CN102492384A - Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid - Google Patents
Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid Download PDFInfo
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- CN102492384A CN102492384A CN2011103824353A CN201110382435A CN102492384A CN 102492384 A CN102492384 A CN 102492384A CN 2011103824353 A CN2011103824353 A CN 2011103824353A CN 201110382435 A CN201110382435 A CN 201110382435A CN 102492384 A CN102492384 A CN 102492384A
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- xylogen
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Abstract
The invention relates to a method of preparing phenolic resin through liquefaction of lignin by using ionic liquid. The invention is characterized in that ionic liquid which comprises mono-core or double-core nitrogen-containing cations of alkyl imidazole, alkyl pyridine, quaternary ammonium salt and the like and anions and is in a liquid state at room temperature is used as a liquefaction reagent to liquefy lignin and a product of liquefaction is used to prepare the phenolic resin. Compared to the traditional phenol/sulfuric acid method, the liquefaction method provided in the invention has the characteristics of simple flow, a high liquefaction ratio, low corrosivity, clean process, capacity of adjusting the structure of the liquefaction reagent, repeatedly using the liquefaction reagent and facilitating environmental protection, etc.; the phenolic resin prepared from lignin does not contain volatile phenol, thereby reducing release amount of formaldehyde and being energy saving and environment friendly.
Description
Technical field
The invention belongs to the adhesive technology field, be specifically related to a kind of method of utilizing ionic liquid liquefaction xylogen to prepare modified phenolic adhesive.
Background technology
Along with the requirement of Sustainable development and the enhancing of people's environmental consciousness, the development of biodegradable environmental friendly product more and more receives international concern and attention with exploitation.In resol; It is all fine that the resol that forms with phenol and formaldehyde condensation polymer is used performances such as the Joint strength of the most extensive its laminated product is strong, water-fast, heat-resisting, corrosion-resistant; But resol exists shortcomings such as hot pressing temperature height, time length; In use receive certain restriction, simultaneously because phenol is petroleum chemicals, so the price of phenolic resin adhesive is higher.Xylogen is one of three big components (Mierocrystalline cellulose, semicellulose and xylogen) of plant fiber material, is a kind of macromolecular material that is only second to cellulosic content more than second, and is the unique non-oil resource that renewable compound aromatic base can be provided of nature.Industrial lignin is mainly derived from the waste liquid of paper-making pulping industry thereby has cheapness, renewable, advantages of environment protection.The complex compound that xylogen is made up of phenylpropyl alcohol alkanes structural unit, the unregulated polymer that is joined together to form through ehter bond and C-C between the structural unit.Contain the group that phenolic hydroxyl group, alcoholic extract hydroxyl group etc. contain active hydrogen in the lignin molecule; Resins such as generation lignin-base phenolic aldehyde, urea aldehyde and urethane under certain conditions can react with plurality of raw materials such as phenol, formaldehyde, isocyanic ester; Practiced thrift the consumption of phenol, the residual volume, this utilization again for natural resource, the protection environment that have reduced formaldehyde have great importance.
Natural lignin's molecular structure is complicated, molecular weight substituting group steric hindrance high, the aromatic ring of xylogen own is bigger, can not effectively react with resol.Through the modification to xylogen this problem is improved, but the xylogen tackiness agent after the modification still has problems: molecular weight is high, viscosity is big, has influenced the widespread use of xylogen tackiness agent.
Have the scholar to adopt liquefaction technology to make xylogen liquefaction for having the available low molecule liquefied product of certain reactive group at present, the product after the liquefaction can be used as the raw material of producing tackiness agent through handling.Present liquifying method mainly contains two types: high temperature liquefaction and the low-temperature liquefaction under catalyzer.No matter be that the liquefaction of low-temperature liquefaction or high temperature all is that xylogen is directly liquefied with organic solvents such as phenol, polyvalent alcohol or cyclic carbonates.。HTHP liquefaction method need be carried out under HTHP, and is not easy to operate, and needs to consume a large amount of energy; The low-temperature liquefaction method need adopt acidity or basic catalyst, and equipment is had certain corrodibility, and environmental pollution is serious.
Ionic liquid at room temperature is not only a kind of Green Chemistry solvent, and can be used as the organic chemicals that the catalyzer conversion of biomass is a petroleum derivation.Effendi etc. propose to utilize the phenolysis reaction of xylogen in the summary of biomass thermal chemical conversion, can produce regeneration resol in the alkaline catalysts choosing.Therefore the objective of the invention is to use ionic liquid liquefaction xylogen to prepare resol.
Summary of the invention
The objective of the invention is to utilize ionic liquid liquefaction xylogen to prepare resol.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
(1) xylogen liquefaction
With the ionic liquid is liquefied reagent, adds xylogen, under normal pressure, in 70～150 ℃ of reacting by heating 0.5h～24h, obtains the xylogen liquefied product;
(2) modified phenolic adhesive is synthetic
After the cooling of xylogen liquefied product; Xylogen liquefied product and formaldehyde was blended in by the ratio of xylogen and the quality of formaldehyde in 1: 1～1: 3 adds reaction under the base catalysis condition; The mass ratio of basic catalyst and xylogen liquefied product is 1: 2～1: 4; Basic catalyst adds with the solution form of mass concentration 30%～45%, under condition of normal pressure, is warming up to 40～60 ℃ of reaction 5～15min, is warming up to 80～100 ℃ of reactions 1～3 hour then; Measure viscosity with the method for falling the bubble and stop heating when meeting gluing the requirement, obtain tackiness agent.
Described xylogen obtains through the ion liquid dissolving stalk
The mass ratio of said ionic liquid and xylogen is 1: 1～20: 1.
Said ionic liquid is that the monokaryon that is made up of alkyl imidazole, alkyl pyridine, quaternary ammonium salt etc. and double-core nitrogenous compound and negatively charged ion constitute (because quaternary ammonium salt ion liquid is at high temperature unstable, so use less), and general structure is:
Wherein constituting ion liquid negatively charged ion is: halogen ion, chlorine aluminic acid ion, carboxylate radical, replacement or non-substituted arylsulphonate, aryl disulfonic salt, phosphate ester salt.
Described method basic catalyst is Pottasium Hydroxide, sodium hydroxide, calcium hydroxide, Marinco H, is preferably sodium hydroxide.
The adding of described method formaldehyde can adopt repeatedly feed way to add.
Described method, wherein xylogen uses the oil bath heating.
The present invention has the following advantages;
1. raw material sources are abundant, environmental protection;
2. the present invention uses ionic liquid at room temperature, and liquefaction condition is gentle, and is little to equipment corrosion, improved liquefaction efficiency, reduced the liquefied residue rate;
3. ionic liquid stable performance can reuse environmental friendliness;
4. the liquefied product that method provided by the invention obtains can directly be used to prepare novel high polymer materials such as tackiness agent, urethane foam.
Embodiment
The present invention explains with following embodiment, but the present invention is not limited to following embodiment, before and after not breaking away from, under the prerequisite of said aim, changes and implements to be included in the technical scope of the present invention.
Embodiment 1
10g [bmin] Cl and 0.5g stalk are added in the there-necked flask, at N
2Under stir oil bath and be heated to 100 ℃, reaction for some time, when the color of solution by colourless when becoming puce; Stopped reaction; The cooling back adds 0.5g formaldehyde and 3g sodium hydroxide (concentration with 30% adds), under condition of normal pressure, is warming up to 40 ℃ of reaction 5min, is warming up to 80 ℃ of reaction 3h then; Measure viscosity (viscosity controller is about 3-6s) with the method for falling the bubble and stop heating when meeting gluing the requirement, obtain tackiness agent.
Embodiment 2
With 5g 3,3 '-ethyl-1,2-two (N-Methylimidazole) villaumite and 0.5g stalk are added in the there-necked flask, at N
2Under stir oil bath and be heated to 80 ℃, reaction for some time, when the color of solution by colourless when becoming puce; Stopped reaction; The cooling back adds 1.5g formaldehyde and 2g sodium hydroxide (concentration with 40% adds), under condition of normal pressure, is warming up to 50 ℃ of reaction 10min, is warming up to 90 ℃ of reaction 2h then; Measure viscosity (viscosity controller is about 3-6s) with the method for falling the bubble and stop heating when meeting gluing the requirement, obtain tackiness agent.
Embodiment 3
10g NMPCl and 0.5g stalk are added in the there-necked flask, at N
2Under stir oil bath and be heated to 120 ℃, reaction for some time, when the color of solution by colourless when becoming puce; Stopped reaction; The cooling back adds 0.5g formaldehyde and 3g sodium hydroxide (concentration with 30% adds), under condition of normal pressure, is warming up to 40 ℃ of reaction 5min, is warming up to 80 ℃ of reaction 3h then; Measure viscosity (viscosity controller is about 3-6s) with the method for falling the bubble and stop heating when meeting gluing the requirement, obtain tackiness agent.
Embodiment 4
With 10g1,1 '-ethyl-1,2-two pyridine villaumites and 0.5g stalk are added in the there-necked flask, at N
2Under stir oil bath and be heated to 100 ℃, reaction for some time, when the color of solution by colourless when becoming puce; Stopped reaction; The cooling back adds 0.5g formaldehyde and 3g sodium hydroxide (concentration with 30% adds), under condition of normal pressure, is warming up to 40 ℃ of reaction 5min, is warming up to 80 ℃ of reaction 3h then; Measure viscosity (viscosity controller is about 3-6s) with the method for falling the bubble and stop heating when meeting gluing the requirement, obtain tackiness agent.
Claims (7)
1. ionic liquid liquefaction xylogen prepares the method for modified phenolic adhesive, it is characterized in that concrete steps are following:
(1) xylogen liquefaction
With the ionic liquid is liquefied reagent, adds xylogen, under normal pressure, in 70～150 ℃ of reacting by heating 0.5h～24h, obtains the xylogen liquefied product;
(2) modified phenolic adhesive is synthetic
After the cooling of xylogen liquefied product; Xylogen liquefied product and formaldehyde was blended in by the ratio of xylogen and the quality of formaldehyde in 1: 1～1: 3 adds reaction under the base catalysis condition; The mass ratio of basic catalyst and xylogen liquefied product is 1: 2～1: 4; Basic catalyst adds with the solution form of mass concentration 30%～45%, under condition of normal pressure, is warming up to 40～60 ℃ of reaction 5～15min, is warming up to 80～100 ℃ of reactions 1～3 hour then; Measure viscosity with the method for falling the bubble and stop heating when meeting gluing the requirement, obtain tackiness agent.
2. preparation method according to claim 1 is characterized in that said xylogen obtains through the ion liquid dissolving stalk.
3. preparation method according to claim 1, the mass ratio that it is characterized in that said ionic liquid and xylogen is 1: 1～20: 1.
4. preparation method according to claim 1; The ionic liquid that it is characterized in that said liquefaction xylogen is that the monokaryon that is made up of alkyl imidazole, alkyl pyridine, quaternary ammonium salt etc. and double-core nitrogenous compound and negatively charged ion constitute (because quaternary ammonium salt ion liquid is at high temperature unstable; So use less), general structure is:
Wherein constituting ion liquid negatively charged ion is: halogen ion, chlorine aluminic acid ion, carboxylate radical, sulfonate radical, replacement or non-substituted arylsulphonate, aryl disulfonic salt, phosphate ester salt.
5. preparation method according to claim 1 is characterized in that said basic catalyst is Pottasium Hydroxide, sodium hydroxide, calcium hydroxide, Marinco H, is preferably sodium hydroxide.
6. preparation method according to claim 1 is characterized in that the adding of formaldehyde can adopt repeatedly feed way to add.
7. the method for xylogen liquefaction according to claim 1 is used the oil bath heating.
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| CN2011103824353A CN102492384A (en) | 2011-11-28 | 2011-11-28 | Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid |
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| CN2011103824353A CN102492384A (en) | 2011-11-28 | 2011-11-28 | Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925188A (en) * | 2012-10-25 | 2013-02-13 | 福建农林大学 | Method for alcoholysis-liquefying wood biomass with sulfonic acid type ionic liquid |
| CN103555236A (en) * | 2013-10-25 | 2014-02-05 | 沈阳工业大学 | High-adhesiveness phenol aldehyde composite adhesive and preparation method thereof |
| CN103554397A (en) * | 2013-10-25 | 2014-02-05 | 沈阳工业大学 | Functionalized ionic liquid reinforced and modified phenolic resin and preparation method of phenolic resin |
| CN103589315A (en) * | 2013-11-13 | 2014-02-19 | 宁德师范学院 | Method for preparing polyurethane coating by timber liquidized by ionic liquid |
| CN103665391A (en) * | 2013-12-10 | 2014-03-26 | 江南大学 | Method for liquefying straws by acidic ionic liquid |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN110054740A (en) * | 2019-04-12 | 2019-07-26 | 江山欧派门业股份有限公司 | Lignin modification phenolic resin and preparation method thereof and recombinant material |
| CN110305274A (en) * | 2019-06-28 | 2019-10-08 | 湖北文理学院 | A kind of preparation method of the Lewis acidic ionic liquid phenol-formaldehyde resin modified of friction material |
| CN112251167A (en) * | 2020-10-16 | 2021-01-22 | 星威国际家居股份有限公司 | Adhesive and bonding method for preventing buckling and cracking of solid wood spliced large board |
| CN113621116A (en) * | 2020-05-08 | 2021-11-09 | 中石化石油工程技术服务有限公司 | Biomass synthetic resin filtrate reducer for drilling fluid and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1836068A (en) * | 2003-08-13 | 2006-09-20 | 维里迪安化学有限公司 | Solvents for use in the treatment of lignin-containing materials |
| CN101260283A (en) * | 2008-04-10 | 2008-09-10 | 黄山学院 | Method for preparing phenolic aldehyde adhesive based on lignin phenolized liquid and application thereof |
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2011
- 2011-11-28 CN CN2011103824353A patent/CN102492384A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1836068A (en) * | 2003-08-13 | 2006-09-20 | 维里迪安化学有限公司 | Solvents for use in the treatment of lignin-containing materials |
| CN101260283A (en) * | 2008-04-10 | 2008-09-10 | 黄山学院 | Method for preparing phenolic aldehyde adhesive based on lignin phenolized liquid and application thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925188A (en) * | 2012-10-25 | 2013-02-13 | 福建农林大学 | Method for alcoholysis-liquefying wood biomass with sulfonic acid type 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 |
| CN103555236A (en) * | 2013-10-25 | 2014-02-05 | 沈阳工业大学 | High-adhesiveness phenol aldehyde composite adhesive and preparation method thereof |
| CN103554397A (en) * | 2013-10-25 | 2014-02-05 | 沈阳工业大学 | Functionalized ionic liquid reinforced and modified phenolic resin and preparation method of phenolic resin |
| CN103589315A (en) * | 2013-11-13 | 2014-02-19 | 宁德师范学院 | Method for preparing polyurethane coating by timber liquidized by ionic liquid |
| CN103589315B (en) * | 2013-11-13 | 2015-11-18 | 宁德师范学院 | A kind of ionic liquid Liquefied wood prepares the method for polyurethane coating |
| CN103665391A (en) * | 2013-12-10 | 2014-03-26 | 江南大学 | Method for liquefying straws by acidic ionic liquid |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN110054740A (en) * | 2019-04-12 | 2019-07-26 | 江山欧派门业股份有限公司 | Lignin modification phenolic resin and preparation method thereof and recombinant material |
| CN110305274A (en) * | 2019-06-28 | 2019-10-08 | 湖北文理学院 | A kind of preparation method of the Lewis acidic ionic liquid phenol-formaldehyde resin modified of friction material |
| CN113621116A (en) * | 2020-05-08 | 2021-11-09 | 中石化石油工程技术服务有限公司 | Biomass synthetic resin filtrate reducer for drilling fluid and preparation method and application thereof |
| CN112251167A (en) * | 2020-10-16 | 2021-01-22 | 星威国际家居股份有限公司 | Adhesive and bonding method for preventing buckling and cracking of solid wood spliced large board |
| CN112251167B (en) * | 2020-10-16 | 2022-04-15 | 星威国际家居股份有限公司 | Adhesive and bonding method for preventing buckling and cracking of solid wood spliced large board |
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Application publication date: 20120613 |