CN107974037B - Application of graded lignin in preparation of phenolic foam thermal insulation material - Google Patents

Application of graded lignin in preparation of phenolic foam thermal insulation material Download PDF

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CN107974037B
CN107974037B CN201711059565.7A CN201711059565A CN107974037B CN 107974037 B CN107974037 B CN 107974037B CN 201711059565 A CN201711059565 A CN 201711059565A CN 107974037 B CN107974037 B CN 107974037B
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lignin
acid
molecular weight
solution
thermal insulation
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CN107974037A (en
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应汉杰
邓彤
朱晨杰
唐成伦
甘涛
陈勇
吴菁岚
柳东
沈涛
蒋忠艳
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00Characterised by the use of lignin-containing materials

Abstract

The invention discloses application of lignin in preparation of a phenolic foam thermal insulation material. Compared with the prior art, the invention directly blends the graded lignin and the expandable phenolic resin to prepare the phenolic foam thermal insulation material by controlling the molecular weight of the lignin, avoids the complicated modification step in the process of preparing the phenolic resin from the lignin, saves the acid and alkali dosage, reduces the energy consumption in the modification process, can greatly improve the lignin content in the final phenolic foam thermal insulation material product, and has economical efficiency and more environmental protection. The phenolic foam heat-insulating material filled with the graded lignin has better mechanical property, thermal stability and ultraviolet aging resistance, the fineness of the foam heat-insulating material is better, the product quality reaches the national standard, and the market demand can be met.

Description

Application of graded lignin in preparation of phenolic foam thermal insulation material
Technical Field
the invention belongs to the field of heat insulation materials, and particularly relates to application of lignin in preparation of a phenolic foam heat insulation material.
Background
the phenolic foam plastic is a novel flame-retardant, fireproof and low-smoke heat-insulating material, and is closed-cell rigid foam plastic prepared by adding a flame retardant, a smoke inhibitor, a foaming agent, a curing agent and other auxiliary agents into phenolic resin. Its outstanding features are flame-retarding, low smoke and high-temp. It can be cast and foamed in situ, and can be moulded, also can be machined, and can be made into plate material, pipe shell and various special-shaped products. The foam plastic type heat-insulating material overcomes the defects of inflammability, smoke and deformation when heated of the original foam plastic type heat-insulating material, and keeps the characteristics of light weight, convenient construction and the like of the original foam plastic type heat-insulating material.
The lignin is a natural high molecular substance which is second to cellulose in the world, 6 x 10 5 million tons of lignin are produced every year in the world, only a small part of lignin is utilized, most of lignin is directly combusted to obtain energy, and resources are greatly wasted.
CN102504477A, CN103756250A, and CN106700001A report methods of acidic or alkaline phenolization modification of lignin from different sources, and lignin phenolic resin prepared by phenolization modified lignin and used for foaming. However, the high acid (or alkali) dosage additionally added in the high-temperature phenolization, the additional energy consumption required for maintaining the high temperature, the existence of insoluble substances in the lignin phenolization liquefaction and the high viscosity of the lignin phenolic resin limit the industrial application of the lignin modified phenolic foam.
CN104403263A reports a method for mixing and foaming lignin and phenolic resin, in which a 40% solid content lignin aqueous solution is mixed and foamed with phenolic resin. However, lignin is not classified, and the physical and chemical properties of lignin with different molecular weights are greatly different, so that the mixing effect with phenolic resin is poor, and the product quality is poor.
Disclosure of Invention
The invention aims to solve the technical problem of providing an application method of lignin in preparation of a phenolic foam heat-insulating material, so as to solve the problems of poor effect and the like in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
The invention protects the application of the graded lignin in preparing the phenolic foam heat-insulating material; wherein, the fractionated lignin is one of the following three lignin with molecular weight distribution ranges:
(1) Lignin with a molecular weight distribution range greater than 3000 Da;
(2) Lignin with molecular weight distribution range greater than 1000Da and less than or equal to 3000 Da;
(3) Lignin with a molecular weight distribution range of 1000Da or less.
Wherein, the fractionated lignin is prepared by the following method:
(1) Adding lignin into an alkaline aqueous solution, stirring and dissolving, and performing solid-liquid separation to obtain a lignin solution;
(2) Carrying out ultrafiltration on the lignin solution obtained in the step (1) to obtain a trapped fluid A1 and a permeate A2; nanofiltration is carried out on the permeate A2 to obtain trapped fluid B1 and permeate C1;
(3) Respectively adding acid solution into the trapped liquid A1, the trapped liquid B1 and the permeate liquid C1 obtained in the step (2), adjusting the pH value, carrying out solid-liquid separation, drying the solid part, and respectively obtaining lignin with a molecular weight distribution range of more than 3000Da, wherein the molecular weight distribution range of the lignin is more than 1000Da, and the molecular weight distribution range of the lignin is less than or equal to 3000Da and the molecular weight distribution range of the lignin is less than or equal to 1000 Da.
In the step (1), the lignin is one or a combination of more of enzymatic hydrolysis lignin, papermaking lignin, alkali lignin, organic solvent lignin, lignosulfonate and lignin modified by acylation, esterification, etherification, phenolization, alkylation and demethylation of the lignin.
In the step (1), the alkaline aqueous solution is any one or a combination of more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a rubidium hydroxide aqueous solution and a cesium hydroxide aqueous solution, and the pH value of the alkaline aqueous solution is 8-13.
In the step (1), the solid content of the lignin solution is 0.5-10 wt%.
In the step (2), the cutoff molecular weight of the ultrafiltration membrane is 3000 Da; during ultrafiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
in the step (2), the molecular weight cut-off of the nanofiltration membrane is 1000 Da; during nanofiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
In the step (3), the acid solution is any one or a combination of more of a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution and an oxalic acid aqueous solution, and the acid solution is an acidic aqueous solution with pH less than 3.
in the step (3), the pH adjustment refers to adding an acid solution until the pH is 1.5-3.
Wherein, the phenolic foam thermal insulation material also comprises the following components:
phenolic resin, a foaming agent, a curing agent and a surfactant.
The weight parts of the components are as follows:
wherein, the phenolic foam thermal insulation material also comprises a flame retardant and/or a toughening agent.
the composite material also comprises the following components in parts by mass: 5-25 parts of a flame retardant and/or 5-15 parts of a toughening agent.
Wherein, the phenolic resin is an expandable phenolic resin.
wherein, the foaming agent is any one or combination of more of n-butane, n-pentane, isobutane, isopentane, cyclopentane, petroleum ether and dichloromonofluoroethane, and n-pentane is preferred.
The foaming agent is any one or combination of a plurality of benzene sulfonic acid, p-toluenesulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid, and a compound system of p-toluenesulfonic acid and phosphoric acid is preferred.
The surfactant is any one or combination of more of polysiloxane, polyoxyethylene ether, polyoxypropylene, polyoxyethylene polyoxypropylene, polyethylene sorbitan fatty acid ester and tween series, and a compound system of polysiloxane and tween series is preferred.
wherein, the flame retardant is any one or combination of more of antimony trioxide, magnesium hydroxide, aluminum hydroxide, halogenated phosphate and zinc borate, and preferably, the aluminum hydroxide.
The toughening agent is any one or a combination of more of ethylene glycol, polyethylene glycol, polyvinyl alcohol, polyester polyol, nitrile rubber, polyurethane prepolymer and epoxy resin, and a compound system of the polyethylene glycol and the polyurethane prepolymer is preferred.
The phenolic foam thermal insulation material is prepared by the following method:
The components are evenly mixed and then are foamed and heated.
The step of uniformly mixing is to uniformly mix the graded lignin and the phenolic resin into the lignin blending type phenolic resin at the rotating speed of 1000-10000 rpm, and then uniformly mix the lignin blending type phenolic resin with other components at the rotating speed of 100-1200 rpm.
Wherein the foaming temperature is 50-90 ℃ and the time is 0.5-4 h.
Has the advantages that:
The invention aims to solve the problems of high lignin modified acid-base dosage, high extra energy consumption and low lignin substitution amount in lignin phenolic foam, and provides a preparation method for preparing phenolic foam thermal insulation material by directly blending graded lignin and expandable phenolic resin through controlling the molecular weight of lignin. According to the invention, the molecular weight of lignin is controlled, and the graded lignin and the expandable phenolic resin are directly blended to prepare the phenolic foam thermal insulation material, so that the complicated modification step in the process of preparing the phenolic resin from the lignin is avoided, the acid and alkali consumption is saved, the energy consumption in the modification process is reduced, the lignin content in the final phenolic foam thermal insulation material product can be greatly increased, and the phenolic foam thermal insulation material has economical efficiency and more environmental protection property. The phenolic foam heat-insulating material filled with the graded lignin has better mechanical property, thermal stability and ultraviolet aging resistance, the fineness of the foam heat-insulating material is better, the product quality reaches the national standard, and the market demand can be met.
compared with the prior art, the invention has the following advantages:
1. compared with the traditional phenolic foam, the addition of the lignin can greatly reduce the cost of the phenolic foam, and meanwhile, the addition of the lignin improves the ultraviolet resistance and toughness of the foam and reduces the slag falling rate.
2. Compared with lignin modified phenolic foam, the method can completely save the additional acid and alkali dosage and high energy consumption in the lignin modification process. Meanwhile, the graded lignin has a net cross-linked structure and uniform molecular weight, so that the structure of the phenolic resin can be directly replaced in the phenolic resin, and the replacement amount is remarkably increased as modified lignin can only replace a phenol component. Meanwhile, the problem that the viscosity is greatly increased and foaming cannot be realized due to the addition of a large amount of lignin in the resin manufacturing process is avoided.
3. Compared with the mixing and foaming of lignin aqueous solution and phenolic resin, the invention adopts the process of directly blending the graded lignin with the phenolic resin at ultrahigh speed, and the graded lignin is more uniformly dispersed in the phenolic resin through the effect of ultrahigh-speed dispersion, homogenization and emulsification, thereby greatly increasing the substitution amount of the lignin and opening up a new way for the large-scale industrial application of the lignin.
Detailed Description
Example 1:
Weighing 100 parts by mass of hairstyle phenolic resin, 10 parts by mass of lignin with the molecular weight of 1000-3000, and stirring for 10min at the rotating speed of 8000rpm of an ultrahigh speed dispersion machine until the mixture is uniformly stirred. Adding tween-806 parts by mass, 10 parts by mass of n-pentane, 14 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 3: 1), 20 parts by mass of aluminum hydroxide and 6 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Example 2:
Weighing 100 parts by mass of hairstyle phenolic resin, 20 parts by mass of lignin with the molecular weight of 1000-3000, and stirring for 10min at the rotating speed of 8000rpm of an ultrahigh speed dispersion machine until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Example 3:
Weighing 100 parts by mass of hairstyle phenolic resin, 30 parts by mass of lignin with the molecular weight of 1000-3000, and stirring for 10min at the rotating speed of 8000rpm of an ultrahigh speed dispersion machine until the mixture is uniformly stirred. Adding tween-808 parts by mass, 10 parts by mass of n-pentane, 13 parts by mass of a curing agent (p-toluenesulfonic acid: phosphoric acid: water: 7: 3: 3), 20 parts by mass of aluminum hydroxide and 10 parts by mass of a flexibilizer (polyethylene glycol: glycerol: 1), mixing and stirring uniformly at 500rpm, introducing into a mold, curing at 80 ℃ for 2 hours, and obtaining the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Comparative example 1:
weighing 100 parts by mass of hairstyle phenolic resin, 20 parts by mass of lignin with the molecular weight less than 1000, and stirring for 10min at the rotating speed of 8000rpm of an ultra-high speed dispersion machine until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Comparative example 2:
Weighing 100 parts by mass of hairstyle phenolic resin with the molecular weight of more than 3000 parts by mass of lignin, and stirring at the rotating speed of 8000rpm of an ultra-high speed dispersion machine for 10min until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
comparative example 3:
Weighing 100 parts by mass of phenolic resin with hairstyle and 20 parts by mass of unfractionated lignin, and stirring at the rotating speed of 8000rpm of an ultra-high speed dispersion machine for 10min until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the unfractionated lignin filled phenolic foam thermal insulation material.
The properties of the prepared unfractionated lignin-filled phenolic foam insulation material are shown in table 1.
TABLE 1
By observing the examples 1 to 3 and the comparative example 3, the enhanced phenolic foam thermal insulation material prepared by adding the graded lignin (with the molecular weight of 1000-3000) is found to have obviously improved compression performance and tensile performance and improved oxygen index compared with the phenolic foam thermal insulation material prepared by adding the unfractionated lignin, because the graded lignin has uniform molecular weight and close physical and chemical properties, and the lignin has a rigid benzene ring structure and can enhance the performance of the foam when dispersed into the foam. Meanwhile, the heat conductivity coefficient and the smoke density of the enhanced foam heat-insulating material prepared by adding the graded lignin are not greatly floated compared with those of the phenolic resin foam heat-insulating material prepared by adding the unfractionated lignin, and the material properties are similar.
Through examples 1 to 3 and comparative examples 1 to 2, it was found that the molecular weight of the added fractionated lignin has a great influence on the properties of the phenolic foam insulation. Along with the reduction of the molecular weight of the added lignin, when the molecular weight is less than 1000, the compressive strength and the tensile strength of the phenolic foam thermal insulation material are greatly reduced, meanwhile, the heat conductivity coefficient is obviously improved, and the heat conductivity is poor. The reason is that the polymerization degree of lignin is reduced along with the reduction of the molecular weight of the lignin, and the lignin with low polymerization degree does not contribute to the performance of the phenolic foam thermal insulation material product. With the increase of the molecular weight of the added lignin, when the molecular weight is more than 3000, the oxygen index of the phenolic foam thermal insulation material is greatly reduced, and the flame retardant property is poor. This is because the hydroxymethyl content of lignin decreases with the increase in the molecular weight of lignin, the activity of lignin molecules decreases, and the increase in molecular weight causes large steric hindrance and uneven dispersion.
The enhanced phenolic foam thermal insulation material prepared by adding the graded lignin can obviously improve the compression performance, the tensile performance and the oxygen index of the foam thermal insulation material, the performances of other materials can not be reduced, and when the molecular weight of the added graded lignin is 1000-3000, the performance of the phenolic foam thermal insulation material is excellent. Meanwhile, due to the direct blending addition of the graded lignin, the cost of the phenolic foam thermal insulation material is greatly reduced, and a new way is opened up for the large-scale industrial application of the lignin.

Claims (17)

1. The application of the graded lignin in preparing phenolic foam heat-insulating materials; wherein the fractionated lignin is
lignin with molecular weight distribution range greater than 1000Da and less than or equal to 3000 Da;
Wherein, the phenolic foam thermal insulation material also comprises the following components: phenolic resin, foaming agent, curing agent and surfactant;
The phenolic foam thermal insulation material is prepared by the following method: uniformly mixing all the components, and then carrying out foaming heating;
The step of uniformly mixing is to uniformly mix the graded lignin and the phenolic resin into the lignin blending type phenolic resin at the rotating speed of 1000-10000 rpm, and then uniformly mix the lignin blending type phenolic resin with other components at the rotating speed of 100-1200 rpm;
Wherein the foaming temperature is 50-90 ℃ and the time is 0.5-4 h.
2. The use according to claim 1, wherein the fractionated lignin is prepared by the following method:
(1) Adding lignin into an alkaline aqueous solution, stirring and dissolving, and performing solid-liquid separation to obtain a lignin solution;
(2) carrying out ultrafiltration on the lignin solution obtained in the step (1) to obtain a trapped fluid A1 and a permeate A2; nanofiltration is carried out on the permeate A2 to obtain trapped fluid B1 and permeate C1;
(3) respectively adding acid solution into the trapped liquid A1, the trapped liquid B1 and the permeate liquid C1 obtained in the step (2), adjusting the pH value, carrying out solid-liquid separation, drying the solid part, and respectively obtaining lignin with a molecular weight distribution range of more than 3000Da, wherein the molecular weight distribution range of the lignin is more than 1000Da, and the molecular weight distribution range of the lignin is less than or equal to 3000Da and the molecular weight distribution range of the lignin is less than or equal to 1000 Da.
3. The use according to claim 2, wherein in the step (1), the lignin is one or more of enzymatic lignin, papermaking lignin, alkali lignin, organosolv lignin, lignosulfonate, and lignin modified by acylation, esterification, etherification, phenolization, alkylation and demethylation of the lignin.
4. The use of claim 2, wherein in step (1), the alkaline aqueous solution is any one or a combination of several of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous rubidium hydroxide solution and aqueous cesium hydroxide solution; wherein the pH value of the alkaline aqueous solution is 8-13.
5. The use according to claim 2, wherein in step (1), the lignin solution has a solid content of 0.5-10 wt%.
6. The use according to claim 2, wherein in step (2), said ultrafiltration membrane has a molecular weight cut-off of 3000 Da; during ultrafiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
7. The use according to claim 2, wherein in step (2), the nanofiltration membrane has a molecular weight cut-off of 1000 Da; during nanofiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
8. The use according to claim 2, wherein in the step (3), the acid solution is any one or a combination of a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution and an oxalic acid aqueous solution; wherein the acid solution is an acidic aqueous solution with the pH value less than 3.
9. the use according to claim 2, wherein in the step (3), the pH adjustment is performed by adding an acid solution to a pH of 1.5 to 3.
10. The application of the compound as claimed in claim 1, wherein the mass parts of the components are as follows:
11. the use of claim 1, wherein the phenolic foam insulation further comprises a flame retardant and/or a toughening agent.
12. The application of the composition as claimed in claim 10, further comprising the following components in parts by mass: 5-25 parts of a flame retardant and/or 5-15 parts of a toughening agent.
13. the use according to claim 1, wherein the blowing agent is any one or a combination of n-butane, n-pentane, isobutane, isopentane, cyclopentane, petroleum ether and dichloromonofluoroethane.
14. The use of claim 1, wherein the curing agent is any one or a combination of benzene sulfonic acid, p-toluene sulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid.
15. The use according to claim 1, wherein the surfactant is any one or a combination of polysiloxanes, polyoxyethylene ethers, polyoxypropylenes, polyoxyethylene polyoxypropylenes, polyethylene sorbitan fatty acid esters, and tweens.
16. The use of claim 11, wherein the flame retardant is any one or a combination of antimony trioxide, magnesium hydroxide, aluminum hydroxide, halogenated phosphate and zinc borate.
17. The use of claim 11, wherein the toughening agent is one or more of ethylene glycol, polyethylene glycol, polyvinyl alcohol, polyester polyol, nitrile rubber, polyurethane prepolymer and epoxy resin.
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CN109970991A (en) * 2019-03-20 2019-07-05 华南理工大学 It is classified the modified method of comprehensive utilization of the small fraction demethoxylation of lignin
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CN102504477B (en) * 2011-10-18 2013-12-25 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
CN104558632B (en) * 2014-12-30 2017-01-11 山东龙力生物科技股份有限公司 Method for preparing lignin derivative products from industrial fiber waste residues
CN104927067B (en) * 2015-06-29 2017-04-19 南京林业大学 Method of extracting lignins different in molecular weight from bamboo pulping black liquor
CN106750362B (en) * 2016-11-30 2019-06-11 海南金海浆纸业有限公司 A kind of stage division of lignin

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