CN109023322A - A kind of aqueous epithelium liquid and preparation method thereof instead of phosphating solution - Google Patents
A kind of aqueous epithelium liquid and preparation method thereof instead of phosphating solution Download PDFInfo
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- CN109023322A CN109023322A CN201811032170.2A CN201811032170A CN109023322A CN 109023322 A CN109023322 A CN 109023322A CN 201811032170 A CN201811032170 A CN 201811032170A CN 109023322 A CN109023322 A CN 109023322A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A kind of aqueous epithelium liquid instead of phosphating solution, raw material including following parts by weight: 30-100 parts of water, 5-10 parts of polar solvent, 1-3 parts of fatty alcohol polyoxyethylene ether nonionic surfactant (AEO), 1-5 parts of alkyl trimethyl ammonium chloride cationic surfactant, 10-30 parts of resol resins, 20-50 parts of water-based emulsion；Replace traditional tannic acid as derusting and converting agent of iron rust a kind of new structural water soluble phenol resin, the shortcomings that overcoming Vehicles Collected from Market product, develop the better oil removing of performance, derusting, phosphatization and passivation four-in-one phosphating solution substitute products, and not phosphoric acid, without heavy metal, the product of the real environmental protection of no acid pickle discharge, the pretreatment before the coating of large-scale workpiece, steelframe, pipeline, metal furniture, door and window, vehicle, ship, bridge, equipment lathe of operation etc. is not easy to suitable for conventional phosphatizing.
Description
Technical field
The chemical surface treatment and corrosion-resistant field of steel of the present invention, and in particular to a kind of aqueous epithelium liquid instead of phosphating solution
And preparation method thereof.
Background technique
The external coating pre-treatment of present steel product is mainly phosphating process, and a full set of technique will generally pass through oil removing, remove
Four procedures such as rust, phosphatization and passivation.Not only long processing period, and to generate in the process a large amount of phosphorous and heavy metal useless
Acid solution, under the increasingly severe major premise of environmental protection pressure, it is necessary to develop environment-friendly high-efficiency, to replace conventional phosphatizing technique,
Realize the novel product of economic benefit and social benefit.
In this context, so-called oil removing, derusting, phosphatization and the product for being passivated four-in-one have been had already appeared in the market, still
Actual effect is barely satisfactory, is mainly manifested in the disadvantages of deoiling effect is poor or adhesive force is not good enough or rotproofness is inadequate, in addition still
Contain phosphoric acid or heavy metal etc..
Such as, application No. is 201710843595.0 to disclose a kind of formula of four-in-one acid-washing phosphating solution, wherein in addition to containing
Have outside phosphoric acid, also containing heavy metals such as tin and molybdenums；Application number 2016103737470 discloses a kind of with oil removing, derusting, phosphatization
With the phosphating solution of the comprehensive function of passivation, the heavy metals such as copper and mickel are contained in addition to phosphoric acid；2014102123148 disclosure of application number
It is a kind of with derusting, oil removing, phosphorization filming and the phosphating solution for the functions such as being passivated, but phosphating solution contains phosphoric acid components.
Summary of the invention
To solve above-mentioned problem of the prior art, the present invention provides a kind of instead of the aqueous epithelium liquid of phosphating solution and its preparation
A kind of new structural water soluble phenol resin is replaced traditional tannic acid as derusting and converting agent of iron rust, overcome by method
The shortcomings that Vehicles Collected from Market product, develops the better oil removing of performance, derusting, phosphatization and passivation four-in-one phosphating solution substitute products,
And not phosphoric acid is free of heavy metal, the product of the real environmental protection of no acid pickle discharge.
In order to reach the goals above, the present invention takes following technical scheme:
A kind of aqueous epithelium liquid instead of phosphating solution, the raw material including following parts by weight: 30-100 parts of water, polar solvent 5-
10 parts, 1-3 parts of fatty alcohol polyoxyethylene ether nonionic surfactant (AEO), alkyl trimethyl ammonium chloride cationic surface is lived
1-5 parts of agent, 10-30 parts of resol resins, 20-50 parts of water-based emulsion of property.
Furtherly, the water-based emulsion is film forming agent, belongs to corrosion-resistant antirust emulsion, is acrylic emulsions, PVDC
Lotion, polyaminoester emulsion, polyurethane-modified acrylic acid lotion, acrylic acid modified polyurethane dispersion liquid it is one or more.
Furtherly, the polar solvent be ethyl alcohol, acetone, isopropanol, glycol dimethyl ether, ethylene glycol diethyl ether one
Kind is a variety of.
The present invention also provides a kind of preparation methods of aqueous epithelium liquid instead of phosphating solution, comprising the following steps:
1) formalin that alkyl phenol and volume fraction are 37% preparation of resol resins: is put into reaction kettle
In, stirring allows alkyl phenol to dissolve, and a small amount of basic catalyst is then added dropwise, and is heated to 70-90 degrees Celsius and reacts 2 hours, is cooled to
Then acidic catalyst and tannin is added in 40-50 degree, react 1-3 hours, water soluble phenol resin can be obtained；
2) water soluble phenol resin obtained by step 1) is added in the water in reaction kettle, is then added while stirring aqueous
Lotion, sequentially adds various surfactants after mixing evenly, and the defoaming relative to solution total amount 0.2-0.5% is finally added dropwise
Agent is to get the aqueous epithelium liquid arrived instead of phosphating solution.
Furtherly, the alkyl phenol in the step 1) is tannic acid, even trisphenol, mesitylene phenol, resorcinol, adjacent benzene
Diphenol, phenol, cresols, anacardol it is one or more.
Furtherly, the preferred tannic acid of alkyl phenol in the step 1), even trisphenol, mesitylene phenol, resorcinol, neighbour
Benzenediol and the strong phenols of iron rust respond.
Furtherly, the basic catalyst in the step 1) is sodium hydroxide, and dosage is the 1% of alkyl phenol quality.
Furtherly, acidic catalyst is ethanedioic acid in the step 1), and dosage is the 0.1-0.5% of tannin quality.
Compared with prior art, the beneficial effects of the present invention are:
1) water solubility of phenolic resin is lower than tannic acid, so product of the invention has better water resistance；
2) molecular weight of phenolic resin is larger, and the atrament of formation has bigger molecular weight, keeps protective film harder
Firmly, intensity is higher；
3) phenolic resin can form the finer and close special construction aligned in the drying process, prevent the external world
Oxygen and moisture infiltration improve corrosivity to steel surface；
4) constituent part in phenolic resin plays the role of surfactant, has better deoiling effect to mention
The high adhesive force to steel surface；
5) phenolic resin and water-based emulsion have good compatibility, can form the protective film of excellent combination property；
6) simple process exploitativeness is strong, can replace oil removing necessary to conventional phosphatizing liquor treating process, derusting, phosphorus
Change and be passivated four processing steps, time cost can be greatlyd save and improves production efficiency；Any commonly employed brushing side can be used
Formula；Zero discharge can be truly realized；
7) film layer and the cohesive force of steel are good, have good phase with common corrosion resistant coating or powdery paints in the market
Capacitive；
8) it is suitable for conventional phosphatizing and is not easy to the large-scale workpiece of operation, steelframe, pipeline, metal furniture, door and window, vehicle, ship
Pretreatment before the coating of oceangoing ship, bridge, equipment lathe etc..
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
A kind of aqueous epithelium liquid instead of phosphating solution, the raw material including following parts by weight: 30-100 parts of water, polar solvent 5-
10 parts, 1-3 parts of fatty alcohol polyoxyethylene ether nonionic surfactant (AEO), alkyl trimethyl ammonium chloride cationic surface is lived
1-5 parts of agent, 10-30 parts of resol resins, 20-50 parts of water-based emulsion of property.
The water-based emulsion is film forming agent, belongs to corrosion-resistant antirust emulsion, is acrylic emulsions, PVDC lotion, poly- ammonia
Ester lotion, polyurethane-modified acrylic acid lotion, acrylic acid modified polyurethane dispersion liquid it is one or more.
The polar solvent be ethyl alcohol, acetone, isopropanol, glycol dimethyl ether, ethylene glycol diethyl ether it is one or more.
The present invention also provides a kind of preparation methods of aqueous epithelium liquid instead of phosphating solution, comprising the following steps:
1) formalin that alkyl phenol and volume fraction are 37% preparation of resol resins: is put into reaction kettle
In, stirring allows alkyl phenol to dissolve, and a small amount of basic catalyst is then added dropwise, and is heated to 70-90 degrees Celsius and reacts 2 hours, is cooled to
Then acidic catalyst and tannin is added in 40-50 degree, react 1-3 hours, water soluble phenol resin can be obtained；
2) water soluble phenol resin obtained by step 1) is added in the water in reaction kettle, is then added while stirring aqueous
Lotion, sequentially adds various surfactants after mixing evenly, and the defoaming relative to solution total amount 0.1-0.5% is finally added dropwise
Agent is to get the aqueous epithelium liquid arrived instead of phosphating solution.
Alkyl phenol in the step 1) is tannic acid, even trisphenol, mesitylene phenol, resorcinol, catechol, benzene
Phenol, cresols, anacardol it is one or more.
The preferred tannic acid of alkyl phenol in the step 1), even trisphenol, mesitylene phenol, resorcinol, catechol with
The strong phenols of iron rust respond.
Basic catalyst in the step 1) is sodium hydroxide, and dosage is the 1% of alkyl phenol quality.
Acidic catalyst is ethanedioic acid in the step 1), and dosage is the 0.1-0.5% of tannin quality.
Embodiment 1:
A kind of preparation method of the aqueous epithelium liquid instead of phosphating solution, comprising the following steps:
1) preparation of water soluble phenol resin: 80kg anacardol is put into 1000L reaction kettle and 150kg volume fraction is
37% formalin, the sodium hydrate aqueous solution that a small amount of volume fraction is 20%, which is added, makes pH value between 8-8.5, then rises
Temperature after reaction 2 hours, cools to 40 degree to 80 degree；300kg tannic acid and 100kg catechol are put into, 1kg second is then added
Diacid, keeps reaction temperature in 40-50 degree, and reaction obtains the water soluble phenol resin of brown in 3 hours.
The reaction sour two-step reaction after first alkali, and after reasonable feeding sequence and proportion, structural arrangement is unique, simultaneously
Formaldehyde total overall reaction, free formaldehyde can control in 500ppm or less.
2) in 39.8 parts of pure water that 15 parts of resol resins obtained by step 1) are added in reaction kettle, then side is stirred
It mixes side and 30 parts of watersoluble polyurethane acrylic acid lotions is added, sequentially add 3 parts of MOA-15 non-ionic surface actives after mixing evenly
0.2 part of defoaming agent is finally added dropwise, i.e., in agent, 2 parts of hexadecyltrimethylammonium chloride cationic surfactants and 10 parts of isopropanols
The aqueous epithelium liquid instead of phosphating solution, the surface preparation of steel product few suitable for iron rust but big oil mass are obtained, such as is stopped
Hull.
Embodiment 2:
A kind of preparation method of the aqueous epithelium liquid instead of phosphating solution, comprising the following steps:
1) preparation of water soluble phenol resin: 80kg anacardol is put into 1000L reaction kettle and 150kg volume fraction is
37% formalin, the sodium hydrate aqueous solution that a small amount of volume fraction is 20%, which is added, makes pH value between 8-8.5, then rises
Temperature after reaction 2 hours, cools to 40 degree to 80 degree；300kg tannic acid and 100kg catechol are put into, 1kg second is then added
Diacid, keeps reaction temperature in 40-50 degree, and reaction obtains the water soluble phenol resin of brown in 3 hours.
The reaction sour two-step reaction after first alkali, and after reasonable feeding sequence and proportion, structural arrangement is unique, simultaneously
Formaldehyde total overall reaction, free formaldehyde can control in 500ppm or less.
2) in 39.9 parts of pure water that 20 parts of resol resins obtained by step 1) are added in reaction kettle, then side is stirred
It mixes side and 30 parts of watersoluble polyurethane acrylic acid lotions is added, sequentially add 1 part of MOA-15 non-ionic surface active after mixing evenly
0.1 part of defoaming agent is finally added dropwise, i.e., in agent, 2 parts of hexadecyltrimethylammonium chloride cationic surfactants and 5 parts of isopropanols
Obtain the aqueous epithelium liquid instead of phosphating solution, the surface preparation of the steel product less suitable for iron rust.
Embodiment 3:
A kind of preparation method of the aqueous epithelium liquid instead of phosphating solution, comprising the following steps:
1) preparation of water soluble phenol resin: 80kg anacardol is put into 1000L reaction kettle and 150kg volume fraction is
37% formalin, the sodium hydrate aqueous solution that a small amount of volume fraction is 20%, which is added, makes pH value between 8-8.5, then rises
Temperature after reaction 2 hours, cools to 40 degree to 80 degree；300kg tannic acid and 100kg catechol are put into, 1kg second is then added
Diacid, keeps reaction temperature in 40-50 degree, and reaction obtains the water soluble phenol resin of brown in 3 hours.
The reaction sour two-step reaction after first alkali, and after reasonable feeding sequence and proportion, structural arrangement is unique, simultaneously
Formaldehyde total overall reaction, free formaldehyde can control in 500ppm or less.
2) in 19.9 parts of pure water that 35 parts of resol resins obtained by step 1) are added in reaction kettle, then side is stirred
It mixes side and 34 parts of aqueous PVDC lotions is added, sequentially add 0.5 part of MOA-15 nonionic surfactant, 0.5 after mixing evenly
0.1 part of defoaming agent is added dropwise finally to get to generation in part hexadecyltrimethylammonium chloride cationic surfactant and 2 parts of ethyl alcohol
Surface preparation for the aqueous epithelium liquid of phosphating solution, suitable for the steel product more than iron rust.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (8)
1. a kind of aqueous epithelium liquid instead of phosphating solution, it is characterised in that: the raw material including following parts by weight: 30-100 parts of water,
5-10 parts of polar solvent, 1-3 parts of fatty alcohol polyoxyethylene ether nonionic surfactant (AEO), alkyl trimethyl ammonium chloride sun
1-5 parts of ionic surface active agent, 10-30 parts of resol resins, 20-50 parts of water-based emulsion.
2. a kind of aqueous epithelium liquid instead of phosphating solution according to claim 1, it is characterised in that: the water-based emulsion,
It is film forming agent, belongs to corrosion-resistant antirust emulsion, is acrylic emulsions, PVDC lotion, polyaminoester emulsion, polyurethane-modified propylene
Yogurt liquid, acrylic acid modified polyurethane dispersion liquid it is one or more.
3. a kind of aqueous epithelium liquid instead of phosphating solution according to claim 1, it is characterised in that: the polar solvent is
Ethyl alcohol, acetone, isopropanol, glycol dimethyl ether, ethylene glycol diethyl ether it is one or more.
4. a kind of preparation method of aqueous epithelium liquid instead of phosphating solution according to claim 1, it is characterised in that: including
Following steps:
1) preparation of resol resins: the formalin that alkyl phenol and volume fraction are 37% is put into reaction kettle, is stirred
It mixes and alkyl phenol is allowed to dissolve, a small amount of basic catalyst is then added dropwise, be heated to 70-90 degrees Celsius and react 2 hours, be cooled to 40-50
Then acidic catalyst and tannin is added in degree, react 1-3 hours, water soluble phenol resin can be obtained；
2) water soluble phenol resin obtained by step 1) is added in the water in reaction kettle, aqueous cream is then added while stirring
Liquid, sequentially adds various surfactants after mixing evenly, and the defoaming relative to solution total amount 0.2-0.5% is finally added dropwise
Agent is to get the aqueous epithelium liquid arrived instead of phosphating solution.
5. a kind of preparation method of aqueous epithelium liquid instead of phosphating solution according to claim 4, it is characterised in that: described
Alkyl phenol in step 1) is tannic acid, even trisphenol, mesitylene phenol, resorcinol, catechol, phenol, cresols, anacardol
It is one or more.
6. a kind of preparation method of aqueous epithelium liquid instead of phosphating solution according to claim 5, it is characterised in that: described
The preferred tannic acid of alkyl phenol, company's trisphenol, mesitylene phenol, resorcinol, catechol and iron rust respond in step 1)
Strong phenols.
7. a kind of preparation method of aqueous epithelium liquid instead of phosphating solution according to claim 4, it is characterised in that: described
Basic catalyst in step 1) is sodium hydroxide, and dosage is the 1% of alkyl phenol quality.
8. a kind of preparation method of aqueous epithelium liquid instead of phosphating solution according to claim 4, it is characterised in that: described
Acidic catalyst is ethanedioic acid in step 1), and dosage is the 0.1-0.5% of tannin quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811032170.2A CN109023322B (en) | 2018-09-05 | 2018-09-05 | Water-based membrane liquid replacing phosphating liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811032170.2A CN109023322B (en) | 2018-09-05 | 2018-09-05 | Water-based membrane liquid replacing phosphating liquid and preparation method thereof |
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| Publication Number | Publication Date |
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| CN109023322A true CN109023322A (en) | 2018-12-18 |
| CN109023322B CN109023322B (en) | 2020-10-09 |
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| CN201811032170.2A Expired - Fee Related CN109023322B (en) | 2018-09-05 | 2018-09-05 | Water-based membrane liquid replacing phosphating liquid and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87101353A (en) * | 1987-06-10 | 1988-12-21 | 山东省冶金研究所 | Iron and steel surface painting preprocessing liquor-one step phosphorus liquid |
| JP2009221395A (en) * | 2008-03-18 | 2009-10-01 | Sumitomo Bakelite Co Ltd | Resorcin-modified water soluble phenolic resin for metal-surface treatment, and metal-surface treatment agent |
| CN104277656A (en) * | 2014-09-16 | 2015-01-14 | 田清峰 | Synthesis process of water-soluble phenolic resin antirust coating |
| CN105017884A (en) * | 2014-04-16 | 2015-11-04 | 镇江德马化工有限公司 | Aqueous rotating rust steel iron surface treatment liquid and preparation method thereof |
-
2018
- 2018-09-05 CN CN201811032170.2A patent/CN109023322B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87101353A (en) * | 1987-06-10 | 1988-12-21 | 山东省冶金研究所 | Iron and steel surface painting preprocessing liquor-one step phosphorus liquid |
| JP2009221395A (en) * | 2008-03-18 | 2009-10-01 | Sumitomo Bakelite Co Ltd | Resorcin-modified water soluble phenolic resin for metal-surface treatment, and metal-surface treatment agent |
| CN105017884A (en) * | 2014-04-16 | 2015-11-04 | 镇江德马化工有限公司 | Aqueous rotating rust steel iron surface treatment liquid and preparation method thereof |
| CN104277656A (en) * | 2014-09-16 | 2015-01-14 | 田清峰 | Synthesis process of water-soluble phenolic resin antirust coating |
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| CN109023322B (en) | 2020-10-09 |
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