CN107033688A - One kind addition chitosan disinfectant type strippable property macromolecule rust-preventing film - Google Patents

Abstract

Chitosan disinfectant type strippable property macromolecule rust-preventing film is added the invention discloses one kind, is made up of following raw materials according：Aluminium isopropoxide, silane coupler KH560, tetraethyl orthosilicate, isostearic acid monoglyceride, polyethylene glycol, methacryloxypropyl trimethoxy silane, polyvinyl alcohol, borax, chitosan, silver-loaded zirconium phosphate, silane coupling A 151, glutaraldehyde, zinc naphthenate, triethanolamine, BTA, lauryl sodium sulfate, appropriate DDAO, appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, appropriate acetic acid, appropriate deionized water；Antirust agent prepared by the present invention antibacterial, hydrophobic, oleophobic, can be not easily broken, heat-resisting and weather resistance is good in workpiece surface formation thin film, play good antirust, anti-corrosive effect, it is convenient that the later stage peels off, and is worthy to be popularized.

Description

One kind addition chitosan disinfectant type strippable property macromolecule rust-preventing film

Technical field

The present invention relates to metal conditioner technical field, more particularly to a kind of addition chitosan disinfectant type strippable property are high Molecule 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- Become rusty agent species it is varied, its Sodium Nitrite because its high rust resistance and it is cheap enjoy always favor and make extensively With, but because natrium nitrosum is that have the material for forcing oncogene, therefore, in the 1980s, just having carried out both at home and abroad a large amount of R＆D work, be prepared for a variety of 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 is natrium nitrosum more safe and reasonable, but during its film forming use, exists and more complicated goes film process to ask Topic, is typically employed to buck processing, or is handled with physical methods such as bamboo knife and scraping blades, and such processing can not only be eliminated Film is it is also possible to damage metal surface, the also 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 of enol strippable property rust-preventing film in recent years is relatively broad, and the starting for studying comparatively China to strippable plastics is It is also more fewer than later, related document report.

Guo Jun exists《The development of PVA water soluble polymer strippable property rust-preventing films》It is anti-by being added into polyvinyl alcohol in one text Become rusty agent and other additives, and it is heated in water-bath to be completely dissolved, and recycles coating the tape casting uniform to coat it In metal surface, the heating, drying film forming in drying box, and utilize 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 meeting 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 film is not readily dissolved the rust-preventing film prepared in cold water at 40 DEG C, but is put into thermostat water bath In be heated in more than 40 DEG C of hot water, it is 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 that there is provided one kind addition chitosan disinfectant type strippable property is high in order to make up the defect of prior art Molecule rust-preventing film.

The present invention is achieved by the following technical solutions：

One kind addition chitosan disinfectant type strippable property macromolecule rust-preventing film, is made up of the raw material of following parts by weight：Isopropanol It is aluminium 6.8-7.5, silane coupler KH560 0.2-0.3, tetraethyl orthosilicate 12-14, isostearic acid monoglyceride 1.8-2, poly- Ethylene glycol 2-2.5, methacryloxypropyl trimethoxy silane 3.3-3.6, polyvinyl alcohol 15-17, borax 1.8-2.5, Chitosan 2.4-2.8, silver-loaded zirconium phosphate 0.6-0.8, the 0.2-0.4 of silane coupling A 151, glutaraldehyde 0.01-0.02, aphthenic acids Zinc 3-4, triethanolamine 2-3, BTA 2-3, lauryl sodium sulfate 1-1.3, appropriate DDAO, Appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, appropriate acetic acid, appropriate deionized water.

A kind of addition chitosan disinfectant type strippable property macromolecule rust-preventing film, 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, which is then added dropwise, is diluted to after continuing return stirring 0.5-1h with deionized water 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 is mixed, 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 is mixed, 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 stirred, and it is 3.5-5.5 that appropriate hydrochloric acid regulation pH value, which 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 it is standby；

（3）By isostearic acid monoglyceride, DDAO according to mass ratio 4:1 mixing is added to deionized water In, the mixed solution that emulsifier concentration is 9-9.5% is made in stirring and dissolving, adds polyethylene glycol magnetic agitation to being completely dissolved 65wt% methacryloxypropyl trimethoxy silane solution is added afterwards, and rise temperature is to 30 DEG C, and rotating speed is 1000- 1200r/min, constant temperature stirring 0.5-1h, it is standby that question response is cooled to room temperature after terminating；

（4）By chitosan with 2% acetic acid aqueous solution stirring and dissolving, be configured to 2% chitosan acetic acid aqueous solution, silver-colored phosphoric acid will be carried Zirconium is dispersed in the 4-5 times of absolute ethyl alcohol measured, ultrasonic vibration 30min, is slowly added to silane coupling A 151, and use dilute salt Acid for adjusting pH value is to 2-3, stirring reaction 1-2h, and it is molten that the mixed liquor is added slowly to chitosan by reaction under magnetic stirring after terminating The glutaraldehyde that 25% is added in liquid, after completion of dropping reacts 3-4h at 30-40 DEG C, still aging, and product is placed in baking oven 105 DEG C of dryings are cooled to standby after room temperature is crushed to constant weight；

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

（6）By step（2）The product and step of preparation（3）The product of preparation is according to mass ratio 2:1 mixing, is mixed under the conditions of 35 DEG C Step is added to after closing stirring 0.5h（5）In the product of preparation, then by composite membrane liquid under the conditions of ultrasonic power 320W it is ultrasonic 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 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, obtained 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 stable silane emulsion, silane emulsion is dispersed in into modified sial and answered Close in colloidal sol, by largely existing 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 caking property of polyvinyl alcohol antirust film liquid, adhesive force, oil resistant, water-fast and wear-resisting etc. performance, chitosan It can dissolve in acid condition, be readily formed thin-film material in neutral conditions, but pure chistosan film bad mechanical property, property Energy is unstable, be unsuitable for the environment such as acidity as widely used bottleneck, utilizes hydrogen bond between chitosan and inorganic nano-particle Combination, increase its mechanical performance, and the amino on chitosan can be closed in the case of crosslinking agent or coupling agent, so as to carry Highly-acidproof energy, the present invention utilizes the hydrolyzed modified silver-loaded zirconium phosphate of silane coupler, and it is mixed and then existed with chitosan solution Gel is formed in the presence of crosslinking agent, the film forming that can promote rust-preventing film after drying, bactericidal properties, raising film is aged acidproof Property etc. performance, the antirust agent for preparing of the present invention can be antibacterial, hydrophobic, oleophobic, not fragile in workpiece surface formation thin film Split, heat-resisting and weather resistance is good, play good antirust, anti-corrosive effect, it is convenient that the later stage peels off, and is worthy to be popularized.

Embodiment

One kind addition chitosan disinfectant type strippable property macromolecule rust-preventing film, by following parts by weight（Kilogram）Raw material prepare system Into：Aluminium isopropoxide 6.8, silane coupler KH560 0.2, tetraethyl orthosilicate 12, isostearic acid monoglyceride 1.8, poly- second two Alcohol 2, methacryloxypropyl trimethoxy silane 3.3, polyvinyl alcohol 15, borax 1.8, chitosan 2.4, silver-loaded zirconium phosphate 0.6th, silane coupling A 151 0.2, glutaraldehyde 0.01, zinc naphthenate 3, triethanolamine 2, BTA 2, dodecyl sulphur Sour sodium 1, appropriate DDAO, appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, appropriate acetic acid, deionization Appropriate amount of water.

A kind of addition chitosan disinfectant type strippable property macromolecule rust-preventing film, is made up of step in detail below：

（1）By aluminium isopropoxide and deionized water according to mol ratio 1：100 mixing, the return stirring at a temperature of 85 DEG C of water bath 1h, it is 3 that nitric acid regulation solution ph, which is then added dropwise, and being diluted to solid content with deionized water after continuation return stirring 0.5h is 5.4%, the silane coupler KH560 ethanol solutions of addition 0.5% after room temperature are cooled to, is stood after stirring and reacts 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, and solution A and solution B are mixed and put Stirred in constant temperature blender with magnetic force, it is 3.5 that appropriate hydrochloric acid regulation pH value, which 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 isostearic acid monoglyceride, DDAO according to mass ratio 4:1 mixing is added to deionized water In, the mixed solution that emulsifier concentration is 9% is made in stirring and dissolving, adds polyethylene glycol magnetic agitation and adds to after being completely dissolved Enter 65wt% methacryloxypropyl trimethoxy silane solution, rise temperature is to 30 DEG C, and rotating speed is 1000r/min, constant temperature 0.5h is stirred, it is standby that question response is cooled to room temperature after terminating；

（4）By chitosan with 2% acetic acid aqueous solution stirring and dissolving, be configured to 2% chitosan acetic acid aqueous solution, silver-colored phosphoric acid will be carried Zirconium is dispersed in the absolute ethyl alcohol of 4 times of amounts, and ultrasonic vibration 30min is slowly added to silane coupling A 151, and use watery hydrochloric acid PH value is adjusted to 2, stirring reaction 1h, the mixed liquor is added slowly in chitosan solution by reaction under magnetic stirring after terminating, The glutaraldehyde that 25% is added after completion of dropping reacts 3h at 30 DEG C, still aging, and product is placed in baking oven into 105 DEG C of dryings extremely Constant weight, is cooled to standby after room temperature is crushed；

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

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

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

Outward appearance：Film is smooth complete, no 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. one kind addition chitosan disinfectant type strippable property macromolecule rust-preventing film, it is characterised in that by the raw material system of following parts by weight Prepare into：Aluminium isopropoxide 6.8-7.5, silane coupler KH560 0.2-0.3, tetraethyl orthosilicate 12-14, isostearic acid list are sweet Grease 1.8-2, polyethylene glycol 2-2.5, methacryloxypropyl trimethoxy silane 3.3-3.6, polyvinyl alcohol 15-17, Borax 1.8-2.5, chitosan 2.4-2.8, silver-loaded zirconium phosphate 0.6-0.8, the 0.2-0.4 of silane coupling A 151, glutaraldehyde 0.01-0.02, zinc naphthenate 3-4, triethanolamine 2-3, BTA 2-3, lauryl sodium sulfate 1-1.3, dodecyl Dimethyl amine is appropriate, appropriate nitric acid, appropriate hydrochloric acid, appropriate absolute ethyl alcohol, appropriate acetic acid, appropriate deionized water.

2. a kind of addition chitosan disinfectant type strippable property macromolecule rust-preventing film according to claim 1, it is characterised in that by with Lower specific steps are made：

（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, which is then added dropwise, is diluted to after continuing return stirring 0.5-1h with deionized water 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 is mixed, 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 is mixed, 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 stirred, and it is 3.5-5.5 that appropriate hydrochloric acid regulation pH value, which 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 it is standby；

（3）By isostearic acid monoglyceride, DDAO according to mass ratio 4:1 mixing is added to deionized water In, the mixed solution that emulsifier concentration is 9-9.5% is made in stirring and dissolving, adds polyethylene glycol magnetic agitation to being completely dissolved 65wt% methacryloxypropyl trimethoxy silane solution is added afterwards, and rise temperature is to 30 DEG C, and rotating speed is 1000- 1200r/min, constant temperature stirring 0.5-1h, it is standby that question response is cooled to room temperature after terminating；

（4）By chitosan with 2% acetic acid aqueous solution stirring and dissolving, be configured to 2% chitosan acetic acid aqueous solution, silver-colored phosphoric acid will be carried Zirconium is dispersed in the 4-5 times of absolute ethyl alcohol measured, ultrasonic vibration 30min, is slowly added to silane coupling A 151, and use dilute salt Acid for adjusting pH value is to 2-3, stirring reaction 1-2h, and it is molten that the mixed liquor is added slowly to chitosan by reaction under magnetic stirring after terminating The glutaraldehyde that 25% is added in liquid, after completion of dropping reacts 3-4h at 30-40 DEG C, still aging, and product is placed in baking oven 105 DEG C of dryings are cooled to standby after room temperature is crushed to constant weight；

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

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