CN1403524A - Modified nano phenolic resin binder and its prepn and use - Google Patents
Modified nano phenolic resin binder and its prepn and use Download PDFInfo
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- CN1403524A CN1403524A CN 01131434 CN01131434A CN1403524A CN 1403524 A CN1403524 A CN 1403524A CN 01131434 CN01131434 CN 01131434 CN 01131434 A CN01131434 A CN 01131434A CN 1403524 A CN1403524 A CN 1403524A
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- phenolic resin
- modified nano
- resin binder
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Abstract
The present invention discloses one kind of modified nano phenolic resin binder and its preparation process and application in refractory material. The modified nano phenolic resin is prepared through condensation of phenol and formaldehyde while adding laminated silicate clay via in-situ insertion. The modified nano phenolic resin binder results in high compression strength of refractory material.
Description
The present invention relates to a kind of phenolic resin binder, more specifically, relate to a kind of modified nano phenolic resin binder and preparation method thereof and the application in refractory materials.
Refractory materials is used for various high temperature services, and the physical chemistry that bears hot conditions corrodes and the physical disturbance effect, must have higher refractoriness and thermal structure intensity and good thermostability and wear resistance.In order to adapt to a series of harsh day by day operational conditions in the current metallurgical industry, should constantly develop new high-performance refractory material.Development of modern science and technology has greatly been enriched the field of investigation of materials, provides more method for preparing new refractory materials.Nanotechnology adds nanoparticle in a kind of approach of Application in Refractory is wedding agent at refractory materials, the use properties that the optimization and the modification of wedding agent microtexture is improved refractory materials by nanoparticle.Nano-particles size is little, the surface energy height, be easy to combine with other atom, produce very strong interfacial interaction, have simultaneously rigidity and thermotolerance again, therefore nanoparticle can make the rigidity of wedding agent and thermotolerance be enhanced, and improves the microtexture that wedding agent forms in the refractory materials process for making, thereby improves breaking tenacity, heat-shock resistance and the high temperature creep-resisting of fire resistive material product.
In recent years, the polymer/nanoclay matrix material is owing to having good physical and mechanical property and specific function and excellent P/C than receiving much attention.With thickness 0.96 nanometer only, flakiness ratio is that 100～1000 silicate thin slice is dispersed in the polymeric matrix, can improve the mechanical property and the resistance toheat of polymkeric substance.What this respect was more successful is composite nano polymer/clay material, and the polymkeric substance that relates to comprises polymeric amide, polypropylene, polystyrene, polyoxyethylene, Resins, epoxy, silicon rubber etc.The present patent application person has prepared nano-class phenolic resin/day composition in Chinese invention patent application 00136246.1 and 0036247.X.
Resol has obtained using widely in carbon containing refractory as wedding agent.But up to the present, Shang Weiyou adds the application report of nanoparticle as binder for fire-resistant materials in resol.
The purpose of this invention is to provide a kind of nano clay modified phenolic resin binder.Said wedding agent is used for the production of fire resistive material product, and the mechanical property of fire resistive material product and high-temperature behavior are greatly improved.Said refractory materials comprises the block refractory materials of magnesia carbon brick, aluminum-carbon brick etc. and comprises the amorphous refractory of ramming mass, Gunning refractory, casting material etc.
The modified nano phenolic resin binder that the present invention adopts is by adding clay of laminar silicate in phenol and formaldehyde condensation reaction process and by in-situ inserted compound obtaining.Concrete steps are included in and add a kind of clay of laminar silicate in the reaction system of phenol and formaldehyde, make phenol and formaldehyde between clay layer by in-situ inserted polymerization formation modified nano phenolic resin.In this modified nano phenolic resin, the laminated structure of clay of laminar silicate is an intercal type, so this modified nano phenolic resin also can be described as intercal type nano clay/resol mixture.This nano modification resin can be used as the preparation that a kind of wedding agent is used for refractory materials.The clay layer of intercal type can further be converted into exfoliated structure in the preparation process of refractory materials, and is dispersed in the phenolic resin as matrix resin.
Modified nano phenolic resin binder of the present invention is reassembled into containing by following component: the phenol of 100 weight parts, the formalin of the 36-40% of 70-110 weight part, the clay of laminar silicate of 1.0～20 weight parts, the catalyzer of 0.1～5.0 weight part.
The used clay of the present invention is that a class contains 80% above polynite or wilkinite, the layer silicate mineral of hectorite or vermiculite type, particle diameter 0.040～0.080mm, specific surface area 700～800m
2/ g, interlayer has Na
+, Li
+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, loading capacity is (CEC) 50～200meq/100g, and thickness of clay soil is 0.9～1.1nm, and interfloor distance is 0.8～2.1nm.
Modified nano phenolic resin of the present invention, the used catalyzer of its building-up reactions is Ba (OH)
2, Na
2CO
3, MgO, NaOH etc.
In one embodiment of the invention, a kind of preparation of modified nano phenolic resin binder can be carried out as follows:
1), the phenol of 100 weight parts and 36～40% formalins of 70～110 weight parts are added in the reaction system together, slowly add the clay of laminar silicate of 1.0～20 weight parts while stirring, temperature remains on 30～60 ℃, stirs 40～80 minutes;
2) Ba (OH) that, adds 0.1～5.0 weight part
2, temperature control to 85～105 ℃ are incubated 1.0～3.0 hours, stopped reaction;
3), dewater to viscosity be 2.0～5.0 the pool after, the cooling blowing, obtain a kind of modified nano phenolic resin.
In another embodiment of the invention, a kind of preparation of modified nano phenolic resin can be carried out as follows:
1), the phenol of 100 weight parts and 36～40% formalins of 70～110 weight parts are added in the reaction together, slowly add the clay of laminar silicate of 1.0～20 weight parts while stirring, temperature remains on 30～60 ℃, stirs 40～80 minutes;
2), add the NaOH of 0.1～5.0 weight part, temperature control to 85～105 ℃ are incubated after 1.0～3.0 hours stopped reaction.
3), dehydration 1.0-3.0 hour, add ethylene glycol to viscosity and be the 30-90 pool after, the cooling blowing obtains modified nano phenolic resin.
The purposes of a kind of modified nano phenolic resin binder of the present invention in refractory materials can realize as wedding agent by adopt modified nano phenolic resin of the present invention in existing refractory materials preparation technology.The preparation technology of refractory materials is known by industry professional and technical personnel.
Modified nano phenolic resin binder of the present invention is used for the preparation of refractory materials, usual method is after refractory particle material, fire-resistant fine powder and carbon materials, metal additive etc. are mixed to scale, add quantitative modified nano phenolic resin of the present invention, mixing, casting or coldmoulding are heat-treated and are promptly got the fire resistive material product that contains modified nano phenolic resin binder.Adopt different materials and technology can make ramming mass, mould material, magnesia carbon brick etc.
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1:
The formalin of 500Kg phenol, 540Kg36% is added in the reactor together, start stirring, added the clay of laminar silicate of 12Kg while stirring in 30 minutes, temperature remains on 35～39 ℃ and continues to stir adding catalyst B a (OH) after 70 minutes
26.0Kg, to wait to be warming up to and stop heating after the boiling, insulation is at 92～102 ℃, stopped reaction after 2.0 hours, decompression dehydration to viscosity is 5 pool postcooling blowings, promptly gets modified nano phenolic resin A.
With corundum alumine particulate material 30Kg and 70Kg such as silicon-carbide particle material and cement, the modified nano phenolic resin A5Kg that the back adding that stirs is made by aforesaid method, it is molded to mix the mold cold of packing into after 15 minutes, about 200 ℃, handled 24 hours, promptly get amorphous refractory in 1450 ℃ of pyroprocessing postcooling then.
Comparing embodiment 1:
The formalin of 500Kg phenol, 540Kg36% is added in the reactor together, start stirring, add catalyst B a (OH)
26.0Kg, stirred 30 minutes, after reaching 70 ℃, temperature stops heating, treat to stop heating after nature is warming up to boiling, be incubated at 92～102 ℃, stopped reaction after 1.2 hours, decompression dehydration to viscosity is 5 pool postcooling blowings, promptly gets phenol-formaldehyde A '.
With particulate material 70Kg such as corundum alumine particulate material 30Kg and silicon carbide, the phenol-formaldehyde A that the back adding that stirs is made by aforesaid method ' 5Kg, it is molded to mix the mold cold of packing into after 15 minutes, about 200 ℃, handled 24 hours, promptly get amorphous refractory in 1450 ℃ of pyroprocessing postcooling then.
The performance of table 1. amorphous refractory relatively
| Amorphous refractory | Cold crushing strength (MPa) | High temperature break resistant intensity (MPa) |
| Embodiment 1 | ????59.0 | ????11.63 |
| Comparing embodiment 1 | ????30.0 | ????8.55 |
Embodiment 2:
Add the formalin of 400Kg phenol, 435Kg36% in the reactor together, start stirring, the clay of laminar silicate that within 25 minutes, adds 9.6Kg while stirring, temperature remains on 38～40 ℃ and continue to stir and to add catalyst n aOH 4.5Kg after 60 minutes, stops heating after waiting to be warming up to boiling, and insulation is at 92～101 ℃, 1.3 stopped reaction after hour, decompression dehydration 1.5 hours, adding ethylene glycol to viscosity is 75 pool postcooling blowings, promptly gets a kind of modified nano phenolic resin B.
With magnesia particle material (10-0.088mm) 30Kg and its fine powder (＜0.088mm) 70Kg, graphite 5kg, aluminium powder 2Kg and silica flour 0.5Kg, the above-mentioned modified nano phenolic resin B 5Kg of back adding stirs, it is molded to mix the mold cold of packing into after 15 minutes, about 200 ℃, handled 24 hours, make product and do not burn magnesia carbon brick.
Comparing embodiment 2:
Add the formalin of 400Kg phenol, 435Kg36% in the reactor together, start stirring, add catalyst n aOH 4.5Kg, stirred 30 minutes, and after temperature reaches 70 ℃, stopped heating, treat to stop heating after nature is warming up to boiling, insulation is at 92～102 ℃, 1.2 it is 75 pool postcooling blowings that stopped reaction after hour, decompression dehydration added ethylene glycol to viscosity in 1.5 hours, promptly gets bakelite B '.
With magnesia particle material (10-0.088mm) 30Kg and its fine powder (＜0.088mm) 70Kg, graphite 5kg, aluminium powder 2Kg and silica flour 0.5Kg, the above-mentioned bakelite B of back adding stirs ' 5Kg, it is molded to mix the mold cold of packing into after 15 minutes, about 200 ℃, handled 24 hours, make product and do not burn magnesia carbon brick.
The performance of table 2. magnesia carbon brick relatively
| The classification of refractory brick | Cold crushing strength (MPa) |
| Embodiment 2 | ????61 |
| Comparing embodiment 2 | ????43 |
Claims (7)
1, a kind of modified nano phenolic resin binder is characterized in that comprising following component: the phenol of 100 weight parts, the formalin of the 36-40% of 70-110 weight part, the clay of laminar silicate of 1.0～20 weight parts, the catalyzer of 0.1～5.0 weight part.
2, a kind of modified nano phenolic resin binder according to claim 1 is characterized in that described clay is particle diameter 0.040～0.080mm, specific surface area 700～800m
2/ g, interlayer has Na
+, Li
+, Ca
2+, Mg
2+The interchangeability positively charged ion, loading capacity is (CEC) 50～200meq/100g, thickness of clay soil is 0.9～1.1nm, interfloor distance is 0.8～2.1nm, content is the polynite of 80-95%.
3,, it is characterized in that described catalyzer is Ba (OH) according to the described a kind of modified nano phenolic resin binder of claim 1
2, Na
2CO
3, MgO, NaOH.
4,, it is characterized in that carrying out as follows according to the preparation method of the described a kind of modified nano phenolic resin binder of claim 1:
(1), the phenol of 100 weight parts and 30～40% formalins of 70～110 weight parts are added in the reactor together, slowly add the clay of laminar silicate of 1.0～20 weight parts while stirring, temperature remains on 30～60 ℃, stirs 40～80 minutes;
(2), the catalyst B a (OH) that adds 0.1～5.0 weight part
2, temperature control to 85～105 ℃ are incubated 1.0-3.0 hour, stopped reaction;
(3), dewater be 2.0-5.0 pool to viscosity after, the cooling blowing promptly gets a kind of modified nano phenolic resin binder.
5, according to the described a kind of modified nano phenolic resin binder of claim 1, it is characterized in that carrying out as follows:
(1), the phenol of 100 weight parts and 30～40% formalins of 70～110 weight parts are added in the reaction together, slowly add the clay of laminar silicate of 1.0～20 weight parts while stirring, temperature remains on 30～60 ℃, stirs 40～80 minutes;
(2), add the catalyst n aOH of 0.1～5.0 weight part, temperature control to 85～105 ℃ are incubated 1.0-3.0 hour, stopped reaction;
(3), dehydration 1.0-3.0 hour, add ethylene glycol to viscosity and be the 30-90 pool after, the cooling blowing promptly gets a kind of modified nano phenolic resin binder.
6, according to the purposes of the described a kind of modified nano phenolic resin binder of claim 1, its feature is used to prepare amorphous refractory, the preparation method of described amorphous refractory is: with corundum alumine particulate material 20-80 weight part and 15-80 weight parts such as silicon-carbide particle material and cement, stir the back adding by above-mentioned modified nano phenolic resin 2-60 weight part, it is molded to mix the mold cold of packing into after 5-20 minute, about 200 ℃, handled 24 hours, make amorphous refractory in 1450 ℃ of pyroprocessing postcooling then.
7, purposes according to the described a kind of modified nano phenolic resin binder of claim 1, its feature is used to prepare magnesia carbon refractory, the preparation method of described magnesia carbon refractory is: with particle diameter is that 0.088-10mm magnesia particle material 30-70 weight part and particle diameter are less than its fine powder of 0.088mm 70-30 weight part, graphite 1-10 weight part, aluminium powder 1-10 weight part and silica flour 0-5 weight part, the above-mentioned modified nano phenolic resin 2-60 weight part of back adding stirs, it is molded to mix the mold cold of packing into after 15 minutes, about 200 ℃, handled 24 hours, make the product magnesia carbon brick.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011314346A CN1185320C (en) | 2001-09-07 | 2001-09-07 | Modified nano phenolic resin binder and its prepn and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011314346A CN1185320C (en) | 2001-09-07 | 2001-09-07 | Modified nano phenolic resin binder and its prepn and use |
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| Publication Number | Publication Date |
|---|---|
| CN1403524A true CN1403524A (en) | 2003-03-19 |
| CN1185320C CN1185320C (en) | 2005-01-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011314346A Expired - Fee Related CN1185320C (en) | 2001-09-07 | 2001-09-07 | Modified nano phenolic resin binder and its prepn and use |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613213A (en) * | 2009-06-26 | 2009-12-30 | 河南省耕生耐火材料有限公司 | Be used for environment-friendly type stemming of blast furnace iron notch and preparation method thereof |
| CN104982243A (en) * | 2015-02-26 | 2015-10-21 | 北华大学 | Standing modified timber, standing timber modifier, and preparation methods thereof |
| CN107540804A (en) * | 2017-08-31 | 2018-01-05 | 武汉科技大学 | A kind of carbon containing refractory phenolic resin and preparation method thereof |
| CN108705458A (en) * | 2018-05-30 | 2018-10-26 | 陈毅忠 | A kind of preparation method of uniform type combination agent material |
| CN109651758A (en) * | 2018-11-06 | 2019-04-19 | 中国神华能源股份有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof, phenol-formaldehyde resin modified plate |
-
2001
- 2001-09-07 CN CNB011314346A patent/CN1185320C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613213A (en) * | 2009-06-26 | 2009-12-30 | 河南省耕生耐火材料有限公司 | Be used for environment-friendly type stemming of blast furnace iron notch and preparation method thereof |
| CN104982243A (en) * | 2015-02-26 | 2015-10-21 | 北华大学 | Standing modified timber, standing timber modifier, and preparation methods thereof |
| CN107540804A (en) * | 2017-08-31 | 2018-01-05 | 武汉科技大学 | A kind of carbon containing refractory phenolic resin and preparation method thereof |
| CN108705458A (en) * | 2018-05-30 | 2018-10-26 | 陈毅忠 | A kind of preparation method of uniform type combination agent material |
| CN109651758A (en) * | 2018-11-06 | 2019-04-19 | 中国神华能源股份有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof, phenol-formaldehyde resin modified plate |
| CN109651758B (en) * | 2018-11-06 | 2021-11-30 | 中国神华能源股份有限公司 | Modified phenolic resin, preparation method thereof and modified phenolic resin plate |
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| Publication number | Publication date |
|---|---|
| CN1185320C (en) | 2005-01-19 |
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