CN103865033A - Multi-carboxyl cage silsesquioxane modified epoxy resin and application thereof in coating - Google Patents
Multi-carboxyl cage silsesquioxane modified epoxy resin and application thereof in coating Download PDFInfo
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Abstract
The invention belongs to the field of epoxy resin coating, and discloses a multi-carboxyl cage silsesquioxane (CSQ) modified epoxy resin and an application thereof in coating. The CSQ modified epoxy resin is prepared by following steps of throwing CSQ and epoxy resin into a reaction kettle according to the mass ratio of (1:4)-(1:7), adding a catalyst and an organic solvent, and mixing uniformly; reacting for 2-4 hours at 105-115DEG C, filtering and discharging, so as to obtain CSQ modified epoxy resin containing high activity hydroxyl; and then carrying out curing reaction on the hydroxyl and polyisocyanate group so as to prepare a high hardness quick curing coating, wherein the mass ratio of the organic coating to the curing agent is (30:50)-(70:25). The CSQ modified epoxy resin has high hardness, good abrasion performance and fast drying speed, so that the coating prepared based on the modified epoxy resin has advantages of high hardness, good toughness, fast drying speed, good shock resistance and good corrosion resistance.
Description
Technical field
The invention belongs to epoxypaint field, particularly a kind of many carboxyls cage-type silsesquioxane modified epoxy and the application in coating thereof.
Background technology
Along with expanding economy, user is more and more higher to the performance requriements of epoxy-based lacquers, not only requires it to have good sticking power and wear resistance, and requires just can, from dry, require very high like this to the quick-drying of epoxy resin after the rear 24h of brushing.On epoxy resin molecular chain, contain the groups such as carboxyl, hydroxyl, epoxy group(ing), therefore there is good mechanical property and physicochemical property.Epoxypaint in drying process by becoming cancellated macromole with solidifying agent is crosslinked.But in epoxy resin paint, use merely solidifying agent cured epoxy resin, its cured article fragility is large, shock strength is low, easy to crack, in the time being subject to External Force Acting, be very easy to destroyed.So become inevitable with other component modification epoxies.Conventionally the way adopting is that epoxy and flexible high molecular material are carried out to blend, or by epoxy and soft segment grafting, copolymerization.Wherein the most frequently used method of modifying is by epoxy resin and Synolac modification by copolymerization, although this modification mode can effectively reduce the fragility of epoxy resin, the every mechanical property of balance, but when improving toughness, can reduce the hardness of epoxy resin, and because the degree of branching of Synolac is lower, the molecular resin amount of simple epoxy and Synolac synthesized is large not, in short period of time, be difficult to complete film-forming to keep out the infiltration of solvent molecule, so should guarantee the solvent resistance of coating, require again paint film dry rapidly, this requirement is difficult to reach.In order to increase cross-linking density, do not make again the easy efflorescence of epoxy resin because cross-linking density is too high, the organic inorganic hybridization body with the high degree of branching is undoubtedly best selection.
Since 20th century, along with the appearance of nano material and the further maturation of hybrid technology, nano material has caused people's extensive concern with its remarkable over-all properties.Organic/inorganic hybridization material is the large focus in field of polymer technology especially, by inorganic nano-particle, polymkeric substance is strengthened toughness reinforcingly, has overcome traditional toughened system and cause in toughening polymer the shortcoming of its strength decreased.Make hybrid material show the over-all properties of organic polymer material and inorganic functional material by the synergy between organic constituent and inorganic component.Thereby can optimize further the interaction of storeroom, effectively improve the performance of material.As everyone knows, by problem of inorganic nano-particle toughening epoxy ubiquity, inorganic nano-particle and epoxy resin can not be compatible, and this will inevitably cause the reunion of nanoparticle in epoxy resin.Therefore, this brand-new hybrid material of cage-type silsesquioxane enters people's the visual field.The molecular dimension of cage-type silsesquioxane is 1～3nm, and inside has the structure of similar silicon-dioxide.Outside can connect organic radicals R, cage-type silsesquioxane has stronger structural symmetry, dimensional stabilizing and high temperature resistant, in view of the designability of R group, by the modification to R group, can improve the consistency between epoxy resin and cage-type silsesquioxane, effectively avoid the reunion and two of electrodeless particle to be separated.In the time introducing soft segment in cage-type silsesquioxane, can allow epoxy resin reach desirable toughening effect simultaneously.But, at home and abroad in epoxide modified research, only embody cage-type silsesquioxane and epoxy resin and carry out physical blending, cage-type silsesquioxane modified epoxy can effectively embody the snappiness of cage-type silsesquioxane, and its hybrid material has again excellent corrosion resistance and the high rigidity of epoxy resin.But this method of modifying is more difficult often, be mainly reflected in cage-type silsesquioxane difficult dispersion in epoxy resin, and this method of modifying can produce any impact hardly on the dry speed of epoxy resin.Therefore, synthetic a kind of hardness is high, wear resistance good, the fast epoxy resin of dry speed, is that manufacturer is pursued always, but is still blank at present in the research both domestic and external of this one side.
Therefore, seek a kind of technique simple, simultaneously product possess again that hardness is high, the production method of the modified epoxy of good toughness, fast drying, tool is of great significance.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of many carboxyls cage-type silsesquioxane (CSQ) modified epoxy.
Another object of the present invention is to provide a kind of preparation method of above-mentioned many carboxyls cage-type silsesquioxane modified epoxy.
Still a further object of the present invention is to provide the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy in coating.
Object of the present invention realizes by following proposal:
A kind of many carboxyls cage-type silsesquioxane modified epoxy, is prepared by following methods:
By many carboxyls cage-type silsesquioxane and epoxy resin in mass ratio 1:4～1:7 feed intake in reactor, and add by the catalyzer of reaction system total mass 0.15～0.3% and account for the organic solvent of resin total amount 20%, evenly mix; Under 105～115 ℃ of conditions, react 2～4h, filter discharging, obtain the many carboxyls cage-type silsesquioxane modified epoxy containing high reactivity hydroxyl;
Described many carboxyls cage-type silsesquioxane, structural formula is: (SiO
1.5)
m(C
6h
4cOOH)
m(m=8,10,12);
Described catalyzer refers at least one in chromium acetylacetonate, 4-butyl-phosphonium acetate, trolamine, triphenyl phosphorus, benzyldimethylamine and Bian base triphenyl phosphonium muriate.
The organic solvent nail benzene adopting in the preparation of described modified epoxy is or/and dimethylbenzene.
Preferably, described epoxy resin refers at least one in bisphenol A type epoxy resin, bisphenol f type epoxy resin, methylol bisphenol A type epoxy resin, bisphenol-A epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.
The present invention also provides the application of above-mentioned many carboxyls cage-type silsesquioxane modified epoxy in coating, adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it includes organic coating and solidifying agent, and the mass ratio of organic coating and solidifying agent is 30:50～70:25; First each organic coating component dispersed with stirring, then carry out curing reaction after adding solidifying agent to mix, obtain the high rigidity expediting setting type coating of use state; Wherein, organic coating comprises following by the component of system total mass per-cent:
Described solidifying agent refers to polyisocyanate-based solidifying agent;
Described pigment refers at least one in titanium dioxide, phthalocyanine blue, phthalocyanine green and carbon black;
Described filler refers at least one in calcium carbonate, white carbon black, kaolin, magnesium hydroxide and barium sulfate.
Described auxiliary agent refers at least one in dispersion agent, flow agent and siccative.
Preferably, described polyisocyanate-based solidifying agent refers at least one in adduct and the HDI biuret of adduct, XDI and TriMethylolPropane(TMP) of adduct, IPDI and the TriMethylolPropane(TMP) of TDI tripolymer, IPDI tripolymer, TDI and TriMethylolPropane(TMP).
It is 70～80% that described many carboxyls cage-type silsesquioxane modified epoxy is diluted to solid content with diluting solvent before using.
Preferably, described diluting solvent nail benzene, dimethylbenzene, petroleum naphtha, raffinate oil, at least one in ethyl acetate, butylacetate, 100# solvent oil and 200# solvent oil.
Preferably, before described solidifying agent use, adding ethyl acetate to solid content is 30～40%.
Preferably, at least one in described siccative finger ring alkanoic acid metallic soap and isocaprylic acid metallic soap.
Preferably, described dispersion agent is at least one in poly carboxylic acid amine type, modified polyorganosiloxane type, modified polyacrylate type and poly carboxylic acid ammonium salt type etc.
Preferably, described flow agent is at least one in organic silicon modified by polyether, polyester modification hydroxyl organosilicon, isocyanate-modified organosilicon, polyacrylic ester and fluorin modified crylic acid ester copolymer.
Mechanism of the present invention is:
(1) the present invention utilizes the epoxy group(ing) on carboxyl and the epoxy resin on CSQ to react, and CSQ is introduced in epoxy resin, and generate and have highly active hydroxyl simultaneously.Molecule aspect, CSQ is introduced in epoxy resin, the macromole that forms high crosslink density, makes its existing CSQ on molecular chain, has again epoxy, both retained the erosion resistance of epoxy resin, the advantage of high rigidity, CSQ can carry out epoxy resin again effectively toughness reinforcing simultaneously.
(2) high rigidity expediting setting type coating of the present invention utilizes hydroxyl to react with polyisocyanate-based being cured, therefore speed of response is fast and can at lower temperature, carry out, in guaranteeing material hardness and wear resistance, can effectively improve coating from dryness.
The present invention, with respect to prior art, has following outstanding advantage and beneficial effect:
(1) CSQ modified epoxy of the present invention adopts chemical bonds, improve molecule consistency, have that sticking power good (0 grade), fullness ratio are good, toughness strong (1mm), physical strength high (6H), shock-resistance good (45kgcm), the good advantage of antiseptic property.
(2), because the too low meeting of the shared ratio of CSQ makes the toughening effect of modified resin undesirable, the shared ratio of CSQ is too high, easily occurs again gel in the process of CSQ modified epoxy.The present invention has optimized the proportioning of CSQ and epoxy resin, and by first CSQ being introduced in epoxy resin, and whole reaction process is not only gentle, but also without any the generation of by product.Both guarantee cross-linking density, there will not be again gel, and can also provide basis for follow-up curing reaction.
(2) high rigidity expediting setting type coating of the present invention is made up of CSQ modified epoxy, pigment, filler, solidifying agent etc., be cured by polyisocyanate-based solidifying agent, molecular weight and the drying rate of resin are improved greatly, solved CSQ modified epoxy in not affecting mechanical property after, do the slow defect of speed, integrate the advantage of various resins, there is good mechanical property, both guaranteed the hardness of coating, kept good snappiness and erosion resistance simultaneously; The feature of hardness high (6H), good toughness (1mm), dry speed fast (5h), shock-resistance good (45kgcm).
(3) raw material of the present invention is easy to get, technique is simple, and the coating solid content that simultaneously makes is high, good leveling property, be easy to film.Speed of response is fast and can at lower temperature, carry out, in guaranteeing material hardness and wear resistance, can effectively improve coating from dryness.Applying of it will meet the demand in manufacturer and market thereof.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Many carboxyls cage-type silsesquioxane modified epoxy of the present invention, is prepared by following methods:
Many carboxyls cage-type silsesquioxane, epoxy resin and catalyzer, organic solvent are pressed the formula shown in table 1, and CSQ and epoxy resin are dropped into reactor, then drop into respectively catalyzer triphenyl phosphorus and organic solvent toluene evenly mixes; Be warming up in the scope of 105～110 ℃, insulation reaction 3 hours, differs termination reaction while being no more than 0.1mgKOH/g to acid number.Being diluted to solid part with the consumption of the ethyl acetate shown in table 1 and butylacetate is 75%, filters discharging, makes the use state CSQ modified epoxy containing high reactivity hydroxyl.
Show the formula table of preparing of 1CSQ modified epoxy
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepares a kind of high rigidity expediting setting type coating, and it includes organic coating and solidifying agent, and it is 30% that solidifying agent adds ethyl acetate to solid content before using; The weight ratio of organic coating and solidifying agent is shown in table 9; First feed intake by the listed pigment of table 9, filler, auxiliary agent each component and content proportioning thereof, in auxiliary agent, siccative is naphthenic acid metallic soap, and dispersion agent is poly carboxylic acid amine type, and flow agent is polyester modification hydroxyl organosilicon; High-speed stirring at least 5 minutes, makes organic coating; Add again the solidifying agent mixing that stirs, be cured reaction, obtain the high rigidity expediting setting type coating of use state, can spray.
Embodiment 2
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy is as follows:
Many carboxyls cage-type silsesquioxane, epoxy resin and catalyzer, organic solvent are pressed the formula shown in table 2, and CSQ and epoxy resin are dropped into reactor, then drop into respectively catalyzer 4-butyl-phosphonium acetate and organic solvent dimethylbenzene evenly mixes; Be warming up in the scope of 110～115 ℃, insulation reaction 2 hours, differs termination reaction while being no more than 0.1mgKOH/g to acid number.Being diluted to solid part with the consumption of the 200# solvent oil shown in table 2 and butylacetate is 75%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 40% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is naphthenic acid metallic soap, and dispersion agent is poly carboxylic acid amine type, and flow agent is polyester modification hydroxyl organosilicon and organic silicon modified by polyether; Its method is with embodiment 1.
Show the formula table of preparing of 2CSQ modified epoxy
Embodiment 3
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy, with embodiment 2, specifically fills a prescription as shown in table 3.Finally being diluted to solid part with the consumption of the 200# solvent oil shown in table 3 is 70%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 35% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is naphthenic acid metallic soap, and dispersion agent is poly carboxylic acid amine type and modified polyorganosiloxane type, and flow agent is polyacrylic ester and organic silicon modified by polyether; Its method is with embodiment 1.
Show the formula table of preparing of 3CSQ modified epoxy
Embodiment 4
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy, with embodiment 2, specifically fills a prescription as shown in table 4.Finally being diluted to solid part with the consumption of the dimethylbenzene shown in table 4 and ethyl acetate is 80%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 30% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is naphthenic acid metallic soap and isocaprylic acid metallic soap, and dispersion agent is modified polyorganosiloxane type and modified polyacrylate type, and flow agent is fluorin modified crylic acid ester copolymer and isocyanate-modified organosilicon; Its method is with embodiment 1.
Show the formula table of preparing of 4CSQ modified epoxy
Embodiment 5
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy is as follows:
Many carboxyls cage-type silsesquioxane, epoxy resin and catalyzer, organic solvent are pressed the formula shown in table 5, and CSQ and epoxy resin are dropped into reactor, then drop into respectively catalyzer chromium acetylacetonate and organic solvent dimethylbenzene evenly mixes; Be warming up in the scope of 110～115 ℃, insulation reaction 4 hours, differs termination reaction while being no more than 0.1mgKOH/g to acid number.Finally being diluted to solid part with the consumption of the 100# solvent oil shown in table 5 is 80%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 40% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is isocaprylic acid metallic soap, and dispersion agent is poly carboxylic acid amine type, and flow agent is polyester modification hydroxyl organosilicon; Its method is with embodiment 1.
Show the formula table of preparing of 5CSQ modified epoxy
Embodiment 6
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy, with embodiment 5, specifically fills a prescription as shown in table 6.Finally being diluted to solid part with raffinating oil shown in table 6 with the consumption of ethyl acetate is 75%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 40% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is naphthenic acid metallic soap and isocaprylic acid metallic soap, and dispersion agent is poly carboxylic acid ammonium salt type and modification acrylate type, and flow agent is organic silicon modified by polyether and isocyanate-modified organosilicon; Its method is with embodiment 1.
Show the formula table of preparing of 6CSQ modified epoxy
Embodiment 7
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy, with embodiment 2, specifically fills a prescription as shown in table 7.Finally being diluted to solid part with the consumption of the toluene shown in table 7 and ethyl acetate is 70%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 35% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is isocaprylic acid metallic soap, and dispersion agent is poly carboxylic acid amine type and poly carboxylic acid ammonium salt type, and flow agent is isocyanate-modified organosilicon; Its method is with embodiment 1.
Show the formula table of preparing of 7CSQ modified epoxy
Embodiment 8
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy, with embodiment 5, specifically fills a prescription as shown in table 8.Finally being diluted to solid part with the consumption of the petroleum naphtha shown in table 6 and butylacetate is 80%, filters discharging, makes the CSQ modified epoxy containing high reactivity hydroxyl.
Adopting above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, prepare a kind of high rigidity expediting setting type coating, it is 35% that solidifying agent adds ethyl acetate to solid content before using, and the each component of organic coating and solidifying agent and content proportioning thereof are shown in table 9; In auxiliary agent, siccative is naphthenic acid metallic soap, and dispersion agent is modified polyacrylate type, and flow agent is polyacrylic ester; Its method is with embodiment 1.
Show the formula table of preparing of 8CSQ modified epoxy
The formulation for coating material table (weight percent %) of table 9 based on CSQ modified epoxy
In the present embodiment, solidifying agent used is directly buied from market, before using, adds a small amount of ethyl acetate that its solid content is reduced to 30～40%.
Those skilled in the art can be according to actual needs, selects suitable auxiliary agent and determine its consumption in each component of the present invention and content ratio range thereof.
The performance test of the high rigidity expediting setting type coating based on CSQ modified epoxy, operates as follows:
Test sample preparation methods: use tinplate as base material, with sand paper, the tinplate sheet polishing of getting ready is removed to oil stain above, clean, dry with deionized water, finally use spreader to apply.Coat-thickness is at 30 ± 5 μ m, solidifies test performance after 10～60min at 30～60 ℃, the results are shown in Table 10.
(1) mensuration of hardness: with reference to standard GB/T/T6739-86, prepare one group of drawing pencil that hardness is 6B～6H, measure the pencil hardness of film by manual method.On the table top that film plate level is placed on, hand-held pencil angle at 45 ° firmly pushes about 1cm, and stay and scratch on film with uniform speed on coated surface.The pencil of same hardness label is repeated to scratch 5 roads, if any 2 roads or the above base plate that does not scratch model, uses the pencil of the large label of hardness instead, until find film be scratched 2 roads or more than.Be the pencil hardness of film than the little label of this pencil hardness.
(2) mensuration of sticking power: with reference to standard GB/T/T9286-1998, cut the 6 parallel cut channels in road with drawing cutter on paint film, should cut the entire depth of wearing paint film; Then in the direction vertical with the former, draw 6 same road cut channels, form many lattices, then the Pressuresensitive Tape of standard is determined the progression of film adhesive.
(3) erosion resistance test: with reference to standard GB/T/T1771-91, adopt Q235 steel as base material, after spraying, the thickness of coating is 150 ± 5 μ m, carries out neutral salt spray test after being fully dried.
(4) snappiness test: with reference to standard GB/T/T1731-93.By test plate (panel) paint film upward, with the hands paint film is pressed on the mandrel rod of specified diameter, in 2～3s, around the bending test plate (panel) of mandrel rod.Observe paint film and whether produce reticulate pattern, crackle and the breakoff phenomenon such as peel off, reference standard is determined suppleness.
(5) test of time of drying: with reference to standard GB/T/T1728-79, paint spay-coating, on tinplate, is measured respectively to the surface drying time of coating, do solid work the time.
(6) shock-resistance test: with reference to standard GB/T/T1732-93, paint spay-coating, on tinplate, by adjusting the descending height of weight, is measured to the impact resistance of paint film.
The performance index of the coating of table 10 based on CSQ modified epoxy
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Hardness of paint film (H) | 6 | 6 | 4 | 5 | 3 | 4 | 6 | 5 |
| Sticking power | 0 | 1 | 1 | 1 | 0 | 0 | 1 | 0 |
| Corrosion-resistant (96h) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Snappiness (mm) | 2 | 1 | 1 | 1 | 2 | 2 | 1 | 1 |
| Surface drying time (min) | 30 | 50 | 20 | 20 | 50 | 40 | 50 | 20 |
| Do solid work the time (h) | 12 | 8 | 12 | 5 | 9 | 6 | 8 | 10 |
| Impact resistance (kgcm) | 30 | 20 | 35 | 45 | 45 | 30 | 35 | 35 |
The coating that the present invention prepares as can be seen from Table 10 has good mechanical property, has both guaranteed the hardness of coating, has kept good snappiness and erosion resistance simultaneously.
At home and abroad, in epoxide modified research, only embody CSQ and epoxy resin and carry out physical blending, CSQ modified epoxy can effectively embody the snappiness of CSQ, and its hybrid material has again excellent corrosion resistance and the high rigidity of epoxy resin.But this method of modifying is more difficult often, be mainly reflected in CSQ difficult dispersion in epoxy resin.And this method of modifying can produce any impact hardly on the dry speed of epoxy resin.Therefore, synthetic a kind of hardness is high, wear resistance good, the fast epoxy resin of dry speed, is that manufacturer is pursued always, but still blank in this part research at home and abroad.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. the cage-type silsesquioxane of carboxyl a more than modified epoxy, is characterized in that being prepared by following methods:
By many carboxyls cage-type silsesquioxane and epoxy resin in mass ratio 1:4～1:7 feed intake in reactor, and add by the catalyzer of reaction system total mass 0.15～0.3% and account for the organic solvent of resin total mass 20%, evenly mix; Under 105～115 ℃ of conditions, react 2～4h, filter discharging, obtain the many carboxyls cage-type silsesquioxane modified epoxy containing high reactivity hydroxyl;
Described catalyzer refers at least one in chromium acetylacetonate, 4-butyl-phosphonium acetate, trolamine, triphenyl phosphorus, benzyldimethylamine and Bian base triphenyl phosphonium muriate;
Described organic solvent nail benzene is or/and dimethylbenzene.
2. many carboxyls of one cage-type silsesquioxane modified epoxy according to claim 1, is characterized in that: the cage-type silsesquioxane of many carboxyls described in preparation method, structural formula is: (SiO
1.5)
m(C
6h
4cOOH)
m(m=8,10,12).
3. many carboxyls of one cage-type silsesquioxane modified epoxy according to claim 1, is characterized in that: described epoxy resin refers at least one in bisphenol A type epoxy resin, bisphenol f type epoxy resin, methylol bisphenol A type epoxy resin, bisphenol-A epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.
4. the application of the modified epoxy of carboxyl cage-type silsesquioxane more than a kind in coating, it is characterized in that: many carboxyls cage-type silsesquioxane modified epoxy prepared by the preparation method described in employing claim 1～3 is raw material, prepare a kind of high rigidity expediting setting type coating, it includes organic coating and solidifying agent, and the mass ratio of organic coating and solidifying agent is 30:50～70:25; First each organic coating component dispersed with stirring, then carry out curing reaction after adding solidifying agent to mix, obtain the high rigidity expediting setting type coating of use state;
Wherein, organic coating comprises following by the component of system total mass per-cent:
Described solidifying agent refers to polyisocyanate-based solidifying agent;
Described pigment refers at least one in titanium dioxide, phthalocyanine blue, phthalocyanine green and carbon black;
Described filler refers at least one in calcium carbonate, white carbon black, kaolin, magnesium hydroxide and barium sulfate;
Described auxiliary agent refers at least one in dispersion agent, flow agent and siccative;
It is 70～80% that described many carboxyls cage-type silsesquioxane modified epoxy is diluted to solid content with diluting solvent before using.
5. the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy according to claim 4 in coating, is characterized in that: described polyisocyanate-based solidifying agent refers at least one in adduct and the HDI biuret of adduct, XDI and TriMethylolPropane(TMP) of adduct, IPDI and the TriMethylolPropane(TMP) of TDI tripolymer, IPDI tripolymer, TDI and TriMethylolPropane(TMP).
6. the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy according to claim 4 in coating, is characterized in that: described diluting solvent nail benzene, dimethylbenzene, petroleum naphtha, raffinate oil, at least one in ethyl acetate, butylacetate, 100# solvent oil and 200# solvent oil.
7. the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy according to claim 4 in coating, is characterized in that: it is 30～40% that described solidifying agent adds ethyl acetate to solid content before using.
8. the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy according to claim 4 in coating, is characterized in that: at least one in described siccative finger ring alkanoic acid metallic soap and isocaprylic acid metallic soap.
9. the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy according to claim 4 in coating, is characterized in that: described dispersion agent is at least one in poly carboxylic acid amine type, modified polyorganosiloxane type, modified polyacrylate type and poly carboxylic acid ammonium salt type etc.
10. the application of a kind of many carboxyls cage-type silsesquioxane modified epoxy according to claim 4 in coating, is characterized in that: described flow agent is at least one in organic silicon modified by polyether, polyester modification hydroxyl organosilicon, isocyanate-modified organosilicon, polyacrylic ester and fluorin modified crylic acid ester copolymer.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN105778717A (en) * | 2016-04-01 | 2016-07-20 | 厦门大学 | Fluorine-silicone containing epoxy resin radiation-resistant coating and preparation method thereof |
| CN114046008A (en) * | 2021-11-17 | 2022-02-15 | 瑞宇建设有限公司 | Waterproof building external wall heat insulation structure and construction method thereof |
| CN114292404A (en) * | 2021-12-30 | 2022-04-08 | 广东盈骅新材料科技有限公司 | POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition |
| CN115093785A (en) * | 2022-08-03 | 2022-09-23 | 长园长通科技有限公司 | Weather-proof double-component solvent-free polyurethane coating for pipeline joint coating and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745017A (en) * | 2015-03-06 | 2015-07-01 | 金湖金龙祥渔业设备有限公司 | High-weather-resistant and wear-resistant coating for lotus root digging machine and preparation method of coating |
| CN104745017B (en) * | 2015-03-06 | 2017-03-01 | 金湖金龙祥渔业设备有限公司 | A kind of high durable wear-resistant paint for lotus root digging harvester and preparation method thereof |
| CN105778717A (en) * | 2016-04-01 | 2016-07-20 | 厦门大学 | Fluorine-silicone containing epoxy resin radiation-resistant coating and preparation method thereof |
| WO2017166913A1 (en) * | 2016-04-01 | 2017-10-05 | 厦门大学 | Radiation-resistant fluorine-silicon containing epoxy-resin coating and preparation method thereof |
| CN114046008A (en) * | 2021-11-17 | 2022-02-15 | 瑞宇建设有限公司 | Waterproof building external wall heat insulation structure and construction method thereof |
| CN114292404A (en) * | 2021-12-30 | 2022-04-08 | 广东盈骅新材料科技有限公司 | POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition |
| CN115093785A (en) * | 2022-08-03 | 2022-09-23 | 长园长通科技有限公司 | Weather-proof double-component solvent-free polyurethane coating for pipeline joint coating and preparation method thereof |
| CN115260890A (en) * | 2022-08-19 | 2022-11-01 | 张滨 | Silane modified epoxy waterborne polyurethane steel structure anticorrosive paint |
| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
| CN115819039A (en) * | 2022-11-24 | 2023-03-21 | 龙岩市宝丽建材科技有限公司 | High-strength environment-friendly artistic micro-cement and preparation method thereof |
| CN115819039B (en) * | 2022-11-24 | 2024-01-19 | 龙岩市宝丽建材科技有限公司 | High-strength environment-friendly artistic micro-cement and preparation method thereof |
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