CN107502879A - One kind is used for metallic surface inorganic agent and preparation method thereof - Google Patents
One kind is used for metallic surface inorganic agent and preparation method thereof Download PDFInfo
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- CN107502879A CN107502879A CN201710893109.6A CN201710893109A CN107502879A CN 107502879 A CN107502879 A CN 107502879A CN 201710893109 A CN201710893109 A CN 201710893109A CN 107502879 A CN107502879 A CN 107502879A
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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
Abstract
The invention discloses one kind to be used for metallic surface inorganic agent, and by weight, its preparing raw material includes：1 10 parts and 1 10 parts 100 parts of deionized water, 5 10 parts of salicylic acid, 2 10 parts of BTA, 2 10 parts of nickel nitrate, 5 10 parts of nickel sulfate, 1 10 parts of fluotitanic acid, 15 parts of sodium gluconate, 15 parts of zinc oxide, lanthanum nitrate hydride modified polyphosphazene polyethersulfone block copolymers.Gained environment-friendly type surface conditioning agent of the invention can low-temperature surface processing, surface processing efficiency it is high and green, there are good market prospects.
Description
Technical field
The present invention relates to field of metal surface treatment technology, in particular to one kind to be used for metallic surface inorganic agent and its system
Preparation Method.
Background technology
Metallic surface processing method is many at present, and chemical passivation facture is exactly the conventional surface treatment skill of one of which
Art, it can be very good to suppress the oxidation stain of metal.At present often using the Passivation Treatment work of chromic anhydride and bichromate
Although skill effect is relatively good, due to the Cr during Passivation Treatment6+The harm of ion pair human body and environment is serious, and caused
Harm be difficult to eliminate in a short time, therefore, disable Cr6+The problem of be increasingly valued by people.European Union was in 2000 9
The moon endorsed a decree (i.e. RoHS instructions) in Brussels, it is specified that being prohibitted the use of from January, 2003 in associated components
Including Cr6+Six kinds of harmful substances inside, subsequent China is also to Cr6+Use take corresponding restriction.
In order to substitute Cr VI passivating technique, just actively the chromium-free deactivation technology of copper and its alloy is ground in the industry at present
Study carefully, wherein having with Cr3+For the low price chromium passivating of main film forming substance, but Cr3+To environment there is also certain harmfulness, and
And it is also possible to change into the larger Cr of harmfulness under certain condition6+, so Cr can not be turned into6+The optimal alternative solution of passivation；
The existing complete Chrome-free handling process for copper and its alloy be usually single use BTA (BTA) or using it with
Other several components are simply used cooperatively, and its handling process is complex, it is often necessary to heat, processing time also compared with
Long, test result shows that effect that its is anti-corrosion is also very undesirable relative to traditional chromic acid salt treatment, can not meet actual production
Need.
For this reason, it may be necessary to developmental research novel surface inorganic agent, the unquestionable inexorable trend for turning into technology development.
The content of the invention
The defects of it is an object of the invention to overcome existing above-mentioned technology, by studying assiduously, and through repetition test, develop
Go out one kind and be used for metallic surface inorganic agent, so as to effectively overcome drawbacks described above.
The present invention provides one kind and is used for metallic surface inorganic agent, and by weight, its preparing raw material includes：Deionized water
100 parts, salicylic acid 1-10 parts, BTA 1-10 parts, nickel nitrate 2-10 parts, nickel sulfate 3-10 parts, fluotitanic acid 2-10 parts, Portugal
Grape sodium saccharate 2-5 parts, zinc oxide 2-5 parts, lanthanum nitrate 3-10 parts and hydride modified polyphosphazene-polyethersulfone block copolymer 2-10
Part.
In a preferred approach, described to be used for metallic surface inorganic agent, by weight, its preparing raw material includes：Go
100 parts of ionized water, salicylic acid 7-9 parts, BTA 4-7 parts, nickel nitrate 4-7 parts, nickel sulfate 7-9 parts, fluotitanic acid 4-8 parts,
Sodium gluconate 2-4 parts, zinc oxide 2-4 parts, lanthanum nitrate 4-8 parts and hydride modified polyphosphazene-polyethersulfone block copolymer 4-8
Part.
In more preferably scheme, described is used for metallic surface inorganic agent, and by weight, its preparing raw material includes：
100 parts of deionized water, salicylic acid 7-8 parts, BTA 4-6 parts, nickel nitrate 4-6 parts, nickel sulfate 7-8 parts, fluotitanic acid 4-7
Part, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, lanthanum nitrate 4-7 parts and hydride modified polyphosphazene-polyethersulfone block copolymer
4-7 parts.
In most preferably scheme, described is used for metallic surface inorganic agent, and by weight, its preparing raw material includes：
100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate, 6 parts of fluotitanic acid,
3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate and hydride modified polyphosphazene -5 parts of polyethersulfone block copolymer.
In a preferred approach, the preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
In a preferred approach, described to be used for metallic surface inorganic agent, by weight, its preparing raw material also includes：
The sulfonated phosphazene of 0.5 parts by weight-nano oxidized caesium compound.
In a kind of scheme, the preparation method of the sulfonated phosphazene-nano oxidized caesium compound is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4, the dissolving of 4 '-dihydroxydiphenylsulisomer
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4h, after reaction terminates, from
The heart removes solvent, distinguishes washed product 3 times with deionized water and acetone, and 24h is finally dried in vacuo at 40 DEG C and obtains white gather
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, adds 10 milliliters of mass fractions
98% concentrated sulfuric acid, it is placed in 60 DEG C of water-baths, reacts 10h under mechanical stirring, after reaction terminates, product is slowly poured into cold
In water, and it is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, it is finally true at 50 DEG C
Sky dries 48h and obtains sulfonated phosphazene powder；
0.5 gram of above-mentioned sulfonated phosphazene powder, epoxy resin E51 0.05 gram, nanometer are added in 50 milliliters of three-neck flasks
0.3 gram and 10 milliliters dimethyl sulfoxide (DMSO)s of cesium oxide, heat up after 120 DEG C of reaction 2h, be down to room temperature and slowly pour into product cold
In water, and it is stirred continuously, product is then washed with deionized 5 times, it is to obtain sulfonation to gather that 48h is finally dried in vacuo at 50 DEG C
Phosphonitrile-nano oxidized caesium compound.
Invention further discloses the preparation method for metallic surface inorganic agent, comprise the following steps：By described original
Obtained after being stirred in material component addition mixer.
In a kind of scheme, the stir speed (S.S.) of the mixer is 1500-3000r/min, mixing time 50-
100min。
In a preferred approach, the stir speed (S.S.) of the mixer is 1800r/min, mixing time 60min.
The advantageous effects of the present invention：Improved using hydride modified polyphosphazene-polyethersulfone block copolymer at surface
Effect, adhesive force and alkali resistant corrosion resistance are managed, and is further improved by adding sulfonated phosphazene-nano oxidized caesium compound
Its adhesive force and corrosion resistant performance, and further improve its durability.
Embodiment
Raw material
Graphene oxide is purchased from permanent ball science and technology.Other reagents are purchased from Alfa reagents.
Embodiment 1
By weight, by 100 parts of deionized water, 1 part of salicylic acid, 1 part of BTA, 2 parts of nickel nitrate, 3 parts of nickel sulfate,
2 parts of fluotitanic acid, 2 parts of sodium gluconate, 2 parts of zinc oxide, 3 parts of lanthanum nitrate and hydride modified polyphosphazene-polyethersulfone block copolymerization
Surface conditioning agent is obtained after being stirred in 2 parts of addition mixers of thing, the stir speed (S.S.) of the mixer is 1800r/min, is stirred
It is 60min to mix the time；
The preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
Embodiment 2
By weight, by 100 parts of deionized water, 10 parts of salicylic acid, 10 parts of BTA, 10 parts of nickel nitrate, nickel sulfate
10 parts, 10 parts of fluotitanic acid, 5 parts of sodium gluconate, 5 parts of zinc oxide, 10 parts of lanthanum nitrate and hydride modified polyphosphazene-polyether sulfone are embedding
Surface conditioning agent is obtained after being stirred in section 0 part of addition mixer of copolymer 1, the stir speed (S.S.) of the mixer is 1800r/
Min, mixing time 60min；
The preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
Embodiment 3
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 4 parts of BTA, 4 parts of nickel nitrate, 7 parts of nickel sulfate,
4 parts of fluotitanic acid, 2 parts of sodium gluconate, 2 parts of zinc oxide, 4 parts of lanthanum nitrate and hydride modified polyphosphazene-polyethersulfone block copolymerization
Surface conditioning agent is obtained after being stirred in 4 parts of addition mixers of thing, the stir speed (S.S.) of the mixer is 1800r/min, is stirred
It is 60min to mix the time；
The preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
Embodiment 4
By weight, by 100 parts of deionized water, 9 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 9 parts of nickel sulfate,
8 parts of fluotitanic acid, 4 parts of sodium gluconate, 4 parts of zinc oxide, 8 parts of lanthanum nitrate and hydride modified polyphosphazene-polyethersulfone block copolymerization
Surface conditioning agent is obtained after being stirred in 8 parts of addition mixers of thing, the stir speed (S.S.) of the mixer is 1800r/min, is stirred
It is 60min to mix the time；
The preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
Embodiment 5
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate,
6 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate and hydride modified polyphosphazene-polyethersulfone block copolymerization
Surface conditioning agent is obtained after being stirred in 5 parts of addition mixers of thing, the stir speed (S.S.) of the mixer is 1800r/min, is stirred
It is 60min to mix the time；
The preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
Embodiment 6
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate,
6 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate, hydride modified polyphosphazene-polyethersulfone block copolymer 5
Surface conditioning agent is obtained after being stirred in part and sulfonated phosphazene -0.5 part of nano oxidized caesium compound addition mixer, institute
The stir speed (S.S.) for stating mixer is 1800r/min, mixing time 60min；
The preparation method of the hydride modified polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
(3) in 250 milliliters of round-bottomed flasks, polyphosphazene/polyethersulfone block copolymer obtained by above-mentioned steps (2) is sequentially added
10g, graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature liter
To 50 DEG C, react 6 hours, discharge in water, obtain fluffy solid, the fluffy solid 3 is washed respectively with deionized water and ethanol
It is secondary, 24h is finally dried in vacuo at 50 DEG C and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer；
The preparation method of the sulfonated phosphazene-nano oxidized caesium compound is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4, the dissolving of 4 '-dihydroxydiphenylsulisomer
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4h, after reaction terminates, from
The heart removes solvent, distinguishes washed product 3 times with deionized water and acetone, and 24h is finally dried in vacuo at 40 DEG C and obtains white gather
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, adds 10 milliliters of mass fractions
98% concentrated sulfuric acid, it is placed in 60 DEG C of water-baths, reacts 10h under mechanical stirring, after reaction terminates, product is slowly poured into cold
In water, and it is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, it is finally true at 50 DEG C
Sky dries 48h and obtains sulfonated phosphazene powder；
0.5 gram of above-mentioned sulfonated phosphazene powder, epoxy resin E51 0.05 gram, nanometer are added in 50 milliliters of three-neck flasks
0.3 gram and 10 milliliters dimethyl sulfoxide (DMSO)s of cesium oxide, heat up after 120 DEG C of reaction 2h, be down to room temperature and slowly pour into product cold
In water, and it is stirred continuously, product is then washed with deionized 5 times, it is to obtain sulfonation to gather that 48h is finally dried in vacuo at 50 DEG C
Phosphonitrile-nano oxidized caesium compound.
Comparative example 1
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate,
6 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate and polyphosphazene -5 parts of polyethersulfone block copolymer add
Surface conditioning agent is obtained after being stirred in mixer, the stir speed (S.S.) of the mixer is 1800r/min, and mixing time is
60min；
The preparation method of the polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer.
Comparative example 2
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate,
Stirred in 5 parts of 6 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate and polyphosphazene addition mixers
After obtain surface conditioning agent, the stir speed (S.S.) of the mixer is 1800r/min, mixing time 60min；
The preparation method of the polyphosphazene is：
In 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4, the dissolving of 4 '-dihydroxydiphenylsulisomer
In 160 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 8h, after reaction terminates, from
The heart removes solvent, distinguishes washed product 3 times with deionized water and acetone, and 15h is finally dried in vacuo at 60 DEG C and obtains white gather
Phosphonitrile powder.
Comparative example 3
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate,
6 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate and sulfonated phosphazene-nano oxidized caesium compound 0.5
Obtain surface conditioning agent after being stirred in part addition mixer, the stir speed (S.S.) of the mixer is 1800r/min, during stirring
Between be 60min；
The preparation method of the sulfonated phosphazene-nano oxidized caesium compound is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4, the dissolving of 4 '-dihydroxydiphenylsulisomer
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4h, after reaction terminates, from
The heart removes solvent, distinguishes washed product 3 times with deionized water and acetone, and 24h is finally dried in vacuo at 40 DEG C and obtains white gather
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, adds 10 milliliters of mass fractions
98% concentrated sulfuric acid, it is placed in 60 DEG C of water-baths, reacts 10h under mechanical stirring, after reaction terminates, product is slowly poured into cold
In water, and it is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, it is finally true at 50 DEG C
Sky dries 48h and obtains sulfonated phosphazene powder；
0.5 gram of above-mentioned sulfonated phosphazene powder, epoxy resin E51 0.05 gram, nanometer are added in 50 milliliters of three-neck flasks
0.3 gram and 10 milliliters dimethyl sulfoxide (DMSO)s of cesium oxide, heat up after 120 DEG C of reaction 2h, be down to room temperature and slowly pour into product cold
In water, and it is stirred continuously, product is then washed with deionized 5 times, it is to obtain sulfonation to gather that 48h is finally dried in vacuo at 50 DEG C
Phosphonitrile-nano oxidized caesium compound.
Comparative example 4
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate,
6 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate, polyphosphazene -5 parts of polyethersulfone block copolymer and sulphur
Change and obtain surface conditioning agent, the mixer after being stirred in polyphosphazene -0.5 part of nano oxidized caesium compound addition mixer
Stir speed (S.S.) be 1800r/min, mixing time 60min；
The preparation method of the polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer
It is dissolved in 160 milliliters of acetonitriles, then adds 1.3 milliliters of triethylamines, be placed in 50 DEG C of ultrasonic water baths and react 8h, reaction terminates
Afterwards, be centrifuged off solvent, distinguish washed product 3 times with deionized water and acetone, be finally dried in vacuo at 60 DEG C 15h obtain it is white
Color polyphosphazene powder；
(2) under nitrogen protection, add to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder obtained by 1.24g above-mentioned steps (1), 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone,
25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
Degree rises to 165 DEG C, reacts 10 hours, discharges in water, obtain bar shaped polymer, obtained bar shaped polymer is smash with bruisher
It is broken, then obtain polyphosphazene/polyethersulfone block within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Copolymer；
The preparation method of the sulfonated phosphazene-nano oxidized caesium compound is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4, the dissolving of 4 '-dihydroxydiphenylsulisomer
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4h, after reaction terminates, from
The heart removes solvent, distinguishes washed product 3 times with deionized water and acetone, and 24h is finally dried in vacuo at 40 DEG C and obtains white gather
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, adds 10 milliliters of mass fractions
98% concentrated sulfuric acid, it is placed in 60 DEG C of water-baths, reacts 10h under mechanical stirring, after reaction terminates, product is slowly poured into cold
In water, and it is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, it is finally true at 50 DEG C
Sky dries 48h and obtains sulfonated phosphazene powder；
0.5 gram of above-mentioned sulfonated phosphazene powder, epoxy resin E51 0.05 gram, nanometer are added in 50 milliliters of three-neck flasks
0.3 gram and 10 milliliters dimethyl sulfoxide (DMSO)s of cesium oxide, heat up after 120 DEG C of reaction 2h, be down to room temperature and slowly pour into product cold
In water, and it is stirred continuously, product is then washed with deionized 5 times, it is to obtain sulfonation to gather that 48h is finally dried in vacuo at 50 DEG C
Phosphonitrile-nano oxidized caesium compound.
Method of testing
Copper test piece is tested by following handling process using 1-6 of the embodiment of the present invention and comparative example 1-4 inorganic agent：
A, sample prepares：Using 0.5mm × 20mm × 40mm brass test piece；
B, pre-process：
Oil removing → flushing → etch → flushing → chemical polishing → flushing → demoulding
Wherein chemical polishing solution main component is：H2O2、H2SO4, ethanol, acetic acid etc.；
C, Passivation Treatment：Copper and its alloy sample are placed in described surface conditioning agent and are passivated film process, located
For reason to stable performance, treatment temperature is room temperature；
D, post-process：Using drying method except copper after depassivation and its moisture of alloy surface residual.
To above-mentioned processing sample with traditional Cr6+The test piece that PROCESS FOR TREATMENT is crossed carries out performance test comparison, wherein specific processing
Technique is：Copper and its alloy sample are placed in described traditional Cr6+In inorganic agent, processing time 1min, treatment temperature is room
Temperature.Its inorganic agent raw material forms：In terms of volume 1L, chromic anhydride 80g/L, sulfuric acid 2%, surplus is water.
Because China there is no the professional standard of the corrosion resistance method of testing of copper and passivation of copper alloy film and country to mark at present
Standard, therefore the inorganic agent of the present invention is tested filming performance using conventional method of testing.Wherein mainly there is nitric acid drop
Determine method (using 65~68% chemical pure nitric acid by the use of one times of distilled water diluting as test fluid, to be added dropwise to tested part surface, measure
There is the time of bubble, in this, as corrosion proof judging basis.), and 5% sodium chloride solution Soak Test method is aided in sample
Tested and tested.
Test result is shown in Table 1.
Table 1
。
Claims (10)
1. one kind is used for metallic surface inorganic agent, it is characterised in that by weight, its preparing raw material includes：
100 parts of deionized water, salicylic acid 1-10 parts, BTA 1-10 parts, nickel nitrate 2-10 parts, nickel sulfate 3-10 parts, fluorine
Metatitanic acid 2-10 parts, sodium gluconate 2-5 parts, zinc oxide 2-5 parts, lanthanum nitrate 3-10 parts and hydride modified polyphosphazene-polyether sulfone
Block copolymer 2-10 parts.
2. according to claim 1 be used for metallic surface inorganic agent, it is characterised in that by weight, it prepares former
Material includes：
100 parts of deionized water, salicylic acid 7-9 parts, BTA 4-7 parts, nickel nitrate 4-7 parts, nickel sulfate 7-9 parts, fluotitanic acid
4-8 parts, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, lanthanum nitrate 4-8 parts and hydride modified polyphosphazene-polyethersulfone block are common
Polymers 4-8 parts.
3. according to claim 2 be used for metallic surface inorganic agent, it is characterised in that by weight, it prepares former
Material includes：
100 parts of deionized water, salicylic acid 7-8 parts, BTA 4-6 parts, nickel nitrate 4-6 parts, nickel sulfate 7-8 parts, fluotitanic acid
4-7 parts, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, lanthanum nitrate 4-7 parts and hydride modified polyphosphazene-polyethersulfone block are common
Polymers 4-7 parts.
4. according to claim 3 be used for metallic surface inorganic agent, it is characterised in that by weight, it prepares former
Material includes：
100 parts of deionized water, 7 parts of salicylic acid, 5 parts of BTA, 5 parts of nickel nitrate, 7 parts of nickel sulfate, 6 parts of fluotitanic acid, grape
3 parts of sodium saccharate, 3 parts of zinc oxide, 6 parts of lanthanum nitrate and hydride modified polyphosphazene -5 parts of polyethersulfone block copolymer.
5. it is used for metallic surface inorganic agent according to claim any one of 1-4, it is characterised in that described hydride modified
The preparation method of polyphosphazene-polyethersulfone block copolymer is：
(1) in 250 milliliters of round-bottomed flasks, by 0.40 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4, the dissolving of 4 '-dihydroxydiphenylsulisomer
In 160 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 8h, after reaction terminates, from
The heart removes solvent, distinguishes washed product 3 times with deionized water and acetone, and 15h is finally dried in vacuo at 60 DEG C and obtains white gather
Phosphonitrile powder；
(2) under nitrogen protection, 1.24g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
White polyphosphazene powder, 4.258g diallyls bisphenol S, 3.810g4,4 '-difluorodiphenyl sulfone, 25ml obtained by above-mentioned steps (1)
Sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature liter after 4 hours
To 165 DEG C, react 10 hours, discharge in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Polyphosphazene/polyethersulfone block copolymerization is obtained within 24 hours with after distilled water boiling washing 3 times, being placed on 50 DEG C of drying in vacuum drying oven again
Thing；
(3) in 250 milliliters of round-bottomed flasks, sequentially add polyphosphazene/polyethersulfone block copolymer 1 0g obtained by above-mentioned steps (2),
Graphene oxide 1g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5ml, KH-550 2g and KH-560 5g, system temperature rise to 50
DEG C, react 6 hours, discharge in water, obtain fluffy solid, wash the fluffy solid respectively 3 times with deionized water and ethanol, most
24h is dried in vacuo at 50 DEG C afterwards and obtains the hydride modified polyphosphazene-polyethersulfone block copolymer.
6. according to claim 5 be used for metallic surface inorganic agent, it is characterised in that by weight, it prepares former
Material also includes：The sulfonated phosphazene of 0.5 parts by weight-nano oxidized caesium compound.
7. according to claim 6 be used for metallic surface inorganic agent, it is characterised in that the sulfonated phosphazene-nanometer
The preparation method of cesium oxide compound is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in 150
In milliliter acetonitrile, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4h, after reaction terminates, be centrifuged off
Solvent, distinguishes washed product 3 times with deionized water and acetone, and 24h is finally dried in vacuo at 40 DEG C obtains white polyphosphazene powder
End；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 60 DEG C of water-baths, reacts 10h under mechanical stirring, after reaction terminates, product is slowly poured into cold water,
And be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally vacuum is done at 50 DEG C
Dry 48h obtains sulfonated phosphazene powder；
0.5 gram of above-mentioned sulfonated phosphazene powder, 0.05 gram of epoxy resin E51, nano oxidized is added in 50 milliliters of three-neck flasks
0.3 gram and 10 milliliters dimethyl sulfoxide (DMSO)s of caesium, heat up after 120 DEG C of reaction 2h, be down to room temperature and slowly pour into product in cold water,
And be stirred continuously, product is then washed with deionized 5 times, finally at 50 DEG C be dried in vacuo 48h i.e. obtain sulfonated phosphazene-
Nano oxidized caesium compound.
8. a kind of preparation method for metallic surface inorganic agent, it is characterised in that comprise the following steps：By claim 1-
Obtained after being stirred in raw material components addition mixer any one of 7.
9. the preparation method of green chromium-free metal passivating solution according to claim 8, it is characterised in that the stirring
The stir speed (S.S.) of machine is 1500-3000r/min, mixing time 50-100min.
10. the preparation method of green chromium-free metal passivating solution according to claim 9, it is characterised in that described to stir
The stir speed (S.S.) for mixing machine is 1800r/min, mixing time 60min.
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| CN107090577A (en) * | 2017-07-07 | 2017-08-25 | 荆门市拓达科技有限公司 | Environmental protection chromium-free metal passivating solution and preparation method thereof |
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| CN103397320A (en) * | 2013-08-20 | 2013-11-20 | 安徽工业大学 | Cathodic electrophoresis pre-treatment liquor used on surface of hot-galvanized plate of automobile |
| CN105420710A (en) * | 2015-11-16 | 2016-03-23 | 刘崴崴 | Golden chrome-free passivation solution used for surface treatment of aluminum profiles |
| CN105349984A (en) * | 2015-11-25 | 2016-02-24 | 安徽红桥金属制造有限公司 | Anti-corrosion treatment agent for metal material surface |
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