CN110964224A - Preparation method of copolymerization type phenolic alkali lignin-based phenolic foam material - Google Patents
Preparation method of copolymerization type phenolic alkali lignin-based phenolic foam material Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003513 alkali Substances 0.000 title claims abstract description 92
- 229920005610 lignin Polymers 0.000 title claims abstract description 92
- 239000006261 foam material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 title claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 29
- 239000005011 phenolic resin Substances 0.000 claims abstract description 29
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 6
- 239000011973 solid acid Substances 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 53
- 238000006467 substitution reaction Methods 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004154 testing of material Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 3
- 229940031826 phenolate Drugs 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010543 cumene process Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-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
- C08J9/14—Working-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
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明涉及一种共聚型酚化碱木质素基酚醛泡沫材料的制备方法，属于泡沫材料领域。该方法包括如下步骤：将碱木质素和熔融苯酚根据碱木质素取代苯酚率混匀，再加入蒸馏水及催化剂140℃反应2h，反应后除去残留催化剂，得到酚化碱木质素液；向酚化碱木质素液中加入甲醛溶液和氢氧化钠溶液混匀，先63‑67℃反应1h，再90‑95℃反应1h，反应后调节pH至8.0‑8.5，得到酚化碱木质素基酚醛树脂，并蒸发水分至酚化碱木质素基酚醛树脂的固含量为55‑65％；向酚化碱木质素基酚醛树脂中加入表面活性剂、发泡剂和固化剂，干燥，得到共聚型酚化碱木质素基酚醛泡沫材料。本发明原料来源广、成本低、碱木质素高值化利用、绿色环保。The invention relates to a preparation method of a copolymerized phenolic alkali lignin-based phenolic foam material, and belongs to the field of foam materials. The method includes the following steps: mixing alkali lignin and molten phenol according to the alkali lignin substitution rate of phenol, adding distilled water and a catalyst to react at 140° C. for 2 hours, and removing the residual catalyst after the reaction to obtain a phenolated alkali lignin solution; Add formaldehyde solution and sodium hydroxide solution to the alkali lignin solution and mix well, first react at 63-67 °C for 1 hour, then at 90-95 °C for 1 hour, and adjust the pH to 8.0-8.5 after the reaction to obtain a phenolic alkali lignin-based phenolic resin , and evaporate the water until the solid content of the phenolic alkali lignin-based phenolic resin is 55-65%; add a surfactant, a foaming agent and a curing agent to the phenolic alkali lignin-based phenolic resin, and dry to obtain a copolymerized phenol Alkali lignin-based phenolic foam. The invention has wide raw material sources, low cost, high-value utilization of alkali lignin, and green environmental protection.
Description
Technical Field
The invention relates to a preparation method of a copolymer phenolic alkali lignin-based phenolic foam material, belonging to the field of foam materials.
Background
The phenolic foam is a closed-cell rigid foam plastic prepared by scientifically mixing phenolic resin, a flame retardant, a smoke suppressant, a curing agent, a foaming agent, other auxiliaries and the like, has a uniform closed-cell structure, is low in heat conductivity coefficient, good in heat insulation performance, low in water absorption and strong in vapor permeation resistance, can resist the corrosion of all inorganic acids, organic acids and organic solvents except for being possibly corroded by strong alkali, has no obvious aging phenomenon after being exposed to sunlight for a long time, has the phenomena of carbon formation, no drop, no curling and no melting under the direct action of flame, and has good flame retardant performance. The phenolic molecules only contain carbon, hydrogen and oxygen atoms, and when the phenolic molecules are subjected to pyrolysis, a small amount of CO gas is generated, no other toxic gas is generated, and the maximum smoke density is 5.0%. Meanwhile, the foam has stable size and small change rate, and the size change rate is less than 4% in the use temperature range. Phenolic foam is low cost, corresponding to only two thirds of polyurethane foam.
Phenolic foam materials have been developed greatly since the 90 s, are firstly valued by the military in English and American, are used in the fields of aerospace, national defense and military industry, are applied to places with strict fire protection requirements such as civil aircrafts, ships, stations, oil wells and the like, and are gradually pushed to the fields of high-rise buildings, hospitals, sports facilities and the like. Because polystyrene foam and polyurethane foam are flammable and do not resist high temperature, the polystyrene foam and the polyurethane foam are restricted by fire departments in some industrially developed countries, and in places with strict fire protection requirements, the government departments have plain regulations that only phenolic foam and sandwich boards thereof can be used. Therefore, the phenolic foam thermal insulation material is a high-performance material which is more suitable for being used under the environment condition with severe requirements, and has good development prospect.
Currently, phenol and formaldehyde (the main raw materials for phenolic foam production) are mainly derived from non-renewable petroleum resources. With increasing concern over the consumption of fossil fuels and their impact on the environment, there is increasing concern over the search for alternative petroleum-derived products to produce phenolic foams without sacrificing the properties of the end-use materials/products. Phenol is a major raw material of phenols, is produced from petroleum crude oil by a conventional cumene process, and has an influence on the environment. Phenol is also expensive and its price fluctuates due to fluctuations in the price of crude oil. Therefore, there is great interest in developing a more environmentally friendly, sustainable and cost effective alternative to petroleum-based phenols.
Disclosure of Invention
The invention solves the problems by using alkali lignin to replace part of phenol to obtain phenolated alkali lignin liquid through catalytic phenolation modification by solid acid, synthesizing alkali lignin-based phenolic resin, and then obtaining the copolymer phenolated alkali lignin-based phenolic foam material through foaming and curing.
The invention provides a preparation method of a copolymer type phenolic alkali lignin-based phenolic foam material, which comprises the following steps: uniformly mixing alkali lignin and molten phenol according to the ratio of the alkali lignin to replace the phenol, adding distilled water and a catalyst for reaction at 140 ℃ for 2 hours, and removing the residual catalyst after the reaction to obtain a phenolated alkali lignin solution; adding a formaldehyde solution and a sodium hydroxide solution into the phenolated alkali lignin liquid, uniformly mixing, reacting at 63-67 ℃ for 1h, then reacting at 90-95 ℃ for 1h, adjusting the pH to 8.0-8.5 after the reaction to obtain phenolated alkali lignin-based phenolic resin, and evaporating water until the solid content of the phenolated alkali lignin-based phenolic resin is 55-65%; and adding a surfactant, a foaming agent and a curing agent into the phenolic alkali lignin phenolic resin, and drying to obtain the copolymer phenolic alkali lignin phenolic foam material.
The invention preferably has the alkali lignin substituted phenol rate of 10-40%.
The invention preferably adds the distilled water in an amount of 10-12% of the mass of the phenol.
According to the invention, the catalyst is preferably HZSM-5 solid acid, and the addition amount of the catalyst is 2-6% of the total mass of the alkali lignin and the phenol.
According to the invention, the formaldehyde solution is preferably formalin, and the addition amount of the formaldehyde solution is 138-172% of the mass of phenol.
The invention is preferably that the sodium hydroxide solution is 20 percent (w/v) of sodium hydroxide solution, and the adding amount of the sodium hydroxide solution is 42 to 94 percent of the mass of the phenol.
According to the invention, preferably, the surfactant is tween-80, and the addition amount of the surfactant is 6-8% of the mass of the phenolic alkali lignin-based phenolic resin.
According to the invention, the foaming agent is preferably n-pentane, and the addition amount of the foaming agent is 10-12% of the mass of the phenolic alkali lignin-based phenolic resin.
According to the invention, the curing agent is preferably concentrated hydrochloric acid, and the addition amount of the concentrated hydrochloric acid is 12-15% of the mass of the phenolic alkali lignin-based phenolic resin.
The invention preferably adopts the following drying method: oven drying at 78-82 deg.C for 1 h.
The invention has the beneficial effects that:
the method has the advantages of wide raw material source, low cost, high-value utilization of the alkali lignin and environmental protection.
Drawings
The invention is shown in the attached figure 4,
FIG. 1 is a microstructure of a copolymer phenolic alkali lignin-based phenolic foam of varying substitution rates;
FIG. 2 is a stress-strain plot of copolyphenol alkali phenolate lignin-based phenolic foams of varying substitution rates;
FIG. 3 is a thermogravimetric plot of co-polymeric alkali-phenolated lignin-based phenolic foams of varying substitution rates;
FIG. 4 is an infrared spectrum of a copolymer phenolic alkali lignin-based phenolic foam of varying substitution.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The lignin content of the alkali lignin described below was 82.25%.
Example 1
Phenolic resin with different alkali lignin substituted phenol rates
Adding alkali lignin and molten phenol (shown in table 1) corresponding to different alkali lignin substituted phenol rates into an intermittent pressure-resistant high-temperature reaction kettle equipped with a thermocouple and a mechanical stirrer, fully mixing the alkali lignin and the phenol at 50 ℃ for 10min, adding distilled water (10% of the mass of the phenol) and HZSM-5 solid acid (4% of the total mass of the alkali lignin and the phenol), stirring at 500r/min, reacting at 140 ℃ for 2h, and removing residual HZSM-5 solid acid after reaction to obtain phenolated alkali lignin liquid;
adding 37% of formaldehyde aqueous solution and 20% (w/v) of sodium hydroxide solution (the addition amount is shown in table 1) into the phenolated alkali lignin solution, mixing for 10min at 50 ℃, reacting for 1h at 65 ℃, then reacting for 1h at 92 ℃, cooling to 40 ℃ after reaction, adjusting the pH to 8.0-8.5 by using 4mol/L hydrochloric acid to obtain phenolated alkali lignin-based phenolic resin I, measuring the pH, the solid content and the viscosity of the phenolated alkali lignin-based phenolic resin I, evaporating water to obtain phenolated alkali lignin-based phenolic resin II, and measuring the solid content of the phenolated alkali lignin-based phenolic resin II, wherein the results are shown in table 2.
TABLE 1 formulation for phenolic alkali lignin based phenolic resin synthesis
TABLE 2 Properties of alkali phenolated lignin-based phenolic resins
Example 2
Influence of different substitution rates on density, slag falling rate and water absorption rate of copolymer type phenolic alkali lignin-based phenolic foam
Adding 10g of phenolic alkali lignin phenolic resin II into a paper container, adding 0.8g of tween-80 and 1.2g of n-pentane, uniformly stirring, adding 1.5g of concentrated hydrochloric acid under stirring, and then placing the paper container filled with the mixture into an oven at 80 ℃ for drying for 1h to obtain the copolymer phenolic alkali lignin phenolic foam material.
Measurement of Density: the apparent density was measured by mass of a phenolic foam of known volume (3cm x 3cm) and the results are shown in figure 1, the test data being the arithmetic mean of 3 replicates per group and the results are shown in table 3;
and (3) measuring the slag falling rate: fixing 800-mesh sand paper, placing a foam sample (the bottom area of the foam sample is 3.5cm multiplied by 3.5cm) for testing on the sand paper, placing a 100g weight on the foam sample, horizontally pulling the foam sample to and fro 20 times within a 15cm interval, weighing the mass of the foam sample before and after, and calculating the slag removal rate, wherein the result is shown in table 3;
measurement of Water absorption: take 30cm3The foam sample of (1) was weighed to have a mass of M1, immersed in distilled water at 25 ℃ for 72 hours, taken out, and the surface of the foam sample was subjected to moisture absorption by a filter paper, weighed to have a mass of M2, and the water absorption was calculated from the water absorption W ═ of (M2-M1)/V × 100%, and the results are shown in table 3;
TABLE 3 Density, slag dropping rate, water absorption rate of copolymerized phenolic alkali lignin phenolic foam with different substitution rates
Example 3
Effect of different substitution rates on the microstructure of copolyphenolized alkali phenolate lignin-based phenolic foams
Adding 10g of phenolic alkali lignin phenolic resin II into a paper container, adding 0.8g of tween-80 and 1.2g of n-pentane, uniformly stirring, adding 1.5g of concentrated hydrochloric acid under stirring, and then placing the paper container filled with the mixture into an oven at 80 ℃ for drying for 1h to obtain the copolymer phenolic alkali lignin phenolic foam material.
The cell structure of the foam samples was observed by an optical microscope and a JVC ccd image sensor having 610 ten thousand pixels, and different foam samples were observed separately at high and low magnification, and the results are shown in fig. 1.
Example 4
Effect of different substitution rates on compressive Strength of copolyphenolized alkali phenolate lignin-based phenolic foam
Adding 10g of phenolic alkali lignin phenolic resin II into a paper container, adding 0.8g of tween-80 and 1.2g of n-pentane, uniformly stirring, adding 1.5g of concentrated hydrochloric acid under stirring, and then placing the paper container filled with the mixture into an oven at 80 ℃ for drying for 1h to obtain the copolymer phenolic alkali lignin phenolic foam material.
A universal material testing machine is adopted to measure the compressive strength of the foam sample, and the specific testing steps are as follows:
a. processing foam into a foam sample with a regular shape, keeping the upper end face and the lower end face of the foam sample parallel, keeping the end faces perpendicular to the central line of the foam sample, measuring the length, the width and the height of the foam sample, calculating the area S, and making the area of the load borne by the foam sample smaller than the area of a pressing plate of a universal material testing machine so as to prepare three foam samples;
b. placing the foam sample on a universal material testing machine, aligning the center line of the foam sample with the centers of an upper pressing plate and a lower pressing plate of the universal material testing machine, applying a load to the foam sample at a constant speed of 2mm/min to deform the foam sample, and recording the maximum compressive force F when the deformation of the foam sample reaches 10% of the original deformation;
c. the compressive strength was calculated from the compressive strength σ m ═ F/S, and the results are shown in fig. 2 and table 4.
TABLE 4 compressive strength at 10% strain for foam samples
Example 5
Effect of different substitution rates on thermal stability of copolyphenol alkali lignin-based phenolic foam
Adding 10g of phenolic alkali lignin phenolic resin II into a paper container, adding 0.8g of tween-80 and 1.2g of n-pentane, uniformly stirring, adding 1.5g of concentrated hydrochloric acid under stirring, and then placing the paper container filled with the mixture into an oven at 80 ℃ for drying for 1h to obtain the copolymer phenolic alkali lignin phenolic foam material.
Thermal stability of foam samples by thermogravimetric analysis (TGA) N at 20mL/min2Heating a 5mg foam sample from room temperature to 650 ℃ at 10 ℃/minStudy, before TGA testing, foam samples were dried in an oven at 120 ℃ for 2h, ground to powder after drying, and then tested on TGA, with the results shown in figure 3.
As shown in FIG. 3, the percent weight loss of the copolymer phenolic alkali lignin-based phenolic foam at 650 ℃ gradually increased with the increase of the substitution rate, and gradually increased from 47.31% of the pure phenolic foam to 52.54% of the copolymer phenolic alkali lignin-based phenolic foam at the substitution rate of 40%.
Example 6
Influence of different substitution rates on infrared spectrum of copolymerization type phenolic alkali lignin-based phenolic foam
Adding 10g of phenolic alkali lignin phenolic resin II into a paper container, adding 0.8g of tween-80 and 1.2g of n-pentane, uniformly stirring, adding 1.5g of concentrated hydrochloric acid under stirring, and then placing the paper container filled with the mixture into an oven at 80 ℃ for drying for 1h to obtain the copolymer phenolic alkali lignin phenolic foam material.
The change of functional groups in the copolymerization type phenolic alkali lignin phenolic aldehyde foam is researched by adopting Fourier transform infrared spectroscopy, a foam sample is dried in a drying oven at 120 ℃ for 2 hours, after drying, 5-10mg of the foam sample is ground into powder, the infrared spectrum of the foam sample is measured on a Fourier transform infrared spectrometer by a KBr tabletting method, and the recording range is 4000--1The results are shown in FIG. 4.
Claims (10)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525492A (en) * | 1982-06-04 | 1985-06-25 | Fiberglas Canada Inc. | Modified phenolic foams |
| CN102504477A (en) * | 2011-10-18 | 2012-06-20 | 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 |
| 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 |
| CN104250361A (en) * | 2013-06-26 | 2014-12-31 | 中国科学院化学研究所 | Lignin modified phenolic resin, foam thereof, preparation method of resin, and preparation method of foam |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525492A (en) * | 1982-06-04 | 1985-06-25 | Fiberglas Canada Inc. | Modified phenolic foams |
| CN102504477A (en) * | 2011-10-18 | 2012-06-20 | 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 |
| 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 |
| CN104250361A (en) * | 2013-06-26 | 2014-12-31 | 中国科学院化学研究所 | Lignin modified phenolic resin, foam thereof, preparation method of resin, and preparation method of foam |
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