CN107699882A - A kind of containing rare earth cerium rust-proof metal treatment fluid and preparation method thereof - Google Patents
A kind of containing rare earth cerium rust-proof metal treatment fluid and preparation method thereof Download PDFInfo
- Publication number
- CN107699882A CN107699882A CN201710892439.3A CN201710892439A CN107699882A CN 107699882 A CN107699882 A CN 107699882A CN 201710892439 A CN201710892439 A CN 201710892439A CN 107699882 A CN107699882 A CN 107699882A
- Authority
- CN
- China
- Prior art keywords
- parts
- milliliters
- polyphosphazene
- water
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C23C22/06—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 using aqueous acidic solutions with pH less than 6
- C23C22/46—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 using aqueous acidic solutions with pH less than 6 containing oxalates
Abstract
The invention discloses a kind of containing rare earth cerium rust-proof metal treatment fluid, by weight, its preparing raw material includes：100 parts of deionized water, 2 10 parts of salicylic acid, 4 10 parts of BTA, 3 10 parts of nickel nitrate, 2 10 parts of nickel sulfate, 1 10 parts of fluotitanic acid, 15 parts of sodium gluconate, 15 parts of zinc oxide, 4 10 parts of cerous nitrate, hydride modified 3 10 parts of polyphosphazene polyethersulfone block copolymer, 5 10 parts of polysorbas20,1 10 parts of n-butanol, 15 parts of sodium metasilicate, 15 parts of polyethylene glycol, 1 10 parts of oxalic acid, 15 parts of ethanol and 3 [(methylol) methyl amine] 15 parts of ethane sulfonic acids.Of the invention gained metal treatment fluid can low-temperature surface be handled, surface processing efficiency is high, green and rustless property is good, has good market prospects.
Description
Technical field
The present invention relates to field of metal surface treatment technology, in particular to a kind of containing rare earth cerium rust-proof metal treatment fluid and its
Preparation method.
Background technology
Phosphatization is carried out to metal surface, is generally all the pre-treating method of sheet metal component application (containing electrophoresis, electrostatic spraying), should
With there is one-hundred-year history, but this method has very big pollution to environment and operator, currently finds other substitute
Technology.
In order to substitute the phosphorization technology of high pollution, it is silane technology to have one kind at present, and another kind is ceramic technology, they
Without phosphorus, heavy metal free, increase are combined with paint film.
Chinese Patent Application No. is 200910116134.9 a kind of environment-friendly type metal surface finishing agent and preparation method thereof,
Disclose it is a kind of by film forming agent with containing dispersant the aqueous solution wetting after add coupling agent, be dispersed with stirring to the glue stablized
Body, the complex compound containing F of water miscible Si or IV races element is added, added as the acid of stabilizer and water and the adjustment of surplus
PH value to system is 1.0~3.0, that is, obtains environment-friendly type metal surface finishing agent.Be diluted with water to during use pH value 3.0~
6.0 working solution, make the environment-friendly type metal surface of pending clean metallic surfaces and the invention using immersing or spraying mode
Inorganic agent is in contact, and can obtain the compound conversion film layer of micro-crystalline ceramic；The invention inorganic agent, which has, to be better than or is equal to existing zinc
System, the performance indications of phosphating liquor of iron series, there is environmentally friendly, harmless, low-temperature treatment, low slag need not do table tune, it is simple to operate etc.
Feature；It is the new generation of environment protection product that may replace traditional metal surface inorganic agent.But this metal conditioner, still
The activity of metal surface film layer can not be better ensured that, is unable to reach the long-term combination with paint film.
In addition, the corrosion of metal is frequently problem in production, metal rusting not only makes metal works in itself outside
Shape, color and luster and mechanical performance etc. are destroyed, and cause the Quality Down of product, and especially severe can also make product
Scrapping, China GDP is 7.43 trillion dollars within 2011, and economic loss is up to 2200~370,000,000,000 dollars caused by corrosion,
Account for the 3%~5% of national GDP total values.In order to slow down the corrosion of steel, loss caused by corrosion is preferably minimized limit, people
Take many anti-corrosion measures, wherein the use of antirust solution be then using it is relatively wide, effect is significantly a kind of.Antirust solution is
A kind of synthesis bleeding agent of super grade high efficiency, it can form thin film in metal surface, prevent corrosion of metal.According to component not
Together, antirust solution is divided into oil base antirust solution and aqueous protective fluids.Aqueous protective fluids are by water soluble anti-rust agent, water-soluble additive, delayed
Lose the composition such as agent and water.Aqueous protective fluids are to add a certain amount of antirust agent in aqueous, to prevent chemistry or electrochemistry from making
Generation, generates insoluble passivation film or reaction film layer plays anti-rust action.But after this kind of antirust solution is applied to metal surface, liquid
Film easily trickles, and after moisture evaporation, can also form one layer of bloom in metal surface, lose due rust-proof effect, rustless property reaches
Less than the effect of antirust oil.Also, traditional aqueous protective fluids are more containing compositions such as nitrite, bichromates, it is well known that
Nitrites are carcinogen, have harm to the health of operator, while bichromate composition is because containing the heavy metals such as chromium, right
Environment is harmful to, and also have impact on the performance and quality of metal.Therefore, exploitation new green environment protection type metal rust-inhibiting liquid has been when business
It is anxious.
A kind of phosphorus substituted to metal surface is provided the invention aims to solve above-mentioned the deficiencies in the prior art
Change is handled, and ceramic membrane is formed in metal surface, and improves the surface-active of metal surface ceramic membrane, so as to improve metal watch
A kind of metal treatment fluid containing cerium of the binding strength of face and paint film, in addition the treatment fluid be also equipped with good antirust energy
Power.
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 a kind of containing rare earth cerium rust-proof metal treatment fluid, so as to effectively overcome drawbacks described above.
The present invention provides a kind of containing rare earth cerium rust-proof metal treatment fluid, and by weight, its preparing raw material includes：Deionization
100 parts of water, salicylic acid 2-10 parts, BTA 4-10 parts, nickel nitrate 3-10 parts, nickel sulfate 2-10 parts, fluotitanic acid 1-10 parts,
Sodium gluconate 1-5 parts, zinc oxide 1-5 parts, cerous nitrate 4-10 parts, hydride modified polyphosphazene-polyethersulfone block copolymer 3-10
Part, polysorbas20 5-10 parts, n-butanol 1-10 parts, sodium metasilicate 1-5 parts, polyethylene glycol 1-5 parts, oxalic acid 1-10 parts, ethanol 1-5 parts
And 3- [(methylol) methyl amine] ethane sulfonic acid 1-5 parts.
Preferably, described containing rare earth cerium rust-proof metal treatment fluid, by weight, its preparing raw material includes：
100 parts of deionized water, salicylic acid 3-8 parts, BTA 5-9 parts, nickel nitrate 4-9 parts, nickel sulfate 3-9 parts, fluorine
Metatitanic acid 2-8 parts, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, cerous nitrate 5-9 parts, hydride modified polyphosphazene-polyethersulfone block are common
Polymers 4-9 parts, polysorbas20 6-9 parts, n-butanol 3-8 parts, sodium metasilicate 2-5 parts, polyethylene glycol 2-5 parts, oxalic acid 3-8 parts, ethanol 2-
4 parts and 3- [(methylol) methyl amine] ethane sulfonic acid 2-4 parts.
It is highly preferred that described containing rare earth cerium rust-proof metal treatment fluid, by weight, its preparing raw material includes：
100 parts of deionized water, salicylic acid 4-7 parts, BTA 6-8 parts, nickel nitrate 5-8 parts, nickel sulfate 4-8 parts, fluorine
Metatitanic acid 3-7 parts, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, cerous nitrate 6-8 parts, hydride modified polyphosphazene-polyethersulfone block are common
Polymers 4-9 parts, polysorbas20 6-9 parts, n-butanol 3-8 parts, sodium metasilicate 2-5 parts, polyethylene glycol 2-5 parts, oxalic acid 3-8 parts, ethanol 2-
4 parts and 3- [(methylol) methyl amine] ethane sulfonic acid 2-4 parts.
Most preferably, described containing rare earth cerium rust-proof metal treatment fluid, by weight, its preparing raw material includes：
100 parts of deionized water, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate, 5 parts of fluotitanic acid,
3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, hydride modified polyphosphazene -8 parts of polyethersulfone block copolymer, polysorbas20 8
Part, 5 parts of n-butanol, 3 parts of sodium metasilicate, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol and 3- [(methylol) methyl amine] ethane
3 parts of sulfonic acid.
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 containing rare earth cerium rust-proof metal treatment fluid, by weight, its preparing raw material is also wrapped
Include：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 of containing rare earth cerium rust-proof metal treatment fluid, comprise the following steps：Will be described
Obtained after being stirred in raw material components 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, 2 parts of salicylic acid, 4 parts of BTA, 3 parts of nickel nitrate, 2 parts of nickel sulfate,
1 part of fluotitanic acid, 1 part of sodium gluconate, 1 part of zinc oxide, 4 parts of cerous nitrate, hydride modified polyphosphazene-polyethersulfone block copolymer 3
Part, 5 parts of polysorbas20,1 part of n-butanol, 1 part of sodium metasilicate, 1 part of polyethylene glycol, 1 part of oxalic acid, 1 part of ethanol and 3- [(methylol)
Methyl amine] stir in 1 part of addition mixer of ethane sulfonic acid after obtain surface conditioning agent, 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 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 cerous nitrate, hydride modified polyphosphazene-polyethersulfone block
0 part of copolymer 1,10 parts of polysorbas20,10 parts of n-butanol, 5 parts of sodium metasilicate, 5 parts of polyethylene glycol, 10 parts of oxalic acid, 5 parts of ethanol and
Surface conditioning agent, the mixer are obtained after being stirred in 3- [(methylol) methyl amine] 5 parts of addition mixers of ethane sulfonic acid
Stir speed (S.S.) be 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, 4.258g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl obtained by 1.24g above-mentioned steps (1)
Sulfone, 25ml sulfolane, 2.4g potassium carbonate, 17ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, body after 4 hours
It is that temperature rises to 165 DEG C, reacts 10 hours, discharge in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing to pieces
Machine is smashed to pieces, then obtains polyphosphazene/polyether sulfone within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Block 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, 4 parts of salicylic acid, 6 parts of BTA, 5 parts of nickel nitrate, 4 parts of nickel sulfate,
3 parts of fluotitanic acid, 2 parts of sodium gluconate, 2 parts of zinc oxide, 6 parts of cerous nitrate, hydride modified polyphosphazene-polyethersulfone block copolymer 4
Part, 6 parts of polysorbas20,3 parts of n-butanol, 2 parts of sodium metasilicate, 2 parts of polyethylene glycol, 3 parts of oxalic acid, 2 parts of ethanol and 3- [(methylol)
Methyl amine] stir in 2 parts of addition mixers of ethane sulfonic acid after obtain surface conditioning agent, 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 4
By weight, by 100 parts of deionized water, 7 parts of salicylic acid, 8 parts of BTA, 8 parts of nickel nitrate, 8 parts of nickel sulfate,
7 parts of fluotitanic acid, 4 parts of sodium gluconate, 4 parts of zinc oxide, 8 parts of cerous nitrate, hydride modified polyphosphazene-polyethersulfone block copolymer 9
Part, 9 parts of polysorbas20,8 parts of n-butanol, 5 parts of sodium metasilicate, 5 parts of polyethylene glycol, 8 parts of oxalic acid, 4 parts of ethanol and 3- [(methylol)
Methyl amine] stir in 4 parts of addition mixers of ethane sulfonic acid after obtain surface conditioning agent, 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 5
By weight, by 100 parts of deionized water, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate,
5 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, hydride modified polyphosphazene-polyethersulfone block copolymer 8
Part, 8 parts of polysorbas20,5 parts of n-butanol, 3 parts of sodium metasilicate, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol and 3- [(methylol)
Methyl amine] stir in 3 parts of addition mixers of ethane sulfonic acid after obtain surface conditioning agent, 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 6
By weight, by 100 parts of deionized water, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate,
5 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, hydride modified polyphosphazene-polyethersulfone block copolymer 8
Part, 8 parts of polysorbas20,5 parts of n-butanol, 3 parts of sodium metasilicate, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol, 3- [(methylol) methyl
Amine] stir in 3 parts of ethane sulfonic acid and sulfonated phosphazene -3 parts of nano oxidized caesium compound addition mixer after obtain table
Face inorganic agent, 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；
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, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate,
5 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, polyphosphazene -8 parts of polyethersulfone block copolymer, polysorbas20
8 parts, 5 parts of n-butanol, 3 parts of sodium metasilicate, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol, 3- [(methylol) methyl amine] ethane sulphur
Surface conditioning agent is obtained after being stirred in sour 3 parts of addition mixers, 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 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, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate,
5 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, 8 parts of polyphosphazene, 8 parts of polysorbas20,5 parts of n-butanol, silicon
In sour 3 parts of sodium, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol, 3- [(methylol) methyl amine] 3 parts of addition mixers of ethane sulfonic acid
Surface conditioning agent is obtained after stirring, 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, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate,
It is 5 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, 8 parts of polysorbas20,5 parts of n-butanol, 3 parts of sodium metasilicate, poly-
3 parts of ethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol, 3- [(methylol) methyl amine] 3 parts of ethane sulfonic acids and sulfonated phosphazene-nano oxygen
Change and obtain surface conditioning agent after being stirred in caesium 3 parts of addition mixers of compound, the stir speed (S.S.) of the mixer is
1800r/min, mixing time 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, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate,
5 parts of fluotitanic acid, 3 parts of sodium gluconate, 3 parts of zinc oxide, 7 parts of cerous nitrate, polyphosphazene -8 parts of polyethersulfone block copolymer, polysorbas20
8 parts, 5 parts of n-butanol, 3 parts of sodium metasilicate, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol, 3- [(methylol) methyl amine] ethane sulphur
Surface conditioning agent is obtained after being stirred in 3 parts of acid and sulfonated phosphazene -3 parts of nano oxidized caesium compound addition mixer,
The stir speed (S.S.) of the mixer is 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
Outward appearance：Range estimation, evaluates its brightness, is evaluated with 1-5 levels, and numeral is bigger, and brightness is better.
Neutral salt spray test：Sprayed using continuous according to national standard GB/T10125-1997, taken out in the different periods, and
With the light brush specimen surface of banister brush, rinsed after taking-up with clear water, the area of " white rust " occurs in observation, is calculated with cross-hatching " white
The area of rust ".
Adhesion test：The adhesive force of galvanized sheet diaphragm after the chromium-free passivation liquid processing of the evaluation present invention is by drawing lattice
Experiment is carried out.Lattice experiment is drawn with reference to national standard GB/T9286-1998, after drawing lattice on passivating film surface using QFH Checker marking knifes, uses fur
Light brush specimen surface is brushed, with Scotch600 adhesive tapes, the wide 19mm × 32.9mm of adhesive tape, will be drawn after lattice part seals 5 minutes, 1
Adhesive tape is pulled out in~2s, observation finds the area that comes off at the edge-smoothing of cut place.
Corrosion resistant test：To under the conditions of 210 DEG C, after dehydrogenation 2 hours, being used using the galvanized sheet after chromium-free passivation liquid processing
The light brush specimen surface of banister brush, is rinsed after taking-up with clear water, and the area of " white rust " occurs in observation, is calculated " white rust " with cross-hatching
Area.
Test result is shown in Table 1.
Table 1
Claims (10)
1. a kind of containing rare earth cerium rust-proof metal treatment fluid, it is characterised in that by weight, its preparing raw material includes：
100 parts of deionized water, salicylic acid 2-10 parts, BTA 4-10 parts, nickel nitrate 3-10 parts, nickel sulfate 2-10 parts, fluorine
Metatitanic acid 1-10 parts, sodium gluconate 1-5 parts, zinc oxide 1-5 parts, cerous nitrate 4-10 parts, hydride modified polyphosphazene-polyethersulfone block
Copolymer 3-10 parts, polysorbas20 5-10 parts, n-butanol 1-10 parts, sodium metasilicate 1-5 parts, polyethylene glycol 1-5 parts, oxalic acid 1-10 parts,
Ethanol 1-5 parts and 3- [(methylol) methyl amine] ethane sulfonic acid 1-5 parts.
2. containing rare earth cerium rust-proof metal treatment fluid according to claim 1, it is characterised in that by weight, it is prepared
Raw material includes：
100 parts of deionized water, salicylic acid 3-8 parts, BTA 5-9 parts, nickel nitrate 4-9 parts, nickel sulfate 3-9 parts, fluotitanic acid
2-8 parts, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, cerous nitrate 5-9 parts, hydride modified polyphosphazene-polyethersulfone block copolymer
4-9 parts, polysorbas20 6-9 parts, n-butanol 3-8 parts, sodium metasilicate 2-5 parts, polyethylene glycol 2-5 parts, oxalic acid 3-8 parts, ethanol 2-4 parts
And 3- [(methylol) methyl amine] ethane sulfonic acid 2-4 parts.
3. containing rare earth cerium rust-proof metal treatment fluid according to claim 2, it is characterised in that by weight, it is prepared
Raw material includes：
100 parts of deionized water, salicylic acid 4-7 parts, BTA 6-8 parts, nickel nitrate 5-8 parts, nickel sulfate 4-8 parts, fluotitanic acid
3-7 parts, sodium gluconate 2-4 parts, zinc oxide 2-4 parts, cerous nitrate 6-8 parts, hydride modified polyphosphazene-polyethersulfone block copolymer
4-9 parts, polysorbas20 6-9 parts, n-butanol 3-8 parts, sodium metasilicate 2-5 parts, polyethylene glycol 2-5 parts, oxalic acid 3-8 parts, ethanol 2-4 parts
And 3- [(methylol) methyl amine] ethane sulfonic acid 2-4 parts.
4. containing rare earth cerium rust-proof metal treatment fluid according to claim 3, it is characterised in that by weight, it is prepared
Raw material includes：
100 parts of deionized water, 6 parts of salicylic acid, 7 parts of BTA, 7 parts of nickel nitrate, 6 parts of nickel sulfate, 5 parts of fluotitanic acid, grape
3 parts of sodium saccharate, 3 parts of zinc oxide, 7 parts of cerous nitrate, hydride modified polyphosphazene -8 parts of polyethersulfone block copolymer, 8 parts of polysorbas20,
5 parts of n-butanol, 3 parts of sodium metasilicate, 3 parts of polyethylene glycol, 5 parts of oxalic acid, 3 parts of ethanol and 3- [(methylol) methyl amine] ethane sulfonic acid
3 parts.
5. the containing rare earth cerium rust-proof metal treatment fluid according to claim any one of 1-4, it is characterised in that the silane is repaiied
Decorations polyphosphazene-polyethersulfone block copolymer preparation method be：
(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. containing rare earth cerium rust-proof metal treatment fluid according to claim 5, it is characterised in that by weight, it is prepared
Raw material also includes：The sulfonated phosphazene of 3 parts by weight-nano oxidized caesium compound.
7. containing rare earth cerium rust-proof metal treatment fluid according to claim 6, it is characterised in that the sulfonated phosphazene-receive
Rice cesium oxide compound preparation method be：
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 of containing rare earth cerium rust-proof metal treatment fluid, it is characterised in that comprise the following steps：By claim
Obtained after being stirred in raw material components addition mixer any one of 1-7.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892439.3A CN107699882A (en) | 2017-09-27 | 2017-09-27 | A kind of containing rare earth cerium rust-proof metal treatment fluid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892439.3A CN107699882A (en) | 2017-09-27 | 2017-09-27 | A kind of containing rare earth cerium rust-proof metal treatment fluid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107699882A true CN107699882A (en) | 2018-02-16 |
Family
ID=61174465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710892439.3A Pending CN107699882A (en) | 2017-09-27 | 2017-09-27 | A kind of containing rare earth cerium rust-proof metal treatment fluid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107699882A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358423A (en) * | 2019-08-01 | 2019-10-22 | 浙江智水环保科技有限公司 | A kind of cleaning anti-oxidant process flow of copper silver protecting agent and copper alloy |
| CN117448828A (en) * | 2023-11-03 | 2024-01-26 | 东莞市德硕化工有限公司 | Metal polishing agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575357A (en) * | 2009-07-02 | 2012-07-11 | 日本帕卡濑精株式会社 | Chromium- and fluorine-free chemical conversion treatment solution for metal surfaces, metal surface treatment method, and metal surface coating method |
| CN104451644A (en) * | 2014-12-04 | 2015-03-25 | 广东达志环保科技股份有限公司 | Trivalent-chromium natural-color passivator with high corrosion resistance for zinc-nickel alloy |
| CN105420710A (en) * | 2015-11-16 | 2016-03-23 | 刘崴崴 | Golden chrome-free passivation solution used for surface treatment of aluminum profiles |
| CN105908168A (en) * | 2016-05-31 | 2016-08-31 | 刘洪建 | Efficient aluminum product passivation agent |
| CN106894009A (en) * | 2017-02-24 | 2017-06-27 | 武汉大学 | A kind of epoxy radicals POSS modified metal surface pretreating reagent and preparation method thereof, application |
| 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 |
-
2017
- 2017-09-27 CN CN201710892439.3A patent/CN107699882A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575357A (en) * | 2009-07-02 | 2012-07-11 | 日本帕卡濑精株式会社 | Chromium- and fluorine-free chemical conversion treatment solution for metal surfaces, metal surface treatment method, and metal surface coating method |
| CN104451644A (en) * | 2014-12-04 | 2015-03-25 | 广东达志环保科技股份有限公司 | Trivalent-chromium natural-color passivator with high corrosion resistance for zinc-nickel alloy |
| CN105420710A (en) * | 2015-11-16 | 2016-03-23 | 刘崴崴 | Golden chrome-free passivation solution used for surface treatment of aluminum profiles |
| CN105908168A (en) * | 2016-05-31 | 2016-08-31 | 刘洪建 | Efficient aluminum product passivation agent |
| CN106894009A (en) * | 2017-02-24 | 2017-06-27 | 武汉大学 | A kind of epoxy radicals POSS modified metal surface pretreating reagent and preparation method thereof, application |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358423A (en) * | 2019-08-01 | 2019-10-22 | 浙江智水环保科技有限公司 | A kind of cleaning anti-oxidant process flow of copper silver protecting agent and copper alloy |
| CN117448828A (en) * | 2023-11-03 | 2024-01-26 | 东莞市德硕化工有限公司 | Metal polishing agent and preparation method thereof |
| CN117448828B (en) * | 2023-11-03 | 2024-04-30 | 东莞市德硕化工有限公司 | Metal polishing agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101418441B (en) | P-Ca-V composite phosphating solution on magnesium alloy surface and chemical conversion processing method | |
| CN107090577A (en) | Environmental protection chromium-free metal passivating solution and preparation method thereof | |
| CN100594263C (en) | chromium-less passivation liquid used for continuous hot dip of galvanized sheet steel | |
| CN105315859A (en) | High-temperature-resistant rust-proof metal surface protectant and preparing method thereof | |
| CN101717930A (en) | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface | |
| KR20110117070A (en) | Surface treatment agent for galvanized steel sheet, galvanized steel sheet and production method thereof | |
| CN101629288A (en) | Passivation treating agent for hot dip aluminum zinc plate and preparation method thereof | |
| CN109385629A (en) | A kind of magnesium alloy high corrosion-resistant passivator and its passivation technology | |
| CN107987591A (en) | A kind of waterborne rust conversion primer base and preparation method thereof | |
| CN104911577A (en) | Chromium-free alkaline passivation solution and passivation method for aluminum alloy | |
| CN103695889A (en) | Chromium-free passivation solution for surface treatment of galvanized plate, aluminum and copper alloy | |
| CN101307448A (en) | Antiseptic treatment process for magnesium alloy section bar, especially for magnesium alloy tube | |
| CN106835108A (en) | A kind of environmentally friendly inorganic organic passivation film of modified graphene oxide | |
| CN109440121A (en) | A kind of processing technology of aluminum veneer | |
| CN107699882A (en) | A kind of containing rare earth cerium rust-proof metal treatment fluid and preparation method thereof | |
| CN105039950A (en) | Environment-friendly metal surface treatment agent | |
| CN106634373A (en) | Waterborne zinc aluminum phosphate anti-rusting primer and preparation method thereof | |
| CN107475704B (en) | Metal surface silane treatment agent and preparation method thereof | |
| CN101476120A (en) | Environment-friendly type metal surface finishing agent and preparation thereof | |
| JP6569194B2 (en) | Surface-treated hot-dip galvanized steel sheet with excellent corrosion resistance | |
| CN107699883A (en) | A kind of green Chrome-free antirust passivating solution and preparation method thereof | |
| CN102747360A (en) | Chromium-free passivation method for galvanized steel sheet by using molybdate/polyphosphate composite system | |
| CN102268664A (en) | Chromium-free passivating solution used for black passivation treatment of zinc plating and preparation method thereof | |
| CN110343412A (en) | Polyphosphoric acid aluminium calcium rust resisting pigment and preparation method thereof | |
| CN106835101A (en) | A kind of modified Nano titanium compound is combined super-hydrophobic passivating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180216 |
|
| WD01 | Invention patent application deemed withdrawn after publication |