CN104072796A - Method for self-foaming preparation of phenolic foam material and foam carbon material - Google Patents
Method for self-foaming preparation of phenolic foam material and foam carbon material Download PDFInfo
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- CN104072796A CN104072796A CN201410334804.5A CN201410334804A CN104072796A CN 104072796 A CN104072796 A CN 104072796A CN 201410334804 A CN201410334804 A CN 201410334804A CN 104072796 A CN104072796 A CN 104072796A
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Abstract
The invention discloses a method for self-foaming preparation of a phenolic foam materiel. Water is used as a solvent, quick copolymerization of phenol, aldehyde and gelatin is aroused by gelatin, and meanwhile, Knoevenagel reaction between organic diacid and aldehyde is utilized for heating decarboxylation to release CO2 as a foamer, so that one-step self-foaming preparation of the phenolic foam materiel is realized. The invention also provides a method for obtaining a foam carbon material through taking the phenolic foam material prepared by adopting the above method as a precursor and further carbonizing the phenolic foam material. According to the invention, the energy consumption is low, the operation is simple, a foamer, a curing agent, a surfactant and the like are not required to be added, the traditional procedure process for preparing the phenolic foam material and the foam carbon material is simplified, the manufacturing cost is greatly lowered, environmental pollution is reduced and a process technology with a favorable market prospect is achieved.
Description
Technical field
The invention belongs to phenolic foam material and foam carbon material field, relate to a kind of spontaneous bubble preparation technology; Particularly, relate to a kind of method of preparing phenolic foam material and foam carbon material from foaming single step reaction.
Background technology
Phenolic foam material is the novel porous plastics of a class, and it has the advantages such as lightweight, low toxicity, fire-retardant, heat insulation, sound insulation, is widely used as insulation, sound insulation and the lagging material in the fields such as building, petrochemical complex, communications and transportation, space flight and aviation.The typical preparation method of phenolic foam material is the resol of previously prepared expandability at present, add whipping agent, solidifying agent and tensio-active agent etc., at high temperature heating, volatilize and form phenolic foam material by whipping agent, but this traditional preparation technology's complicated operation, energy consumption are large, partial foaming agent (as Hydrochlorofluorocarbons (HCFC)), the solidifying agent (example hydrochloric acid, phosphoric acid etc.) in its preparation process, used have larger harm to environment and equipment.
For above problem, existing patent is improved the preparation technology of phenol formaldehyde foam.As: Chinese patent CN1955206B discloses a kind of method that low normal temp can be sent out the synthetic of resol and prepare phenol formaldehyde foam, blowing temperature is down to 5～30 DEG C by the method, and with alkane as whipping agent, reduced environmental pollution.Chinese patent CN103059503A discloses the preparation method of a kind of phenolic foamed plastics and preparation method thereof and Carbon foam, and the method adopts green-blowing agent without chlorine-hydrogen-fluorine hydrocarbon or hydrocarbon compound.But compared with traditional phenol formaldehyde foam preparation technology, the existing technical process that these improve technology is without obvious improvement, and its preparation technology is still very complicated, Technology more simple and direct, energy-conservation and environmental protection is still badly in need of for phenol formaldehyde foam preparation is industrial.
Meanwhile, phenolic foam material, because its Heat stability is good, high temperature carbon residue amount are high, is again the desirable precursor of foam carbon material.Foam carbon material is that a class has the porous carbon material that enriches macropore and three-dimensional netted skeleton structure, because it has that density is low, porosity is high, the advantage such as good conductivity, chemical stability and Heat stability is good, be widely used as electrode materials, sorbent material, support of the catalyst, also show wide application prospect in the field such as aerospace and clean environment, thereby the Study on Preparation of foam carbon material has also been subject to paying close attention to widely.The preparation of phenolic resin based foam carbon material is taking phenol formaldehyde foam preparation technology as basis, obtains by the method for pyrolysis phenol formaldehyde foam under inert atmosphere, and therefore, the preparation technology of foam carbon material also exists complex process, energy consumption greatly and the problem of environmental pollution.
Summary of the invention
For above-mentioned background, one of object of the present invention is the defect in order to overcome existing phenol formaldehyde foam technology of preparing, utilizes the Knoevenagel decarboxylic reaction of organic diacid and aldehyde to emit CO
2gas, as whipping agent and phenol, aldehyde, the quick copolyreaction of gelatin, provides a kind of novel method of simple and direct spontaneous brewed standby phenolic foam material.
The present invention adopts following technical scheme:
Taking water as solvent, taking phenol, aldehyde, gelatin and organic diacid as reaction raw materials, when gelatin causes phenol, aldehyde, the quick copolyreaction of gelatin, organic diacid and aldehyde carry out Knoevenagel and react and add thermal decarboxylation and emit CO
2gas, as whipping agent, is realized the spontaneous brewed standby phenolic foam material of single stage method, specifically preparation according to the following steps:
Phenol, gelatin, organic diacid are dissolved in to 40～90 DEG C of hot water, are stirred to completely and dissolve, then add aldehyde to obtain reaction solution; Above-mentioned reaction solution is heated to 60～90 DEG C and foams and solidify, the reaction times is 60～240min, obtains phenolic foam material after cooling drying; Described organic diacid is the organic diacid that contains active methylene group; Wherein,
Wherein, described phenol is phenol and its derivatives; Described aldehyde is one or both of monoaldehyde, dialdehyde, paraformaldehyde or unsaturated aldehyde.
In preferred scheme, foaming and curing process are carried out under 0-1.5MPa impressed pressure described in the application; Or by reaction solution sealing, foaming and curing process are carried out under its autogenous pressure.
Phenol described in the application, is preferably Resorcinol, phenol, dihydroxyphenyl propane.
Aldehyde described in the application, is preferably one or both in 37% formaldehyde solution, paraformaldehyde, propenal, 25% glutaraldehyde solution.
Described in the application, contain the organic diacid of active methylene group, preferably propanedioic acid.
Based on aforesaid method, another object of the present invention is the defect in order to overcome existing foam carbon material technology of preparing, and a kind of method of preparing foam carbon material taking spontaneous brewed standby phenolic foam material as presoma is provided.Specifically comprise the following steps:
(1) prepare phenolic foam material: by above-mentioned from foaming legal system for phenolic foam material;
(2) prepare foam carbon material: the phenolic foam material (1) obtaining taking step is presoma, obtains foam carbon material through carbonization reaction.
Step of the present invention (2) described carbonization reaction is, (1) step is placed in to charring furnace from the standby phenolic foam material of foaming legal system, under the protection of inert nitrogen gas or argon gas, gas flow 20～100ml/min, rise to 300 DEG C from room temperature with 1-3 DEG C/min, constant temperature 60min carries out preliminary pyrolysis; Be warming up to again charing final temperature 500-900 DEG C, constant temperature 60-240min, charing obtains foam carbon material.
The application's beneficial effect:
1, the method described in the application utilizes organic diacid to react with the Knoevenagel of aldehyde, adds thermal decarboxylation and generates CO
2carry out bubbling as whipping agent, introduce gelatin simultaneously and cause phenol, aldehyde, the quick copolyreaction of gelatin, developed thus the novel technique of preparing phenolic foam material and foam carbon material.Gelatin is a kind of bioabsorbable polymer material, contains a large amount of amidos, can cause phenol, aldehyde, the quick copolyreaction of gelatin, and copolymerized polymer crosslinking degree prepared by introducing gelatin is high, is more suitable for foaming.
2, the application, by regulation and control reaction raw materials proportioning, can realize the pore texture control to phenolic foam material and foam carbon material; The increase of gelatin, organic diacid consumption, makes the phenolic foam material that makes and the more horn of plenty of macropore of foam carbon material, and porosity increases.Can regulate and control physical strength and the pore texture of phenolic foam material and foam carbon material by controlling blow(ing) pressure; Increase blow(ing) pressure, especially under impressed pressure, foam, make to make phenolic foam material and foam carbon material more closely knit, though porosity declines to some extent, the physical strength of material is higher.
3, the method that the application provides, process energy consumption is low, simple to operate, without adding the auxiliary agents such as whipping agent, solidifying agent, tensio-active agent, preparation technology's flow process of traditional phenolic foam material and foam carbon material is simplified, greatly reduce production cost, reduced environmental pollution.
Brief description of the drawings
Fig. 1 is the optical photograph of the prepared phenolic foam material of the embodiment of the present invention 2
Fig. 1 a is along foaming direction sectional elevation; Fig. 1 b is the cross-sectional view along foaming direction
Fig. 2 is the optical photograph of the prepared foam carbon material of the embodiment of the present invention 2
Fig. 2 a is along foaming direction sectional elevation; Fig. 2 b is the cross-sectional view along foaming direction
Fig. 3 is the intrusive mercury curve of the prepared phenolic foam material of the embodiment of the present invention 2
Fig. 4 is the intrusive mercury curve of the prepared foam carbon material of the embodiment of the present invention 2
Specific examples mode
Embodiment 1
100 parts of Resorcinols, 150 parts of gelatin, 20 parts of propanedioic acid are dissolved in to 600 parts of 40～90 DEG C of hot water, and stirring and dissolving 60～120min, after dissolving completely, obtains faint yellow viscous solution; Then under agitation condition, inject fast 150 part of 37% formaldehyde solution, above-mentioned reaction soln PhastGel, is white in color; Reaction vessel is placed in to 60～90 DEG C of baking ovens and carries out normal pressure (being that pressure is 0) foaming and solidify, the time is 4h, after cooling and dry 24h, obtains block phenolic foam material.Its compressive strength is 0.16MPa, presses mercury test to show that its total hole pore volume reaches 7.4cm
3g
-1, porosity is 83%.
Certainly the phenolic foam material standby legal system that foams is placed in to charring furnace charing, and under the protection of inert nitrogen gas or argon gas, gas flow 20～100ml/min, rises to 300 DEG C from room temperature with 1-3 DEG C/min, and constant temperature 60min carries out preliminary pyrolysis; Be warming up to again charing final temperature 500-900 DEG C, constant temperature 60-240min, charing obtains foam carbon material.Its compressive strength is 0.20MPa, presses mercury test to show that its total hole pore volume reaches 6.0cm
3g
-1, porosity is 88%.
Embodiment 2
100 parts of Resorcinols, 150 parts of gelatin, 20 parts of propanedioic acid are dissolved in to 600 parts of 40～90 DEG C of hot water, and stirring and dissolving 60～120min, after dissolving completely, obtains faint yellow viscous solution; Then under agitation condition, inject fast 150 part of 37% formaldehyde solution, above-mentioned reaction soln PhastGel, is white in color; By reaction vessel sealing, be placed in 60～90 DEG C of baking ovens, under its autogenous pressure, to foam and solidify, the time is 4h, after cooling and dry 24h, obtains block phenolic foam material.Its compressive strength is 4.30MPa, presses mercury test to show that its total hole pore volume reaches 5.1cm
3g
-1, porosity is 76%.
Certainly the phenolic foam material standby legal system that foams is placed in to charring furnace charing, and under the protection of inert nitrogen gas or argon gas, gas flow 20～100ml/min, rises to 300 DEG C from room temperature with 1-3 DEG C/min, and constant temperature 60min carries out preliminary pyrolysis; Be warming up to again charing final temperature 500-900 DEG C, constant temperature 60-240min, charing obtains foam carbon material.Its compressive strength is 0.38MPa, presses mercury test to show its total hole pore volume 6.1cm
3g
-1, porosity is 81%.
Embodiment 3
100 parts of Resorcinols, 80 parts of gelatin, 8 parts of propanedioic acid are dissolved in to 600 parts of 40～90 DEG C of hot water, and stirring and dissolving 60～120min, after dissolving completely, obtains faint yellow viscous solution; Then under agitation condition, inject fast 150 part of 37% formaldehyde solution, above-mentioned reaction soln PhastGel, is white in color; By reaction vessel sealing, be placed in 60～90 DEG C of baking ovens, under its autogenous pressure, to foam and solidify, the time is 4h, after cooling and dry 24h, obtains block phenolic foam material.Its compressive strength is 1.42MPa.
Certainly the phenolic foam material standby legal system that foams is placed in to charring furnace charing, and under the protection of inert nitrogen gas or argon gas, gas flow 20～100ml/min, rises to 300 DEG C from room temperature with 1-3 DEG C/min, and constant temperature 60min carries out preliminary pyrolysis; Be warming up to again charing final temperature 500-900 DEG C, constant temperature 60-240min, charing obtains foam carbon material.Its compressive strength is 0.26MPa.
Embodiment 4
100 parts of Resorcinols, 150 parts of gelatin, 20 parts of propanedioic acid are dissolved in to 600 parts of 40～90 DEG C of hot water, and stirring and dissolving 60～120min, after dissolving completely, obtains faint yellow viscous solution; Then under agitation condition, inject fast 150 part of 37% formaldehyde solution, above-mentioned reaction soln PhastGel, is white in color; By reaction vessel sealing, be placed in 60～90 DEG C of baking ovens, under impressed pressure 1.5MPa, to foam and solidify, the time is 4h, after cooling and dry 24h, obtains block phenolic foam material.Its compressive strength is 9.48MPa.
Certainly the phenolic foam material standby legal system that foams is placed in to charring furnace charing, and under the protection of inert nitrogen gas or argon gas, gas flow 20～100ml/min, rises to 300 DEG C from room temperature with 1-3 DEG C/min, and constant temperature 60min carries out preliminary pyrolysis; Be warming up to again charing final temperature 500-900 DEG C, constant temperature 60-240min, charing obtains foam carbon material.Its compressive strength is 0.95MPa, presses mercury test to show its total hole pore volume 1.02cm
3g
-1, porosity is 50%.
Embodiment 5
170 parts of phenol, 150 parts of gelatin, 20 parts of propanedioic acid are dissolved in to 600 parts of 40～90 DEG C of hot water, and stirring and dissolving 60～120min, after dissolving completely, obtains faint yellow viscous solution; Then under agitation condition, inject fast 150 part of 37% formaldehyde solution, above-mentioned reaction soln PhastGel, is white in color; Reaction vessel is placed in to 60～90 DEG C of baking ovens and carries out normal pressure (being that pressure is 0) foaming and solidify, the time is 4h, after cooling and dry 24h, obtains block phenolic foam material.
Embodiment 6
100 parts of Resorcinols, 150 parts of gelatin, 20 parts of propanedioic acid are dissolved in to 600 parts of 40～90 DEG C of hot water, and stirring and dissolving 60～120min, after dissolving completely, obtains faint yellow viscous solution; Then under agitation condition, inject fast 360 part of 25% glutaraldehyde solution, above-mentioned reaction soln PhastGel, is white in color; Reaction vessel is placed in to 60～90 DEG C of baking ovens and carries out normal pressure (being that pressure is 0) foaming and solidify, the time is 4h, after cooling and dry 24h, obtains block phenolic foam material.
Claims (9)
1. the method for spontaneous brewed standby phenolic foam material, it is characterized in that: taking water as solvent, taking phenol, aldehyde, gelatin and organic diacid as reaction raw materials, when gelatin causes phenol, aldehyde, the quick copolyreaction of gelatin, organic diacid and aldehyde carry out Knoevenagel and react and add thermal decarboxylation and emit CO
2gas, as whipping agent, is realized the spontaneous brewed standby phenolic foam material of single stage method, specifically preparation according to the following steps:
Phenol, gelatin, organic diacid are dissolved in to 40～90 DEG C of hot water, are stirred to completely and dissolve, then add aldehyde to obtain reaction solution; Above-mentioned reaction solution is heated to 60～90 DEG C and foams and solidify, the reaction times is 60～240min, obtains phenolic foam material after cooling drying; Described organic diacid is the organic diacid that contains active methylene group; Wherein,
Wherein, described phenol is phenol and its derivatives; Described aldehyde is one or both of monoaldehyde, dialdehyde, paraformaldehyde or unsaturated aldehyde.
2. method according to claim 1, is characterized in that: described foaming and curing process are carried out under 0-1.5MPa impressed pressure; Or by reaction solution sealing, foaming and curing process are carried out under its autogenous pressure.
3. method according to claim 1 and 2, is characterized in that: described phenol is Resorcinol, phenol, dihydroxyphenyl propane.
4. method according to claim 1 and 2, is characterized in that, described aldehyde is one or both in formaldehyde solution, paraformaldehyde, trioxymethylene, propenal, glutaraldehyde solution.
5. method according to claim 1 and 2, is characterized in that, described in contain active methylene group organic diacid be propanedioic acid.
6. the preparation method of foam carbon material, is characterized in that preparing according to following steps:
(1) prepare phenolic foam material: prepare phenolic foam material by claim 1 method;
(2) prepare foam carbon material: the phenolic foam material (1) obtaining taking step is presoma, obtains foam carbon material through carbonization reaction.
7. method according to claim 6, is characterized in that; Described charing, for presoma is placed in to charring furnace, is carried out charing under protection of inert gas, and charing finishes rear furnace cooling and obtains foam carbon material.
8. method according to claim 7, is characterized in that: described rare gas element is nitrogen or argon gas, and gas flow is 20～100ml/min.
9. method according to claim 7, is characterized in that: the process of described charing is: from room temperature, rise to 300 DEG C with 1-3 DEG C/min, constant temperature 60min carries out preliminary pyrolysis; Be warming up to again charing final temperature 500-900 DEG C, constant temperature 60-240min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858784A (en) * | 2016-04-21 | 2016-08-17 | 厦门建霖工业有限公司 | Antibacterial foaming activated-carbon water purifying filtering element capable of being molded once and preparation method |
| CN106976863A (en) * | 2017-05-18 | 2017-07-25 | 武汉科技大学 | A kind of lignin modification phenolic resin foam carbon and preparation method thereof |
| CN110066416A (en) * | 2019-04-29 | 2019-07-30 | 山东师范大学 | A kind of preparation method of phenolic resin foam and Carbon foam |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705537A (en) * | 1997-02-24 | 1998-01-06 | Armstrong World Industries, Inc. | Phenolic foams having a low formaldehyde evolution |
| CN101768422A (en) * | 2009-01-05 | 2010-07-07 | 邱培莹 | Preparation method of crosslinking agent for compound high-density wood-based panels |
-
2014
- 2014-07-14 CN CN201410334804.5A patent/CN104072796B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705537A (en) * | 1997-02-24 | 1998-01-06 | Armstrong World Industries, Inc. | Phenolic foams having a low formaldehyde evolution |
| CN101768422A (en) * | 2009-01-05 | 2010-07-07 | 邱培莹 | Preparation method of crosslinking agent for compound high-density wood-based panels |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858784A (en) * | 2016-04-21 | 2016-08-17 | 厦门建霖工业有限公司 | Antibacterial foaming activated-carbon water purifying filtering element capable of being molded once and preparation method |
| CN105858784B (en) * | 2016-04-21 | 2019-09-06 | 厦门百霖净水科技有限公司 | One kind can one-time formed antibacterial foaming activity charcoal water purification catridge and preparation method |
| CN106976863A (en) * | 2017-05-18 | 2017-07-25 | 武汉科技大学 | A kind of lignin modification phenolic resin foam carbon and preparation method thereof |
| CN106976863B (en) * | 2017-05-18 | 2019-01-04 | 武汉科技大学 | A kind of lignin modification phenolic resin foam carbon and preparation method thereof |
| CN110066416A (en) * | 2019-04-29 | 2019-07-30 | 山东师范大学 | A kind of preparation method of phenolic resin foam and Carbon foam |
| CN110066416B (en) * | 2019-04-29 | 2021-07-20 | 山东师范大学 | Preparation method of phenolic resin foam and carbon foam |
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