CN109023403A - A kind of low bubble cleaning agent of copper product - Google Patents
A kind of low bubble cleaning agent of copper product Download PDFInfo
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- CN109023403A CN109023403A CN201810981202.7A CN201810981202A CN109023403A CN 109023403 A CN109023403 A CN 109023403A CN 201810981202 A CN201810981202 A CN 201810981202A CN 109023403 A CN109023403 A CN 109023403A
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
Abstract
The invention discloses a kind of low bubble cleaning agents of copper product, its raw material includes: 0.2-1 parts of sodium citrate by weight, 0.5-1.7 parts of sodium metasilicate, 0.1-0.7 parts of 4A type molecular sieve, 0.2-0.5 parts of propandiol butyl ether, 0.2-0.8 parts of fatty alcohol polyoxyethylene ether AEO-9, 0.3-1 parts of alkyl glycosides, 1-1.5 parts of Triton X-100, 0.1-1 parts of anionic surfactant, N- lauryl-β -0.2-0.75 parts of dipropionic acid sodium, 0.2-1 parts of EDTA, 0.5-1.3 parts of corrosion inhibiter, 0.1-0.5 parts of dimethicone, 0.1-0.35 parts of silane coupling agent, 0.1-0.35 parts of graphene oxide, 0.3-1 parts of plant extracts, water 80-9 0 part.The low bubble cleaning agent of copper product proposed by the present invention, strong detergency, cleaning effect is good, high rust resistance, and foam is few.
Description
Technical field
The present invention relates to metal cleaner technical field more particularly to a kind of low bubble cleaning agents of copper product.
Background technique
In intermetallic composite coating, food, weaving, traffic, ship, medical treatment, plating, printing, PETROLEUM PROCESSING, automobile manufacture, instrument
The industrial circles such as instrument, electronics, optics, the either processing, assembly of part, process cleaning, heat treatment and product seal packet up for safekeeping
Dress etc., requires to clean metal surface.The good cleaning agent of existing cleaning effect largely generates a large amount of foam, difficult
With rinsing, to influence mechanical efficiency, while existing metal cleaner rust inhibition is not very well, to limit its application.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of copper product low bubble cleaning agent, decontaminations
Power is strong, and cleaning effect and rust inhibition are good, and high rust resistance, foam is few, is able to satisfy the requirement of copper product cleaning.
A kind of low bubble cleaning agent of copper product proposed by the present invention, raw material includes: sodium citrate 0.2-1 by weight
Part, 0.5-1.7 parts of sodium metasilicate, 0.1-0.7 parts of 4A type molecular sieve, 0.2-0.5 parts of propandiol butyl ether, fatty alcohol polyoxyethylene ether
0.2-0.8 parts of AEO-9,0.3-1 parts of alkyl glycosides, 1-1.5 parts of Triton X-100, anionic surfactant
0.1-1 parts, N- lauryl-β -0.2-0.75 parts of dipropionic acid sodium, 0.2-1 parts of EDTA, 0.5-1.3 parts of corrosion inhibiter, diformazan
0.1-0.5 parts of base silicone oil, 0.1-0.35 parts of silane coupling agent, 0.1-0.35 parts of graphene oxide, 0.3-1 parts of plant extracts,
80-90 parts of water.
Preferably, the anionic surfactant is rosin acid polyethenoxy ether sodium sulfate salt, N- disproportionated rosin
Acyl group sarcosine, iso-octyl polyethenoxy ether polyethenoxy ether sodium sulfate, in glyceryl monooleate monomester succinate carboxylic acid sodium salt
One or more kinds of mixtures.
Preferably, the corrosion inhibiter be sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole from
The mixture of sub- liquid, modified benzimidazole, and sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, three nitrogen of benzo
Oxazolinium ion liquid, the weight ratio for being modified benzimidazole are 2-10:1-5:3-9:1-5:3-8:1-5.
Preferably, the benzotriazole ionic liquid is 1,3- diethyl bromo benzo triazole ionic liquid, 3- second
Base -1- butyl bromide is for one of benzotriazole ionic liquid or two kinds of mixture.
Preferably, the modified benzimidazole is prepared according to following technique: by 2-mercaptobenzimidazole, potassium hydroxide
It is uniformly mixed, is added to two benzyl chlorides, back flow reaction 100-150min with acetone, water is added after cooling, filters, wash after removing acetone
It washs, be dried to obtain material A；2- tolimidazole, sodium hydrate aqueous solution and tetrabutylammonium bromide are uniformly mixed, are warming up to
80-95 DEG C, material A is added, is stirred to react 3-8h, oil reservoir is dry, evaporation obtains object after cooling after reaction, water-oil separating
Expect B；Material B, bromooctane are uniformly mixed with acetonitrile, 5-8h is stirred to react at 65-75 DEG C, cooling after reaction, steaming
It sends out, recrystallize, filtering, being dried to obtain the modified benzimidazole.
Preferably, 2-mercaptobenzimidazole, be 1:1.1-1.5 to the molar ratios of two benzyl chlorides；2- tolimidazole, material
The molar ratio of A is 1:1.1-1.35；Material B, bromooctane molar ratio be 1:2.5-3.
Preferably, the silane coupling agent is silane coupling agent KH-560.
Preferably, the graphene oxide is the modified graphene oxide of triethanolamine.
Preferably, the plant extract be one of tea extract, Herba Galii Teneri extract, black bamboo bamboo extractive or
The a variety of mixture of person.
The low bubble cleaning agent of copper product of the present invention, in raw material, with sodium citrate, sodium metasilicate, 4A type molecular sieve
Cooperation is used as builder, has chelation to the various metals ion in water, and dispersibility, antiredeposition ability are strong, with
Fatty alcohol polyoxyethylene ether AEO-9, alkyl glycosides, Triton X-100, anionic surfactant, N- lauryl-
β-dipropionic acid sodium cooperation, plays synergistic effect, enhances the hydrophily and wetability of cleaning agent, reduce the table of liquid
Face tension can act on organic matter not soluble in water, be dissolved into the greasy dirt on copper product surface preferably in liquid, improve
The cleaning rate of cleaning agent makes cleaning rate reach 99.6% or more, and foam is few in cleaning process, easy to dissolve；Corrosion inhibiter and plant
Object extract cooperation, hence it is evident that slow down in cleaning process to corrosion of metal；Corrosion inhibiter is specifically chosen sodium molybdate, mahogany acid
Barium, methionine, benzotriazole, benzotriazole ionic liquid, the mixture for being modified benzimidazole, have excellent collaboration
Effect, can inhibit cathode reaction and inhibit anode reaction, form a variety of shielding compounds in metal surface, simultaneously
Smooth, fine and close film layer is formd in metal surface, a variety of effect collaborations reduce the erosion of corrosive medium, make inhibition efficiency
Reach 97.3% or more；It is first original with 2-mercaptobenzimidazole and to two benzyl chlorides in the preparation process of modified benzimidazole
Material, controls the condition of reaction, reacts the sulfydryl in 2-mercaptobenzimidazole with to the chlorine in two benzyl chlorides, thus by right
Two benzyl chlorides are combined as a whole with 2-mercaptobenzimidazole, have obtained material A；It is later original with 2- tolimidazole and material A
Material, reacts the chlorine in material A further with the N-H in 2- tolimidazole, has obtained material B, material B and bromine
After octane mixing, quaternization reaction is had occurred in the two, has obtained modified benzimidazole, because containing sulphur atom and nitrogen in molecule
Atom, lone pair electrons therein have suction-operated, and cyclic structure energy and metal in molecule to the atom of metal surface
Surface action forms stable protective film, while introducing alkyl in the molecule, enhances the electropositive of nitrogen-atoms in molecule, benefit
The protective film for forming metal surface with the hydrophobicity of alkyl is finer and close, and corrosion inhibition is more excellent；Benzotriazole ion
Liquid is specially 1,3- diethyl bromo benzo triazole ionic liquid, 3- ethyl -1- butyl bromide for benzotriazole ionic liquid
One of body or two kinds of mixture have water solubility well, timely can be complexed to form layer protecting film with copper,
And the steric hindrance of ionic liquid is larger, with the protective film densification formed after copper complexing, has filled up simple benzotriazole and copper shape
At protective film gap, make the corrosion potential of copper electrode and polarization curve that negative shifting occur after addition, it is slow to play cathode type
The effect of erosion significantly improves the corrosion inhibition of cleaning agent；Graphene oxide large specific surface area, through triethanolamine functionalization,
A large amount of tertiary amine nitrogen and hydroxyl activity functional group are contained in surface, there is very strong complexing, not only remain the parent of triethanolamine
Aqueous and edible vegetable oil, is also equipped with very strong adsorption capacity, significantly improves the cleaning effect of cleaning agent.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of low bubble cleaning agent of copper product proposed by the present invention, raw material include: by weight 1 part of sodium citrate, partially
0.5 part of sodium metasilicate, 0.7 part of 4A type molecular sieve, 0.2 part of propandiol butyl ether, 0.8 part of fatty alcohol polyoxyethylene ether AEO-9, alkyl
0.3 part of glucosides, 1.5 parts of Triton X-100,0.1 part of anionic surfactant, N- lauryl-β-imino group dipropyl
0.75 part of sour sodium, 0.2 part of EDTA, 1.3 parts of corrosion inhibiter, 0.1 part of dimethicone, 0.35 part of silane coupling agent, graphene oxide
0.1 part, 1 part of plant extracts, 80 parts of water.
Embodiment 2
A kind of low bubble cleaning agent of copper product proposed by the present invention, raw material include: by weight 0.2 part of sodium citrate,
1.7 parts of sodium metasilicate, 0.1 part of 4A type molecular sieve, 0.5 part of propandiol butyl ether, 0.2 part of fatty alcohol polyoxyethylene ether AEO-9, alkane
1 part of base glucosides, 1 part of Triton X-100,1 part of anionic surfactant, N- lauryl-β-dipropionic acid sodium
0.2 part, 1 part of EDTA, 0.5 part of corrosion inhibiter, 0.5 part of dimethicone, 0.1 part of silane coupling agent, 0.35 part of graphene oxide,
0.3 part of plant extracts, 90 parts of water.
Embodiment 3
A kind of low bubble cleaning agent of copper product proposed by the present invention, raw material include: by weight 0.8 part of sodium citrate,
0.7 part of sodium metasilicate, 0.6 part of 4A type molecular sieve, 0.28 part of propandiol butyl ether, 0.7 part of fatty alcohol polyoxyethylene ether AEO-9, alkane
0.5 part of base glucosides, 1.4 parts of Triton X-100,0.2 part of anionic surfactant, N- lauryl-β-imino-diacetic
0.7 part of sodium propionate, 0.5 part of EDTA, 1.1 parts of corrosion inhibiter, 0.28 part of dimethicone, 0.32 part of silane coupling agent, graphite oxide
0.17 part of alkene, 0.8 part of plant extracts, 83 parts of water；
Wherein, the anionic surfactant is rosin acid polyethenoxy ether sodium sulfate salt；
The corrosion inhibiter be sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole ionic liquid,
The mixture of modified benzimidazole, and sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole ionic liquid
Body, the weight ratio for being modified benzimidazole are 2:5:3:5:3:5；
The benzotriazole ionic liquid is 1,3- diethyl bromo benzo triazole ionic liquid；
The modified benzimidazole is prepared according to following technique: by 2-mercaptobenzimidazole, potassium hydroxide and acetone
It is uniformly mixed, is added to two benzyl chlorides, back flow reaction 100min, water is added after cooling, is filtered, washed, dries after removing acetone
To material A；2- tolimidazole, sodium hydrate aqueous solution and tetrabutylammonium bromide are uniformly mixed, are warming up to 95 DEG C, is added
Material A is stirred to react 3h, and oil reservoir is dry, evaporation obtains material B after cooling after reaction, water-oil separating；By material B, bromine
It is uniformly mixed for octane with acetonitrile, 5h is stirred to react at 75 DEG C, cooling after reaction, evaporation, recrystallization, filtering, drying
Obtain the modified benzimidazole；Wherein, 2-mercaptobenzimidazole, be 1:1.5 to the molar ratios of two benzyl chlorides；2- methyl benzo miaow
Azoles, material A molar ratio be 1:1.1；Material B, bromooctane molar ratio be 1:3；
The silane coupling agent is silane coupling agent KH-560；
The graphene oxide is the modified graphene oxide of triethanolamine；
The plant extract is tea extract.
Embodiment 4
A kind of low bubble cleaning agent of copper product proposed by the present invention, raw material include: by weight 0.3 part of sodium citrate,
1.5 parts of sodium metasilicate, 0.3 part of 4A type molecular sieve, 0.42 part of propandiol butyl ether, 0.4 part of fatty alcohol polyoxyethylene ether AEO-9, alkane
0.8 part of base glucosides, 1.2 parts of Triton X-100,0.8 part of anionic surfactant, N- lauryl-β-imino-diacetic
0.38 part of sodium propionate, 0.8 part of EDTA, 0.7 part of corrosion inhibiter, 0.42 part of dimethicone, 0.18 part of silane coupling agent, oxidation stone
0.32 part of black alkene, 0.4 part of plant extracts, 88 parts of water；
Wherein, the anionic surfactant is N- disproportionated rosin acyl group sarcosine, iso-octyl polyethenoxy ether polyoxy
The mixture of ethylene ether sodium sulfate, and N- disproportionated rosin acyl group sarcosine, iso-octyl polyethenoxy ether polyethenoxy ether sodium sulfate
Weight ratio be 1:3；
The corrosion inhibiter be sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole ionic liquid,
The mixture of modified benzimidazole, and sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole ionic liquid
Body, the weight ratio for being modified benzimidazole are 10:1:9:1:8:1；
The benzotriazole ionic liquid is 3- ethyl -1- butyl bromide for benzotriazole ionic liquid；
The modified benzimidazole is prepared according to following technique: by 2-mercaptobenzimidazole, potassium hydroxide and acetone
It is uniformly mixed, is added to two benzyl chlorides, back flow reaction 150min, water is added after cooling, is filtered, washed, dries after removing acetone
To material A；2- tolimidazole, sodium hydrate aqueous solution and tetrabutylammonium bromide are uniformly mixed, are warming up to 80 DEG C, is added
Material A is stirred to react 8h, and oil reservoir is dry, evaporation obtains material B after cooling after reaction, water-oil separating；By material B, bromine
It is uniformly mixed for octane with acetonitrile, 8h is stirred to react at 65 DEG C, cooling after reaction, evaporation, recrystallization, filtering, drying
Obtain the modified benzimidazole；Wherein, 2-mercaptobenzimidazole, be 1:1.1 to the molar ratios of two benzyl chlorides；2- methyl benzo miaow
Azoles, material A molar ratio be 1:1.35；Material B, bromooctane molar ratio be 1:2.5；
The silane coupling agent is silane coupling agent KH-560；
The graphene oxide is the modified graphene oxide of triethanolamine；
The plant extract is the mixture of Herba Galii Teneri extract, black bamboo bamboo extractive, and Herba Galii Teneri extract, black bamboo
The weight ratio of bamboo extractive is 2:5.
Embodiment 5
A kind of low bubble cleaning agent of copper product proposed by the present invention, raw material include: by weight 0.7 part of sodium citrate,
1.5 parts of sodium metasilicate, 0.6 part of 4A type molecular sieve, 0.38 part of propandiol butyl ether, 0.5 part of fatty alcohol polyoxyethylene ether AEO-9, alkane
0.7 part of base glucosides, 1.3 parts of Triton X-100,0.6 part of anionic surfactant, N- lauryl-β-imino-diacetic
0.58 part of sodium propionate, 0.7 part of EDTA, 1 part of corrosion inhibiter, 0.38 part of dimethicone, 0.26 part of silane coupling agent, graphite oxide
0.9 part of alkene, 0.7 part of plant extracts, 86 parts of water；
Wherein, the anionic surfactant is rosin acid polyethenoxy ether sodium sulfate salt, N- disproportionated rosin acyl
Base sarcosine, iso-octyl polyethenoxy ether polyethenoxy ether sodium sulfate, glyceryl monooleate monomester succinate carboxylic acid sodium salt it is mixed
Close object, and rosin acid polyethenoxy ether sodium sulfate salt, N- disproportionated rosin acyl group sarcosine, iso-octyl polyethenoxy ether polyoxy
Ethylene ether sodium sulfate, glyceryl monooleate monomester succinate carboxylic acid sodium salt weight ratio be 1:5:3:2；
The corrosion inhibiter be sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole ionic liquid,
The mixture of modified benzimidazole, and sodium molybdate, barium mahogany sulfonate, methionine, benzotriazole, benzotriazole ionic liquid
Body, the weight ratio for being modified benzimidazole are 7:3:6:4:5:3.2；
The benzotriazole ionic liquid is 1,3- diethyl bromo benzo triazole ionic liquid, 3- ethyl -1- fourth
Mixture of the bromide for benzotriazole ionic liquid, and 1,3- diethyl bromo benzo triazole ionic liquid, 3- ethyl -1-
Butyl bromide is 3:2 for the weight ratio of benzotriazole ionic liquid；
The modified benzimidazole is prepared according to following technique: by 2-mercaptobenzimidazole, potassium hydroxide and acetone
It is uniformly mixed, is added to two benzyl chlorides, back flow reaction 138min, water is added after cooling, is filtered, washed, dries after removing acetone
To material A；2- tolimidazole, sodium hydrate aqueous solution and tetrabutylammonium bromide are uniformly mixed, are warming up to 85 DEG C, is added
Material A is stirred to react 6.5h, and oil reservoir is dry, evaporation obtains material B after cooling after reaction, water-oil separating；By material B,
Bromooctane is uniformly mixed with acetonitrile, and 7h is stirred to react at 72 DEG C, and cooling after reaction, evaporation, filtering, is done recrystallization
It is dry to obtain the modified benzimidazole；Wherein, 2-mercaptobenzimidazole, be 1:1.32 to the molar ratios of two benzyl chlorides；2- methylbenzene
And the molar ratio of imidazoles, material A is 1:1.26；Material B, bromooctane molar ratio be 1:2.8；
The silane coupling agent is silane coupling agent KH-560；
The graphene oxide is the modified graphene oxide of triethanolamine；
The plant extract is the mixture of tea extract, Herba Galii Teneri extract, black bamboo bamboo extractive, and tealeaves mentions
Take object, Herba Galii Teneri extract, black bamboo bamboo extractive weight ratio be 4:5:2.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of low bubble cleaning agent of copper product, which is characterized in that its raw material include: by weight 0.2-1 parts of sodium citrate, partially
0.5-1.7 parts of sodium metasilicate, 0.1-0.7 parts of 4A type molecular sieve, 0.2-0.5 parts of propandiol butyl ether, fatty alcohol polyoxyethylene ether AEO-9
0.2-0.8 parts, 0.3-1 parts of alkyl glycosides, 1-1.5 parts of Triton X-100,0.1-1 parts of anionic surfactant,
N- lauryl-β -0.2-0.75 parts of dipropionic acid sodium, 0.2-1 parts of EDTA, 0.5-1.3 parts of corrosion inhibiter, dimethicone
0.1-0.5 parts, 0.1-0.35 parts of silane coupling agent, 0.1-0.35 parts of graphene oxide, 0.3-1 parts of plant extracts, water 80-90
Part.
2. the low bubble cleaning agent of copper product according to claim 1, which is characterized in that the anionic surfactant is pine
Botany bar gum acid polyethenoxy ether sodium sulfate salt, N- disproportionated rosin acyl group sarcosine, iso-octyl polyethenoxy ether polyoxyethylene ether sulphur
The mixture of one or more of sour sodium, glyceryl monooleate monomester succinate carboxylic acid sodium salt.
3. the low bubble cleaning agent of copper product according to claim 1 or claim 2, which is characterized in that the corrosion inhibiter is sodium molybdate, stone
Oily barium sulfonate, methionine, benzotriazole, benzotriazole ionic liquid, the mixture for being modified benzimidazole, and molybdic acid
Sodium, methionine, benzotriazole, benzotriazole ionic liquid, is modified the weight ratio of benzimidazole as 2- at barium mahogany sulfonate
10:1-5:3-9:1-5:3-8:1-5.
4. the low bubble cleaning agent of copper product according to claim 3, which is characterized in that the benzotriazole ionic liquid is
1,3- diethyl bromo benzo triazole ionic liquid, 3- ethyl -1- butyl bromide are for one of benzotriazole ionic liquid
Or two kinds of mixture.
5. according to the low bubble cleaning agent of the copper product of claim 3 or 4, which is characterized in that the modified benzimidazole according to
Prepared by following technique: 2-mercaptobenzimidazole, potassium hydroxide and acetone being uniformly mixed, are added to two benzyl chlorides, reflux is anti-
100-150min is answered, water is added after cooling, is filtered, washed after removing acetone, is dried to obtain material A；By 2- tolimidazole,
Sodium hydrate aqueous solution and tetrabutylammonium bromide are uniformly mixed, and are warming up to 80-95 DEG C, and material A is added, is stirred to react 3-8h, instead
Oil reservoir is dry, evaporation obtains material B after cooling, water-oil separating after answering；Material B, bromooctane are mixed with acetonitrile
It is even, it is stirred to react 5-8h at 65-75 DEG C, cools down, evaporate after reaction, recrystallizing, filtering, being dried to obtain the modified benzene
And imidazoles.
6. the low bubble cleaning agent of copper product according to claim 5, which is characterized in that 2-mercaptobenzimidazole, to two benzyl chlorides
Molar ratio be 1:1.1-1.5；2- tolimidazole, material A molar ratio be 1:1.1-1.35；Material B, bromooctane
Molar ratio is 1:2.5-3.
7. the low bubble cleaning agent of copper product described in any one of -6 according to claim 1, which is characterized in that the silane coupling agent
For silane coupling agent KH-560.
8. the low bubble cleaning agent of copper product described in any one of -7 according to claim 1, which is characterized in that the graphene oxide
For the modified graphene oxide of triethanolamine.
9. the low bubble cleaning agent of copper product described in any one of -8 according to claim 1, which is characterized in that the plant extract is
The mixture of one or more of tea extract, Herba Galii Teneri extract, black bamboo bamboo extractive.
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Application publication date: 20181218 |