CN103613728A - Preparation method of lignin phenolic foams - Google Patents
Preparation method of lignin phenolic foams Download PDFInfo
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- CN103613728A CN103613728A CN201310684779.9A CN201310684779A CN103613728A CN 103613728 A CN103613728 A CN 103613728A CN 201310684779 A CN201310684779 A CN 201310684779A CN 103613728 A CN103613728 A CN 103613728A
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- xylogen
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- phenolic aldehyde
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Abstract
The invention relates to a preparation method of lignin phenolic foams. Lignin is used for partially replacing phenol through chemical degradation and is subjected to an addition polycondensation reaction with paraformaldehyde in the presence of a basic catalyst which is compounded from a basic oxide and a phosphorated sodium salt. The prepared resin is relatively high in activity, and conventional foaming agents, curing agents and surfactants are adopted to meet requirements for the curing speed of a phenolic foam production line, so that the industrial production can be performed. The preparation method disclosed by the invention not only can reduce the cost of the phenolic foams but also can alleviate the environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation method who utilizes lignin modification foamex and phenol formaldehyde foam thereof.Specially refer to the selection of catalyzer in resin preparation process, be suitable for industrialization continuity and produce.
Background technology
China is second-biggest-in-the-world energy expenditure state, wherein building energy consumption compare Gao， unit floor area of building energy consumption be developed country 2-3 doubly more than, the energy consumption of building materials and building accounts for 47.3% of energy wastage in bulk or weight, surpasses the summation of all developed countries.Phenol formaldehyde foam is because its excellent performance is called as " king of lagging material ".China has formulated two targets aspect building energy conservation at present: the one, and by 2010, all town buildings are energy-conservation will reach 50% fractional energy savings, and megalopolis and urban take the lead in reaching 65%; The 2nd, to the year two thousand twenty, town building is energy-conservation all will reach 65%.It is reported, the rural area of Beijing suburb has come into effect exterior-wall heat insulation measure, so China's lagging material good market prospects.
Along with the shortage increasingly of fossil resource, the research of biological material more and more comes into one's own.Xylogen is important natural phenolic compound, and there is abundant Liginon Resource in China, and existing lot of documents report utilizes its alternative phenol to prepare based Wood Adhesives, and what have carries out suitability for industrialized production.But it is less to substitute the applied research of phenol in phenol formaldehyde foam, major cause is xylogen complicated component, reactive behavior is low, at present literature search to xylogen or the application of waste wood in foamex passed through Liquefaction Products in Phenol, react with formaldehyde (being mostly liquid formaldehyde) again, because xylogen or timber molecular weight reduce not obvious, cause the larger foaming difficulty of foamex viscosity, catalyzer used is generally aqueous sodium hydroxide solution, or aqueous sodium hydroxide solution and divalence basic oxide is composite, or hydrated barta, but be applied in lignin modification foamex and still occur that the resin solidification time is long, the foaming of employing frame, need 0.5h-2h.The purification processes of some employing organic solvents to papermaking waste, resulting xylogen is used for substituting phenol and prepares foamex, has increased cost.Therefore be necessary to improve xylogen foamex reactive behavior, realize industrialization and produce continuously, reduce the usage quantity of fossil feedstock, also protected environment, reduced foam cost.
Summary of the invention
The invention provides a kind of preparation method of xylogen phenolic aldehyde foams, a kind of preparation method of the xylogen phenolic aldehyde foams of can industrialization continuity producing is provided, the catalyzer specially referring in resin preparation process is selected.
The present invention is achieved through the following technical solutions: a kind of preparation method of xylogen phenolic aldehyde foams, step is: the preparation of (1) lignin modification foamex: by the xylogen through chemical degradation of stoichiometric ratio, phenol and catalyzer are disposable all to add in reactor, paraformaldehyde divides 3～5 times and adds, every minor tick 10～20min, temperature maintains 65～75 ℃, until paraformaldehyde all adds, be warming up to after 80 ℃～85 ℃ insulation 30～50min, continue to be warming up to 95～100 ℃ of insulation 1～1.5h, then add urea to catch free formaldehyde, be cooled to 60 ℃ of dischargings and obtain lignin modification foamex, catalyzer used is the compound that basic oxide and phosphorous sodium salt form according to the mass ratio of 1:1～3, (2) preparation of phenol formaldehyde foam: lignin modification foamex and whipping agent, tensio-active agent and solidifying agent blended under agitation, on phenol formaldehyde foam streamline, carry out industrialization continuity production.
Described basic oxide are any in magnesium oxide, zinc oxide, calcium oxide; Described phosphorous sodium salt is any in tertiary sodium phosphate, Sodium phosphate dibasic, tripoly phosphate sodium STPP or trisodium phosphate.
Described catalyst levels accounts for 1～3% of phenol quality.
After lignin modification foamex described in step (2) and whipping agent, tensio-active agent and solidifying agent blended under agitation, controlling pH value is 7.5～9.2.
The xylogen of described chemical degradation is the xylogen xylogen that in process hydrolysis, oxidation, reduction, supercritical reaction, arbitrary middle reaction degradation treatment obtains under alkaline condition, wherein the xylogen mass percent >=55%wt of number-average molecular weight≤500.
Xylogen used is any one in diluted acid in wood saccharification industry, paper industry waste or Concentrated acid hydrolysis xylogen, lignin-sulphonate, alkali lignin, sulfonated lignin, organic solvent xylogen, high-boiling alcohol lignin, enzymolysis xylogen.
Described phenol and the mol ratio of paraformaldehyde are 1:1.3～2.0.
Solidifying agent used is that phosphoric acid, p-methyl benzenesulfonic acid and water are the blend of 30～20:100～90:20～30 in mass ratio, and consumption is 6～8% of lignin modification foamex quality.
Whipping agent used is Skellysolve A, and consumption is 4～6.5% of lignin modification foamex quality; Tensio-active agent used is tween-80, and consumption is 2～6% of lignin modification foamex quality.
On described phenol formaldehyde foam streamline, metal sheet temperature is 68～70 ℃.
Beneficial effect
1. the present invention can make phenol formaldehyde foam cost greatly reduce, and in suitability for industrialized production, xylogen can replace phenol 20%-30%wt.
2. the present invention adopts a kind of basic oxide and a kind of phosphorous sodium salt compound to make catalyzer, and reaction system pH is 7.5-9.2, and the pH value that the general routine that is 9.2-10 compared with pH is prepared phenolic foam resin system is low.Reaction is mild, and reaction finishes to add urea to catch free formaldehyde, during cooling discharge, without using acid neutralization, has simplified suitability for industrialized production operation steps, and the active raising of resin is simultaneously suitable for streamline and produces.
3. the present invention adopts paraformaldehyde to substitute liquid formaldehyde, emits no waste water, and the production cycle shortens, and has improved production efficiency.
4. in conventional phenolic foam, generally need to adopt organic silicone oil to make suds-stabilizing agent, in the present invention without adopting organic silicone oil.
Embodiment:
The lignin degradation product that chemistry of lignin's degradation method obtains, part substitutes phenol and paraformaldehyde is prepared lignin modification foamex through addition polycondensation under alkaline condition.Basic catalyst used is a kind of basic oxide and a kind of phosphorous sodium salt compound, phenol and paraformaldehyde mol ratio are 1:1.3-1:2.0, chemical degradation xylogen, phenol and the catalyzer of metering are disposable all adds 5 tons of reactors, paraformaldehyde divides 5 times and adds, every minor tick 10-20min, temperature maintains 70 ℃, until paraformaldehyde all adds, be warming up to after 80 ℃-85 ℃ insulation 30-50min, continue to be warming up to 95-100 ℃ of insulation 1-1.5h, then the urea that adds metering, is cooled to 60 ℃ of dischargings.This catalyst compounded system pH lower (7.5-9.2) that makes, reaction is mild, reaction finishes to add urea to catch free formaldehyde, during cooling discharge without with acid neutralization (ordinary method need to acid neutralization).Adopt this xylogen foamex and conventional frothing aid (whipping agent, solidifying agent and tensio-active agent) blend, on phenol formaldehyde foam streamline, foam, adopt non-woven fabrics, aluminium foil or aluminium sheet as mask, streamline metal sheet temperature is suitably 68-70 ℃.
The xylogen of described chemical degradation is the xylogen xylogen that in process hydrolysis, oxidation, reduction, supercritical reaction, arbitrary middle reaction degradation treatment obtains under alkaline condition, wherein the xylogen mass percent >=55%wt of number-average molecular weight≤500.Described oxidizing reaction comprises electrochemical oxidation, cupric oxide oxidation, silver suboxide oxidation, molecular oxygen oxidation, organic composite burning, ozone oxidation etc.Such as adopting application number, be that the method described in 201110314750.2 embodiment 1 obtains.
Described xylogen is any one in diluted acid (concentrated acid) hydrolytic lignin in wood saccharification industry, paper industry waste, lignin-sulphonate, alkali lignin, sulfonated lignin, organic solvent xylogen, high-boiling alcohol lignin, enzymolysis xylogen.
Described xylogen phenolic aldehyde foam density is 52-65kg/m
3, abscess is fine and closely woven, compressive strength, and toughness increases.
Described resin is a kind of basic oxide and a kind of phosphorous strong base-weak acid salt compound for catalyzer used, basic oxide can be magnesium oxide, zinc oxide, calcium oxide, phosphorous sodium salt can be tertiary sodium phosphate, Sodium phosphate dibasic, tripoly phosphate sodium STPP and trisodium phosphate.
Described whipping agent is Skellysolve A.
Described solidifying agent is the mixture of phosphoric acid, tosic acid and water.
Described tensio-active agent is tween-80.
Embodiment 1
In still, add 280kg diluted acid (concentrated acid) hydrolytic lignin degradation of mixture (content of lignin approximately 50%), 590kg phenol, the catalyzer compound of 1% phenol quality (zinc oxide: tertiary sodium phosphate mass ratio 1:1), mix rear holding temperature at 70 ℃, divide and add paraformaldehyde five times, every minor tick 10min, after be warming up to 80 ℃ insulation 35min after, continue to be warming up to 98 ℃ of insulation 1h, then add the urea of metering, be cooled to 60 ℃ of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 6kg, in steel basin high speed, stir, with solidifying agent (10kg, phosphoric acid, tosic acid and quality are than being 30:95:20) in the high-speed stirring blend of pouring head place, then be cast on non-woven fabrics, enter 68 ℃ of streamlines, foam and solidify, foam density 63-65kg/m
3.
Embodiment 2
In still, add 300kg lignin-sulphonate/alkali lignin/sulfonated lignin degradation of mixture (the about 50%wt of content of lignin), 590kg phenol, the catalyzer compound of 1.5% phenol quality (calcium oxide: Sodium phosphate dibasic mass ratio 1:2), mix rear holding temperature at 70 ℃, divide and add paraformaldehyde five times, every minor tick 15min, after be warming up to 83 ℃ insulation 40min after, continue to be warming up to 96 ℃ of insulation 1.2h, then add the urea of metering, be cooled to 60 ℃ of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 6.75kg, in steel basin high speed, stir, with solidifying agent (11kg, phosphoric acid, tosic acid and quality are than being 25:95:22) in the high-speed stirring blend of pouring head place, then be cast on non-woven fabrics, enter 68 ℃ of streamlines, foam and solidify, foam density 60-63kg/m
3.
Embodiment 3
In still, add 320kg lignin-sulphonate/alkali lignin/sulfonated lignin degradation of mixture (content of lignin approximately 50%), 590kg phenol, the catalyzer compound of 2.0% phenol quality (magnesium oxide: tripoly phosphate sodium STPP mass ratio 2:1), mix rear holding temperature at 70 ℃, divide and add paraformaldehyde five times, every minor tick 20min, after be warming up to 85 ℃ insulation 50min after, continue to be warming up to 96 ℃ of insulation 1.5h, then add the urea of metering, be cooled to 60 ℃ of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, in steel basin high speed, stir, with solidifying agent (11.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26) in the high-speed stirring blend of pouring head place, then be cast on non-woven fabrics, enter 68 ℃ of streamlines, foam and solidify, foam density 60-63kg/m
3.
Embodiment 4
In still, add 330kg organic solvent xylogen/high-boiling alcohol lignin/enzymolysis xylogen degradation of mixture (content of lignin approximately 50%), 590kg phenol, the catalyzer compound of 2.5% phenol quality (magnesium oxide: trisodium phosphate mass ratio 2:1), mix rear holding temperature at 70 ℃, divide and add paraformaldehyde five times, every minor tick 20min, after be warming up to 83 ℃ insulation 50min after, continue to be warming up to 98 ℃ of insulation 1.2h, then add the urea of metering, be cooled to 60 ℃ of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, in steel basin high speed, stir, with solidifying agent (10.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26) in the high-speed stirring blend of pouring head place, then be cast on non-woven fabrics, enter 70 ℃ of streamlines, foam and solidify, foam density 52-56kg/m
3.
Comparative example 1
In still, add 330kg organic solvent xylogen/high-boiling alcohol lignin/enzymolysis xylogen degradation of mixture (content of lignin approximately 50%), 590kg phenol, the catalyzer compound of 2.5% phenol quality (magnesium oxide: sodium hydroxide mass ratio 2:1), mix rear holding temperature at 70 ℃, divide and add paraformaldehyde five times, every minor tick 20min, after be warming up to 83 ℃ insulation 50min after, continue to be warming up to 98 ℃ of insulation 1.2h, then add the urea of metering, be cooled to 60 ℃ of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, in steel basin high speed, stir, with solidifying agent (10.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26) in the high-speed stirring blend of pouring head place, then be cast on non-woven fabrics, enter 70 ℃ of streamlines, foam is softer, cannot apply.
Comparative example 2
In still, add 330kg organic solvent xylogen/high-boiling alcohol lignin/enzymolysis xylogen degradation of mixture (content of lignin approximately 50%), 590kg phenol, the catalyzer compound of 2.5% phenol quality (calcium oxide: hydrated barta mass ratio 2:1), mix rear holding temperature at 70 ℃, divide and add paraformaldehyde five times, every minor tick 20min, after be warming up to 83 ℃ insulation 50min after, continue to be warming up to 98 ℃ of insulation 1.2h, then add the urea of metering, be cooled to 60 ℃ of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, in steel basin high speed, stir, with solidifying agent (10.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26) in the high-speed stirring blend of pouring head place, then be cast on non-woven fabrics, enter 70 ℃ of streamlines, foam is softer, cannot apply.
Claims (10)
1. the preparation method of xylogen phenolic aldehyde foams, it is characterized in that, step is: the preparation of (1) lignin modification foamex: by the xylogen through chemical degradation of stoichiometric ratio, phenol and catalyzer are disposable all to add in reactor, paraformaldehyde divides 3～5 times and adds, every minor tick 10～20min, temperature maintains 65～75 ℃, until paraformaldehyde all adds, be warming up to after 80 ℃～85 ℃ insulation 30～50min, continue to be warming up to 95～100 ℃ of insulation 1～1.5h, then add urea to catch free formaldehyde, be cooled to 60 ℃ of dischargings and obtain lignin modification foamex, catalyzer used is the compound that basic oxide and phosphorous sodium salt form according to the mass ratio of 1:1～3, (2) preparation of phenol formaldehyde foam: lignin modification foamex and whipping agent, tensio-active agent and solidifying agent blended under agitation, on phenol formaldehyde foam streamline, carry out industrialization continuity production.
2. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, is characterized in that, described basic oxide are any in magnesium oxide, zinc oxide, calcium oxide; Described phosphorous sodium salt is any in tertiary sodium phosphate, Sodium phosphate dibasic, tripoly phosphate sodium STPP or trisodium phosphate.
3. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, is characterized in that, described catalyst levels accounts for 1～3% of phenol quality.
4. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, is characterized in that, after the lignin modification foamex described in step (2) and whipping agent, tensio-active agent and solidifying agent blended under agitation, controlling pH value is 7.5～9.2.
5. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, it is characterized in that, the xylogen of described chemical degradation is the xylogen xylogen that in process hydrolysis, oxidation, reduction, supercritical reaction, arbitrary middle reaction degradation treatment obtains under alkaline condition, wherein the xylogen mass percent >=55%wt of number-average molecular weight≤500.
6. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 5, it is characterized in that, xylogen used is any one in diluted acid in wood saccharification industry, paper industry waste or Concentrated acid hydrolysis xylogen, lignin-sulphonate, alkali lignin, sulfonated lignin, organic solvent xylogen, high-boiling alcohol lignin, enzymolysis xylogen.
7. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, is characterized in that, described phenol and the mol ratio of paraformaldehyde are 1:1.3～2.0.
8. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, it is characterized in that, solidifying agent used is that phosphoric acid, p-methyl benzenesulfonic acid and water are the blend of 30～20:100～90:20～30 in mass ratio, and consumption is 6～8% of lignin modification foamex quality.
9. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, is characterized in that, whipping agent used is Skellysolve A, and consumption is 4～6.5% of lignin modification foamex quality; Tensio-active agent used is tween-80, and consumption is 2～6% of lignin modification foamex quality.
10. the preparation method of xylogen phenolic aldehyde foams as claimed in claim 1, is characterized in that, on described phenol formaldehyde foam streamline, metal sheet temperature is 68～70 ℃.
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| CN104087217A (en) * | 2014-06-25 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing hydroxymethylated stalk ethanol byproduct and composite wood adhesive |
| CN105837769A (en) * | 2016-05-16 | 2016-08-10 | 华南理工大学 | Low-formaldehyde-emission high-water-solution-multiple high-temperature-resistant phenolic resin and preparation method thereof |
| CN108250479A (en) * | 2018-01-17 | 2018-07-06 | 天津科技大学 | A kind of preparation method of high lignin content phenol formaldehyde foam |
| CN109293941A (en) * | 2018-08-08 | 2019-02-01 | 中国林业科学研究院林产化学工业研究所 | A kind of depolymerization lignin and its preparation method and application |
| CN109384897A (en) * | 2017-08-12 | 2019-02-26 | 江苏乾翔新材料科技有限公司 | A method of enhancing biomass phenolic foam heat resistance |
| CN111234455A (en) * | 2020-03-26 | 2020-06-05 | 南京工业大学 | Preparation method for preparing phenolic foam by enzymatic modification of lignin |
| CN112175198A (en) * | 2020-10-14 | 2021-01-05 | 中国林业科学研究院林产化学工业研究所 | Novel reactive lignin-based flame retardant and preparation method and application thereof |
| CN112521566A (en) * | 2020-10-13 | 2021-03-19 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-based flame-retardant phenolic foam |
| CN113462119A (en) * | 2021-08-12 | 2021-10-01 | 北海市传创环保科技有限公司 | Heat-insulation and heat-preservation plastic and preparation method thereof |
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| CN104087217A (en) * | 2014-06-25 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing hydroxymethylated stalk ethanol byproduct and composite wood adhesive |
| CN105837769A (en) * | 2016-05-16 | 2016-08-10 | 华南理工大学 | Low-formaldehyde-emission high-water-solution-multiple high-temperature-resistant phenolic resin and preparation method thereof |
| CN109384897A (en) * | 2017-08-12 | 2019-02-26 | 江苏乾翔新材料科技有限公司 | A method of enhancing biomass phenolic foam heat resistance |
| CN108250479A (en) * | 2018-01-17 | 2018-07-06 | 天津科技大学 | A kind of preparation method of high lignin content phenol formaldehyde foam |
| CN108250479B (en) * | 2018-01-17 | 2021-03-02 | 天津科技大学 | Preparation method of phenolic foam with high lignin content |
| CN109293941A (en) * | 2018-08-08 | 2019-02-01 | 中国林业科学研究院林产化学工业研究所 | A kind of depolymerization lignin and its preparation method and application |
| CN111234455A (en) * | 2020-03-26 | 2020-06-05 | 南京工业大学 | Preparation method for preparing phenolic foam by enzymatic modification of lignin |
| CN111234455B (en) * | 2020-03-26 | 2021-05-11 | 南京工业大学 | Preparation method for preparing phenolic foam by enzymatic modification of lignin |
| CN112521566A (en) * | 2020-10-13 | 2021-03-19 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-based flame-retardant phenolic foam |
| CN112175198A (en) * | 2020-10-14 | 2021-01-05 | 中国林业科学研究院林产化学工业研究所 | Novel reactive lignin-based flame retardant and preparation method and application thereof |
| CN113462119A (en) * | 2021-08-12 | 2021-10-01 | 北海市传创环保科技有限公司 | Heat-insulation and heat-preservation plastic and preparation method thereof |
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