CN106752459A - One kind addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film - Google Patents

Abstract

The invention discloses one kind addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, it is made up of following raw materials according：Aluminium isopropoxide, silane coupler KH560, tetraethyl orthosilicate, Emulsifier EL-60, polyethylene glycol, methyltrimethylsilane, polyvinyl alcohol, borax, normal octane, NPE, phosphoric acid, sodium metaaluminate, micaceous iron oxide, borate, disodium hydrogen phosphate, sodium metasilicate, tartaric acid, triethanolamine, lauryl sodium sulfate, appropriate n-butanol, appropriate fatty acid distribution of coconut oil diglycollic amide, appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, appropriate deionized water；Antirust agent prepared by the present invention can form a tunic in workpiece surface, and with good sustained release, rustless property, formula economy, function persistently, can meet antirust requirement and the demand in market of steel alloy and aluminium alloy etc..

Description

One kind addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film

Technical field

It is peelable the present invention relates to metal conditioner technical field, more particularly to a kind of addition aluminium triphosphate corrosion inhibition type Property macromolecule rust-preventing film.

Background technology

According to statistics, steel product of the gross weight equivalent to metal year amount 10-20% is had every year in the world because burn into becomes rusty The reasons such as erosion cause to use, and are that this people takes various rust-proofing methods, than avoiding corrosion, to reduce loss.It is anti- The species of rust agent is varied, and its Sodium Nitrite is because of its high rust resistance and cheap enjoying always is favored and made extensively With, but because natrium nitrosum is that have the material for forcing oncogene, therefore, in the eighties in 20th century, just carry out both at home and abroad a large amount of R＆D work, be prepared for various with alkyl, alkoxy, halogeno-group, naphthoic acid class and its derivative, nitrobenzoyl acids and boron Material based on acid esters, borate and molybdate etc. replaces the new type water-solubility antirust agent of natrium nitrosum.Although these are new Antirust agent has more complicated film process of going and asks natrium nitrosum more safe and reasonable, but during its film forming use Topic, is typically employed to buck treatment, or is processed with physical methods such as bamboo knife and scraping blades, and such treatment can not only be eliminated Film is it is also possible to damage metal surface, goes back the time-consuming increase cost of work consuming, therefore continuing to develop with antirust technology, people couple Gradually stepping up for the application requirement of antirust solution and its film forming, just occurs in that new rust-preventing film, strippable property rust-preventing film.Wherein poly- second The application in recent years of enol strippable property rust-preventing film is relatively broad, and the starting for studying comparatively China to strippable plastics is Than later, related document report is also fewer.

Guo Jun exists《The development of PVA water soluble polymer strippable property rust-preventing films》By anti-to being added in polyvinyl alcohol in one text Rust agent and other additives, it is heated in water-bath to be completely dissolved, and recycles coating the tape casting by its uniform coating In metal surface, the heating, drying film forming in drying box, and using neutral salt spray test, water-soluble determination experiment and Electronic Speculum Experiment etc. is characterized to polyvinyl alcohol rust prevention packaging film properties, is as a result shown, PVA rust-preventing films not only have good rust-preventing characteristic Can, and with good strippable property and water solubility, the characteristics of meet green package, with preferable application prospect, but it is literary It is that polyvinyl alcohol and polyethylene glycol are all using polyvinyl alcohol and polyethylene glycol compounding use as the carrier film forming agent of rust-preventing film in chapter With good water solubility, and the rust-preventing film for preparing film in cold water at 40 DEG C is not readily dissolved, but is put into thermostat water bath In be heated in more than 40 DEG C of hot water, it can be observed that polyvinyl alcohol film can first gradually soften, caudacoria become thinner, most All dissolvings afterwards, illustrate that the rust-preventing film has water solubility, belong to high-temperature water-soluble film, can recycle, and can ensure normal Good rust-proof effect is played in transport under temperature or less than 40 DEG C of temperature, greatly limit the application field of rust-preventing film, it is necessary to right It is modified, and improves its anticorrosive, oil resistant, high temperature resistant and the performance such as water-fast, expands application field, it is met various conditions Under rust resistance and corrosion resistance requirement.

The content of the invention

The object of the invention is exactly to make up the defect of prior art, there is provided one kind addition aluminium triphosphate corrosion inhibition type is peelable Property macromolecule rust-preventing film.

The present invention is achieved by the following technical solutions：

One kind addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, is made up of the raw material of following weight portion：It is different Aluminium propoxide 6.8-7.5, silane coupler KH560 0.2-0.3, tetraethyl orthosilicate 12-14, Emulsifier EL-60 1.6- 1.8th, polyethylene glycol 2-2.5, methyltrimethylsilane 3.6-4, polyvinyl alcohol 15-17, borax 1.8-2.5, normal octane 14-16, NPE 0.4-0.6, phosphoric acid 3.5-4, sodium metaaluminate 3.8-4.5, micaceous iron oxide 1.5-1.8, borate 3- 4th, disodium hydrogen phosphate 1-1.5, sodium metasilicate 2-3, tartaric acid 2-2.5, triethanolamine 3-4, lauryl sodium sulfate 1-1.3, positive fourth Appropriate alcohol, appropriate fatty acid distribution of coconut oil diglycollic amide, appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, appropriate deionized water.

A kind of addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, is prepared by step in detail below and made Into：

（1）By aluminium isopropoxide and deionized water according to mol ratio 1：100 mixing, flow back at a temperature of 85-95 DEG C of water bath and stir 1-1.5h is mixed, it is 3-3.5 that nitric acid regulation solution ph is then added dropwise, and continues to be diluted to deionized water after being refluxed 0.5-1h Solid content is 5.4-5.8%, is cooled to the silane coupler KH560 ethanol solutions of addition 0.5% after room temperature, is stood after stirring 3-5h is reacted, it is standby；

（2）By deionized water and absolute ethyl alcohol according to mol ratio 1:5-8 mixes, and magnetic agitation uniformly obtains solution A, by positive silicic acid Tetra-ethyl ester, absolute ethyl alcohol are according to mol ratio 1:15-20 mixes, and magnetic agitation is well mixed to obtain solution B, and solution A and solution B are mixed Conjunction is placed in constant temperature blender with magnetic force and stirs, and it is 3.5-5.5 that appropriate hydrochloric acid regulation pH value is added dropwise, and wherein temperature is set to 30 DEG C, turns Speed is 1300-1500r/min, and constant temperature stirring 0.5-1h, question response adds step after terminating（1）The product of preparation mixes 1- 1.5h is standby；

（3）By Emulsifier EL-60, fatty acid distribution of coconut oil diglycollic amide according to mass ratio 4:1 mixing is added in deionized water, Stirring and dissolving is made the mixed solution that emulsifier concentration is 9-9.5%, adds polyethylene glycol magnetic agitation and adds to after being completely dissolved Enter 75wt% methyltrimethylsilane solution, rise high-temperature to 30 DEG C, rotating speed is 1000-1200r/min, and constant temperature stirs 0.5-1h, It is standby that question response is cooled to room temperature after terminating；

(4) by normal octane and n-butanol according to volume ratio 10：1 mixing, adds NPE, phosphoric acid and appropriate Deionized water is stirred to transparent and is designated as mixed solution a, will add sodium metaaluminate in 1/2 times of mixed solution a of amount and stirring is to saturating Bright mark is b, b is slowly dropped in remaining solution a with the rotating speed of 1400-1600r/min, and add mica to aoxidize Iron reacts 2-3h, and reaction is aged after terminating, rotates and be simultaneously washed with deionized for several times, and 60 DEG C of dryings are extremely in vacuum drying chamber , then be placed in product in 0.33% phosphoric acid solution and stir 1.5-2h by constant weight, filtering, by solids in Muffle furnace 200-300 3-4h is calcined at DEG C, crushes standby after being cooled to room temperature；

（5）Polyvinyl alcohol is added in deionized water, heating water bath to 95 DEG C of stirring and dissolvings is made concentration gathering for 10-12wt% Glycohol solution, adds step（4）It is placed in ultrasonic washing instrument after the product stirring mixing of preparation, under conditions of 320W Ultrasonic 15min, adds remaining the remaining material in addition to borax to continue ultrasound 10min after being uniformly dispersed, be subsequently adding 0.5% Borax soln, room temperature is cooled to after cross-linking reaction 45min at 55 DEG C；

（6）By step（2）The product and step of preparation（3）The product of preparation is according to mass ratio 2:1 mixing, mixes under the conditions of 35 DEG C Step is added to after closing stirring 0.5h（5）It is then that composite membrane liquid is ultrasonic under the conditions of ultrasonic power 320W in the product of preparation 15min deaerations, are then coated in surface of workpiece, drying and forming-film by composite membrane liquid.

It is an advantage of the invention that：The present invention according to polyvinyl alcohol because surface has substantial amounts of hydroxyl, with it is good into Film properties, the strippable property rust-preventing film with rustless property is prepared by adding antirust agent and other additives, but because of its film With water-soluble and non-refractory, cause range of application to be limited to, use aluminium isopropoxide to be prepared for precursor herein to this Go out Alumina gel and it is modified using silane coupler, be then combined with Ludox and obtain modified sial complex sol, obtain To with good dispersiveness, do not assemble, the complex sol of the characteristic such as not polycondensation, then use the method for emulsion polymerization with silane list Body is raw material, and tetraethyl orthosilicate is presoma, prepares the silane emulsion of stabilization, silane emulsion is dispersed in into modified sial and is answered Close in colloidal sol, largely exist by with particle surface in complex sol, the hydroxyl reaction with greater activity, make virgin rubber grain table Face-Si-OH ,-Al-OH- are replaced by alkyl, form more non-silicone hydrophobic chain, improve waterproof effect, and molecule easily oozes Penetrate into metal surface, improve the performance, the present invention such as the caking property of polyvinyl alcohol antirust film liquid, adhesive force, oil resistant, water-fast and wear-resisting Also by microemulsion system, micaceous iron oxide/sodium tripolyphosphate powder being prepared by sol-gel process, aluminium triphosphate is A kind of non-polar high-polymer antirust, anti-corrosion, resistant to elevated temperatures chemical products, are coated on the surface of micaceous iron oxide, can be played Go out rustless property higher, and can be good be attached to metallic substrate surface, form fine and close passivating film, play excellent The effect of Antirust corrosion-resistant, antirust agent prepared by the present invention can form a tunic in workpiece surface, with good sustained release, prevent Rust performance, formula economy, function persistently, can meet antirust requirement and the demand in market of steel alloy and aluminium alloy etc..

Specific embodiment

One kind addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, by following weight portion（Kilogram）Raw material system Prepare into：Aluminium isopropoxide 6.8, silane coupler KH560 0.2, tetraethyl orthosilicate 12, Emulsifier EL-60 1.6, poly- second Glycol 2, methyltrimethylsilane 3.6, polyvinyl alcohol 15, borax 1.8, normal octane 14, NPE 0.4, phosphoric acid 3.5th, sodium metaaluminate 3.8, micaceous iron oxide 1.5, borate 3, disodium hydrogen phosphate 1, sodium metasilicate 2, tartaric acid 2, triethanolamine 3, Lauryl sodium sulfate 1, appropriate n-butanol, appropriate fatty acid distribution of coconut oil diglycollic amide, appropriate nitric acid, appropriate hydrochloric acid, anhydrous second Appropriate alcohol, appropriate deionized water.

A kind of addition aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, is prepared by step in detail below and made Into：

（1）By aluminium isopropoxide and deionized water according to mol ratio 1：100 mixing, are refluxed at a temperature of 85 DEG C of water bath 1h, it is 3 that nitric acid regulation solution ph is then added dropwise, and to continue to be refluxed and be diluted to solid content with deionized water after 0.5h and be 5.4%, the silane coupler KH560 ethanol solutions of addition 0.5% after room temperature are cooled to, stood after stirring and react 3h, it is standby；

（2）By deionized water and absolute ethyl alcohol according to mol ratio 1:5 mixing, magnetic agitation uniformly obtains solution A, by positive silicic acid four Ethyl ester, absolute ethyl alcohol are according to mol ratio 1:15 mixing, magnetic agitation is well mixed to obtain solution B, solution A and solution B is mixed and is put Stirred in constant temperature blender with magnetic force, it is 3.5 that appropriate hydrochloric acid regulation pH value is added dropwise, and wherein temperature is set to 30 DEG C, and rotating speed is 1300r/min, constant temperature stirring 0.5h, question response adds step after terminating（1）It is standby that the product of preparation mixes 1h；

（3）By Emulsifier EL-60, fatty acid distribution of coconut oil diglycollic amide according to mass ratio 4:1 mixing is added in deionized water, Stirring and dissolving is made the mixed solution that emulsifier concentration is 9%, adds polyethylene glycol magnetic agitation and is added to after being completely dissolved 75wt% methyltrimethylsilane solution, rises high-temperature to 30 DEG C, and rotating speed is 1000r/min, constant temperature stirring 0.5h, question response knot Room temperature is cooled to after beam standby；

(4) by normal octane and n-butanol according to volume ratio 10：1 mixing, adds NPE, phosphoric acid and appropriate Deionized water is stirred to transparent and is designated as mixed solution a, will add sodium metaaluminate in 1/2 times of mixed solution a of amount and stirring is to saturating Bright mark is b, b is slowly dropped in remaining solution a with the rotating speed of 1400r/min, and add micaceous iron oxide anti- Answer 2h, reaction is aged after terminating, and rotates and is simultaneously washed with deionized for several times, in vacuum drying chamber 60 DEG C of dryings to constant weight, so Product is placed in 0.33% phosphoric acid solution afterwards stirs 1.5h, filtered, solids is calcined into 3h in the Muffle furnace at 200 DEG C, it is cold But to crushing standby after room temperature；

（5）Polyvinyl alcohol is added in deionized water, heating water bath to 95 DEG C of stirring and dissolvings is made the polyethylene that concentration is 10wt% Alcoholic solution, adds step（4）It is placed in ultrasonic washing instrument after the product stirring mixing of preparation, the ultrasound under conditions of 320W 15min, adds remaining the remaining material in addition to borax to continue ultrasound 10min after being uniformly dispersed, be subsequently adding 0.5% borax Solution, room temperature is cooled to after cross-linking reaction 45min at 55 DEG C；

（6）By step（2）The product and step of preparation（3）The product of preparation is according to mass ratio 2:1 mixing, mixes under the conditions of 35 DEG C Step is added to after closing stirring 0.5h（5）It is then that composite membrane liquid is ultrasonic under the conditions of ultrasonic power 320W in the product of preparation 15min deaerations, are then coated in surface of workpiece, drying and forming-film by composite membrane liquid.

The metal works that will be cleaned up are impregnated into the antirust solution prepared according to embodiment, and performance is carried out after drying and forming-film Test, it is as a result as follows：

Outward appearance：Film is smooth complete, without broken hole and unnecessary, not easy mold release；Hardness：＞ 2H；Salt water immersion test（3% sodium chloride, 25±2℃）：＞ 26h, neutral salt spray test（5% sodium chloride, 35 ± 2 DEG C）：＞ 48h；It is water-soluble：70 DEG C of ＞.

Claims (2)

1. it is a kind of to add aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, it is characterised in that by the original of following weight portion Material preparation is made：Aluminium isopropoxide 6.8-7.5, silane coupler KH560 0.2-0.3, tetraethyl orthosilicate 12-14, polyoxyethylene Castor oil 1.6-1.8, polyethylene glycol 2-2.5, methyltrimethylsilane 3.6-4, polyvinyl alcohol 15-17, borax 1.8-2.5, just Octane 14-16, NPE 0.4-0.6, phosphoric acid 3.5-4, sodium metaaluminate 3.8-4.5, micaceous iron oxide 1.5- 1.8th, borate 3-4, disodium hydrogen phosphate 1-1.5, sodium metasilicate 2-3, tartaric acid 2-2.5, triethanolamine 3-4, dodecyl sulphate Sodium 1-1.3, appropriate n-butanol, appropriate fatty acid distribution of coconut oil diglycollic amide, appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, go Ion appropriate amount of water.

It is 2. a kind of according to claim 1 to add aluminium triphosphate corrosion inhibition type strippable property macromolecule rust-preventing film, it is characterised in that It is made up of step in detail below：

（1）By aluminium isopropoxide and deionized water according to mol ratio 1：100 mixing, flow back at a temperature of 85-95 DEG C of water bath and stir 1-1.5h is mixed, it is 3-3.5 that nitric acid regulation solution ph is then added dropwise, and continues to be diluted to deionized water after being refluxed 0.5-1h Solid content is 5.4-5.8%, is cooled to the silane coupler KH560 ethanol solutions of addition 0.5% after room temperature, is stood after stirring 3-5h is reacted, it is standby；

（2）By deionized water and absolute ethyl alcohol according to mol ratio 1:5-8 mixes, and magnetic agitation uniformly obtains solution A, by positive silicic acid Tetra-ethyl ester, absolute ethyl alcohol are according to mol ratio 1:15-20 mixes, and magnetic agitation is well mixed to obtain solution B, and solution A and solution B are mixed Conjunction is placed in constant temperature blender with magnetic force and stirs, and it is 3.5-5.5 that appropriate hydrochloric acid regulation pH value is added dropwise, and wherein temperature is set to 30 DEG C, turns Speed is 1300-1500r/min, and constant temperature stirring 0.5-1h, question response adds step after terminating（1）The product of preparation mixes 1- 1.5h is standby；

（3）By Emulsifier EL-60, fatty acid distribution of coconut oil diglycollic amide according to mass ratio 4:1 mixing is added in deionized water, Stirring and dissolving is made the mixed solution that emulsifier concentration is 9-9.5%, adds polyethylene glycol magnetic agitation and adds to after being completely dissolved Enter 75wt% methyltrimethylsilane solution, rise high-temperature to 30 DEG C, rotating speed is 1000-1200r/min, and constant temperature stirs 0.5-1h, It is standby that question response is cooled to room temperature after terminating；

(4) by normal octane and n-butanol according to volume ratio 10：1 mixing, adds NPE, phosphoric acid and appropriate Deionized water is stirred to transparent and is designated as mixed solution a, will add sodium metaaluminate in 1/2 times of mixed solution a of amount and stirring is to saturating Bright mark is b, b is slowly dropped in remaining solution a with the rotating speed of 1400-1600r/min, and add mica to aoxidize Iron reacts 2-3h, and reaction is aged after terminating, rotates and be simultaneously washed with deionized for several times, and 60 DEG C of dryings are extremely in vacuum drying chamber , then be placed in product in 0.33% phosphoric acid solution and stir 1.5-2h by constant weight, filtering, by solids in Muffle furnace 200-300 3-4h is calcined at DEG C, crushes standby after being cooled to room temperature；

（5）Polyvinyl alcohol is added in deionized water, heating water bath to 95 DEG C of stirring and dissolvings is made concentration gathering for 10-12wt% Glycohol solution, adds step（4）It is placed in ultrasonic washing instrument after the product stirring mixing of preparation, under conditions of 320W Ultrasonic 15min, adds remaining the remaining material in addition to borax to continue ultrasound 10min after being uniformly dispersed, be subsequently adding 0.5% Borax soln, room temperature is cooled to after cross-linking reaction 45min at 55 DEG C；

（6）By step（2）The product and step of preparation（3）The product of preparation is according to mass ratio 2:1 mixing, mixes under the conditions of 35 DEG C Step is added to after closing stirring 0.5h（5）It is then that composite membrane liquid is ultrasonic under the conditions of ultrasonic power 320W in the product of preparation 15min deaerations, are then coated in surface of workpiece, drying and forming-film by composite membrane liquid.