CN103113712B - Preparation method and application of modified nano-silicon dioxide toughened epoxy resin - Google Patents
Preparation method and application of modified nano-silicon dioxide toughened epoxy resin Download PDFInfo
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- CN103113712B CN103113712B CN201310043119.2A CN201310043119A CN103113712B CN 103113712 B CN103113712 B CN 103113712B CN 201310043119 A CN201310043119 A CN 201310043119A CN 103113712 B CN103113712 B CN 103113712B
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Abstract
The invention relates to a preparation method of modified nano-silicon dioxide toughened epoxy resin; the preparation method comprises the following steps of: (1), adding 1-2g of amino silane coupling agent into 48-50g of absolute ethyl alcohol firstly, adding glacial acetic acid to adjust the pH (potential of hydrogen) value to be 3-4, shaking by ultrasonic wave in order to fully dissolve the amino silane coupling agent into the absolute ethyl alcohol; (2), putting 5-6g of nano-SiO2 into a flask, pouring 20-30g of the solution obtained in step (1), dispersing by ultrasonic wave for 30min, stirring for 3-5 hours at the constant temperature of 75 DEG C at the stirring speed of 450rpm, cooling, centrifugally separating, and drying for 24 hours at 140 DEG C, so as to obtain modified nano-silicon dioxide; and (3), adding 50-150g of liquid epoxy resin into a reaction container, heating to 60 DEG C, slowly adding 0.1-1% by weight of liquid epoxy resin of modified nano-silicon dioxide prepared by step (2) while stirring, after adding, stirring uniformly, dispersing by high-speed shearing, heating to 90 DEG C within 1 hour, and then reacting for 3-5 hours at a constant temperature, cooling, finally the product is obtained. The resin prepared by the preparation method is stable in property, and the property of the prepared coating is greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy resin, specifically relate to the preparation method of a kind of modified manometer silicon dioxide chemical toughening epoxy resin and environment-friendly type protective coating, the environment-friendly type coating produced by this method preparation can be widely used in the anticorrosive coating of steel construction.
Background technology
Epoxy resin has excellent performance, and such as cohesive force is strong, processibility good and shrinking percentage is little etc., is apply one of maximum thermosetting resin at present.But epoxy resin, the low-molecular-weight epoxy resin that particularly viscosity is low, a large amount of epoxide groups is there is in molecule, during solidification, cross-linking density is very large, property is very crisp, fatigue strength and impelling strength poorer, and thermotolerance, stripping strength are especially poor, have influence on sticking power and the antiseptic property of epoxy coat, be difficult to the demand for development meeting modern industrial technology.Therefore, need to carry out toughening modifying to improve the performance of its excellence to epoxy resin, but while raising epoxy resin toughness, often reduce the mechanical modulus of cured article and thermotolerance etc.
Along with the development of nanotechnology, nano material obtains investigation and application widely, and its application in coating also gets more and more.The small-size effect that nano material does not possess with the physics of its uniqueness, chemical property and conventional material, surface-interface effect, quantum size effect and macro quanta tunnel effect and its special photoelectric characteristic, high Magnetoresistance Phenomena, non-linear resistance phenomenon and at high temperature still there is high-strength, the characteristic such as high-ductility, excellent stability, increase substantially coatingsurface toughness and hardness, water-wash resistance, sticking power, smooth finish, the resistance to deterioration of coating products, also there is wear resistance and excellent resistance to chemical corrosion.Nano particle, as toughner, is a kind of novel method that nanocomposite applications is expanded.By improving epoxy-resin systems internal structure to the modification of nano material functionalization, and then the method promoting coating overall performance have also been obtained and approves widely.
Chinese patent CN 102190858 A discloses a kind of epoxide resin material toughness reinforcing by nano silicon and preparation method thereof.The method is with dendritic macromole Grafted Nano-scale silicon-dioxide, then is base-material with epoxy resin, nano silicon toughner and solidifying agent is added to wherein, and then obtains nanometer toughening-modifiedepoxy resin material.This invention prepared by epoxide resin material toughness obtain certain raising.But described in invention and dendritic macromole (Changchun should change produced) be special, can not be commercially.So, in the present invention, by the silane coupler modified nano silicon adopting band amino, and then Toughening Modification of Epoxy, add reactive thinner, defoamer and solidifying agent, make environment-friendly type solvent-free epoxy coating, toughness reinforcing anticorrosion for steel construction.The solvent-free environment-protection epoxy coating utilizing the present invention to make, by greatly improving the impact of coating on environment, reaches VOC zero release, improves the performance of film each side.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, nano material technology is the object of the invention is to combine with epoxy resin roughening technology, adopt a kind of new modified method, first modified manometer silicon dioxide, and then carry out chemical bonding with the nano material of modification and low-molecular-weight liquid epoxies.Thus overcome the technical barrier of toughness enhancing in existing Toughening Epoxy Resin and the excellent properties reduction of epoxy resin own.
For achieving the above object, the technical solution used in the present invention step is as follows:
(1) first get 1g ~ 2g amino silicane coupling agent and join 48g ~ 50g dehydrated alcohol, then add between Glacial acetic acid adjust ph to 3 ~ 4, ultrasonic oscillation 10min ~ 20 min, make it be dissolved completely in dehydrated alcohol;
(2) 5g ~ 6g Nano-meter SiO_2 is taken
2put into there-necked flask, pour ethanol solution scattered in 20g ~ 30g step (1) into, ultrasonic disperse 30min, then put into thermostat water bath, under the stirring velocity of 450r/min, constant temperature 75 DEG C stirs 3 ~ 5 hours, cools afterwards, centrifugation, 140 DEG C of dry 24h, obtain modified manometer silicon dioxide powder;
(3) 50g ~ 150g liquid epoxies is joined in reaction vessel, load onto electrodynamictype homogenizer, be heated to 60 DEG C, the modified manometer silicon dioxide obtained by step (2) being equivalent to liquid epoxies weight 0.1% ~ 1% is slowly added under whipped state, after adding, stir, under high speed shear dispersion condition, 90 DEG C are heated in 1 hour, then isothermal reaction 3 ~ 5 hours.After remove heating installation, stir cooling after, products therefrom is exactly the toughness reinforcing epoxy resin product of modified manometer silicon dioxide.
As further measure of the present invention, prepare solvent-free environment-protection epoxy coating, comprise the following steps:
By mass percentage, the improved silica by obtained is epoxy resin toughened: polypropylene glycol diglycidyl ether reactive thinner: defoamer=50 ~ 60%:15 ~ 20%:0.1 ~ 0.6% mixes under moderate-speed mixer condition, for subsequent use.Before brushing, add the epoxy hardener of mass percent 25 ~ 28% in above-mentioned material, after short mix slaking, brush at pretreated steel structure surface immediately, controlling sealing bottom coating layer thickness is (30 ± 5) μm.
By the enforcement of technique scheme, obtain solvent-free environment-protection epoxypaint, the snappiness of epoxy resin is greatly improved, and other performances of epoxy resin have well been kept.
Compared with prior art, in the present invention, through the reaction of silane coupling agent and nano silicon, make silane coupling agent by chemical bond and nano silicon grafting, obtain modified manometer silicon dioxide.Owing to containing Amino End Group in silane coupling agent, and then the object with epoxy resin ring-opening reaction can be reached, prepare the epoxy resin that modified manometer silicon dioxide is toughness reinforcing.This resin property is stablized, and the coating property prepared is greatly improved.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation, but the present invention is never limited to these embodiments.
Embodiment 1
(1) preparation of modified manometer silicon dioxide
First get 1gKH-550 and join 48g dehydrated alcohol, then to add Glacial acetic acid adjust ph be 3.5, ultrasonic oscillation 10min, makes it be dissolved completely in dehydrated alcohol.
Take 5g Nano-meter SiO_2
2, put into there-necked flask, pour the ethanol solution of the scattered KH-550 of 20g into, ultrasonic disperse 30min, then put into thermostat water bath, under the stirring velocity of 450r/min, constant temperature 75 DEG C stirs 3.5 hours.Cool afterwards, centrifugation, 140 DEG C of dry 24h, obtain modified manometer silicon dioxide powder.
(2) preparation that modified manometer silicon dioxide is epoxy resin toughened
100g liquid epoxies is joined in reaction vessel, load onto electrodynamictype homogenizer, be heated to 60 DEG C, under whipped state, add the modified manometer silicon dioxide of 0.1g, slowly add, after adding, stir, under high speed shear dispersion condition, in 1 hour, be heated to 90 DEG C, then isothermal reaction 4 hours.After remove heating installation, stir cooling after, products therefrom is exactly the toughness reinforcing epoxy resin product of modified manometer silicon dioxide.
By 56.8g modified epoxy, 16.1g polypropylene glycol diglycidyl ether and 0.3g defoamer (BYK-141, BYK company of Germany produces) mix under moderate-speed mixer condition, after a while by 26.8g solidifying agent (NX-2007, Ka Delai company of the U.S. produce) add and short mix slaking after, brush at pretreated steel structure surface immediately, obtained film has following performance:
Shock resistance/cm:50
Snappiness/mm:1
Coating hardness: H
Sticking power/Mpa: >=12A/B
Salt fog resistance/h: >=800.
Embodiment 2
(1) preparation of modified manometer silicon dioxide
First get 1.5gKH-550 and join 49g dehydrated alcohol, then to add Glacial acetic acid adjust ph be 4, ultrasonic oscillation 15min, makes it be dissolved completely in dehydrated alcohol.
Take 5.5g Nano-meter SiO_2
2, put into there-necked flask, pour the ethanol solution of the scattered KH-550 of 25g into, ultrasonic disperse 30min, then put into thermostat water bath, under the stirring velocity of 450r/min, constant temperature 75 DEG C stirs 4 hours.Cool afterwards, centrifugation, 140 DEG C of dry 24h, obtain modified manometer silicon dioxide powder.
(2) preparation that modified manometer silicon dioxide is epoxy resin toughened
100g liquid epoxies is joined in reaction vessel, load onto electrodynamictype homogenizer, be heated to 60 DEG C, under whipped state, add the gauge of 0.5g(by epoxy resin) modified manometer silicon dioxide, slowly add, after adding, stir, under high speed shear dispersion condition, in 1 hour, be heated to 90 DEG C, then isothermal reaction 4 hours.After remove heating installation, stir cooling after, products therefrom is exactly the toughness reinforcing epoxy resin product of modified manometer silicon dioxide.
By 55.8g modified epoxy, 17.2g polypropylene glycol diglycidyl ether and 0.4g defoamer (BYK-141, BYK company of Germany produces) mix under moderate-speed mixer condition, after a while by 26.6g solidifying agent (NX-2007, Ka Delai company of the U.S. produce) add and short mix slaking after, brush at pretreated steel structure surface immediately, obtained film has following performance:
Shock resistance/cm:50
Snappiness/mm:1
Coating hardness: H
Sticking power/Mpa: >=12A/B
Salt fog resistance/h: >=800
Embodiment 3
(1) preparation of modified manometer silicon dioxide
First get 2gKH-550 and join 50g dehydrated alcohol, then to add Glacial acetic acid adjust ph be 3.6, ultrasonic oscillation 20 min, makes it be dissolved completely in dehydrated alcohol.
Take 6g Nano-meter SiO_2
2, put into there-necked flask, pour the ethanol solution of the scattered KH-550 of 30g into, ultrasonic disperse 30min, then put into thermostat water bath, under the stirring velocity of 450r/min, constant temperature 75 DEG C stirs 4.5 hours.Cool afterwards, centrifugation, 140 DEG C of dry 24h, obtain modified manometer silicon dioxide powder.
(2) preparation that modified manometer silicon dioxide is epoxy resin toughened
100g liquid epoxies is joined in reaction vessel, load onto electrodynamictype homogenizer, be heated to 60 DEG C, under whipped state, add the gauge of 1g(by epoxy resin) modified manometer silicon dioxide, slowly add, after adding, stir, under high speed shear dispersion condition, in 1 hour, be heated to 90 DEG C, then isothermal reaction 5 hours.After remove heating installation, stir cooling after, products therefrom is exactly the toughness reinforcing epoxy resin product of modified manometer silicon dioxide.
By 54.8g modified epoxy, 19.1g polypropylene glycol diglycidyl ether and 0.5g defoamer (BYK-141, BYK company of Germany produces) mix under moderate-speed mixer condition, after a while by 25.6g solidifying agent (NX-2007, Ka Delai company of the U.S. produce) add and short mix slaking after, brush at pretreated steel structure surface immediately, obtained film has following performance:
Shock resistance/cm:50
Snappiness/mm:1
Coating hardness: H
Sticking power/Mpa: >=12A/B
Salt fog resistance/h: >=800.
The examples of implementation of the above are only the preferred embodiment of the present invention, not limit practical range of the present invention with this, therefore the change that all shapes according to the present invention, principle are done, all should be encompassed in protection scope of the present invention.
Claims (2)
1. the preparation method that modified manometer silicon dioxide is epoxy resin toughened, is characterized in that: concrete steps are
(1) first get 1g ~ 2g amino silicane coupling agent and join 48g ~ 50g dehydrated alcohol, then add between Glacial acetic acid adjust ph to 3 ~ 4, ultrasonic oscillation 10min ~ 20 min, make it be dissolved completely in dehydrated alcohol;
(2) 5g ~ 6g Nano-meter SiO_2 is taken
2put into there-necked flask, pour ethanol solution scattered in 20g ~ 30g step (1) into, ultrasonic disperse 30min, then put into thermostat water bath, under the stirring velocity of 450r/min, constant temperature 75 DEG C stirs 3 ~ 5 hours, cools afterwards, centrifugation, 140 DEG C of dry 24h, obtain modified manometer silicon dioxide powder;
(3) 50g ~ 150g liquid epoxies is joined in reaction vessel, load onto electrodynamictype homogenizer, be heated to 60 DEG C, the modified manometer silicon dioxide powder obtained by step (2) being equivalent to liquid epoxies weight 0.1% ~ 1% is slowly added under whipped state, after adding, stir, under high speed shear dispersion condition, 90 DEG C are heated in 1 hour, isothermal reaction 3 ~ 5 hours again, after remove heating installation, stir cooling after, products therefrom is exactly the toughness reinforcing epoxy resin product of modified manometer silicon dioxide.
2. the application of epoxy resin that obtains of a method according to claim 1, it is characterized in that: prepare solvent-free environment-protection epoxy coating with it, comprise the following steps: by mass percentage, by epoxy resin toughened for obtained improved silica: polypropylene glycol diglycidyl ether reactive thinner: defoamer=54.8 ~ 56.8%:15 ~ 20%:0.1 ~ 0.6% mixes under moderate-speed mixer condition, for subsequent use; Before brushing, add the epoxy hardener of mass percent 25 ~ 28% in above-mentioned material, after short mix slaking, brush at pretreated steel structure surface immediately, controlling sealing bottom coating layer thickness is 30 ± 5 μm.
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| CN104530647B (en) * | 2014-12-25 | 2016-09-28 | 太原理工大学 | Centrifugal auxiliary law prepares the method for Epoxy/nano silica composite material |
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| CN115536601A (en) * | 2022-10-14 | 2022-12-30 | 重庆交通大学 | Curing agent capable of resisting flame, strengthening and toughening epoxy resin, epoxy resin material and application |
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