CN102757620A - Heat-resistant phenolic resin produced by taking cresol residues as raw material and application of heat-resistant phenolic resin in heat-resistant anti-corrosion paint - Google Patents
Heat-resistant phenolic resin produced by taking cresol residues as raw material and application of heat-resistant phenolic resin in heat-resistant anti-corrosion paint Download PDFInfo
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- CN102757620A CN102757620A CN2012102445890A CN201210244589A CN102757620A CN 102757620 A CN102757620 A CN 102757620A CN 2012102445890 A CN2012102445890 A CN 2012102445890A CN 201210244589 A CN201210244589 A CN 201210244589A CN 102757620 A CN102757620 A CN 102757620A
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Abstract
The invention provides a heat-resistant phenolic resin produced by taking cresol residues as a main raw material. The heat-resistant phenolic resin is obtained after a series of chemical reaction through utilizing the active functional groups of various compounds in the cresol residues. A heat-resistant anti-corrosion paint is produced by taking the heat-resistant phenolic resin as a main film forming matter and compounding with glass flakes and other lamellar inorganic mineral materials, has the advantages of high drying speed, good adhesion, high hardness, good heat resistance, strong water resistance and solvent resistance and the like, and is suitable for the heat-resistant anticorrosion coating of the surfaces of chemical mechanical equipment, pipelines, flues, storage tanks, heat dissipation devices and other devices. According to the heat-resistant phenolic resin, the cresol residues are comprehensively utilized, therefore, the pollution problem of the cresol residues is fundamentally solved, and the effects of comprehensive treatment and waste material recycle are realized; and moreover, new paint products are increased, and the application field of the phenolic paint is broadened.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of processing and comprehensive utilization of phenols residue, relating in particular to a kind of is the heat-resistant phenolic resins of main raw material preparation with the cresols residue; The present invention also relates to the application of this resin in producing the heat-resistant anticorrosive lacquer simultaneously.
Background technology
Cresols is a kind of fine chemical product that is widely used in fields such as industrial or agricultural, medical and health.But in the process of producing cresols, can produce a large amount of residues; Staple is mixed phenol (phenol, cresols, dihydroxy-benzene, cresorcin, tolyl pyrogallol, NP etc.), mixed ether (methyl-phenoxide, ditolyl ether etc.), mixed ketone (diformazan benzophenone etc.), inorganic salt, ash content, water, polyaromatic polymkeric substance etc.; Approximately per 100 tons will produce 10 ~ 12 tons of residues, and wherein residue contains the phenol amount and is about 30%.
Aldehydes matter contains aromatic ring, is discharged in the physical environment and can causes air, water, soil pollution, makes environmental degradation, influences the establishment of HUMAN HEALTH and harmonious environment, and therefore, the disposal of waste gas, water and industrial residue problem that production cresols causes has become the bottleneck of restriction enterprise development.
At present, the cresols draff processing method mainly contains both at home and abroad: 1) washing distillation method, 2) extraction separation method, 3) biochemical process, 4) heavy benzene pulse extraction method, 5) burning method etc.These methods can only reduce the harmful substance contents in the cresols residue to a certain extent; But it is not thorough; Still have a large amount of hazardous and noxious substances to be thrown into the Nature, do not accomplish zero disposal of pollutants, tradition is polluted the treatment scheme complicacy simultaneously, investment is big, cost is high; Therefore, it is extremely urgent to widen cresols residue treatment channel.
Summary of the invention
The objective of the invention is to realize the comprehensive utilization of cresols residue in order to solve the problem that prior art exists in the p-cresol residue treatment, providing a kind of is the heat-resistant phenolic resins of feedstock production with the cresols residue.
Another object of the present invention provides the application of a kind of above-mentioned heat-resistant phenolic resins in producing the heat-resistant anticorrosive lacquer.
(1) heat-resistant phenolic resins
Heat-resistant phenolic resins of the present invention is to be formed by following raw material and prepared:
Composition of raw materials: in weight part
100 parts of cresols residues, formaldehyde 10-100 part, vegetables oil or vegetable oil acid 10-200 part; Polyvalent alcohol 10-200 part; Polyprotonic acid 10-200 part, properties-correcting agent 10-200 part, composite catalyst
1-10 part; Composite catalyst II 1-50 part; Skimmer 0-10 part, organic solvent 10-50 part, water 1-200 part;
Said properties-correcting agent is at least a in NSC 7352, two methyl cyclopentadiene, petroleum resin, coumarone indene resin, furane resin, terpine resin, unsaturated carboxylic acid, the unsaturated acid anhydride.Wherein said unsaturated carboxylic acid, unsaturated acid anhydride are toxilic acid (acid anhydride), fumaric acid, methylene-succinic acid (acid anhydride), Ba Dousuan, styracin, rosin or the like.The effect of properties-correcting agent is oil soluble and the mechanical strength of resin that improves resol.
Said composite catalyst
is oxyhydroxide or oxide compound or vitriol by K, Na, Zn, Ca, Cu metals ion, mixes with 1 ~ 99%, 99 ~ 1% weight percent with aminated compounds; Said aminated compounds is at least a in ammoniacal liquor, hexamethylenetetramine, dimethyl amine, the triethylamine.Composite catalyst
is when playing katalysis; Can form the inner complex of metallic compound with reactant, thereby improve the performance of modified resin.
Said organic solvent is at least a in toluene, YLENE, the aromatic solvent naphtha.The effect of organic solvent is the viscosity and the solids constituent of reflux dewatering, adjustment resin and coating.
Said vegetables oil or vegetable oil acid are siccative oil or its oleic acid of iodine number at 150-200g/100g, like tung oil, eleostearic acid, oleum lini, linolic acid, talloleic acid etc.Its effect is the linking agent of resol, improves coating dryness, intensity, snappiness and sticking power.
Said polyvalent alcohol is for to be the alcohols of high functionality, like tetramethylolmethane, USP Kosher, and TriMethylolPropane(TMP) etc.The effect of polyvalent alcohol is to improve resin's crosslinkage, improves performances such as coating intensity.
Said polyprotonic acid is that said polyprotonic acid is the carboxylic acid of functionality >=2, like PMA, pyromellitic acid dianhydride, the inclined to one side front three acid anhydrides of benzene, phthalic acid/acid anhydride, terephthalic acid, toxilic acid/acid anhydride, fumaric acid etc.The effect of polyprotonic acid is to improve resin's crosslinkage and paint film adhesion.
Said composite catalyst II is at least a in oxyhydroxide or the oxide compound of Li, Ca, Pb, Mn metals ion.Its effect is to quicken polymerization rate.
Said skimmer is silicone based (like silicone oil, silicone, ZGK 5 etc.), polyethers (polyether glycol, propylene glycol block polyether etc.) or polyacrylic polymer (ROHM or PEMULEN TR2).The effect of skimmer is more when the system foam, when rising pot, plays froth breaking, the effect of stabilising system.
Preparation technology:
(1) with the cresols residue; Properties-correcting agent, composite catalyst
, water; Under agitation add in the reaction kettle; Be warming up to 50-300 ℃, add formaldehyde again, reacted 0.5-8 hour; Detect sylvic oil dissolubility and solvability, make the resin can be in toluene, siritch fully after the dissolving, dry, obtain hardened resin, pulverize, subsequent use;
(2) with above-mentioned hardened resin, vegetables oil or vegetable oil acid, polyvalent alcohol, polyprotonic acid, the composite catalyst II, skimmer, organic solvent under agitation adds reaction kettle, is warming up to 150-280 ℃, reacts 1-20 hour; Survey viscosity and acid number, when the system viscosity is 25 ℃ of 1-30s/ Ge Shi pipes, during solid acid number≤20mgKOH/g; Solids constituent 60 ± 20% cools to 150 ℃ to room temperature, uses organic solvent latting drown to viscosity to be 25 ℃ of 5-50s/ Ge Shi pipes; Filter, packing promptly gets heat-resistant phenolic resins.
(2) performance of heat-resistant phenolic resins
The performance index of the heat-resistant phenolic resins of the present invention's preparation are following:
Viscosity 5-50s (25 ℃ of Ge Shi pipes), acid number≤20mgKOH/g, solids constituent 60 ± 20%.
With resin liquid direct brushing (being equivalent to process phenolic varnish), 300 ~ 450 ℃ of heat decomposition temperatures, and its application property is good, are done solid work time≤10h, snappiness 1mm, water tolerance>=48h, anti-120 at surface drying time≤1h
#Solvent oiliness>=48h.
Can find out that from above-mentioned performance index advantage such as the heat-resistant phenolic resins of the present invention preparation and coating thereof have that rate of drying is fast, sticking power good, hardness is big, water tolerance and solvent resistance are strong can be used for producing phenolic aldehyde heat-resistant anticorrosive of all kinds and coats with lacquer.
(3) preparation of heat-resistant anticorrosive lacquer
Feed proportioning: in weight part
100 parts of heat-resistant phenolic resins
Glass flake 5-50 part
Graphite scale 0-50 part
Pigment 0-20 part
Filler 0-50 part
Auxiliary agent 1-10 part
Organic solvent 10-50 part
Above-mentioned filler is at least a in talcum powder, chalk powder, stone flour, silica powder, ground barium sulfate, light calcium carbonate, water-ground limestone, kaolin, zeyssatite, polynite, wilkinite, potter's clay, attapulgite, process white, silicon-dioxide, wollastonite, the zinc oxide;
Above-mentioned auxiliary agent is at least a in naphthenic soap, octylate, 2-ethylhexoate, dibutyl tin dilaurate, zirconium driers, rare earth drier, silane coupling agent, the titanate coupling agent;
Above-mentioned organic solvent is at least a in toluene, YLENE, the aromatic solvent naphtha.
Preparation technology: above-mentioned each raw material through pre-mixing, is ground packing.
Advantages such as the heat-resistant anticorrosive lacquer of the present invention preparation has that rate of drying is fast, sticking power good, hardness is big, good heat resistance, water tolerance, solvent resistance are strong are applicable to the heat-resistant anticorrosive application of device surfaces such as chemical mechanical equipment, pipeline, flue, storage tank, scatterer.
The present invention has following beneficial effect with respect to prior art:
1, the present invention utilizes the effective efficiency group of all cpds in the cresols residue, through series of chemical, but the cresols residue is processed the heat-resistant phenolic resins of suitability for industrialized production; Product need not to separate; And then directly be used to prepare corresponding phenolic aldehyde heat-resistant anticorrosive lacquer, realized cresols production zero waste discharge, promptly when obtaining major product p-cresol, ortho-cresol, meta-cresol; Residue and raffinate are also fully utilized at last; Fundamentally solve the cresols pollution problem, reached the comprehensive regulation, the effect that turns waste into wealth.
2, the present invention is through optimizing and combining starting material and production technique; Design the phenolic aldehyde heat-resistant anticorrosive lacquer of high, medium and low different mass and different performance requirement,, make the range of product variation to satisfy the product demand of different class, different performance; Technology is oversimplified, profit maximization.
3, to have production technique simple for the inventive method, and facility investment is few, and exploitativeness is strong, and comprehensive cost is low, the characteristics of remarkable in economical benefits.
Embodiment
Through specific embodiment the preparation of resol of the present invention and the preparation of corresponding phenolic aldehyde heat-resistant anticorrosive lacquer are described further below.
Embodiment one
1, the preparation of heat-resistant phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 50 parts of furane resin, 100 parts of NSC 7352s, 50 parts in water, 0.2 part in zinc oxide, 0.6 part of hexamethylenetetramine, add in the reaction kettle, heat up, when system reaches 90 ℃, drip 50 parts in formaldehyde; After dripping off, under this temperature, kept 3 hours, make it abundant reaction; Add 60 parts of tetramethylolmethanes, 40 parts of MALEIC ANHYDRIDEs then, continue to heat up, after keeping 2 hours under 180-230 ℃, begin to survey acid number, oil soluble and solvability; As acid number≤20mgKOH/g, resin: oleum lini=1:4, complete dissolving; Resin: toluene=1:1, complete dissolving is for qualified.The beginning blowing dries, and pulverizes, and obtains hardened resin, and is subsequent use.
(2) with 300 parts of above-mentioned hardened resin, 100 parts of tung oil, 50 parts of tetramethylolmethanes, 60 parts of phthalic anhydrides, 0.1 part of silicone oil; 20 parts of YLENE add reaction kettle, are warming up to 220-230 ℃; Reacted 2 hours, and began sampling, survey viscosity and acid number; When the system viscosity is 8-10s (Ge Shi pipe 25 ℃), acid number is≤15mgKOH/g to be cooled to below 200 ℃; With the toluene latting drown to viscosity 10-20s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, solids constituent 50 ± 2% is filtered, packing promptly gets heat-resistant phenolic resins toluene liquid.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of heat-resistant phenolic resins are following:
The heat-resistant phenolic resins performance index are viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 50 ± 2%; Resin liquid and cobalt naphthenate, zinc naphthenate, calcium naphthenate and silane coupling agent are mixed; Direct brushing (is equivalent to varnish) on the standard detection model, its application property is good, surface drying≤1h; Do solid work≤10h; Behind the drying and forming-film, 370 ℃ of heat decomposition temperatures, snappiness 1mm, the 1h of anti-boiling water is non-foaming does not come off anti-120
#Solvent oiliness>=48h.Add an amount of pigment, filler, can be made into coating such as phenolic aldehyde transparent varnish of all kinds, enamel paint, priming paint, rust-inhibiting paint, hard floor paint, steelwork lacquer.Add stratiform or vesicular fillers such as an amount of glass flake, graphite scale, zeyssatite, silicon-dioxide; Can be made into phenolic aldehyde heat-resistant anticorrosive lacquer; Thermotolerance reaches 350-450 ℃, and like glass flake phenolic aldehyde heat-resisting varnish, graphite scale phenolic aldehyde heat-resisting varnish, heat decomposition temperature is greater than 420 ℃.
2, the preparation of phenolic aldehyde heat-resistant anticorrosive lacquer
Proportioning raw materials is seen table 1.
Table 1 proportioning raw materials
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 40 μ m, then with projects such as organic solvents such as toluene, YLENE adjustment paint viscosity, detects qualified after, packing promptly gets and deceives the phenolic aldehyde heat-resistant anticorrosive and coat with lacquer.Because the singularity of this research, this type of coating does not have respective standard, and according to the Application Areas of this product, main performance index detects with reference to ZB G51 028-2006 " iron oxide red phenolic antirust paint ", qualified after, packing.
The black phenolic aldehyde heat-resistant anticorrosive lacquer performance index of preparation are seen table 1-1.
The purposes of black phenolic aldehyde heat-resistant anticorrosive lacquer: be applicable to external coatings such as mechanical means, scatterer, flue, pipeline, baking oven, storage tank.
Table 1-1 phenolic aldehyde heat-resistant anticorrosive lacquer
Embodiment two
1, the preparation of heat-resistant phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 50 parts of two methyl cyclopentadienes, 100 parts of terpine resins, 50 parts in water, 1 part in plumbous oxide, 2 parts of ammoniacal liquor, add in the reaction kettle, heat up, when system reaches 90 ℃, drip 50 parts in formaldehyde; After dripping off, under this temperature, kept 5 hours, make it abundant reaction; Detect sylvic oil dissolubility and solvability (resin: oleum lini=1:4, complete dissolving; Resin: toluene=1:1, complete dissolving), dissolving is qualified fully, and blowing dries, and pulverizes, and obtains hardened resin, and is subsequent use.
(2) with 200 parts of above-mentioned hardened resin, 100 parts of oleum lini, 45 parts of tetramethylolmethanes, 0.2 part in plumbous oxide, 0.1 part of Lithium Hydroxide MonoHydrate, be warming up to 240 ℃, behind the maintenance 2h, detect pure dissolubility; Work as resin: ethanol (95%)>=1:5 is qualified, is cooled to 200 ℃ again, adds 60 parts of cis-butenedioic anhydrides, 1 part of zinc acetate, 0.1 part of silicone oil, 40 parts of YLENE; Add reaction kettle, when being warming up to 230 ℃, behind the maintenance 2h, begin sampling; Survey viscosity and acid number, when the system viscosity is 8-10s, acid number is≤15mgKOH/g to be cooled to below 200 ℃; With the toluene latting drown to viscosity 20-30s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, solids constituent 60 ± 2%; Filter, packing promptly gets heat-resistant phenolic resins toluene liquid.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of heat-resistant phenolic resins are following:
The heat-resistant phenolic resins fluidity can index be viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 60 ± 2%; Resin liquid and rare earth drier and silane coupling agent are mixed, be painted on the test sample plate, its application property is good, and surface drying≤1h does solid work≤10h, behind the drying and forming-film, and 350 ℃ of its heat decomposition temperatures, snappiness 1mm, water tolerance>=48h, anti-120
#Solvent oiliness>=48h.Glass flake of all kinds (graphite scale) phenolic aldehyde heat-resistant anticorrosive with its preparation coats with lacquer heat decomposition temperature greater than 400 ℃.
2, the preparation of the heat-resisting priming paint of phenolic aldehyde
Proportioning raw materials is seen table 2.
Table 2 proportioning raw materials
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 50 μ m, then performance such as organic solvent such as YLENE adjustment paint viscosity; With reference to F06-1 phenolic primer (XQ/G-51-0023-90; Also can detect according to separately company standard) standard detects, qualified after, packing.
The performance index of the heat-resisting priming paint of ash phenolic aldehyde are seen table 2-1.
The purposes of the heat-resisting priming paint of phenolic aldehyde: be used for iron and steel and wooden device surface bottoming, the especially device of long-term exposure in hot environment.
The heat-resisting priming paint of table 2-1 phenolic aldehyde
Embodiment three
1, the preparation of heat-resistant phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 50 parts of rosin, 200 parts of coumarone indene resins, 50 parts in water, 1 part in zinc oxide, 1 part of ammoniacal liquor, add in the reaction kettle, heat up, when system reaches 90 ℃, drip 50 parts in formaldehyde; After dripping off, under this temperature, kept 5 hours, make it abundant reaction; Detect qualified back and (detect oil soluble and solvability, resin: oleum lini=1:4, complete dissolving; Resin: toluene=1:1, complete dissolving), blowing dries, and pulverizes, and obtains hardened resin, and is subsequent use;
(2) with 350 parts of above-mentioned hardened resin, 200 parts of oleum lini, 60 parts of tetramethylolmethanes, 20 parts of TriMethylolPropane(TMP)s, 0.1 part of Lithium Hydroxide MonoHydrate, be warming up to 250 ℃, keep 1h after, detect pure dissolubility; Work as resin: ethanol (95%)>=1:5 is qualified, is cooled to 200 ℃ again, and 50 parts of phthalic anhydrides add 30 parts of fumaric acid, 10 parts of maleic anhydrides, 1 part in zinc oxide, 0.2 part of polyethers; 40 parts of YLENE continue to heat up, and when system reaches 240 ℃, keep 2h; Begin sampling, survey viscosity and acid number, when the system viscosity is 8-12s, acid number is≤15mgKOH/g; Be cooled to below 200 ℃, with the YLENE latting drown to viscosity 7-15s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, solids constituent 40%; Filter, packing promptly gets heat-resistant phenolic resins YLENE liquid.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of heat-resistant phenolic resins are following:
The heat-resistant phenolic resins fluidity can index be viscosity 7-15s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 40 ± 2%; Resin liquid, zinc octoate, cobalt octoate, calcium octoate and titanate coupling agent are mixed, be painted on the model to be measured, its application property is good; Surface drying≤1h; Do solid work≤10h, behind the drying and forming-film, 310 ℃ of its heat decomposition temperatures, snappiness 1mm, water tolerance>=48h, anti-120
#Solvent oiliness>=48h can be used for preparing coating such as phenolic antirust paint, phenolic aldehyde steelwork lacquer, and heat resisting temperature reaches 350-370 ℃.
2, the preparation of iron oxide red phenolic aldehyde primer for rusty surface
Proportioning raw materials is seen table 3.
Table 3 proportioning raw materials
Preparation technology: with above-mentioned each raw material through pre-mixing; Be ground to below the fineness 50 μ m; Then with projects such as organic solvents such as YLENE adjustment paint viscosity, with reference to F06-15 iron oxide red phenolic aldehyde primer for rusty surface standard detection (XQ/G-51-0025-90 also can detect according to company standard separately); After qualified, packing.
The performance index of the iron oxide red phenolic aldehyde primer for rusty surface of above-mentioned preparation are seen table 3-1.
Phenolic aldehyde primer for rusty surface purposes: direct brushing also can be used for the woodwork bottoming in metal products surface, the especially device of long-term exposure in hot environment of not rust cleaning.
Table 3-1 F06-15 iron oxide red phenolic aldehyde primer for rusty surface (XQ/G-51-0025-90)
Embodiment four
1, the preparation of heat-resistant phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 100 parts of rosin, 100 parts of NSC 7352s, 200 parts in water, 0.3 part of slaked lime, 2 parts of hexamethylenetetramines, add in the reaction kettle, heat up, when system reaches 100 ℃, drip 50 parts in formaldehyde; After dripping off, under this temperature, kept 5 hours, make it abundant reaction; Detect sylvic oil dissolubility and solvability, work as resin: oleum lini=1:4, complete dissolving; Resin: toluene=1:1, complete dissolving then is qualified, blowing dries, and pulverizes, and obtains hardened resin, and is subsequent use;
(2) with 300 parts of above-mentioned hardened resin, 40 parts of adding YLENE, 400 parts of linolenic acid, 30 parts of NSC 7352s, 200 parts of tetramethylolmethanes, 180 parts of phthalic anhydrides, 20 parts of cis-butenedioic anhydrides, 5 parts in zinc oxide continue slowly to heat up, and when system reaches 170 ℃, keep 0.5h; 180 ℃ of 0.5h, 190 ℃ of 0.5h, 200 ℃ of 1h, 210 ℃ of 1h; 220 ℃ of 1h begin sampling, survey viscosity and acid number, when the system viscosity is 8-10s; Acid number is≤15mgKOH/g, be cooled to below 200 ℃, with latting drowns such as toluene to viscosity 20-30s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g; Solids constituent 70 ± 2% is filtered, and packing promptly gets heat-resistant phenolic resins.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of heat-resistant phenolic resins are following:
Heat-resistant phenolic resins liquid viscosity 20-30s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 70 ± 2%; Resin liquid, manganese iso-octoate, isocaprylic acid zinc, dibutyl tin dilaurate and titanate coupling agent are mixed, be painted on the model to be measured, its application property is good; Surface drying≤1h; Do solid work≤10h, behind the drying and forming-film, 330 ℃ of its heat decomposition temperatures, snappiness 1mm, water tolerance>=48h, anti-120
#Solvent oiliness>=48h.Add an amount of pigment, filler, can be made into coating such as phenolic aldehyde transparent varnish of all kinds, enamel paint, priming paint, rust-inhibiting paint, hard floor paint, steelwork lacquer.Add stratiform or vesicular fillers such as an amount of glass flake, graphite scale, zeyssatite, silicon-dioxide, can be made into phenolic aldehyde heat-resistant anticorrosive lacquer, thermotolerance reaches 350-400 ℃.
2, the preparation of aluminium azoic coupling component aldehyde heat-resisting varnish
Proportioning raw materials is seen table 4.
Table 4 proportioning raw materials
The performance index of the aluminium azoic coupling component aldehyde heat-resisting varnish of above-mentioned preparation are seen table 4-1.
Preparation technology: stir after above-mentioned each raw material assorted, with reference to XQ/G-51-0057-90 aluminium azoic coupling component aldehyde enamel paint standard detection, qualified after, packing promptly gets.
The purposes of aluminium azoic coupling component aldehyde heat-resisting varnish: be applicable to external coatings such as steam-heating pipe, scatterer, baking oven, flue, pipeline, equipment, guard rail rod.
Table 4-1 aluminium azoic coupling component aldehyde heat-resisting varnish (XQ/G-51-0057-90)
Embodiment five
1, the preparation of heat-resistant phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 50 parts of furane resin, 50 parts of rosin, 50 parts of NSC 7352s; 50 parts of terpine resins, 100 parts in water, 1 part in zinc oxide, 1 part of hexamethylenetetramine, 1 part of dimethyl amine; Add in the reaction kettle; Heat up, when system reaches 100 ℃, drip 50 parts in formaldehyde; After dripping off, under this temperature, kept 5 hours, make it abundant reaction; Detect oil soluble and solvability, work as resin: oleum lini=1:4, complete dissolving; Resin: toluene=1:1, complete dissolving, for qualified, blowing dries, and pulverizes, and obtains hardened resin, and is subsequent use;
(2) with 400 parts of above-mentioned hardened resin, 200 parts of talloleic acids, 30 parts of two methyl cyclopentadienes, 100 parts of tetramethylolmethanes, 80 parts of phthalic anhydrides, 50 parts of cis-butenedioic anhydrides, 3 parts in zinc oxide, 1 part of slaked lime, 30 parts of YLENE heat up, when system reaches 170 ℃; Keep 0.5h, 180 ℃ of 0.5h, 190 ℃ of 0.5h, 200 ℃ of 1h; 210 ℃ of 1h, 220 ℃ of 1h, 230 ℃ of 1h begin sampling; Survey viscosity and acid number, when the system viscosity is 10-15s, acid number is≤15mgKOH/g to be cooled to below 200 ℃; Use toluene: the mixed solvent latting drown that YLENE=1:1 processes is to viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 50%; Filter, packing promptly gets heat-resistant phenolic resins.
Through measuring, the performance index of heat-resistant phenolic resins are following:
Heat-resistant phenolic resins liquid viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 50% mixes resin liquid, manganese iso-octoate, isocaprylic acid zinc, isocaprylic acid cerium and silane coupling agent; Be painted on the model to be measured, its application property is good; Its application property is good, and surface drying≤1h does solid work≤10h; Behind the drying and forming-film, its snappiness 1mm, the 1h of anti-boiling water is non-foaming does not come off anti-120
#Solvent oiliness>=48h.
Add an amount of pigment, filler, can be made into coating such as phenolic aldehyde transparent varnish of all kinds, enamel paint, priming paint, rust-inhibiting paint, hard floor paint, steelwork lacquer.Add stratiform or vesicular fillers such as an amount of glass flake, graphite scale, zeyssatite, silicon-dioxide, can be made into phenolic aldehyde heat-resistant anticorrosive lacquer, thermotolerance reaches 300-400 ℃.
2, the preparation of the heat-resisting hammer paint of phenolic aldehyde of all kinds
Proportioning raw materials is seen table 5.
Table 5 proportioning raw materials
Preparation technology: with above-mentioned each raw material through pre-mixing; Be ground to below the fineness 50 μ m; With performances such as organic solvents such as toluene adjustment paint viscosity, this type of coating does not have respective standard, so according to product applications then; Detect qualified back packing with reference to ZB G 510 46-87 A16-51 standards.
The performance index of the heat-resisting hammer paint of silver-colored green phenolic aldehyde of method for preparing are seen table 5-1.
The Color harmony of the heat-resisting phenolic aldehyde hammer paint of phthalocyanine green, decorative pattern is attractive in appearance, easy construction, the room temperature air dry can be used for metal products surface anticorrosion, heat-resisting, high-decoration applications such as mechanical means, medicine equipment, instrument, metal door cabinet.
The heat-resisting hammer paint of table 5-1 phenolic aldehyde of all kinds (silver is green)
Embodiment six
1, the preparation of heat-resistant phenolic resins: with embodiment one.
2, the preparation of phenolic aldehyde heat-resistant enamel paint of all kinds
Because the phenolic aldehyde heat-resistant enamel paint gloss of this method preparation is high, anticorrosion resistance toheat is good, and the room temperature air dry is used for the anticorrosion and decorative painting of various product surfaces, and concrete proportioning raw materials is seen table 6.
Table 6 proportioning raw materials
Preparation technology: with above-mentioned each raw material through pre-mixing; Be ground to below the fineness 20 μ m; With performances such as organic solvents such as YLENE adjustment paint viscosity, this type of coating does not have respective standard, so according to product applications then; National standard with reference to F04-1 phenolic enamel of all kinds detects (ZB G51 020-87), qualified back packing.
The performance index of the phenolic aldehyde heat-resistant enamel paint of above-mentioned preparation are seen table 6-1.
Phenolic aldehyde heat-resistant enamel paint: be used for the protection and the decorative painting of metal, woodwork and building surface, especially can using in the hot environment more than 300 ℃.
Table 6-1 phenolic aldehyde heat-resistant enamel paint of all kinds
Claims (10)
1. being the heat-resistant phenolic resins of raw material with the cresols residue, is to be formed by following raw material and prepared:
Composition of raw materials: in weight part
100 parts of cresols residues, formaldehyde 10-100 part, vegetables oil or vegetable oil acid 10-200 part; Polyvalent alcohol 10-200 part; Polyprotonic acid 10-200 part, properties-correcting agent 10-200 part, composite catalyst
1-10 part; Composite catalyst II 1-50 part; Skimmer 0-10 part, organic solvent 10-50 part, water 1-200 part;
Preparation technology:
(1) with the cresols residue; Properties-correcting agent, composite catalyst
, water; Under agitation add in the reaction kettle; Be warming up to 50-300 ℃, add formaldehyde again, reacted 0.5-8 hour; Detect sylvic oil dissolubility and solvability, make the resin can be in toluene, siritch fully after the dissolving, dry, obtain hardened resin, pulverize, subsequent use;
(2) with above-mentioned hardened resin, vegetables oil or vegetable oil acid, polyvalent alcohol, polyprotonic acid, the composite catalyst II, skimmer, organic solvent under agitation adds reaction kettle, is warming up to 150-280 ℃, reacts 1-20 hour; Survey viscosity and acid number, when the system viscosity is 25 ℃ of 1-30s/ Ge Shi pipes, during solid acid number≤20mgKOH/g; Solids constituent 60 ± 20% cools to 150 ℃ to room temperature, uses organic solvent latting drown to viscosity to be 25 ℃ of 5-50s/ Ge Shi pipes; Filter, packing promptly gets heat-resistant phenolic resins.
2. be the heat-resistant phenolic resins of raw material with the cresols residue according to claim 1, it is characterized in that: said properties-correcting agent is at least a in NSC 7352, two methyl cyclopentadiene, petroleum resin, coumarone indene resin, furane resin, terpine resin, unsaturated carboxylic acid, the unsaturated acid anhydride.
3. be the method for feedstock production heat-resistant phenolic resins according to claim 1 with the cresols residue; It is characterized in that: said composite catalyst
is oxyhydroxide or oxide compound or vitriol by K, Na, Zn, Ca, Cu metals ion, mixes with 1 ~ 99%, 99 ~ 1% weight percent with aminated compounds; Said aminated compounds is at least a in ammoniacal liquor, hexamethylenetetramine, dimethyl amine, the triethylamine.
4. be the heat-resistant phenolic resins of raw material with the cresols residue according to claim 1, it is characterized in that: said organic solvent is at least a in toluene, YLENE, the aromatic solvent naphtha.
5. be the heat-resistant phenolic resins of raw material with the cresols residue according to claim 1, it is characterized in that: said vegetables oil or vegetable oil acid are siccative oil or its oleic acid of iodine number at 150-200g/100g.
6. be the heat-resistant phenolic resins of raw material with the cresols residue according to claim 1, it is characterized in that: said polyvalent alcohol is tetramethylolmethane, USP Kosher, at least a in the TriMethylolPropane(TMP).
7. be the heat-resistant phenolic resins of raw material with the cresols residue according to claim 1, it is characterized in that: said polyprotonic acid is at least a in PMA, pyromellitic acid dianhydride, the inclined to one side front three acid anhydrides of benzene, phthalic acid/acid anhydride, terephthalic acid, toxilic acid/acid anhydride, the fumaric acid.
8. be the method for feedstock production heat-resistant phenolic resins with the cresols residue according to claim 1, it is characterized in that: said composite catalyst II is at least a in oxyhydroxide or the oxide compound of Li, Ca, Pb, Mn metals ion.
9. be heat-resistant phenolic resins application in producing the heat-resistant anticorrosive lacquer of raw material according to claim 1 with the cresols residue.
10. of claim 9 is that the heat-resistant phenolic resins of raw material is used in producing the heat-resistant anticorrosive lacquer with the cresols residue, it is characterized in that:, ground through pre-mixing by the raw material of following weight part, packing promptly gets:
100 parts of heat-resistant phenolic resins
Glass flake 5-50 part
Graphite scale 0-50 part
Pigment 0-20 part
Filler 0-50 part
Auxiliary agent 1-10 part
Organic solvent 10-50 part
Above-mentioned filler is at least a in talcum powder, chalk powder, stone flour, silica powder, ground barium sulfate, light calcium carbonate, water-ground limestone, kaolin, zeyssatite, polynite, wilkinite, potter's clay, attapulgite, process white, silicon-dioxide, wollastonite, the zinc oxide;
Above-mentioned auxiliary agent is at least a in naphthenic soap, octylate, 2-ethylhexoate, dibutyl tin dilaurate, zirconium driers, rare earth drier, silane coupling agent, the titanate coupling agent;
Above-mentioned organic solvent is at least a in toluene, YLENE, the aromatic solvent naphtha.
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|---|---|---|---|
| CN2012102445890A CN102757620A (en) | 2012-07-16 | 2012-07-16 | Heat-resistant phenolic resin produced by taking cresol residues as raw material and application of heat-resistant phenolic resin in heat-resistant anti-corrosion paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102445890A CN102757620A (en) | 2012-07-16 | 2012-07-16 | Heat-resistant phenolic resin produced by taking cresol residues as raw material and application of heat-resistant phenolic resin in heat-resistant anti-corrosion paint |
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| CN114671988B (en) * | 2020-12-24 | 2023-10-17 | 上海彤程电子材料有限公司 | Multifunctional group-containing substituted benzyl phenolic polymer and preparation method and application thereof |
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Application publication date: 20121031 |