CN103613728B - Preparation method of lignin phenolic foams - Google Patents
Preparation method of lignin phenolic foams Download PDFInfo
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- CN103613728B CN103613728B CN201310684779.9A CN201310684779A CN103613728B CN 103613728 B CN103613728 B CN 103613728B CN 201310684779 A CN201310684779 A CN 201310684779A CN 103613728 B CN103613728 B CN 103613728B
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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 utilizing lignin modification foamex and phenol formaldehyde foam thereof.Be related specifically 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, and wherein building energy consumption is higher, and unit floor area of building energy consumption is more than 2-3 times of developed country, and the energy consumption of building materials and building accounts for 47.3% of energy wastage in bulk or weight, exceedes the summation of all developed countries.Phenol formaldehyde foam is called as " king of lagging material " due to the performance of its excellence.Current China has formulated two targets in building energy conservation: one is by 2010, all town buildings are energy-conservation to reach 50% fractional energy savings, megalopolis and urban take the lead in reaching 65%; Two is to the year two thousand twenty, and 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, therefore the good market prospects of China's lagging material.
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 that lignin component is complicated, reactive behavior is low, current literature search to xylogen or the application of waste wood in foamex be all through Liquefaction Products in Phenol by it, react with formaldehyde (being mostly liquid formaldehyde) again, because xylogen or Wood molecules amount 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 resin curing time is long, employing frame foams, need 0.5h-2h.Some employing organic solvents are to the purification processes of papermaking waste, and the xylogen obtained is used for alternative phenol and prepares foamex, adds cost.Therefore be necessary to improve xylogen foamex reactive behavior, realize industrialization continuous seepage, reduce the usage quantity of fossil feedstock, also protect environment, reduce foam cost.
Summary of the invention
The invention provides a kind of preparation method of Lignin phenolic foam body, provide a kind of can the preparation method of Lignin phenolic foam body that produces of industrialization continuity, be related specifically to the catalyst choice in resin preparation process.
The present invention is achieved through the following technical solutions: a kind of preparation method of Lignin phenolic foam body, step is: the preparation of (1) lignin modification foamex: the xylogen through chemical degradation stoichiometrically, phenol and catalyzer is disposable all adds in reactor, paraformaldehyde divides 3 ~ 5 times and adds, every minor tick 10 ~ 20min, temperature maintains 65 ~ 75 DEG C, until paraformaldehyde all adds, after being warming up to 80 DEG C ~ 85 DEG C insulation 30 ~ 50min, continue to be warming up to 95 ~ 100 DEG C of insulation 1 ~ 1.5h, then add urea and catch free formaldehyde, be cooled to 60 DEG C 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, phenol formaldehyde foam streamline carries out industrialization continuity production.
Described basic oxide are any one in magnesium oxide, zinc oxide, calcium oxide; Described phosphorous sodium salt is any one 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, control ph is 7.5 ~ 9.2.
The xylogen of described chemical degradation is the xylogen xylogen that arbitrary middle reaction degradation treatment obtains in hydrolysis, oxidation, reduction, supercritical reaction in the basic conditions, the wherein lignin quality per-cent >=55%wt of number-average molecular weight≤500.
Xylogen used is wood saccharification industry, diluted acid in paper industry waste or Concentrated acid hydrolysis xylogen, lignin-sulphonate, alkali lignin, sulfonated lignin, organic solvent xylogen, high-boiling alcohol lignin, any one in enzymolysis xylogen.
Described phenol and the mol ratio of paraformaldehyde are 1:1.3 ~ 2.0.
The blend of solidifying agent used to be phosphoric acid, p-methyl benzenesulfonic acid and water be in mass ratio 30 ~ 20:100 ~ 90:20 ~ 30, 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 DEG C.
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 preparing phenolic foam resin system compared with the pH general routine that is 9.2-10 is low.React mild, reaction end adds urea and catches free formaldehyde, without the need to acid neutralization during cooling discharge, simplifies industrial production operation step, and resin activity raising is simultaneously suitable for production line balance.
3. the present invention adopts paraformaldehyde to substitute liquid formaldehyde, emits no waste water, and the production cycle shortens, and improves production efficiency.
4. generally need to adopt organic silicone oil to make suds-stabilizing agent, without the need to adopting organic silicone oil in the present invention in Conventional phenol-formaldehyde foaming.
Embodiment:
The lignin degradation products that chemistry of lignin's degradation method obtains, Some substitute phenol and paraformaldehyde prepare lignin modification foamex through addition polycondensation in the basic conditions.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, the phenol of metering and catalyzer is disposable all adds 5 tons of reactors, paraformaldehyde divides 5 times and adds, every minor tick 10-20min, temperature maintains 70 DEG C, until paraformaldehyde all adds, after being warming up to 80 DEG C-85 DEG C insulation 30-50min, continue to be warming up to 95-100 DEG C of insulation 1-1.5h, then add the urea of metering, be cooled to 60 DEG C of dischargings.This is catalyst compounded makes system pH lower (7.5-9.2), and reaction is mild, and reaction end adds urea and catches free formaldehyde, without the need to acid neutralization (ordinary method needs with acid neutralization) during cooling discharge.Adopt this xylogen foamex blended with conventional frothing aid (whipping agent, solidifying agent and tensio-active agent), phenol formaldehyde foam streamline foams, adopt non-woven fabrics, aluminium foil or aluminium sheet as mask, pipeline metal plate temperature is suitably 68-70 DEG C.
The xylogen of described chemical degradation is the xylogen xylogen that arbitrary middle reaction degradation treatment obtains in hydrolysis, oxidation, reduction, supercritical reaction in the basic conditions, the wherein lignin quality per-cent >=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.Application number such as can be adopted to obtain for the method described in 201110314750.2 embodiments 1.
Described xylogen is wood saccharification industry, diluted acid (concentrated acid) hydrolytic lignin in paper industry waste, lignin-sulphonate, alkali lignin, sulfonated lignin, organic solvent xylogen, high-boiling alcohol lignin, any one in enzymolysis xylogen.
Described Lignin phenolic foam density is 52-65kg/m
3, abscess is fine and closely woven, compressive strength, and toughness increases.
Described resin-made 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
280kg diluted acid (concentrated acid) hydrolytic lignin degradation of mixture (content of lignin about 50%) is added in still, 590kg phenol, the catalyzer compound (zinc oxide: tertiary sodium phosphate mass ratio 1:1) of 1% phenol quality, after mixing, holding temperature is at 70 DEG C, divides and adds paraformaldehyde five times, every minor tick 10min, after be warming up to 80 DEG C insulation 35min after, continue to be warming up to 98 DEG C of insulation 1h, then add the urea of metering, be cooled to 60 DEG C of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 6kg, stir in steel basin high speed, blended in pouring head place high-speed stirring with solidifying agent (10kg, phosphoric acid, tosic acid and quality are than being 30:95:20), then be cast on non-woven fabrics, enter 68 DEG C of streamlines, foam and solidify, foam density 63-65kg/m
3.
Embodiment 2
300kg lignin-sulphonate/alkali lignin/sulfonated lignin degradation of mixture (content of lignin is about 50%wt) is added in still, 590kg phenol, the catalyzer compound (calcium oxide: Sodium phosphate dibasic mass ratio 1:2) of 1.5% phenol quality, after mixing, holding temperature is at 70 DEG C, divides and adds paraformaldehyde five times, every minor tick 15min, after be warming up to 83 DEG C insulation 40min after, continue to be warming up to 96 DEG C of insulation 1.2h, then add the urea of metering, be cooled to 60 DEG C of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 6.75kg, stir in steel basin high speed, blended in pouring head place high-speed stirring with solidifying agent (11kg, phosphoric acid, tosic acid and quality are than being 25:95:22), then be cast on non-woven fabrics, enter 68 DEG C of streamlines, foam and solidify, foam density 60-63kg/m
3.
Embodiment 3
320kg lignin-sulphonate/alkali lignin/sulfonated lignin degradation of mixture (content of lignin about 50%) is added in still, 590kg phenol, the catalyzer compound (magnesium oxide: tripoly phosphate sodium STPP mass ratio 2:1) of 2.0% phenol quality, after mixing, holding temperature is at 70 DEG C, divides and adds paraformaldehyde five times, every minor tick 20min, after be warming up to 85 DEG C insulation 50min after, continue to be warming up to 96 DEG C of insulation 1.5h, then add the urea of metering, be cooled to 60 DEG C of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, stir in steel basin high speed, blended in pouring head place high-speed stirring with solidifying agent (11.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26), then be cast on non-woven fabrics, enter 68 DEG C of streamlines, foam and solidify, foam density 60-63kg/m
3.
Embodiment 4
330kg organic solvent xylogen/high-boiling alcohol lignin/enzymolysis xylogen degradation of mixture (content of lignin about 50%) is added in still, 590kg phenol, the catalyzer compound (magnesium oxide: trisodium phosphate mass ratio 2:1) of 2.5% phenol quality, after mixing, holding temperature is at 70 DEG C, divides and adds paraformaldehyde five times, every minor tick 20min, after be warming up to 83 DEG C insulation 50min after, continue to be warming up to 98 DEG C of insulation 1.2h, then add the urea of metering, be cooled to 60 DEG C of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, stir in steel basin high speed, blended in pouring head place high-speed stirring with solidifying agent (10.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26), then be cast on non-woven fabrics, enter 70 DEG C of streamlines, foam and solidify, foam density 52-56kg/m
3.
Comparative example 1
330kg organic solvent xylogen/high-boiling alcohol lignin/enzymolysis xylogen degradation of mixture (content of lignin about 50%) is added in still, 590kg phenol, the catalyzer compound (magnesium oxide: sodium hydroxide mass ratio 2:1) of 2.5% phenol quality, after mixing, holding temperature is at 70 DEG C, divides and adds paraformaldehyde five times, every minor tick 20min, after be warming up to 83 DEG C insulation 50min after, continue to be warming up to 98 DEG C of insulation 1.2h, then add the urea of metering, be cooled to 60 DEG C of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, stir in steel basin high speed, blended in pouring head place high-speed stirring with solidifying agent (10.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26), then be cast on non-woven fabrics, enter 70 DEG C of streamlines, foam is softer, cannot apply.
Comparative example 2
330kg organic solvent xylogen/high-boiling alcohol lignin/enzymolysis xylogen degradation of mixture (content of lignin about 50%) is added in still, 590kg phenol, the catalyzer compound (calcium oxide: hydrated barta mass ratio 2:1) of 2.5% phenol quality, after mixing, holding temperature is at 70 DEG C, divides and adds paraformaldehyde five times, every minor tick 20min, after be warming up to 83 DEG C insulation 50min after, continue to be warming up to 98 DEG C of insulation 1.2h, then add the urea of metering, be cooled to 60 DEG C of dischargings.Take the resin of 150kg cool to room temperature, 4.5kg tween-80, whipping agent Skellysolve A 7.5kg, stir in steel basin high speed, blended in pouring head place high-speed stirring with solidifying agent (10.5kg, phosphoric acid, tosic acid and quality are than being 24:92:26), then be cast on non-woven fabrics, enter 70 DEG C of streamlines, foam is softer, cannot apply.
Claims (8)
1. the preparation method of a Lignin phenolic foam body, it is characterized in that, step is: the preparation of (1) lignin modification foamex: the xylogen through chemical degradation stoichiometrically, phenol and catalyzer is disposable all adds in reactor, paraformaldehyde divides 3 ~ 5 times and adds, every minor tick 10 ~ 20min, temperature maintains 65 ~ 75 DEG C, until paraformaldehyde all adds, after being warming up to 80 DEG C ~ 85 DEG C insulation 30 ~ 50min, continue to be warming up to 95 ~ 100 DEG C of insulation 1 ~ 1.5h, then add urea and catch free formaldehyde, be cooled to 60 DEG C 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, phenol formaldehyde foam streamline carries out industrialization continuity production,
The described quality of xylogen in chemical degradation xylogen accounts for the 20%-30% of phenol quality; For described basic oxide are any one in magnesium oxide, zinc oxide, calcium oxide; Described phosphorous sodium salt is any one in tertiary sodium phosphate, Sodium phosphate dibasic, tripoly phosphate sodium STPP or trisodium phosphate; The xylogen of described chemical degradation is the xylogen xylogen that arbitrary middle reaction degradation treatment obtains in hydrolysis, oxidation, reduction, supercritical reaction in the basic conditions, the wherein lignin quality per-cent >=55%wt of number-average molecular weight≤500.
2. the preparation method of Lignin phenolic foam body as claimed in claim 1, it is characterized in that, described catalyst levels accounts for 1 ~ 3% of phenol quality.
3. the preparation method of Lignin phenolic foam body 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, control ph is 7.5 ~ 9.2.
4. the preparation method of Lignin phenolic foam body as claimed in claim, it is characterized in that, xylogen used is wood saccharification industry, diluted acid in paper industry waste or Concentrated acid hydrolysis xylogen, lignin-sulphonate, alkali lignin, sulfonated lignin, organic solvent xylogen, high-boiling alcohol lignin, any one in enzymolysis xylogen.
5. the preparation method of Lignin phenolic foam body as claimed in claim 1, it is characterized in that, described phenol and the mol ratio of paraformaldehyde are 1:1.3 ~ 2.0.
6. the preparation method of Lignin phenolic foam body as claimed in claim 1, it is characterized in that, the blend of solidifying agent used to be phosphoric acid, p-methyl benzenesulfonic acid and water be in mass ratio 30 ~ 20:100 ~ 90:20 ~ 30, consumption is 6 ~ 8% of lignin modification foamex quality.
7. the preparation method of Lignin phenolic foam body as claimed in claim 1, it 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.
8. the preparation method of Lignin phenolic foam body as claimed in claim 1, it is characterized in that, on described phenol formaldehyde foam streamline, metal sheet temperature is 68 ~ 70 DEG C.
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| CN104087217B (en) * | 2014-06-25 | 2015-09-16 | 中国林业科学研究院林产化学工业研究所 | The preparation method of a kind of straw ethanol by product methylolation and composite wood sizing agent |
| CN105837769B (en) * | 2016-05-16 | 2018-06-29 | 华南理工大学 | High water-soluble multiple thermostable phenolic resin of low burst size of methanal 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 |
| 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 |
| 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 |
| WO2024047556A1 (en) * | 2022-08-30 | 2024-03-07 | Tata Steel Limited | An organic polymer, blend, and methods thereof |
| CN116905124B (en) * | 2023-07-05 | 2024-02-27 | 南京林业大学 | Preparation method of bio-based liquefied resin nano composite fiber membrane material |
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| CN101440170B (en) * | 2008-12-17 | 2012-02-22 | 中国林业科学研究院林产化学工业研究所 | Preparation of biomass modified phenolic foam plastic |
| CN102936323A (en) * | 2012-12-03 | 2013-02-20 | 山东圣泉化工股份有限公司 | Preparation method of lignin-phenol-formaldehyde resin and preparation method of lignin-phenol-formaldehyde resin foam |
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