CN1062570C - Process for producing modified phenolic resin from still bottom oil - Google Patents
Process for producing modified phenolic resin from still bottom oil Download PDFInfo
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- CN1062570C CN1062570C CN94118771A CN94118771A CN1062570C CN 1062570 C CN1062570 C CN 1062570C CN 94118771 A CN94118771 A CN 94118771A CN 94118771 A CN94118771 A CN 94118771A CN 1062570 C CN1062570 C CN 1062570C
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- bottom oil
- still bottom
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- formaldehyde
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Abstract
The present invention discloses a preparation method of modified phenolic resin from kettle bottom oil, which comprises: the modified phenolic resin is obtained by using the kettle bottom oil, formaldehyde, phenol, etc. as raw materials through a two-step reaction. Besides the general purposes of universal phenolic resin, the resin obtained by the present invention is especially suitable for use on occasions having a strict requirement for heat resistance and occasions of high temperature friction, such as matrix resin as a heat resisting structural material and engineering plastics, high-grade friction braking products, manufacturing materials for electric elements, etc. The softening point of the phenolic resin prepared by the present invention is higher than 110DEG C, the free phenol content is lower than 1%, and therefore, the phenolic resin can be used for a long term at the temperature of 300DEG C.
Description
The present invention is a kind of manufacture method of producing modified phenolic resins with still bottom oil.In more detail, it is with petroleum refining aromatic hydrocarbons---after dimethylbenzene, trimethylbenzene or the durene, the cut between 170～270 ℃ (abbreviating still bottom oil as) is a raw material, reacts and the modified phenolic resins of generation through two steps with formaldehyde, phenol.The present invention can be applied to aspects such as heat-stable material, senior friction materials, high-grade braking product, insulating material, coating, high-temperature-resistant adhesive.It has high temperature resistant, characteristics such as rub resistance weares and teares, high insulation.
Usually people will obtain thermotolerance resol, adopt raw materials such as the high wolframic acid of price, molybdic acid, silicoorganic compound, with phenol, formaldehyde reaction, and synthetic tungsten resol, molybdenum resol, the organic silicon modified phenolic resin etc. of obtaining.
Usually people also adopt cresols instead of part phenol, synthetic thermotolerance cresol-novolak resin.
Usually, people adopt the cashew nut shell oil of price height and source of goods anxiety to make raw material, with phenol, formaldehyde reaction, obtain the cashew nut oil modified alkyd resin of high rub resistance.
Along with developing rapidly of China Petroleum, the degree of depth refining capacity of petroleum industry improves constantly.Oil is refining aromatic hydrocarbons---and after dimethylbenzene, trimethylbenzene or the durene, the cut between 170～270 ℃ is because the component complexity can not can not act as a fuel as solvent.Still bottom oil is when burning, because incomplete combustion, smog is big, causes serious environmental to pollute.Therefore, still bottom oil fails to be utilized effectively so far.China's oil that is richly stored with, petroleum industry presses for carries out comprehensive development and utilization to still bottom oil.
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, do not adopt the price height.The wolframic acid of source anxiety, molybdic acid, silicoorganic compound, cresols, cashew nut shell oil etc. are raw material, thereby can reduce cost.
Another purpose of the present invention is to adopt petroleum industry byproduct still bottom oil as raw material, can not only make a large amount of still bottom oils obtain comprehensive utilization, having opened up raw material newly originates, reduced production cost, and pass through chemical reaction, synthetic modified phenolic resins free phenol content is extremely low, and softening temperature is very high, and heat-resisting crocking resistance excellence and electrical insulation capability are outstanding.
In order to achieve the above object, a kind of method of producing modified phenolic resins with still bottom oil of the present invention comprises that with still bottom oil, formaldehyde, phenol be raw material, through the reaction of two steps, and the preparation modified phenolic resins.
Purpose of the present invention can reach by following measure, promptly of the present inventionly a kind ofly produces the method for resol with still bottom oil, it is characterized in that:
The first step reaction:
Add formalin in the reactor earlier, under agitation condition, drip concentrated hydrochloric acid, afterwards, drop into still bottom oil again, its mass fraction is: still bottom oil and aldehyde compound can be reinforced with any ratio, still bottom oil: mineral acid=1: 0.1～0.55, temperature of reaction is controlled at reflux operation under 85～105 ℃ of normal pressures, reaction 3～9h, stopped reaction, in reaction system, feed water vapor and steam the oil content of not participating in reaction in the reactant, subsequently resin is separated with sour water, washes with water, obtain still bottom oil---formaldehyde resin.
The reaction of second step:
At still bottom oil---in the formaldehyde resin, add phenol and still bottom oil, its mol ratio is still bottom oil-formaldehyde resin: phenol: still bottom oil=1: 1～1.8: 0.1～0.5, and adding hydroxy-benzoic acid compounds is made catalyzer, as P-hydroxybenzoic acid, mol ratio is still bottom oil-formaldehyde resin: P-hydroxybenzoic acid=1: 0.01～0.05, react 2～5h down at 100～150 ℃.After being cooled to 80 ℃, add formaldehyde, add formaldehyde by following mol ratio, residue phenol: formaldehyde=1: 0.85～0.9, regulate pH value to 2.0～2.9, under the atmospheric pressure reflux condition, react 3～5h, add the ortho position conversion catalyst again, as magnesium oxide, the magnesium oxide add-on is 1%～3% of a system gross weight, react 1-3h under the atmospheric pressure reflux condition, after vacuum hydro-extraction, when system vacuum tightness is-0.095MPa, when system temperature reaches 200～220 ℃, stop vacuum hydro-extraction, so just obtained a kind of modified phenolic resins of producing with still bottom oil
The modified phenolic resins that the inventive method is made, outward appearance is brown translucent solid, and free phenol content is less than 1%, and softening temperature is greater than 110 ℃, not water content and free formaldehyde.
After the modified phenolic resins that the inventive method is made solidifies, have outstanding thermotolerance, initial weightless temperature is greater than 200 ℃, and heat decomposition temperature is greater than 450 ℃.
The modified phenolic resins that the inventive method is made, the friction materials of making at high temperature has very high frictional behaviour, reaches about 0.45 at 350 ℃ of following frictional coefficient, and wear rate is less than 0.30 * 10
-7Cm
3/ N-m.
The modified phenolic resins that the inventive method is made, its matrix material have excellent electrical insulation capability, and 10 ° of Hz electrical strengths are 18.0MV/m, and volume specific resistance reaches 2 * 10
11Ω .m, 10 ° of Hz dielectric dissipation factors are 1.7 * 10
-2
The modified phenolic resins that the present invention makes, except that general use with universal resol, be particularly suitable for thermotolerance have relatively high expectations and the high temperature friction occasion under use, as as heat resistant structure material and the matrix resin of engineering plastics, the matrix resin of senior friction braking material, electrical element manufactured materials, or the like.Can be widely used in industries such as chemical industry, machinery, electronics, electrician, vehicle, building materials, soldier be mutual.
The embodiment of the inventive method manufacturing modified phenolic resins method is as follows:
Embodiment 1 takes by weighing technical grade formalin (more than 36%) 10g, under the agitation condition, drips after the concentrated hydrochloric acid 3g, drop into the 12g still bottom oil again, stirring is warmed up to 85 ℃, atmospheric pressure reflux operation, reaction 8h, stopped reaction, water vapor is fed in the reaction system, steam the unreacted oil content, resin is separated with sour water, wash the acid in the resin with water, can obtain still bottom oil---formaldehyde resin.
Take by weighing still bottom oil---formaldehyde resin 10g, add still bottom oil 1g, add phenol 5.1g, P-hydroxybenzoic acid 0.17g, 100 ℃ are reacted 5h down, are cooled to 80 ℃, add industrial formol aqueous solution 1.2g, regulate pH value to 2.0, back flow reaction 3h under normal pressure, add magnesium oxide 0.16g again, back flow reaction 3h under the normal pressure carries out vacuum hydro-extraction again, vacuum tightness is-0.095MPa, when temperature to 220 ℃, stop vacuum hydro-extraction, just can obtain modified phenolic resins of the present invention.
Above-mentioned resulting modified phenolic resins is brown translucent solid, free phenol content is less than 1%, softening temperature is greater than 110 ℃, not water content and free formaldehyde, density is about 1.2, but conditions suitable is long storage down, is used for dry process after can pulverizing, and is used for wet processing after the useable solvents dissolving, has good construction technology.
Embodiment 2
Take by weighing technical grade formalin (more than 36%) 50g, under the agitation condition, dripping hydrochloric acid 25g drops into still bottom oil 70g afterwards again, is warmed up to 95 ℃.Under the agitation condition, the atmospheric pressure reflux operation, reaction 5h, stopped reaction feeds water vapor in reaction system, steam the unreacted oil content, and resin is separated with sour water, washes the acid in the resin with water, obtains still bottom oil---formaldehyde resin.
Take by weighing still bottom oil---formaldehyde resin 50g, add still bottom oil 10g, add phenol 34g, P-hydroxybenzoic acid 1.13g reacts 3h down at 130 ℃, is cooled to 80 ℃, add industrial formol aqueous solution 8g, regulate pH value to 2.5, back flow reaction 4h under the normal pressure, add magnesium oxide 1.8g again, back flow reaction 2h under the normal pressure carries out vacuum hydro-extraction again, vacuum tightness is-0.095MPa, when temperature to 220 ℃, stop to vacuumize, just can obtain modified phenolic resins of the present invention.
The result of use of embodiment 2 is substantially the same manner as Example 1.
Embodiment 3
Take by weighing technical grade formalin 100g, agitation condition drips concentrated hydrochloric acid 40g down, drops into still bottom oil 150g, is warmed up to 105 ℃, and reflux operation under the normal pressure stirs insulation 3h, stopped reaction.In reaction system, feed water vapor, steam unreacted oil content, resin is separated with sour water, wash the acid in the resin with water, obtain still bottom oil---formaldehyde resin.
Taking by weighing still bottom oil---formaldehyde resin 100g adds still bottom oil 21g, phenol 76.5g, P-hydroxybenzoic acid 2.8g reacts 2h down at 150 ℃, is cooled to 80 ℃, add industrial formol aqueous solution 26g, regulate pH value to 2.8, back flow reaction 5h under normal pressure, add magnesium oxide 6.15g again, react 1h under the atmospheric pressure reflux, carry out vacuum hydro-extraction again, vacuum tightness is-0.095MPa, when temperature is raised to 220 ℃, stop vacuum hydro-extraction, just can obtain modified phenolic resins of the present invention.
The result of use of embodiment 3 is substantially the same manner as Example 1.
Claims (1)
- A kind of with petroleum refining aromatic hydrocarbons---after toluene, trimethylbenzene or the durene, the fraction between 170～270 ℃ (abbreviating still bottom oil as) is produced the method for modified phenolic resins, it is characterized in that in turn including the following steps:Add formalin in the reactor earlier, under agitation condition, drip after the concentrated hydrochloric acid, drop into still bottom oil again, its mass fraction is: still bottom oil and aldehyde compound can be reinforced with any ratio, still bottom oil: mineral acid=1: 0.1～0.55, temperature of reaction is controlled at 85～105 ℃, reflux operation under the normal pressure, reaction 3～9h, stopped reaction, in reaction system, feed water vapor, steam the oil content of not participating in reaction in the reactant, subsequently resin is separated with sour water, wash with water, obtain still bottom oil---formaldehyde resin, at still bottom oil---in the formaldehyde resin, add still bottom oil and phenol, its mol ratio is still bottom oil a---formaldehyde resin: phenol: still bottom oil=1: 1～1.8: 0.1～0.5, and adding hydroxy-benzoic acid compounds is made catalyzer, mol ratio is still bottom oil a---formaldehyde resin: hydroxy-benzoic acid=1: 0.01～0.05, at 100～150 ℃ of following reaction 3～5h, be cooled to 80 ℃ after, add formaldehyde, its mol ratio is residue phenol: formaldehyde=1: 0.85～0.90, regulate pH value to 2.0～2.9, and under the atmospheric pressure reflux condition, react 1～3h, after vacuum hydro-extraction, vacuum tightness is-0.095MPa when system temperature reaches 200～220 ℃, to stop vacuum hydro-extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94118771A CN1062570C (en) | 1994-12-06 | 1994-12-06 | Process for producing modified phenolic resin from still bottom oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94118771A CN1062570C (en) | 1994-12-06 | 1994-12-06 | Process for producing modified phenolic resin from still bottom oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1124255A CN1124255A (en) | 1996-06-12 |
| CN1062570C true CN1062570C (en) | 2001-02-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94118771A Expired - Fee Related CN1062570C (en) | 1994-12-06 | 1994-12-06 | Process for producing modified phenolic resin from still bottom oil |
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| Country | Link |
|---|---|
| CN (1) | CN1062570C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883416B (en) * | 2015-12-16 | 2020-01-21 | 华奇（中国）化工有限公司 | C9 resin modified phenol formaldehyde resin and preparation method and application thereof |
Citations (3)
| 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 |
| JPS60210616A (en) * | 1984-04-03 | 1985-10-23 | Hitachi Chem Co Ltd | Production of phenolic resin |
| GB2271357A (en) * | 1992-09-04 | 1994-04-13 | Mitsui Toatsu Chemicals | Phenolic resin composition |
-
1994
- 1994-12-06 CN CN94118771A patent/CN1062570C/en not_active Expired - Fee Related
Patent Citations (3)
| 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 |
| JPS60210616A (en) * | 1984-04-03 | 1985-10-23 | Hitachi Chem Co Ltd | Production of phenolic resin |
| GB2271357A (en) * | 1992-09-04 | 1994-04-13 | Mitsui Toatsu Chemicals | Phenolic resin composition |
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| Publication number | Publication date |
|---|---|
| CN1124255A (en) | 1996-06-12 |
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