CN102002139B - Method for preparing modified phenolic resin for coating with cresol residue - Google Patents
Method for preparing modified phenolic resin for coating with cresol residue Download PDFInfo
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- CN102002139B CN102002139B CN2010105176346A CN201010517634A CN102002139B CN 102002139 B CN102002139 B CN 102002139B CN 2010105176346 A CN2010105176346 A CN 2010105176346A CN 201010517634 A CN201010517634 A CN 201010517634A CN 102002139 B CN102002139 B CN 102002139B
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Abstract
The invention provides a method for preparing modified phenolic resin for coating with cresol residue, belonging to the technical field of treatment and comprehensive use of cresol residues. The method uses effective functional groups of each compound in the cresol residue to prepare the cresol residue into modified phenolic resin which can be industrially prepared through a serial of chemical reactions. The modified phenolic resin can be directly used for preparing the corresponding coating so as to realize the zero waste exhaust in the production of the cresol, thereby fundamentally solving the pollution problem of the cresol, achieving the purpose of comprehensive treatment and changing waste into valuable; and simultaneously, the quality of the prepared coating product is better than the traditional industry standard, but the production cost is lower than that of the existing corresponding product. The method is simple in production technique, little in device investment, strong in enablement, low in comprehensive cost, and obvious in economical benefit.
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 method for feedstock production modified phenolic resins with the cresols residue; The present invention also relates to the application of modified phenolic resins in producing coating simultaneously.
Background technology
Cresols has another name called paracresylol, colourless crystallization; 30.9 ℃ of fusing points have the phenol smell, and are flammable; It is the general designation of ortho-cresol, meta-cresol, three kinds of isomer mixtures of p-cresol; Similar with the chemically reactive and the toxicity of phenol, be widely used in fields such as medicine, health, agricultural chemicals, spices, dyestuff, oxidation inhibitor, stopper, softening agent, UV light absorber, tensio-active agent, coating, tackiness agent and synthetic resins, be the fine chemical product that supply falls short of demand both at home and abroad.
Along with technical development, widening of cresols and verivate thereof and derived product stimulates and promoted the consumption and the demand of cresols product more, makes cresols production and application appear good growth momentum suddenly.But along with cresols output is uprushed, its cresols level of residue also grows with each passing day.In the cresols residue except that containing a large amount of residual cresols (adjacent// p-cresol); Also contain other a large amount of mixed phenol (phenol, dihydroxy-benzene, cresorcin, tolyl cresylol, tolyl first biphenol, tolyl dihydroxy-benzene, tolyl pyrogallol etc.), mixed ether (methyl-phenoxide, toluene methyl ether, ditolyl ether etc.), mix quinone (benzoquinones, toluquinone, tolyl benzoquinones, tolyl toluquinone etc.), ketone (diformazan benzophenone etc.), benzoyl toluene, inorganic salt slag (sodium sulfate, ferrous sulfate, tosylate etc.), ash content, water, polyaromatic oligopolymer and polyaromatic superpolymer 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 all contains aromatic ring, some high volatility, and some is water-soluble, and some is insoluble molten, causes atmospheric pollution, water pollution, soil pollution, makes environmental degradation, has a strong impact on ecotope and HUMAN HEALTH, influences the establishment of harmonious environment.It is outstanding that environmental pollution also more shows, and the disposal of waste gas, water and industrial residue difficulty 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 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; Also make the entire treatment flow process complicated simultaneously, investment is big, and the enterprise pollution processing cost is increased substantially.Therefore, it is extremely urgent to widen cresols residue treatment channel!
Summary of the invention
The objective of the invention is the problem that exists in the processing that solves prior art p-cresol residue, realize the recycling of cresols residue, providing a kind of is the method for feedstock production modified phenolic resins with the cresols residue.
Another object of the present invention provides the application of a kind of above-mentioned modified phenolic resins in preparation coating.
(1) preparation of modified phenolic resins
The preparation method of modified phenolic resins of the present invention comprises following process step:
(1) be with cresols residue 100 weight parts, properties-correcting agent 1-500 weight part, water 1-200 weight part, composite catalyst 0.1-10 weight part; Add in the reaction kettle, be warming up to 50-300 ℃, in reaction kettle, add formaldehyde 1-100 weight part; Reacted 0.5-8 hour, detection is dried after dissolving fully; Obtain hardened resin, pulverize, subsequent use;
(2) with above-mentioned hardened resin 100 weight parts, vegetables oil or vegetable oil acid 10-500 weight part, polyvalent alcohol 10-500 weight part, polyprotonic acid 10-500 weight part; Composite catalyst 0.1-50 weight part; Skimmer 0-10 weight part, organic solvent 1-50 weight part adds reaction kettle; Be warming up to 180-280 ℃, reacted 1-20 hour; Survey viscosity and acid number, when the system viscosity is 25 ℃ of 5-10s/ Ge Shi pipes, during acid number≤15mgKOH/g, cool to 200 ℃ to room temperature; Use organic solvent latting drown to viscosity to be 25 ℃ of 10-30s/ Ge Shi pipes, acid number≤15mgKOH/g, solids constituent 60 ± 20%; Filter, packing promptly gets modified phenolic resins; The metering of above-mentioned each raw material is weight part.
Said properties-correcting agent is at least a in rosin, petroleum resin, coumarone indene resin, NSC 7352, the methyl cycle pentadiene dimer.The effect of properties-correcting agent is the oil soluble that improves resol.
Said composite catalyst is by the oxyhydroxide of K, Na, Mg, Zn, Ca, Ba, Cu, Ni, Co, Pb, Mn, Cr, Fe metals ion or oxide compound or salt, 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 can form the inner complex of metallic compound with reactant when playing katalysis, thereby has improved the performance of modified resin.
Said organic solvent is 200
#Solvent oil, YLENE, aromatic solvent naphtha (like lightweight benzene, heavy benzene etc.) or 120
#Solvent.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 dryness or semi-drying oil or its oleic acid of iodine value at 100-160g/100g.Like soya-bean oil, oleum lini, Semen Maydis oil, Oleum Gossypii semen, dehydrated castor wet goods vegetables oil or vegetable oil acid, its effect is as the staple of painting the film thing from dryness, also changes resin viscosity simultaneously, improves coating application property and sticking power.
Said polyvalent alcohol is tetramethylolmethane, USP Kosher, at least a in TriMethylolPropane(TMP), terepthaloyl moietie, glycol ether, the tetraethylene-glycol.The effect of polyvalent alcohol is to improve resin's crosslinkage, reduces resinous acid value, improves the coating stability in storage.
Said polyprotonic acid is at least a in phenylformic acid, phthalic acid/acid anhydride, terephthalic acid, toxilic acid/acid anhydride, fumaric acid, hexanodioic acid, the pentanedioic acid.The effect of polyprotonic acid is to improve resin's crosslinkage and paint film adhesion.
Said skimmer be silicone based (like silicone oil, silicone, ZGK 5 etc.), polyethers (polyethers,?,?) 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.
The modification mixed phenol urea formaldehyde of the present invention's preparation, its resin liquid performance index are viscosity 10-30s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 60 ± 20%; With resin liquid direct brushing (being equivalent to process corresponding phenolic varnish), its application property is good, and surface drying time≤5h does solid work time≤15h, behind the drying and forming-film, and its gloss>=110%, snappiness 1mm, after tackiness≤2 grade, water tolerance>=48h, anti-120
#Solvent oiliness>=48h.
Can find out from above-mentioned performance index, the modified phenolic resins of the present invention preparation, this coating have that rate of drying is fast, sticking power good, hardness is big, water tolerance and solvent resistance is strong, in jar skinning not, open advantages such as jar is effective.Thereby can be used for producing coating such as serial phenolic antirust paint, phenolic aldehyde antifouling paste, phenolic ready-mixed paint, ester gum ready mixed paint, prepared alkyd paint, alcohol acid antirust paint, be applicable to chemical plant, pipeline and indoor and outdoor external coating.
(2) preparation of coating
Feed proportioning: in weight part
100 parts of modified phenolic resinss
Pigment 1-100 part
Filler 0-200 part
Auxiliary agent 0.1-10 part
Organic solvent 1-100 part
Assisted resin 0-100 part
Above-mentioned filler is 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, zinc oxide, Zinic stearas or zn phosphate;
Above-mentioned auxiliary agent is with naphthenic soap (like calcium naphthenate, manganese, lead, zinc, cobalt and mixture thereof), 2-ethylhexoate (like calcium iso-octoate, manganese, lead, zinc, cobalt and mixture thereof), zirconium driers, rare earth drier; Its effect is to improve the coating drying property.
Above-mentioned organic solvent is 200
#Solvent oil, YLENE, aromatic solvent naphtha or 120
#Solvent;
Above-mentioned assisted resin is Synolac, alkyd mediation resin or epoxy resin;
Preparation technology: above-mentioned each raw material through pre-mixing, is ground packing.
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 modified phenolic resins of suitability for industrialized production; Product need not to separate, and then directly is used to prepare corresponding coating, has 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 modified phenolic resins 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; The coating products quality of preparation is superior to existing industry standard, and production cost is lower than the cost of existing corresponding product.
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 modified phenolic resins of the present invention and the preparation of phenolic coating are described further below.
The preparation of embodiment 1, modified phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 200 parts of rosin, 20 parts in water, CuSO
40.3 0.5 part of part, hexamethylenetetramine add in the reaction kettle, heat up, and when system reaches 90 ℃, drip 50 parts in formaldehyde; After dripping off, under this temperature, kept 3 hours, make it abundant reaction; Add 25 parts of tetramethylolmethanes then, continue to heat up, kept 2 hours down, keep beginning to survey acid number, oil soluble and solvability behind the 2h down at 270 ℃ at 180-200 ℃; As acid number≤20mgKOH/g, portions of resin oleum lini=1: 4, complete dissolving; Portions of 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 behenic acids, 45 parts of tetramethylolmethanes, 40 parts of phthalic anhydrides, 0.2 part of silicone oil; 20 parts of YLENE add reaction kettle, are warming up to 220 ℃; Reacted 2 hours, and began sampling, survey viscosity and acid number; When the system viscosity is 5-10s (Ge Shi pipe 25 ℃), acid number is≤15mgKOH/g to be cooled to below 200 ℃; With 200
#The solvent oil latting drown is to viscosity 10-20s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, and solids constituent 70 ± 2% is filtered, and packing promptly get modified phenolic resins and lowers the temperature.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of modified phenolic resins are following:
Modification mixed phenol urea formaldehyde fluidity can index be viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤10mgKOH/g, solids constituent 70 ± 2%; With resin liquid direct brushing (being equivalent to process corresponding phenolic varnish), its application property is good, and surface drying≤5h does solid work≤15h, behind the drying and forming-film, and its gloss (20 °)>=130%, snappiness 1mm, after tackiness≤2 grade, the 0.5h of anti-boiling water is non-foaming does not come off anti-120
#Solvent oiliness>=48h.Can be used for preparing coating such as phenolic ready-mixed paint, phenolic enamel, prepared alkyd paint, ester gum ready mixed paint, also can be used for phenolic antirust paint and phenolic primer.
The preparation of embodiment 2, modified phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 50 parts of rosin, 100 parts of petroleum resin, 50 parts in water, 1 part of zinc acetate, 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 sylvic oil dissolubility and solvability (portions of resin oleum lini=1: 4, complete dissolving; Portions of 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 250 parts of above-mentioned hardened resin, 100 parts of oleum lini, 45 parts of tetramethylolmethanes, be warming up to 240 ℃, keep 2h after, detect pure dissolubility, when portions of resin ethanol (95%)>=1: 5 is qualified; Be cooled to 200 ℃ again, add 60 parts of phthalic anhydrides, 8 parts of zinc acetates, 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 8-12s, acid number is≤15mgKOH/g to be cooled to below 200 ℃, with 200
#Solvent oil and aromatic solvent naphtha latting drown be to viscosity 10-20s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, and solids constituent 70 ± 2% is filtered, and packing promptly get modified phenolic resins and lowers the temperature.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of modified phenolic resins are following:
The modified phenolic resins fluidity can index be viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 70 ± 2%; With resin liquid direct brushing (being equivalent to process corresponding phenolic varnish), its application property is good, and surface drying≤5h does solid work≤15h, behind the drying and forming-film, and its snappiness 1mm, after tackiness≤2 grade, water tolerance>=48h, anti-120
#Solvent oiliness>=48h.Can be used for preparing coating such as phenolic antirust paint, alcohol acid antirust paint, phenolic aldehyde primer for rusty surface.
The preparation of embodiment 3, modified 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, portions of resin oleum lini=1: 4, complete dissolving; Portions of 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 in soya-bean oil, 60 parts of tetramethylolmethanes, be warming up to 240 ℃, behind the maintenance 2h, detect pure dissolubility; When portions of resin ethanol (95%)>=1: 5 is qualified, be cooled to 200 ℃ again, add 50 parts of phthalic anhydrides, 10 parts in phenylformic acid, 10 parts of cis-butenedioic anhydrides, 7 parts in zinc oxide, 0.2 part of polyethers, 40 parts of YLENE; Continue to heat up, 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 to be cooled to below 200 ℃, with 200
#With 120
#Solvent oiliness latting drown is to viscosity 10-20s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, and solids constituent 70% is filtered, and packing promptly get modified phenolic resins and lowers the temperature.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of modified phenolic resins are following:
The modified phenolic resins fluidity can index be viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤15mgKOH/g, solids constituent 70 ± 2%; With resin liquid direct brushing (being equivalent to process corresponding phenolic varnish), its application property is good, and surface drying≤5h does solid work≤15h, behind the drying and forming-film, and its snappiness 1mm, after tackiness≤2 grade, water tolerance>=48h, anti-120
#Solvent oiliness>=48h.Can be used for preparing coating such as phenolic antirust paint, alcohol acid antirust paint, phenolic aldehyde primer for rusty surface.
The preparation of embodiment 4, modified phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 100 parts of rosin, 100 parts of petroleum resin, 200 parts in water, 0.5 part of slaked lime, 1 part of hexamethylenetetramine, 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, when portions of resin oleum lini=1: 4, complete dissolving; Portions of 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, 500 parts of behenic acids, 30 parts of NSC 7352s, 150 parts of tetramethylolmethanes, 50 parts of glycol ethers, 180 parts of phthalic anhydrides, 20 parts of cis-butenedioic anhydrides, 5 parts in zinc oxide continue slowly to heat up; When system reaches 150 ℃, keep 0.5h, 170 ℃ of 0.5h, 200 ℃ of 1h; 220 ℃ of 1h begin sampling, survey viscosity and acid number, when the system viscosity is 5-10s; Acid number is≤10mgKOH/g to be cooled to below 200 ℃, with 200
#Solvent wet goods latting drown is to viscosity 10-20s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, and solids constituent 70 ± 2% is filtered, and packing promptly gets modified phenolic resins.The metering of above-mentioned each raw material is weight part.
Through measuring, the performance index of modified phenolic resins are following:
The modified phenolic resins fluidity can index be viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤10mgKOH/g, solids constituent 70 ± 2%; With resin liquid direct brushing (being equivalent to process corresponding phenolic varnish), its application property is good, and surface drying≤4h does solid work≤10h, behind the drying and forming-film, and its gloss (20 °)>=130%, snappiness 1mm, after tackiness≤1 grade, the 1h of anti-boiling water is non-foaming does not come off anti-120
#Solvent oiliness>=48h.Can be used for preparing coating such as phenolic enamel, phenolic ready-mixed paint, prepared alkyd paint, ester gum ready mixed paint, also can be used for phenolic antirust paint and phenolic primer.
The preparation of embodiment 5, modified phenolic resins
(1) accurately takes by weighing 100 parts of cresols residues, 100 parts of petroleum resin, 150 parts of coumarone indene resins; 1 part of 50 parts of rosin, 100 parts in water, zinc oxide 1 phenol, hexamethylenetetramine 1, 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, when portions of resin oleum lini=1: 4, complete dissolving; Portions of 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, 30 parts of YLENE, 300 parts of oleic acids, 30 parts of methyl cycle pentadiene dimers, 100 parts of tetramethylolmethanes, 20 parts of Tri Ethyleneglycols, 100 parts of phthalic anhydrides, 10 parts of cis-butenedioic anhydrides, 20 parts in phenylformic acid, 5 parts in zinc oxide continue to heat up; When system reaches 160 ℃, keep 0.5h, 180 ℃ of 0.5h; 200 ℃ of 1h, 220 ℃ of 1h, 230 ℃ of 1h; Begin sampling, survey viscosity and acid number, when the system viscosity is 5-10s; Acid number is≤15mgKOH/g to be cooled to below 200 ℃, with 200
#Solvent wet goods latting drown is to viscosity 10-20s (Ge Shi pipe 25 ℃), acid number≤15mgKOH/g, and solids constituent 70% is filtered, and packing promptly gets modified phenolic resins.
Through measuring, the performance index of modified phenolic resins are following:
The modified phenolic resins fluidity can index be viscosity 10-20s (25 ℃ of Ge Shi pipes), acid number≤10mgKOH/g, solids constituent 70 ± 2%; With resin liquid direct brushing (being equivalent to process corresponding phenolic varnish), its application property is good, and surface drying≤4h does solid work≤10h, behind the drying and forming-film, and its gloss (20 °)>=130%, snappiness 1mm, after tackiness≤1 grade, the 1h of anti-boiling water is non-foaming does not come off anti-120
#Solvent oiliness>=48h.Can be used for preparing coating such as phenolic enamel, phenolic ready-mixed paint, prepared alkyd paint, ester gum ready mixed paint, also can be used for phenolic antirust paint and phenolic primer.
The preparation of embodiment 6, phenolic ready-mixed paint
Proportioning raw materials is seen table 1.
Table 1
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 1 preparation | 56 | Organobentonite | Technical grade | 1 |
| The hard carbon black | Technical grade | ～0.1 | Talcum powder | Technical grade | 18 |
| Zinc sulfide white | Technical grade | 7 | Rare earth drier | W-2000 | 2 |
| White titanium pigment | Technical grade | 3 | 200 #Solvent etc. | Technical grade | 5 |
| Light calcium carbonate | Technical grade | 8 | Add up to | 100 |
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 40 μ m, uses 200 then
#Projects such as solvent wet goods organic solvent adjustment paint viscosity press XQ/G-51-0021-90 standard (also can detecting according to company standard separately), detects qualified after, pack, promptly get the grey phenolic ready-mixed paint of F03-1.
The performance index of the phenolic ready-mixed paint of preparation are seen table 1-1.
Table 1-1 F03-1 phenolic ready-mixed paint of all kinds (XQ/G-51-0021-90)
The purposes of phenolic ready-mixed paint: be applicable to indoor and outdoor common metal and wood surface application.
The preparation of embodiment 7, aluminium azoic coupling component aldehyde enamel paint
Proportioning raw materials is seen table 2.
Table 2
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 4 preparations | 60 | 200 #Solvent etc. | Technical grade | 23 |
| Aluminium paste | Floating type | 10 | Rare earth drier | W-2000 | 2 |
| YLENE | Technical grade | 5 | Add up to | 100 |
Preparation technology: stir after above-mentioned each raw material assorted, press XQ/G-51-0057-90 standard (also can detecting) according to company standard separately, detects qualified after, pack, promptly get F04-1 aluminium azoic coupling component aldehyde enamel paint.
The performance index of the aluminium azoic coupling component aldehyde enamel paint of above-mentioned preparation are seen table 2-1.
Table 2-1 F04-1 aluminium azoic coupling component aldehyde enamel paint (XQ/G-51-0057-90)
The purposes of aluminium azoic coupling component aldehyde enamel paint: be applicable to external coatings such as steam-heating pipe, scatterer, guard rail rod, pipeline, equipment.
The preparation of embodiment 8, phenolic primer
Proportioning raw materials: see table 3.
Table 3
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 2 preparations | 30 | Organobentonite | Technical grade | 1 |
| The hard carbon black | Technical grade | ～0.1 | 200 #Solvent oil | Technical grade | 8 |
| Zinc sulfide white | Technical grade | 10 | Zinc naphthenate | Technical grade | 0.5 |
| The CT rust-stabilising pigment | Technical grade | 19 | Calcium naphthenate | Technical grade | 1.5 |
| Light calcium carbonate | Technical grade | 10 | Cobalt naphthenate | Technical grade | 0.1 |
| Stone flour | Technical grade | 20 | Add up to | 100 |
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 60 μ m then 200
#Projects such as solvent wet goods organic solvent adjustment paint viscosity, press XQ/G-51-0023-90 (also can detecting) according to company standard separately detect qualified after, packing promptly gets the grey phenolic primer of F06-1.
The performance index of phenolic primer are seen table 3-1.
Table 3-1 F06-1 phenolic primer of all kinds (XQ/G-51-0023-90)
The purposes of phenolic primer: be used for the bottoming of iron and steel and wood surface.
The preparation of embodiment 9, iron oxide red phenolic aldehyde primer for rusty surface
Proportioning raw materials: see table 4.
Table 4
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 3 preparations | 32 | The CT rust-stabilising pigment | Technical grade | 13 |
| Iron oxide red | Technical grade | 10 | Cobalt naphthenate | Technical grade | 0.1 |
| Zinc oxide | Technical grade | 10 | Zinc naphthenate | Technical grade | 0.4 |
| Stone flour | Technical grade | 20 | Calcium naphthenate | Technical grade | 1.5 |
| Zn phosphate | Technical grade | 4 | 200 #Solvent oil | Technical grade | 7 |
| Organobentonite | Technical grade | 2 | Add up to | 100 |
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 50 μ m, uses 200 then
#Projects such as solvent wet goods organic solvent adjustment paint viscosity, press XQ/G-51-0025-90 (also can detecting) according to company standard separately detect qualified after, pack, promptly get F06-15 iron oxide red phenolic aldehyde primer for rusty surface.
The performance index of the iron oxide red phenolic aldehyde primer for rusty surface of above-mentioned preparation are seen table 4-1.
Table 4-1 F06-15 iron oxide red phenolic aldehyde primer for rusty surface (XQ/G-51-0025-90)
The iron oxide red phenolic aldehyde primer for rusty surface purposes of above-mentioned preparation: be used for the bottoming of iron and steel (whether corrosion all can) and wood surface.
The preparation of embodiment 10, phenolic antirust paint
Proportioning raw materials: see table 5.
Table 5
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 4 preparations | 40 | Attapulgite | Technical grade | 1 |
| Red lead | Technical grade | 5 | Stone flour | Technical grade | 14 |
| Medium chrome yellow medium yellow | Technical grade | 7 | Cobalt naphthenate | Technical grade | 0.1 |
| Yellow oxide of iron | Technical grade | 3 | Calcium naphthenate | Technical grade | 1.0 |
| 986 reds | Technical grade | 0.5 | Zinc naphthenate | Technical grade | 0.4 |
| The CT rust-stabilising pigment | Technical grade | 10 | 200 #Solvent etc. | Technical grade | 8 |
| Light calcium carbonate | Technical grade | 5 | |||
| Zinc oxide | Technical grade | 5 | Add up to | 100 |
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 60 μ m, uses 200 then
#Projects such as solvent wet goods organic solvent adjustment paint viscosity, press ZB G51 090-87 (also can detecting) according to company standard separately detect qualified after, pack, promptly get F53-31 red lead phenolic antirust paint.
The performance index of the phenolic antirust paint of above-mentioned preparation are seen table 5-1.
Table 5-1 phenolic antirust paint of all kinds
The purposes of phenolic antirust paint: be applicable to the application of steel surface, make the usefulness of antirust bottoming.
The preparation of embodiment 11, phenolic aldehyde ester gum ready mixed paint
Proportioning raw materials: see table 6.
Table 6
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 5 preparations | 40 | Organobentonite | Technical grade | 1 |
| White titanium pigment | Technical grade | 10 | 200 #Solvent oil | Technical grade | 7 |
| Process white | Technical grade | 10 | Cobalt iso-octoate | Technical grade | 0.3 |
| Phthalocyanine blue | Technical grade | 4 | Isocaprylic acid zinc | Technical grade | 0.7 |
| Talcum powder | Technical grade | 7 | Calcium iso-octoate | Technical grade | 2 |
| Stone flour | Technical grade | 18 | Add up to | 100 |
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to below the fineness 40 μ m, uses 200 then
#Projects such as solvent wet goods organic solvent adjustment paint viscosity, press ZB/TG51089-87 (also can detecting) according to company standard separately detect qualified after, pack, promptly get the peacock blue ester gum ready mixed paint of T03-1.
The performance index of the phenolic aldehyde ester gum ready mixed paint of above-mentioned preparation are seen table 6-1.
Table 6-1 T03-1 ester gum ready mixed paint of all kinds (ZB/TG51089-87)
The purposes of phenolic aldehyde ester gum ready mixed paint: be used for the application of indoor and outdoor common metal, wooden object and building surface, make the usefulness of protection and decoration.
The preparation of embodiment 12, prepared alkyd paint of all kinds
Proportioning raw materials: see table 7.
Table 7
| Raw material | Specification | Weight part (Kg) | Raw material | Specification | Weight part (Kg) |
| Modified phenolic resins | Embodiment 4 preparations | 50 | 200 #Solvent oil | Technical grade | 7 |
| Medium chrome yellow medium yellow | Technical grade | 10 | Process white | Technical grade | 5 |
| Yellow oxide of iron | Technical grade | 5 | Isocaprylic acid zinc | Technical grade | 0.7 |
| 986 reds | Technical grade | 3 | Calcium iso-octoate | Technical grade | 2.5 |
| Organobentonite | Technical grade | 2 | Cobalt iso-octoate | Technical grade | 0.5 |
| Talcum powder | Technical grade | 15 | Add up to | 100 |
Preparation technology: above-mentioned each raw material through pre-mixing, is ground to fineness 35 following μ m, uses 200 then
#Projects such as solvent wet goods organic solvent adjustment paint viscosity, press HG/T 2455-1993 (also can detecting) according to company standard separately detect qualified after, pack, promptly get the orange prepared alkyd paint of C03-1.
The performance index of the glue priming paint of above-mentioned preparation are seen table 7-1.
Table 7-1 C03-1 prepared alkyd paint of all kinds (HG/T 2455-1993)
The purposes of prepared alkyd paint: be used to apply common metal, wooden object and building surface, play protection and decoration function.
Claims (10)
1. be the method for feedstock production modified phenolic resins with the cresols residue, comprise following process step:
(1) be with cresols residue 100 weight parts, properties-correcting agent 1-500 weight part, water 1-200 weight part, composite catalyst 0.1-10 weight part; Add in the reaction kettle, be warming up to 50-300 ℃, in reaction kettle, add formaldehyde 1-100 weight part; Reacted 0.5-8 hour, detection is dried after dissolving fully; Obtain hardened resin, pulverize, subsequent use;
(2) with above-mentioned hardened resin 100 weight parts, vegetables oil or vegetable oil acid 10-500 weight part, polyvalent alcohol 10-500 weight part, polyprotonic acid 10-500 weight part; Composite catalyst 0.1-50 weight part; Skimmer 0-10 weight part, organic solvent 1-50 weight part adds reaction kettle; Be warming up to 180-280 ℃, reacted 1-20 hour; Survey viscosity and acid number, when the system viscosity is 25 ℃ of 5-10s/ Ge Shi pipes, during solid acid number≤20mgKOH/g; Cool to 200 ℃ to room temperature, use organic solvent latting drown to viscosity to be 25 ℃ of 5-50s/ Ge Shi pipes, solid acid number≤15mgKOH/g; Solids constituent 60 ± 20%; Filter, packing promptly gets modified phenolic resins; The metering of above-mentioned each raw material is weight part.
2. be the method for feedstock production modified phenolic resins with the cresols residue according to claim 1, it is characterized in that: said properties-correcting agent is at least a in rosin, petroleum resin, coumarone indene resin, NSC 7352, the methyl cycle pentadiene dimer.
3. be the method for feedstock production modified phenolic resins according to claim 1 with the cresols residue; It is characterized in that: said composite catalyst is by the oxyhydroxide of K, Na, Mg, Zn, Ca, Ba, Cu, Ni, Co, Pb, Mn, Cr, Fe metals ion or oxide compound or salt, 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 method for feedstock production modified phenolic resins with the cresols residue according to claim 1, it is characterized in that: said organic solvent is 200
#Solvent oil, YLENE, aromatic solvent naphtha or 120
#Solvent oil.
5. be the method for feedstock production modified phenolic resins with the cresols residue according to claim 1, it is characterized in that: said vegetables oil or vegetable oil acid are dryness or semi-drying oil or its oleic acid of iodine value at 100-160g/100g.
6. be the method for feedstock production modified phenolic resins with the cresols residue according to claim 1, it is characterized in that: said polyvalent alcohol is tetramethylolmethane, USP Kosher, at least a in TriMethylolPropane(TMP), terepthaloyl moietie, glycol ether, the tetraethylene-glycol.
7. be the method for feedstock production modified phenolic resins with the cresols residue according to claim 1, it is characterized in that: said polyprotonic acid is at least a in phthalic acid/acid anhydride, terephthalic acid, toxilic acid/acid anhydride, fumaric acid, hexanodioic acid, the pentanedioic acid.
8. be the method for feedstock production modified phenolic resins with the cresols residue according to claim 1, it is characterized in that: said skimmer is silicone based, polyethers or polyacrylic polymer.
9. the modified phenolic resins of method preparation is used in producing coating according to claim 1.
10. like the application of the said modified phenolic resins of claim 9 in producing coating, it is characterized in that: raw material and prepared by following prescription form: feed proportioning: in weight part
100 parts of modified phenolic resinss
Pigment 1-100 part
Filler 0-200 part
Auxiliary agent 0.1-10 part
Organic solvent 1-100 part
Assisted resin 0-100 part
Above-mentioned filler is stone flour, kaolin, zeyssatite, polynite, wilkinite, potter's clay, attapulgite, process white, silicon-dioxide, zinc oxide, Zinic stearas or zn phosphate;
Above-mentioned auxiliary agent is naphthenic soap, 2-ethylhexoate, zirconium driers or rare earth drier;
Above-mentioned organic solvent is 200
#Solvent oil, YLENE, aromatic solvent naphtha or 120
#Solvent oil;
Above-mentioned assisted resin is Synolac, alkyd mediation resin or epoxy resin;
Preparation technology: above-mentioned each raw material through pre-mixing, is ground packing.
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| CN102492340B (en) * | 2011-11-28 | 2013-06-05 | 兰州石化职业技术学院 | Preparation method of perchloroethylene anticorrosion static conductive coating |
| CN102757620A (en) * | 2012-07-16 | 2012-10-31 | 兰州石化职业技术学院 | 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 |
| CN102757544B (en) * | 2012-07-16 | 2014-06-11 | 兰州石化职业技术学院 | High-hydroxy phenolic resin prepared by using phenols residues as raw material, and application of high-hydroxy phenolic resin to production of high-temperature-resistant paint |
| CN103467682B (en) * | 2013-08-20 | 2015-05-13 | 计菁婕 | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method |
| CN104312364A (en) * | 2013-11-14 | 2015-01-28 | 青岛伊森化学有限公司 | Anti-rust paint and preparation method thereof |
| CN104086728A (en) * | 2014-07-25 | 2014-10-08 | 广西众昌树脂有限公司 | Preparation method of modified phenolic resin |
| CN104387823A (en) * | 2014-11-05 | 2015-03-04 | 蚌埠金宇印刷物资有限公司 | Phenolic aldehyde antirust coating and preparation method thereof |
| CN107177244A (en) * | 2017-07-20 | 2017-09-19 | 苏州文仓乐器有限公司 | A kind of metal musical instrument blackish green phenolic resin coating |
| CN107177241A (en) * | 2017-07-20 | 2017-09-19 | 苏州文仓乐器有限公司 | A kind of metal musical instrument red phenolic resin coating |
| CN107384114A (en) * | 2017-08-16 | 2017-11-24 | 天津市津海特种涂料装饰有限公司 | A kind of phenolic group antirust paint |
| CN111138870B (en) * | 2019-02-14 | 2022-03-22 | 兰州石化职业技术学院 | Cresol residue modified asphalt and preparation method and application thereof |
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| JPS63305116A (en) * | 1987-06-05 | 1988-12-13 | Aisin Chem Co Ltd | Reuse of concentrated solution formed in phenolic resin production |
| CN100516127C (en) * | 2006-03-22 | 2009-07-22 | 北京林业大学 | Phenolic resin additive, phenolic resin with the additive and its preparation process |
| US20080073615A1 (en) * | 2006-07-24 | 2008-03-27 | Sumitomo Chemical Company, Limited | Method for producing resorcin/formaldehyde resin |
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