesis equipped with stirring and condensing unit
Answer in device, add the raw material wood element of phenol quality 10%~50% in step (1), be incubated under the conditions of being warming up to 80 DEG C -100 DEG C
Modified lignin resin and DES mixtures are obtained after 1-2h；
(3) the product 50-70 mass parts that obtain step (2), the formalin 15-25 mass parts that mass concentration is 37% and the
A collection of mass concentration is 20% sodium hydroxide solution 15-25 mass parts, that is, accounts for the 40% of sodium hydroxide gross mass, addition is equipped with
In the synthesis reactor of stirring and condensing unit, 85-95 DEG C is warming up in 30-60min, is cooled automatically after reacting 15-30min
To 75-85 DEG C；
(4) formalin that the mass concentration of 30-40 mass parts is 37% is added in the product reacted to step (3), is warming up to
85-95 DEG C, react 15-20min；
(5) product that step (4) is reacted is cooled to 75-85 DEG C automatically, insulation at such a temperature carries out polycondensation reaction 1-3h, surveys
After examination viscosity reaches required viscosity, add after second batch accounts for the sodium hydroxide of sodium hydroxide gross mass 60% and discharge, wood is made
Quality phenol-formaldehyde resin modified LPF；
(6) prepared by glued board：It is 280- by two-sided resin added using the flour of the LPF additions 8%~10% of preparation as filler
320g/m2Veneer surface is applied to, glued board is hot pressed into after 30~40min is displayed after gluing, 130~140 DEG C of its hot pressing temperature, heat
1.0~1.5MPa of pressure pressure, hot pressing time 1~1.5min/mm thicknesss of slab.
2. the preparation method of eutectic ionic liquid modified lignin resin-phenolic resin according to claim 1, its feature exist
In the eutectic ionic liquid of the step (1) is the Choline Chloride using cheap and nontoxic Choline Chloride and phenol as raw material
Mol ratio with phenol is 1: 9~1: 3；
3. the preparation method of eutectic ionic liquid modified lignin resin-phenolic resin according to claim 1, its feature exist
In, the raw material wood element in the step (2) be lignosulfonates, alkali lignin, one kind in dealkalize lignin.
4. the preparation method of eutectic ionic liquid modified lignin resin-phenolic resin according to claim 1, its feature exist
In, hot compression parameterses in the step (6) be 130~140 DEG C, 1.0~1.5MPa of hot pressing pressure of hot pressing temperature, hot pressing time 1
~1.5min/mm thicknesss of slab.
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| CN109369886B (en) * | 2017-08-04 | 2021-07-20 | 南京林业大学 | Method for applying eutectic solvent modified lignin to epoxy resin curing agent |
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| CN115260540B (en) * | 2022-08-22 | 2023-11-21 | 南京林业大学 | Method for rapidly preparing lignin/zinc oxide composite material based on DES |
| CN115368604B (en) * | 2022-08-22 | 2023-11-21 | 湖州市南浔区绿色家居产业研究院 | Anti-ultraviolet polyurethane film and preparation method thereof |
| CN118063790B (en) * | 2024-01-11 | 2024-07-09 | 北京林业大学 | Demethoxy lignin and preparation method and application thereof |
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| CN102250361B (en) * | 2010-11-16 | 2013-07-10 | 大连天宝化学工业有限公司 | Method for preparing modified lignin in ionic liquid solvent system |
| CN102321251B (en) * | 2011-05-27 | 2014-02-26 | 华南理工大学 | Method for separating xylogen from agricultural waste by using compound ion liquid |
| CN102492384A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid |
| CN103554397B (en) * | 2013-10-25 | 2016-01-20 | 沈阳工业大学 | Functionalized ion liquid enhancing modified resol and preparation method thereof |
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Application publication date: 20160420 Assignee: Nanjing Mai Wen environmental protection equipment Engineering Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: X2019320000342 Denomination of invention: Preparation method of eutectic ionic liquid modified lignin-phenolic resin Granted publication date: 20180202 License type: Common License Record date: 20191211 Application publication date: 20160420 Assignee: Nanjing Cheng Shan Technology Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: X2019320000341 Denomination of invention: Preparation method of eutectic ionic liquid modified lignin-phenolic resin Granted publication date: 20180202 License type: Common License Record date: 20191211 |
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Address after: Kuangkeng Zhen Tang Lin Cun Cun Dong, Lanling County, Linyi City, Shandong Province Patentee after: Lanling Jason decoration materials Co., Ltd Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Patentee before: NANJING FORESTRY University |