CN1302037C - Modified phenol aldehyde resin and its producing process - Google Patents
Modified phenol aldehyde resin and its producing process Download PDFInfo
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- CN1302037C CN1302037C CNB2005100189438A CN200510018943A CN1302037C CN 1302037 C CN1302037 C CN 1302037C CN B2005100189438 A CNB2005100189438 A CN B2005100189438A CN 200510018943 A CN200510018943 A CN 200510018943A CN 1302037 C CN1302037 C CN 1302037C
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Abstract
The present invention relates to a method for preparing modified phenolic resin from coal tar or a coal tar component, which has the following technical scheme: firstly, 1 wt% of phenol, 0.35 to 0.50 wt% of formaldehyde, 0.1 to 0.45 wt% of coal tar or coal tar component and 0.015 to 0.075 wt% of sodium hydroxide solution with the concentration of 20 to 40% are added into a reaction kettle and thermally insulated for 3 to 4 hours when heated and stirred to 80 to 90DEG C, and the mixture is dewatered in vacuum under the conditions of the temperature of 60 to 90DEG C and the pressure of 0.080 to 0.085MPa; secondly, the mixture is heated to 90 to 110DEG C, thermally insulated for 2 to 4 hours and dewatered once more in vacuum under the conditions of the pressure of 0.080 to 0.085MPa. The present invention can improve the heat resistance of phenolic resin. The modified phenolic resin prepared by leading in the low price coal tar or the low price coal tar component has the advantages of simple process, little investment, high oxidation resistance, no use of addition of an antioxidant and obvious reduction of production cost. All the properties can meet the use requirements of a refractory material.
Description
One, technical field
The invention belongs to the phenolic resins field.Relate in particular to a kind of method of utilizing coal tar or coal tar component to produce modified phenolic resins.
Two, background technology
Resol is widely used in carbon-containing refractory article, as goods such as magnesium carbon, magnalium carbon, aluminium carbon, magnesium calcium carbon because raw material is easy to get, good heat resistance.But phenolic hydroxyl group in the common resol molecule and the easy oxidation of methylene radical are affected its thermotolerance.On the other hand, the resin-bonded material is difficult to form combined carbon when reality is used, and therefore, the resin-bonded material is easy to oxidation than carbon in conjunction with material.Carbonizing production for resol, because resol is typical thermosetting resin, in solid phase, carry out charing, the normally isotropic vitreous carbon of carbonizing production, after pyroprocessing, also be difficult to greying, and leave a large amount of fine pores structures in the carbonizing production, so resistance of oxidation is generally poor in conjunction with material (easily graphitized carbon) than carbonaceous.
In recent years, magnesia carbon brick generally adopts liquid phenolic resin to make wedding agent, the wedding agent of domestic-developed has the L872 heat-reactive phenolic resin, and (analogy is red fragrant, the noisy an ancient unit of weight of Peng, the development of rainbow .L872 heat-reactive phenolic resin wedding agent and the research [J] of physical and chemical performance thereof in what. Wuhan Iron ﹠ Steel College's journal, 1990,13 (2): 143-152), FT type anhydrous binder (Wang Yanhua, Zhou Yanjun, He Junqiu etc., the development of FT type anhydrous binder, fuel and chemical industry, 1999,30 (2): 71-73) with LW901 waterless resin (Song Yuqin, the development [J] of Chen Zhi .LW901 waterless resin binding agent. refractory materials, 1991,25 (4): 221-224) etc.But be raw material with phenol all, the price of wedding agent is all higher.
The main quality index of several trade mark resins of table 1
| Resin property | The L872 heat-reactive phenolic resin | FT type anhydrous binder | The LW901 waterless resin |
| Viscosity (Pas) carbon residue rate (%) solid content (%) free phenol (%) moisture (%) | 40.0～80.0 ＞40.0 75.0～84.0 ＜11.0 ＜5.0 | 20.0-～30.0 38.0～42.0 65.0～70.0 4.0～5.0 ＜0.2 | 6.0～10.0 28.0～30.0 85.0～90.0 ＜2.5 ＜0.2 |
Three, summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, less investment, good in oxidation resistance, the thermotolerance that can improve resin, the modified phenolic resins that reduces production costs and production method thereof.
For achieving the above object, the technical solution adopted in the present invention is: with phenol, formaldehyde, coal tar or coal tar component, catalyzer is that 1/0.35～0.50/0.1～0.45/0.015～0.075 adds in the reactor by weight percentage, during heated and stirred to 80～90 ℃, be incubated 3～4 hours, vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition; Reheat to 90～110 ℃ are incubated 2～4 hours, vacuum hydro-extraction again under 60～90 ℃, 0.080～0.085Mpa condition.
Described catalyzer is 20～40% sodium hydroxide solutions.Coal tar is high-temperature anhydrous coal tar, and the coal tar component is a kind of in carbolic oil, naphtalene oil, carbolineum I, carbolineum II, washing oil, the coal-tar pitch.
Owing to adopt technique scheme, the polycyclic aromatic hydrocarbons in coal tar or the coal tar component and phenol, formaldehyde condensation, each condensation product be further condensation generation three dimensional structure macromole all, thereby can improve the thermotolerance of resol.The modified phenolic resins technology of introducing the production of cheap coal tar or coal tar component is simple, less investment, and good in oxidation resistance need not be added oxidation inhibitor, and the resin cost significantly reduces.Every performance all can reach the requirement that refractory materials uses.
Four, embodiment:
Embodiment 1
A kind of method of utilizing coal tar to produce modified phenolic resins, with phenol, formaldehyde, coal tar and concentration is that 20～40% sodium hydroxide solution catalyzer are that 1/0.35～0.48/0.1～0.4/0.025～0.075 adds in the reactor by weight percentage, during heated and stirred to 80～90 ℃, be incubated 3～4 hours, vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition; Reheat to 60～90 ℃ are incubated 2～4 hours, and vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition adds anhydrous solvent then the viscosity of modified phenolic resins is transferred to 20～30Pas.
The solid content of the modifying coal tar resol of present embodiment production is 89.0～98.0%, and carbon residue is 40.0～45.0%, and moisture is less than 1.5%, and free phenol is less than 3.0%, and heat decomposition temperature is up to being 769.1 ℃, and resin oxidation of coal thermal spike is 865.8 ℃.
Embodiment 2
A kind of method of utilizing washing oil to produce modified phenolic resins, with phenol, formaldehyde, washing oil and concentration is that 20～40% sodium hydroxide solution catalyzer are that 1/0.35～0.48/0.10～0.25/0.03～0.06 adds in the reactor by weight percentage, during heated and stirred to 80～90 ℃, be incubated 3～4 hours, vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition; Reheat to 60～90 ℃ are incubated 2～4 hours, and vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition adds anhydrous solvent then the viscosity of modified phenolic resins is transferred to 20～30Pas.
The solid content of the washing oil modified phenolic resins of present embodiment production is 89.0～98.0%, and carbon residue is 40.0～43.0%, and moisture is less than 1.5%, and free phenol is less than 3.0%, and heat decomposition temperature is up to being 637.5 ℃, and resin oxidation of coal thermal spike is 861.8 ℃.
Embodiment 3
A kind of method of utilizing carbolineum to produce modified phenolic resins, with phenol, formaldehyde, carbolineum and concentration is that 20～40% sodium hydroxide solution catalyzer are that 1/0.35～0.48/0.10～0.20/0.03～0.06 adds in the reactor by weight percentage, during heated and stirred to 80～90 ℃, be incubated 3～4 hours, vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition; Reheat to 60～90 ℃ are incubated 2～4 hours, and vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition adds anhydrous solvent then the viscosity of modified phenolic resins is transferred to 20～30Pas.
The solid content of the carbolineum modified phenolic resins of present embodiment production is 95.0～98.0%, and carbon residue is 39.0～43.0%, and moisture is less than 1.5%, and free phenol is less than 3.0%, and heat decomposition temperature is up to being 639.1 ℃, and resin oxidation of coal thermal spike is 845.7 ℃.
Embodiment 4
A kind of method of utilizing coal-tar pitch to produce modified phenolic resins, with phenol, formaldehyde, coal-tar pitch and concentration is that 20～40% sodium hydroxide solution catalyzer are that 1/0.35～0.48/0.10～0.40/0.03～0.06 adds in the reactor by weight percentage, during heated and stirred to 80～90 ℃, be incubated 3～4 hours, vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition; Reheat to 60～90 ℃ are incubated 2～4 hours, and vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition adds anhydrous solvent then the viscosity of modified phenolic resins is transferred to 20～30Pas.
The solid content of the coal-tar pitch modified phenolic resins of present embodiment production is 95.0～98.0%, and carbon residue is 42.0～47.0%, and moisture is less than 1.5%, and free phenol is less than 3.0%, and heat decomposition temperature is up to being 761.3 ℃, and resin oxidation of coal thermal spike is 869.8 ℃.
Claims (3)
1, a kind of production method of modified phenolic resins, it is characterized in that with phenol, formaldehyde, coal tar or coal tar component, catalyzer being that 1/0.35～0.50/0.1～0.45/0.015～0.075 adds in the reactor by weight percentage, during heated and stirred to 80～90 ℃, be incubated 3～4 hours, vacuum hydro-extraction under 60～90 ℃, 0.080～0.085Mpa condition; Reheat to 90～110 ℃ are incubated 2～4 hours, vacuum hydro-extraction again under 60～90 ℃, 0.080～0.085Mpa condition.
2, the production method of modified phenolic resins according to claim 1 is characterized in that described catalyzer is 20～40% sodium hydroxide solutions.
3, the production method of modified phenolic resins according to claim 1 is characterized in that described coal tar is high-temperature anhydrous coal tar; The coal tar component is a kind of in carbolic oil, naphtalene oil, carbolineum I, carbolineum II, washing oil, the coal-tar pitch.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100189438A CN1302037C (en) | 2005-06-17 | 2005-06-17 | Modified phenol aldehyde resin and its producing process |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100189438A CN1302037C (en) | 2005-06-17 | 2005-06-17 | Modified phenol aldehyde resin and its producing process |
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| CN1693331A CN1693331A (en) | 2005-11-09 |
| CN1302037C true CN1302037C (en) | 2007-02-28 |
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| CNB2005100189438A Expired - Fee Related CN1302037C (en) | 2005-06-17 | 2005-06-17 | Modified phenol aldehyde resin and its producing process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333429B (en) * | 2007-06-28 | 2010-12-22 | 上海梅山钢铁股份有限公司 | Gastight repairing material for hot repairing work |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755904B (en) * | 2013-12-31 | 2015-08-19 | 陕西师范大学 | A kind of Asphalt resin binder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1047945A1 (en) * | 1982-02-01 | 1983-10-15 | Центральное Проектно-Конструкторское И Технологическое Бюро Министерства Автодорог Казсср | Method of producing phenophormolites |
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2005
- 2005-06-17 CN CNB2005100189438A patent/CN1302037C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1047945A1 (en) * | 1982-02-01 | 1983-10-15 | Центральное Проектно-Конструкторское И Технологическое Бюро Министерства Автодорог Казсср | Method of producing phenophormolites |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333429B (en) * | 2007-06-28 | 2010-12-22 | 上海梅山钢铁股份有限公司 | Gastight repairing material for hot repairing work |
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| CN1693331A (en) | 2005-11-09 |
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